CN103842431B - Heat resisting flame retardant resin composition, insulated electric conductor and pipe - Google Patents
Heat resisting flame retardant resin composition, insulated electric conductor and pipe Download PDFInfo
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- CN103842431B CN103842431B CN201380003384.6A CN201380003384A CN103842431B CN 103842431 B CN103842431 B CN 103842431B CN 201380003384 A CN201380003384 A CN 201380003384A CN 103842431 B CN103842431 B CN 103842431B
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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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
- 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
- H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
- H01B3/445—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 vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08L23/10—Homopolymers or copolymers of propene
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Abstract
The invention provides a kind of heat resisting flame retardant resin composition, it is by inorganic filler and/or fire retardant are blended into the resin combination of also further making with this mixture of ionization radiation irradiation in the mixture of tetrafluoroethene-alpha olefin copolymer and random polypropylene, this heat resisting flame retardant resin composition is characterised in that, mixing ratio between described tetrafluoroethene-alpha olefin copolymer and described random polypropylene is 60:40 to 90:10(mass ratio), this heat resisting flame retardant resin composition is cheap and balancedly have an excellent insulating properties, heat resistance, flexible and anti-flammability and such as cut the general character can and crimping processability mechanical strength. the present invention also provides a kind of insulated electric conductor with the insulating sheath of being made up of described resin combination, and a kind of pipe of being made up of described heat resisting flame retardant resin composition.
Description
Technical field
The present invention relates to be configured for the heat resisting flame retardant resin composition of the wire covering materials under hot environment, the pipe that there is the insulated electric conductor of the insulating coating being formed by this heat resisting flame retardant resin composition and formed by this heat resisting flame retardant resin composition.
Background technology
Wire harness in distribution, automobile engine nacelle in the utensils such as gas-cooker etc. is exposed in hot environment. Therefore,, as the material of insulating coating of electric wire that is used to form this distribution and wire harness, resin combination not only needs to have high-insulativity, also needs to have high-fire resistance and high flame retardant. In addition, also need high flexible so that distribution. Especially in the case of the distribution in electrical equipment, need to have flexible. Insulating coating also needs to have high mechanical properties, for example, need to have the good so-called general character energy of cutting, and cutting the general character can be clad not impaired performance in the time contacting with blade. In addition,, in the time of insulated electric conductor end and crimp type terminal crimping, in order to prevent the problem such as insulation cracking, also expect to have in some cases good crimping processability. That is to say, for the material for insulating coating, need such resin combination: this resin combination such as high-fire resistance, high flexible, high flame retardant, high-insulativity and (for example) cut the general character can and crimping processability aspect the performance such as good mechanical strength be high balance, and its cost is low.
Known example for the wire insulation clad material under hot environment is fluorine class elastomer. Fluorine class elastomer is balancedly to have had heat resistance, mechanical strength, flexible etc. electrically insulating material concurrently. But their expensive and low cost performance has also caused people's worry conventionally.
In addition, fluorine class elastomer is not containing crystal composition. Therefore, compared with having the resin-coating electric wire of the insulating coating being made up of resins such as polyethylene, there is the problem of mechanical strength aspect in the fluorubber electric wire with the insulating coating being made up of fluorine class elastomer, particularly, has the problem that the general character can be low of cutting. In addition, fluorine class elastomer also has following problem: in the time that insulating coating forms by extrusion molding, extrude rear fluorine class elastomer and can not vulcanize immediately, therefore easily under the effect of load and be out of shape. Thereby in the time the fluorine class elastomer of extruding being rolled with spool, elastomer is easily deformable. Therefore,, in the production of fluorubber electric wire, need expensive rubber extruding special production line extrude continuously and vulcanize.
Another known example that is arranged in the electric wire under hot environment is the silicone rubber wire with the insulating coating being made up of silicon rubber. But organic siliconresin is containing crystal composition, and intermolecular force very a little less than. Therefore, compared with the resin-coating electric wire of the resin-coating such as polyethylene, the mechanical strength of silicon rubber is low, and particularly, it cuts the general character can be low. In addition, silicon rubber also has following problem: silicon rubber conventionally can not vulcanize immediately after extruding, and therefore easily under the effect of load, is out of shape. Thereby in the time the silicon rubber of extruding being rolled with spool, silicon rubber is easily out of shape. Therefore,, in the production of electric wire that comprises the insulating coating forming with silicon rubber, need expensive rubber extruding special production line extrude continuously and vulcanize.
