CN104893059A - Silane crosslinking polyolefin resin composition, electric wire and cable - Google Patents
Silane crosslinking polyolefin resin composition, electric wire and cable Download PDFInfo
- Publication number
- CN104893059A CN104893059A CN201510066751.8A CN201510066751A CN104893059A CN 104893059 A CN104893059 A CN 104893059A CN 201510066751 A CN201510066751 A CN 201510066751A CN 104893059 A CN104893059 A CN 104893059A
- Authority
- CN
- China
- Prior art keywords
- polyolefin resin
- silane
- resin combination
- weight part
- silane compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Conductors (AREA)
Abstract
The invention provides a silane crosslinking polyolefin resin composition without Sn and with good appearance and insulativity and capable of crosslinking fast and reliably, an electric wire and a cable. Provided is the silane crosslinking polyolefin resin composition, the electric wire and the cable. The silane crosslinking polyolefin resin composition is characterized in that the silane crosslinking polyolefin resin composition is the resin composition without Sn, relative to 100 weight part of polyolefin with the density under 0.920g/cm<3>, contains 0.1-1 part of alkylated naphthalene sulfonic acid, and 1.5-5 parts of silane compound. The weight ratio of the silane compound and free radical generating agent (silane compound/free radical generating agent) is 25-100.
Description
Technical field
The present invention relates to silane cross-linked polyolefin resin combination, electric wire and cable.
Background technology
At present, in also known as the coating material of electric wire or cable etc. silane cross-linked polyolefin resin combination, in catalyzer when carrying out the silanol condensation as the reaction producing crosslinked with silicane, use the situation many (such as patent documentation 1 or patent documentation 2) of Sn compound.This is because when adopting Sn compound as this catalyzer, rate of crosslinking when can guarantee high degree of crosslinking, normal temperature and good extrude outward appearance.
And on the other hand, in recent years, so-called Pb (lead) or the element such as Hg (mercury), Cd (cadmium) are designated as ROHS banned substance.Not only ROHS banned substance as above, and for various metallic element, all problem is regarded as to the toxic of human body.Such as, organic Sn (tin) compound is likely equivalent to environmental hormone.Be conceived to this point, by applicant has developed following technology: as the catalyzer of silanol condensation, use inorganic tin (Sn) compound, and as promotor, use containing Sn (after, be called " without Sn (Sn-free) ".) organic acid compound (such as patent documentation 3).
Wherein, also there will be a known the sulfo group that has as strong acid and the Witco 1298 Soft Acid (DDBSA) that rate of crosslinking is high compared with the situation that Sn compound is used as catalyzer as the crosslinked with silicane resin combination (such as patent documentation 4) of catalyzer.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2012-241129 publication
Patent documentation 2: Japanese Unexamined Patent Application Publication 2004-526808 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2012-197404 publication
Patent documentation 4: Japanese Kohyo 9-506915 publication
Summary of the invention
Invent problem to be solved
But the polarity of DDBSA is strong, relative to nonpolar polyolefin resin, bad dispersibility.At that rate, easily produce coking (result from scorching burn), also likely have problems in appearance.In addition, when the heating carried out when forming process and life-time service goods, the sulfo group as the polar group in DDBSA also likely departs from.At that rate, when using the catalyzer of DDBSA as silanol condensation, when using the coating material of crosslinked with silicane resin combination as such as electric wire or cable etc., also likely insulativity is deteriorated.
The object of the invention is to, providing a kind of for carrying out being cross-linked and outward appearance and good silane cross-linked polyolefin resin combination, the electric wire and cable of insulativity without Sn, quickly and reliably.For solving the method for problem
The 1st aspect of the present invention is a kind of silane cross-linked polyolefin resin combination, it is characterized in that, it is the resin combination without Sn, is 0.920g/cm relative to density
3following polyolefine 100 weight part, containing alkylated naphthalene sulfonic acid 0.1 ~ 1 weight part, and containing silane compound 1.5 ~ 5 weight part, and the weight ratio of this silane compound and free free radical generating agent (silane compound/free free radical generating agent) is 25 ~ 100.
The 2nd aspect of the present invention is the mode as described in first method, wherein, relative to said polyolefins 100 weight part, also containing anion-trapping agent 0.01 ~ 10 weight part.
The 3rd aspect of the present invention is the mode as described in second method, and wherein, above-mentioned anion-trapping agent is hydrotalcite.
The 4th aspect of the present invention is the mode as described in the either type in the first ~ three, and wherein, abovementioned alkyl naphthene sulfonic acid replaces 1 ~ 2 sulfo group, and replaces and have 1 ~ 4 alkyl,
This alkyl is straight chain type or branched chain type and the alkyl of carbonatoms 5 ~ 20,
Carbonatoms in the whole alkyl replaced add up to 20 ~ 80,
When this alkyl is multiple, the kind of each alkyl is different.
