CN108503754A - Silane Grafted resin combination, electric wire and cable - Google Patents
Silane Grafted resin combination, electric wire and cable Download PDFInfo
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- CN108503754A CN108503754A CN201810119189.4A CN201810119189A CN108503754A CN 108503754 A CN108503754 A CN 108503754A CN 201810119189 A CN201810119189 A CN 201810119189A CN 108503754 A CN108503754 A CN 108503754A
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- Prior art keywords
- silane
- resin combination
- peroxide
- silane grafted
- electric wire
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Classifications
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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
- H01B7/02—Disposition of insulation
- H01B7/0275—Disposition of insulation comprising one or more extruded layers of insulation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
-
- 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
-
- 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
Abstract
The present invention provides the Silane Grafted resin combination of the coating timber-used of the electric wire, cable with good appearance and uses its electric wire and cable.The Silane Grafted resin combination is squeezed out in a manner of coated conductor periphery, then, makes Silane Grafted resin combination and reaction of moisture and carries out crosslinked with silicane.The Silane Grafted resin combination has and makes Silane Grafted resin and additive obtained by silane compound and Halogen resin graft reaction using peroxide.Moreover, it is methylacryloyl that silane compound, which has unsaturated keyness group and hydrolysable silanes base, unsaturated keyness group,.In addition, the range that the compounding ratio Rc of silane coupling agent and peroxide is 1.5~20.Thereby, it is possible to reduce the localization of graft, the undesirable cross-linking reaction etc. caused by the mutual condensation of silane in the grafting portion to have localized can be inhibited, can make electric wire, cable coated material (insulating layer) appearance it is good.
Description
Technical field
The present invention relates to Silane Grafted resin combination, electric wire and cables.
Background technology
Cable has electric wire and the serving (restrictive coating) on the electric wire periphery.Said wires have conductor and are set to
Insulating layer on conductor periphery, above-mentioned serving (restrictive coating) are set on above-mentioned insulating layer periphery.
For the coated material as the insulating layer of the serving of above-mentioned cable, electric wire, in order to improve headed by heat resistance
Various characteristics, often implement the intermolecular crosslinking Treatment being chemically combined for making polymer as coated material.Crosslinking side
Formula has makes silane compound (so-called silane coupling agent) be chemically bonded in polymer molecule in advance, utilizes the silicon for being incorporated into polymer
Hydride compounds carry out crosslinked crosslinked with silicane mode.
For example, Patent Document 1 discloses being existed using the resin combination containing the uncrosslinked polyolefin through Silane Grafted
Conductor periphery forms the technology of coating.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-105257 bulletins
Invention content
Problems to be solved by the invention
The present inventor be engaged in as the serving of cable, electric wire insulating layer coated material research, exploitation, grinding
Study carefully the polymer for using Halogen resin as coated material, effective crosslinking technological.It specifies in this process, according to Halogen tree
The difference of the combination of fat and silane compound generates bad order when cable is coating sometimes (surface generates concave-convex).Especially
In the case of being kneaded fire retardant in resin combination, bad order is easy tod produce.
The present invention makes in view of the above subject, it is intended that providing the electric wire or cable with good appearance
The Silane Grafted resin combination of coating timber-used.
The method for solving problem
(1) the Silane Grafted resin combination of a mode of the invention is that have in Halogen resin and use peroxide
With Silane Grafted resin and additive obtained by silane compound graft reaction, above-mentioned silane compound has unsaturated bond
Property group and hydrolysable silanes base, above-mentioned unsaturation keyness group is methylacryloyl, silane coupling agent shown in following formula with
Range of the compounding ratio (Rc) of peroxide 1.5~20.
Rc=(WS/MS)/(2 α WO/MO)
Wherein, WS is the use level (g) of silane coupling agent, and WO is the use level (g) of peroxide, and MS is silane coupling agent
Molecular weight, MO be peroxide molecular weight, α be every 1 molecule peroxide o-o bond number.
(2) gel fraction after preferably above-mentioned Silane Grafted resin combination crosslinking is 50% or more.
(3) preferably above-mentioned Halogen resin contains vinyl-vinyl acetate copolymer.
(4) preferably above-mentioned silane compound is 3- methacryloxypropyl trimethoxy silanes or 3- methacryls
Oxygroup propyl-triethoxysilicane.
(5) preferably above-mentioned additive is fire retardant.
(6) electric wire of a mode of the invention is preferably provided with by the Silane Grafted tree described in any one of above-mentioned (1)~(5)
The insulating layer that the cross-linking agent of oil/fat composition is formed.
(7) cable of a mode of the invention is preferably provided with by the Silane Grafted tree described in any one of above-mentioned (1)~(5)
The serving that the cross-linking agent of oil/fat composition is formed.
The effect of invention
By the way that the Silane Grafted resin combination of a mode of the invention to be used as to the coated material of electric wire, cable, can make
Electric wire, the appearance of cable are good.
Description of the drawings
Fig. 1 is the sectional view for the structure for showing electric wire.
Fig. 2 is the sectional view for the structure for showing cable.
Fig. 3 is the schematic diagram of the situation of grafting processing of the display using single screw extrusion machine.
Fig. 4 is the schematic diagram for the situation that display makes cable.
Symbol description
1：Electric wire；2：Cable；10：Conductor；11：Insulating layer；12：Serving；100：Single screw extrusion machine；101：Hopper；
102：Screw rod；103a：Machine barrel；103b：Machine barrel；104：Die section；105：Mold；106：Sink；107：Air wiper；108：
Comminutor；109：Machine neck；110：Cross-head dies portion.
Specific implementation mode
(embodiment)
Electric wire, cable are covered by coated material, the coated material by having carried out crosslinking Treatment to Silane Grafted resin combination and
The resin obtained is formed.