Patent documentation 1 discloses a kind of fluoroelastomer composition, and it,, keeping the fluorine class intrinsic stable on heating while of elastomer, has higher mechanical strength and good cost performance. Particularly, this fluoroelastomer composition obtains by the following method: with respect to the tetrafluoroethene-alpha olefin copolymer of 100 weight portions, add the polyolefin composition that contains the unsaturated polar compound of olefinic of 10 weight portion to 70 weight portions. This polyolefin composition is by being obtained by mixing polyethylene and ethene-olefinic unsaturated polar monomer copolymer with the weight ratio of 20:80 to 98:2. Reference listing
Patent documentation
Patent documentation 1: the Patent Application Publication No.10-316821 of Japanese unexamined
Summary of the invention
Technical problem
But, in the fluoroelastomer composition of describing at patent documentation 1, the compatibility deficiency between tetrafluoroethene-alpha olefin copolymer and the polyolefin composition that contains the unsaturated polar compound of olefinic. Therefore, can be improved although cut the general character, this improvement is still not enough. Thereby people expect to obtain forming the resin combination with the higher insulating coating of cutting general character energy.
As mentioned above, existing insulating coating not yet for example, reaches sufficient equilibrium with resin combination between insulating properties, heat resistance, flexible, anti-flammability and () are cut the mechanical strength of logical aspect of performance, and also meets requirement in recent years. And, about mechanical strength, except hot strength and cutting general character energy, also expect to have good crimping processability.
The object of this invention is to provide there is the insulating properties, heat resistance of abundant equilibrium, flexible, anti-flammability and (for example) cut the general character can and the low cost resin combination of the mechanical strength of crimping processability aspect, comprise the insulated electric conductor of the insulating coating being formed by this resin combination, and the pipe being formed by this heat resisting flame retardant resin composition.
The scheme of dealing with problems
In order to realize above object, the present inventor conducts in-depth research, find following result: by containing tetrafluoroethene-alpha olefin copolymer, random polypropylene, inorganic filler (as calcium carbonate), and/or the resin combination of fire retardant (as bromide fire retardant or antimony oxide) is cross-linked, can make insulating properties, heat resistance, flexible, anti-flammability and (for example) are cut the mechanical strength high balance of general character energy and crimping processability aspect, can also realize low cost, wherein in this resin combination, the ratio of components of each component is in particular range. this discovery is accomplished the present invention.
Be a kind of heat resisting flame retardant resin composition according to the invention of claim 1, comprise: the mixture of tetrafluoroethene-alpha olefin copolymer and random polypropylene; And inorganic filler, with respect to the mixture of 100 mass parts, the amount of inorganic filler is 10 mass parts to 100 mass parts, tetrafluoroethene-alpha olefin copolymer and random polypropylene are cross-linked by the irradiation of ionising radiation, and wherein the mixing ratio of tetrafluoroethene-alpha olefin copolymer and random polypropylene is 60:40 to 90:10(mass ratio).
Tetrafluoroethene-alpha olefin copolymer is the fluorubber by tetrafluoroethene and alpha-olefin copolymer are obtained, and be to provide except thering is high-insulativity, also there is high mechanical properties, heat resistance and the flexible necessary component of resin combination.
The random polypropylene mixing in resin combination of the present invention is by making ethene and propylene carry out the copolymer that random copolymerization obtains. The random polypropylene of fusing point below 150 DEG C is preferred. By mixing random polypropylene with special ratios, can in the situation that not using rubber extruding special production line, carry out extrusion molding, and can obtain the high general character energy of cutting. Mixing of random polypropylene further brought the effect reducing production costs.
In the present invention, the mixing ratio of tetrafluoroethene-alpha olefin copolymer and random polypropylene is at 60:40 to 90:10(mass ratio) scope in. With respect to the total amount of tetrafluoroethene-alpha olefin copolymer and random polypropylene, when the mixing ratio of random polypropylene is during lower than 10 quality %, cannot obtain the high general character energy of cutting. When the mixing ratio of tetrafluoroethene-alpha olefin copolymer lower than 60 quality %(, in the time that the mixing ratio of random polypropylene exceedes 40 quality %) time, the mechanical strength of (for example) tensile property aspect reduces, especially, heat resistance reduces, and flexible also poor.
If replace random polypropylene with the homo-polypropylene homopolymers of propylene (its for) or block polypropylene (it is the block copolymer of ethene and propylene), only can obtain thering is low tensile property, low heat resistant and low cut the general character can resin combination, and cannot reach object of the present invention. In addition, flexible also poor. Its reason thinks as follows: it can be by the resin crosslinks comprising in this resin combination is realized that high tensile property, high-fire resistance and height are cut the general character. For the irradiation by ionising radiation makes resin crosslinks, this resin must be random polypropylene. On the contrary, the irradiation of ionising radiation can make homo-polypropylene and block polypropylene decompose.