The 5th aspect of the present invention is a kind of electric wire, and the above-mentioned silane cross-linked polyolefin resin combination described in either type in its use the first ~ four is as the coating material for conductor.
The 6th aspect of the present invention is a kind of cable, and the above-mentioned silane cross-linked polyolefin resin combination described in either type in its use the first ~ four is as the coating material for conductor.
The effect of invention
According to the present invention, can provide and carry out being cross-linked and outward appearance and good silane cross-linked polyolefin resin combination, the electric wire and cable of insulativity without Sn, quickly and reliably.
Accompanying drawing explanation
Fig. 1 uses the silane cross-linked polyolefin resin combination in present embodiment as the sectional skeleton diagram of the electric wire of coating material.
Fig. 2 uses the silane cross-linked polyolefin resin combination in present embodiment as the sectional skeleton diagram of the cable of coating material.
Embodiment
About the method solving above-mentioned problem, the present inventor is studied.As previously mentioned, the polarity of DDBSA is strong, for the bad dispersibility as nonpolar polyolefin resin.Therefore, the present inventor is nonpolar in view of polyolefin resin, as the catalyzer of silanol condensation, explores about compound polyolefin resin being achieved to polarity and nonpolar balance.Its result, the present inventor obtains following opinion: the catalyzer as silanol condensation uses alkylated naphthalene sulfonic acid, becomes a formation for solving above-mentioned problem.
But as shown in the content of the project of embodiment described later, the present inventor draws and only uses alkylated naphthalene sulfonic acid to be not enough to solve such opinion of above-mentioned problem as the catalyzer of silanol condensation.Its result, the present inventor draws following opinion: become the very important key element of the above-mentioned problem of solution as the density of the polyolefin resin of the raw material of silanol condensation, the same amount as the silane compound of raw material, the amount of the alkylated naphthalene sulfonic acid as catalyzer and the weight ratio of silane compound and free free radical generating agent.
In addition, in patent documentation 2, as the catalyzer of silanol condensation, describe alkylated naphthalene list sulfonic acid.And on the other hand, in view of polyolefin resin is nonpolar, as the catalyzer of silanol condensation, explore about compound polyolefin resin being achieved to polarity and nonpolar balance, result obtains opinion of the present invention as above.Be not content with this, the present inventor has also drawn following opinion: as shown in the content of the project of embodiment described later, only uses alkylated naphthalene sulfonic acid to be not enough to solve above-mentioned problem as the catalyzer of silanol condensation.Such opinion is neither present in patent documentation 2, is not also present in the above-mentioned each patent documentation enumerated.The present invention foundes based on above opinion.
First, to using the silane cross-linked polyolefin resin combination without Sn in present embodiment to be described as the electric wire of coating material.Afterwards, as other example, the cable using the silane cross-linked polyolefin resin combination in present embodiment as coating material is described.
Be explained, in the present embodiment, do not have the item of special records also can adopt known technology.Such as, the content recorded in disclosed in the applicant patent documentation 1 or patent documentation 3 can suitably be quoted.
Below, with reference to accompanying drawing, while explain embodiments of the present invention.
As shown in Figure 1, the electric wire 10 in present embodiment is provided with isolator 2 at the outer circumferential side of long conductor 1.As conductor 1, use known conductor.Silane cross-linked polyolefin resin combination in present embodiment is used as isolator 2.
The silane cross-linked polyolefin resin combination forming the isolator 2 in present embodiment to be made the polyolefine after silane compound graft copolymerization by free free radical generating agent, to be cross-linked under the existence of silanol condensation catalyst and moisture.
The density 0.920g/cm of the polyolefine preferred moisture perviousness excellence used
3below.If density is 0.920g/cm
3below, then the macromolecular chain in polyolefine is too not intensive, therefore, even if can maintain sufficient rate of crosslinking under ambient temperature and moisture (23 DEG C and 50%) yet.Be explained, polyolefinic kind is not particularly limited, and both can be a kind, and also can mix two or more.
Be not particularly limited being used as this polyolefinic compound.When row are given one example, polyethylene can be enumerated.As this polyethylene, such as, in patent documentation 1 described such, the polyethylene made manufactured by ethene and alpha-olefin copolymer can be enumerated.Be explained, as alpha-olefin, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc. can be used, also can manufacture and have polyethylene of more than two kinds alone or in combination.In the present embodiment, also these polyethylene can be used alone or be mixed with two or more.Melt index (MI) is not particularly limited.
