CN106397947B - Halogen-free flame-retardant resin composition, insulated wire and cable - Google Patents
Halogen-free flame-retardant resin composition, insulated wire and cable Download PDFInfo
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- CN106397947B CN106397947B CN201610602162.1A CN201610602162A CN106397947B CN 106397947 B CN106397947 B CN 106397947B CN 201610602162 A CN201610602162 A CN 201610602162A CN 106397947 B CN106397947 B CN 106397947B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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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
- H01B7/187—Sheaths comprising extruded non-metallic layers
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention provides a halogen-free flame-retardant resin composition, an insulated wire and a cable, which can maintain extrudability, thermal shock property and flexibility and improve flame retardancy even though a large amount of metal hydrate is used. The halogen-free flame-retardant resin composition contains 100 to 250 parts by mass of aluminum hydroxide surface-treated with silane and 5 to 50 parts by mass of at least one selected from melamine cyanurate, zinc stannate and amorphous silica, based on 100 parts by mass of a polyolefin resin containing 55 parts by mass or more in total of two or more ethylene-vinyl acetate copolymers, wherein the two or more ethylene-vinyl acetate copolymers have an average vinyl acetate content (unit: mass%) of 37.5 to 45 and an average MFR (unit: g/10 min) of 10 to 50.
Description
Technical Field
The present invention relates to a halogen-free flame-retardant resin composition and an insulated wire and cable having a coating layer formed of the resin composition.
Background
The flexible vinyl chloride resin composition is inexpensive and excellent in processability, and the flexibility thereof can be freely changed in accordance with the amount of the plasticizer added. Further, since it has the advantage of self-extinguishing property and relatively good mechanical properties, a soft vinyl chloride resin composition is widely used for electric wire coating materials, building materials, and daily necessities.
However, the soft vinyl chloride resin composition has problems of embrittlement itself and contamination of peripheral parts due to migration of the plasticizer. In addition, since chlorine is contained as a halogen, when it is incinerated, a harmful di-compound is generated
And organic compounds such as quartz. In addition, there are many problems in that lead compounds which may cause environmental pollution are sometimes used as stabilizers.
As a method for solving the above problem, some techniques have been proposed (for example, see patent documents 1 to 3).
For example, patent documents 1 and 2 disclose halogen-free flame-retardant resin compositions obtained by adding a large amount of a metal hydrate as a flame retardant to a polyolefin resin.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2000-294036
Patent document 2: japanese laid-open patent publication No. 2009-19190
Patent document 3: japanese patent laid-open publication No. 2003-147131
Disclosure of Invention
Problems to be solved by the invention
However, if a large amount of metal hydrate is added as a flame retardant, there is a risk that extrudability, thermal shock and flexibility are reduced.
In recent years, further improvement in flame retardancy has been demanded for electric wire coating materials in order to improve reliability.
It is an object of the present invention to provide a halogen-free flame retardant resin composition which can maintain extrudability, thermal shock property and flexibility and improve flame retardancy even when a metal hydrate is used in a large amount, and to provide an insulated wire and a cable having a coating layer formed of the resin composition.
Means for solving the problems
In order to achieve the above objects, there are provided according to the present invention the halogen-free flame retardant resin composition, the insulated wire and the cable described below.
(1) A halogen-free flame-retardant resin composition which comprises 100 to 250 parts by mass of aluminum hydroxide surface-treated with silane and 5 to 50 parts by mass of at least one selected from the group consisting of melamine cyanurate, zinc stannate and amorphous silica, based on 100 parts by mass of a polyolefin resin, wherein the polyolefin resin contains 55 parts by mass or more in total of two or more ethylene-vinyl acetate copolymers, the two or more ethylene-vinyl acetate copolymers have an average vinyl acetate content (unit: mass%) of 37.5 to 45 and an average MFR (unit: g/10 min) of 10 to 50.
(2) The halogen-free flame-retardant resin composition according to the item (1), wherein the two or more ethylene-vinyl acetate copolymers each have a vinyl acetate content (unit: mass%) of 30 to 65.