Similarly, if replace random polypropylene with polyethylene, only can obtain having low cut the general character can resin combination.
Mixing according to the inorganic filler in the resin combination of the present invention of claim 1 is the inorganic particle mixing with the object of increment in order to strengthen. The example of inorganic filler comprises powdered whiting, precipitated calcium carbonate, magnesium silicate mineral matter, aluminium silicate mineral matter, zinc oxide, silica, carbon, metal hydroxides and any these materials is carried out to surface treatment and the product that obtains. These inorganic fillers can be used separately or two or more filler combination is used. Inorganic filler add heat resistance and the anti-flammability that can improve resin combination. Adding of inorganic filler also can be played the effect that reduces product price. , can make high-fire resistance, high flame retardant and low cost obtain high balance adding of inorganic filler.
In the present invention, with respect to the tetrafluoroethene-alpha olefin copolymer of 100 mass parts and the mixture of random polypropylene, the combined amount of inorganic filler is in the scope of 10 mass parts to 100 mass parts.
Even in the situation that not mixing inorganic filler, resin combination of the present invention also has " continue heat resisting temperature " (at this temperature 10, after 000 hour, can guarantee that insulator has the temperature of 100% percentage elongation) be 200 DEG C of above heat resistances, this lasting heat resisting temperature (JASO) has regulation in the D609:2001 of standard and D611:2009 at Japan Automobile Standard organization (JapanAutomobileStandardOrganization). When the combined amount of inorganic filler is 10 mass parts when above, can obtain higher heat resistance. And, also improve anti-flammability by mixing inorganic filler. Even in the situation that not mixing fire retardant (as bromide fire retardant or antimony oxide), also can obtain the anti-flammability that meets the common required standard of insulated electric conductor. In the time that the amount of inorganic filler exceedes 100 mass parts, tensile property reduces and is flexiblely also tending towards deteriorated.
Be a kind of heat resisting flame retardant resin composition according to the present invention of claim 2, comprise: the mixture of tetrafluoroethene-alpha olefin copolymer and random polypropylene; Inorganic filler, with respect to the mixture of 100 mass parts, the amount of inorganic filler is less than 10 mass parts; And fire retardant, with respect to the mixture of 100 mass parts, the amount of fire retardant is 3 mass parts to 20 mass parts, tetrafluoroethene-alpha olefin copolymer and random polypropylene are cross-linked by the irradiation of ionising radiation, and wherein the mixing ratio of tetrafluoroethene-alpha olefin copolymer and random polypropylene is 60:40 to 90:10(mass ratio).
Tetrafluoroethene-alpha olefin copolymer, random polypropylene and the inorganic filler comprising in resin combination of the present invention with according in the invention of claim 1, use those are identical. Tetrafluoroethene-alpha olefin copolymer is also identical with the mixing ratio scope according to the invention of claim 1 with the mixing ratio scope of random polypropylene. But in this invention, the combined amount of inorganic filler is lower than 10 mass parts, and mixed the fire retardant of 3 mass parts to 20 mass parts.
When the combined amount of inorganic filler is during lower than 10 mass parts, can keep good crimping processability, and can prevent that following problem from occurring: insulation cracking for example occurs in the time of wire terminations and terminal compression joint. Inorganic filler must not be mixed.
In addition,, by mixing fire retardants more than 3 mass parts, even very little or do not mix inorganic filler in the combined amount of inorganic filler, also can obtain the anti-flammability that meets the common required standard of insulated electric conductor. The fire retardant mixing more than 20 mass parts is not preferred, because mechanical strength and flexible can decline. The example of fire retardant used herein comprises: produce the fire retardant of nonflammable gas, as halide-containing; The fire retardant of endothermic decomposition, as metal hydroxides; And can form the fire retardant of the combustion residue of starvation, as phosphate. Its object lesson comprises bromide fire retardant, antimony oxide, chlorine-based flame retardant, magnesium hydroxide, aluminium hydroxide, phosphate, APP, polyphosphoric acid piperazine, red phosphorus, metal phosphinates and melamine cyanurate.
Obtain by the following method according to the resin combination of claim 1 or 2: mix above component by conventional method, carry out subsequently the irradiation of ionising radiation (as electron beam or gamma ray) so that tetrafluoroethene-alpha olefin copolymer and random polypropylene are crosslinked. In the case of resin combination of the present invention being applied to the insulating coating of insulated electric conductor, from the angle of the easy degree of production process, preferably and conventionally adopt following methods: by the resin combination coating conductor such as extrusion molding, then by this resin combination of ionization radiation irradiation.