Be explained, numerical value (number of such as density or weight part) in this specification sheets both can be as the numerical value in the silane cross-linked polyolefin resin combination of present embodiment, also can be the numerical value in the raw material used when making this resin combination.After, be described accordingly.
Silane compound preferably adds 1.5 ~ 5 weight parts relative to polyolefine 100 weight part contained in composition.If be more than 1.5 weight parts relative to polyolefine 100 weight part, silane compound, then can obtain sufficient degree of crosslinking, and then sufficient rate of crosslinking can be maintained.On the other hand, if be below 5 weight parts relative to polyolefine 100 weight part, silane compound, then silane compound reaction each other can be suppressed when graft copolymerization.Its result, can suppress to produce foreign matter by silane compound reaction each other.And then, this foreign matter can be suppressed to be attached in reactor, also can to suppress the generation of the bad order of forming composition.
Be explained, silane compound needs have and can form crosslinked both alkoxyl groups with the group of polymer reaction with by silanol condensation.Specifically, the vinyl silane compounds such as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tris silane are preferably.
The weight ratio (silane compound/free free radical generating agent) of free free radical generating agent is in the scope of 25 ~ 100.If weight ratio is more than 25, then can suppress the generation that outward appearance is coarse.On the other hand, if weight ratio is less than 100, then can obtain sufficient degree of crosslinking, and then sufficient rate of crosslinking can be maintained.It is relative to silane compound, the ratio higher (weight ratio is lower) of free free radical generating agent, then the cross-linking set of polymkeric substance is more, and the speed that is cross-linked to form of initial reaction stage more improves.But, when free free radical generating agent becomes too much, carry out polymkeric substance high molecular each other, form particle because of the difference of viscosity, become the major cause that outward appearance is coarse.Be explained, as free free radical generating agent, use and to decompose because of heat and to produce the organo-peroxide of free radical of dissociating.Specifically, dicumyl peroxide, benzoyl peroxide, 1,1-two (tert-butyl hydroperoxide)-3,3,5-trimethyl-cyclohexane, t-butylperoxyisopropyl carbonic ether, tert butyl peroxy benzoate etc. are preferably.
The catalyzer used when silanol condensation is the large characteristic in present embodiment.In the present embodiment, as this catalyzer, use alkylated naphthalene sulfonic acid.As previously mentioned, alkylated naphthalene sulfonic acid is compound polyolefin resin being achieved to polarity and nonpolar balance.Therefore, relative to polyolefin resin, the intermiscibility of alkylated naphthalene sulfonic acid (catalyzer namely in silanol condensation reaction) is excellent, and then becomes good relative to the dispersiveness of the catalyzer of polyolefin resin.
Be explained, the silane cross-linked polyolefin resin combination in present embodiment needs without Sn.Therefore, in the present embodiment, the Sn salt of alkylated naphthalene sulfonic acid is not at least used.Certainly can use other metal-salt, but preferred as far as possible in isolator 2 not containing metal, therefore, very preferably use alkylated naphthalene sulfonic acid self.
In addition, in the present embodiment, need to contain alkylated naphthalene sulfonic acid 0.1 ~ 1 weight part relative to polyolefine 100 weight part contained in composition.If be more than 0.1 weight part, then can obtain sufficient degree of crosslinking, and then sufficient rate of crosslinking can be maintained.On the other hand, if be below 1 weight part, then polymkeric substance high molecular each other becomes suitable, does not produce the difference of large viscosity, can suppress the generation of the particle becoming the coarse major cause of outward appearance.
Being explained, with regard to alkylated naphthalene sulfonic acid, meeting the alkylated naphthalene sulfonic acid of following condition, is preferred in the balance of polarity obtaining.
Replace and have 1 ~ 2 sulfo group.
Replace and have 1 ~ 4 alkyl.
This alkyl is straight chain type or branched chain type and the alkyl of carbonatoms 5 ~ 20.
Carbonatoms in the whole alkyl replaced add up to 20 ~ 80.
When this alkyl is multiple, the kind of each alkyl is different.
As concrete alkylated naphthalene sulfonic acid, can enumerate: two dodecyl naphthalene list sulfonic acid, three-dodecyl naphthalene list sulfonic acid, four-dodecyl naphthalene list sulfonic acid and their combination etc.
Preferred relative to polyolefine 100 weight part further, containing anion-trapping agent 0.01 ~ 10 weight part.If be more than 0.01 weight part, then as shown in embodiment described later, can trapping negative ions fully, desired crosslinking reaction can be caused, the raising of the insulativity of composition can be contributed to further.On the other hand, if be below 10 weight parts, then can suppress the contribution of the electroconductibility of trapping agent self, the raising of the insulativity of composition can be contributed to further.Be explained, as anion-trapping agent, usefully hydrotalcite, aqua oxidation bismuth, hydrated magnesium, hydrated aluminum oxide, hydrotalcite is particularly useful.