(1) Silane Grafted resin combination
Silane Grafted resin combination has Silane Grafted resin and additive.
(Silane Grafted resin)
Silane Grafted resin is to mix resin (base polymer, polymer), silane coupling agent and peroxide, in mistake
In the presence of oxide, silane coupling agent is made to be graft-polymerized obtained from resin.
Therefore, Silane Grafted resin has the silylation from the silane coupling agent through graft polymerization in strand.Silicon
For alkane graft resin when being contacted with water, the silylation in strand is hydrolyzed into silanol group, silanol group dehydrating condensation each other
And form cross-linked structure (crosslinked with silicane).In addition, the crosslinking Treatment as resin, although existing by applying heat, electron ray
The method for waiting energy and carrying out, but this method needs large-scale equipment, a large amount of energy.In contrast, crosslinked with silicane mode
Without large-scale equipment, a large amount of energy, it is advantageous in terms of economy, the feature of environmental protection.
Use Halogen resin as resin in present embodiment.Halogen resin is the resin being halogen-free in molecular structure,
Due to not generating two in burningThe toxic gases such as English, thus it is also suitable for the coated material of electric wire, cable.As Halogen
Resin, representative is polyethylene, but from most cases as electric wire, cable coated material and the oil resistant that is required
, it is preferable to use the polyolefin-based resins containing vinyl acetate ester group, specifically ethylene-from the perspective of property, anti-flammability etc.
Vinyl acetate copolymer (EVA).
Vinyl-vinyl acetate copolymer (EVA) is the copolymer of ethylene and vinyl acetate (VA).In view of with it is aftermentioned
The workability such as compatibility, the viscosity of the silane coupling agent containing methylacryloyl, VA amounts in polymer with 10wt%~
60wt% or so is preferred.In addition, as resin, the polyolefin-based resins containing vinyl acetate ester group such as EVA and its can be used
The mixture of his Halogen resin.
Silane coupling agent has unsaturated keyness group and hydrolysable silanes base.Silane coupling agent passes through unsaturated keyness base
It rolls into a ball and is graft-polymerized in Halogen resin, to which silylation is imported resin.Then, Silane Grafted resin is made by being contacted with water
Hydrolysable silanes base is hydrolyzed into silanol group, silanol group dehydrating condensation each other forms cross-linked structure.
Here, in present embodiment, as the unsaturated keyness group of silane coupling agent, there is methylacryloyl (H2C
=C (CH3)-CO-).It, can by carrying out grafting processing using the silane coupling agent with methylacryloyl in this way
Reduce the localization of graft.As a result, can inhibit in the grafting portion to have localized because of the mutual condensation institute of silane
Caused undesirable cross-linking reaction (cross-linking reaction before crosslinking Treatment).Thereby, it is possible to reduce be used as electric wire, cable it is coating
Bad order when material.
As hydrolysable silanes base, it can enumerate to have and be capable of water formal similarity such as alkoxy, acyloxy, phenoxy group
Group.As the silylation for capableing of water formal similarity with these, it can be mentioned, for example alkoxysilyl, acyloxy monosilanes
Base, phenoxy group silicyl etc..
As silane coupling agent, it is preferable to use 3- methacryloxypropyl trimethoxy silanes, 3- methyl-props
Alkene acryloxypropylethoxysilane triethoxysilane.About other silane coupling agents, as described later.
Relative to 100 mass parts Halogen resins, the use level of silane coupling agent is preferably 0.1 mass parts or more, 10 mass parts
Hereinafter, more than more preferably 1.0 mass parts 5.0 below mass part.If use level is less than 0.1 mass parts, it is graft-polymerized
Silane coupling agent tails off, thus there is the worry for making not obtaining the sufficient degree of cross linking when silane grafted composition crosslinked with silicane.
On the other hand, if it exceeds 10 mass parts, then be easy to carry out partial cross-linking, exist and generate concave-convex load on the surface of formed body
Sorrow.
Peroxide is for making silane coupling agent be graft-polymerized in the ingredient of Halogen resin.Specifically, peroxide
Oxygen radical is generated due to thermal decomposition.Oxygen radical is by capturing the hydrogen in Halogen resin (such as EVA), to generate Halogen
The free radical of resin (such as EVA).Then, pass through unsaturated bond possessed by Halogen resin (such as EVA) and silane coupling agent
Property group (methylacryloyl etc.) react, to generate Silane Grafted resin (such as Silane Grafted EVA).
It, can be with use example such as organic peroxide as peroxide.The ability for capturing hydrogen of organic peroxide is strong.Tool
The peroxide of body is as described later.
Furthermore it is preferred that with the compounding ratio (Rc) of silane coupling agent and peroxide become range appropriate (such as 1.5~
20) mode is adjusted.
The compounding ratio (Rc) of the silane coupling agent and peroxide is shown below.
Rc=(WS/MS)/(2 α WO/MO)
WS is the use level (g) of silane coupling agent, and WO is the use level (g) of peroxide, and MS is point of silane coupling agent
Son amount, MO are the molecular weight of peroxide, and α is the o-o bond number of every 1 molecule peroxide.
Adjustment in this way, it can be ensured that the free base unit weight generated by the decomposition of peroxide can keep grafting anti-
While should fully carrying out, inhibit undesirable cross-linking reaction when grafting processing.Details is as described later.
(additive)
Other than Silane Grafted resin, Silane Grafted resin combination can also contain additive as shown below.
<Silanol condensation catalyst>
Silanol condensation catalyst, which has, to be promoted the reaction of crosslinked with silicane, Silane Grafted resin combination is made effectively to be crosslinked
Effect.
