CN113597445A - Flame-retardant termite-resistant resin composition, power cable, and method for producing and laying same - Google Patents
Flame-retardant termite-resistant resin composition, power cable, and method for producing and laying same Download PDFInfo
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- CN113597445A CN113597445A CN202080022418.6A CN202080022418A CN113597445A CN 113597445 A CN113597445 A CN 113597445A CN 202080022418 A CN202080022418 A CN 202080022418A CN 113597445 A CN113597445 A CN 113597445A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
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- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B9/00—Power cables
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
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Abstract
The invention provides a flame-retardant and termite-proof resin composition which can form a sheath with excellent flame retardancy and termite-proof performance by a single layer and is suitable for forming the sheath by extrusion processing, a power cable using the sheath as a raw material, and a manufacturing method and an laying method thereof. The flame-retardant termite-resistant resin composition contains a base resin having a solubility parameter of 7.1 to 11.6 inclusive, a compound having an isocyanurate structure, and a boron-containing compound, wherein the content of the compound having an isocyanurate structure is in the range of 0.05 to 10 parts by mass relative to 100 parts by mass of the base resin, and the content of the boron-containing compound is in the range of 10 to 55 parts by mass relative to 100 parts by mass of the base resin. The flame-retardant ant-proof resin composition is preferably used for the raw material of the sheath 13 constituting the outermost layer of the power cable 1.
Description
Technical Field
The present invention relates to a flame-retardant and termite-resistant resin composition containing a component having flame retardancy and termite resistance, a power cable having a sheath formed using the flame-retardant and termite-resistant resin composition, a method for producing the power cable, and a method for laying the power cable.
Background
As cables such as communication cables, such as power cables and optical cables, cables in which a sheath (protective outer coating) is formed as the outermost layer on the outer peripheral side of a core wire are widely used. The sheath is required to have various functions depending on the place where the cable is laid, and for example, in the cable laid underground in an area where movement of termites is active, flame retardancy is required in addition to termite resistance which is a characteristic of preventing insect damage by termites such as termites.
Among them, as a method for imparting termite resistance to a cable, the following methods can be mentioned: a method of physically preventing termite damage by preventing termite bite by hardening sheath of cable; and a method of preventing termite damage by incorporating an ingredient effective for controlling termites (hereinafter referred to as "termite control agent") into the sheath to kill the bitten termites.
As the former method, for example, patent document 1 describes that a sheath constituting a cable is composed of two layers, a flame-retardant ethylene layer and an outermost layer made of a polypropylene resin composition containing a polymer resin composed of a propylene homopolymerization part and a resin component having a solubility parameter of 7.0 or more and 9.5 or less, and a flame retardant, and has a rockwell hardness of 85 or more and a flexural modulus of 1500MPa or more. The sheath constituting the outermost layer of the cable is provided with flame retardancy by the flame-retardant ethylene layer constituting the sheath and the flame retardant contained in the outermost layer, and is provided with termite resistance by setting the mass ratio of the propylene homopolymer portion contained in the polymer resin forming the outermost layer to a predetermined range and high hardness and high flexural modulus.
As the latter method, for example, patent document 2 describes an ant-preventing electric wire having a sheath made of polyethylene or the like, in which triallyl isocyanurate, tripropyl isocyanurate, or triethyl isocyanurate is contained as an ant-preventing component as a resin composition in which volatilization and outflow (exudation) of the ant-preventing component is little. Further, in the ant-proof electric wire, the sheath contains the ant-proof component, thereby imparting the cable with ant-proof property.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-096583
Patent document 2: japanese laid-open patent publication No. H02-078110
Disclosure of Invention
Problems to be solved by the invention
In the cable described in patent document 1, since the sheath is formed of two layers, i.e., the flame-retardant ethylene layer and the outermost layer made of the polypropylene resin composition, the manufacturing cost increases, the number of manufacturing steps increases, and the workability is poor, and in addition, the termite resistance is assumed on the premise that the sheath is bitten by termites, and therefore, the insect damage to the cable cannot be completely prevented.
In addition, the ant-proof electric wire described in patent document 2 has a problem that insect damage to the cable cannot be completely prevented because a material design is performed on the premise that termites bite the sheath by using an ant-proof component (compound) having good compatibility with a base resin constituting the sheath in the sheath, and the ant-proof component is not allowed to flow out from the sheath (ant-proof layer).
In addition, a method of disposing the ant repellent around the cable without incorporating the ant repellent into the material is also conceivable, but particularly in a cable having a certain length, attachment of the ant repellent takes time, and therefore, it is not practical.
In addition, in order to form a sheath as an outermost layer of a cable, it is necessary to extrude a resin kneaded at a predetermined temperature to the outer periphery of a core wire of the cable to coat the outer periphery with the resin to form the sheath.
The purpose of the present invention is to provide a flame-retardant and termite-resistant resin composition which can form a sheath having excellent flame retardancy and termite resistance from a single layer and which is suitable for forming a sheath by extrusion processing, a power cable having a sheath formed using the same as a raw material, and a method for producing and a method for laying the same.
Means for solving the problems
The inventors of the present application paid attention to the relationship between the compatibility of the base resin and the compound having an isocyanurate structure and the contents of the boron-containing compound and the isocyanurate, and made intensive studies to highly satisfy flame retardancy, termite resistance and suitability for extrusion processing. As a result, it has been found that a sheath excellent in both flame retardancy and termite resistance can be formed in a single layer by using a base resin having a solubility parameter in the range of 7.1 to 11.6 and containing a compound having an isocyanurate structure and a boron-containing compound.
However, in the case where the sheath having the above-described composition is formed in a single layer, the following new problems arise: if the amount of the compound having an isocyanurate structure added during extrusion processing is too large, white smoke and odor of the organic compound are likely to be generated, and therefore, an exhaust device such as a local exhaust device is required, which leads to an increase in production cost.
The present inventors have further studied and found that white smoke and odor of organic compounds are not generated during extrusion processing and that the compound having an isocyanurate structure and a boron-containing compound are suitable for extrusion processing by limiting the proportion of the compound having an isocyanurate structure and the compound having a boron-containing structure to the base resin.