Than that described above, also known additive can be added as required in the scope not hindering effect of the present invention.Also the additives such as such as process oil, processing aid, fire retardant, flame retardant, crosslinking coagent, antioxidant, UV light absorber, copper(greening)inhibitor, lubricant, inorganic filler, solubilizing agent, softening agent, stablizer, carbon black, tinting material can be added.
Being explained, in order to manufacture the electric wire 10 of present embodiment, also can using the method recorded in patent documentation 1 or patent documentation 3.As an example of the method manufactured, following method can be enumerated.(1) is such as had to make silane compound and polyolefine carry out the operation of graft copolymerization; (2) graft copolymerization had the polyolefine of silane compound and silanol condensation catalyst to carry out mixing, the isolator 2 as electric wire 10 carries out extruding coated operation; (3), under electric wire 10 being placed in the existence of moisture, these three operations of polyolefinic crosslinked operation are promoted.Useful single screw extrusion machines etc. carry out the method for operation (1), (2) by once extruding; Or separately operation (1) is carried out with single screw extrusion machine, twin screw extruder, kneader, Banbury, roller etc. respectively, by the method etc. that operation (2) is carried out with single screw extrusion machine, be not particularly limited.The Synergist S-421 95 such as antioxidant or tinting material can add at any time.In operation (3), there are the temperature applying below normal temperature or polyolefinic fusing point, the method etc. be positioned under high humidity environment.
In above-mentioned example, the electric wire 10 using the silane cross-linked polyolefin resin combination in present embodiment as coating material is described.And on the other hand, may not be electric wire 10, and also present embodiment is suitable for cable.Such as shown in Fig. 2, many said wires 10 can be done up, to the periphery of the plurality of electric wire 10, apply as required resin strip (PET strip etc.) writing that surpasses all the others band 3 or by metal braid (Knitting Group) etc. after the metal level (not diagram) that forms etc., at most peripheral, vinyl chloride resin composition etc. is set as sheath 4, makes cable 20.
But much less, the silane cross-linked polyolefin resin combination in present embodiment is not limited to above-mentioned purposes.
According to the present embodiment, use polarity is weak compared with the DDBSA of the catalyzer as the silanol condensation recorded in patent documentation 4 alkylated naphthalene sulfonic acid as catalyzer.Therefore, it is possible to improve the intermiscibility with resin.In addition, as mentioned above, the weight ratio of the density of the polyolefin resin of the raw material as silanol condensation, the amount of alkylated naphthalene sulfonic acid, the amount of silane compound and silane compound and free free radical generating agent is specified.Carry out being cross-linked and outward appearance and the good silane cross-linked polyolefin resin combination of insulativity thereby, it is possible to provide without Sn, quickly and reliably.
Embodiment
The summary of the present embodiment is described.
First, consist of raw material with the component recorded in table 1 described later (embodiment 1 ~ 8) and table 2 (comparative example 1 ~ 10), make silane cross-linked polyolefin resin combination.Specifically, following operation is carried out.
(operation A) makes the operation of silane compound and polyolefin copolymer;
The production process of (process B) catalyst masterbatch;
(operation C) is to the operation of the mixing catalyzer of the polyolefine after silane compound graft copolymerization;
(step D) is by the crosslinked with silicane operation of silanol condensation.
Afterwards, evaluation test is carried out to each sample.Specifically, following test is carried out.
(evaluation test 1) confirms the coarse confirmation of extruding outward appearance of outward appearance
(evaluation test 2) is confirmed whether the hot set test quickly and reliably carrying out being cross-linked
(evaluation test 3) is for confirming the volume specific resistance determination test of the degree of insulativity
Below, the present embodiment is described in detail.
[making of silane cross-linked polyolefin resin combination]
(operation A) makes the operation of silane compound and polyolefin copolymer
Use 40mm forcing machine (L/D=24), the polyolefine of the composition recorded in table 1 described later (embodiment) and table 2 (comparative example) and component is put in container from hopper.Further, with adding liquid pump, the solution being dissolved with free free radical generating agent in the silane compound recorded in table 1 (embodiment) and table 2 (comparative example) is injected in container.Barrel temperature is set as 200 DEG C, the residence time in forcing machine is set as 100 ~ 150 seconds, carry out material strip (strand) and extrude.Then, the partical that the polyolefine after silane compound graft copolymerization utilizes tablets press to make diameter 2 ~ 3mm is made.
