CN104204048A - Method for producing heat-resistant resin composition, heat-resistant resin composition produced by method for producing heat-resistant resin composition, and molded article using heat-resistant resin composition - Google Patents

Method for producing heat-resistant resin composition, heat-resistant resin composition produced by method for producing heat-resistant resin composition, and molded article using heat-resistant resin composition Download PDF

Info

Publication number
CN104204048A
CN104204048A CN201380018536.XA CN201380018536A CN104204048A CN 104204048 A CN104204048 A CN 104204048A CN 201380018536 A CN201380018536 A CN 201380018536A CN 104204048 A CN104204048 A CN 104204048A
Authority
CN
China
Prior art keywords
mass parts
heat
resistant resin
resin composition
coupling agent
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.)
Granted
Application number
CN201380018536.XA
Other languages
Chinese (zh)
Other versions
CN104204048B (en
Inventor
西口雅己
松村有史
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Furukawa Electric Co Ltd
Original Assignee
Furukawa Electric Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Furukawa Electric Co Ltd filed Critical Furukawa Electric Co Ltd
Publication of CN104204048A publication Critical patent/CN104204048A/en
Application granted granted Critical
Publication of CN104204048B publication Critical patent/CN104204048B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/241—Preventing premature crosslinking by physical separation of components, e.g. encapsulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • H01B3/34—Waxes
    • 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
    • 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
    • H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Insulated Conductors (AREA)
  • Organic Insulating Materials (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

A method for producing a heat-resistant resin composition, which is characterized by comprising (a) a step wherein a silane master batch is prepared by melting and kneading a resin composition that contains a polyolefin resin, 0.01-0.6 part by mass of an organic peroxide and 10-400 parts by mass of an inorganic filler per 100 parts by mass of the resin composition, and 0.5-15.0 parts by mass of a silane coupling agent per 100 parts by mass of the inorganic filler at a temperature not less than the decomposition temperature of the organic peroxide, without mixing a silanol condensation catalyst thereinto, (b) a step wherein the silane master batch is melted and kneaded with a silanol condensation catalyst, and then the resulting is molded, and (c) a step wherein the molded product of the step (b) is crosslinked by being brought into contact with a water content; a heat-resistant resin composition which is produced by this method for producing a heat-resistant resin composition; and a molded article which contains a molded product of this heat-resistant resin composition.

Description

The manufacture method of heat-resistant resin composition and the heat-resistant resin composition by this manufacture method manufacturing and used the products formed of this heat-resistant resin composition
Technical field
The present invention relates to the manufacture method of heat-resistant resin composition and the heat-resistant resin composition by this manufacture method manufacturing and used the products formed of this heat-resistant resin composition, particularly relate to the manufacture method of the heat-resistant resin composition of mechanical characteristics and then excellent heat resistance; The heat-resistant resin composition obtaining by the manufacture method of this heat-resistant resin composition; With the products formed such as isolator and sheath of electric wire that has used this heat-resistant resin composition.
Background technology
For the insulated line/cable/cable (cord) of the inside and outside distribution for electric/electronic and optical fibre core, optical fiber cable etc., require the various characteristicses such as flame retardant resistance, thermotolerance, mechanical characteristics (such as tensile properties, wear resistant).As the material for these distribution materials, the resin combination of the mineral filler such as magnesium hydroxide, aluminium hydroxide that used a large amount of mixtures.
In addition, sometimes under the state using continuously, can be warming up to 80 DEG C～105 DEG C and then be warming up to 125 DEG C of left and right for the distribution material of electric/electronic, sometimes require the thermotolerance for this situation.In this case, in order to give distribution material high heat resistance, taked to make the crosslinked method of coating material by electron rays crosslinking or chemical crosslink technique etc.
In the past, as by the method crosslinked polyolefin resines such as polyethylene, known: to irradiate electron rays and make its crosslinked electron rays crosslinking; Make the decomposition such as organo-peroxide in the after-applied heat of moulding, thereby make it that chemical crosslink technique of crosslinking reaction occur; Silane cross-linking method.Silane cross-linking method refers to following method: under the existence of organo-peroxide, make to have the silane coupling agent reaction of unsaturated group and obtain silane grafted polymer, afterwards under the existence of silanol condensation catalyst with contact with moisture, thereby obtain cross moulding body.In these crosslinkings, especially silane cross-linking method is not owing in most cases needing special equipment, therefore can be using in field widely.