That is, the gist of the present invention is as follows.
(1) A flame-retardant termite-resistant resin composition which comprises a base resin having a solubility parameter of 7.1 to 11.6 inclusive, a compound having an isocyanurate structure, and a boron-containing compound, wherein the content of the compound having an isocyanurate structure is in the range of 0.05 to 10 parts by mass relative to 100 parts by mass of the base resin, and the content of the boron-containing compound is in the range of 10 to 55 parts by mass relative to 100 parts by mass of the base resin.
(2) The flame-retardant ant-repelling resin composition according to the above (1), wherein the solubility parameter of the base resin is in the range of 7.1 or more and 10.8 or less.
(3) The flame-retardant ant-repelling resin composition according to the above (1) or (2), wherein the content of the compound having an isocyanurate structure is in the range of 0.05 to 1 part by mass based on 100 parts by mass of the base resin.
(4) The flame-retardant ant-repellent resin composition according to the above (1), (2) or (3), wherein the content of the boron-containing compound is in the range of 10 to 45 parts by mass with respect to 100 parts by mass of the base resin.
(5) The flame-retardant ant-controlling resin composition as described in any one of (1) to (4) above, which is used for a raw material of a sheath constituting an outermost layer of a power cable.
(6) A method for manufacturing a power cable having a sheath formed as an outermost layer on an outer peripheral side of a core wire, the method comprising: the flame-retardant ant-controlling resin composition described in any one of (1) to (5) above is extrusion-molded on the outer peripheral side of the core wire, thereby being coated to form a sheath.
(7) An electric power cable having a core wire coated on the outer periphery thereof with a sheath formed from the flame-retardant termite-resistant resin composition according to any one of the above (1) to (5) as a raw material as an outermost layer.
(8) The power cable according to (7) above, wherein the sheath is formed of a single layer.
(9) The power cable according to the above (7) or (8), wherein the sheath contains the compound having an isocyanurate structure, and the compound having an isocyanurate structure is exposed on an outer surface of the sheath.
(10) The method of laying a power cable according to any one of (7) to (9) above, comprising a step of directly burying the power cable in the ground.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a flame-retardant and termite-resistant resin composition which can provide a sheath having excellent flame retardancy and termite resistance even in a single-layer structure and has suitability for extrusion processing, a power cable using the same, and a method for producing and a method for laying the same can be obtained. Accordingly, when the flame-retardant and termite-resistant resin composition is used as a sheath of a power cable, a single layer exhibits desired flame retardancy and termite resistance, and therefore, the outer diameter of the power cable can be reduced, and the power cable can be efficiently manufactured.
Drawings
Fig. 1 is a cross-sectional view schematically showing a conceptual configuration of a power cable according to the present invention.
Fig. 2 is a cross-sectional view schematically showing an example of a specific configuration of a power cable according to the present invention.
Fig. 3 is a cross-sectional view schematically showing the structure of a conventional cable.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the present invention.
< flame retardant Ant-repellent resin composition >
The flame-retardant termite-resistant resin composition of the present invention comprises a base resin having a solubility parameter in the range of 7.1 to 11.6, a compound having an isocyanurate structure, and a boron-containing compound, wherein the content of the compound having an isocyanurate structure is in the range of 0.05 to 10 parts by mass relative to 100 parts by mass of the base resin, and the content of the boron-containing compound is in the range of 10 to 55 parts by mass relative to 100 parts by mass of the base resin.
In the case where the flame-retardant and termite-proof resin composition according to the present embodiment is applied to, for example, a sheath forming the outermost layer of a power cable as a raw material, the sheath contains a boron-containing compound, and therefore, a desired flame-retardant performance can be exhibited, and a compound having an isocyanurate structure with low volatility is allowed to permeate (exude) to a degree of covering only a thin layer on the surface of the sheath to be exposed and attached, and the state in which the compound is attached can be maintained for a long period of time. Further, the boron-containing compound contained in the flame-retardant ant-preventing resin composition also has an ant-preventing property when the ant bites the sheath, and therefore, even in the case where the compound having an isocyanurate structure exposed and attached to the sheath is wiped off from the surface of the sheath or the case where the exposure of the compound having an isocyanurate structure by bleeding is small, for example, the ant-preventing property generated when the ant bites the sheath can be exhibited, and therefore, insect damage of the power cable by the ant can be continuously prevented. Therefore, even when the sheath of the power cable is formed as a single layer by using the flame-retardant and termite-resistant resin composition according to the present embodiment, both flame retardancy and termite resistance can be imparted to the power cable.
[ flame-retardant Ant-controlling resin composition ]
The flame-retardant termite-resistant resin composition according to the present embodiment comprises a base resin (a), a compound (B) having an isocyanurate structure (hereinafter, may be simply referred to as "isocyanurate compound (B)"), and a boron-containing compound (C).
(base resin (A))
Wherein the base resin (A) has a solubility parameter (SP value) of 7.1 to 11.6. Here, by containing a resin having a solubility parameter (SP value) of 11.6 or less as the base resin (a), the compatibility with the isocyanurate compound (B) is lowered, and therefore the isocyanurate compound (B) can be exuded from the base resin (a). Further, by containing a resin having a solubility parameter (SP value) of 7.1 or more and 11.6 or less as the base resin (a), the intermolecular interaction of the base resin (a) can be appropriately adjusted, and therefore the isocyanurate compound (B) described later can be gradually exuded from the base resin (a) over a long period of time.
The base resin (a) is not particularly limited as long as it has a solubility parameter of 7.1 to 11.6. Examples of such resins include polyolefins including ethylene resins, diene rubbers, polyamide resins, ethylene-propylene rubbers, ethylene-propylene-diene rubbers, and thermoplastic elastomers.
