CN106397947A - Halogen-free flame-retarding resin composition, insulation wire, and cable - Google Patents
Halogen-free flame-retarding resin composition, insulation wire, and cable Download PDFInfo
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- CN106397947A CN106397947A CN201610602162.1A CN201610602162A CN106397947A CN 106397947 A CN106397947 A CN 106397947A CN 201610602162 A CN201610602162 A CN 201610602162A CN 106397947 A CN106397947 A CN 106397947A
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 invention provides a halogen-free flame-retarding resin composition, an insulation wire, and a cable. The halogen-free flame-retarding resin composition can maintain extrusion property, thermal impact property and flexibility even under large quantity of usage of a metal hydrate, and flame retarding performance improved. The halogen-free flame-retarding resin composition includes, on the basis of 100 parts by mass of polyolefin resin, 100-250 parts by mass of Al(OH)3 which has been subjected to surface treatment with silane, and 5-50 parts by mass of more than one selected from melamine cyanurates, zinc stannate, and amorphous silicon dixoide, wherein the polyolefin resin includes more than two ethylene-vinyl acetate copolymers being more than 55 parts in mass in total, the average vinyl acetate content of the more than two ethylene-vinyl acetate copolymers is 37.5-45 mass%, average MFR being 10-50 (gram per ten minutes).
Description
Technical field
The present invention relates to halogen-free fire resistance resin composite and there is the exhausted of the coating being formed by this resin combination
Edge electric wire and cable.
Background technology
The price of soft vinyl chloride resin composition is low and excellent in workability, and can be with the addition of plasticizer
Change its flexibility freely.It is additionally, since with self-gravitation, mechanical property also compares good advantage, therefore with electric wire
Headed by lining material, in building materials, article of everyday use, widely use soft vinyl chloride resin composition.
But, for soft vinyl chloride resin composition, exist because of its own caused by migration of plasticizer
Embrittlement, the problem of the pollution of peripheral part.Further, since containing the chlorine as halogen, therefore when by its burning disposal, meeting
Produce harmful twoThe organic compound such as English.And, also a lot of problems, such as sometimes using the danger having pollution environment
Lead compound as stabilizer etc..
As solving the method for above-mentioned problem it has been proposed that some technology (for example, referring to patent documentation 1～3).
For example, in patent documentation 1,2, a large amount of metal water added as fire retardant in polyolefin-based resins are disclosed
Halogen-free fire resistance resin composite obtained from compound.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2000-294036 publication
Patent documentation 2：Japanese Unexamined Patent Publication 2009-19190 publication
Patent documentation 3：Japanese Unexamined Patent Publication 2003-147131 publication
Content of the invention
Invent problem to be solved
But, if adding substantial amounts of metal hydrate as fire retardant, have extrudability, thermal impact and pliability fall
Low danger.
Additionally, in recent years, for wire coating material, in order to improve reliability it is desirable to improve anti-flammability further.
Here, it is an object of the invention to provide a kind of halogen-free fire resistance resin composite, even if it is in a large number using metal
Hydrate can also maintain extrudability, thermal impact and pliability, and improves anti-flammability, provide simultaneously and have by this resin combination
The insulated electric conductor of coating and cable that thing is formed.
Method for solve problem
To achieve these goals, halogen-free fire resistance resin composite, the insulated electro of described below are provided according to the present invention
Line and cable.
(1) a kind of halogen-free fire resistance resin composite, wherein, with respect to polyolefin-based resins 100 mass parts, contains 100
The aluminium hydroxide being surface-treated by silane below more than mass parts 250 mass parts, and containing more than 5 mass parts 50 matter
Amount part below select from melamine cyanurate, zinc and amorphous silica more than one, wherein, described
Polyolefin-based resins contain the two or more vinyl-vinyl acetate copolymer of more than total 55 mass parts, described two with
On vinyl-vinyl acetate copolymer average acetic acid ethylene ester content (unit：Quality %) it is less than more than 37.5 45, and
Average MFR (unit：G/10 minute) it is less than more than 10 50.
(2) halogen-free fire resistance resin composite according to above-mentioned (1), wherein, described two above ethylene-acetates
Vinyl acetate content (the unit of vinyl ester copolymers：Quality %) it is less than more than 30 65.