Specifically, for example, the manufacture method of the thermotolerance crosslinked with silicane resin of halogen be the silane coupling agent that makes to have unsaturated group is grafted to polyolefin resin and the silane masterbatch that obtains, by polyolefine and the mixing thermotolerance masterbatch forming of mineral filler, carry out the method for melting mixing with the catalyst masterbatch that contains silanol condensation catalyst.But, in the method, if exceed 100 mass parts with respect to polyolefin resin 100 mass parts mineral fillers, be difficult to silane masterbatch and thermotolerance masterbatch to carry out the mixed melting mixing equably that is incorporated in single screw extrusion machine or twin screw extruder of dry type, cause sometimes degraded appearance, physical property significantly to reduce, extrude load high and cannot moulding.In addition, because the ratio that comprises silane masterbatch is restricted, be therefore difficult to further high resistant burning/high heat-resistingization.
Conventionally,, in mixing in the time that such mineral filler exceedes 100 mass parts with respect to polyolefin resin 100 mass parts, generally use the hermetic type mixing tanks such as continuous mixer, adding pressure type kneader or Banbury.
On the other hand, in the situation that utilizing kneader or Banbury to carry out Silane Grafted, the general volatility of silane coupling agent with unsaturated group is high, carrying out i.e. volatilization before graft reaction, is therefore very difficult to make desired silane cross linked mother batch.
Therefore, in the situation that utilizing Banbury or kneader to manufacture thermotolerance silane masterbatch, can consider following method: in the thermotolerance masterbatch that polyolefin resin and fire retardant melting mixing are formed, add silane coupling agent and the organo-peroxide with water-disintegrable unsaturated group, utilize single screw extrusion machine to make its graft polymerization.But, in the method, can make formed body produce bad order due to the deviation of reaction, must make the mixture amount of mineral filler of masterbatch very many, extruding load and becoming very large, manufacture very difficultly, cannot obtain desired material and formed body.And be two operations, aspect cost, also there is very large problem.
Following method has been proposed in patent documentation 1: utilize kneader in polyolefin-based resins fully melting mixing silane coupling agent carried out surface-treated mineral filler, silane coupling agent, organo-peroxide, crosslinking catalyst, utilize afterwards single screw extrusion machine to carry out moulding.
In addition, following technology is proposed: using segmented copolymer etc. as base resin in patent documentation 2～4, add the non-aromatic family softener of rubber as tenderizer, for obtained vinyl aromatic based thermoplastic elastic composition, by the mineral filler through silane surface treatment, utilize organo-peroxide to carry out partial cross-linked.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-101928 communique
Patent documentation 2: TOHKEMY 2000-143935 communique
Patent documentation 3: TOHKEMY 2000-315424 communique
Patent documentation 4: TOHKEMY 2001-240719 communique
Summary of the invention
Invent problem to be solved
But, in the method that patent documentation 1 is recorded, not only in the melting mixing that utilizes kneader, can occur crosslinked, cause the bad order of formed body, and likely volatilize except the major part of mineral filler having been carried out to the silane coupling agent surface-treated silane coupling agent, or there is condensation in silane coupling agent each other.Therefore, not only cannot obtain desired thermotolerance, and silane coupling agent condensation each other also likely becomes the major cause of electric wire degraded appearance.
In addition, even in the technology proposing in patent documentation 2～4, resin does not form sufficient reticulated structure yet, resin at high temperature can make in conjunction with separating with the combination of mineral filler, therefore at high temperature there is melting, for example, there is insulating material in the welding processing of electric wire and melt or moulding is being added to the problem that deforms man-hour, produces foaming to carrying out 2 times.And if then carry out short period of time heating 200 DEG C of left and right, exist outward appearance significantly deteriorated, distortion problem.
Problem of the present invention is to address the above problem, and provides a kind of silane coupling agent that suppresses to have unsaturated group to volatilize from reaction system and the heat-resistant resin composition of flame retardant resistance, thermotolerance, mechanical characteristics excellence; And manufacture method and used the products formed of this heat-resistant resin composition.
For the means of dealing with problems
, problem of the present invention reaches by following method.
(1) manufacture method for heat-resistant resin composition, is characterized in that, above-mentioned manufacture method comprises following operation:
(a) by the resin combination that contains polyolefin-based resins, be the organo-peroxide of 0.01 mass parts～0.6 mass parts and the mineral filler of 10 mass parts～400 mass parts and be 0.5 mass parts～15.0 mass parts with respect to these mineral filler 100 mass parts silane coupling agent carries out melting mixing more than the decomposition temperature of above-mentioned organo-peroxide with respect to these resin combination 100 mass parts, not mixed silanes alcohol condensation catalyst and prepare the operation of silane masterbatch;
(b) by the operation of carrying out moulding after above-mentioned silane masterbatch and silanol condensation catalyst melting mixing; With
(c) make the forming composition of above-mentioned (b) operation and contact with moisture and carry out crosslinked operation.