Specific examples of the polyolefin include polyethylene (SP value: 7.7 to 8.4), polypropylene (SP value: 9.3), polybutene (SP value: 9.4), polystyrene (SP value: 8.5 to 10.3), polyester (SP value: 10.7), acrylonitrile-styrene resin (SP value: 9.8 to 10.7), ethylene-vinyl acetate copolymer (SP value: 8.8 to 9.4), ethylene-ethyl acrylate copolymer (SP value: 9.4), polyisobutylene (SP value: 7.1 to 8.3), polyvinyl chloride (SP value: 9.4 to 10.8), polyvinyl acetate (SP value: 9.4 to 9.6), and the like.
Specific examples of the diene rubber include butyl rubber (SP value: 7.7 to 8.1), butadiene rubber (SP value: 8.1 to 8.6), chloroprene rubber (SP value: 8.2 to 9.4), and nitrile rubber (SP value: 8.7 to 10.5).
Specific examples of the polyamide resin include nylon 6(SP value: 11.6), nylon 66(SP value: 11.6), nylon 11(SP value: 10.1), nylon 12(SP value: 9.9), and the like.
Among these, 1 or more selected from polyethylene, polypropylene, and polyvinyl chloride are preferably used as the base resin (a).
The solubility parameter (SP value) of the base resin (a) in the present embodiment is 11.6 or less, preferably 10.8 or less. By using such a base resin (a), the difference in solubility parameter between the isocyanurate compound (B) and the base resin (a) becomes large, and the compatibility becomes low, so that the isocyanurate compound (B) can be easily exuded from the base resin (a). On the other hand, in order to release the isocyanurate compound (B) from the base resin (A) slowly, the lower limit of the solubility parameter (SP value) of the base resin (A) is preferably 7.1 or more, more preferably 7.7 or more.
Here, as the base resin (a), only 1 kind of resin having a solubility parameter (SP value) within the above-mentioned suitable range may be used, or 2 or more kinds of resins having a solubility parameter (SP value) within the above-mentioned suitable range may be used in combination.
The base resin (a) is preferably composed of only a resin having a solubility parameter of 7.1 to 11.6, but may include a resin having a solubility parameter outside the above-described suitable range as long as the mass ratio of the base resin (a) is within 10%.
(Compound (B) having an isocyanurate structure)
The compound (B) having an isocyanurate structure in the molecule functions as an ant-controlling agent, and is exposed by bleeding and attached to the surface of the flame-retardant ant-controlling resin obtained from the composition, thereby protecting the flame-retardant ant-controlling resin, and thus has an effect of effectively reducing insect damage caused to the flame-retardant ant-controlling resin by termites such as termites.
The isocyanurate compound (B) may be a conventionally known isocyanurate compound, and is not particularly limited, but is preferably a compound represented by the following general formula (I).
[ chemical formula 1]
(wherein, R1～R3Each independently represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. )
R as a constituent of the above general formula (I)1～R3The aliphatic hydrocarbon group (b) may be a saturated hydrocarbon group, an unsaturated hydrocarbon group, or a cyclic hydrocarbon group. More specifically, examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a cycloalkenyl group, and an alkyl group and an alkenyl group are preferable. In addition, the number of carbon atoms contained in the aliphatic hydrocarbon group is excellentIs selected from 1 to 20, more preferably 1 to 12, still more preferably 1 to 8, and particularly preferably 1 to 6. In the combination, the aliphatic hydrocarbon group is more preferably an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms. Specific examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl, decyl, vinyl, allyl, isopropenyl, ethynyl, cyclopropyl, cyclopentyl, cyclohexyl and cyclohexenyl.
R constituting the above general formula (I)1～R3The number of carbon atoms of the aryl group(s) is preferably 6 to 20, more preferably 6 to 16, and still more preferably 6 to 10. Specific examples of the aryl group include a phenyl group and a naphthyl group.
R constituting the above general formula (I)1～R3The heterocyclic group of (b) preferably has at least 1 atom selected from an oxygen atom, a nitrogen atom and a sulfur atom as a constituent atom of the heterocyclic ring. Here, the heterocyclic ring included in the heterocyclic group may be a saturated ring, an unsaturated ring, or an aromatic ring. The number of carbon atoms of the heterocyclic group is preferably 0 to 20, more preferably 1 to 12. Examples of the heterocyclic ring included in the heterocyclic group include a tetrahydrofuran ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a thiazole ring, and a pyridine ring.
For the compounds represented by the above general formula (I), R is preferred1～R3Each independently is a hydrogen atom or an aliphatic hydrocarbon group, more preferably R1～R3Are all aliphatic hydrocarbon groups, and further R is preferable1～R3Are each a group selected from an alkyl group or an alkenyl group, wherein R is more preferred1～R3Are the same group.
Among the compounds represented by the above general formula (I), preferable compounds are trimethyl isocyanurate, triethyl isocyanurate, tripropyl isocyanurate and triallyl isocyanurate. Among them, triethyl isocyanurate, tripropyl isocyanurate, and triallyl isocyanurate are more preferable, and triallyl isocyanurate (i.e., 1, 3, 5-tris (2-propenyl) -1, 3, 5-triazine-2, 4, 6(1H,3H,5H) -trione) is most preferable.
The content of the isocyanurate compound (B) is necessarily 0.05 parts by mass or more, and preferably 0.50 parts by mass or more, based on 100 parts by mass of the base resin (a). Thus, the compound having an isocyanurate structure, which is low in volatility and has termite resistance, is exposed by bleeding and adheres to the surface of the flame-retardant termite-resistant resin produced from the flame-retardant termite-resistant resin composition, and therefore, when the flame-retardant termite-resistant resin composition is used as a raw material of a sheath, insect damage to a power cable by termites can be reduced. On the other hand, the upper limit of the content of the isocyanurate compound (B) must be set to 10 parts by mass, preferably 5 parts by mass, and more preferably 1 part by mass in view of not generating white smoke and odor of an organic compound when the flame-retardant ant-controlling resin composition is extrusion-processed, and suitability for extrusion-processing.
(boron-containing Compound (C))
The boron-containing compound (C) is a compound having a boron atom in the molecule, and has the following effects: improve flame retardancy when used as a raw material for sheaths, and improve termite-proof performance by becoming a toxic food for termites such as termites.