(3) halogen-free fire resistance resin composite according to above-mentioned (1) or (2), wherein, as described polyolefin tree
Fat, containing from ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-ethylacrylate, maleic acid modified high density
Select in polyethylene, metallocene straight-chain Low Density Polyethylene and metallocene system polypropylene more than one.
(4) a kind of insulated electric conductor, is characterised by, has the halogen-free flame-retardance tree any one of above-mentioned (1)～(3)
The insulating barrier that oil/fat composition is formed.
(5) a kind of cable, is characterised by, has the halogen-free flame-retardance resin group any one of above-mentioned (1)～(3)
The sheath that compound is formed.
(6) cable according to (5), is characterised by, has described insulated electric conductor described in (4).
Invention effect
According to the present invention, provide a kind of halogen-free fire resistance resin composite, even if it also may be used using metal hydrate in a large number
To maintain extrudability, thermal impact and pliability, and improve anti-flammability, provide simultaneously and there is the quilt being formed by this resin combination
The insulated electric conductor of coating and cable.
Brief description
Fig. 1 is the sectional view of an embodiment of the insulated electric conductor showing the present invention.
Fig. 2 is the sectional view of an embodiment of the cable showing the present invention.
Fig. 3 is the SEM photograph before extension when implementing to extend test in an embodiment.
Fig. 4 is the SEM photograph after the extension 30% when implementing to extend test in an embodiment.
Symbol description
1：Conductor, 2 insulating barriers, 10：Insulated electric conductor, 3：Strapping tape, 4：Woven shield, 5：Sheath, 20：Cable.
Specific embodiment
Hereinafter, illustrate an embodiment party of halogen-free fire resistance resin composite, insulated electric conductor and the cable of the present invention
Formula.
1. halogen-free fire resistance resin composite
Halogen-free fire resistance resin composite involved by embodiments of the present invention, with respect to polyolefin-based resins 100 matter
Amount part, containing the aluminium hydroxide being surface-treated by silane below more than 100 mass parts 250 mass parts, and contains 5 matter
More than amount part one kind selected from melamine cyanurate, zinc and amorphous silica below 50 mass parts with
On, described polyolefin-based resins contain the two or more vinyl-vinyl acetate copolymer of more than total 55 mass parts, described
The average acetic acid ethylene ester content (unit of two or more vinyl-vinyl acetate copolymers：Quality %) it is more than 37.5 45
Hereinafter, and average MFR (unit：G/10 minute) it is less than more than 10 50.
1.1 vinyl-vinyl acetate copolymer
Halogen-free fire resistance resin composite contains resin based on polyolefin-based resins.
In halogen-free fire resistance resin composite, as polyolefin-based resins, containing two or more ethane-acetic acid ethyenyl esters
Copolymer (EVA).Preferably comprise 2～5 kinds of EVA, further preferably 2～4 kinds EVA, more preferably contain 2～3 kinds of EVA.
The average acetic acid ethylene ester content (average VA amount) of contained two or more EVA is more than 37.5 45 mass %
Below.The lower limit of average VA amount is preferably 38 mass %, more preferably 38.5 mass %.The upper limit of average VA amount is preferably 44
Quality %, more preferably 43 mass %.If average VA amount is less than 37.5 mass %, the anti-flammability required for cannot presenting,
If it exceeds 45 mass %, then cohesiveness increase, extrudability variation.
Average VA amount can be obtained by following formula.It should be noted that EVA1～EVA3 refers to the various EVA being added.
Average VA amount=(VA that the VA of the addition × EVA1 of EVA1 measures the addition × EVA2 of+EVA2 measures adding of+EVA3
The VA amount of dosage × EVA3+...)/(addition of the addition+EVA3 of the addition+EVA2 of EVA1+...)
For EVA more than above two, preferably vinyl acetate content (VA amount) is more than 30 mass % 65 matter
Amount below %, is more preferably below more than 33 mass % 60 mass %.
Additionally, average MFR (melt mass flow rate, the melt mass flow of contained two or more EVA
Speed) it is less than more than 10 50 (units：G/10 minute).The lower limit of average MFR is preferably 11, more preferably 15.Average MFR
Higher limit be preferably 45, more preferably 25, more preferably 20.From the viewpoint of extrudability, preferably average MFR is set
For in above-mentioned scope.If average MFR is less than 10, the extrudability variation because of high load capacity, if it exceeds 50, then it is unsatisfactory for making
For the tensile properties of wire coating material, and extrudability also it is deteriorated.
