CN111138746A - Flame-retardant insulated wire and flame-retardant cable - Google Patents
Flame-retardant insulated wire and flame-retardant cable Download PDFInfo
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- CN111138746A CN111138746A CN201911071256.0A CN201911071256A CN111138746A CN 111138746 A CN111138746 A CN 111138746A CN 201911071256 A CN201911071256 A CN 201911071256A CN 111138746 A CN111138746 A CN 111138746A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- H01B7/02—Disposition of insulation
- H01B7/0275—Disposition of insulation comprising one or more extruded layers of insulation
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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
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The invention provides a flame-retardant insulated wire and a flame-retardant cable, which have flame retardancy and extrusion processability. A flame-retardant insulating wire resin (10) has a conductor (1) and an insulating layer (2) covering the periphery of the conductor (1). The insulating layer (2) contains a flame-retardant resin composition containing a vinyl polymer, a metal hydroxide, and a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group. The flame-retardant resin composition contains 100 parts by mass or more and 180 parts by mass or less of the metal hydroxide per 100 parts by mass of the ethylene polymer, and contains 2 parts by mass or more of the compound per 100 parts by mass of the ethylene polymer.
Description
Technical Field
The present invention relates to a flame-retardant insulated wire and a flame-retardant cable.
Background
The insulated wire has a conductor and an insulating layer as a covering material provided around the conductor. The cable includes, for example, a stranded wire obtained by twisting the electric wires and a sheath provided around the stranded wire. The insulating layer of the insulated wire and the sheath of the cable comprise an electrically insulating material mainly composed of rubber or resin. The necessary characteristics of such insulated wires and cables vary depending on the application. For example, for electric wires for electronic equipment or railway vehicles, high flame retardancy is required, and specifically, the wire is required to be qualified in the vertical flame test VW-1 specified in the flame retardancy standard UL 1581.
As an example of such an electric wire, patent document 1 describes a flame-retardant insulated electric wire including a conductor and an insulating layer covering the periphery of the conductor, wherein the insulating layer includes a resin composition in which a metal hydroxide is added to a resin component mainly composed of a vinyl polymer.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-2062
Disclosure of Invention
Problems to be solved by the invention
However, according to the studies of the present inventors, it was confirmed that the flowability of the resin composition is lowered and the extrusion processability is impaired in some cases when the insulating layer of the flame-retardant insulated wire is formed.
The present invention has been made in view of the above problems, and an object thereof is to provide a flame-retardant insulated wire and a flame-retardant cable having flame retardancy and extrusion processability.
Means for solving the problems
A brief description will be given below of a typical embodiment of the invention disclosed in the present application.
[1] A flame-retardant insulated wire comprising a conductor and an insulating layer covering the periphery of the conductor, wherein the insulating layer comprises a flame-retardant resin composition comprising a vinyl polymer, a metal hydroxide and a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group. The flame-retardant resin composition contains 100 to 180 parts by mass of the metal hydroxide per 100 parts by mass of the ethylene polymer, and the flame-retardant resin composition contains 2 or more parts by mass of the compound per 100 parts by mass of the ethylene polymer.
[2] The flame-retardant insulated wire according to [1], wherein the compound is an ester derivative of gallic acid.
[3] The flame-retardant insulated wire according to [1], wherein the compound is at least one compound selected from the group consisting of methyl gallate, propyl gallate, 2,3, 4-trihydroxybenzophenone, and bisphenol A.
[4] A flame-retardant cable comprising a core wire and a sheath provided around the core wire, wherein the core wire comprises an insulated wire comprising a conductor and an insulating layer covering the periphery of the conductor, and the sheath comprises a flame-retardant resin composition comprising a vinyl polymer, a metal hydroxide and a compound having a plurality of phenolic hydroxyl groups in the molecule and having no carboxyl group. The flame-retardant resin composition contains 100 to 180 parts by mass of the metal hydroxide per 100 parts by mass of the ethylene polymer, and the flame-retardant resin composition contains 2 or more parts by mass of the compound per 100 parts by mass of the ethylene polymer.
[5] The flame-retardant cable according to [4], wherein the compound is an ester derivative of gallic acid.
[6] The flame-retardant cable according to [4], wherein the compound is at least one compound selected from the group consisting of methyl gallate, propyl gallate, 2,3, 4-trihydroxybenzophenone and bisphenol A.
Effects of the invention
According to the present invention, a flame-retardant insulated wire and a flame-retardant cable having flame retardancy and extrusion processability can be provided.
Drawings
Fig. 1 is a cross-sectional view showing the structure of an electric wire of one embodiment.
Fig. 2 is a cross-sectional view showing the structure of the electric wire of the second embodiment.
Fig. 3 is a cross-sectional view showing the structure of a cable of one embodiment.
Description of the symbols
1: conductor, 2: insulating layer, 2 a: insulating inner layer, 2 b: insulating outer layer, 4: sheath, 5: mediator, 6: spacer, 10, 20: flame-retardant insulated wire, 30: a flame retardant cable.
Detailed Description
(matters of study)
Before describing the embodiments, the matters studied by the present inventors will be described first.