(2) manufacture method of the heat-resistant resin composition as described in (1), is characterized in that, above-mentioned manufacture method comprises following operation:
(a-1) with respect to resin combination 100 mass parts that contain polyolefin-based resins, by the mineral filler of the organo-peroxide of 0.01 mass parts～0.6 mass parts and 10 mass parts～400 mass parts and the silane coupling agent that is 0.5 mass parts～15.0 mass parts with respect to mineral filler 100 mass parts mix the operation of preparing mixture;
(a-2) said mixture and resin combination are carried out to melting mixing more than the decomposition temperature of organo-peroxide, not mixed silanes alcohol condensation catalyst and prepare the operation of silane masterbatch;
(b-1) silanol condensation catalyst and vector resin are mixed and the operation of manufacture catalyst masterbatch;
(b-2) by the operation of carrying out moulding after the silane masterbatch of preparing respectively in above-mentioned (a-2) and above-mentioned (b-1) operation and catalyst masterbatch melting mixing; With
(c) make the forming composition of above-mentioned (b-2) operation and contact with moisture and carry out crosslinked operation.
(3) manufacture method of the heat-resistant resin composition as described in (1), is characterized in that, above-mentioned manufacture method comprises following operation:
(a) by the resin combination that contains polyolefin-based resins, be the organo-peroxide of 0.01 mass parts～0.6 mass parts and the mineral filler of 10 mass parts～400 mass parts and be 0.5 mass parts～15.0 mass parts with respect to mineral filler 100 mass parts silane coupling agent carries out melting mixing more than the decomposition temperature of organo-peroxide with respect to these resin combination 100 mass parts, not mixed silanes alcohol condensation catalyst and prepare the operation of silane masterbatch;
(b-1) silanol condensation catalyst and vector resin are mixed and the operation of manufacture catalyst masterbatch;
(b-3) by the operation of carrying out moulding after the silane masterbatch of preparing respectively in above-mentioned (a) and above-mentioned (b-1) operation and catalyst masterbatch melting mixing; With
(c) make the forming composition of above-mentioned (b-3) operation and contact with moisture and carry out crosslinked operation.
(4) manufacture method of the heat-resistant resin composition as described in any one in (1)～(3), it is characterized in that, with respect to above-mentioned resin combination 100 mass parts, the above-mentioned silane coupling agent that contains 0.5 mass parts～18.0 mass parts forms.
(5) manufacture method of the flame retardant resistance cross-linked composition as described in (4), is characterized in that, contains below above-mentioned silane coupling agent and forms to exceed 4 mass parts and 15 mass parts.
(6) manufacture method of the flame retardant resistance cross-linked composition as described in (4), is characterized in that, contains above-mentioned silane coupling agent form with 5 mass parts～12 mass parts.
(7) manufacture method of the flame retardant resistance cross-linked composition as described in (4), is characterized in that, contains above-mentioned silane coupling agent form with 6 mass parts～10 mass parts.
(8) manufacture method of the flame retardant resistance cross-linked composition as described in any one in (1)～(7), it is characterized in that, above-mentioned resin combination contains at least one and alkane hydrocarbon system oil in ethene-alpha-olefin copolymer and styrene series elastomer with the mass ratio of 4 quality %～70 quality %.
(9) manufacture method of the flame retardant resistance cross-linked composition as described in (8), is characterized in that, above-mentioned mass ratio is 8 quality %～70 quality %.
(10) manufacture method of the flame retardant resistance cross-linked composition as described in (8) or (9), is characterized in that, at least one in above-mentioned ethene-alpha-olefin copolymer and styrene series elastomer is above-mentioned styrene series elastomer.
(11) manufacture method of the flame retardant resistance cross-linked composition as described in any one in (8)～(10), is characterized in that, above-mentioned ethene-alpha-olefin copolymer is terpolymer EP rubber.
(12) manufacture method of the heat-resistant resin composition as described in any one in (1)～(11), is characterized in that, above-mentioned silane coupling agent is vinyltrimethoxy silane or vinyltriethoxysilane.
(13) manufacture method of the heat-resistant resin composition as described in any one in (1)～(12), it is characterized in that, above-mentioned mineral filler is at least one that select in the group of free silicon-dioxide, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, zinc borate, zinc hydroxyl stannate and talcum composition.
(14) manufacture method of the heat-resistant resin composition as described in any one in (1)～(13), is characterized in that the melting mixing carry out the manufacture of above-mentioned silane masterbatch in the mixing tank of hermetic type time.
(15) products formed, is characterized in that, it comprises by the forming composition of the heat-resistant resin composition of the manufacture method manufacturing of the heat-resistant resin composition described in any one in (1)～(14).
(16) products formed as described in (15), is characterized in that, above-mentioned products formed is electric wire or optical cable coating body.
(17) a kind of heat-resistant resin composition, it is the heat-resistant resin composition of the manufacture method manufacturing of the heat-resistant resin composition by described in any one in (1)～(14), it is characterized in that, this heat-resistant resin composition is said polyolefins resin by silanol bonds and mineral filler is crosslinked forms.