The production process of (process B) catalyst masterbatch
It according to the raw material recorded in table 1 (embodiment) and table 2 (comparative example) (composition and component), makes the masterbatch (catalyzer MB) of the catalyzer being used for silanol condensation on the other hand.Specifically, 6 inch open roll (open roll) are used.And, alkylated naphthalene sulfonic acid is added for the polyolefine of copolymerization (polyolefine in the stage namely before operation A) that do not have prepared in addition, 160 DEG C carry out 5 minutes mixing.Then, use tablets press, corresponding to each embodiment and comparative example, make the catalyzer MB of the size of 3mm × 3mm × 0.5mm.
(operation C) is to the operation of the mixing catalyzer of the polyolefine after silane compound graft copolymerization
Then, use 40mm forcing machine (L/D=24), " the catalyzer MB " that make in " polyolefine after silane compound graft copolymerization " and (process B) that make in above-mentioned (operation A) is dropped into the ratio of the composition becoming regulation from hopper simultaneously.And, be set as 100 ~ 150 seconds residence times in barrel temperature 200 DEG C, forcing machine, carry out being with (tape) to extrude.The die head of 37mm × 1.8mm is used in this band is extruded.Each sample is carried out air cooling, carries out one side cutting, make thickness 1.5mm after extruding by band.In time, make to terminate to terminate within 30 minutes from after just extruding to cutting.
Be explained, when measuring for (evaluation test 3) volume specific resistance, take in addition in the metal frame of 1mm steel bands extrude after each sample.And, under the condition of 200 DEG C × 10MPa × 2 minute, each sample is carried out extrusion forming, obtain 1mm sheet material.
(step D) is by the crosslinked with silicane operation of silanol condensation
The 1mm sheet coupon that the sample cut in (operation C) and (evaluation test 3) volume specific resistance measure is placed 48 ~ 120 hours under the ambient temperature and moisture condition of temperature 23 DEG C (± 1), humidity 50% (± 5).The 1mm sheet coupon that (evaluation test 3) volume specific resistance measures places 120 hours.Be explained, the moment of placement is set to the crosslinked time opening.
For each sample obtained through above-mentioned operation, carry out following evaluation test.
[evaluation test]
(evaluation test 1) extrudes the confirmation of outward appearance
In this test, for each sample, evaluated the smoothness being with the surface after extruding by " feel ", " presence or absence of granular projection ".The situation of granular projection will do not had to be set to " especially good ◎ " for level and smooth feel, though the situation of melt fracture will be produced be set to " △ " for level and smooth feel, by learnt by feel coarse, have the coarse situation of granular projection, outward appearance to be set to "×".
(evaluation test 2) hot set test
In this test, to after sample is heated whether moderately Control Assay elongation, namely " whether be quickly and reliably cross-linked " and confirm.Each sample carries out crosslinked with silicane at identical conditions.Therefore, rate of crosslinking is higher, is cross-linked more fully, and naturally, the result of this test becomes good.Its result, also can be evaluated rate of crosslinking by this test.
As the concrete method of this test, as described below.
To each sample through (step D), implement the hot set test shown in 9 of JIS C 3660-2-1.In the thermostat container of air themperature 200 DEG C, suspend the test film of dumbbell shaped in midair, measure and apply 20N/cm
2the elongation of load after 15 minutes (during load elongation).Then remove load, after 5 minutes, test film is taken out in groove.Then, to this test film, be determined at normal temperature and place elongation (permanent elongation) after 5 minutes.In the present embodiment, it is qualified that the situation of the standard by elongation≤175% when meeting load and below permanent elongation≤15% is set to.Be explained, respectively above test carried out for situation crosslinking time being set to 48h, 72h, 120h.
(evaluation test 3) volume specific resistance determination test
In this test, confirm the degree of insulativity.As concrete method, as described below.
For (time needed for crosslinked with silicane is set to 120h) each sample through (step D), according to the apparatus and method shown in JIS K 6723-6-8, measure the 500V charging normal temperature volume specific resistance of 1 minute.Being explained, is " volume specific resistance>=5 × 10 by measurement result
16Ω cm " sample be set to " insulativity especially excellent (i.e. ◎) ".In addition, be " 5 × 10 by measurement result
16Ω cm > volume specific resistance>=5 × 10
15Ω cm " sample be set to " insulativity excellence (namely zero) ".On the other hand, be " volume specific resistance < 5 × 10 by measurement result
15Ω cm " sample be set to " poor insulativity (namely ×) ".
[evaluation result]
Table 1 (embodiment) and table 2 (comparative example) is shown in by carrying out the result that above-mentioned evaluation test obtains.