Conventionally, it has been known to add a metal hydroxide such as magnesium hydroxide as a flame retardant to a resin composition in order to improve the flame retardancy of the resin composition. Therefore, the present inventors have studied a flame-retardant insulated wire comprising a conductor and an insulating layer covering the periphery of the conductor, wherein the insulating layer contains a resin composition obtained by adding (B) a metal hydroxide to a resin component mainly composed of (a) a vinyl polymer (hereinafter referred to as a flame-retardant insulated wire of a study example).
As described above, the flame-retardant insulated wire of the study example is required to have a flame retardancy that is acceptable in the vertical flame test VW-1 specified in the flame retardancy Standard UL 1581. As shown in examples described later, the present inventors confirmed that the resin composition constituting the insulating layer was not defective in VW-1 if 220 parts by mass or more of magnesium hydroxide (B1), which is one of the metal hydroxides (B), was added to 100 parts by mass of the resin component (A) mainly composed of the ethylene polymer. Here, the flame retarding effect of the metal hydroxide is brought about by suppressing the thermal decomposition of the resin by the endothermic reaction. If the generation of combustible gas due to the thermal decomposition of the resin cannot be completely suppressed, the reaction of the combustible gas with oxygen continues and the product cannot be qualified in the VW-1. Therefore, it is considered that the thermal decomposition of the resin can be completely suppressed only by adding the metal hydroxide at a high ratio to the resin component.
On the other hand, as shown in examples described later, the present inventors confirmed that in the flame-retardant insulated wire of the study example, if 165 parts by mass or more of (B1) magnesium hydroxide, which is one of (B) metal hydroxides, is added to 100 parts by mass of (a) a resin component mainly composed of an ethylene polymer in the resin composition constituting the insulating layer, the material components in the resin composition collide with each other, rub against each other, adhere to each other, and aggregate, and the fluidity of the resin composition is lowered, and the extrusion processability is impaired. Namely, the following problems occur: if the fluidity of the resin composition is lowered, the extrusion speed of the extruder must be lowered when extruding the insulating layer of the coated electric wire, and therefore, the production efficiency of the electric wire is lowered.
Namely, the following problems are clarified: in the resin composition constituting the insulating layer of the insulated wire, if the ratio of the metal hydroxide (B) to the resin component (a) mainly composed of the ethylene polymer is too low, flame retardancy cannot be maintained, while if the ratio of the metal hydroxide (B) is too high, extrusion processability is impaired.
Such a problem occurs not only in the insulating layer of the insulated wire but also in the sheath of the cable formed by extrusion coating.
As described above, it is desired to provide a flame-retardant insulated wire and a flame-retardant cable having flame retardancy and extrusion processability by devising the structures of the flame-retardant insulated wire and the flame-retardant cable.
(embodiment mode)
< composition of flame-retardant insulated wire and method for producing the same
Fig. 1 and 2 are cross-sectional views showing a flame-retardant insulated electric wire according to an embodiment of the present invention. As shown in fig. 1, a flame-retardant insulated electric wire 10 according to a first embodiment includes a conductor 1 and an insulating layer 2 covering the periphery of the conductor 1. The insulating layer 2 contains a flame-retardant resin composition according to an embodiment of the present invention described in detail below. The thickness of the insulating layer 2 is not particularly limited, but is preferably 0.15 to 2 mm.
As the conductor 1, besides a generally used metal wire, for example, a copper wire or a copper alloy wire, an aluminum wire, a gold wire, a silver wire, an optical fiber, or the like can be used. As the conductor 1, a conductor plated with a metal such as tin or nickel around a metal wire may be used. Further, a stranded conductor in which metal wires are stranded may be used as the conductor 1.
Further, a spacer 6 made of, for example, a polyester tape or the like may be provided between the conductor 1 and the insulating layer 2. By providing the spacer 6, when a stranded conductor is used as the conductor 1, the flame-retardant resin composition can be prevented from entering the conductor 1 when the flame-retardant resin composition is extruded, that is, when the insulating layer 2 is formed.
The flame-retardant insulated wire 10 of the present embodiment is manufactured, for example, as follows. First, a material containing (a) a vinyl polymer, (B) a metal hydroxide, and (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group is melt-kneaded to obtain a flame-retardant resin composition of the present embodiment.
Then, the conductor 1 is prepared, and the flame-retardant resin composition of the present embodiment is extruded by an extrusion molding machine so as to cover the periphery of the conductor 1 (the separator 6), thereby forming the insulating layer 2 having a predetermined thickness. By doing so, the flame-retardant insulated wire 10 can be manufactured.
The kneading apparatus for producing the flame-retardant resin composition of the present embodiment may be a known kneading apparatus such as a batch kneader such as a banbury mixer or a pressure kneader, a continuous kneader such as a twin-screw extruder, or the like.
In the present embodiment, after the flame-retardant insulated wire 10 is manufactured, the flame-retardant resin composition constituting the insulating layer 2 is crosslinked by, for example, an electron beam crosslinking method or a chemical crosslinking method. Such crosslinking is not essential in the flame-retardant insulated wire 10 of the present embodiment, but is preferably performed because the heat resistance of the flame-retardant resin composition is improved by the crosslinking.
