CN106189015A - Semi-conducting resin composition and power transmission cable - Google Patents
Semi-conducting resin composition and power transmission cable Download PDFInfo
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- CN106189015A CN106189015A CN201510358928.1A CN201510358928A CN106189015A CN 106189015 A CN106189015 A CN 106189015A CN 201510358928 A CN201510358928 A CN 201510358928A CN 106189015 A CN106189015 A CN 106189015A
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Abstract
The present invention provides semi-conducting resin composition and power transmission cable.Offer can be formed can be easily from semi-conducting resin composition and the power transmission cable of the external semi-conductive layer of insulation displacement.Described semi-conducting resin composition contains thermoplastic resin, conductivity-imparting agent and viscosity modifier, and the solubility parameter SP value of thermoplastic resin is 9.3 (cal/cm3)1/2Above, 10.1 (cal/cm3)1/2Hereinafter, relative to thermoplastic resin 100 mass parts, containing the conductivity-imparting agent more than 40 mass parts, below 80 mass parts, containing the viscosity modifier more than 10 mass parts, below 30 mass parts.
Description
Technical field
The present invention relates to semi-conducting resin composition and employ the transmission of electricity of semi-conducting resin composition
Cable.
Background technology
Power transmission cable such as possesses insulating barrier, screen layer and enclosing cover layer in the way of coated conductor periphery successively
(sheath).Generally, insulating barrier has micro concavo-convex on surface, the most directly arranges shielding
In the case of Ceng, sometimes it is formed with space because of the concavo-convex of insulating barrier at the interface of insulating barrier Yu screen layer.As
Fruit is formed with space at the interface of insulating barrier Yu screen layer, then, when power transmission cable is applied high voltage, having can
Shelf depreciation can occur because of space.Shelf depreciation promotes by making air ionization near power transmission cable
The deterioration of insulating barrier, produces insulation breakdown.
Therefore, high-tension high pressure power transmission cable is being applied, such as used in the vehicle of rapid transit railway etc.
Extra-high-tension cable in, in order to suppress shelf depreciation, semi-conductive layer is set at the interface of insulating barrier Yu screen layer
(external semi-conductive layer).External semi-conductive layer landfill is present in the concavo-convex of surface of insulating layer, and suppression becomes product
The formation in the space of the main cause of raw shelf depreciation.Additionally, external semi-conductive layer is by containing conductive imparting
The semi-conducting resin composition of agent is formed, and suppresses local to put by making the surface potential homogenization of insulating barrier
Electricity.
From the viewpoint of suppression shelf depreciation, external semi-conductive layer need to fill surface of insulating layer concavo-convex and
Closely sealed with insulating barrier.On the other hand, the end at power transmission cable adds and strips external semi-conductive layer man-hour, therefore
External semi-conductive layer is required that Damage to insulation layer ground can be easily from insulation displacement.Thus demand is following
External semi-conductive layer: the most closely sealed with insulating barrier, the end at power transmission cable adds man-hour can be easily from absolutely
Edge layer is peeled off.
For forming the matrix resin of the semi-conducting resin composition of such external semi-conductive layer, use such as
Under thermoplastic resin: will not be the most closely sealed and have with the resin (such as EP rubbers) forming insulating barrier
The adaptation of appropriateness.Such as, as the thermoplastic resin forming external semi-conductive layer, it is proposed that containing 10～40
The ethylene vinyl acetate copolymer (EVA) (for example, referring to patent documentation 1) of quality % vinyl acetate.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2001-302856 publication
Summary of the invention
The problem that invention is to be solved
But, the thermoplastic resin of patent documentation 1 is high with the adaptation of the resin forming insulating barrier, therefore by
The external semi-conductive layer that semi-conducting resin composition shown in patent documentation 1 is formed is not easy from insulation
Layer is peeled off.Therefore, in the power transmission cable shown in patent documentation 1, exist and be difficult to make external semi-conductive layer
Stripping, the low such problem of process at ends.
Therefore, it is an object of the invention to, it is provided that can be formed can easily from the outside of insulation displacement partly
The semi-conducting resin composition of conductive layer and use its power transmission cable.
For the method solving problem
According to an embodiment of the invention, it is provided that a kind of semi-conducting resin composition, it contains thermoplastic
Property resin, conductivity-imparting agent and viscosity modifier, the solubility parameter SP value of described thermoplastic resin is
9.3(cal/cm3)1/2Above, 10.1 (cal/cm3)1/2Hereinafter, relative to described thermoplastic resin 100 mass parts,
Containing the described conductivity-imparting agent more than 40 mass parts, below 80 mass parts, containing 10 mass parts with
Above, the described viscosity modifier below 30 mass parts.
According to another implementation of the invention, it is provided that a kind of power transmission cable, it possesses conductor, to surround
Insulating barrier that the mode of described conductor periphery is arranged and arrange in the way of surrounding described insulating barrier periphery half
Conductive layer, it is 9.3 (cal/cm that described semi-conductive layer contains solubility parameter SP value3)1/2Above,
10.1(cal/cm3)1/2Following thermoplastic resin, conductivity-imparting agent and viscosity modifier, relative to described
Thermoplastic resin 100 mass parts, composes containing the described electric conductivity more than 40 mass parts, below 80 mass parts
Give agent, containing the described viscosity modifier more than 10 mass parts, below 30 mass parts.
Invention effect
Can be easily from the external semi-conductive layer of insulation displacement according to the present invention it is possible to obtain being formed
Semi-conducting resin composition and use its power transmission cable.
Accompanying drawing explanation
Fig. 1 is the sectional view of the power transmission cable of an embodiment of the invention.
Description of reference numerals
1: power transmission cable, 10: conductor, 11: internal semi-conductive layer, 12: insulating barrier, 13: outside half
Conductive layer, 14: screen layer, 15: enclosing cover layer (sheath), 20: interface.