By using ionization radiation irradiation resin combination, improve tensile property, heat resistance and cut general character energy. Ionising radiation is particularly preferably electron beam, and it is industrially being widely used, is easily controlling and by utilizing electron beam to be cross-linked with low cost. In electron beam irradiation, can use the known electron beam irradiation method that is generally used for (for example) resin crosslinks. Electron beam irradiation can be undertaken by conventional method.
Select the dosage of ionising radiation so that resin crosslinks, and obtain tensile property, the heat resistance of expecting and cut general character energy. The in the situation that of electron beam irradiation, the dosage of preferred about 30kGy to 500kGy conventionally.
Be according to the heat resisting flame retardant resin composition of claim 1 or 2 according to the invention of claim 3, wherein tetrafluoroethene-alpha olefin copolymer is tetrafluoroethylene propylene copolymer. The object lesson of tetrafluoroethene-alpha olefin copolymer is the copolymer of tetrafluoroethene and propylene.
Be according to the heat resisting flame retardant resin composition of any one in claims 1 to 3 according to the invention of claim 4, wherein inorganic filler is calcium carbonate. From the angle of heat resistance, mechanical performance and cost, this inorganic filler is preferably calcium carbonate. The example of calcium carbonate comprises: powdered whiting, it will be by containing CaCO3As natural material (as the lime stone) mechanical crushing of main component, then the powder classification of pulverizing is manufactured; And the precipitated calcium carbonate of producing by chemical method (precipitated calcium carbonate). From the angle of cost, preferably powdered whiting.
Be a kind of insulated electric conductor according to the invention of claim 5, comprise: conductor; And be arranged on conductor and by the clad forming according to the heat resisting flame retardant resin composition of any one in claim 1 to 4. Particularly, are a kind of electric wires that comprise insulating coating according to the invention of claim 5, the heat resisting flame retardant resin composition of this insulating coating the application of the invention and forming. Therefore, this electric wire have high-fire resistance, high flame retardant, high flexible and (for example) height cut the general character can and the high mechanical properties of high-voltage connecting processability aspect, and be suitable for (for example) electric wire and expose in environment at high temperature. It should be noted that; term " insulated electric conductor " not only refers to sense stricto insulated electric conductor (comprising the insulated electric conductor of conductor and insulating coating); and referring to so-called cable, it is by obtaining with the further coated one or more sense stricto insulated electric conductor of protection package coating.
This insulated electric conductor can make by the following method: with resin combination coating conductor of the present invention with form insulating coating, thereby then make this resin crosslinks with this insulating coating of ionization radiation irradiation. Can be coated by producing method used in existing insulated electric conductor, for example, be undertaken by method resin combination being extruded on conductor. As for conductor, for example can use up to now, as included conductor, copper cash in the insulated electric conductor of electric appliance wiring or automobile distribution or insulated cable.
Except insulated electric conductor, the present invention also provides the pitch tube of making by resin combination being configured as to pipe. Particularly, be a kind of heat-shrinkable tube according to the invention of claim 6, it is by making be configured as pipe according to the heat resisting flame retardant resin composition of any one in claim 1 to 4. The example of pitch tube of the present invention is heat-shrinkable tube, and in the time heating at the fusing point of this resin combination or higher temperature, this heat-shrinkable tube shrinks on internal diameter direction. Beneficial effect of the present invention
Resin combination of the present invention there is the insulating properties, heat resistance of high balance, flexible, anti-flammability and for example, at () tensile property, cut the mechanical strength aspect general character energy and crimping processability, and with regard to cost performance better. Particularly, good according to the heat resistance of the resin combination of claim 1, and good according to the crimping processability of the resin combination of claim 2. Therefore, the insulated electric conductor of the present invention that comprises the insulating coating being made up of this resin combination is better with regard to above performance, and be suitable as the electric wire using under hot environment, for example, the distribution in distribution or automobile engine nacelle in the utensils such as gas-cooker.
Brief Description Of Drawings
[Fig. 1] Fig. 1 is the schematic sectional view that schematically shows the measurement mechanism of cutting general character energy.
Detailed description of the invention
Now will describe and implement embodiment of the present invention. But scope of the present invention is not limited to these embodiments, can under the prerequisite of not damaging the object of the invention, carry out various amendments.
Tetrafluoroethene-alpha olefin copolymer is the copolymer of the alpha-olefin such as tetrafluoroethene and polypropylene. Can with other comonomer copolymerization, as acrylate, hexafluoropropene, PVF, vinylidene fluoride, perfluoroalkyl vinyl ether, CTFE, ethene, 1-butylene and (methyl) glycidyl acrylate, only otherwise damage object of the present invention.