In the case of using the electron beam crosslinking method, the flame-retardant resin composition is molded in the form of the insulating layer 2 of the flame-retardant insulated wire 10, and then, for example, is irradiated with 1 to 30Mrad of electron beams to crosslink the flame-retardant resin composition. In the case of using the chemical crosslinking method, a crosslinking agent is added to the flame-retardant resin composition in advance, and the flame-retardant resin composition is molded as the insulating layer 2 of the flame-retardant insulated wire 10 and then crosslinked by heat treatment. In the following examples, electron beam crosslinking was used.
As shown in fig. 2, the flame-retardant insulated wire 20 according to the second embodiment includes a conductor 1, an inner insulating layer 2a provided around the conductor 1, and an outer insulating layer 2b provided around the inner insulating layer 2 a. The flame-retardant insulated wire 20 of the second embodiment is different from the flame-retardant insulated wire 10 of the first embodiment in that the insulating layer includes an insulating inner layer 2a and an insulating outer layer 2 b. The insulating outer layer 2b contains the flame-retardant resin composition of the present embodiment. The insulating inner layer 2a contains an insulating resin such as polyethylene.
The flame-retardant resin composition used in the present embodiment is not limited to the electric wire produced in the examples, and can be applied to all uses and sizes, and can be used for insulating layers of electric wires for in-tray wiring, vehicles, automobiles, in-machine wiring, and electric power.
< construction of flame retardant Cable >
Fig. 3 is a cross-sectional view showing a flame-retardant cable 30 according to an embodiment of the present invention. As shown in fig. 3, the flame-retardant cable 30 according to the present embodiment includes a core wire including a three-core stranded wire formed by twisting 3 flame-retardant insulated wires 10 and a dielectric 5 provided around the three-core stranded wire, and a sheath 4 provided around the core wire. The sheath 4 contains the flame-retardant resin composition described above.
The flame-retardant cable 30 of the present embodiment is manufactured, for example, as follows. First, 3 flame-retardant insulated electric wires 10 were manufactured by the aforementioned method. Then, the flame-retardant insulated wire 10 is twisted together with a short fiber, kraft paper, paper tape, jute or other intermediate 5, and a flame-retardant resin composition is extruded so as to cover the twisted product, the flame-retardant resin composition being obtained by kneading a material containing (a) a vinyl polymer, (B) a metal hydroxide, and (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and having no carboxyl group. Then, for example, the flame-retardant resin composition is irradiated with an electron beam to crosslink the ethylene polymer (a) in the flame-retardant resin composition, thereby forming a sheath 4 having a predetermined thickness. By doing so, the flame-retardant cable 30 of the present embodiment can be manufactured.
The cable 11 of the present embodiment has been described by way of example as having a three-core stranded wire formed by twisting 3 flame-retardant insulated wires 10 as a core wire, but the core wire may be a single core wire (1 wire) or a multi-core stranded wire other than a three-core wire. The intermediate body 5 may not be provided between the flame-retardant insulated wire 10 and the sheath 4, and a multilayer sheath structure in which another insulating layer (sheath) is formed between the flame-retardant insulated wire 10 and the sheath 4 may be employed. Further, a shield layer of a braided structure including a metal tape or a copper wire may be provided between the flame-retardant insulated electric wire 10 and the sheath 4.
Further, the flame-retardant cable 30 of the present embodiment has been described by taking as an example the case where the flame-retardant insulated wire 10 is used, but the present invention is not limited thereto, and a wire using a general-purpose material such as polyethylene may be used.
< constitution of flame-retardant resin composition >
The flame-retardant resin composition of the present embodiment will be described in detail below. The flame-retardant resin composition according to the present embodiment contains (a) a vinyl polymer, (B) a metal hydroxide, and (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group. Hereinafter, in the present embodiment, the vinyl polymer (a) constituting the flame-retardant resin composition is sometimes described as a base polymer. In addition, the metal hydroxide (B) and the compound (C) having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group, which constitute the flame-retardant resin composition, may be combined as a flame retardant in some cases.
The ethylene polymer (a) of the present embodiment includes, for example, an ethylene-vinyl acetate copolymer, an ethylene-acrylic ester copolymer, an ethylene- α -olefin copolymer, and the like, and since it may be buried in the soil depending on the type of the cable, a polymer having no biodegradability is preferable, and an ethylene-vinyl acetate copolymer is preferable as the ethylene polymer (a).
Examples of the metal hydroxide (B) in the present embodiment include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hard clay, hydrotalcite, and the like, and among them, magnesium hydroxide (B1) and aluminum hydroxide (B2) are preferable. Examples of the magnesium hydroxide (B1) include those without surface treatment (natural magnesium hydroxide or synthetic magnesium hydroxide obtained by crushing brucite ore) and those surface-treated with a silane coupling agent, a phosphate ester, or a fatty acid such as stearic acid or oleic acid. In particular, as the magnesium hydroxide (B1), it is preferable to use a magnesium hydroxide surface-treated with a silane coupling agent. Since magnesium hydroxide surface-treated with a silane coupling agent has high affinity with a polymer, a flame-retardant resin composition using the same has good tensile properties. The metal hydroxide is contained in an amount of 100 to 180 parts by mass based on 100 parts by mass of the ethylene polymer. As shown in examples described later, when magnesium hydroxide (B1) is used, it is preferably 100 parts by mass or more and 160 parts by mass or less with respect to 100 parts by mass of the base polymer. If the amount of magnesium hydroxide (B1) is less than 100 parts by mass based on 100 parts by mass of the base polymer, flame retardancy required for an insulating layer of an electric wire cannot be obtained, and if it exceeds 160 parts by mass, the material components collide with each other, rub, adhere, aggregate, and deteriorate in fluidity, and extrusion processability is impaired when forming an insulating layer of an electric wire. Examples of the (B2) aluminum hydroxide include those without surface treatment and those surface-treated with a silane coupling agent, a phosphate ester, or a fatty acid such as stearic acid or oleic acid. When the (B2) aluminum hydroxide is used, it is preferably 100 parts by mass or more and 180 parts by mass or less with respect to 100 parts by mass of the base polymer.