Average MFR can be obtained by following formula.It should be noted that EVA1～EVA3 refers to the various EVA being added.
Average MFR=(the interpolation of the MFR+EVA3 of addition × EVA2 of the MFR+EVA2 of addition × EVA1 of EVA1
The MFR+ ... of amount × EVA3)/(addition of the addition+EVA3 of the addition+EVA2 of EVA1+...)
For described two above EVA, preferably MFR (unit：G/10 minute) it is less than more than 0.2 110, more excellent
Choosing is less than more than 0.3 100.
With regard to halogen-free fire resistance resin composite, in polyolefin-based resins 100 mass parts, containing total 55 mass parts with
On two or more EVA.The lower limit of the content of two or more EVA is preferably 70 mass parts, more preferably 80 mass parts.
The higher limit of the content of two or more EVA is preferably 100 mass parts, more preferably 95 mass parts.Go out from flexual viewpoint
Send out, preferably the content of two or more EVA is set in above-mentioned scope.If the content of two or more EVA is less than 55 matter
Amount part, then the pliability required for cannot presenting, thermal impact.
1.2 other polyolefin-based resins
In halogen-free fire resistance resin composite, as polyolefin-based resins, in addition to EVA more than above two, also
Other polyolefin-based resins can be contained.Other polyolefin-based resins can add one or more.
As other polyolefin-based resins, it is not particularly limited, can enumerate when for example polyolefin-based resins being polymerized
Or after polymerization, reacted with the unsaturated carboxylic acids such as maleic anhydride, acrylic acid or these derivant and the acid modification of modification
Polyolefin.As the polyolefin of acid modified polyolefin, can enumerate ultra-low density polyethylene, Low Density Polyethylene, high density gather
Ethylene, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butene-1 copolymer, ethylene -1- are own
Alkene copolymer, ethylene-l-octane copolymer etc., as acid, can enumerate maleic acid, maleic anhydride, fumaric acid etc..
As other polyolefin-based resins, preferably comprise from ethylene-ethyl acrylate-maleic anhydride copolymer
(maleic acid modified EEA), ethylene-ethylacrylate (EEA), maleic acid modified high density polyethylene (HDPE) (maleic acid modified HDPE),
Choosing in metallocene straight-chain Low Density Polyethylene (M-LLDPE) and metallocene system polypropylene (reaction type PP, Reactor PP)
Go out more than one.
In halogen-free fire resistance resin composite involved by present embodiment, in the limit playing effect of the present invention, also
Can be containing the component of polymer beyond said polyolefins system resin, but the content of said polyolefins system resin is preferably polymer
More than 90 mass % in composition, more than more preferably 95 mass %, more preferably 100 mass %.
1.3 fire retardant
In halogen-free fire resistance resin composite involved by embodiments of the present invention, with respect to said polyolefins system resin
100 mass parts, contain, with the ratio below more than 100 mass parts 250 mass parts, the hydroxide being surface-treated by silane
Aluminum is as fire retardant.This is because, if the content of the aluminium hydroxide being surface-treated by silane is less than 100 mass parts,
Even if then combine the anti-flammability required for also cannot presenting with flame retardant, and if it exceeds 250 mass parts, then under thermal impact
Fall.
With regard to the particle diameter of aluminium hydroxide, preferably mean diameter is adjusted to 0.5 μm～2 μm, dry type granularity at ambient pressure
In mensure, preferably more than 10 μm of corase particleses are suppressed below 1 mass %.
If specifically illustrating the silane for being surface-treated, vinyltrimethoxy silane, ethylene can be enumerated
Ethyl triethoxy silicane alkane, vinyl-dimethyl epoxide Ethoxysilane, vinyl-dimethyl epoxide butoxy silane, vinyl diethoxy
Base butoxy silane, vinyltriacetoxy silane, methacryloxypropyl trimethoxy silane, methacryloxypropyl
Base propyl-triethoxysilicane, methacryloyloxypropyl methyl dimethoxysilane, glycydoxy front three
The silane couplers such as TMOS.These silane couplers can be used alone it is also possible to and with two or more.