In the flame-retardant and termite-proof resin composition according to the present embodiment, by using the boron-containing compound (C) in combination with the isocyanurate compound (B), even when the isocyanurate compound (B) is wiped off from the surface of the flame-retardant and termite-proof resin and the exposure of the isocyanurate compound (B) due to bleeding is small, insect damage to the flame-retardant and termite-proof resin by ants can be reduced.
More specifically, the boron-containing compound (C) includes 1 or more selected from borate compounds, boron oxides, boron sulfides, and boron nitrides. Among them, a borate compound is preferably used, and zinc borate is particularly preferably used.
The content of the boron-containing compound (C) must be 10 parts by mass or more per 100 parts by mass of the base resin (a). Thus, the flame-retardant and termite-resistant resin produced from the flame-retardant and termite-resistant resin composition can be improved in both flame retardancy and termite resistance. On the other hand, in view of the ability to uniformly contain the boron-containing compound (C) in the flame-retardant ant-controlling resin composition and the suitability for extrusion processing, the upper limit of the content of the boron-containing compound (C) must be set to 55 parts by mass, more preferably 45 parts by mass, still more preferably 35 parts by mass, and particularly preferably 20 parts by mass, based on 100 parts by mass of the base resin (a).
The ratio of the content (part by mass) of the boron-containing compound (C) to the content (part by mass) of the isocyanurate compound (B) is preferably 1 or more and less than 1000, and more preferably 5 or more and 200 or less. In particular, by making the value of the ratio of the content of the boron-containing compound (C) to the content of the isocyanurate compound (B) 1 or more, more preferably 5 or more, the suitability of the flame-retardant ant-repellent resin composition for extrusion processing can be improved, and the oxygen index of the flame-retardant ant-repellent resin composition can be improved. On the other hand, when the value of the ratio of the content of the boron-containing compound (C) to the content of the isocyanurate compound (B) is less than 1000, more preferably 200 or less, bleeding of the compound having an isocyanurate structure onto the surface of the flame-retardant ant-repellent resin is likely to occur, whereby damage by termites can be made less likely to occur.
(other component (D))
The flame-retardant ant-controlling resin composition according to the present embodiment may contain other components as needed.
For example, the flame-retardant ant-repellent resin composition according to the present embodiment may contain one or both of a flame retardant and a flame-retardant auxiliary in addition to the boron-containing compound (C). The flame retardant and the flame retardant aid are not particularly limited, and examples thereof include antimony trioxide, polytetrafluoroethylene, silica, hydrotalcite, magnesium hydrogen carbonate, metal hydroxides such as magnesium hydroxide and calcium hydroxide, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, vanadium oxide, molybdenum oxide, phosphorus compounds and surface-treated products thereof, melamine cyanurate, pentaerythritol, dipentaerythritol, tripentaerythritol, polytetrafluoroethylene, and the like. Among these, from the viewpoint of further improving flame retardancy, one or both of antimony trioxide and a metal hydroxide are preferably contained. The content of these flame retardant and flame retardant auxiliary may be within a range not to impair the characteristics of the flame-retardant ant-controlling resin composition of the present invention.
The flame-retardant and termite-proof resin composition according to the present embodiment may contain, if necessary, additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, a lubricant, a crystal nucleus agent, a softening agent, an antistatic agent, a metal deactivator, an antibacterial/antifungal agent, a colorant, a pigment, a dye, and a phosphor.
[ method for manufacturing Power Cable ]
The method for manufacturing the power cable according to the present embodiment is not particularly limited, and includes, for example, the following steps: the sheath is formed by extruding the flame-retardant termite-resistant resin composition on the outer peripheral side of the core wire to coat the core wire. Thus, a power cable having a sheath formed on the outer peripheral side of the core wire as the outermost layer can be obtained.
Here, as a means for extrusion molding the flame-retardant ant-controlling resin composition, a known means for extrusion molding can be used.
Further, before the above flame-retardant and termite-resistant resin composition is extrusion-molded, it is preferable to knead the flame-retardant and termite-resistant resin composition. As a means for kneading the flame-retardant and termite-resistant resin composition, known means can be used, and for example, a means for melting and kneading the base resin (a), the isocyanurate compound (B) and the boron-containing compound (C) can be used.
The kneading of the flame-retardant and termite-resistant resin composition and the molding of the flame-retardant and termite-resistant resin may be carried out not as separate steps but by, for example, melting, kneading and extruding the flame-retardant and termite-resistant resin composition by using the same apparatus.
< Power Cable >
The power cable 1 according to the present embodiment is formed by coating the outer periphery of the core wire 11 with the sheath 13 made of the flame-retardant and termite-resistant resin composition as described above as an outermost layer as conceptually shown in fig. 1, and is not particularly limited as long as the intermediate layer 12 is provided between the core wire 11 and the sheath 13. The power cable 1 can be obtained by the method described above, for example.
More specifically, as shown in fig. 2, the power cable 1A may be configured as follows: at least an insulating layer 122 is laminated as an intermediate layer on the outer periphery of the conductor of the core wire 11, and more preferably, an inner semiconductive layer 121, an insulating layer 122, an outer semiconductive layer 123, and a metal shield layer 124 are laminated in this order, and a sheath 13 is laminated as an outermost layer on the outer periphery thereof.
The power cable 1 according to the present embodiment can exhibit desired flame retardancy and termite resistance, and therefore can be suitably laid in places where insect damage by termites is likely to occur, places where fire damage by termite insect damage is likely to occur, and places where damage by surrounding fire is likely to occur.
In addition, since the power cable 1 according to the present embodiment can exhibit both of the desired flame retardancy and the desired termite resistance even if the sheath 13 is formed of a single layer, the power cable can be manufactured efficiently by reducing the outer diameter of the power cable as compared with a power cable in which the sheath is formed of a double layer and by having suitability for extrusion processing.