(3) The halogen-free flame-retardant resin composition according to the item (1) or (2), wherein the polyolefin resin includes at least one selected from the group consisting of an ethylene-ethyl acrylate-maleic anhydride terpolymer, an ethylene-ethyl acrylate, a maleic acid-modified high-density polyethylene, a metallocene linear low-density polyethylene, and a metallocene polypropylene.
(4) An insulated wire comprising an insulating layer formed from the halogen-free flame-retardant resin composition according to any one of the above (1) to (3).
(5) A cable comprising a sheath made of the halogen-free flame-retardant resin composition according to any one of the above (1) to (3).
(6) The cable according to (5), characterized by having the insulated electric wire of (4).
Effects of the invention
According to the present invention, there is provided a halogen-free flame retardant resin composition which can maintain extrudability, thermal shock property and flexibility and improve flame retardancy even when a metal hydrate is used in a large amount, and at the same time, provides an insulated wire and a cable having a coating layer formed of the resin composition.
Drawings
Fig. 1 is a sectional view showing one embodiment of an insulated electric wire of the present invention.
Fig. 2 is a cross-sectional view showing one embodiment of the cable of the present invention.
Fig. 3 is an SEM photograph before extension when the extension test was performed in the examples.
Fig. 4 is an SEM photograph after 30% extension when the extension test was performed in the examples.
Description of the symbols
1: conductor, 2 insulating layer, 10: insulated wire, 3: strapping tape, 4: braided shield layer, 5: sheath, 20: an electrical cable.
Detailed Description
Hereinafter, one embodiment of the halogen-free flame retardant resin composition, the insulated wire and the cable of the present invention will be specifically described.
1. Halogen-free flame-retardant resin composition
The halogen-free flame-retardant resin composition according to the embodiment of the present invention contains 100 to 250 parts by mass of aluminum hydroxide surface-treated with silane and 5 to 50 parts by mass of at least one selected from melamine cyanurate, zinc stannate, and amorphous silica, based on 100 parts by mass of a polyolefin resin containing 55 parts by mass or more in total of two or more ethylene-vinyl acetate copolymers, the two or more ethylene-vinyl acetate copolymers having an average vinyl acetate content (unit: mass%) of 37.5 to 45 and an average MFR (unit: g/10 min) of 10 to 50.
1.1 ethylene-vinyl acetate copolymer
The halogen-free flame-retardant resin composition contains a polyolefin resin as a base resin.
The halogen-free flame-retardant resin composition contains two or more kinds of ethylene-vinyl acetate copolymers (EVA) as the polyolefin resin. Preferably 2 to 5 kinds of EVA, more preferably 2 to 4 kinds of EVA, and still more preferably 2 to 3 kinds of EVA.
The average vinyl acetate content (average VA amount) of two or more EVA contained therein is from 37.5 to 45 mass%. The lower limit of the average VA amount is preferably 38% by mass, more preferably 38.5% by mass. The upper limit of the average VA amount is preferably 44% by mass, more preferably 43% by mass. If the average VA content is less than 37.5% by mass, the desired flame retardancy cannot be exhibited, and if it exceeds 45% by mass, the tackiness increases and the extrudability deteriorates.
The average VA content can be determined by the following equation. The EVA1 to EVA3 mean various EVA to be added.
Average amount of VA (amount of added EVA1 × amount of added EVA1 + amount of added EVA2 × amount of added EVA2 + amount of added EVA3 × amount of added EVA3 + amount of added EVA …)/(amount of added EVA1 + amount of added EVA2 + amount of added EVA3 + …)
The above two or more EVA s preferably have a vinyl acetate content (VA amount) of 30 mass% or more and 65 mass% or less, and more preferably 33 mass% or more and 60 mass% or less.