Detailed description of the invention
As it has been described above, in the periphery of the insulating barrier formed by EP rubbers, arrange by comprising vinyl acetate content
In the case of being the external semi-conductive layer of semi-conducting resin composition formation of the EVA of 10～40 mass %,
There is the tendency that external semi-conductive layer is high with the adaptation of insulating barrier.Thus it is not easy to from insulation displacement
Portion's semi-conductive layer.That is, the peel strength when insulation displacement external semi-conductive layer is high.
As the main cause that peel strength is high, it is believed that the resin of above-mentioned EVA and formation insulating barrier
The difference of solubility parameter SP value is little.Solubility parameter SP value is to be measured, by material by Fedors method
The value that (resin) evaporation can calculate with molal volume, it is as the index of resin polarity.It is known that the most such as
Fruit tree fat poor with the polarity of resin (solubility parameter SP value difference) is little, then 2 kinds of resins affinity each other
Uprising, their adaptation becomes big.The solubility parameter SP value of above-mentioned EVA is 8.7 (cal/cm3)1/2With
Upper, 9.2 (cal/cm3)1/2Hereinafter, therefore EVA and EP rubbers (solubility parameter SP value is
8.2(cal/cm3)1/2) solubility parameter SP value difference be 0.5 (cal/cm3)1/2Above, 1.0 (cal/cm3)1/2With
Under.
It is 0.5 (cal/cm at solubility parameter SP value difference3)1/2Above, 1.0 (cal/cm3)1/2Time following, obtain not
To being easily peeled off the peel strength of external semi-conductive layer, therefore the research such as the present inventor uses dissolubility ginseng
The number higher thermoplastic resin of SP value forms external semi-conductive layer.But know, only use such thermoplastic
Property resin, it is impossible to fully reduce peel strength.
Then, the method for the peel strength to reducing external semi-conductive layer further such as the present inventor is ground
Study carefully.It is found that following opinion: in semi-conducting resin composition, if using solubility parameter
Thermoplastic resin that SP value is high and being then advisable containing substantial amounts of viscosity modifier.Viscosity modifier is by making
Thermoplastic resin lowering viscousity and promote conductivity-imparting agent dispersion in thermoplastic resin, and by making
Thermoplastic resin grease lubrication and improve the extrusion molding of semi-conducting resin composition.
Generally, it is considered that from the viewpoint of suppression the oozing out of viscosity modifier, the addition of viscosity modifier is few
It is advisable.So-called oozing out is that viscosity modifier dissolution contained in resin combination is in by resin combination shape
The situation of the resin forming surface become, it can make resin-formed body tacky and reduce operability etc..
But, in external semi-conductive layer, by making viscosity modifier ooze out, it is possible to suppression and insulating barrier
Adaptation.Specifically, the viscosity modifier oozed out from external semi-conductive layer invades insulating barrier and partly leads with outside
The interface of electric layer, suppression insulating barrier is the most closely sealed with external semi-conductive layer.As a result of which it is, can reduce from
Peel strength during insulation displacement external semi-conductive layer.And, external semi-conductive layer is coating by enclosing cover layer etc.,
Therefore viscosity modifier is not had to ooze out the worry making the operability of power transmission cable reduce in power transmission cable surface.
The present invention makes based on above-mentioned opinion.
1. an embodiment of the invention
Below an embodiment of the invention is illustrated.
(1) semi-conducting resin composition
In the semi-conducting resin composition of present embodiment, containing thermoplastic resin, conductivity-imparting agent
And viscosity modifier.Below each composition is illustrated.
Thermoplastic resin
Thermoplastic resin is the matrix resin of semi-conducting resin composition.Thermoplastic resin with regard to present embodiment
For fat, solubility parameter SP value is 9.3 (cal/cm3)1/2Above, 10.1 (cal/cm3)1/2Below.This heat
Plastic resin is becomes poor with the polarity of the thermoplastic resin forming insulating barrier owing to solubility parameter SP value is big
Big such resin.Such as, at insulating barrier, by EP rubbers, (solubility parameter SP value is 8.2 (cal/cm3)1/2)
In the case of formation, the solubility parameter SP value difference of the thermoplastic resin of present embodiment and EP rubbers is extremely
Become 1.1 (cal/cm less3)1/2.If the solubility parameter SP value of thermoplastic resin is less than 9.3 (cal/cm3)1/2,
Then the solubility parameter SP value difference with the resin forming insulating barrier diminishes, and therefore external semi-conductive layer is formed as
The most closely sealed with insulating barrier, the peel strength of external semi-conductive layer can uprise.Additionally, due to be difficult to make viscosity
Regulator is exuded to the interface of external semi-conductive layer and insulating barrier, therefore to reduce the stripping of external semi-conductive layer
From intensity.On the other hand, if the solubility parameter SP value of thermoplastic resin is more than 10.1 (cal/cm3)1/2,
Then the solubility parameter SP value difference with the resin forming insulating barrier becomes excessive, and outside therefore cannot be made partly to lead
Electric layer is closely sealed with insulating barrier to the degree that can suppress shelf depreciation.
As thermoplastic resin, from the viewpoint of not producing toxic gas when external semi-conductive layer burns, make
It is advisable with the most halogen-containing thermoplastic resin.Such as can use ethylene vinyl acetate copolymer (EVA)
(solubility parameter SP value is 9.3 (cal/cm3)1/2Above, 10.1 (cal/cm3)1/2Below) or nitrile rubber
(NBR) (solubility parameter SP value is 9.6 (cal/cm3)1/2) etc..These thermoplastic resins can be used
In one, or two or more kinds may be used.Wherein preferably EVA.EVA is by ethylene unit and acetic acid
Ethylene unit is constituted, and can change dissolubility ginseng according to the ratio (so-called VA amount) of vinyl acetate unit
Number SP value.Specifically, by make EVA VA measure be more than 44.0 mass %, it is possible to make EVA
Solubility parameter SP value be 9.3 (cal/cm3)1/2Above.On the other hand, the VA amount by making EVA is
Below 83.4 mass %, it is possible to the solubility parameter SP value making EVA is 10.1 (cal/cm3)1/2Hereinafter, and
And the tolerance to cold of EVA can be suppressed to reduce owing to the glass transition temperature of EVA uprises.