In the above-described embodiment, the power cable 1 is described, but the flame-retardant and termite-resistant resin composition of the present invention can exhibit the same effect as that of the power cable of the present invention if it is used as a material for a sheath constituting the cable, and therefore, it is needless to say that it can be applied to the entire cable including a communication cable such as an optical fiber cable.
Further, it is also preferable that the power cable 1 according to the present embodiment is laid by a laying method having a step of directly burying the cable underground. Thus, even if the component oozing from the surface of the power cable 1 is washed away by rainfall or the like, the component can be adsorbed by the soil or the like existing around the power cable 1 and left around the power cable 1, and therefore, the termite resistance of the power cable 1 can be continued and insect damage by termites can be made less likely to occur.
Examples
Next, the present invention examples and comparative examples will be described in order to make the effects of the present invention more clear, but the present invention is not limited to these present invention examples.
< evaluation of Properties in sheath-Forming Material (sheet) >
[ inventive examples 1 and 2]
After a resin composition was obtained by blending polyethylene, triallyl isocyanurate and zinc borate at the proportions (parts by mass) shown in table 1, the resin composition was kneaded using a roll mill set at a kneading temperature of 110 ℃ to produce a resin, and 2 sheet-like samples having different thicknesses were prepared. These 2 samples were heated to a molding temperature of 120 ℃ and press-molded at a pressure of 11MPa for 15 minutes to obtain smooth sheets having a thickness of 2mm and 3mm, respectively.
[ inventive examples 3 to 5]
After polyvinyl chloride, triallyl isocyanurate, and zinc borate were compounded in the proportions (parts by mass) shown in table 1 to obtain a resin composition, the resin composition was kneaded using a roll mill set at a kneading temperature of 150 ℃ to produce a resin, and 2 sheet-like samples having different thicknesses were prepared. These 2 samples were heated to a molding temperature of 170 ℃ and press-molded at a pressure of 11MPa for 15 minutes to obtain smooth sheets having a thickness of 2mm and 3mm, respectively.
[ inventive example 6]
Pellets of nylon 66, triallyl isocyanurate, and zinc borate were dry-blended in the proportions (parts by mass) shown in table 1 to obtain a resin composition, and the resin composition was kneaded at a kneading temperature of 210 ℃ by single-screw extrusion to produce a resin. The obtained resin was heated to a molding temperature of 220 ℃ and pressure-molded at a pressure of 11MPa for 10 minutes to obtain 2 smooth sheets having a thickness of 2mm and 3 mm.
Comparative example 1
After obtaining a resin composition composed of polyethylene at the ratio (parts by mass) shown in table 2, the resin composition was kneaded using a roll mill set at a kneading temperature of 110 ℃ to produce a resin, and 2 sheet-like samples having different thicknesses were prepared. These 2 samples were heated to a molding temperature of 120 ℃ and press-molded at a pressure of 11MPa for 15 minutes to obtain 2 smooth sheets having a thickness of 2mm and 3mm, respectively.
Comparative example 2
After a resin composition was obtained by blending polyethylene and triallyl isocyanurate in the proportions (parts by mass) shown in table 2, the resin composition was kneaded using a roll mill set at a kneading temperature of 110 ℃ to produce a resin, and 2 sheet-like samples having different thicknesses were prepared. These 2 samples were heated to a molding temperature of 120 ℃ and press-molded at a pressure of 11MPa for 15 minutes to obtain 2 smooth sheets having a thickness of 2mm and 3mm, respectively.
[ comparative examples 3 to 5]
After a resin composition was obtained by blending polyethylene, triallyl isocyanurate and zinc borate at the proportions (parts by mass) shown in table 2, the resin composition was kneaded using a roll mill set at a kneading temperature of 150 ℃ to produce a resin, and 2 sheet-like samples having different thicknesses were prepared. These 2 samples were heated to a molding temperature of 170 ℃ and press-molded at a pressure of 11MPa for 15 minutes to obtain 2 smooth sheets having a thickness of 2mm and 3mm, respectively.
Comparative example 6
Pellets of nylon 46 and triallyl isocyanurate were dry-blended at the proportions (parts by mass) shown in table 2 to obtain a resin composition, and the resin composition was kneaded at a kneading temperature of 295 ℃ by single-screw extrusion to produce a resin, thereby preparing 2 sheet-like samples having different thicknesses. These 2 samples were heated to a molding temperature of 305 ℃ and press-molded at a pressure of 11MPa for 10 minutes to obtain 2 smooth sheets having a thickness of 2mm and 3mm, respectively.
Comparative example 7
Pellets of nylon 66 were dry-blended at the proportions (parts by mass) shown in table 2 below to obtain a resin composition, and the resin composition was kneaded at a kneading temperature of 210 ℃ by single-screw extrusion to produce a resin, thereby preparing 2 sheet-like samples having different thicknesses. These 2 samples were heated to a molding temperature of 220 ℃ and press-molded at a pressure of 11MPa for 10 minutes to obtain 2 smooth sheets having a thickness of 2mm and 3mm, respectively.
[ evaluation of inventive examples 1 to 6 and comparative examples 1 to 7]
Using the sheets produced from the resin compositions according to inventive examples 1 to 6 and comparative examples 1 to 7, the following characteristic evaluations were carried out. The evaluation conditions for each property are as follows. The results are shown in tables 1 and 2.
[1] Anti-termite property
The sheets having a thickness of 2mm obtained in the present invention examples and comparative examples were cut out to prepare 3 samples each having a length of 20mm, a width of 20mm and a thickness of 2mm, and a forced food intake test was carried out in accordance with JIS K1571 (2010) "test method for wood preservative-performance standard". A cylindrical container made of acryl having an inner diameter of 80mm and a height of 60mm, the bottom of which is reinforced with anhydrite, was used, and a net made of plastic was disposed in the cylindrical container. On the net, 1 small piece of the sample, 150 workers of termites, and 15 soldiers were put into each test container, and the lid of the container was closed, and left to stand in a dark place at room temperature of 28 ℃. + -. 2 ℃ and a relative humidity of 80% or more for 3 weeks. Here, as the lid of the container, a lid having a small hole for ventilation is used. After 3 weeks, the termite resistance was quantified by comparing the mass of the chip samples before and after the test using the following equation 1 to determine the damage rate X caused by termites.