The EVA contained in the resin composition has an average MFR (melt mass flow rate) of 10 to 50 (unit: g/10 min). The lower limit of the average MFR is preferably 11, more preferably 15. The upper limit of the average MFR is preferably 45, more preferably 25, and still more preferably 20. From the viewpoint of extrudability, the average MFR is preferably within the above range. If the average MFR is less than 10, the extrudability is deteriorated by a high load, and if it exceeds 50, the tensile properties as a covering material for electric wire are not satisfied and the extrudability is also deteriorated.
The average MFR can be determined from the following equation. The EVA1 to EVA3 mean various EVA to be added.
Average MFR (addition amount of EVA1, MFR of EVA1, addition amount of EVA2, MFR of EVA2, addition amount of EVA3, MFR of EVA3, …)/(addition amount of EVA1, addition amount of EVA2, addition amount of EVA3, …)
The two or more EVA groups preferably have MFR (unit: g/10 min) of 0.2 to 110, more preferably 0.3 to 100.
The halogen-free flame-retardant resin composition contains 55 parts by mass or more of EVA in total to 100 parts by mass of the polyolefin resin. The lower limit of the content of two or more kinds of EVA is preferably 70 parts by mass, and more preferably 80 parts by mass. The upper limit of the content of two or more kinds of EVA is preferably 100 parts by mass, and more preferably 95 parts by mass. From the viewpoint of flexibility, the content of two or more kinds of EVA is preferably within the above range. If the content of two or more kinds of EVA is less than 55 parts by mass, the desired flexibility and thermal shock property cannot be exhibited.
1.2 other polyolefin-based resins
The halogen-free flame-retardant resin composition may contain, as the polyolefin resin, other polyolefin resins in addition to the above two or more kinds of EVA. One or more kinds of other polyolefin resins may be added.
The other polyolefin-based resin is not particularly limited, and examples thereof include acid-modified polyolefins modified by reacting with unsaturated carboxylic acids such as maleic anhydride and acrylic acid or derivatives thereof at the time of or after polymerization of the polyolefin-based resin. Examples of the polyolefin of the acid-modified polyolefin include ultra-low density polyethylene, high density polyethylene, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-1-octene copolymer, and examples of the acid include maleic acid, maleic anhydride, and fumaric acid.
The other polyolefin resin preferably contains at least one selected from the group consisting of ethylene-ethyl acrylate-maleic anhydride terpolymer (maleic acid-modified EEA), ethylene-ethyl acrylate (EEA), maleic acid-modified high-density polyethylene (maleic acid-modified HDPE), metallocene linear low-density polyethylene (M-LLDPE), and metallocene polypropylene (Reactor PP).
The halogen-free flame-retardant resin composition according to the present embodiment may contain a polymer component other than the polyolefin resin within the limit of exerting the effect of the present invention, but the content of the polyolefin resin is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass in the polymer component.
1.3 flame retardants
In the halogen-free flame-retardant resin composition according to the embodiment of the present invention, aluminum hydroxide surface-treated with silane is contained as a flame retardant in a ratio of 100 parts by mass to 250 parts by mass with respect to 100 parts by mass of the polyolefin resin. This is because if the content of the aluminum hydroxide surface-treated with silane is less than 100 parts by mass, the desired flame retardancy cannot be exhibited even in combination with the flame retardant aid, and if it exceeds 250 parts by mass, the thermal shock property is lowered.
The average particle diameter of the aluminum hydroxide is preferably adjusted to 0.5 to 2 μm, and coarse particles having a particle diameter of 10 μm or more are preferably suppressed to 1 mass% or less in dry granulometry under normal pressure.
Specific examples of the silane used for the surface treatment include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutyloxysilane, vinyltriacetoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane and glycidyloxypropyltrimethoxysilane. These silane coupling agents may be used alone, or two or more of them may be used in combination.
The amount of surface treatment with silane is preferably controlled to 0.02% or more and 0.05% or less as the Si mass in the fluorescent X-ray analysis of the treated aluminum hydroxide.