As silanol condensation catalyst, such as magnesium, Gai Deng II races element can be used, the VIII group element such as cobalt, iron,
The metallic elements such as tin, zinc and titanium；Metallic compound containing these elements.Further, it is also possible to use octanoic acid, the metal of adipic acid
Salt, amine compound, acid etc..Specifically, as metal salt, two neodecanoic acid ester of dioctyl tin, dibutyl tin two can be used
Laurate, dibutyltin bisacetate, dibutyl tin dicaprylate, stannous acetate, stannous octoate, lead naphthenate, zinc octoate,
Cobalt naphthenate etc..As amine compound, ethamine, dibutylamine, hexylamine, pyridine etc. can be used.As acid, sulphur can be used
The inorganic acids such as acid, hydrochloric acid, the organic acids such as toluenesulfonic acid, acetic acid, stearic acid, maleic acid.
<Antioxidant>
As antioxidant, amine antioxidant, sulfur antioxidant etc. can be used.
<Colorant>
As colorant, carbon black etc. can be used.
<Fire retardant>
As fire retardant, metal hydroxides etc. can be used.
<Other additives>
As other additives, plasticizer, filler, lubricant, anti-copper evil colour-changing agent, crosslinking coagent, steady can be used
Determine agent etc..
(2) manufacturing method of Silane Grafted resin combination
Silane coupling agent is set to be graft-polymerized in Halogen resin.Such as peroxidating two of the addition as peroxide in EVA
Isopropylbenzene and silane coupling agent with methylacryloyl, heating are kneaded.Make in the presence of peroxide with first as a result,
The silane coupling agent of base acryloyl group is graft-polymerized in EVA, forms Silane Grafted EVA.
Next, in the middle mixing various additives of Halogen resin (Silane Grafted EVA) for having silane coupling agent that are graft-polymerized,
It is kneaded, to manufacture Silane Grafted resin combination.
(3) manufacturing method of electric wire and cable
Fig. 1 is the sectional view for the structure for showing electric wire, and Fig. 2 is the sectional view for the structure for showing cable.
As shown in Figure 1, electric wire 1 has the insulating layer 11 of conductor 10 and coated conductor 10.In addition, as shown in Fig. 2, cable 2
Serving (restrictive coating) 12 with electric wire 1 and coated electric wire 1.
As said wires, the coated material (insulating layer 11, serving 12) of cable, above-mentioned Silane Grafted resin can be used
The cross-linking agent of composition.
For example following manufacture of electric wire 1.First, prepare copper wire as conductor 10.Then, using extruder, by aforementioned silane
Graft resin composition is squeezed out in a manner of 10 periphery of coated conductor, forms the insulating layer 11 of predetermined thickness.Then, by will be exhausted
Edge layer 11 is exposed to such as 60 DEG C of saturated steam atmosphere, to make to be formed the Silane Grafted resin combination of insulating layer 11 with
Reaction of moisture simultaneously carries out crosslinked with silicane.In addition, similarly, by by aforementioned silane graft resin composition with coated electric wire 1
The mode of (10,11) periphery squeezes out, and the serving (restrictive coating) 12 of predetermined thickness is formed, so as to form cable 2.In Fig. 2
The cable 2 with 1 electric wire is shown, but can also be with 2 or more electric wires.Such as can also by 2 to power on
It twists thread made of line is twisted periphery, serving (restrictive coating) 12 is formed in object etc. across being situated between.
Embodiment
Next, being illustrated to the embodiment of the present invention.
The material used in embodiment and comparative example is as follows.
Halogen resin：Vinyl-vinyl acetate copolymer (MFR [190 DEG C, 2.16kg load]：6.0 (g/10min), second
Vinyl acetate content：28 (wt%), fusing point：2℃)
Peroxide：Cumyl peroxide
Silane coupling agent：Vinyltrimethoxysilane, 3- methacryloxypropyl trimethoxy silanes, 3- methyl
Acryloxypropyl triethoxysilane
Antioxidant：Sulfur antioxidant, amine antioxidant
Fire retardant：Surface conditioning agent different metal hydroxides A, B
Colorant：Carbon black
Silanol condensation catalyst：Two neodecanoic acid ester of dioctyl tin
(1) modulation of Silane Grafted resin combination
In Examples 1 to 4, comparative example 1~4, using above-mentioned material, it is formulated according to shown in table 1 " Silane Grafted " column,
Grafting processing is carried out, to modulate Silane Grafted resin, then, is formulated according to shown in " additive mixing " column, with addition
Agent mixes, to modulate Silane Grafted resin combination.Embodiment 1 is specifically described below.Each treatment conditions are one
Example.
(grafting processing)
Before grafting processing, vinyl-vinyl acetate copolymer (EVA) is implemented to pre-process.
Specifically, as shown in table 1,100 mass parts EVA are kneaded using 8 inch roller machines.At this point, by the surface temperature of roller
Degree is set as 100 DEG C, is kneaded 5 minutes.Then, the sheet material that mixing obtains is granulated into the shape of 5mm square, is obtained containing EVA's
Pellet.
Next, implementing grafting processing to obtained pellet.Specifically, in polybag, in obtained pellet
Impregnation makes peroxide be dissolved in silane mixture obtained from silane coupling agent.At this point, as shown in table 1, with relative to 100 matter
Part EVA is measured, peroxide becomes 0.1 mass parts, silane coupling agent and is impregnated with silane in pellet as the mode of 3.92 mass parts
Mixture.It then, will be containing the 101 input machine of hopper for being soaked with the single screw extrusion machine 100 of the pellet of silane mixture as shown in Figure 3
In cylinder 103a, machine barrel 103b is sent to by machine barrel 103a using the rotation of screw rod 102.At this point, by by pellet machine barrel 103a,
It is heated in 103b and carries out softening mixing, to make silane coupling agent be graft-polymerized in EVA.Silane Grafted EVA is consequently formed.So
Afterwards, Silane Grafted EVA is sent to the die section 104 of single screw extrusion machine 100, the beam of Silane Grafted EVA is squeezed out by mold 105
(strand) 20 (length 150cm).Then, beam 20 is imported in sink 106 and carries out water cooling, removed using air wiper 107
Moisture.Then, beam 20 is granulated using comminutor 108, obtains the Silane Grafted processed material of partical.