[table 1]
[table 2]
When observing table 1 (embodiment) and table 2 (comparative example), distinguish following situation.That is, showing: in (evaluation test 1 ~ 3), in the sample meeting the such condition of " evaluation of more than zero ", " qualified ", is 0.920g/cm relative to density
3following polyolefine 100 weight part, containing alkylated naphthalene sulfonic acid 0.1 ~ 1 weight part, and containing silane compound 1.5 ~ 5 weight part, and the weight ratio of this silane compound and free free radical generating agent (silane compound/free free radical generating agent) is 25 ~ 100.
Below, the result obtained by each embodiment or each comparative example is described in detail.
First, embodiment 7 and comparative example 1,2 are compared.These samples are except the catalyzer used in silanol condensation, and the composition of raw material is identical with component.The catalyzer of embodiment 7 is alkylated naphthalene sulfonic acid.On the other hand, the catalyzer of comparative example 1 is existing Sn catalyzer, and the catalyzer of comparative example 2 is not alkylated naphthalene sulfonic acid, and is Witco 1298 Soft Acid described in patent documentation 4.
Such as, when embodiment 7 and comparative example 2 (namely without the example of Sn) compare with comparative example 1 (namely containing the example of Sn), the result in hot set test is good, namely sees the raising of rate of crosslinking.As its reason, think: the water-disintegrable promotion silanol condensation reaction of strong acid, its result, what strong acid water-disintegrable contributed to being cross-linked carries out in early days.
But, as two kinds of sulfonic acid catalysts of embodiment 7 and comparative example 2 (namely without the example of Sn) in volume specific resistance determination test, compared with comparative example 1 (namely containing the example of Sn), cause the reduction of insulativity.Its reason is considered to because the sulfo group of polarity departs from when forming process produce electroconductibility thus.Particularly in comparative example 2 as catalyzer use Witco 1298 Soft Acid, the reduction of insulativity is large.In addition, after the extrusion see multiple granular projection in appearance.Its reason is considered to, and compared with embodiment 7 (catalyzer=alkylated naphthalene sulfonic acid), the polarity of comparative example 2 (catalyzer=Witco 1298 Soft Acid) is strong, therefore, is likely deteriorated to the dispersiveness of nonpolar polyolefin resin.In other words, alternatively embodiment 7 (catalyzer=alkylated naphthalene sulfonic acid) polarity to nonpolar polyolefin resin dispersed in obtain extraordinary balance.
As a result, embodiment 7 (catalyzer=alkylated naphthalene sulfonic acid) has the rate of crosslinking equal with comparative example 2 (catalyzer=Witco 1298 Soft Acid).About the confirmation of extruding outward appearance, in embodiment 7, do not produce coking.And, about insulativity, although for poor in comparative example 1 (Sn catalyzer), display 5 × 10
15the good result of more than Ω cm.
Then, embodiment 3,5 and comparative example 3,4 are compared.These samples are except the component of the alkylated naphthalene sulfonic acid as the catalyzer used in silanol condensation, and the composition of raw material is identical with component.The component of the alkylated naphthalene sulfonic acid in embodiment 3,5 is in the scope of 0.1 ~ 1 weight part relative to polyolefine 100 weight part.On the other hand, the component of the alkylated naphthalene sulfonic acid in comparative example 3,4 is outside above-mentioned scope.
In comparative example 3,4, the result of the confirmation and hot set test of extruding outward appearance is separately for bad.This result shows: if as the component of the alkylated naphthalene sulfonic acid of the catalyzer of silanol condensation not in above-mentioned scope, then can not meet high rate of crosslinking and good outward appearance.
Then, embodiment 5,6 and comparative example 9,10 are compared.These samples are except the polyolefinic density becoming the raw material of silane cross-linked polyolefin resin combination, and the composition of raw material is identical with component.Polyolefinic density in embodiment 5,6 is 0.920g/cm
3below.On the other hand, comparative example 9, the polyolefinic density in 10 is outside above-mentioned scope.
In comparative example 9,10, the result of the hot set test of the crosslinking time hot set test of 48 hours, crosslinking time 48 hours and 72 hours is bad separately.
On the other hand, in embodiment 5,6, even if crosslinking time is 48 hours, also can obtain hot set test is qualified high cross-linking properties.Therefore showing: in order to obtain high cross-linking properties, needing polyolefinic density to be set to above-mentioned scope.
Then, " containing silane compound 1.5 ~ 5 weight part relative to polyolefine 100 weight part " such condition is studied.Being limited to the result of the comparative example 5 seen, when relative to polyolefine 100 weight part only containing silane compound lower than 1.5 weight parts, in hot set test, although be set to by crosslinking time 72 little constantly for qualified, 48 hours is defective.