It addition, the high thermoplastic resin of solubility parameter SP value be hard and viscosity high, it is therefore possible to make
Extrusion molding during extrusion semi-conducting resin composition reduces.If squeezing of semi-conducting resin composition
Go out mouldability step-down, then cannot be with the most coating thickness extrusion semi-conducting resin composition, it is difficult to uniformly
Thickness forms external semi-conductive layer.Still another problems that due to the high thermoplastic resin of solubility parameter SP value
Fat is hard, therefore, it is difficult to make conductivity-imparting agent disperse.If the dispersibility step-down of conductivity-imparting agent,
The most sometimes the conductivity-imparting agent cohesion when being scattered in thermoplastic resin, it is difficult to adjust semiconduction resin combination
The electric conductivity of thing.About this point, in the present embodiment, by using substantial amounts of aftermentioned viscosity modifier,
The dispersibility of the reduction of the extrusion molding of semi-conducting resin composition, conductivity-imparting agent can be suppressed
Reduce.
Viscosity modifier
By making thermoplastic resin lowering viscousity, viscosity modifier promotes that conductivity-imparting agent is at thermoplastic resin
Dispersion in fat, and by making thermoplastic resin grease lubrication improve being extruded into of semi-conducting resin composition
Type.Additionally, when semi-conducting resin composition is formed as external semi-conductive layer, viscosity modifier oozes out
To the inner peripheral surface of external semi-conductive layer, suppression external semi-conductive layer is the most closely sealed with insulating barrier.
As viscosity modifier, such as, can use following viscosity modifier: in semiconduction resin combination
Near the forming temperature (more than 80 DEG C, less than 110 DEG C) of thing, there is fusing point, and the viscosity when 100 DEG C
It is preferably 20mm2Below/the second, it is more preferably 5mm2More than/the second, 15mm2Below/the second.If viscosity surpasses
Cross 20mm2/ the second, it is likely that cannot fully reduce the viscosity of semi-conducting resin composition, and cannot carry
High extrusion molding.As a result, it is difficult to carry out shape with the most coating thickness extrusion semi-conducting resin composition
The uniformly external semi-conductive layer of thickness.Being explained, the viscosity of viscosity modifier is according to JIS K2283
It is measured.
As viscosity modifier, such as, can use branched-chain hydrocarbons, saturated cyclic hydrocarbon or straight-chain hydrocarbons.Can use
1 kind therein, or two or more kinds may be used.Specifically can enumerate paraffin, microwax etc..Paraffin is
The straight-chain hydrocarbon of carbon number 18～about 30, fusing point is 40 DEG C～about 70 DEG C.Microwax is that carbon number 36～70 is left
Right branched hydrocarbon or saturated cyclic hydrocarbon, fusing point is 60 DEG C～about 90 DEG C.
Relative to thermoplastic resin 100 mass parts, the content of viscosity modifier be more than 10 mass parts, 30
Below mass parts, more than preferably 10 mass parts, below 25 mass parts, more preferably 10 mass parts with
Above, below 20 mass parts.If the content of viscosity modifier is less than 10 mass parts, then viscosity modifier is difficult
To ooze out, it is impossible to reduce the peel strength of external semi-conductive layer.If viscosity modifier is more than 30 mass parts,
Then the peel strength of external semi-conductive layer becomes too low, and therefore external semi-conductive layer 13 can be because of external stress
Peel off.
Conductivity-imparting agent
Conductivity-imparting agent is dispersed in thermoplastic resin and gives electric conductivity.Conductivity-imparting agent has on surface
Having OH base, conductivity-imparting agent the most easily condenses, therefore, it is difficult to be dispersed in thermoplastic resin.
And, in the thermoplastic resin of solubility parameter SP value height and hard, conductivity-imparting agent easily condenses,
Its dispersibility reduces further.About this point, in the present embodiment, semi-conducting resin composition is made
The lowering viscousity containing substantial amounts of viscosity modifier, therefore improves conductivity-imparting agent in thermoplastic resin
Dispersibility.
As conductivity-imparting agent, such as, can use conductive carbon.This conductive carbon have particle diameter little, ratio
Surface area is big, structure (shape of particle) is big, the few such feature of surface compound.Conductive carbon is due to logical
Too small amount of interpolation and electric conductivity can be given, therefore need not to add a large amount of, do not exist and make semiconduction tree
The worry that the excess stickiness of oil/fat composition improves.As conductive carbon, it is not particularly limited, it is possible to use public
The conductive carbon known.Such as there are furnace black, acetylene black and Ketjen black etc..Specifically can enumerate East Sea carbon element strain formula
The SEAST G116 (registered trade mark) of commercial firm, Ketjen Black International Co., Ltd.
Ketjen black EC (Ketjen Black EC, registered trade mark), the acetylene of Deuki Kagaku Kogyo Co., Ltd
Black (Acetylene Black, registered trade mark) etc..It addition, conductive carbon can use a kind, or can
With and use two or more.
Relative to thermoplastic resin 100 mass parts, the content of conductivity-imparting agent be more than 40 mass parts,
Below 80 mass parts.If the content of conductivity-imparting agent is less than 40 mass parts, then give due to electric conductivity
The content of agent is few and is difficult to meet the electric conductivity required by external semi-conductive layer (such as, in terms of specific insulation
It is 102More than Ω cm, 105Below Ω cm).On the other hand, if it exceeds 80 mass parts, the most partly lead
Electrically the viscosity of resin combination becomes too high, and therefore extrusion molding can reduce.
Other additive
In the semi-conducting resin composition of present embodiment, cross-linking agent, crosslinking can be contained as required
Auxiliary agent, antiaging agent, lubricant, working oil, antiozonant, ultraviolet screening agent, fire retardant, filler,
Other additive such as antistatic agent, antitack agent.From the viewpoint of the deformation resistance improving external semi-conductive layer,
Preferably comprise cross-linking agent.By improving deformation resistance, it is possible to destruction during suppression strip external semi-conductive layer.