Above-mentioned and further feature of the present invention and advantage can be suitable clearer according to following record with reference to accompanying drawing.
The effect of invention
According to the present invention, can obtain the products formed of a kind of heat-resistant resin composition and heat-resistant resin composition, its flame retardant resistance, thermotolerance, mechanical characteristics excellence, simultaneously by with before polyolefin-based resins mixing and/or when mixing, mix mineral filler and silane coupling agent, the volatilization of the silane coupling agent can suppress mixing time, can obtain the products formed of heat-resistant resin composition and heat-resistant resin composition efficiently.And then can not use the special machineries such as electron rays cross-linking machine and manufacture the heat-resisting cross-linked composition of height that is added with high amount of inorganic filler.
Embodiment
Describe the preferred embodiment of the present invention below in detail.
The manufacture method of heat-resistant resin composition of the present invention comprises following operation: (a) by the resin combination that contains polyolefin-based resins, be the organo-peroxide of 0.01 mass parts～0.6 mass parts and the mineral filler of 10 mass parts～400 mass parts, carry out melting mixing with the silane coupling agent that is 0.5 mass parts～15.0 mass parts with respect to these mineral filler 100 mass parts more than the decomposition temperature of above-mentioned organo-peroxide with respect to these resin combination 100 mass parts, and not mixed silanes alcohol condensation catalyst and prepare the operation of silane masterbatch; (b) by the operation of carrying out moulding after above-mentioned silane masterbatch and silanol condensation catalyst melting mixing; (c) make the forming composition of above-mentioned (b) operation and contact with moisture and carry out crosslinked operation.
(A) resin combination that contains polyolefin-based resins
The resin combination using in the present invention contains polyolefin-based resins as neccessary composition, according to expecting to contain styrene series elastomer, alkane hydrocarbon system oil, various additives etc.In the time using ethene-alpha-olefin copolymer described later as one of polyolefin-based resins, or in the time using styrene series elastomer as a kind of composition of resin combination (A), if contain alkane hydrocarbon system oil, flexibility and outward appearance excellence, is preferred from this respect.
It should be noted that, in the present invention, " resin " and " multipolymer " uses according to comprising rubber and elastomeric implication.In addition, " multipolymer " uses according to the implication that comprises the various multipolymers such as random copolymers, segmented copolymer and alternating copolymer.
Content to the each composition in resin combination is not particularly limited, and the content of polyolefin-based resins can be separately 100 quality %, also can contain other composition with suitable mass ratio.
For example, the content of the polyolefin-based resins in resin combination (A) is 100 quality % to the maximum, but be not limited to this, from the viewpoint of mechanical characteristics and stable on heating, be preferably 30 quality %～100 quality %, 30 quality %～92 quality % more preferably with respect to resin combination (A) entirety.Therefore,, in this situation, the content of the composition beyond the polyolefin-based resins in resin combination (A) is preferably 70 quality %～0 quality %, 70 quality %～8 quality % more preferably with respect to resin combination (A) entirety.
In addition, in resin combination (A), the aspect producing from the concavo-convex point (Block Star) suppressing while stopping forcing machine and the aspect of flexibility, be preferably 4 quality %～70 quality %, more preferably 8 quality %～70 quality %, 15 quality %～70 quality % more preferably as the total content of ethene-alpha-olefin copolymer, styrene series elastomer and the alkane hydrocarbon system oil of polyolefin-based resins.Therefore, in this situation, the total content of the composition beyond ethene-alpha-olefin copolymer, styrene series elastomer and the alkane hydrocarbon system oil in resin combination (A) is preferably 30 quality %～96 quality %, more preferably 30 quality %～92 quality %, 30 quality %～85 quality % more preferably with respect to resin combination entirety.
(A-1) polyolefin-based resins
As the polyolefin-based resins using in the present invention, be not particularly limited, can use the known polyolefin-based resins for heat-resistant resin composition in the past.Can enumerate for example polyethylene, polypropylene, ethene-alpha-olefin copolymer, the polyolefin copolymer with sour copolymer composition or acid esters copolymer composition and their rubber, elastomerics.Wherein, even from the high a large amount of mixture mineral fillers of consistency of the various mineral fillers for taking metal hydrate etc. as representative also have the physical strength of maintaining effect and also can guarantee the stable on heating reduction that simultaneously suppresses the voltage-resistent characteristic proof voltage, particularly high temperature aspect consider, preferably polyethylene, ethene-alpha-olefin copolymer and there is the multipolymer of sour copolymer composition.These polyolefin-based resins can use separately a kind, also two or more can be mixed and use.
As polyethylene (PE), can enumerate high density polyethylene(HDPE) (HDPE), Low Density Polyethylene (LDPE), ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE), straight chain type Low Density Polyethylene (LLDPE), ultra-low density polyethylene (VLDPE).Wherein, preferred straight chain type Low Density Polyethylene (LLDPE), Low Density Polyethylene (LDPE).