Manufacturing the copolyreaction of this copolymer can be undertaken by known method. But the tetrafluoroethene-alpha olefin copolymer with various copolymerization ratios and molecular weight is commercially available, therefore can use the commercially available copolymer of this class.
Copolymerization ratio scope and the molecular weight ranges of Paratetrafluoroethylene-alpha olefin copolymer are not particularly limited. But copolymerization ratio is conventionally preferably at tetrafluoroethene: in the scope of alpha-olefin=30:70 to 70:30, in the scope particularly preferably in 40:60 to 60:40. In the time that the ratio of tetrafluoroethene is less than 30%, heat resistance reduces. In the time that the ratio of tetrafluoroethene exceedes 70%, flexible variation. The mooney viscosity (ML1+10:121 DEG C) of tetrafluoroethene-alpha olefin copolymer is preferably in 30 to 300 scopes, in 50 to 200 scopes. When Mooney viscosity is lower than 30 time, cut the general character and can reduce. In the time that Mooney viscosity is greater than 300, the appearance degradation after extruding.
Random polypropylene is by making propylene and ethene carry out the polymer that random copolymerization obtains. Conventionally, the content of ethene is preferably below above 10 % by weight of 1 % by weight. When the content of ethene is during lower than 1 % by weight, crystallinity increases, even and when the random polypropylene obtaining with electron beam irradiation, be also not easy to occur to be cross-linked. In the time that the content of ethene exceedes 10 % by weight, the cutting the general character and can reduce of the resin combination obtaining. Or, can use by further carrying out with 1-butylene except ethene etc. the terpolymer (trimer) that copolymerization obtains. Conventionally, the melt flow rate (MFR) of random polypropylene (MFR) is preferably in 0.1 to 5 scope, and MFR measures at the temperature of the load of 2.16kg and 190 DEG C. In the time that MFR is less than 0.1, the appearance degradation after extruding. In the time that MFR is greater than 5, cuts the general character and can reduce.
Except above-mentioned necessary component, not damaging under the prerequisite of object of the present invention, can contain additive according to the resin combination of claim 1, the halogen-free flame retardants such as such as magnesium hydroxide, aluminium hydroxide, calcium hydroxide and phosphorus flame retardant; Bromide fire retardant; Chlorine-based flame retardant; Antimony oxide; Phenol is that antioxidant, amine are that antioxidant, sulphur are the antioxidant such as antioxidant and phosphorous antioxidant; The lubricants such as stearic acid, fatty acid amide, organosilicon and Tissuemat E; And color pigment. Except above-mentioned necessary component, do not damaging under the prerequisite of object of the present invention, can contain additive according to the resin combination of claim 2, such as phenol is that antioxidant, amine are that antioxidant, sulphur are the antioxidant such as antioxidant and phosphorous antioxidant; The lubricants such as stearic acid, fatty acid amide, organosilicon and Tissuemat E; And color pigment. These additives can add separately or two or more compound combination adds.
Example
Material for embodiment and comparative example is as described below.
Tetrafluoroethylene propylene copolymer: AFLAS150C(AsahiGlass Co., Ltd. produces)
Random polypropylene (132 DEG C of fusing points): NOBLENS131(SumitomoChemical Co., Ltd. produces)
Random polypropylene (145 DEG C of fusing points): NOVATECPPEG6D(JapanPolypropylene Co., Ltd. produces)
Block polypropylene: 160 DEG C of JapanPolypropyleneNOVATECPPEC7(fusing points) (production of JapanPolypropylene Co., Ltd.)
Polyethylene: UE320(JapanPolyethylene Co., Ltd. produces)
Calcium carbonate: Softon2200(ShiraishiCalciumKaisha Co., Ltd. produces, powdered whiting)
Bromide fire retardant: SAYTEXBT-93(Albemarle company produces, the two tetrabromo phthalimides of ethylene)
Antimony oxide: AntimonytrioxideMSA(Yamanaka&Co., Ltd. produces, average grain diameter: 1 μ m)
Embodiment 1 to 4 and comparative example 1 to 7
Mediate the component that in Table I or II, (representing by mass parts in table) illustrates with mill, and the mixture after this kneading is made granular with comminutor. Subsequently the particle of gained is supplied to coating electric wire extruder, is then extruded on the conductor of TA12/0.18 by this extruder. Thus, to be wrapped by make it outer insulation diameter be 1.5mm φ (coating thickness: 0.375mm) to this conductor. Then use the coating conductor of the electron beam irradiation gained of electron beam illuminating device 100kGy. Thereby make the insulated electric conductor with the insulating coating being formed by crosslinked resin composition. The tensile property (hot strength and tensile elongation) of the insulated electric conductor of the method by the following stated to manufacture described above, heat resistance, flexible, anti-flammability, insulating properties and cut the general character and can evaluate. Its result is shown in Table I and II.