As cross-linking agent, such as, can use α, α '-two (t-butylperoxy) diisopropyl benzene (Japan's oils and fats strain formula
The Perbutyl P of commercial firm), cumyl peroxide (the Percumyl D of NOF Corp) etc.
Organic peroxide.
(2) manufacture method of semi-conducting resin composition
The semi-conducting resin composition of present embodiment is by giving above-mentioned thermoplastic resin, electric conductivity
Agent, viscosity modifier, as required other additive mixing, heat mixing and formed.Respectively
The order of addition of composition is not particularly limited.In the present embodiment, although use solubility parameter SP value
High and hard thermoplastic resin, but owing to adding substantial amounts of viscosity modifier, therefore, it is possible to make thermoplastic resin
Fat lowering viscousity, well dispersed electro-conductive imparting agent.Be explained, mixing can use mixing mill,
Banbury mixer (banbury mixer), brabender plasticorder (brabender Plastograph),
Batch-type mixer, the uniaxially or biaxially extruders such as pressure-type kneader, simultaneously or sequentially carried out.Time mixing
Heating-up temperature be set to more than the fusing point of thermoplastic resin (such as more than 80 DEG C, less than 110 DEG C).
(3) composition of power transmission cable
It follows that the power transmission cable of an embodiment of the invention is illustrated.Fig. 1 is the present invention
The sectional view of the power transmission cable of one embodiment.
Conductor
As it is shown in figure 1, the power transmission cable 1 of present embodiment possesses conductor 10.As conductor 10, such as
Can use and comprise the copper cash of hypoxia copper, oxygen-free copper etc., copper alloy wire, comprise other metal wire etc. of silver etc.,
Or the twisted wire stranded by them.The external diameter of conductor 10 can be suitable according to the purposes of power transmission cable 1
Change.
Internal semi-conductive layer
Internal semi-conductive layer 11 it is provided with in the way of surrounding conductor 10 periphery.Such as, internal semi-conductive layer
11 peripheries being arranged to coated conductor 10.Internal semi-conductive layer 11 is arranged to close with insulating barrier 12 described later
Close, suppress shelf depreciation for filling the concavo-convex of insulating barrier 12 surface.The thickness of internal semi-conductive layer 11
For example, more than 0.3mm, below 3mm.
Internal semi-conductive layer 11 is formed by known semi-conducting resin composition.Form inside partly to lead
The semi-conducting resin composition of electric layer 11 such as contains matrix resin and conductivity-imparting agent.As formation
The matrix resin of internal semi-conductive layer 11, from guaranteeing and the adaptation of insulating barrier 12 described later, uses such as
The thermoplastic resin such as EP rubbers, butyl rubber is advisable.It addition, forming the half of internal semi-conductive layer 11
In conductive resin composition, can contain as required cross-linking agent, crosslinking coagent and antiaging agent etc. other
Additive.Additionally, internal semi-conductive layer 11 is in addition to being formed by semi-conducting resin composition, it is possible to
With by by semiconduction rubberized fabric roll around and formed, described semiconduction adhesive plaster is at the end of such as chopped fiber
Applying conductive butyl rubber on cloth and formed.
Insulating barrier
It is provided with insulating barrier 12 in the way of surrounding internal semi-conductive layer 11.Such as, insulating barrier 12 is arranged
Become the periphery of coating internal semi-conductive layer 11.The thickness of insulating barrier 12 for example, more than 3mm, 30mm
Below.
Insulating barrier 12 is formed by the insulating resin composition containing thermoplastic resin.As forming insulating barrier
The thermoplastic resin of 12, the resin of selection to make the thermoplastic resin used with external semi-conductive layer 13
The difference of solubility parameter SP value be at least 1.1 (cal/cm3)1/2.Such as can use EP rubbers, poly-second
Alkene etc..Wherein preferred EP rubbers.It addition, in insulating barrier 12, cross-linking agent can be contained, cross-links and help
Other additive such as agent and antiaging agent.
External semi-conductive layer
It is provided with external semi-conductive layer 13 in the way of surrounding insulating barrier 12.Such as, external semi-conductive layer 13
It is arranged to by the periphery of insulating layer coating 12.External semi-conductive layer 13 is used in the same manner as internal semi-conductive layer 11
Shelf depreciation is suppressed in landfill the concavo-convex of insulating barrier 12 surface.The thickness of external semi-conductive layer 13 is for example,
More than 0.3mm, below 3mm.
External semi-conductive layer 13 is become by containing the solubility parameter SP value difference with the resin forming insulating barrier 12
The semi-conducting resin composition of big such thermoplastic resin is formed.Therefore, external semi-conductive layer 13 is not
Can the periphery that be snugly arranged on insulating barrier 12 excessive with insulating barrier 12.Additionally, external semi-conductive layer 13
Containing substantial amounts of viscosity modifier, at the interface 20 of external semi-conductive layer 13 with insulating barrier 12, ooze out and have
Viscosity modifier contained by external semi-conductive layer 13.The viscosity modifier oozed out is present in the whole of interface 20
Body or a part, therefore, external semi-conductive layer 13 with viscosity modifier between with the interface of insulating barrier 12
State is arranged on the periphery of insulating barrier 12.Thus, external semi-conductive layer 13 is configured to: will not be with insulating barrier
12 is the most closely sealed, the peel strength step-down when insulating barrier 12 is peeled off.It is additionally contemplated that, promote that viscosity adjusts
Agent is oozed out and is because in interface 20, and external semi-conductive layer 13 is by being difficult to the thermoplasticity the most closely sealed with insulating barrier
Resin formation and adaptation at interface 20 is little.
About the peel strength of external semi-conductive layer 13, in the case of insulating barrier 12 is formed by EP rubbers,
Preferably more than 10N/12.7mm, below 50N/12.7mm, more preferably more than 15N/12.7mm,
Below 25N/12.7mm.If peel strength is less than 10N/12.7mm, it is likely that external semi-conductive layer
13 peel off because of external stresses such as vibration, the bendings adding man-hour.On the other hand, if peel strength exceedes
50N/12.7mm, then external semi-conductive layer 13 is closely sealed too strong, it is therefore possible at strip external semiconductive
During layer 13, external semi-conductive layer 13 itself is destroyed or insulating barrier 12 is destroyed.It addition, for peeling off
Intensity, is specifically described in embodiment described later.