X＝(W0-W1)/W0×100[％]DEG (mathematic formula 1)
(wherein, W0The mass of the small piece at the beginning of the test, W1Is the mass of the small piece at the end of the test. )
The average value of the numerical value [% ] of the termite damage X obtained by the above mathematical formula 1 is shown in tables 1 and 2. The "damage rate" is preferably a small value, more specifically, 0.03% or less.
[2] Flame retardancy
The sheets having a thickness of 3mm obtained in the present invention examples and comparative examples were cut out to prepare small samples having a length of 130mm × a width of 6.5mm × a thickness of 3mm, and a test was performed in accordance with "test method for flammability based on plastic-oxygen index" of JISK 7201-2. The oxygen index [% ] obtained by this test is shown in tables 1 and 2. The numerical value of the oxygen index is preferably large, more specifically, 22% or more, and more preferably 25% or more, for flame retardancy.
[3] Presence or absence of bleeding
The sheets having a thickness of 2mm obtained in the present invention examples and comparative examples were cut to prepare 3 samples having a length of 100mm, a width of 100mm and a thickness of 2mm, and the samples were allowed to stand in a suspended state for 1 month under an environment having a room temperature of 20 ℃ C. + -. 2 ℃ and a relative humidity of 60%. + -. 10%. After 1 month, the presence or absence of surface gloss was visually confirmed for each sheet, and after the quality was measured, the total surface area (200 cm) of the sheet was measured using BEMCOT2) The swab was taken and the mass was measured again. As a result, a case where gloss was seen on the surface before wiping and the mass was reduced before and after wiping in any of the 3 samples was regarded as "having" bleeding. In addition, the case where only either one of the gloss and the mass reduction was confirmed in at least any one of the 3 samples, and the case where neither one of the gloss and the mass reduction was confirmed were regarded as "no" bleeding. The presence or absence of bleeding confirmed by this test is shown in tables 1 and 2.
[4] Suitability for extrusion processing
(examples 1 and 2 of the present invention)
The resin compositions obtained in inventive examples 1 and 2 were kneaded using twin-screw roll mills (manufactured by Dazhuchao corporation) set to a kneading temperature of 110 ℃ and then pelletized using an extrusion processing machine (manufactured by IKG corporation, model number: PMS25-25) set to an extrusion temperature of 110 ℃ to process the resulting resins into pellets.
(examples 3 to 5 of the present invention)
The resin compositions obtained in inventive examples 3 to 5 were kneaded using twin-screw roll mills (manufactured by Dazhuchai Co., Ltd.) set to a kneading temperature of 150 ℃ and then pelletized using an extrusion processing machine (manufactured by IKG Co., Ltd., model number: PMS25-25) set to an extrusion temperature of 150 ℃ to process the resulting resins into pellets.
(inventive example 6)
The resin composition obtained in inventive example 6 was kneaded using a Henschel mixer (Nippon cake & Engineering Co., Ltd., model FM) set to a kneading temperature of 150 ℃ and then pelletized using an extrusion processing machine (manufactured by IKG Co., Ltd., model PMS25-25) set to an extrusion temperature of 210 ℃ to thereby prepare pellets.
Comparative examples 1 to 5
The resin compositions obtained in comparative examples 1 to 5 were kneaded using twin-screw roll mills (manufactured by Dazhucho Co., Ltd.) set to a kneading temperature of 110 ℃ and then pelletized using an extrusion processing machine (manufactured by IKG Co., Ltd., model number: PMS25-25) set to an extrusion temperature of 110 ℃.
Comparative example 6
The resin composition obtained in comparative example 6 was kneaded using a Henschel mixer (model FM, manufactured by Nippon Coke & Engineering Co., Ltd.) set to a kneading temperature of 150 ℃ and then the obtained resin was pelletized using an extrusion processing machine (model PMS25-25, manufactured by IKG) set to an extrusion temperature of 295 ℃ to thereby process the resulting resin into pellets.
Comparative example 7
The resin composition obtained in comparative example 7 was kneaded using a Henschel mixer (model FM, manufactured by Nippon Coke & engineering Co., Ltd.) set to a kneading temperature of 150 ℃ and then the obtained resin was pelletized using an extrusion processing machine (model PMS25-25, manufactured by IKG) set to an extrusion temperature of 210 ℃ to thereby process the resulting resin into pellets.
(evaluation of suitability for extrusion processing)
The resin compositions of the present invention examples and comparative examples were each processed into pellets 3 times by a method corresponding to each of the present invention examples and comparative examples, and the resin compositions were evaluated as "a" grade when the pellets could be extruded in a uniformly kneaded state without generating white smoke 3 times, as "B" grade when the phenomenon that white smoke was generated or the pellets were extruded in a non-uniform kneaded state or extrusion of the pellets was not performed was only 1 time out of 3 times, and as "C" grade when 2 or more times were generated out of 3 times. The evaluation results are shown in tables 1 and 2.
The details of each component used for the preparation of the resin compositions described in tables 1 and 2 are as follows.
[ base resin (A) ]
Polyethylene (Prime Polymer Co., Ltd., model number: HIZEX5000S, SP value: 8.0)
Polyvinyl chloride (manufactured by Shin Dai-Ichi Vinyl Corporation, model: ZEST1400Z, SP value: 10.8)
Nylon 66 (model number: UBEC NYLON 3024LU, SP value: 11.6, manufactured by Yu Yong K.K.)
Nylon 46 (made by Extron corporation, model No. N46, SP value: 12.2)
[ Compound (B) having an isocyanurate Structure ]
Triallyl isocyanurate (product name: TAIC (registered trademark), SP value: 14.9, manufactured by Nippon Kabushiki Kaisha)
[ boron-containing Compound (C) ]
Zinc borate (model: FIREBEAK 290, manufactured by Borax, USA)
From the evaluation results in tables 1 and 2, it was confirmed that the resin produced from the resin compositions of examples 1 to 6 of the present invention containing the base resin (a), the isocyanurate compound (B), and the boron-containing compound (C) having the predetermined SP values and the contents of the isocyanurate compound (B) and the boron-containing compound (C) being within the suitable ranges of the present invention had a termite damage rate X of 0.01% or less, an oxygen index of 25% or more, and suitability for extrusion processing was evaluated as "a" or "B".