1.4 flame-retardant auxiliary
The halogen-free flame-retardant resin composition according to the embodiment of the present invention contains at least one selected from melamine cyanurate, zinc stannate, and amorphous silica as a flame retardant auxiliary in a proportion of 5 to 50 parts by mass relative to 100 parts by mass of the polyolefin resin. This is because, if the content of the flame retardant auxiliary is less than 5 parts by mass, the flame retardancy is deteriorated since the flame retardant cannot maintain the slag, and if it exceeds 50 parts by mass, the thermal shock property, flexibility and extrudability are deteriorated.
When two or more of the above flame retardant aids are used in combination, the following four combinations may be made: melamine cyanurate with zinc stannate, melamine cyanurate with amorphous silica, zinc stannate with amorphous silica, all three; the combination of melamine cyanurate and zinc stannate is particularly preferred. The mixing ratio of melamine cyanurate to zinc stannate (melamine cyanurate/zinc stannate) is preferably 2 to 6, and more preferably 3 to 5.
(1) Melamine cyanurate
The melamine cyanurate to be used is preferably adjusted to have an average particle diameter of 1.5 to 8 μm. More preferably, the thickness is adjusted to 2 μm to 5 μm. This is because if it is less than 1.5 μm, the resin tends to aggregate, and if it exceeds 8 μm, the tensile strength is lowered when the resin is added. For the purpose of suppressing agglomeration, it may be subjected to surface treatment with a fatty acid or the like, or may be subjected to surface treatment with an organic silicon, a silane coupling agent or the like after supporting an inorganic substance such as silica.
(2) Zinc stannate
Suitable zinc stannate is selected from zinc stannate trioxide and zinc stannate hexahydrate (zinc hydroxystannate). The average particle diameter is preferably adjusted to 1 to 8 μm. More preferably, the thickness is adjusted to 2 μm to 5 μm. This is because if it is less than 1 μm, it is liable to aggregate, and if it exceeds 8 μm, it will cause a decrease in tensile strength when added to a resin. For the purpose of suppressing agglomeration, it may be subjected to surface treatment with a fatty acid or the like, or may be subjected to surface treatment with an organic silicon, a silane coupling agent or the like after supporting an inorganic substance such as silica.
(3) Amorphous silica
The amorphous silica preferably has an average particle diameter of 50nm to 400 nm. More preferably, the particle diameter is adjusted to 100nm to 250 nm. This is because, if less than 50nm, the handling property is deteriorated, and if more than 400nm, the tensile strength is lowered when added to the resin. The shape is preferably spherical. Preferably, the BET specific surface area is adjusted to 15 to 28m2/g。
1.5 other additives
The halogen-free flame-retardant resin composition according to the embodiment of the present invention may further contain additives such as an antioxidant, a processing aid, a lubricant, a softener, a plasticizer, an inorganic filler, a compatibilizer, a stabilizer, carbon black, and a colorant, as necessary, in addition to the flame retardant and the flame retardant aid.
1.6 characteristics
The halogen-free flame-retardant resin composition according to the embodiment of the present invention is excellent in heat shock property, extrudability, flexibility, and flame retardancy, which are basic properties required for an electric wire coating material. Particularly, since flame retardancy is comparable to flame retardancy of flame retardant polyvinyl chloride (PVC), a cable to be subjected to a vertical burning test can be provided with the halogen-free flame retardant resin composition according to the embodiment of the present invention instead of a sheath material having a structure in which an insulator made of flammable Polyethylene (PE) or polypropylene (PP) and a sheath made of flame retardant PVC are provided. The halogen-free flame-retardant resin composition according to the embodiment of the present invention is difficult to burn in the event of fire and has a small smoke emission. In addition, since it does not contain halogen, it does not generate di-alcohol upon combustion
Toxic gases such as quartz and halogen gases can be incinerated, and no toxic gas is generated in case of fire. Further, since the lead-free filler does not contain a phosphorus-based compound, it is environmentally preferable, and since no lead is eluted, it can be buried.