In addition, using the single screw extrusion machine 100 of screw diameter 40mm in grafting processing.In addition, by screw diameter D and spiral shell
The ratio L/D of pole length L is set as 25.In addition, the temperature of machine barrel 103a is set as 80 DEG C, the temperature of machine barrel 103b is set as 200
DEG C, the temperature of die section 104 is set as 200 DEG C.In addition, the rotating speed of screw rod 102 is set as 20rpm (about 120g/ points of extrusion capacities
Clock), screw rod 102 is set as full thread shape, compression ratio is set as 2.0.In addition, as mold 105, aperture diameter 5mm, hole are used
The mold that number is 3.
(additive mixing process)
Next, being kneaded above-mentioned Silane Grafted processed material (Silane Grafted EVA) and additive using 8 inch roller machines, obtain
To the additive mixture of sheet.In addition, as additive, it is anti-oxidant that 2.5 mass parts of sulfur antioxidant, amine system are added respectively
1.5 mass parts of agent, 5 matter of 35 mass parts of metal oxide A, 65 mass parts of metal oxide B and carbon black as fire retardant
Measure part.In addition, when being kneaded, the surface temperature of roller is set as 170 DEG C, is kneaded 5 minutes, obtains after having put into whole additives
The sheet material of above-mentioned additive mixture.Obtained sheet material is granulated into the shape of 5mm square, the additive for obtaining partical is mixed
Refine object.
(modulation of catalyst masterbatch)
Next, other than above-mentioned Silane Grafted processed material (Silane Grafted EVA), in addition modulation contains silanol condensation
The catalyst masterbatch of catalyst.
Specifically, as shown in table 1 " catalyst masterbatch " column, relative to the EVA of 99 mass parts, 1 mass parts are added
Silanol condensation catalyst is kneaded using 8 inch roller machines.At this point, the surface temperature of roller is set as 80 DEG C, it is being added to silicon
It is kneaded 3 minutes after alkanol condensation catalyst, obtains the sheet material formed by mixture.Then, obtained sheet material is granulated into
The shape of 5mm square, has modulated catalyst masterbatch.
(modulation of Silane Grafted resin combination)
Finally, dry-mixed by adding the catalyst masterbatch progress of 5 mass parts in above-mentioned additive mixture, modulate reality
Apply the Silane Grafted resin combination of example 1.
The amount for changing silane coupling agent, peroxide as shown in table 1, with above-described embodiment 1 the case where in the same manner as operate, adjust
Made embodiment 2~3, comparative example 1~4 Silane Grafted resin combination (table 1).In addition, in table 1, it is with silane coupling agent
Equimolar mode adjusts use level.
(2) making of electric wire
Next, the Silane Grafted resin combination using Examples 1 to 4, comparative example 1~4 makes electric wire.
Specifically, sectional area of the insert as conductor 10 in the mold 105 of single screw extrusion machine 100 shown in Fig. 4
8mm2Copper conductor (outer diameter 3.7mm), squeeze out the aforementioned silane graft resin composition that is put by hopper 101, shape in its periphery
At the insulating layer (coated material) of thickness 1.0mm, to make electric wire.Then, by electric wire 1 in temperature 60 C, relative humidity 95%
Constant temperature and humidity cabinet in preserve 24 hours, so that insulating layer is crosslinked.
In addition, using the single screw extrusion machine 100 of 20mm single screw rods in the making of electric wire 1.In addition, by screw diameter D with
The ratio L/D of spiro rod length L is set as 15.In addition, the temperature of machine barrel 103a is set as 150 DEG C, the temperature of machine barrel 103b is set as
180 DEG C, the temperature of machine neck 109 is set as 180 DEG C, the temperature in cross-head dies portion 110 is set as 180 DEG C, by the temperature of mold 105
It is set as 180 DEG C.In addition, the rotating speed of screw rod 102 is set as 15rpm, the shape of screw rod 102 is set as full thread shape.
(3) evaluation method
By the following method, for the Silane Grafted resin combination and electric wire of Examples 1 to 4, comparative example 1~4, evaluation
Appearance and gel fraction.Gel fraction is the index for the degree of cross linking for indicating material.
(appearance)
For the insulating layer (coated material) of said wires, appearance is evaluated by range estimation.Specifically, for electric wire
Very smooth situation is set as " ◎ " by the surface state of insulating layer, it will be observed that as coated material, that there is no problem is horizontal thick
The case where rough (Roughness etc.), as "○", as " △ ", will will produce significant table the case where producing rough surface
The coarse situation in face is as "×" (with reference to table 1 " coated material appearance " column).Wherein, " ◎ " "○" is set as " qualification ", it will
" △ " "×" is set as " bad order ".
(the front and back gel fraction of crosslinking)
Measure Examples 1 to 4, comparative example 1~4 Silane Grafted resin combination crosslinking before and after gel fraction.It is right
In above-mentioned Silane Grafted processed material and above-mentioned mixing process object, the gel fraction before crosslinking is measured.Gel fraction after crosslinking makes
It is measured with the insulating layer of said wires.