[tensile property (hot strength and tensile elongation)]
Measure hot strength and tensile elongation according to JISC3005 (1986). (standard: hot strength >=8MPa, tensile elongation >=100%)
[heat resistance]
Insulated electric conductor is left standstill to 4 days in the thermostatic chamber that remains 250 DEG C, then from this thermostatic chamber, take out. Measure hot strength and the tensile elongation of this insulated electric conductor according to JISC3005 (1986). By measured value tensile strength calculated conservation rate and tensile elongation conservation rate respectively. (standard: stretching strength retentivity >=85%, tensile elongation conservation rate >=85%)
[flexible]
Measure secant modulus to evaluate the flexible of insulated electric conductor according to JISK7127. (standard: secant modulus≤80MPa)
[anti-flammability]
Evaluate anti-flammability according to UL15811080 by vertical sample combustion test (ULVW-1 combustion test). Particularly, test is carried out as follows: make insulated electric conductor keep vertical. With 20 ° of angles, the flame of burner is applied on insulated electric conductor, then light 15 seconds, stop 15 seconds, repeat 5 times. After this,, in the time that burning (burning causing due to residual flame) continues below 60 seconds, this insulated electric conductor is evaluated as to " qualified ". In the time that burning (burning causing due to residual flame) continues to exceed 60 seconds, this insulated electric conductor is evaluated as to " defective ".
[insulating properties]
By specific insulation measurement mechanism measurement volumes resistivity (Ω cm). (standard: >=1015) [cutting general character energy]
Cut general character energy with the measurement mechanism measurement shown in Fig. 1. In Fig. 1, label 1 represents conductor, and label 2 represents insulating coating, and label 3 represents insulated electric conductor. To there is the blade of the blade 4(5 mil thick of 90 ° of sharp edges (edge R=0.125mm, 90 ° of edge angles)) be applied on insulated electric conductor 3, then measure the electric current flowing through between conductor 1 and sharp edge. Under original state, conductor 1 and sharp edge are due to insulating coating 2 therebetween and insulated from each other, thereby electric current cannot flow through. In the time that insulating coating 2 is cut off by blade 4, electric current flows through between conductor 1 and sharp edge. Blade 4 applies load, and measures the maximum load that insulating coating 2 bears in not cut situation. In test environment, temperature is 23 DEG C, and humidity is 50%RH. Be standard (qualified level) by load definition more than 150N.
[Table I]
The ratio of each component is represented by mass parts.
[Table II]
The ratio of each composition is represented by mass parts.
Result shown in Table I and II shows, the resin combination of embodiment 1 to 4 (it meets according to the constitutive characteristic of the invention of claim 1) meet tensile property, heat resistance, flexible, anti-flammability, insulating properties and cut the general character can standard, and these performances are high balances. In contrast, in comparative example (its do not meet according to the constitutive characteristic of the invention of claim 1), following 1) to 4) described in, tensile property, heat resistance, flexible, anti-flammability and cut the general character and can all not meet standard, do not reach object of the present invention.
1) when the total amount with respect to tetrafluoroethene-alpha olefin copolymer and random polypropylene, the mixed proportion of random polypropylene is during lower than 10 quality % (comparative example 3 and 4), and cutting the general character can be low.
2) when the mixed proportion of tetrafluoroethene-alpha olefin copolymer is during lower than 60 quality % (comparative example 1), heat resistance is low and flexible also poor.
3) when with homo-polypropylene (its homopolymers that be propylene) or block polypropylene (it is the block copolymer of ethene and propylene) replacement random polypropylene (comparative example 6), tensile property, heat resistance, flexible and cut logical poor performance. Similarly, in the time replacing random polypropylene with polyethylene (comparative example 7), cut logical poor performance.
4) when the combined amount of inorganic filler (powdered whiting) is during lower than 10 mass parts (comparative example 2), heat resistance and anti-flammability are low. Cutting the general character can be also low. On the other hand, in the time that the amount of inorganic filler (powdered whiting) exceedes 100 mass parts (comparative example 5), tensile property (tensile elongation) is low and flexible poor.