1.7 uses
The halogen-free flame-retardant resin composition according to the embodiment of the present invention has the above-described characteristics, and thus can be used for various applications. For example, the resin composition can be used as an insulating material, a sheathing material, a tape material, and an intermediate material for various electric wires and cables such as an insulated wire, an electric wire for electronic equipment wiring, an electric wire for automobiles, an electric wire for equipment, a power supply line, an insulated wire for outdoor distribution, an electric power cable, a control cable, a communication cable, an instrument cable, a signal cable, a mobile cable, and a ship cable. Further, the present invention can be applied to electric materials such as wires, cable accessories, and electric conduits, such as boxes, plugs, tapes, and the like. In addition, the resin composition can be used for agricultural sheets, water pipes, gas pipe coating materials, building interior materials, furniture materials, toy materials, floor materials, and the like.
2. Insulated wire
Fig. 1 is a sectional view showing one embodiment of an insulated electric wire of the present invention.
An insulated wire 10 according to the present embodiment shown in fig. 1 includes a conductor 1 made of a common material (e.g., tin-plated copper) and an insulating layer 2 formed on the outer periphery of the conductor 1.
The insulating layer 2 is composed of the halogen-free flame-retardant resin composition according to the embodiment of the present invention.
In this embodiment, the insulating layer may be formed of a single layer or may have a multilayer structure. As a specific example of the case of the multilayer structure, there is a structure obtained by extrusion coating the halogen-free flame retardant resin composition on the outermost layer and extrusion coating a polyolefin resin or a rubber material on the outside of the outermost layer. As the polyolefin resin, for example, the polyolefin resin described above can be used. Further, a spacer, a braid, or the like may be applied as necessary. For the insulating layer, crosslinking treatment may be performed after molding. The crosslinking method is not particularly limited, and may be carried out by a known method.
3. Cable with a protective layer
Fig. 2 is a cross-sectional view showing one embodiment of the cable of the present invention.
A cable 20 according to the present embodiment shown in fig. 2 includes twisted wires obtained by twisting 3 double-core twisted wires 2 of the insulated wires 10 according to the present embodiment, a binding tape 3 wound around the twisted wires, a braided shield layer 4 provided on the outer periphery of the binding tape 3, and a sheath 5 provided on the outer periphery of the braided shield layer 4. The insulated electric wire may be a single core, or may be a multi-core twisted wire other than the above.
The sheath 5 is made of the halogen-free flame-retardant resin composition. The thickness of the sheath 5 may be 1mm or less, for example.
In the present embodiment, the sheath may be formed of a single layer or may have a multilayer structure. As a specific example of the case of the multilayer structure, there is a structure in which the halogen-free flame retardant resin composition is extrusion-coated on the outermost layer, and a polyolefin resin is extrusion-coated on the outside of the outermost layer. Examples of the polyolefin resin include the polyolefin resins described above. Further, if necessary, a spacer or the like may be added. For the sheath, a crosslinking treatment may be performed after molding. The crosslinking method is not particularly limited, and may be carried out by a known method.
In the present embodiment, the insulated wire 10 according to the present embodiment is used, but an insulated wire using a general-purpose material may be used.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples. It should be noted that the present invention is not limited in any way by the following examples.
Examples and comparative examples
The cable shown in fig. 2 was made as follows.
At 0.5mm2An outer periphery of a tin-plated soft copper twisted wire 1 (outer diameter 0.96mm) (7 wires/0.32 mm) was covered with polyethylene 0.3mm thick to provide an insulating layer 2, thereby obtaining an insulated wire 10. A twisted wire is obtained by twisting 2 insulated wires 10 to obtain a double-core twisted wire, 3 double-core twisted wires are twisted to obtain a twisted wire, a binding tape 3 made of PET is applied around the twisted wire, and a braided shield layer 4 made of a tin-plated annealed copper wire is provided thereon. In braided shield layer 4The outer periphery was covered with a resin composition in the compounding ratio shown in tables 1 to 2 to provide a sheath 5 having a sheath thickness of 1mm, thereby obtaining a cable having an outer diameter of 8.1 mm. The resin compositions in the blending ratios shown in tables 1 to 2 were weighed with a weighing machine, kneaded at 160 ℃ with a 3L kneader, flaked with a mixing roll, and the obtained flakes were pelletized with a pelletizer. The coating of the jacket is carried out as follows: a90 mm extruder was used, and extrusion was carried out at a linear speed of 30 m/min using a tube extrusion method under conditions of a cylinder temperature of 160 ℃, a head temperature of 180 ℃ and a die temperature of 185 ℃.