Examples of the compound (C) having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group in the present embodiment include ester derivatives of gallic acid (e.g., (C1) methyl gallate and (C2) propyl gallate), pyrogallol, catechol, gallotannin (ガロタンニン), (C3)2,3, 4-trihydroxybenzophenone, and (C4) bisphenol a.
The reason why the compound (C) having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group is referred to as "having a plurality of phenolic hydroxyl groups" is that the inventors have confirmed that the radical trapping effect of the phenolic hydroxyl groups cannot be sufficiently exhibited in the case of a compound having only 1 phenolic hydroxyl group in the molecule. The radical trapping effect is an effect of stabilizing the flame retardant by reacting with radicals in the gas-phase combustion product and suppressing the reaction with oxygen.
The reason why the compound (C) having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group is "no carboxyl group" is that, as shown in the comparative example described later, if a compound having a carboxyl group is added, the fluidity of the resin composition is lowered by the interaction with the metal hydroxide (B), and the evaluation of processability at the time of extrusion is not satisfactory. Further, gallic acid has a melting point of 280 ℃ or higher due to the strong polarity of hydroxyl groups, does not melt at a normal processing temperature, and is present as aggregates in the resin composition, and thus is likely to become a starting point of mechanical fracture. Therefore, propyl (C2) gallate, (C3)2,3, 4-trihydroxybenzophenone, and (C4) bisphenol A, which have a low melting point, for example, a melting point of 200 ℃ or lower, are suitable.
Further, as the compound (C) having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group, several compounds selected from ester derivatives of gallic acid (e.g., (C1) methyl gallate, and (C2) propyl gallate), pyrogallol, catechol, gallotannin, (C3)2,3, 4-trihydroxybenzophenone, and (C4) bisphenol a may be used in combination.
As shown in examples described later, (C) the compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group is preferably 2 parts by mass or more per 100 parts by mass of the base polymer. This is because if the amount of the compound (C) having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group is less than 2 parts by mass per 100 parts by mass of the base polymer, (B) a metal hydroxide needs to be added in a large amount to obtain flame retardancy necessary for an insulating layer of an electric wire. (C) The upper limit value of the content of the compound having a plurality of phenolic hydroxyl groups and no carboxyl group in the molecule is 40 parts by mass or less, and more preferably 20 parts by mass or less, but is not particularly limited thereto.
The total of the metal hydroxide (B) and the compound (C) having a plurality of phenolic hydroxyl groups and no carboxyl groups in the molecule, which are the flame retardant of the present embodiment, is preferably 100 parts by mass or more and less than 220 parts by mass per 100 parts by mass of the base polymer. If the total amount of the flame retardants is less than 100 parts by mass with respect to 100 parts by mass of the base polymer, flame retardancy that is acceptable in the VW-1 test cannot be obtained, and if it is 220 parts by mass or more, extrusion processability may be reduced and processability evaluation may be unsatisfactory.
In addition to the above materials, the flame-retardant resin composition of the present embodiment may contain, if necessary, other flame retardants, flame-retardant aids, crosslinking agents, crosslinking aids, processing aids, coupling agents, surface treatment agents, colorants, lubricants, antioxidants, ozone deterioration inhibitors, ultraviolet absorbers, light stabilizers, metal chelating agents, softeners, plasticizers, and the like, as long as the properties are not affected.
The flame-retardant resin composition of the present embodiment is not limited to the electric wire produced in the examples described below, and can be applied to all uses and sizes including electric cables, and can be used for insulating layers of electric wires and sheaths of electric cables for railway vehicles, automobiles, wiring in trays, wiring in machines, and electric power.
< features and effects of the present embodiment >
One feature of the flame-retardant insulated electric wires 10 and 20 according to the present embodiment shown in fig. 1 and 2 is that the insulated electric wires include a conductor 1 and an insulating layer 2 (insulating inner layer 2a) covering the periphery of the conductor 1, and the insulating layer 2 (insulating outer layer 2B) is composed of a flame-retardant resin composition containing (a) a vinyl polymer, (B) a metal hydroxide, and (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and having no carboxyl group.
Further, as shown in fig. 3, a flame-retardant cable 30 according to the present embodiment is characterized by comprising a sheath 4 provided around a flame-retardant insulated wire 10, wherein the sheath 4 is made of the flame-retardant resin composition.
In the present embodiment, by adopting such a configuration, it is possible to provide a flame-retardant insulated wire and a flame-retardant cable having flame retardancy and extrusion processability. The reason for this will be specifically described below.