External semi-conductive layer 13 is by the semi-conducting resin composition shape of the excellent dispersion of conductivity-imparting agent
Becoming, the specific insulation of external semi-conductive layer 13 is 102More than Ω cm, 105Below Ω cm.
External semi-conductive layer 13 is by the semiconduction excellent containing substantial amounts of viscosity modifier and extrusion molding
Resin combination is formed, and is therefore coated to thickness and becomes uniformly.
It addition, although viscosity modifier is exuded to the surface of the inner side and outer side of external semi-conductive layer 13, but
It is that external semi-conductive layer 13 is coated to by screen layer 14 described later and enclosing cover layer 15, therefore, it is difficult to be exuded to defeated
The surface of electrical cables 1.Therefore, it is possible to suppression operation of power transmission cable 1 due to oozing out of viscosity modifier
Property reduce.
Screen layer
Screen layer 14 is arranged on the periphery of external semi-conductive layer 13, when bucking current flows through conductor 10
The noise produced.In order to obtain flexibility, screen layer 14 is by by yarn woven such as many such as annealed copper wires
Formed.
Enclosing cover layer
Enclosing cover layer 15 (hereinafter also referred to sheath 15) is arranged on the periphery of screen layer 14, and coating and protection is led
Body 10, insulating barrier 12 etc..Sheath 15 is formed by known resin combination, such as by vinyl chloride
Resin is constituted.
(4) manufacture method of power transmission cable
Power transmission cable 1 such as can manufacture as follows.First, conductor 10 is prepared, by inside semi-conductive layer 11
Conductive resin composition be expressed on the periphery of conductor 10 and form internal semi-conductive layer 11.Then,
Internal semi-conductive layer 11 is made to crosslink.Such as in the case of using organic peroxide to cross-link,
Internal semi-conductive layer 11 is exposed in high temperature (140 DEG C～190 DEG C) and the steam of high pressure (13MPa)
Within 15 minutes, carry out.Then, the resin combination of insulating barrier 12 is expressed into internal semi-conductive layer 11
Periphery and form insulating barrier 12, make insulating barrier 12 crosslink.Then, by external semi-conductive layer 13
Semi-conducting resin composition be expressed into the periphery of insulating barrier 12 and form external semi-conductive layer 13.It
After, screen layer 14 and sheath 15 are set in the periphery of external semi-conductive layer 13 thus obtain present embodiment
Power transmission cable 1.
As it has been described above, internal semi-conductive layer 11, insulating barrier 12 and external semi-conductive layer 13 can squeeze successively
Go out to be coated to and formed, it is also possible to extrude 3 layers simultaneously and formed.
2. the effect of embodiment of the present invention
According to present embodiment, play one or more effects shown below.
A (), according to present embodiment, semi-conducting resin composition contains solubility parameter SP value and is
9.3(cal/cm3)1/2Above, 10.1 (cal/cm3)1/2Following thermoplastic resin and relative to thermoplastic resin 100
Mass parts is the viscosity modifier of below more than 10 mass parts, 30 mass parts.Semi-conducting resin composition
Big such thermoplastic resin is become containing the solubility parameter SP value difference with the resin forming insulating barrier 12,
Therefore, it is possible to external semi-conductive layer 13 will not the most snugly be formed with insulating barrier 12.Additionally, semiconduction
Resin combination contains the substantial amounts of viscosity modifier that can ooze out, therefore when forming external semi-conductive layer 13
Viscosity modifier is made to be exuded to the interface 20 with insulating barrier 12, it is possible to suppression external semi-conductive layer 13 is with exhausted
Edge layer 12 the most closely sealed.Thus, according to the semi-conducting resin composition of present embodiment, it is possible to shape
Become the peel strength when insulating barrier 12 is peeled off low and add the outside semiconductive can being easily peeled off man-hour at end
Layer 13.
B (), according to present embodiment, semi-conducting resin composition contains relative to thermoplastic resin 100
Mass parts is the conductivity-imparting agent of below more than 40 mass parts, 80 mass parts.Solubility parameter SP value
High thermoplastic resin is hard, it is difficult to dispersed electro-conductive imparting agent well, but in the present embodiment,
By containing substantial amounts of viscosity modifier, improve conductivity-imparting agent dispersibility in thermoplastic resin.By
This can make the specific insulation of external semi-conductive layer 13 be 102More than Ω cm, 105Below Ω cm.
C (), according to present embodiment, semi-conducting resin composition contains substantial amounts of viscosity modifier and glues
Spending low, extrusion molding when therefore extruding is excellent.Therefore, it is possible to extrude semiconduction tree with uniform thickness
Oil/fat composition, it is possible to form external semi-conductive layer 13 in uniform thickness.
D (), according to present embodiment, thermoplastic resin is preferably ethylene vinyl acetate copolymer or butyronitrile
At least one in rubber, more preferably contains more than 44.0 mass %, the 83.4 following vinyl acetates of mass %
Ethylene vinyl acetate copolymer.According to such thermoplastic resin, it is possible to make and form insulating barrier 12
The solubility parameter SP value difference of resin become big, therefore, it is possible to suppression external semi-conductive layer 13 and insulating barrier
12 closely sealed at interface 20.And then, by closely sealed at interface 20 of suppression, it is possible to promote that viscosity adjusts
Agent is oozed out to interface 20.By the effect of these superpositions, it is possible to reduce external semi-conductive layer 13 further
Peel strength.
(e) according to present embodiment, preferred viscosities regulator be in saturated cyclic hydrocarbon or straight-chain hydrocarbons at least
1 kind, and the viscosity when temperature 100 DEG C is 20mm2Below/the second.Such viscosity modifier is by making half
The viscosity of conductive resin composition reduces, it is possible to increase the extrusion molding of semi-conducting resin composition with
And the dispersibility of conductivity-imparting agent.