The obtained cables were evaluated by the following test methods, and the evaluation results are shown in tables 1 to 2.
Tensile strength: the sheath (sample) was peeled from the prepared cable, and the tensile strength was measured according to the method of JISK 7113. Specifically, the tensile breaking strength of the specimen was measured under test conditions of a tensile speed of 200 m/min and a distance between gauge lines of 20 mm. A specimen having a tensile breaking strength of 10MPa or more is regarded as a pass specimen, and a specimen having a tensile breaking strength of less than 10MPa is regarded as a fail specimen.
Tensile elongation: the sheath (sample) was peeled from the prepared cable, and the tensile elongation was measured according to the method of JISK 7113. Specifically, the tensile breaking elongation of the specimen was measured under test conditions of a tensile speed of 200 m/min and a distance between gauge lines of 20 mm. The specimen having a tensile elongation at break of 150% or more was regarded as a pass, and the specimen having a tensile elongation at break of less than 150% was regarded as a fail.
Flexibility: as the evaluation of flexibility, a 100% modulus value as an index of hardness was applied.
The sheath (sample) was peeled from the prepared cable, and the tensile elongation was measured according to the method of JISK 7113. The 100% modulus value is preferably 10MPa or less. As a reference test, the cable manufactured as described above was fixed in a freely movable state of 30cm, and a weight of 100g was hung at the tip of the freely movable end, and a sample having an angle of 45 degrees or more when bent was satisfactory.
Thermal shock property: based on UL standard, table 50.133 of UL1581, the cable produced as described above was wound around a mandrel having a diameter of 2 times for 6 full turns, and after applying a heat load of 100 ℃x1 hour, a sample having no crack on the surface of the sheath was regarded as a pass and a sample having a crack was regarded as a fail.
Extrudability: in the case of performing the sheath extrusion operation using the above 90mm extruder, the operation can be performed with an allowable torque at the time of extrusion of less than 90%, and a sample which is operated at a linear speed of 30 m/min or more is good. The sample which can be handled only when the allowable torque is 90% or more and less than 30 m/min was regarded as defective.
Flame retardancy: the cable produced in the above manner was subjected to VW-1 (Vertical Wire Flame Test) based on UL standard, UL 1581. The number of experiments performed was 10. Good results were obtained when 10 of them were acceptable. Among 10, the failure was determined as 1 out of the 10.
TABLE 1
TABLE 2
In examples 1 to 8, the halogen-free flame retardant resin composition according to the embodiment of the present invention was used as a sheath material, and as shown in tables 1 to 8, the flexibility, thermal shock property, extrudability, and flame retardancy of examples 1 to 8 were all good results.
In comparative example 1, silane-treated magnesium hydroxide was used instead of silane-treated aluminum hydroxide. Comparative example 1 did not exhibit a predetermined elongation, and good results were not obtained in flexibility and thermal shock property.
Comparative example 2 is a system in which the content of the flame retardant auxiliary is less than 5 parts by mass, and comparative example 3 is a system in which the content of the silane-treated aluminum hydroxide is less than 100 parts by mass and the content of the flame retardant auxiliary exceeds 50 parts by mass. Neither comparative example 2 nor comparative example 3 gave the desired flame retardancy.
Comparative example 4 is a system in which the average VA content of EVA exceeds 45 mass%, and comparative example 5 is a system in which the average VA content of EVA is less than 37.5 mass%. In comparative example 4, the extrusion outer diameter was unstable due to the adhesion caused by EVA, and the extrusion operation could not be performed at a desired speed. The flame retardancy of comparative example 5 was poor.