As described above, the present inventors have confirmed that, in the resin composition constituting the insulating layer of the flame-retardant insulated wire of the study example, if the ratio of (B) the metal hydroxide to (a) the resin component mainly composed of the ethylene polymer is too low, the flame retardancy cannot be maintained, while if the ratio of (B) the metal hydroxide is too high, the extrusion processability is impaired.
Therefore, the present inventors have constituted the insulating layer of the flame-retardant insulated wire according to the present embodiment by a flame-retardant resin composition containing (a) a vinyl polymer, (B) a metal hydroxide, and (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group. In this way, by adding (C) the compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group as the flame retardant to the flame-retardant resin composition, the ratio of (B) the metal hydroxide to (a) the vinyl polymer can be reduced, and the extrusion processability of the flame-retardant resin composition when forming the coating layer of the electric wire can be improved. Similarly, the extrusion processability of the flame-retardant resin composition when forming a sheath of a cable can be improved.
Further, by adding (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group as a flame retardant to the flame-retardant resin composition, the flame retardancy of the flame-retardant insulated wire having the insulating layer containing the flame-retardant resin composition can be improved even when the ratio of (B) the metal hydroxide to (a) the vinyl polymer is reduced. Similarly, the flame retardancy of a flame-retardant cable provided with a sheath containing the flame-retardant resin composition can be improved.
As described above, the flame retardant action of the metal hydroxide (B) is brought about by suppressing the thermal decomposition of the resin by the endothermic reaction. Further, the flame retarding effect of the compound (C) having a plurality of phenolic hydroxyl groups and no carboxyl group in the molecule is achieved by a radical trapping effect. In this way, the flame-retardant insulated wire and the flame-retardant cable of the present embodiment use these flame retardants having different flame-retardant effects in combination, and therefore, by utilizing the synergistic effect thereof, the flame retardancy can be further improved as compared with the case where these flame retardants are used alone.
Further, since the compound (C) having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group has the same radical trapping effect as that of the halide, it is not necessary to add a halide to the resin composition in order to exert flame retardancy. Therefore, according to the flame-retardant resin composition of the present embodiment, it is possible to provide a halogen-free flame-retardant insulated wire and a halogen-free flame-retardant cable which can prevent generation of toxic gas in fire, secondary disaster, and the like, and which have no problem in incineration disposal.
(examples)
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples.
< overview of examples and comparative examples >
The flame-retardant insulated wires of examples 1 to 10 and the insulated wires of comparative examples 1 to 6 will be described below. The flame-retardant insulated wires of examples 1 to 10 correspond to the flame-retardant insulated wire 10 shown in fig. 1. That is, the insulating layer 2 of the flame-retardant insulated wire 10 contains the flame-retardant resin composition according to the present embodiment. The insulated wires of comparative examples 1 to 6 have the same shape as the flame-retardant insulated wire 10 shown in fig. 1, and the insulating layer 2 contains a resin composition having a different composition from the flame-retardant resin composition of the present embodiment. The compositions of the flame-retardant resin compositions of examples 1 to 10 and comparative examples 1 to 6 are shown in table 1.
Table 1 shows examples and comparative examples in which an ethylene-vinyl acetate copolymer (EV170, manufactured by mitsui du pont polymer chemical) was used as the ethylene-based polymer (a), and the same results were obtained when other ethylene-based polymer (a) was used or a plurality of ethylene-based polymers (a) were used in combination as the evaluation results. Further, as the (B) metal hydroxide, (B1) silane-treated magnesium hydroxide (Magseeds (registered trademark) S4, product of shenisai chemical industries co., ltd.) or (B2) fatty acid-treated magnesium hydroxide (BF-013S (product of japan light metals corporation)) was used. Methyl (C1) gallate, propyl (C2) gallate, 2,3, 4-trihydroxybenzophenone (C3), and gallic acid (C5) were obtained from tokyo chemical co.
[ Table 1]
[ Table 2]
[ Table 3]
The flame-retardant insulated electric wires of examples 1 to 10 were produced as follows. First, the respective materials of examples 1 to 10 shown in table 1 were dry-blended at room temperature, and the blended materials were melt-kneaded at a take-out temperature of 150 ℃ by means of a pressure kneader to produce a flame-retardant resin composition. Then, an insulating layer containing a flame-retardant resin composition was formed around 22AWG copper strands to a coating thickness of 0.41mm by using a Toyo Seiki Labo Plastomill 20mm single-screw extruder as an extrusion coating apparatus for manufacturing electric wires (cylinder temperature 160 ℃ C., wire drawing speed 4.0 m/min). The flame-retardant resin composition constituting the insulating layer was crosslinked by subjecting the electric wire to electron beam crosslinking treatment (6Mrad), thereby producing flame-retardant insulated electric wires of examples 1 to 10. The methods for producing the insulated wires of comparative examples 1 to 6 are the same as those of the flame-retardant insulated wires of examples 1 to 10, and therefore, are omitted.
< evaluation methods of examples and comparative examples >
(1) Evaluation of processability
For the workability evaluation, the torque of the extruder at the time of forming the insulation layer of the electric wire was measured, and it was judged as passed if the torque was 50N · m or less, and it was judged as failed if the torque exceeded 50N · m.