In addition, in all of the resin sheets (samples) produced from the resin compositions of examples 1 to 6 of the present invention, it was confirmed that one or both of the isocyanurate compound (B) and the boron-containing compound (C) as the ant-controlling component was oozed out (exuded) on the surface. Here, neither comparative example 3 in which the content of the isocyanurate compound (B) is less than the suitable range of the present invention nor comparative example 5 in which the content of the boron-containing compound (C) is more than the suitable range of the present invention was observed to bleed out on the surface.
From the above results, it was confirmed that the resin compositions of examples 1 to 6 of the present invention can provide sheaths having excellent flame retardancy and termite resistance, and also have suitability for extrusion processing.
In addition, the ratio of the content (parts by mass) of the boron-containing compound (C) to the content (parts by mass) of the isocyanurate compound (B) is shown in table 1 and table 2. As a result, it was found that, particularly when the ratio of the content of the boron-containing compound (C) to the content of the isocyanurate compound (B) is 1 or more, there is a tendency that the suitability for extrusion processing is high and the oxygen index is high. In addition, it was also confirmed that, particularly when the value of the ratio of the content of the boron-containing compound (C) to the content of the isocyanurate compound (B) is less than 1000, bleeding tends to be observed on the surface.
In contrast, the resin composition of comparative example 1 does not contain either of the isocyanurate compound (B) and the boron-containing compound (C), and therefore, the damage rate X by termites is high, the oxygen index is low, no bleeding is observed on the surface, and the termite resistance and flame retardancy are poor.
The resin composition of comparative example 2 does not contain the boron-containing compound (C), and therefore, has a low oxygen index and poor flame retardancy.
With the resin composition of comparative example 3, since the content of the isocyanurate compound (B) is less than 0.05 part by mass, that is, less than the suitable range of the present invention, no bleeding is observed on the surface, the damage rate X by termites is high, and the termite resistance is poor.
The resin composition of comparative example 4 contained 15 parts by mass of the isocyanurate compound (B), that is, more than the preferable range of the present invention, and therefore, the evaluation of suitability for extrusion processing was poor and was "C".
With the resin composition of comparative example 5, since the content of the boron-containing compound (C) is 60 parts by mass, that is, more than the suitable range of the present invention, no bleeding is observed on the surface, the damage rate X by termites is high, and the termite resistance is poor.
The resin composition of comparative example 6 had an SP value of 12.2, i.e., a more suitable range than that of the present invention, of nylon 46 used as a base resin, and contained no boron-containing compound (C), and therefore, no bleeding was observed on the surface, the oxygen index was low, the flame retardancy was poor, and the evaluation of suitability for extrusion processing was poor, and was "C".
The resin composition of comparative example 7 does not contain any of the isocyanurate compound (B) and the boron-containing compound (C), and therefore, the oxygen index is low, and further, bleeding is not observed on the surface, and the flame retardancy is poor.
< evaluation of Performance in Power Cable >
[ inventive example 7]
A power cable 1A as shown in fig. 2 is manufactured by using the resin composition of example 2 of the present invention, in which an inner semiconductive layer 121, an insulating layer 122, an outer semiconductive layer 123, and a metal shield layer 124 are sequentially laminated on the outer periphery of a conductor as a core wire 11, and a sheath 13 is laminated on the outer periphery thereof as the outermost layer.
As the core wire 11, a core wire having a cross-sectional area of 800mm was used2The round compressed conductor of copper (1 mm in thickness) was provided with an inner semiconductive layer 121 made of carbon-doped crosslinked polyethylene (NUCV-9563, manufactured by NUC corporation), an insulating layer 122 made of crosslinked polyethylene (NUCV-9253, manufactured by NUC corporation), having a thickness of 11mm, an outer semiconductive layer 123 made of carbon-doped crosslinked polyethylene, having a thickness of 0.5mm, and a metallic shield layer 124 made of aluminum metal, having a thickness of 3mm, in this order. Then, the resin composition of example 2 of the present invention was coated to a thickness by extrusion processing on the outer periphery of the metal shield layer 124A 5.0mm sheath 13.
Comparative example 8
A power cable was produced in the same manner as in example 7 of the present invention, except that the resin composition of comparative example 3 was used, the outer periphery of the metal shield layer 124 was covered and formed with a sheath 13 having a thickness of 4mm as a flame-retardant sheath, and the outer periphery of the flame-retardant sheath was covered and formed with an ant-proof sheath having a thickness of 1.5mm made of a polypropylene composite (CALP (trade name) manufactured by Lion Composites co. At this time, as shown in fig. 3, the power cable 9 is configured such that an inner semiconductive layer, an insulating layer, an outer semiconductive layer, and a metal shield layer (not shown) are sequentially stacked as an intermediate layer 92 between a core wire 91 and a sheath 93, and the sheath 93 provided on the outer periphery thereof has a double-layer structure of a flame-retardant sheath 931 and an ant-proof sheath 932.
[ evaluation of inventive example 7 and comparative example 8]
The power cables according to inventive example 7 and comparative example 8 were used to evaluate the characteristics described below. The evaluation conditions for each property are as follows. The results are shown in Table 3.
[1] Evaluation of flammability of Power Cable
The power cables obtained in inventive example 7 and comparative example 8 were subjected to a vertical tray combustion test in accordance with IEEEstd.383-1974, and it was judged whether or not they satisfy the 3 vinyl sheaths described in JEC 3403-2001. In the combustion test, each power cable was subjected to 3 times using different portions, and the average value was obtained for the measured combustion length and residual combustion time from the burner port. In addition, the combustion lengths were all 1200mm or less from the burner port, and the residual combustion time was all within 1 hour, and the sheath was regarded as conforming to 3 types of ethylene sheaths described in JEC3403-2001, and described as "good" in the judgment column of table 3.