F () possesses by semiconduction tree in the periphery of insulating barrier 12 according to present embodiment, power transmission cable 1
Oil/fat composition formed external semi-conductive layer 13, described semi-conducting resin composition contain have regulation molten
The thermoplastic resin of solution degree parameter SP value and substantial amounts of viscosity modifier.Therefore, from external semi-conductive layer 13
The viscosity modifier oozed out is present in the interface 20 of insulating barrier 12 and external semi-conductive layer 13.It is possible to
Reduce the peel strength when insulating barrier 12 strip external semi-conductive layer 13.Specifically, at insulating barrier
In the case of 12 are formed by EP rubbers, the peel strength of external semi-conductive layer 13 be 10N/12.7mm with
Upper, below 50N/12.7mm.Thereby, it is possible to easily from insulating barrier 12 strip external semi-conductive layer 13,
Therefore power transmission cable 1 is excellent in terms of process at ends.
Embodiment
Below, the present invention is further described by embodiment.
(1) modulation of the semi-conducting resin composition of internal semi-conductive layer
First, the semi-conducting resin composition of internal semi-conductive layer has been modulated.Specifically, relative to
EP rubbers 100 mass parts, add the conductivity-imparting agent of below more than 40 mass parts, 80 mass parts with
And the additive such as organic peroxide, antioxidant, carry out mixing with Banbury mixer, thus in modulation
The semi-conducting resin composition of portion's semi-conductive layer.
(2) modulation of the resin combination of insulating barrier
Then, the resin combination of insulating barrier has been modulated.Specifically, relative to solubility parameter SP
Value is 8.2 (cal/cm3)1/2EP rubbers 100 mass parts, add more than 30 mass parts, 70 mass parts with
Under clay and the additive such as organic peroxide, antioxidant, carry out mixing with Banbury mixer,
Thus modulate the resin combination of insulating barrier.
(3) modulation of the semi-conducting resin composition of external semi-conductive layer
Then, the semi-conducting resin composition of external semi-conductive layer has been modulated.In embodiment and comparative example
The material used is as follows.
As (A) thermoplastic resin, employ vinyl acetate content (VA amount) difference, dissolubility ginseng
The ethylene vinyl acetate copolymer (EVA) that number SP value is different.
(a1) VA amount is that (solubility parameter SP value is 10.1 (cal/cm for the EVA of 80 mass %3)1/2):
" Levapren800HV " (Lanxess Co., Ltd. system)
(a2) VA amount is that (solubility parameter SP value is 9.8 (cal/cm for the EVA of 70 mass %3)1/2):
" Levapren700HV " (Lanxess Co., Ltd. system)
(a3) VA amount is that (solubility parameter SP value is 9.6 (cal/cm for the EVA of 60 mass %3)1/2):
" Levapren600HV " (Lanxess Co., Ltd. system)
(a4) VA amount is that (solubility parameter SP value is 9.4 (cal/cm for the EVA of 50 mass %3)1/2):
" Levapren500HV " (Lanxess Co., Ltd. system)
(a5) VA amount is that (solubility parameter SP value is 9.3 (cal/cm for the EVA of 46 mass %3)1/2):
" EVA45LX " (three polymeric chemical Co., Ltd. of well Du Pont systems)
(a6) VA amount is that (solubility parameter SP value is 9.1 (cal/cm for the EVA of 33 mass %3)1/2):
" EV150 " (three polymeric chemical Co., Ltd. of well Du Pont systems)
As (B) viscosity modifier, employ following material.
(b1) paraffin (fusing point 58 DEG C, viscosity 3.9mm2/ the second (100 DEG C)): " Paraffin Wax 135 "
(Shi Co., Ltd. of JX Japan Airline system)
(b2) microwax (fusing point 88 DEG C, viscosity 14.3mm2/ the second (100 DEG C)): " Microcrystalline
Wax Hi-Mic1090 " (Shi Co., Ltd. of JX Japan Airline system)
As (C) conductivity-imparting agent, employ following material.
(c1) white carbon black (mean diameter 38nm): " DENKA BLACK " (DENKA strain formula meeting
Society's system)
(c2) white carbon black (mean diameter 38nm): " SEAST G116 " (Tokai Carbon Company Ltd.'s system)
As cross-linking agent (D), employ following material.
Organic peroxide: " Perbutyl P " (Japan Oil Co's system)
Use above-mentioned material, modulate the semi-conducting resin composition of embodiment 1～7.Modulation condition is shown
In table 1 below.
Table 1
In embodiment 1, as shown in table 1, relative to (a1) VA as (A) thermoplastic resin
Amount is that (solubility parameter SP value is 10.1 (cal/cm for the EVA of 80 mass %3)1/2) 100 mass parts, add
Add (b1) paraffin 18 mass parts of (B) viscosity modifier, (c1) charcoal of (C) conductivity-imparting agent
Black 60 mass parts and organic peroxide 2 mass parts of (D) cross-linking agent, carried out with Banbury mixer
Mixing, thus modulated the semi-conducting resin composition of embodiment 1.In embodiment 2～9, such as table 1
As shown in suitably change modulation condition, modulated semiconduction resin the most similarly to Example 1
Compositions.
Additionally, use above-mentioned material, modulate the semi-conducting resin composition of comparative example 1～9.Will modulation
Condition is shown in Table 2.In comparative example 1～9, suitably change modulation condition, except this like that as shown in table 2
Outside modulated semi-conducting resin composition similarly to Example 1.
Table 2
(4) manufacture of evaluation power transmission cable
In the present embodiment, the evaluation power transmission cable of simulation power transmission cable has been manufactured.