On the contrary, be limited to the result of the comparative example 6 seen, when relative to polyolefine 100 weight part, silane compound more than 5 weight part, degraded appearance.This result shows: take into account outward appearance and rate of crosslinking in, need the component of silane compound to be set to above-mentioned scope.
Then, " weight ratio (silane compound/free free radical generating agent) of silane compound and free free radical generating agent is 25 ~ 100 " such condition is studied.At this, embodiment 1,2 and comparative example 7,8 are compared.These samples are except weight ratio (silane compound/free free radical generating agent), and the composition of raw material is identical with component.Weight ratio (silane compound/free free radical generating agent) in embodiment 1,2 is 25 ~ 100.On the other hand, the weight ratio (silane compound/free free radical generating agent) in comparative example 7,8 is outside above-mentioned scope.
Be limited to the result of whole embodiment and the whole comparative example seen, then weight ratio (silane compound/free free radical generating agent) is lower, can obtain higher rate of crosslinking.
Particularly, be limited to the result of the embodiment 1,2 seen, then, when weight ratio (silane compound/free free radical generating agent) is less than 100, even if when crosslinking time is 48 hours, hot set test is also qualified.On the contrary, being limited to the result of the comparative example 8 seen, then, when weight ratio (silane compound/free free radical generating agent) is more than 100, in hot set test, although be set to by crosslinking time 72 little constantly for qualified, 48 hours is defective.
On the other hand, be limited to the result of the comparative example 7 seen, then weight ratio (silane compound/free free radical generating agent) lower than 25 time, extrude degraded appearance.This result shows: take into account outward appearance and rate of crosslinking in, need weight ratio (silane compound/free free radical generating agent) to be set to above-mentioned scope.
Finally, as preferred example, " relative to polyolefine 100 weight part, also containing anion-trapping agent 0.01 ~ 10 weight part " such condition is studied.Be limited to the result of the embodiment 1,4,7,8 seen, then, relative to polyolefine 100 weight part contained in silane cross-linked polyolefin resin combination, when adding the hydrotalcite as anion-trapping agent, insulativity improves.And show: more preferably the component of hydrotalcite is set to 0.01 ~ 10 weight part.Its reason is because hydrotalcite has polarization structure.That is, if be above-mentioned scope, then the addition of hydrotalcite can not be too much.That is, the outside that also can suppress to be positioned at hydrotalcite should with the position ionization of anionresin.Its result is considered to, also suppressed with conductive situation, makes insulativity become good.
Nomenclature
1 conductor
2 isolators
3 writing that surpasses all the others bands
4 sheaths
10 electric wires
20 cables
Claims (6)
1. a silane cross-linked polyolefin resin combination, is characterized in that:
It is the resin combination without Sn,
Be 0.920g/cm relative to density
3following polyolefine 100 weight part, containing alkylated naphthalene sulfonic acid 0.1 ~ 1 weight part, and containing silane compound 1.5 ~ 5 weight part, and the weight ratio of this silane compound and free free radical generating agent (silane compound/free free radical generating agent) is 25 ~ 100.
2. silane cross-linked polyolefin resin combination as claimed in claim 1, is characterized in that:
Relative to described polyolefine 100 weight part, also containing anion-trapping agent 0.01 ~ 10 weight part.
3. silane cross-linked polyolefin resin combination as claimed in claim 2, is characterized in that:
Described anion-trapping agent is hydrotalcite.
4. the silane cross-linked polyolefin resin combination according to any one of claims 1 to 3, is characterized in that:
Described alkylated naphthalene sulfonic acid replaces 1 ~ 2 sulfo group, and replacement has 1 ~ 4 alkyl,
This alkyl is straight chain type or branched chain type and the alkyl of carbonatoms 5 ~ 20,
Carbonatoms in the whole alkyl replaced add up to 20 ~ 80,
When this alkyl is multiple, the kind of each alkyl is different.
5. an electric wire, is characterized in that:
The silane cross-linked polyolefin resin combination of use according to any one of claim 1 ~ 4 is as coating material.