[ Table 3]
| Inventive example 7 | Comparative example 8 | |
| Length of combustion | 1000mm | 800mm |
| Residual combustion time | 3 minutes | 20 minutes |
| Determination | 〇 | 〇 |
| Thickness of sheath | 5.0mm | 5.5mm (two layers in total) |
| Relative cost | 0.87 | 1.00 |
From the evaluation results in table 3, it was confirmed that the power cable having a single-layer sheath according to example 7 of the present invention, like the power cable having a two-layer sheath described in comparative example 8, satisfied 3 ethylene-based sheaths described in JEC3403-2001 since the combustion length was 1200mm or less from the burner port and the remaining combustion time was within 1 hour.
On the other hand, in the power cable having a single-layer sheath according to example 7 of the present invention, the thickness of the sheath was 5.0mm, and the sheath could be reduced by about 10% as compared with the power cable having a double-layer sheath described in comparative example 8. Further, since the power cable having a single-layer sheath according to example 7 of the present invention can form a sheath by 1-time extrusion molding, the relative cost of the sheath material can be suppressed to about 13% as compared with the sheath having a two-layer structure described in comparative example 8.
From the above results, it was confirmed that the power cable of invention example 7 has flame retardancy equivalent to that of a two-layer structure even in a single layer, and the sheath can be made thin to reduce the outer diameter of the power cable, and the power cable can be efficiently manufactured.
Description of the reference numerals
1. 1A, 9 power cable
11. 91 core wire
12. 92 intermediate layer
121 inner semiconducting layer
122 insulator layer
123 outer semiconducting layer
124 metal shielding layer
13. 93 sheath
931 flame-retardant sheath
932 sheath for preventing ant
Claims (10)
1. A flame-retardant ant-controlling resin composition comprising a base resin having a solubility parameter in the range of 7.1 or more and 11.6 or less, a compound having an isocyanurate structure, and a boron-containing compound,
the content of the compound having an isocyanurate structure is in the range of 0.05 to 10 parts by mass relative to 100 parts by mass of the base resin,
the content of the boron-containing compound is within a range of 10 to 55 parts by mass with respect to 100 parts by mass of the base resin.
2. The flame-retardant ant-control resin composition according to claim 1, wherein a solubility parameter of said base resin is in a range of 7.1 or more and 10.8 or less.
3. The flame-retardant ant-repellent resin composition according to claim 1 or 2, wherein the content of the compound having an isocyanurate structure is in the range of 0.05 to 1 part by mass with respect to 100 parts by mass of the base resin.
4. The flame-retardant ant-repellent resin composition according to claim 1, 2 or 3, wherein the content of said boron-containing compound is in the range of 10 to 45 parts by mass with respect to 100 parts by mass of said base resin.
5. The flame retardant ant-controlling resin composition as set forth in any one of claims 1 to 4, which is used for a raw material of a sheath constituting an outermost layer of a power cable.
6. A method for manufacturing a power cable having a sheath formed as an outermost layer on an outer peripheral side of a core wire, the method comprising:
the flame-retardant ant-control resin composition according to any one of claims 1 to 5 is extrusion-molded on the outer peripheral side of the core wire, thereby being coated to form a sheath.
7. An electric power cable in which the outer periphery of a core wire is covered with a sheath formed from the flame-retardant termite-resistant resin composition according to any one of claims 1 to 5 as a raw material as an outermost layer.
8. A power cable according to claim 7, wherein the sheath is formed from a single layer.
9. A power cable according to claim 7 or 8, wherein the sheath contains the compound having an isocyanurate structure,
the compound having an isocyanurate structure is exposed at the outer surface of the sheath.
10. A method of laying a power cable according to any one of claims 7 to 9, comprising a step of directly burying the power cable in the ground.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019071626 | 2019-04-03 | ||
| JP2019-071626 | 2019-04-03 | ||
| PCT/JP2020/014949 WO2020204048A1 (en) | 2019-04-03 | 2020-03-31 | Flame retardant anti-termite resin composition, power cable, and method for producing and method for laying same |
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| Publication Number | Publication Date |
|---|---|
| CN113597445A true CN113597445A (en) | 2021-11-02 |
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| CN202080022418.6A Pending CN113597445A (en) | 2019-04-03 | 2020-03-31 | Flame-retardant termite-resistant resin composition, power cable, and method for producing and laying same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2020204048A1 (en) |
| CN (1) | CN113597445A (en) |
| TW (1) | TW202104405A (en) |
| WO (1) | WO2020204048A1 (en) |
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| JPH0278110A (en) * | 1988-09-12 | 1990-03-19 | Fujikura Ltd | Ant-proofing wire/cable |
| JPH0290412A (en) * | 1988-09-28 | 1990-03-29 | Fujikura Ltd | Electric cable |
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| JP6734243B2 (en) * | 2017-10-06 | 2020-08-05 | 古河電気工業株式会社 | Flame-retardant ant composition, power cable and method for producing the same |
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2020
- 2020-03-31 WO PCT/JP2020/014949 patent/WO2020204048A1/en active Application Filing
- 2020-03-31 JP JP2021512159A patent/JPWO2020204048A1/ja active Pending
- 2020-03-31 CN CN202080022418.6A patent/CN113597445A/en active Pending
- 2020-04-01 TW TW109111196A patent/TW202104405A/en unknown
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| JPH0278110A (en) * | 1988-09-12 | 1990-03-19 | Fujikura Ltd | Ant-proofing wire/cable |
| JPH0290412A (en) * | 1988-09-28 | 1990-03-29 | Fujikura Ltd | Electric cable |
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| CN105745723A (en) * | 2013-11-15 | 2016-07-06 | 住友电气工业株式会社 | Flame-resistant, termite-repellent cable |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW202104405A (en) | 2021-02-01 |
| WO2020204048A1 (en) | 2020-10-08 |
| JPWO2020204048A1 (en) | 2020-10-08 |
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