By the semi-conducting resin composition of inside semi-conductive layer of above-mentioned modulation, the resin group of insulating barrier
Each composition of the semi-conducting resin composition of compound and external semi-conductive layer is fed separately to extruder.Right
In these each compositions, at 85 DEG C of semi-conducting resin compositions by internal semi-conductive layer, incite somebody to action at 60 DEG C
The resin combination of insulating barrier, at 85 DEG C, the semi-conducting resin composition of external semi-conductive layer is divided
After not adding hot milling, to copper cash (the sectional area 95mm as conductor2) periphery, partly lead with inside
The thickness of electric layer is 1mm, the thickness of insulating barrier is 9mm, the thickness of external semi-conductive layer is 1mm's
Mode extrudes 3 layers simultaneously.Then, by making each composition of extrusion cross-link, manufacture in the periphery of conductor successively
It is laminated with internal semi-conductive layer, insulating barrier and the evaluation power transmission cable of external semi-conductive layer.
(5) evaluation methodology
For the evaluation power transmission cable manufactured, the adaptation and the outside that have rated external semi-conductive layer are partly led
The electrical characteristics of electric layer.
The adaptation of external semi-conductive layer
For the adaptation of external semi-conductive layer, according to from insulation displacement external semi-conductive layer time stripping strong
Degree is evaluated.Specifically, with cutter, power transmission cable rip cutting is used in evaluation, made 3 width
12.7mm, the test film of length about about 15cm.For this each test film, utilize Xiao Baier (Schopper)
Disbonded test implemented by tensile testing machine, determines the draw speed with 500mm/ minute from copper cash strip external
Peel strength during semi-conductive layer.It is explained, in the present embodiment, if the peel strength measured
For more than 10N/12.7mm, below 50N/12.7mm, then it represents that external semi-conductive layer can be easily peeled off.
Additionally, the stripping state of external semi-conductive layer when observing stripping.About external semi-conductive layer, will
Situation that is the most closely sealed with insulating barrier and that peel off well is set to " A ", is destroyed excessive for adaptation and insulating barrier
Situation be set to " B ", the situation that excessive for adaptation and external semi-conductive layer destroys is set to " C ", by adaptation
Too small situation is set to " D ".
The electrical characteristics of external semi-conductive layer
For the electrical characteristics of external semi-conductive layer, it is evaluated according to the specific insulation of external semi-conductive layer.
Specifically, make length 80mm, width 50mm, the test film of thickness 1mm, according to JIS K7194,
It is evaluated the indoor of 23 DEG C ± 2 DEG C by 9 mensuration.In external semi-conductive layer, as long as volume is electric
Resistance rate is 102More than Ω cm, 105Below Ω cm.
(6) evaluation result
Confirm as shown in table 1, in embodiment 1～9, peel strength, stripping state, specific insulation
Well.Know according to embodiment 1～5, as (A) thermoplastic resin, more use solubility parameter SP value
High thermoplastic resin, more can reduce peel strength.Additionally, know according to embodiment 6,7, even if
The content of (C) conductivity-imparting agent is suitably changed to 45 mass parts, 75 mass parts, it is also possible to reality
Execute the scope that example 2 similarly makes peel strength be more than 10N/12.7mm, below 50N/12.7mm.This
Outward, know according to embodiment 8, even if the kind of (B) viscosity modifier is changed to by (b1) paraffin
(b2) microwax, it is also possible to obtain result similarly to Example 3.Additionally, know according to embodiment 9,
Even if the kind of (C) conductivity-imparting agent being changed, it is also possible to obtain result similarly to Example 3.
It addition, in embodiment 1～9, owing to the extrusion molding of semi-conducting resin composition is good, the most all
External semi-conductive layer can be formed with uniform thickness.
Confirm as shown in table 2, in comparative example 1,3, due to the content by (B) viscosity modifier
It is reduced to 5 mass parts, the therefore a height of 55N/12.7mm of peel strength, and cannot strip external half well
Conductive layer.On the other hand confirm, in comparative example 2,4, due to containing (B) viscosity modifier
Amount increases to 35 mass parts, and therefore peel strength is low for 5N/12.7mm, and cannot be by external semi-conductive layer
The most closely sealed with insulating barrier.Additionally confirm, in comparative example 1,3, due to (B) viscosity modifier
Content few, therefore the extrusion molding of semi-conducting resin composition is low, and cannot be formed with uniform thickness
External semi-conductive layer.
Confirm, in comparative example 5,7, owing to the content of (C) conductivity-imparting agent is reduced to 30
Mass parts, therefore the specific insulation of external semi-conductive layer goes above 105Ω·cm.On the other hand confirm,
In comparative example 6,8, owing to the content of (C) conductivity-imparting agent being increased to 90 mass parts, therefore
The specific insulation of external semi-conductive layer becomes less than 102Ω·cm。
Confirm, in comparative example 9, be 9.1 (cal/cm owing to employing solubility parameter SP value3)1/2's
(a6) VA amount is the EVA, the therefore a height of 60N/12.7mm of peel strength of 33 mass %.Its reason quilt
Thinking, (solubility parameter SP value is 8.2 (cal/cm to form the EP rubbers of insulating barrier3)1/2) with formed outside
(solubility parameter SP value is 9.1 (cal/cm to the EVA of portion's semi-conductive layer3)1/2) solubility parameter SP value
Difference is little is 0.9 (cal/cm3)1/2Left and right, and external semi-conductive layer is formed as the most closely sealed with insulating barrier.In addition
Thinking, the adaptation of external semi-conductive layer and insulating barrier is high, and viscosity modifier be difficult to be exuded to insulating barrier with
The interface of external semi-conductive layer.
As it has been described above, according to the present invention, by using solubility parameter in semi-conducting resin composition
Thermoplastic resin that SP value is high and substantial amounts of viscosity modifier, it is possible to form extrusion molding excellent and absolutely
The adaptation of edge layer and the external semi-conductive layer of fissility excellence.
2. the preferred embodiment of the present invention
Hereinafter, the preferred embodiment of the present invention is carried out remarks.
[1] according to an embodiment of the invention, it is provided that a kind of semi-conducting resin composition, it contains
Thermoplastic resin, conductivity-imparting agent and viscosity modifier；Solubility parameter SP of described thermoplastic resin
Value is 9.3 (cal/cm3)1/2Above, 10.1 (cal/cm3)1/2Below；Relative to described thermoplastic resin 100 matter
Amount part, containing the described conductivity-imparting agent more than 40 mass parts, below 80 mass parts, containing 10 matter
Described viscosity modifier more than amount part, below 30 mass parts.