Embodiment 5 to 8
Mediate the component that (representing by mass parts in table) illustrates in Table III with mill, and the mixture after this kneading is made granular with comminutor. Subsequently the particle of gained is supplied to coating electric wire extruder, is then extruded on the conductor of TA12/0.18 by this extruder. Thus, to be wrapped by make it outer insulation diameter be 1.5mm φ (coating thickness: 0.375mm) to this conductor. Then use the coating conductor of the electron beam irradiation gained of electron beam illuminating device 100kGy. Thereby make the insulated electric conductor with the insulating coating being formed by crosslinked resin composition. Tensile property (hot strength and tensile elongation) by the insulated electric conductor to manufacture described above with method identical in embodiment 1 to 4, flexible, anti-flammability, insulating properties and cut the general character and can evaluate. In addition, measure and continue heat resisting temperature (heat resistance) and crimping processability by method as described below. Its result is shown in Table III.
[continuing heat resisting temperature (heat resistance)]
Lasting heat resisting temperature based on regulation in car gage (JASO) is evaluated heat resistance. Particularly, at 230 DEG C, 250 DEG C, 270 DEG C and 290 DEG C, carry out respectively degradation. Determine until the time of tensile elongation lower than 100% time, and determine and continue heat resisting temperature with Arrhenius figure (Arrheniusplot).
[crimping processability]
Manufacture electric wire for test, this test has been used crimp type terminal (model: SNAC3-A021T-M064) and the compression bonding apparatus (model: AP-K2N) manufactured by JapanSolderlessTerminalMfg. Co., Ltd.. Wire terminations is carried out to crimping, and whether have the cracking of insulating barrier with microscopic examination. While observing cracking, this electric wire is evaluated as to " defective ". While not observing cracking, this electric wire is evaluated as to " qualified ".
[Table III]
Each component represents by mass parts.
With reference to the result shown in Table III, the resin combination of embodiment 5 and 6 (it meets according to the constitutive characteristic of the invention of claim 2, and containing powdered whiting or the powdered whiting that contains 5 mass parts) meets tensile property, continues heat resisting temperature (heat resistance), flexible, anti-flammability, insulating properties and cut the general character can standard. In addition, the crimping processability of the resin combination of embodiment 5 and 6 is also qualified. This result shows that these performances are high balances. Powdered whiting on the other side, embodiment 7 and 8(contain 10 mass parts) do not meet the standard of crimping processability.
List of numerals
1. conductor
2. insulating coating
3. insulated electric conductor
4. blade (thering is sharp edge)
Claims (6)
1. a heat resisting flame retardant resin composition, comprises: tetrafluoroethene-alpha olefin copolymer andThe mixture of random polypropylene; And inorganic filler, with respect to the described mixing of 100 mass partsThing, the amount of described inorganic filler is 10 mass parts to 100 mass parts, described tetrafluoroethene-α-Olefin copolymer and described random polypropylene are cross-linked by the irradiation of ionising radiation, wherein saidThe mixing ratio of tetrafluoroethene-alpha olefin copolymer and described random polypropylene is in mass60:40 to 90:10,
The copolymerization ratio of wherein said tetrafluoroethene-alpha olefin copolymer is at tetrafluoroethene: alpha-olefinIn the scope of=30:70 to 70:30, the ethylene contents of described random polypropylene be 1 % by weight withBelow upper 10 % by weight, the melt flow rate (MFR) of described random polypropylene is at 0.1 to 5 modelIn enclosing, wherein melt flow rate (MFR) is measured at the temperature of the load of 2.16kg and 190 DEG C,And the mooney viscosity of described tetrafluoroethene-alpha olefin copolymer is in 30 to 300 scopes, itsMiddle mooney viscosity is measured under the condition of ML1+10:121 DEG C.
2. a heat resisting flame retardant resin composition, comprises: tetrafluoroethene-alpha olefin copolymer andThe mixture of random polypropylene; Inorganic filler, with respect to the described mixture of 100 mass parts,The amount of described inorganic filler is less than 10 mass parts; And fire retardant, with respect to 100 mass partsDescribed mixture, the amount of described fire retardant is 3 mass parts to 20 mass parts, described tetrafluoroEthene-alpha-olefin copolymer and described random polypropylene are cross-linked by the irradiation of ionising radiation,The mixing ratio of wherein said tetrafluoroethene-alpha olefin copolymer and described random polypropylene is with qualityCount 60:40 to 90:10,
The copolymerization ratio of wherein said tetrafluoroethene-alpha olefin copolymer is at tetrafluoroethene: alpha-olefinIn the scope of=30:70 to 70:30, the ethylene contents of described random polypropylene be 1 % by weight withBelow upper 10 % by weight, the melt flow rate (MFR) of described random polypropylene is at 0.1 to 5 modelIn enclosing, wherein melt flow rate (MFR) is measured at the temperature of the load of 2.16kg and 190 DEG C,And the mooney viscosity of described tetrafluoroethene-alpha olefin copolymer is in 30 to 300 scopes, itsMiddle mooney viscosity is measured under the condition of ML1+10:121 DEG C.