6. a cable, is characterized in that:
The silane cross-linked polyolefin resin combination of use according to any one of claim 1 ~ 4 is as coating material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014041183A JP2015166425A (en) | 2014-03-04 | 2014-03-04 | Silane-crosslinked polyolefin resin composition, electric wire, and cable |
| JP2014-041183 | 2014-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104893059A true CN104893059A (en) | 2015-09-09 |
Family
ID=54026050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510066751.8A Pending CN104893059A (en) | 2014-03-04 | 2015-02-09 | Silane crosslinking polyolefin resin composition, electric wire and cable |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2015166425A (en) |
| CN (1) | CN104893059A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679237A (en) * | 2017-10-18 | 2019-04-26 | 日立金属株式会社 | Resin formed product and its forming method and cable and its manufacturing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002012354A1 (en) * | 2000-08-03 | 2002-02-14 | King Industries, Inc. | Alkylaryl and arylalkyl monosulfonic acid catalysts for crosslinking polyethylene |
| CN102786727A (en) * | 2011-05-20 | 2012-11-21 | 日立电线株式会社 | Resin composition, and wire and cable using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02235628A (en) * | 1989-03-08 | 1990-09-18 | Showa Electric Wire & Cable Co Ltd | Resin coated metal body |
-
2014
- 2014-03-04 JP JP2014041183A patent/JP2015166425A/en active Pending
-
2015
- 2015-02-09 CN CN201510066751.8A patent/CN104893059A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002012354A1 (en) * | 2000-08-03 | 2002-02-14 | King Industries, Inc. | Alkylaryl and arylalkyl monosulfonic acid catalysts for crosslinking polyethylene |
| CN102786727A (en) * | 2011-05-20 | 2012-11-21 | 日立电线株式会社 | Resin composition, and wire and cable using the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679237A (en) * | 2017-10-18 | 2019-04-26 | 日立金属株式会社 | Resin formed product and its forming method and cable and its manufacturing method |
| CN109679237B (en) * | 2017-10-18 | 2023-09-15 | 株式会社博迈立铖 | Resin molded article, molding method thereof, cable and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015166425A (en) | 2015-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5896626B2 (en) | Method for producing electric wire molded body comprising silane crosslinkable flame retardant polyolefin and silanol catalyst resin composition | |
| US8378009B2 (en) | Process of producing flame-retardant silane-crosslinked olefin resin, insulated wire, and process of producing insulated wire | |
| JP6376463B2 (en) | cable | |
| CN103834088B (en) | Non-halogen resin composition and electric wire, cable | |
| US20120273268A1 (en) | Composition for wire coating member, insulated wire, and wiring harness | |
| CN105473654A (en) | Heat-resistant silane crosslinked resin molded article and method for producing same, heat-resistant silane crosslinking resin composition and method for producing same, silane master batch, and heat-resistant product produced using heat-resistant silane crosslinked resin molded article | |
| CN105473645A (en) | Heat-resistant, silane-crosslinked resin molded article and production method for same, heat-resistant, silane-crosslinkable resin composition and production method for same, silane masterbatch, and heat-resistant product employing heat-resistant, silane-crosslinked resin molded article | |
| JP6140140B2 (en) | Heat-resistant silane cross-linked resin molded body, cross-linkable resin molded body, heat-resistant silane cross-linkable resin composition and production method thereof, silane masterbatch, and heat-resistant product | |
| CN105308102A (en) | Heat-resistant silane crosslinked resin molded article and method for manufacturing same, and heat-resistant product equipped with heat-resistant silane crosslinked resin molded article | |
| US11499067B2 (en) | Resin composition, resin-coating material, vehicle wire harness and method of producing vehicle wire harness | |
| CN105579519A (en) | Heat-resistant silane cross-linked resin molded article and production method for same, heat-resistant silane cross-linking resin composition and production method for same, silane masterbatch, and heat-resistant product employing heat-resistant silane cross-linked resin molded article | |
| CN104893059A (en) | Silane crosslinking polyolefin resin composition, electric wire and cable | |
| EP3666823B1 (en) | Thermoplastic resin composition for wire-coating and heat resistant wire | |
| JP6053641B2 (en) | Flame retardant silane crosslinkable resin composition, method for producing the same, molded product, electric wire / cable, and method for producing the same | |
| CN105670195A (en) | Crosslinkable halogen-free resin composition, cross-linked insulated wire and cable | |
| JP2015193690A (en) | Flame-retardant composition and insulated wire using the same | |
| KR20090087259A (en) | Semiconductive peelable closslinked resin composition and manufactured insulating cable using the same | |
| JP2013006993A (en) | Method for producing silane crosslinked resin molded product and molded product using the same | |
| JP5769321B2 (en) | Process for producing silane-crosslinked resin molded body and molded body using the method | |
| CN103665724B (en) | Halogen-free flame-retardant resin composition and manufacturing method for, insulated wire using same and cable | |
| JP5666921B2 (en) | Method for producing silane cross-linked resin molded body and molded body using the same | |
| US8829345B2 (en) | Covered conductor for wire harness and wire harness produced using the same | |
| JP5705558B2 (en) | Method for producing silane cross-linked resin molded body and molded body using the same | |
| CN104916352B (en) | Cable and its manufacturing method | |
| JP6969082B2 (en) | Catalyst batch, electric wire / cable formed using it, and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150909 |