Specifically, the gel fraction before crosslinking measures by the following method.First, from above-mentioned Silane Grafted processed material or on
It states mixing process object and obtains 0.5g samples, which is put into the brass metal mesh of 40 mesh.Then, to sample at 110 DEG C
Oil bath in dimethylbenzene carry out extraction processing 24 hours.After extraction processing, remaining sample is taken out from dimethylbenzene, it is naturally dry
After a dry night, it is dried in vacuo 4 hours at 80 DEG C.Then, the quality after the drying of residual sample is weighed, based on before xylene extraction
Sample quality (charge) W1 and carried out xylene extraction and it is dry after sample quality W2, pass through following formula (1)
Calculate the gel fraction F1 of sample.
F1 (%)=(W2/W1) × 100 ... (1)
For the gel fractions after crosslinking, 0.5g samples are obtained from the insulating layer of said wires, are operated as described above,
It carries out xylene extraction, drying, quality (charge) W1 based on the sample before xylene extraction and has carried out xylene extraction
With the quality W2 of the sample after drying, the gel fraction F2 of sample is calculated by following formula (2).
F2 (%)=(W2-W1 × (z/x))/× 100 ... (2) (W1 × (y/x))
In formula (2), x is total use level (parts by weight), and y is basic polymer complex amount (parts by weight), and z is metal hydroxide
Object use level (parts by weight).As above, gel fraction after the crosslinking of formula (2) defined is calculated with following polymer gel
, in the polymer gel, metal hydroxides (100 parts by weight) is not counted in gel as the ingredient insoluble in dimethylbenzene
Ingredient.
In the present embodiment, the situation that the gel fraction after crosslinking is 50% or more is set as qualified "○", will be less than 50%
The case where be set as bad "×".In addition, with the gel of the gel fraction of above-mentioned Silane Grafted processed material and above-mentioned mixing process object
It is reference value to divide rate, is shown in " after Silane Grafted " column, " after additive is kneaded " column of table 1.
(4) judge
It will judge (overall merit) bottom column shown in table 1.Gel fraction after appearance and crosslinking is both qualified
The case where be set as good (zero), the bad situation of any evaluation is set as can not (×).The judgement of Examples 1 to 4 is good (zero), than
Judgement compared with example 1~4 is can not (×).
[table 1]
In embodiment 1, in the EVA of 100 parts by weight, the 3- methacryloxypropyls as silane coupling agent are mixed
3.92 parts by weight of triethoxysilane, 0.1 parts by weight of cumyl peroxide as peroxide, carry out grafting processing.Silicon
The gel fraction that alkane is grafted processed material is 2%, does not find special problem in Silane Grafted operation.In addition, having with using
It is compared when silane coupling agent (such as vinyltrimethoxysilane) of vinyl, the irritation gas generated by silane coupling agent
Taste is few, and operation environment protection is not pinpointed the problems.In addition, the gel fraction (polymer gel) of additive mixture is 15%, sheet
The appearance of additive mixture does not observe special exception.There is catalyst masterbatch by dry-mixed in the above-mentioned additive mixture
Pellet (Silane Grafted resin combination) puts into extruder and makes electric wire, and as a result the appearance of electric wire is very smooth, at 60 DEG C
In saturated steam crosslinking Treatment for 24 hours after gel fraction (polymer gel) be 56%, be the sufficient degree of cross linking.
In embodiment 2, in the EVA of 100 parts by weight, the 3- methacryloxypropyls as silane coupling agent are mixed
3.35 parts by weight of trimethoxy silane, 0.1 parts by weight of cumyl peroxide as peroxide, carry out grafting processing.Silicon
The gel fraction that alkane is grafted processed material is 3%, does not find special problem in Silane Grafted operation.In addition, having with using
It is compared when silane coupling agent (such as vinyltrimethoxysilane) of vinyl, the irritation gas generated by silane coupling agent
Taste is few, and operation environment protection is not pinpointed the problems.In addition, the gel fraction (polymer gel) of additive mixture is 17%, sheet
The appearance of additive mixture does not observe special exception.There is catalyst masterbatch by dry-mixed in the above-mentioned additive mixture
Pellet (Silane Grafted resin combination) puts into extruder and makes electric wire, and as a result the appearance of electric wire is very smooth, at 60 DEG C
In saturated steam crosslinking Treatment for 24 hours after gel fraction (polymer gel) be 57%, be the sufficient degree of cross linking.
In embodiment 3, in the EVA of 100 parts by weight, the 3- methacryloxypropyls as silane coupling agent are mixed
3.35 parts by weight of trimethoxy silane, 1.0 parts by weight of cumyl peroxide as peroxide, carry out grafting processing.Silicon
The gel fraction that alkane is grafted processed material is 8%, does not find special problem in Silane Grafted operation.In addition, having with using
It is compared when silane coupling agent (such as vinyltrimethoxysilane) of vinyl, the irritation gas generated by silane coupling agent
Taste is few, and operation environment protection is not pinpointed the problems.In addition, the gel fraction (polymer gel) of additive mixture is 22%, sheet
The appearance of additive mixture does not observe special exception.There is catalyst masterbatch by dry-mixed in the above-mentioned additive mixture
Pellet (Silane Grafted resin combination) puts into extruder and makes electric wire, and as a result the appearance of electric wire is very smooth, at 60 DEG C
In saturated steam crosslinking Treatment for 24 hours after gel fraction (polymer gel) be 69%, be the sufficient degree of cross linking.