As ethene-alpha-olefin copolymer, be preferably ethene and carbonatoms and be the multipolymer of 3～12 alpha-olefin, as the concrete example of alpha-olefin, can enumerate propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene etc.As ethene-alpha-olefin copolymer, there are specifically ethylene-propylene copolymer (EPR), ethylene-butene copolymer (EBR) and synthetic ethene-alpha-olefin copolymer etc. under single site catalysts exists.Be preferably ethylene-propylene copolymer, can enumerate such as ethylene-propylene-diene copolymer etc.
As the polyolefin copolymer with sour copolymer composition or acid esters copolymer composition, can enumerate vinyl-vinyl acetate copolymer (EVA), ethene-(methyl) acrylic copolymer, ethene-(methyl) alkyl acrylate copolymer etc.Wherein optimal ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, and then from the viewpoint of with the consistency of mineral filler and stable on heating, particularly preferably vinyl-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer.
The content of polyolefin-based resins (A-1) in resin combination (A) is described above.
In the situation that polyolefin-based resins (A-1) contains ethene-alpha-olefin copolymer, the content of ethene-alpha-olefin copolymer according to the content of the polyolefin-based resins (A-1) in resin combination (A) mode in above-mentioned scope carry out suitable setting, for example, be preferably 30 quality %～100 quality % with respect to resin combination (A).
In addition, in the situation that resin combination (A) contains alkane hydrocarbon system oil described later (A-3), the content of ethene-alpha-olefin copolymer according to the total content of styrene series elastomer (A-2) and alkane hydrocarbon system oil (A-3) mode in above-mentioned scope carry out suitable setting, for example, be preferably 4 quality %～70 quality % with respect to resin combination (A).If the content of ethene-alpha-olefin copolymer is in above-mentioned scope, by the outward appearance excellence of flame retardant resistance cross-linked resin composition of the present invention electric wire when the electric wire.
(A-2) styrene series elastomer
In the present invention, as the composition of resin combination (A), can also use styrene series elastomer (A-2).Styrene series elastomer (A-2) in molecule using aromatic ethenyl compounds such as vinylbenzene as constituent.Therefore,, in the present invention, even if comprise ethene constituent in molecule, be categorized as styrene series elastomer (A-2) as long as comprise aromatic ethenyl compound constituent.
As such styrene series elastomer (A-2), can enumerate the multipolymer of conjugated diene compound and aromatic ethenyl compound or their hydride.As conjugated diene compound, can enumerate for example divinyl, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene etc.In addition, as aromatic ethenyl compound, for example can enumerate vinylbenzene, to (tertiary butyl) vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, 1,1-diphenyl benzene ethene, N, N-diethyl-to amino-ethyl vinylbenzene, Vinyl toluene, to (tertiary butyl) vinylbenzene etc.
As styrene series elastomer (A-2), specifically, can enumerate SEBS (styrene-ethylene-butylene-styrene block copolymer), SIS (styrene isoprene styrene block copolymer (SIS)), Hydrogenated SBS, SEEPS (styrene-ethylene-ethylene-propylene-styrene block copolymer), SEPS (styrene-ethylene-propylene-styrene segmented copolymer), hydrogenation SIS, HSBR (HSBR), HNBR (hydrogenated nitrile-butadiene rubber) etc.As commercially available product, can enumerate such as SEPTON (trade(brand)name, the KURARAY of Co., Ltd. manufacture), Dynaron (trade(brand)name, JSR Corp. manufacture) etc.
It should be noted that, as styrene series elastomer (A-2), SEPS, the SEEPS, the SEBS that are preferably 10%～40% by styrene content use separately, or two or more in them is used in combination.
The content of styrene series elastomer (A-2) according to the content of the polyolefin-based resins (A-1) in resin combination (A) mode in above-mentioned scope carry out suitable setting, for example, be preferably 2 quality %～50 quality % with respect to resin combination (A).
In addition, in the situation that resin combination (A) contains alkane hydrocarbon system oil described later (A-3), the content of styrene series elastomer (A-2) according to the total content of ethene-alpha-olefin copolymer and alkane hydrocarbon system oil (A-3) mode in above-mentioned scope carry out suitable setting, for example, be preferably 4 quality %～70 quality % with respect to resin combination (A).If the content of styrene series elastomer (A-2) is within the scope of this, by the outward appearance excellence of flame retardant resistance cross-linked resin composition of the present invention electric wire when the electric wire.
