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CN1969007A - Resin composition resistant to thermal deformation and cut-through and the insulation material and the cable using the same - Google Patents

Resin composition resistant to thermal deformation and cut-through and the insulation material and the cable using the same Download PDF

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Publication number
CN1969007A
CN1969007A CNA2004800433500A CN200480043350A CN1969007A CN 1969007 A CN1969007 A CN 1969007A CN A2004800433500 A CNA2004800433500 A CN A2004800433500A CN 200480043350 A CN200480043350 A CN 200480043350A CN 1969007 A CN1969007 A CN 1969007A
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resin combination
ethylene
crosslinking
resin
weight part
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CN1969007B (en
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朴度炫
南振镐
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LS Corp
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LG Cable Ltd
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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 atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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 atoms other than carbon or hydrogen
    • 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
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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 atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Inorganic Insulating Materials (AREA)
  • Insulated Conductors (AREA)

Abstract

The present invention provides a resin composition, which comprises: a base resin comprising ethylene copolymer and ethylene propylene rubber; 10-120 parts by weight, based on 100parts by weight of the base material, of a flame retardant; 5-50 parts by weight of an inorganic additive; and a given crosslinking coagent. The inventive resin composition contains the polymer resins with high crosslinking efficiency, such as low-crystalline ethylene copolymer and ethylene copolymer and ethylene propylene rubber, which may have high crosslinking density even upon exposure to a given amount of electron beam. Thus, after crosslinking, the resin composition shows little or no change in mechanical properties (e.g., reduction in elongation) and in thermal properties. Also, the present invention provides a resin composition having a suitable crosslinking structure to meet thermal deformation resistance at high temperature and cut-through resistance, which are very important in high-voltage cables, as well as an insulation material made of the composition and a cable including the insulation material.

Description

The resin combination of heat-resistant deforming and anti-cut-out and the insulating material and the cable that use it
Technical field
The present invention relates to a kind ofly have the resin combination of resistance to heat distorsion and anti-cuttability under the excellent high temperature and relate to the insulating material of making by said composition and comprise the cable of this insulating material.
Such as used herein, the implication of term " cut off (cut-through) " is, when insulating material with to have the insulating material that is used for cable when the sharp edge metallics contacts destroyed.Anti-cuttability for example method shown in Fig. 1 is measured.Such as used herein, the implication of term " anti-cuttability (cut-throughresistant) " is for suppressing or prevent to represent the performance of this destructive cut-out of insulating material.
Background technology
In the prior art,, often use and contain chlorine, halogen atom polar resin as the resin combination that is used for cable insulation material.This polar resin comprises chlorinatedpolyethylene, polyvinyl chloride etc.In addition, chlorinatedpolyethylene also is incorporated into the resin combination use of ethylene vinyl acetate with vinylchlorid.
In the prior art, in a kind of trial, suitably regulate the content of ethylene copolymer such as ethylene vinyl acetate or ethylene-ethyl acetate copolymer and itself and polyethylene are used in combination, improve physicals such as electric property, thermotolerance and resistance to heat distorsion thus.
Use aforesaid resin combination can guarantee especially flame retardant resistance required in cable insulation material to a certain extent.The flame retardant resistance that is used for the cable of equipment usually must be carried out level to final product and testing vertical flammability is estimated by employing UL (Underwriters Laboratory) standard.Be well known that, in when burning, halogen-containing resin produce incombustible heavy halogen gas and and additive reaction, form the solid ash content thus, suppress the burning of material thus.
The measurement of flame retardant resistance can be passed through horizontal firing, vertical combustion and the board-like testing method among the UL (Underwriters Laboratory), and oxygen index method and FMVSS[country MotorVehicleSafetyStandard (Federa] Motor Vehicle Safety Standards)] 302 methods carry out.
Because this halogen-containing resin combination has flame retardant resistance in essence, so they contain the organic or inorganic fire retardant that is used to improve flame retardant resistance on a small quantity.As a result, kept the essential performance of this resin combination, therefore the insulating material of being made by this resin combination shows excellent electricity and mechanical property.In addition, can not cause the viscosity of this insulating material to increase owing to added a spot of organic or inorganic fire retardant, so this insulating material also have the excellent processibility of extruding.
If only use various polar resins used in the prior art, will be difficult to satisfy the performance requriements of insulating material.But halogen-containing polar resin is each other on the physics and chemically all compatible.Therefore, had multiple trial, the opposed polarity resin that will have different performance uses together, develops excellent essential performance or synergistic insulating material with each resin thus.