For the surface treatment amount being carried out by silane, in the x-ray fluorescence analysis of treated aluminium hydroxide, preferably
As Si quality control less than 0.05% more than 0.02%.
1.4 flame retardant
In halogen-free fire resistance resin composite involved by embodiments of the present invention, with respect to said polyolefins system resin
100 mass parts, are contained from melamine cyanurate, zinc and amorphous with the ratio below more than 5 mass parts 50 mass parts
More than one selected in matter silicon dioxide are as flame retardant.This is because, if the content of above-mentioned flame retardant is less than 5 matter
Amount part, then be unable to maintain that combustion slag, and anti-flammability is deteriorated, and if it exceeds 50 mass parts, then thermal impact, pliability and extrudability fall
Low.
And during with two or more above-mentioned flame retardant, following four kinds of combinations can be carried out：Melamine cyanurate
With zinc, melamine cyanurate and amorphous silica, zinc and amorphous silica, three kinds all；Special
Not preferred melamine cyanurate is combined with zinc.Melamine cyanurate and the match ratio (melamine of zinc
Amine cyanurate/zinc) it is preferably 2～6, more preferably 3～5.
(1) melamine cyanurate
For applicable melamine cyanurate, preferably mean diameter is adjusted to 1.5 μm～8 μm.More preferably adjust
For 2 μm～5 μm.This is because, if less than 1.5 μm, then it is easy to coagulation, if it exceeds 8 μm, then the meeting when being added in resin
Tensile strength is made to reduce.For suppression coagulation block purpose, with fatty acid etc., its own can be surface-treated it is also possible to
After supporting the inorganic matters such as silicon dioxide, it is surface-treated with organosilicon, silane coupler etc..
(2) zinc
Applicable zinc selects from three zinc tin oxide and hexahydro zinc tin oxide (zinc hydroxyl stannate).Preferably by average grain
Footpath is adjusted to 1 μm～8 μm.More preferably it is adjusted to 2 μm～5 μm.This is because, if less than 1 μm, then it is easy to coagulation, and if
More than 8 μm, then tensile strength can be made to reduce when being added in resin.For the purpose of suppression coagulation block, fatty acid can be used
It is surface-treated it is also possible to after supporting the inorganic matters such as silicon dioxide, be entered with organosilicon, silane coupler etc. Deng to its own
Row surface treatment.
(3) amorphous silica
For applicable amorphous silica, preferably mean diameter is adjusted to 50nm～400nm.More preferably it is adjusted to
100nm～250nm.This is because, if less than 50nm, then operability variation, and if it exceeds 400nm, then it is being added to tree
Tensile strength can be made when in fat to reduce.It is preferably shaped to spherical.Preferably BET specific surface area is adjusted to 15～28m2/g.
1.5 other additives
In halogen-free fire resistance resin composite involved by embodiments of the present invention, except above-mentioned fire retardant, fire-retardant
Outside auxiliary agent, as needed, antioxidant, processing aid, lubricant, softening agent, plasticizer, inorganic fill can also be added
The additives such as agent, compatibility agent, stabilizer, white carbon black, coloring agent.
1.6 characteristic
Halogen-free fire resistance resin composite involved by embodiments of the present invention, as required by wire coating material
The thermal impact of fundamental characteristics, extrudability, pliability, excellent in flame retardance.Especially with regard to anti-flammability, poly- with fire-retardant due to having
The anti-flammability of vinyl chloride (PVC) equal extent, therefore in the cable needing to carry out testing vertical flammability, can use the present invention's
Halogen-free fire resistance resin composite involved by embodiment is substituting following sheath material, i.e. have by flammable poly- second
Insulator that alkene (PE) or polypropylene (PP) are formed and there is the sheath material in the such structure of the sheath being formed by flame-proof PVC
Material.Halogen-free fire resistance resin composite involved by embodiments of the present invention, is difficult to burn when there is fire, the amount of being fuming
Few.Further, since not halogen-containing, therefore do not produce two in burningThe toxic gas such as English, halogen gas, therefore can burn
Burning is processed, and does not also produce toxic gas when there is fire.Further, since not containing phosphorus series compound, therefore excellent in terms of environment
Choosing, and due to there is no the dissolution of lead, therefore can be with landfill disposal.