(A-3) alkane hydrocarbon system oil
In the present invention, as the composition of resin combination (A), can also use alkane hydrocarbon system oil (A-3).As alkane hydrocarbon system oil (A-3), can use mineral oil softener or liquid or the low-molecular-weight synthetic tenderizer etc. of such as non-aromatic family.In general, be the mixture that aromatic nucleus, naphthenic hydrocarbon ring and this three of alkane hydrocarbon chain combine as rubber with the mineral oil softener using, more than 50% material that paraffinic hydrocarbons chain carbon atom number is accounted for to total carbon atom number is called alkane hydrocarbon system oil; The material that is 30%～40% by naphthenic hydrocarbon ring carbon atom number is called cycloalkanes hydrocarbon system oil; Be that more than 30% material is called fragrant family oil by aromatic series carbonatoms, distinguish with this.In the present invention, in these materials, can use alkane hydrocarbon system oil.
As the commercially available material of alkane hydrocarbon system oil, can enumerate for example Dyna process oil (trade(brand)name, Idemitsu Kosen Co., Ltd. manufacture).
The content of alkane hydrocarbon system oil (A-3) according to the content of the polyolefin-based resins (A-1) in resin combination (A) mode in above-mentioned scope carry out suitable setting, for example, be preferably 2 quality %～40 quality % with respect to resin combination (A).
In addition, contain at least one in ethene-alpha-olefin copolymer and styrene series elastomer (A-2) at resin combination (A), the content of alkane hydrocarbon system oil (A-3) according to the total content of ethene-alpha-olefin copolymer and styrene series elastomer the mode in above-mentioned scope carry out suitable setting, for example, be preferably 4 quality %～70 quality %, 8 quality %～70 % by weight more preferably with respect to resin combination (A).If the content of alkane hydrocarbon system oil (A-3) is within the scope of this, in the time of melting mixing, can make styrene series elastomer disperse well, reduce the generation of concavo-convex point, and the oozing out of electric wire in the time that flame retardant resistance cross-linked resin composition of the present invention can be prevented to high temperature when the electric wire.
Contain at least one in ethene-alpha-olefin copolymer and styrene series elastomer (A-2) at resin combination (A), if make the total content of ethene-alpha-olefin copolymer, styrene series elastomer (A-2) and alkane hydrocarbon system oil (A-3) in electric wire outward appearance excellence of above-mentioned scope, detailed mechanism for this effect is still not clear, but can consider as follows.Side reaction when Silane Grafted occurs reacting as silane coupling agent (D) and polyolefin-based resins (A), there is polyolefin-based resins (A-1) crosslinking reaction and silane coupling agent (D) polyreaction each other each other, think that this is the reason of the concavo-convex point of formed body.Now, by the styrene series elastomer that coexists, styrene series elastomer crosslinking reaction each other occurs quickly compared with polyolefin-based resins (A-1) crosslinking reaction each other, is therefore difficult to generate each other crosslinked of polyolefin-based resins (A-1).Styrene series elastomer (A-2) crosslinking reaction each other forms the situation of the dynamic crosslinking that approaches rubber, although can improve viscosity, is difficult to produce concavo-convex point, therefore can significantly reduce concavo-convex point.In addition think, by add alkane hydrocarbon system oil (A-3) in this styrene series elastomer (A-2), can further relax this styrene series elastomer (A-2) local reaction each other, realize the minimizing of concavo-convex point.And think, also there is each other crosslinking reaction by alkane hydrocarbon system oil (A-3), thereby also there is the effect of inhibition polyolefin-based resins (A-1) crosslinking reaction each other.
On the other hand, think that the coexist situation of ethene-alpha-olefin copolymer is substantially the same with the situation of the styrene series elastomer that coexists.
As mentioned above, the aspect that electric wire from the outward appearance of obtained products formed and can prevent high temperature time oozes out, it is at least one and the alkane hydrocarbon system oil (A-3) in rubber and styrene series elastomer (A-2) that resin combination (A) preferably contains as the ethylene-alpha-olefin of polyolefin-based resins (A-1).More preferably resin combination (A) contains styrene series elastomer (A-2) and alkane hydrocarbon system oil (A-3).Among above-mentioned, ethene-alpha-olefin is that rubber is preferably terpolymer EP rubber.
(B) organo-peroxide
The organo-peroxide using in the present invention has following effects: produce free radical by thermolysis, the grafting that the free radical reaction (comprise from polyolefin-based resins (A-1) etc. and extract reacting of hydroperoxyl radical) of the unsaturated group that promotes aftermentioned silane coupling agent and polyolefin-based resins (A-1) etc. causes reacts.This organo-peroxide (B) needs only generation free radical and is not particularly limited, preferably R 1-OO-R 2, R-OO-C (=O) R 3, R 3c (=O)-OO (C=O) R 4the compound representing.Herein, R 1, R 2, R 3and R 4represent independently of one another alkyl, aryl, acyl group.Wherein, in the present invention, preferably R 1, R 2, R 3and R 4be alkyl, or any one be alkyl, all the other are acyl group.