In the prior art, halogen-containing polar resin such as chlorinatedpolyethylene, polyvinyl chloride and ethylene vinyl acetate-vinylchlorid are used as base resin.Insulating material of being made by this resin combination or the cable that applies with this insulation layer are undertaken crosslinkedly by electron beam, prevent that thus they at high temperature are subjected to specified load and the influence of being out of shape, and cut off preventing.
But, in process, be contained in as the halogen atom in the resin combination of base resin and be decomposed with this resin combination of electron beam crosslinking.The insulating material that is decomposed during the cross-linking process may show stable on heating obvious reduction, makes that resistance to heat distorsion and anti-cuttability can be unsatisfactory.
In order to satisfy the performance of thermal deformation resistant, resin combination must have high crosslink density, and for this purpose, resin combination must be exposed to excessive electron beam.If melt temperature is higher than crystalline resins to fixed temperature when being exposed to excessive electron beam, mechanical property such as elongation will reduce fast, and be exposed in the process of electron beam at resin,, make the resistance to heat distorsion of material significantly to reduce promoting the decomposition of fluoropolymer resin.Therefore, if when for a long time material being exposed to certain temperature, it will show low elongation.If consider the required comprehensive mechanical performance of insulating material, excessive organic or inorganic additive can not add in the crystalline resins.As a result, insulating material will show low flame retardant resistance, and initial product can not meet the desired flame retardant resistance.
Usually, contain the sufficient quantity ethylene copolymer and poly resin combination has high-melting-point.Crystalline polymer demonstrates the increase of molecular arrangement regularity along with the increase of degree of crystallinity, make them have higher fusing point with respect to the polymkeric substance of low-crystallinity.The concrete data of polymer crystallization degree and crystalline polymer fusing point aspect provide in following reference: (1) P.J.Flory, Principles of PolymerChemistry, 1953; (2) F W.Billmeye, Textbook of Polymer Science, the 4th edition; (3) J.F Sharckefold, Introduction to materials science and engineering, MacmillanPublishing Company, 1988; (4) J.D.Ferry, Viscoelastic Properties of Polymers; (5) P.C.Hiemenz, Polymer Chemistry-The Basic Concepts.
As mentioned above, this resin is extremely low by the efficient of electron beam crosslinking, and the evaluation of the resistance to heat distorsion of resin component (it is used for the electric wire of equipment) and anti-cuttability is to carry out under the high temperature of about 100 ℃ (the crystalline resins composition is near fusions this temperature).
In addition, because the decomposition of halogen atom in the resin combination, it is unstable that the flame retardant resistance of insulating material becomes, and have flame retardant resistance difference between the cable on insulating material and the finished product.The insulating material of being made by halogen-containing resin combination demonstrates the considerable change of performance according to crosslinked condition, it makes and is difficult to determine crosslinked condition.
Description of drawings
Fig. 1 is for measuring the synoptic diagram of the anti-cuttability of final cable product according to the present invention.
The disclosure of the Invention content
Therefore, the present invention is intended to solve the above-mentioned problems in the prior art, and the objective of the invention is, it provides a kind of resin combination that contains high crosslink density fluoropolymer resin such as low-crystalline ethylene multipolymer and ethylene propylene rubber, even can also have high crosslink density when being exposed to the electron beam of specified rate.Therefore, crosslinked after, this resin combination is showing very little or is not showing variation aspect mechanical property (for example elongation reduction) or the thermal characteristics.Another object of the present invention is, a kind of insulating material is provided, and it has the suitable crosslinking structure that satisfies resistance to heat distorsion and anti-cuttability under the high temperature, and it is extremely important in high-tension cable.
To achieve these goals, the invention provides a kind of resin combination, it comprises: the base resin that contains ethylene copolymer and ethylene propylene rubber; Based on 100 weight part base resins is the fire retardant of 10～120 weight parts; The inorganic additives of 5～50 weight parts; With given crosslinking coagent (giVencrosslinking coagent).
Low-crystalline ethylene multipolymer in the resin combination of the present invention is preferably and is selected from least a in ethylene vinyl acetate, ethylene ethyl acrylate, ethylene butyl acrylate, ethylene-butylene copolymer and the POE; And the content of ethylene copolymer is preferably 20～80 weight parts based on 100 weight part base resins.