1.7 purposes
Halogen-free fire resistance resin composite involved by embodiments of the present invention, due to having above-mentioned characteristic, thus
Can be used for various uses.For example, it is possible to as insulated electric conductor, electronic device wiring electric wire, electric wire for automobiles, machine electricity consumption
Line, power line, outdoor distribution insulated electric conductor, electric power cable, control cable, communication electric cable, cable for instrument,
The various electric wires such as signal cable, movement cable and cable for ship, the insulant of cable, sheath material, adhesive tape class and
Between Jie's thing using.In addition it is also possible to for case, plug and the electricity such as adhesive tape isoelectric line, the appurtenances of cable, conduit
Material product etc..In addition to this it is possible to for agriculture thin slice, water channel pipe, gas tube lining material, build built-in material,
Furniture material, toy material and flooring material etc..
2. insulated electric conductor
Fig. 1 is the sectional view of an embodiment of the insulated electric conductor showing the present invention.
Insulated electric conductor 10 involved by present embodiment shown in Fig. 1 has and is formed by versatile material (such as tin-coated copper etc.)
Conductor 1 and the periphery of conductor 1 formed insulating barrier 2.
Insulating barrier 2 is made up of involved above-mentioned halogen-free fire resistance resin composite in embodiments of the present invention.
In present embodiment, insulating barrier can be made up of monolayer it is also possible to be set to multiple structure.As being set to multiple structure
When concrete example, can enumerate by outermost layer extrusion be coated to above-mentioned halogen-free fire resistance resin composite, and outermost layer with
The polyolefin coated resin of outer extrusion, structure obtained from elastomeric material.As vistanex, it is possible to use such as hereinbefore institute
The vistanex stated.And then, as needed, spacing body, fabric etc. can also be applied.For insulating barrier, can be after shaping
Implement crosslinking Treatment.For cross-linking method, it is not particularly limited, it is possible to use known method is implementing.
3. cable
Fig. 2 is the sectional view of an embodiment of the cable showing the present invention.
Cable 20 involved by present embodiment shown in Fig. 2 have by 3 twin-cores twist thread the twisting thread of twisted,
Twist thread the strapping tape 3 around winding, the periphery of strapping tape 3 setting woven shield 4, woven shield 4 periphery setting
Sheath 5, wherein, insulated electric conductor 10 twisted that described twin-core is twisted thread involved by 2 basic embodiments forms.Insulated electric conductor can
To be single or multicore other than the above is twisted thread.
Sheath 5 is made up of above-mentioned halogen-free fire resistance resin composite.The wall thickness of sheath 5 can be set to such as 1mm thick with
Under.
In present embodiment, sheath can be made up of monolayer it is also possible to be set to multiple structure.During as being set to multiple structure
Concrete example, can be set forth in outermost layer extrusion be coated to above-mentioned halogen-free fire resistance resin composite, and beyond outermost layer extrude
Structure obtained from polyolefin coated resin.As vistanex, vistanex for example described above can be enumerated.
And then, as needed, spacing body etc. can also be applied.For sheath, crosslinking Treatment can be implemented after shaping.For crosslinking side
Method, is not particularly limited, it is possible to use known method is implementing.
It should be noted that, in present embodiment, show the example using the insulated electric conductor 10 involved by present embodiment,
But can also be using the insulated electric conductor employing versatile material.
Embodiment
Hereinafter, it is described in further detail using embodiment.It should be noted that the present invention is not subject to following examples
Any restriction.
Embodiment and comparative example
Cable shown in following making Fig. 2.
In 0.5mm2The tin plating soft copper of (7/0.32mm) is twisted thread the periphery of 1 (external diameter 0.96mm), thick poly- of coating 0.3mm
Ethylene, to arrange insulating barrier 2, obtains insulated electric conductor 10.2 insulated electric conductor 10 twisteds are obtained twin-core and twist thread, by 3 twin-cores
Twist thread twisted and twisted thread, apply the strapping tape 3 being formed by PET around this is twisted thread, arrange thereon by tin plating soft copper
The woven shield 4 that line is formed.In the periphery of woven shield 4, it is coated to the resin combination of the mixing ratio shown in table 1～2
Thing, to arrange the sheath 5 as 1mm for the jacket thickness, obtains the cable that the outside diameter of cable is 8.1mm.For mixing ratio shown in table 1～2
Resin combination, using following resin combination, i.e. after being weighed each composition with quantifier, with 3L kneader at 160 DEG C
Lower mixing, using mixing mill by its sheet, carries out pelletize by comminutor to obtained thin slice so as to tree after granulating
Oil/fat composition.The coating of sheath is carried out as follows：Using 90mm extruder, it is set to 160 DEG C of barrel zone temperature, 180 DEG C of head temperature, mould
185 DEG C of temperature of tool, is extruded with linear speed 30m/ minute using pipe extrusion molding.
By each test method shown below, obtained cable is evaluated, its evaluation result is shown in table 1～2.