As organo-peroxide, can enumerate for example dicumyl peroxide, ditertiary butyl peroxide, 2, 5-dimethyl-2, 5-bis--(tert-butyl hydroperoxide) hexane, 2, 5-dimethyl-2, 5-bis-(tert-butyl hydroperoxide)-3-hexin, 1, two (tert-butyl hydroperoxide sec.-propyl) benzene of 3-, 1, two (tert-butyl hydroperoxide)-3 of 1-, 3, 5-trimethyl-cyclohexane, normal-butyl-4, two (tert-butyl hydroperoxide) valerates of 4-, benzoyl peroxide, p-chlorobenzoyl peroxide, 2, 4-dichlorobenzoperoxide, peroxidized t-butyl perbenzoate, tert-butylperoxy isopropyl carbonate, diacetyl superoxide, lauroyl peroxide, tertiary butyl cumyl peroxide etc.Among these, from the viewpoint of peculiar smell, tint permanence, coking stability, most preferably dicumyl peroxide, 2,5-dimethyl-2,5-bis--(tert-butyl hydroperoxide) hexane, 2,5-dimethyl-2,5-bis--(tert-butyl hydroperoxide)-3-hexin.
The decomposition temperature of organo-peroxide (B) is preferably 80 DEG C～195 DEG C, more preferably 125 DEG C～180 DEG C.
In the present invention, the decomposition temperature of organo-peroxide refers to, in the time that the organo-peroxide of single composition (B) is heated, cause the temperature of the decomposition reaction that himself is decomposed into two or more compounds in certain certain temperature or temperature province, in the time heating from room temperature with the heat-up rate of 5 DEG C/min under nitrogen atmosphere by the analysis of the heat such as DSC method, refer to the temperature that starts neither endothermic nor exothermic.
The mixture amount of organo-peroxide with respect to resin combination (A) 100 mass parts be 0.01 mass parts～0.6 mass parts scope, be preferably 0.1 mass parts～0.5 mass parts.By making organo-peroxide within the scope of this, can carry out polymerization in suitable scope, can not produce the cohesion piece that cross linked gel etc. causes and obtain the composition of extrudability excellence.
, when the mixture amount of organo-peroxide is less than 0.01 mass parts, when crosslinked, likely can not carry out by silane coupling agent the crosslinking reaction of polyolefin-based resins, and produce silane coupling agent polymerization each other.On the other hand, if exceed 0.6 mass parts, silane coupling agent easily volatilizees, or likely produces concavo-convex point by side reaction.
(C) mineral filler
As mineral filler (C), can form the position of hydrogen bond etc. or can utilize covalent linkage to carry out the position of chemical bonding with the reactive site such as the silanol group of water-disintegrable silane coupling agent as long as have on the surface of mineral filler, can use with no particular limitation.As the position that can carry out with the reactive site of water-disintegrable silane coupling agent chemical bonding in mineral filler, can enumerate OH base (the OH yl of water molecules, the carboxyl etc. of hydroxyl, moisture or crystal water), amino, SH base etc.
Be not particularly limited as such mineral filler (C), can use such as aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, Calucium Silicate powder, Magnesium Silicate q-agent, calcium oxide, magnesium oxide, aluminum oxide, aluminium nitride, aluminum borate, whisker, hydrated aluminium silicate, aluminum oxide, hydrated magnesium silicate, magnesium basic carbonate, hydrotalcite etc. to there is metal hydroxides and the metal hydrate of metallic compound of hydroxyl or crystal water and so on; And boron nitride, silicon-dioxide (crystalline silica, amorphous silica etc.), carbon, clay, zinc oxide, stannic oxide, titanium dioxide, molybdenum oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, silicoorganic compound, quartz, talcum, zinc borate, white carbon black, zinc borate, zinc hydroxyl stannate, zinc.
In addition, mineral filler (C) can mix with silane coupling agent use.Be not particularly limited as the method for mixing mineral filler and silane coupling agent, there is following method: in non-processor or carried out in surface-treated mineral filler with stearic acid, oleic acid, phosphoric acid ester or a part of silane coupling agent in advance, add Hybrid Heating or the method for the silane coupling agent of heating; Under the state that makes fillers dispersed in water equal solvent, add the method for silane coupling agent; Etc., details is as described later.In the present invention, preferably to adding Hybrid Heating or the silane coupling agent of heating in mineral filler.
Above-mentioned mineral filler (C) can be used by silane coupling agent has carried out surface-treated mineral filler.For example, as silane coupling agent surface treatment magnesium hydroxide, can enumerate commercially available product (Kisuma 5L, Kisuma5P (being trade(brand)name, the manufacture of consonance chemical company) etc.), the aluminium hydroxide etc. of magnesium hydroxide.
These mineral fillers (C) a kind of mixture separately, also can mix two or more to use.
In these mineral fillers, preferably at least one in silicon-dioxide, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, zinc borate, zinc hydroxyl stannate and talcum.