In embodiment 4, in the EVA of 100 parts by weight, the 3- methacryloxypropyls as silane coupling agent are mixed
3.35 parts by weight of trimethoxy silane, 1.25 parts by weight of cumyl peroxide as peroxide, carry out grafting processing.Silicon
The gel fraction that alkane is grafted processed material is 15%, although observing that several discharges is uneven, workability is not pinpointed the problems.This
Outside, compared with when using silane coupling agent (such as vinyltrimethoxysilane) with vinyl, due to silane coupling agent
The penetrating odor of generation is few, does not find special problem in Silane Grafted operation.In addition, the gel of additive mixture point
Rate (polymer gel) is 28%, and the appearance of sheet additive mixture does not observe special exception.It will be in above-mentioned additive
It is dry-mixed in mixture to have pellet (Silane Grafted resin combination) the input extruder of catalyst masterbatch and make electric wire, it is as a result electric
The visual inspection of line arrived it is several coarse, but for as the coated material level that there is no problem, in 60 DEG C of saturated steam
Crosslinking Treatment for 24 hours after gel fraction (polymer gel) be 72%, be the sufficient degree of cross linking.
In comparative example 1, in the EVA of 100 parts by weight, the vinyltrimethoxysilane 2 as silane coupling agent is mixed
Parts by weight, 0.05 parts by weight of cumyl peroxide as peroxide, carry out grafting processing.Silane Grafted processed material is coagulated
Glue divides rate to be 0%, but has the penetrating odor caused by the vinyltrimethoxysilane to volatilize when Silane Grafted operation, needs
It is useful for improving the countermeasure of operating environment.In addition, the gel fraction (polymer gel) of additive mixture is 42%, sheet adds
The visual inspection of agent mixture is added to arrive significant coarse.By the dry-mixed grain for having catalyst masterbatch in above-mentioned additive mixture
Material (Silane Grafted resin combination) puts into extruder and makes electric wire, and as a result the appearance of electric wire also observed significant thick
It is rough, to be judged as that as coated material be bad order.In addition, in 60 DEG C of saturated steam crosslinking Treatment for 24 hours after
Gel fraction (polymer gel) is 67%, is the sufficient degree of cross linking.
In comparative example 2, in the EVA of 100 parts by weight, the vinyltrimethoxysilane 2 as silane coupling agent is mixed
Parts by weight, 0.1 parts by weight of cumyl peroxide as peroxide, carry out grafting processing.Silane Grafted processed material is coagulated
Glue divides rate to be 22%, but has the penetrating odor caused by the vinyltrimethoxysilane to volatilize when Silane Grafted operation, needs
It is useful for improving the countermeasure of operating environment.In addition, the gel fraction (polymer gel) of additive mixture is 54%, sheet
The visual inspection of additive mixture has arrived significant coarse.There is catalyst masterbatch by dry-mixed in the above-mentioned additive mixture
Pellet (Silane Grafted resin combination) puts into extruder and makes electric wire, and as a result the appearance of electric wire also observed significant thick
It is rough, to be judged as that as coated material be bad order.In addition, in 60 DEG C of saturated steam crosslinking Treatment for 24 hours after
Gel fraction (polymer gel) is 72%, is the sufficient degree of cross linking.
In comparative example 3, in the EVA of 100 parts by weight, the 3- methacryloxypropyls as silane coupling agent are mixed
3.35 parts by weight of trimethoxy silane, 0.05 parts by weight of cumyl peroxide as peroxide, carry out grafting processing.Silicon
The gel fraction that alkane is grafted processed material is 0%, does not find special problem in Silane Grafted operation.In addition, with using with second
It is compared when silane coupling agent (such as vinyltrimethoxysilane) of alkenyl, the penetrating odor generated by silane coupling agent
Few, operation environment protection is not pinpointed the problems.In addition, the gel fraction (polymer gel) of additive mixture is 16%, sheet adds
The appearance of agent mixture is added not observe special exception.By the dry-mixed grain for having catalyst masterbatch in above-mentioned additive mixture
Material (Silane Grafted resin combination) puts into extruder and makes electric wire, and as a result the appearance of electric wire is very smooth, in 60 DEG C satisfy
With crosslinking Treatment in vapor for 24 hours after gel fraction (polymer gel) be 43%, observe the reduction of the degree of cross linking.
In comparative example 4, in the EVA of 100 parts by weight, the 3- methacryloxypropyls as silane coupling agent are mixed
3.35 parts by weight of trimethoxy silane, 1.5 parts by weight of cumyl peroxide as peroxide, carry out grafting processing.Silicon
The gel fraction that alkane is grafted processed material is 23%, observes that discharge is uneven, thus can consider workability there are some problems.But
It is, compared with when using silane coupling agent (such as vinyltrimethoxysilane) with vinyl, due to silane coupling agent
The penetrating odor of generation is few, and operation environment protection is not pinpointed the problems.In addition, (polymer is solidifying for the gel fraction of additive mixture
Glue) it is 36%, the visual inspection of sheet additive mixture has arrived coarse.There is catalyst by dry-mixed in above-mentioned additive mixture
The pellet (Silane Grafted resin combination) of masterbatch puts into extruder and makes electric wire, and as a result the visual inspection of electric wire has arrived slightly
It is rough, to be judged as that as coated material be bad order.In addition, in 60 DEG C of saturated steam crosslinking Treatment for 24 hours after
Gel fraction (polymer gel) is 79%, is the sufficient degree of cross linking.
By above-mentioned Comparative Examples 1 and 2, Examples 1 to 4 as it can be seen that with use vinyltrimethoxysilane as silane coupling agent
The case where compare, by using the silane coupling agent with methylacryloyl, the bad order of the coated material of electric wire is subtracted
It is few.
By having used the Silane Grafted processed material of vinyltrimethoxysilane to constitute electric wire as above-mentioned Comparative Examples 1 and 2
Coated material in the case of, bad order can be caused.In addition, in above-mentioned Comparative Examples 1 and 2, relative to the solidifying of Silane Grafted processed material
Glue divides rate, the gel fraction of mixing process object to be substantially increased.