(2) Evaluation of flame retardancy
For the flame retardancy evaluation, the flame-retardant insulated wire thus produced was subjected to a vertical flame test VW-1 specified in flame retardancy Standard UL1581, and was judged to be passed or failed.
As another index for evaluating flame retardancy, the oxygen index specified in JIS K7201-2 was also measured. However, the flame retardancy was evaluated based on the results of the vertical burning test VW-1.
With respect to examples 4 to 7, comparative example 4 and comparative example 5, as reference tests, low temperature characteristics were evaluated. The copper stranded wire was pulled out from the flame-retardant insulated wire thus produced, and a tensile test of the insulator at-40 ℃ was carried out by a method based on JISC3005 using a tensile tester with a low temperature tank. The sample was formed into a tubular shape, left in a cryotank for 2 hours, and then subjected to a tensile test at a speed of 25 mm/min. The elongation of 30% or more was regarded as pass, and the elongation of less than 30% was regarded as fail.
< detailed information and evaluation results of examples 1 to 10 >
As shown in table 1, the flame-retardant resin compositions constituting the insulating layers of the flame-retardant insulated wires of examples 1 to 10 contained, as materials thereof, (a) a vinyl polymer, (B) a metal hydroxide, and (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group.
The flame-retardant resin compositions of examples 1 and 3 used (C1) methyl gallate as the compound (C) having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl groups.
The flame-retardant resin compositions of examples 2 and 4, and examples 6 and 8 to 10 used (C2) propyl gallate as (C) the compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group.
The flame-retardant resin composition of example 5 used (C4) bisphenol a as (C) the compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group.
The flame-retardant resin composition of example 7 used (C3)2,3, 4-trihydroxybenzophenone as (C) the compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group.
In the flame-retardant resin compositions of examples 1 and 2, 125 parts by mass of (B1) magnesium hydroxide and 15 parts by mass of (C) a compound having a plurality of phenolic hydroxyl groups and no carboxyl group in the molecule were added to 100 parts by mass of (a) a vinyl polymer.
On the other hand, in the flame-retardant resin compositions of examples 3 and 4, 100 parts by mass of (a) the vinyl polymer, (B1) magnesium hydroxide, and 30 parts by mass of (C) the compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group are used. Therefore, the compounding ratio of (B1) magnesium hydroxide and (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group in examples 3 and 4 is different from that in examples 1 and 2.
In addition, in the flame-retardant resin composition of example 5, 130 parts by mass of (B1) magnesium hydroxide and 20 parts by mass of (C) a compound having a plurality of phenolic hydroxyl groups in a molecule and no carboxyl group were added to 100 parts by mass of (a) the vinyl polymer.
In addition, in the flame-retardant resin composition of example 6, 130 parts by mass of (B1) magnesium hydroxide and 2 parts by mass of (C) a compound having a plurality of phenolic hydroxyl groups and no carboxyl group in the molecule were added to 100 parts by mass of (a) the vinyl polymer.
The flame-retardant resin composition of example 7 contained 160 parts by mass of magnesium hydroxide (B1) and 15 parts by mass of a compound having a plurality of phenolic hydroxyl groups and no carboxyl group in the molecule, per 100 parts by mass of the vinyl polymer (a).
In the flame-retardant resin composition of example 8, 100 parts by mass of the (a) vinyl polymer, 100 parts by mass of the (B2) aluminum hydroxide, and 15 parts by mass of the (C) compound having a plurality of phenolic hydroxyl groups in the molecule and having no carboxyl group were used.
In the flame-retardant resin composition of example 9, 130 parts by mass of (B2) aluminum hydroxide and 15 parts by mass of (C) a compound having a plurality of phenolic hydroxyl groups and no carboxyl group in the molecule were added to 100 parts by mass of (a) a vinyl polymer.
In the flame-retardant resin composition of example 10, 180 parts by mass of (B2) aluminum hydroxide and 30 parts by mass of (C) a compound having a plurality of phenolic hydroxyl groups and no carboxyl group in the molecule were added to 100 parts by mass of (a) the vinyl polymer. As shown in table 1, in examples 1 to 10, although the types of the materials and the blending ratios of the materials were different, both (1) the processability evaluation and (2) the flame retardancy evaluation were acceptable.
< detailed information and evaluation results of comparative examples 1 to 6 >
In comparative examples 1 to 6 shown in table 1, the kinds of the materials used in examples 1 to 10 and the blending ratio of the materials were changed.
As shown in table 1, the resin compositions of comparative examples 1 to 3 contain (a) a vinyl polymer and (B1) magnesium hydroxide as materials thereof, but do not contain (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group, unlike examples 1 to 10.
The resin compositions of comparative examples 4 and 5 contained, as materials, (a) a vinyl polymer, (B1) magnesium hydroxide, and (C5) gallic acid which is a compound having a plurality of phenolic hydroxyl groups and also having carboxyl groups in the molecule.
The resin composition of comparative example 6 was the same as the flame-retardant resin compositions of examples 1 and 3 in that it contained, as its material, (a) a vinyl polymer, (B1) magnesium hydroxide, and (C1) methyl gallate. However, comparative example 6 is different from example 1 in that 80 parts by mass of magnesium hydroxide (B1) per 100 parts by mass of the ethylene-based polymer (a) is used.