[2] in the semi-conducting resin composition described in [1], the most described thermoplastic resin is vinyl acetate
At least one in vinyl ester copolymers or nitrile rubber.
[3] in the semi-conducting resin composition described in [2], the most described thermoplastic resin is containing 44.0
More than quality %, the ethylene vinyl acetate copolymer of the 83.4 following vinyl acetates of mass %.
[4] in the semi-conducting resin composition according to any one of [1]～[3], the most described viscosity modifier
For at least one in branched-chain hydrocarbons, saturated cyclic hydrocarbon or straight-chain hydrocarbons, the viscosity when temperature 100 DEG C is
20mm2Below/the second.
[5] according to another implementation of the invention, it is provided that a kind of power transmission cable, it possess conductor, with
Surround insulating barrier that the mode of described conductor periphery arranges and arrange in the way of surrounding described insulating barrier periphery
Semi-conductive layer；It is 9.3 (cal/cm that described semi-conductive layer contains solubility parameter SP value3)1/2Above,
10.1(cal/cm3)1/2Following thermoplastic resin, conductivity-imparting agent and viscosity modifier；Relative to described
Thermoplastic resin 100 mass parts, composes containing the described electric conductivity more than 40 mass parts, below 80 mass parts
Give agent, containing the described viscosity modifier more than 10 mass parts, below 30 mass parts.
[6] in the power transmission cable described in [5], the most described insulating barrier is formed by EP rubbers.
[7] in the power transmission cable described in [5] or [6], the most described semi-conductive layer is configured to from described insulating barrier
Peel strength when peeling off described semi-conductive layer is more than 10N/12.7mm, below 50N/12.7mm.
[8] in the power transmission cable according to any one of [5]～[7], the most described semi-conductive layer is configured to volume electricity
Resistance rate is 102More than Ω cm, 105Below Ω cm.
Claims (8)
1. a semi-conducting resin composition, it contains thermoplastic resin, conductivity-imparting agent and viscosity
Regulator,
The solubility parameter SP value of described thermoplastic resin is 9.3 (cal/cm3)1/2Above, 10.1 (cal/cm3)1/2
Hereinafter,
Relative to described thermoplastic resin 100 mass parts, containing more than 40 mass parts, below 80 mass parts
Described conductivity-imparting agent, containing the described viscosity modifier more than 10 mass parts, below 30 mass parts.
Semi-conducting resin composition the most according to claim 1, described thermoplastic resin is ethylene
At least one in vinyl acetate copolymer or nitrile rubber.
Semi-conducting resin composition the most according to claim 2, described thermoplastic resin is for containing
More than 44.0 mass %, the ethylene vinyl acetate copolymer of the 83.4 following vinyl acetates of mass %.
4., according to the semi-conducting resin composition according to any one of claims 1 to 3, described viscosity is adjusted
Whole dose is at least one in branched-chain hydrocarbons, saturated cyclic hydrocarbon or straight-chain hydrocarbons, and the viscosity when temperature 100 DEG C is
20mm2Below/the second.
5. a power transmission cable, it possesses conductor, the insulation arranged in the way of surrounding described conductor periphery
Layer and the semi-conductive layer arranged in the way of surrounding described insulating barrier periphery,
It is 9.3 (cal/cm that described semi-conductive layer contains solubility parameter SP value3)1/2Above, 10.1 (cal/cm3)1/2
Following thermoplastic resin, conductivity-imparting agent and viscosity modifier, relative to described thermoplastic resin 100
Mass parts, containing the described conductivity-imparting agent more than 40 mass parts, below 80 mass parts, containing 10
Described viscosity modifier more than mass parts, below 30 mass parts.
Power transmission cable the most according to claim 5, described insulating barrier is formed by EP rubbers.
7. according to the power transmission cable described in claim 5 or 6, described semi-conductive layer be configured to from described absolutely
Peel strength during the edge layer described semi-conductive layer of stripping is more than 10N/12.7mm, below 50N/12.7mm.
8., according to the power transmission cable according to any one of claim 5～7, described semi-conductive layer is configured to body
Long-pending resistivity is 102More than Ω cm, 105Below Ω cm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015050245A JP6521362B2 (en) | 2015-03-13 | 2015-03-13 | Power transmission cable |
| JP2015-050245 | 2015-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106189015A true CN106189015A (en) | 2016-12-07 |
Family
ID=56982149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510358928.1A Pending CN106189015A (en) | 2015-03-13 | 2015-06-25 | Semi-conducting resin composition and power transmission cable |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6521362B2 (en) |
| CN (1) | CN106189015A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933107A (en) * | 1988-03-29 | 1990-06-12 | Hitachi Cable Ltd. | Easily peelable semiconductive resin composition |
| JPH11297121A (en) * | 1998-04-03 | 1999-10-29 | Hitachi Cable Ltd | Easily peelable semiconductive resin composition and electric wire/cable |
| JP2008130367A (en) * | 2006-11-21 | 2008-06-05 | Hitachi Cable Ltd | High-voltage cabtire cable |
-
2015
- 2015-03-13 JP JP2015050245A patent/JP6521362B2/en not_active Expired - Fee Related
- 2015-06-25 CN CN201510358928.1A patent/CN106189015A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933107A (en) * | 1988-03-29 | 1990-06-12 | Hitachi Cable Ltd. | Easily peelable semiconductive resin composition |
| JPH11297121A (en) * | 1998-04-03 | 1999-10-29 | Hitachi Cable Ltd | Easily peelable semiconductive resin composition and electric wire/cable |
| JP2008130367A (en) * | 2006-11-21 | 2008-06-05 | Hitachi Cable Ltd | High-voltage cabtire cable |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6521362B2 (en) | 2019-05-29 |
| JP2016169312A (en) | 2016-09-23 |
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