Comparative example 6 is a system in which the average MFR of EVA is less than 10 and the amount of EVA added is less than 55 parts by mass, and comparative example 7 is a system in which the average MFR of EVA exceeds 50. Comparative example 6 was only operated at 3 m/min due to the problem of extrusion torque, and the thermal shock property was also unsatisfactory. The tensile strength of comparative example 7 did not satisfy the predetermined value, and the same sticking phenomenon as in comparative example 4 occurred, and the extrudability was poor.
Comparative example 8 is a system in which the content of the flame-retardant auxiliary exceeds 50 parts by mass. Good results were not obtained in all of flexibility, thermal shock and extrudability.
Comparative example 9 is a system in which the content of silane-treated aluminum hydroxide is more than 250 parts by mass. The tensile strength did not satisfy the predetermined value, the elongation did not become the predetermined value, and the flexibility, the thermal shock property and the extrudability were all not good results.
Based on the above, the present inventors have found that in a system using a large amount of silane-treated aluminum hydroxide (in combination with a flame retardant aid), if the amount of the silane-treated aluminum hydroxide and a predetermined flame retardant aid are set within a predetermined range and the average VA amount, average MFR, and amount of addition of two or more kinds of EVA are limited within a predetermined range, sufficient tensile strength, thermal shock property, and flame retardancy can be obtained, and furthermore, flexibility can be exhibited, and extrusion moldability can be improved.
Of particular interest was the elongation characteristic not exhibited when using silane-treated magnesium hydroxide (comparative example 1), and exhibited when using silane-treated aluminum hydroxide (example 3). To examine the mechanism, the components in the blending ratio of example 3 were kneaded by a mixing roll, and a sheet having a thickness of 1mm was prepared by a press machine, and a stretching test was performed thereon.
SEM photographs before and after the extension are shown in FIGS. 3 and 4. The white particles seen on the surface were silane-treated aluminum hydroxide particles. After 30% elongation (fig. 4), the scattered dark fine pores due to fracture were observed, but the aluminum hydroxide particles were elongated with maintaining the disk shape, as compared with the ones before elongation (fig. 3). From this, it was found that the aluminum hydroxide in the present composition flowed in a regular particle disk shape against the resin flow at the time of extrusion without reversing. It is believed that the regular particle disc surface dispersion morphology contributes to the uniform orientation of the polymer components, thereby achieving elongation.
Claims (5)
1. A halogen-free flame-retardant resin composition which comprises 100 parts by mass or more and 250 parts by mass or less of aluminum hydroxide surface-treated with silane and 5 parts by mass or more and 50 parts by mass or less of one or more selected from melamine cyanurate, zinc stannate and amorphous silica per 100 parts by mass of a base resin comprising 55 parts by mass or more of two or more ethylene-vinyl acetate copolymers and one or more selected from ethylene-ethyl acrylate-maleic anhydride terpolymer, ethylene-ethyl acrylate, maleic acid-modified high-density polyethylene, metallocene linear low-density polyethylene and metallocene polypropylene,
the two or more ethylene-vinyl acetate copolymers have an average vinyl acetate content of 37.5 to 45 mass% and an average MFR of 10 to 10 minutes and 50g/10 minutes.
2. The halogen-free flame-retardant resin composition according to claim 1, wherein the vinyl acetate content of each of the two or more ethylene-vinyl acetate copolymers is 30 mass% or more and 65 mass% or less.
3. An insulated wire comprising an insulating layer formed from the halogen-free flame-retardant resin composition according to claim 1 or 2.
4. A cable characterized by having a sheath formed of the halogen-free flame-retardant resin composition according to claim 1 or 2.