According to the above phenomenon, it is believed that bad order is influenced by following factor：
<<1>>The compatibility of silane coupling agent and resin when grafting processing；
<<2>>The progress of undesirable cross-linking reaction when mixing additive.
For above-mentioned<<1>>, compared with the silane coupling agent with methylacryloyl, contain the silane coupled of vinyl
Agent (such as vinyltrimethoxysilane) is low with the compatibility of Halogen resin (such as EVA), therefore the grafting of silane coupling agent
Part is easy localization.It then,, can be due to the mutual condensation of silane in the grafting portion to have localized when being kneaded additive
And carry out undesirable cross-linking reaction.
As described above, other than hydrolization group as alkoxy, silane coupling agent also has (to be polymerize with resin
Object) combine functional group's (unsaturated keyness group).According to the difference of the type of the functional group, solubility parameter can become
Change.The solubility parameter is the numerical value calculated according to molecular structure, is learnt by experience, in storeroom not of the same race, numerical value more it is close then
Compatibility is higher.The difference of solubility parameter is then more probably within 1.0 to show preferable compatibility.
Although additionally depending on such as vinyl acetate content, the solubility parameter of EVA is 9.0~9.5 or so.Relative to
This, the solubility parameter of the silane coupling agent (vinyl silanes) with vinyl is 7.5, low with the compatibility of EVA.Another party
Face, it is 8.7 to contain methylacryloyl as the solubility parameter of the silane coupling agent (methacryl base silane) of functional group,
It is high with the compatibility of EVA.
Therefore, in the case of having carried out grafting processing to EVA using methacryl base silane, their compatibility is high,
Thus silane coupling agent more combines (grafting) in EVA molecules in heterogeneity.Therefore, for above-mentioned<<2>>, mixing can be inhibited to add
Add cross-linking reaction when agent (metal hydroxides especially in fire retardant).
In particular, there are the low tendencies of the anti-flammability of resin itself for the Halogens such as EVA resin, in the quilt applied to electric wire, cable
In the case of covering material, more fire retardant can be mostly added.The additive amount of fire retardant is, for example, parts by weight of 50 parts by weight~250 or so.
As above, in the case where adding fire retardant, cross-linking reaction when can also inhibit to mix fire retardant.
In turn, according to above-mentioned comparative example 3,4, Examples 1 to 4, use methacryl base silane as silane coupled
In the case of agent, if the adding proportion of peroxide when grafting processing is very few, the gel fraction after crosslinking understands that some are small,
The degree of cross linking can slightly reduce (comparative example 3).On the contrary, if the adding proportion of peroxide is excessive, cross-linking reaction when being grafted processing
It is easy to carry out, the surface of coated material will produce coarse (comparative example 4).But it is not significantly coarse as Comparative Examples 1 and 2.
In above-described embodiment 1~4, the compounding ratio (Rc) of silane coupling agent and peroxide is respectively 18.2,18.2,
1.8,1.5 (table 1).It is preferred that in this way, compounding ratio (Rc) is adjusted to range appropriate (such as 1.5~20).Pass through
Such adjustment, it can be ensured that the free base unit weight generated due to the decomposition of peroxide, can make graft reaction fully into
While row, inhibit undesirable cross-linking reaction when grafting processing.
Use cumyl peroxide as peroxide in above-described embodiment, but not limited thereto.Peroxidating two is different
The hydrogen-taking capacity of propyl benzene is high, one minute half life temperature is about 175 DEG C, is preferably used as peroxide.In addition to this, it is preferable to use
The peroxide that hydrogen-taking capacity is higher, one minute half life temperature is 120 DEG C~200 DEG C.
If it is considered that graft reaction time when manufacture, then it is 150 DEG C~200 more preferably to use one minute half life temperature
DEG C peroxide.Specifically, as peroxide, 1,1- bis- (tert-butyl hydroperoxide) hexamethylene, tertiary butyl can be used
Isopropyl peroxide carbonic ester, t-amyl peroxy butylperoxyisopropyl carbonate, 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) oneself
Alkane, di-tert-butyl peroxide, two t-amyl peroxy compounds, 1,1- bis- (t-amyl peroxy) hexamethylene, tert-butyl hydroperoxide
2- ethylhexyl carbonates etc..In addition, these peroxide can be used alone, it can also be in the form of combination of more than two kinds
It uses.
3- methacryloxypropyls, 3- methacryloxypropyls are used in above-described embodiment
Trimethoxy silane is as methacryl base silane, alternatively, it is also possible to use 3- methacryloyloxypropyl methyl diformazans
Oxysilane, 3- methacryloxypropyl methyl diethoxysilanes etc..In addition, as silane coupling agent, these silane
Compound can be used alone, and can also be used in the form of combination of more than two kinds.
In addition, if contain above-mentioned methacryl base silane, then can also in silane coupling agent mixed ethylene base silicon
Other silane compounds such as alkane and use.
It uses EVA as Halogen resin in above-described embodiment, other polyolefin-based resins, such as ethylene propylene can also be used
Olefin(e) acid methacrylate copolymers (EEA), ethylene methyl acrylate copolymer (EMA), alpha olefin copolymer, polyethylene, polypropylene, ethylene
The mixture etc. of propylene copolymer, propylene diene copolymer and their modifier, these substances.
It uses metal hydroxides as fire retardant in above-described embodiment, such as phosphorus flame retardant, phosphorus can be used
Acid esters, (poly-) ammonium phosphate, red phosphorus etc.；As boric acid flame retardant, borax, zinc borate, poly- Boratex etc. can be used；As containing
Nitrogenated flame retardant can use melamine cyanurate, guanidine compound, triaizine compounds, ammonium phosphate, ammonium carbonate etc.；As
Silicone flame retardant can use organic siliconresin etc.；As other fire retardants, zinc stannate, molybdenum compound etc. can be used.