Tensile strength：From the cable stripping sheath (sample) making, the method according to JISK7113 measures tensile strength.Tool
The tensile break strength of sample for body, is measured under the experimental condition of 20mm in draw speed 200m/ minute, distance between bench marks.
It is qualified that the sample for more than 10MPa for the tensile break strength is set to, and the sample less than 10MPa is set to unqualified.
Tensile elongation：From the cable stripping sheath (sample) making, the method according to JISK7113 measures tensile elongation
Rate.Specifically, the tension failure of sample is measured under the experimental condition of 20mm in draw speed 200m/ minute, distance between bench marks
Percentage elongation.It is qualified that the sample that tension fracture elongation rate is more than 150% is set to, and the sample less than 150% is set to unqualified.
Pliability：As flexual evaluation, it is suitable for 100% modulus value of the index as hardness.
From the cable stripping sheath (sample) making, the method according to JISK7113 measures tensile elongation.100% modulus
It is worth and be set to well for below 10MPa.Additionally, as reference test, can be free with 30cm by the cable making in the manner described above
Activity state be fixed, be set to can freely activity one end front end hang 100g counterweight, by bending when angle
Sample for more than 45 degree is set to well.
Thermal impact：Based on the table 50.133 of UL standard, UL1581, by the cable making in the manner described above in 2 times of footpaths
Mandrel on wind 6 whole circles, after applying the thermic load of 100 DEG C × 1 hour, the sample that jacket surface is not cracked is set to
Qualified, create crackle sample be set to unqualified.
Extrudability：Carried out with above-mentioned 90mm extruder sheathing operation when, can extrusion when allowable torque little
Operated in the case of 90%, and the sample being operated with 30m/ minute or faster linear speed is set to well.Can only
The sample operating in the case that allowable torque is more than 90%, is less than 30m/ minute is set to bad.
Anti-flammability：Based on UL standard, UL1581, VW-1 (vertical combustion is implemented for the cable making in the manner described above
Test, Vertical Wire Flame Test).The quantity implementing test is 10.It is set to good when 10 all qualified.10
As long as have in root 1 unqualified be just set to bad.
Table 1
Table 2
In embodiment 1～8, employ halogen-free fire resistance resin composite involved by embodiments of the present invention as shield
Cover material, as shown in table 1～8, the pliability of embodiment 1～8, thermal impact, extrudability, anti-flammability be every be obtained for good
Result.
In comparative example 1, employ magnesium hydroxide through silane treatment to substitute the aluminium hydroxide through silane treatment.Comparative example
1 percentage elongation not assuming regulation, pliability and thermal impact do not obtain good result.
Comparative example 2 is the system being set to less than 5 mass parts by flame retardant content, and comparative example 3 is by through silane treatment
Aluminium hydroxide content is set to, less than 100 mass parts, flame retardant content is set to the system more than 50 mass parts.Comparative example 2 He
Comparative example 3 does not all obtain required anti-flammability.
Comparative example 4 is the system more than 45 mass % for the average VA amount of EVA, and comparative example 5 is to be set to the average VA amount of EVA
System less than 37.5 mass %.Comparative example 4 due to the adhesion causing because of EVA, thus extrusion external diameter unstable it is impossible to required
The speed wanted carries out extrusion operation.The anti-flammability of comparative example 5 is bad.
Comparative example 6 is that the average MFR of EVA is set to less than 10, and EVA addition is set to the body less than 55 mass parts
System, comparative example 7 is the system being set to the average MFR of EVA more than 50.Comparative example 6, can only be with 3m/ because extruding the problem of moment of torsion
Minute is operated, and thermal impact is also unqualified.The tensile strength of comparative example 7 is unsatisfactory for setting, and creates and compare
The same adherent phenomenon of example 4, extrudability bad.