In addition, the ethylene copolymer in the resin combination of the present invention preferably includes the modified ethylene copolymer that contains polar group.This modified ethylene copolymer is preferably and is selected from the ethylene vinyl acetate that contains maleic anhydride, contain the ethylene butyl acrylate of maleic anhydride and contain at least a in the ethene butyl multipolymer of maleic anhydride.And the content of modified ethylene copolymer is preferably 1～20 weight part based on 100 weight part base resins.
In addition, the ethylene propylene rubber in the resin combination of the present invention is preferably and is selected from least a in ethylene-propylene copolymer and the ethylene-propylene-diene terpolymer.
In addition, the fire retardant in the resin combination of the present invention preferably includes at least a organic fire-retardant that is selected from halogen such as bromine or chlorine, nitrogen and phosphorus, and wherein the consumption of organic fire-retardant is 5～60 weight parts based on 100 weight part base resins.In addition, this fire retardant preferably includes at least a inorganic combustion inhibitor that is selected from aluminium hydroxide, magnesium hydroxide, hydrocarbonate of magnesia calcium, boron and zinc, and wherein the consumption of inorganic combustion inhibitor is 5～60 weight parts based on 100 weight part base resins.
In addition, the inorganic additives in the present composition is preferably and is selected from talcum and clay and at least a with in the surface-treateds such as lipid acid or silane.
From preferred enforcement, will be expressly understood other purpose of the present invention, feature and advantage more according to the following detailed description that provides with accompanying drawing.
Hereinafter, describe formation of the present invention with reference to the accompanying drawings in detail.The invention provides a kind of that have a resistance to heat distorsion and anti-cuttability under the excellent high temperature and can come crosslinked resin combination by chemistry, water or radiation crosslinking, and insulating material of making by this resin combination and the cable that comprises this insulating material.In order to prepare the base resin of the present invention among this insulating material component, ethylene copolymer and ethylene-propylene copolymer have been used.
As ethylene copolymer, used to be selected from least a in ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), ethylene-butylene copolymer and the POE.
For mechanical property and the thermal characteristics of improving insulating material among the present invention, base resin can contain the modified ethylene copolymer of having introduced polar group.Be used for modified ethylene copolymer of the present invention and be being selected from least a of the ethylene vinyl acetate, ethylene butyl acrylate and the ethylene-butylene copolymer that contain maleic anhydride.
The fire retardant example that is used for insulating material flame retardant resistance of the present invention comprises organic fire-retardant and inorganic combustion inhibitor.Organic fire-retardant contains halogen such as bromine or chlorine or nitrogen or phosphorus.Can be used for inorganic combustion inhibitor example of the present invention and comprise aluminium hydroxide, magnesium hydroxide, hydrocarbonate of magnesia calcium, boron and zinc.This inorganic combustion inhibitor has carried out surface treatment with lipid acid, silane etc.
Insulating material of the present invention contains inorganic additives such as talcum or clay.This inorganic additives has carried out surface treatment with lipid acid, silane etc.Insulating material can be undertaken crosslinked by chemical process, water or radiation, satisfies thermal characteristics required in the cable and mechanical property thus.For chemically crosslinked, use organo-peroxide as linking agent, and use to be selected from least a in TriMethylolPropane(TMP), trimethacrylate, cyanacrylate and the organo-peroxide, increase cross-linking density thus as crosslinking coagent.For water crosslinking, add silane, tin or platinum.For radiation crosslinking, use to be selected from least a in TriMethylolPropane(TMP), trimethacrylate and the cyanacrylate as crosslinking coagent.
The invention provides a kind of insulating material that is used for the high-tension apparatus cable, it has resistance to heat distorsion and anti-cuttability under the excellent high temperature, and can be undertaken crosslinked by chemical process, water and radiation.
As the base resin among the insulating material component, ethylene copolymer and ethylene propylene rubber have been used.If necessary, can in this base resin, use modified ethylene copolymer in addition.
As ethylene propylene rubber, having used ethylene content is the ethylene-propylene copolymer or the ethylene-propylene-diene terpolymer of 40～85 weight parts.