As shown in table 1, in comparative example 1, (1) the processability evaluation and (2) the flame retardancy evaluation failed.
In comparative examples 2 to 5, (2) the flame retardancy evaluation was acceptable and (1) the processability evaluation was not acceptable.
In comparative example 6, (1) the processability evaluation was passed and (2) the flame retardancy evaluation was not passed.
< summary of examples and comparative examples >
As shown in examples 1 to 10, the flame-retardant insulated wire of the present embodiment can have flame retardancy and extrusion processability by forming the insulating layer from a flame-retardant resin composition containing (a) a vinyl polymer, (B) a metal hydroxide, and (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group.
Specifically, as shown in comparative examples 1 to 3, in the resin composition containing (A) an ethylene polymer and (B) magnesium hydroxide, 220 parts by mass or more of (B1) magnesium hydroxide was added to 100 parts by mass of (A) an ethylene polymer, and (2) the flame retardancy evaluation was passed. However, if the amount of magnesium hydroxide (B1) added to the ethylene polymer (A) is large, the flowability of the resin composition decreases, and the processability evaluation fails (1). Actually, as shown in comparative example 1, if the amount of magnesium hydroxide (B1) added to the ethylene polymer (a) was smaller, the processability evaluation (1) was still not acceptable, but the flame retardancy evaluation (2) was also not acceptable at the time point when the amount of magnesium hydroxide (B1) was 165 parts by mass based on 100 parts by mass of the ethylene polymer (a). From these results, it is clear that there is no insulated wire having an insulating layer of a resin composition containing (a) a vinyl polymer and (B) a metal hydroxide, which satisfies both flame retardancy and extrusion processability.
On the other hand, in examples 1 and 2, 15 parts by mass of (C) a compound having plural phenolic hydroxyl groups in the molecule and no carboxyl group as a flame retardant was added to 100 parts by mass of (a) the ethylene polymer, and even if the amount of (B1) magnesium hydroxide was 125 parts by mass, the evaluation of (2) flame retardancy was acceptable. Further, since the amount of magnesium hydroxide (B1) added can be reduced to 125 parts by mass per 100 parts by mass of the ethylene polymer (a), the processability evaluation (1) was also acceptable.
This is the same as in examples 5 to 7, and the addition amount of magnesium hydroxide (B1) can be set to 130 to 160 parts by mass by adding 2 to 20 parts by mass of (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group to 100 parts by mass of (a) the vinyl polymer, and (1) the processability evaluation and (2) the flame retardancy evaluation can be passed.
Further, as shown in examples 3 and 4, by adding 30 parts by mass of (C) a compound having plural phenolic hydroxyl groups in the molecule and no carboxyl group to 100 parts by mass of (a) the vinyl polymer, the flame retardancy evaluation (2) was acceptable even when the amount of (B1) magnesium hydroxide added was 100 parts by mass. In examples 3 and 4, since the amount of magnesium hydroxide (B1) added can be reduced to 100 parts by mass per 100 parts by mass of the ethylene-based polymer (a), the processability evaluation (1) is certainly acceptable, and the extrusion torque of the extruder can be further reduced as compared with examples 1 and 2, thereby further improving the production efficiency of the electric wire.
As shown in examples 1 to 10, it is found that ester derivatives of gallic acid such as (C1) methyl gallate and (C2) propyl gallate are useful as flame retardants. In particular, in example 6, even when only 2 parts by mass of the compound (C) having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group was added to 100 parts by mass of the ethylene polymer (A), it was acceptable in the flame retardancy evaluation (VW-1 flame test). This is considered to be a synergistic effect by using a flame retardant which acts differently from the metal hydroxide (B). Furthermore, there was little difference in characteristics between (C1) methyl gallate and (C2) propyl gallate if example 1 and example 2, or example 3 and example 4, respectively, were compared. Therefore, it is assumed that ethyl gallate, butyl gallate and the like, which are ester derivatives of gallic acid, exhibit the same characteristics. Further, as shown in examples 8 to 10, in the case of using (B2) aluminum hydroxide as (B) metal hydroxide, even if 180 parts by mass or more is added, not only (2) the flame retardancy evaluation is passed, but also (1) the processability evaluation is passed. Although the reason is not clear, it is considered that the reason is related to the magnitude of friction when the metal hydroxide particles collide with each other.
On the other hand, as shown in comparative examples 4 and 5, when the resin composition was composed of (a) a vinyl polymer, (B1) magnesium hydroxide, and (C5) gallic acid which is a compound having a plurality of phenolic hydroxyl groups and also having a carboxyl group in the molecule, (2) the evaluation of flame retardancy was passed, and (1) the evaluation of processability was not passed. This is considered to be because (C5) gallic acid has carboxyl groups in its molecules, and thus the carboxyl groups in (C5) gallic acid molecules are bonded to the surface of (B1) magnesium hydroxide, which lowers the fluidity of the resin composition.