The structure and size of the electric wire made in the above-described embodiments are an examples, are not limited to this.In addition, above-mentioned
It in embodiment, has used Silane Grafted EVA as the coated material of electric wire, but Silane Grafted EVA can also be used as cable
Coated material.
In addition, in above-described embodiment, roller machine, extruder are used in grafting processing, mixing process, but in addition to this,
Kneader, mixer, autoclave etc. can also be used.In addition, above-mentioned grafting processing, mixing process treatment conditions (temperature, when
Between etc.) it is an example, it is not limited to these conditions.
In above-described embodiment, temperature 60 C, relative humidity 95% constant temperature and humidity cabinet in preserve 24 hours and carry out
Crosslinking Treatment, but as crosslinking Treatment, as long as being acted at least through the coated material of moisture and electric wire etc. and carrying out cross-linking reaction i.e.
Can, specific crosslinking condition can suitably change.Such as the conditions such as humidity, temperature, time can suitably change, such as in addition to perseverance
Other than constant temperature and humidity slot, vaporium can also be utilized or simply rest on the medium processing place of indoor or outdoors of building.
As it appears from the above, the present invention is not limited to the above-described embodiment and examples, it, can in range without departing from the spirit
To make various changes.
[note 1]
A kind of manufacturing method of Silane Grafted resin combination, has：
(a) process by making silane compound with forming Silane Grafted resin by Halogen resin graft reaction；
(b) additive is added in the Silane Grafted resin and is kneaded, to form the work of additive mixture
Sequence,
The silane compound has unsaturated keyness group and hydrolysable silanes base,
The unsaturation keyness group is methylacryloyl,
The range that the compounding ratio (Rc) of silane coupling agent and peroxide shown in following formula is 1.5~20.
Rc=(WS/MS)/(2 α WO/MO)
Wherein, WS is the use level (g) of silane coupling agent, and WO is the use level (g) of peroxide, and MS is silane coupling agent
Molecular weight, MO be peroxide molecular weight, α be every 1 molecule peroxide o-o bond number.
[note 2]
According to the manufacturing method of the Silane Grafted resin combination of note 1, have：
(c) process that silanol condensation catalyst is added in the additive mixture.
[note 3]
The manufacturing method of a kind of electric wire or cable has note 1 or is attached 2 Silane Grafted resin combination and is coated on
Conducting wire or electric wire periphery implement to act on come the process of the crosslinking Treatment carried out by the Silane Grafted resin combination and water.
Claims (7)
1. a kind of Silane Grafted resin combination, contain makes silane compound and Halogen resin graft reaction using peroxide
Obtained by Silane Grafted resin and additive,
The silane compound has unsaturated keyness group and hydrolysable silanes base,
The unsaturation keyness group is methylacryloyl,
The range that the compounding ratio Rc of silane coupling agent and peroxide shown in following formula is 1.5~20,
Rc=(WS/MS)/(2 α WO/MO)
Wherein, WS is the use level of silane coupling agent, and WO is the use level of peroxide, and MS is the molecular weight of silane coupling agent,
MO is the molecular weight of peroxide, and α is the o-o bond number of every 1 molecule peroxide, and the unit of the use level is g.
2. Silane Grafted resin combination according to claim 1, wherein the gel fraction after crosslinking is 50% or more.
3. Silane Grafted resin combination according to claim 1, wherein the Halogen resin contains ethylene-acetate second
Enoate copolymer.
4. Silane Grafted resin combination according to claim 3, wherein the silane compound is 3- methacryls
Oxygroup propyl trimethoxy silicane or 3- methacryloxypropyls.
5. Silane Grafted resin combination according to claim 4, wherein the additive is fire retardant.
6. a kind of electric wire has and is formed by the cross-linking agent of Silane Grafted resin combination according to any one of claims 1 to 5
Insulating layer.
7. a kind of cable has and is formed by the cross-linking agent of Silane Grafted resin combination according to any one of claims 1 to 5
Serving.
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| JP2017-035970 | 2017-02-28 | ||
| JP2017035970A JP6951658B2 (en) | 2017-02-28 | 2017-02-28 | Silane graft resin composition, electric wires and cables |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004034A1 (en) * | 1978-03-03 | 1979-09-19 | The Furukawa Electric Co., Ltd. | Method of crosslinking poly-alpha-olefin series resins |
| JPS62177046A (en) * | 1986-01-31 | 1987-08-03 | Nippon Telegr & Teleph Corp <Ntt> | Acid-resistant flame-retardant resin composition |
| CN101880417A (en) * | 2010-06-29 | 2010-11-10 | 武汉新天地特种电缆有限公司 | Silane crosslinked halogen-free flame-retardant polyethylene cable material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6758077B2 (en) * | 2016-04-21 | 2020-09-23 | リケンテクノス株式会社 | Thermoplastic resin composition for wire coating and heat-resistant wire |
-
2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004034A1 (en) * | 1978-03-03 | 1979-09-19 | The Furukawa Electric Co., Ltd. | Method of crosslinking poly-alpha-olefin series resins |
| JPS62177046A (en) * | 1986-01-31 | 1987-08-03 | Nippon Telegr & Teleph Corp <Ntt> | Acid-resistant flame-retardant resin composition |
| CN101880417A (en) * | 2010-06-29 | 2010-11-10 | 武汉新天地特种电缆有限公司 | Silane crosslinked halogen-free flame-retardant polyethylene cable material and preparation method thereof |
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