3. heat resisting flame retardant resin composition according to claim 1 and 2, wherein saidTetrafluoroethene-alpha olefin copolymer is tetrafluoroethylene propylene copolymer.
4. heat resisting flame retardant resin composition according to claim 1 and 2, wherein saidInorganic filler is calcium carbonate.
5. an insulated electric conductor, comprising: conductor; And be arranged on this conductor and by rootWhat form according to the heat resisting flame retardant resin composition described in any one in claim 1 to 4 is coatedLayer.
6. a heat-shrinkable tube, it is by will be according to any one in claim 1 to 4Described heat resisting flame retardant resin composition is configured as pipe and makes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-153868 | 2012-07-09 | ||
| JP2012153868 | 2012-07-09 | ||
| PCT/JP2013/068390 WO2014010508A1 (en) | 2012-07-09 | 2013-07-04 | Heat-resistant flame-retardant resin composition, insulated electric wire, and tube |
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| Publication Number | Publication Date |
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| CN103842431A CN103842431A (en) | 2014-06-04 |
| CN103842431B true CN103842431B (en) | 2016-05-04 |
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| CN201380003384.6A Expired - Fee Related CN103842431B (en) | 2012-07-09 | 2013-07-04 | Heat resisting flame retardant resin composition, insulated electric conductor and pipe |
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| Country | Link |
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| JP (1) | JP5648985B2 (en) |
| CN (1) | CN103842431B (en) |
| WO (1) | WO2014010508A1 (en) |
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| JP6361144B2 (en) * | 2014-01-20 | 2018-07-25 | 住友電気工業株式会社 | Insulated wire and manufacturing method thereof |
| JP6810888B2 (en) * | 2016-11-18 | 2021-01-13 | 日立金属株式会社 | Manufacturing method of fluorine-containing elastomer coated insulated wire |
| CN109867890B (en) * | 2017-12-05 | 2022-01-07 | 日立金属株式会社 | Insulated wire |
| JP6575777B2 (en) * | 2018-02-14 | 2019-09-18 | 日立金属株式会社 | Electrical wire |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102347102A (en) * | 2010-05-31 | 2012-02-08 | 日立电线株式会社 | Fluorine-containing elastomer covered electric wire, and method for making same |
| CN102568662A (en) * | 2010-11-29 | 2012-07-11 | 住友电气工业株式会社 | Insulated electric wire and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2852524B2 (en) * | 1989-03-18 | 1999-02-03 | 株式会社クラベ | Fluorine-containing elastomer composition |
| JPH07179705A (en) * | 1993-12-22 | 1995-07-18 | Asahi Glass Co Ltd | Method for crosslinking fluororubber composition and its crosslinked molded product |
| JPH09288915A (en) * | 1996-04-24 | 1997-11-04 | Hitachi Cable Ltd | Fluorine-containing-elastomer-covered wire or cable |
| JP3812064B2 (en) * | 1997-05-20 | 2006-08-23 | 株式会社クラベ | Fluorine-containing elastomer composition |
| JP2000030543A (en) * | 1998-07-10 | 2000-01-28 | Hitachi Cable Ltd | Wire and cable covered with fluorine containing elastomer |
| JP2005239976A (en) * | 2004-02-27 | 2005-09-08 | Fujikura Ltd | Abrasion resistant, flame retardant resin composition, and insulated electric supply cable |
| JP2007119515A (en) * | 2005-10-25 | 2007-05-17 | Swcc Showa Cable Systems Co Ltd | Electrical insulating composition and insulated wire |
| JP5563771B2 (en) * | 2009-02-10 | 2014-07-30 | 日立金属株式会社 | Fluorine-containing elastomer covered wire |
-
2013
- 2013-07-04 CN CN201380003384.6A patent/CN103842431B/en not_active Expired - Fee Related
- 2013-07-04 WO PCT/JP2013/068390 patent/WO2014010508A1/en active Application Filing
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102347102A (en) * | 2010-05-31 | 2012-02-08 | 日立电线株式会社 | Fluorine-containing elastomer covered electric wire, and method for making same |
| CN102568662A (en) * | 2010-11-29 | 2012-07-11 | 住友电气工业株式会社 | Insulated electric wire and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103842431A (en) | 2014-06-04 |
| JPWO2014010508A1 (en) | 2016-06-23 |
| JP5648985B2 (en) | 2015-01-07 |
| WO2014010508A1 (en) | 2014-01-16 |
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