Comparative example 8 is the system being set to flame retardant content more than 50 mass parts.Its pliability, thermal impact and extrusion
Property does not all obtain good result.
Comparative example 9 is the system being set to the aluminium hydroxide content through silane treatment more than 250 mass parts.Tensile strength does not have
Have and meet setting, and do not assume the percentage elongation of regulation, pliability, thermal impact and extrudability all do not obtain good knot
Really.
Based on above-mentioned, the discovery such as the present inventor, a large amount of using the aluminium hydroxide (and using flame retardant) through silane treatment
System in, if the addition of the aluminium hydroxide through silane treatment and predetermined flame retardant is set in predetermined scope
Interior, and the average VA amount of two or more EVA, average MFR, addition are limited in predetermined scope, then can be filled
Point tensile strength, thermal impact, anti-flammability, and then assume pliability additionally it is possible to improve extrusion molding.
The elongation characteristics not presented when especially ironically, using magnesium hydroxide (comparative example 1) through silane treatment,
Presented when using aluminium hydroxide (embodiment 3) through silane treatment.In order to study its mechanism, by the cooperation of embodiment 3
The composition of ratio is kneaded with mixing mill, makes the thick thin slice of 1mm using press, it is implemented extend test.
SEM photograph before and after extension is as shown in Figure 3,4.The white particle seen from the teeth outwards is the hydrogen through silane treatment
Aluminium oxide particles.After extending 30% (Fig. 4) with extend before compared with (Fig. 3) although can see be scattered because fracture caused
Thick black micro hole, but aluminum hydroxide particles keep card shape and extend.It follows that the aluminium hydroxide in this composition
With respect to resin stream during extrusion, can not flowed with regular particle card shape on contrary ground.It is believed that regular grain
Sub-disk face dispersing morphology contributes to being uniformly directed of component of polymer, it is achieved thereby that elongation.
Claims (6)
1. a kind of halogen-free fire resistance resin composite, wherein, with respect to polyolefin-based resins 100 mass parts, containing 100 mass parts
The aluminium hydroxide being surface-treated by silane below above 250 mass parts, and containing more than 5 mass parts 50 mass parts with
Under select from melamine cyanurate, zinc and amorphous silica more than one, wherein, described polyolefin
It is the two or more vinyl-vinyl acetate copolymer that resin contains more than total 55 mass parts,
The average acetic acid ethylene ester content of described two above vinyl-vinyl acetate copolymers is more than 37.5 mass % 45
Below quality %, and average MFR is below 10g/10 minute above 50g/10 minute.
2. halogen-free fire resistance resin composite according to claim 1, wherein, described two above ethylene-acetate second
The vinyl acetate content of enoate copolymer is below more than 30 mass % 65 mass %.
3. halogen-free fire resistance resin composite according to claim 1 and 2, wherein, as described polyolefin-based resins, contains
Have from ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-ethylacrylate, maleic acid modified high-density polyethylene
Select in alkene, metallocene straight-chain Low Density Polyethylene and metallocene system polypropylene more than one.
4. a kind of insulated electric conductor, is characterised by, has the halogen-free flame-retardance resin group any one of claims 1 to 3
The insulating barrier that compound is formed.
5. a kind of cable, is characterised by, has the halogen-free fire resistance resin composite any one of claims 1 to 3
The sheath being formed.
6. cable according to claim 5, is characterised by, has the insulated electric conductor described in claim 4.
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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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111640535A (en) * | 2019-03-01 | 2020-09-08 | 日立金属株式会社 | Electric wire and cable |
| 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 |
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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 |
| 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 |
| 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 |
Citations (5)
| 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 |
| 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 |
Family Cites Families (2)
| 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 |
-
2015
- 2015-08-03 JP JP2015153442A patent/JP6657643B2/en active Active
-
2016
- 2016-07-27 CN CN201610602162.1A patent/CN106397947B/en active Active
Patent Citations (5)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 段予忠: "《塑料母料生产及应用技术》", 31 August 1999 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111640535A (en) * | 2019-03-01 | 2020-09-08 | 日立金属株式会社 | Electric wire and cable |
| 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 |
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| JP2017031337A (en) | 2017-02-09 |
| JP6657643B2 (en) | 2020-03-04 |
| CN106397947B (en) | 2021-04-09 |
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