5. The cable of claim 4, characterized by the insulated wire of claim 3.
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| JP2015-153442 | 2015-08-03 | ||
| JP2015153442A JP6657643B2 (en) | 2015-08-03 | 2015-08-03 | Halogen-free flame-retardant resin composition, insulated wires and cables |
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| CN106397947A CN106397947A (en) | 2017-02-15 |
| CN106397947B true CN106397947B (en) | 2021-04-09 |
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| KR101804906B1 (en) | 2017-09-11 | 2017-12-05 | 오켈케이블주식회사 | Power cable |
| JP7119361B2 (en) * | 2017-12-05 | 2022-08-17 | 東ソー株式会社 | Resin composition and laminate comprising the same |
| JP7272218B2 (en) * | 2018-10-31 | 2023-05-12 | 株式会社プロテリアル | Flame-retardant insulated wire |
| CN111640535A (en) * | 2019-03-01 | 2020-09-08 | 日立金属株式会社 | Electric wire and cable |
| JP6947857B2 (en) * | 2019-03-01 | 2021-10-13 | 日立金属株式会社 | Wires and cables |
| JP7092090B2 (en) * | 2019-04-15 | 2022-06-28 | 日立金属株式会社 | Power transmission cable using non-halogen flame-retardant resin composition |
| CN112397242A (en) * | 2019-08-15 | 2021-02-23 | 江苏亨通电力电缆有限公司 | Fire-resistant 1100 ℃ mineral low-voltage cable and preparation method thereof |
| EP4002395A1 (en) * | 2020-11-11 | 2022-05-25 | Prysmian S.p.A. | Flame-retardant cable with self-extinguishing coating layer |
| CN113881180A (en) * | 2021-10-08 | 2022-01-04 | 广州敬信高聚物科技有限公司 | Insulating polypropylene material and preparation method and application thereof |
| CN115850870B (en) * | 2023-03-02 | 2023-09-19 | 南京中超新材料股份有限公司 | Polypropylene modified insulating material and preparation method thereof |
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| JP2003034793A (en) * | 2001-07-24 | 2003-02-07 | Fujikura Ltd | Silane-treated magnesium hydroxide and silane-treated aluminum hydroxide |
| KR100797222B1 (en) * | 2007-01-25 | 2008-01-23 | 엘에스전선 주식회사 | Flame retardant polymer composition |
| JP2008150532A (en) * | 2006-12-19 | 2008-07-03 | Furukawa Electric Co Ltd:The | Insulating resin composition and insulated wire |
| CN102585322A (en) * | 2012-02-27 | 2012-07-18 | 广州凯恒科塑有限公司 | Easily-processed low-smoke halogen-free flame-retardant heat shrinkable label sleeve as well as preparation and application thereof |
| JP2013222518A (en) * | 2012-04-13 | 2013-10-28 | Hitachi Cable Ltd | Wire/cable for railway vehicle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5733352B2 (en) * | 2013-07-23 | 2015-06-10 | 日立金属株式会社 | Insulated electric wire for vehicle and cable for vehicle using non-halogen crosslinkable resin composition |
| JP2015072743A (en) * | 2013-10-01 | 2015-04-16 | 日立金属株式会社 | Wire and cable |
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2015
- 2015-08-03 JP JP2015153442A patent/JP6657643B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003034793A (en) * | 2001-07-24 | 2003-02-07 | Fujikura Ltd | Silane-treated magnesium hydroxide and silane-treated aluminum hydroxide |
| JP2008150532A (en) * | 2006-12-19 | 2008-07-03 | Furukawa Electric Co Ltd:The | Insulating resin composition and insulated wire |
| KR100797222B1 (en) * | 2007-01-25 | 2008-01-23 | 엘에스전선 주식회사 | Flame retardant polymer composition |
| CN102585322A (en) * | 2012-02-27 | 2012-07-18 | 广州凯恒科塑有限公司 | Easily-processed low-smoke halogen-free flame-retardant heat shrinkable label sleeve as well as preparation and application thereof |
| JP2013222518A (en) * | 2012-04-13 | 2013-10-28 | Hitachi Cable Ltd | Wire/cable for railway vehicle |
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| JP2017031337A (en) | 2017-02-09 |
| JP6657643B2 (en) | 2020-03-04 |
| CN106397947A (en) | 2017-02-15 |
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