Be used for ethylene copolymer example of the present invention and comprise ethylene vinyl acetate, ethylene ethyl acrylate, ethylene butyl acrylate, ethylene-butylene copolymer and POE.The consumption that ethylene copolymer and ethylene propylene rubber are used in combination is 20～80 weight parts based on 100 weight part base resins.The ethylene copolymer consumption will cause the reduction of tensile strength and thermal characteristics, consumption will cause the obvious reduction of resistance to heat distorsion under the high temperature greater than 80 weight parts less than 20 weight parts and can not satisfy anti-cuttability in the cable.
The example that is used for improving the modified ethylene copolymer of insulating material mechanical property of the present invention and thermal characteristics comprises ethylene vinyl acetate, ethylene butyl acrylate and the ethylene-butylene copolymer that contains maleic anhydride.The consumption of modified ethylene copolymer is preferably 1～20 weight part based on 100 weight part base resins.If the consumption of modified ethylene copolymer is less than 1 weight part, modified resin can not produce a desired effect on tensile strength and thermotolerance, if and consumption will cause the remarkable reduction of elongation and the increase of viscosity greater than 20 weight parts, the feasible thus processibility variation of extruding.
Among the present invention, for the flame retardant resistance of insulating material, used the organic fire-retardant that contains halogen such as bromine or chlorine, nitrogen or phosphorus, its consumption is 5～60 weight parts.If the consumption of organic fire-retardant is 5 weight parts, the insulating material flame retardant resistance can not produce a desired effect, and consumption will cause insulating material tensile strength, elongation and stable on heating reduction when being 60 weight parts.
Used inorganic combustion inhibitor in combination with organic fire-retardant, as aluminium hydroxide, magnesium hydroxide, hydrocarbonate of magnesia calcium, boron or zinc, its consumption is 10～60 weight parts.If the consumption of inorganic combustion inhibitor is less than 10 weight parts, insulating material can not ensure flame retardant resistance, and if the consumption of inorganic combustion inhibitor during greater than 60 weight parts, insulating material will show tensile strength, thermotolerance and extrude the remarkable reduction of processibility.
Resin combination of the present invention can be undertaken crosslinked by water, radiation or chemical process.For chemically crosslinked, use at least a chemically crosslinked auxiliary agent that is selected from organo-peroxide, TriMethylolPropane(TMP), trimethacrylate, cyanacrylate and polyhutadiene, its consumption is 1～15 weight part.The consumption of chemically crosslinked auxiliary agent is during less than 1 weight part, and insulating material will have low cross-linking density, and have low tensile strength and thermotolerance thus.Consumption is during greater than 15 weight parts, and this crosslinking coagent will cause the remarkable reduction of insulating material elongation.For radiation crosslinking, used at least a crosslinking coagent that is selected from TriMethylolPropane(TMP), trimethacrylate, cyanacrylate and polyhutadiene, its consumption is 1～5 weight part.Consumption is during less than 1 weight part, and the tensile strength of insulating material and thermotolerance can not be improved; And consumption is during greater than 5 weight parts, and the elongation of insulating material will reduce.For water crosslinking, used silane, tin or platinum as the water crosslinking auxiliary agent.In chemically crosslinked, used organo-peroxide as linking agent.
Except above-mentioned component, resin combination of the present invention can contain additive such as the oxidation inhibitor or the talcum of specified rate, and these additives are for being contained in those of the insulating material that is used for the high-tension apparatus cable usually.
Resin combination of the present invention can be by crosslinked resistance to heat distorsion and anti-cuttability with expectation.
The invention preferred forms
Embodiment
Hereinafter, will describe the flame retardant resistance insulating material of the present invention that is used for the high-tension apparatus cable in detail by the following example, this insulating material has resistance to heat distorsion and anti-cuttability under the excellent high temperature, and can be undertaken crosslinked by radiation, chemical mode or water.
In foundation embodiments of the invention 1～4, ethylene copolymer only contains ethylene vinyl acetate, and in embodiment 1～6, base resin is made up of ethylene propylene rubber and ethylene copolymer.As inorganic additives, used talcum; As organic fire-retardant, used bromine flame retardant.And,, used aluminium hydroxide and magnesium hydroxide as inorganic combustion inhibitor.In addition, as the radiation crosslinking auxiliary agent, used TriMethylolPropane(TMP); As the chemically crosslinked auxiliary agent, used organo-peroxide.
In addition, among the embodiment, used specified rate, be contained in the oxidation inhibitor and the talcum of the insulating material that is used for the high-tension apparatus cable usually.
Below table 1 shown component according to the resin combination of each embodiment.