Further, as shown in comparative example 6, even when 15 parts by mass of (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group was added to 100 parts by mass of (a) the vinyl polymer, (2) the evaluation of flame retardancy was failed if the amount of (B1) magnesium hydroxide added was 80 parts by mass. Therefore, it is understood from the results of examples 3,4, 5 and 6 that the metal hydroxide (B) is preferably 100 parts by mass or more and 180 parts by mass or less based on 100 parts by mass of the ethylene polymer (a).
In addition, regarding the evaluation of the processability (1), as shown in examples 1 to 10 and comparative examples 1 to 6, the extrusion torque was substantially proportional to the addition amount of magnesium hydroxide (B1). Among them, it is found that in the case of example 2 or 4 in which (C2) propyl gallate is added, the extrusion torque is smaller than that in example 1 or 3 in which (B1) magnesium hydroxide is added in the same amount. For one reason, it is considered that (C2) propyl gallate (melting point 150 ℃ C.) having a melting point lower than the processing temperature (160 ℃ C.) of the resin composition acts as a lubricant to improve the fluidity of the resin composition. Therefore, (C2) propyl gallate is preferably used as (C) the compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group, from the viewpoint of improving extrusion processability.
Further, regarding the evaluation of flame retardancy (2), as shown in examples 1 to 10 and comparative examples 1 to 6, it is considered as one of the requirements that the oxygen index is at least 30 or more in order to be acceptable in VW-1. Among them, as shown in comparative example 1, in some cases, the wire failed in VW-1 even if the oxygen index was 30 or more, and it can be said that it is preferable to evaluate the flame retardancy of the wire based on VW-1.
As for the evaluation of the (3) low-temperature characteristics carried out as the reference test, as shown in examples 4 to 7, comparative example 4 and comparative example 5, the low-temperature characteristics were acceptable for examples 4 to 7 using (C2) propyl gallate (melting point 150 ℃), (C3)2,3, 4-trihydroxybenzophenone (melting point 140 ℃), and (C4) bisphenol a (melting point 158 ℃) as (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and having no carboxyl group; in comparative examples 4 and 5 in which (C5) gallic acid (melting point 285 ℃ C.) was used, the low temperature characteristics were not satisfactory. This is considered to be because, in comparative examples 4 and 5 using (C5) gallic acid (melting point 285 ℃) having a melting point higher than the processing temperature at the time of manufacturing the flame-retardant insulated wire, the gallic acid does not melt at a normal processing temperature and exists as a coagulated mass in the resin composition, and thus easily becomes a starting point of mechanical breakage. Therefore, propyl gallate (C2) (melting point 150 ℃ C.), 2,3, 4-trihydroxybenzophenone (melting point 140 ℃ C.), and bisphenol A (melting point 158 ℃ C.) having a low melting point are suitable (C2). Therefore, in order to pass the low-temperature characteristics, it is preferable to use (C) a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group, which has a melting point higher than the processing temperature at the time of manufacturing the flame-retardant insulated wire.
The present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit thereof.
Claims (6)
1. A flame-retardant insulated electric wire having excellent flame retardancy,
having a conductor and an insulating layer covering the periphery of the conductor,
the insulating layer contains a flame-retardant resin composition containing a vinyl polymer, a metal hydroxide, and a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group,
the flame-retardant resin composition contains 100 to 180 parts by mass of the metal hydroxide per 100 parts by mass of the ethylene polymer,
the flame-retardant resin composition contains the compound in an amount of 2 parts by mass or more per 100 parts by mass of the ethylene polymer.
2. The flame-retardant insulated wire according to claim 1, wherein the compound is an ester derivative of gallic acid.
3. The flame retardant insulated wire according to claim 1, wherein the compound is at least one compound selected from the group consisting of methyl gallate, propyl gallate, 2,3, 4-trihydroxybenzophenone, and bisphenol A.
4. A flame-retardant cable is provided, which comprises a cable core,
having a core wire including an insulated wire including a conductor and an insulating layer coated around the conductor, and a sheath provided around the core wire,
the sheath contains a flame-retardant resin composition containing a vinyl polymer, a metal hydroxide, and a compound having a plurality of phenolic hydroxyl groups in the molecule and no carboxyl group,
the flame-retardant resin composition contains 100 to 180 parts by mass of the metal hydroxide per 100 parts by mass of the ethylene polymer,
the flame-retardant resin composition contains the compound in an amount of 2 parts by mass or more per 100 parts by mass of the ethylene polymer.
5. The flame retardant cable according to claim 4, wherein the compound is an ester derivative of gallic acid.
6. The flame retardant cable according to claim 4, wherein the compound is at least one compound selected from the group consisting of methyl gallate, propyl gallate, 2,3, 4-trihydroxybenzophenone and bisphenol A.
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| JP2019-199476 | 2019-11-01 | ||
| JP2019199476A JP6860833B2 (en) | 2018-11-05 | 2019-11-01 | Flame-retardant insulated wires and flame-retardant cables |
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| CN111138746B CN111138746B (en) | 2023-08-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116102813A (en) * | 2021-11-10 | 2023-05-12 | 中化学科学技术研究有限公司 | Halogen-free flame-retardant resin composition, preparation method thereof and insulated wire |
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| CN116102813A (en) * | 2021-11-10 | 2023-05-12 | 中化学科学技术研究有限公司 | Halogen-free flame-retardant resin composition, preparation method thereof and insulated wire |
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