(table 1)
Component (weight part) Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 5 Embodiment 6 Embodiment 7
Ethylene propylene rubber 50 50 30 30 60 40 40 30
Ethene Ethylene vinyl acetate 50 40 50 50
Multipolymer Ethylene ethyl acrylate 30
Ethylene-butylene copolymer 60 50
POE 60
The ethylene copolymer of modification The ethylene butene resin of modification 20 20 10 10
The ethylene vinyl acetate resin of modification 10 10
Oxidation inhibitor 2 2 2 2 2 2 2 2
Lubricant 6 6 3 3 6 6 3 3
Inorganic additives Talcum 20 20 30 30 20 20 30 20
Organic fire-retardant 30 30 40 40 40 40 30 30
Inorganic combustion inhibitor 40 40 20 20 40
20 20 40
The radiation crosslinking auxiliary agent 3 3 3 3 3 3 3 3
The chemically crosslinked auxiliary agent 4 4
In the comparative example 1～5 of foundation prior art, the all or part of base resin that is used for the insulating material of cable is by high density polyethylene(HDPE) or linear low density polyethylene (it has high-melting-point and high-crystallinity, and is hard) or ethylene vinyl acetate, polyvinyl chloride, polyvinyl chloride or chlorinatedpolyethylene.In view of flame retardant resistance, also used polyvinyl chloride, chloride ethylene vinyl acetate or chlorinatedpolyethylene as fire retardant material, to satisfy resistance to heat distorsion and the anti-cuttability under the high temperature.Among the comparative example 4 and 5, used polyvinyl chloride and chlorinatedpolyethylene that halogens is provided.
Below table 2 shown component according to each comparative example of prior art.
(table 2)
Component (weight part) The comparative example 1 The comparative example 2 The comparative example 3 The comparative example 4 The comparative example 5
High density polyethylene(HDPE) 80
Linear low density polyethylene 70 60
Ethylene vinyl acetate 20 30 40
Polyvinyl chloride 100
Chlorinatedpolyethylene 100
Stablizer 6 6
Softening agent 45 5
Oxidation inhibitor 1 1 1
Lubricant 1.5 1.5 1.5 1.0 2.0
Bromine flame retardant 40 40 40 1.5
Magnesium hydroxide 30 30 40 20 30
ANTIMONY TRIOXIDE SB 203 99.8 PCT 20 20
Lime carbonate 40 40
Cyanacrylate 3
Trimethylolpropane trimethacrylate 3 3 3 3
Organo-peroxide
It is as follows to satisfy between the embodiment of excellent properties and the comparative example performance result relatively.In an embodiment of the present invention, bromine flame retardant, aluminium hydroxide and talcum are joined in ethylene propylene rubber and the ethylene copolymer.As a result, the thermal distortion under the high temperature among the embodiment is starkly lower than the thermal distortion among the comparative example, and the anti-cuttability among all comparative examples is not satisfied, but the anti-cuttability among all embodiment is gratifying.
Below table 3 shown between embodiment and the comparative example performance relatively.
(table 3)
Embodiment The comparative example
1 2 3 4 5 6 7 8 1 2 3 4 5
Tensile strength (kgf/mm 2) 1.1 1.4 1.38 1.49 1.42 1.21 1.33 1.52 1.4 1.31 1.27 1.82 1.1
Elongation (%) 426 340 284 326 283 456 310 377 480 540 572 230 583
Thermal distortion (%) 56 47 43 41 47 52 51 45 80 84 86 100 100
Anti-cuttability S S S S S S S S U U U U U
S: gratifying
U: not satisfied
Tensile strength in the table 3 and elongation are measured according to ASTM (American Society for Testingand Materials) D 638.Thermal distortion is as the evaluation of getting off: under 105 ℃, blade shape (blade-shaped) anchor clamps are placed on the sample, and apply the load of 450g on anchor clamps.As shown in fig. 1, final cable product is estimated anti-cuttability.As shown in fig. 1, anti-cuttability is as the measurement of getting off: final cable product of the present invention is suspended on the metal axle that is supported by through metal, and by high-voltage connection high-voltage is applied on the cable product.
By embodiment and comparative example's mode the present invention has been described in further detail.But scope of the present invention is not to be defined in these embodiment, and any technician in this area is accessible is, under not deviating from as the scope of the invention disclosed in the accompanying claims and spirit, and various improvement, change and to substitute all be possible.
Industrial applicibility
Resin combination of the present invention comprises the combination as the ethylene copolymer and the ethylene propylene rubber of base resin, and the fire retardant of specified rate, inorganic additives and crosslinking coagent.Even resin combination of the present invention and when being exposed to the electron beam of specified rate, also can have high crosslink density by its insulating material of making.After crosslinked, this resin combination is showing very little or is not showing variation aspect mechanical property (for example elongation reduction) and the thermal characteristics.In addition, even when high pressure was applied to cable of the present invention, the cable that comprises the insulation layer of being made by resin combination of the present invention also can satisfy resistance to heat distorsion and anti-cuttability, and it is extremely important in high-tension cable.
Though disclose preferred implementation of the present invention, can carry out multiple other improvement and change under the scope of the invention and the spirit not deviating from.Therefore, these improvement and change will be as the scope of the invention disclosed in the accompanying claims within.

Claims (19)

1, the resin combination of heat-resistant deforming and anti-cut-out, it comprises:
The base resin that contains ethylene copolymer and ethylene propylene rubber;
Based on 100 weight part base mateirals is the fire retardant of 10～120 weight parts;
The inorganic additives of 5～50 weight parts; With
Crosslinking coagent.
2, the resin combination of claim 1, therein ethylene multipolymer are to be selected from least a in ethylene vinyl acetate, ethylene ethyl acrylate, ethylene butyl acrylate, ethylene-butylene copolymer and the POE.
3, the resin combination of claim 1, the consumption of therein ethylene multipolymer is 20～80 weight parts based on 100 weight part base resins.
4, the resin combination of claim 1, wherein base resin further comprises the modified ethylene copolymer that contains polar group.
5, the resin combination of claim 4, wherein modified ethylene copolymer is to be selected from the ethylene vinyl acetate that contains maleic anhydride, to contain the ethylene butyl acrylate of maleic anhydride and to contain at least a in the ethene butyl multipolymer of maleic anhydride.
6, the resin combination of claim 4, wherein the consumption of modified ethylene copolymer is 1～20 weight part based on 100 weight part base resins.
7, the resin combination of claim 1, therein ethylene acrylic rubber are to be selected from least a in ethylene-propylene copolymer and the ethylene-propylene-diene terpolymer.
8, the resin combination of claim 1, wherein fire retardant is an organic fire-retardant, its consumption is 5～60 weight parts based on 100 weight part base resins.
9, the resin combination of claim 8, wherein organic fire-retardant contains and is selected from least a in halogen such as bromine or chlorine, nitrogen and the phosphorus.
10, the resin combination of claim 1, wherein fire retardant is an inorganic combustion inhibitor, its consumption is 5～60 weight parts based on 100 weight part base resins.
11, the resin combination of claim 10, wherein inorganic combustion inhibitor is to be selected from least a in aluminium hydroxide, magnesium hydroxide, hydrocarbonate of magnesia calcium, boron and the zinc.
12, the resin combination of claim 1, wherein inorganic additives is to be selected from talcum and clay and at least a with in lipid acid or the silane surface-treated.
13, the resin combination of claim 1, wherein crosslinking coagent is at least a radiation crosslinking auxiliary agent that is selected from TriMethylolPropane(TMP), trimethacrylate, cyanacrylate and the polyhutadiene, and it is used for by this resin combination of radiation crosslinking.
14, the resin combination of claim 13, wherein the consumption of radiation crosslinking auxiliary agent is 1～5 weight part.
15, the resin combination of claim 1, wherein crosslinking coagent is at least a chemically crosslinked auxiliary agent that is selected from organo-peroxide, TriMethylolPropane(TMP), trimethacrylate, cyanacrylate and the polyhutadiene, and it is used for this resin combination of chemically crosslinked.
16, the resin combination of claim 15, wherein the consumption of chemically crosslinked auxiliary agent is 1～15 weight part.
17, the resin combination of claim 1, wherein crosslinking coagent is for being selected from the water crosslinking agent in silane, tin and the platinum at least, and it is used for this resin combination of water crosslinking.
18, the insulating material of making by the resin combination of claim 1～17 described in each.
19, cable, it comprises the insulating material of being made by the resin combination of claim 1～17 described in each.
CN2004800433500A 2004-06-15 2004-06-15 Resin composition resistant to thermal deformation and cut-through and the insulation material and the cable using the same Expired - Fee Related CN1969007B (en)

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