In the situation that mineral filler (C) is powder, median size is preferably 0.2 μ m～10 μ m, more preferably 0.3 μ m～8 μ m, more preferably 0.4 μ m～5 μ m, 0.4 μ m～3 μ m.
When the median size of mineral filler (C) is less than 0.2 μ m, in the time mixing with the silane coupling agent in silane masterbatch, mineral filler (C) likely causes secondary aggregation, makes the outward appearance of formed body occur to reduce and concavo-convex point.On the other hand, if exceed 10 μ m, the maintenance effect of outward appearance reduction, silane coupling agent (D) reduces, and is cross-linked and likely goes wrong.
It should be noted that, median size refers to the median size of disperseing and utilizing the optical profile type particle size determination devices such as laser diffraction/diffuse transmission type particle size distribution analyzer to obtain with alcohol or water.
The mixture amount of mineral filler (C) is 10 mass parts～400 mass parts, is preferably 30 mass parts～280 mass parts, 30 mass parts～200 mass parts more preferably with respect to resin combination (A) 100 mass parts.
The mixture amount of mineral filler (C) is less than in the situation of 10 mass parts, and the graft reaction of silane coupling agent (D) is inhomogeneous, cannot obtain desired thermotolerance, or likely reduces because inhomogeneous reaction makes outward appearance.On the other hand, if exceed 400 mass parts, load when moulding and when mixing becomes very large, is likely difficult to carry out 2 moulding.
(D) silane coupling agent
Silane coupling agent (D) is not particularly limited as long as have the group that can the group of graft reaction occur with polyolefin-based resins (A) and can be hydrolyzed under the existence of free radical, in the past, the silane coupling agent with unsaturated group used in crosslinked with silicane can be used, the compound that for example following general formula (1) represents can be used.
(in formula, R a11represent the group that contains ethylenic unsaturated group, R b11represent aliphatic alkyl, hydrogen atom or Y 13.Y 11, Y 12and Y 13represent independently of one another the organic group being hydrolyzed.Y 11, Y 12and Y 13mutually can be identical, also can be different.)
The R of the silane coupling agent that above-mentioned general formula (1) represents a11be preferably the group that contains ethylenic unsaturated group, such as can enumerate vinyl, allyl group, (methyl) acryloxy alkylidene group, to styryl etc., more preferably vinyl.
R b11represent aliphatic alkyl, hydrogen atom or Y described later 13, as aliphatic alkyl, be the aliphatic alkyl beyond unsaturated aliphatic hydrocarbon base, preferably can enumerate carbonatoms and be 1～8 1 valency aliphatic alkyl.R b11be preferably Y described later 13.
Y 11, Y 12and Y 13represent the organic group being hydrolyzed, can enumerate alkoxyl group that for example carbonatoms is 1～4, aryloxy that carbonatoms is 6～8, acyloxy, especially carbonatoms that carbonatoms is 1～4 alkoxyl group that is 1～4, the acyloxy (OCOCH that preferably carbonatoms is 1 3), alkoxyl group that further preferably carbonatoms is 1～2.As the organic group being hydrolyzed, can enumerate specifically such as methoxyl group, oxyethyl group, butoxy, acetoxyl group, (methyl) acryloxy etc.Wherein from the viewpoint of reactive, preferably methoxy or ethoxy.
As above-mentioned silane coupling agent, preferably there is the silane coupling agent of the fast unsaturated group of hydrolysis rate, more preferably R b11for Y 13, and Y 11, Y 12and Y 13identical silane coupling agent mutually.Specifically, can enumerate the ends such as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-dimethyl oxygen base oxethyl silane, vinyl-dimethyl oxygen base butoxy silane, vinyl diethoxy butoxy silane, vinyltriacetoxy silane, methacryloxypropyl trimethoxy silane, methacryloxypropyl triethoxyl silane, methacryloxypropyl methyl dimethoxysilane and have the silane coupling agent etc. of the two keys of ethylenic.These silane coupling agents can use separately or two or more be share.In the silane coupling agent of such bridging property, further preferred end has the silane coupling agent of vinyl and alkoxyl group, particularly preferably vinyltrimethoxy silane, vinyltriethoxysilane.
Silane coupling agent (D) is 0.5 mass parts～15.0 mass parts, is preferably 1.0 mass parts～12.0 mass parts with respect to mineral filler (C) 100 mass parts.Silane coupling agent (D) can be its state originally, also can be with using after solvent cut.
The consumption of silane coupling agent (D) is less than in the situation of 0.5 mass parts, crosslinked cannot fully carrying out, and heat-resistant resin composition likely cannot obtain desired thermotolerance and mechanical characteristics.On the other hand, if exceed 15.0 mass parts, more silane coupling agent cannot be adsorbed to mineral filler (C) surface, and in mixing middle volatilization, not only unfavorable economically, but also can there is condensation, and formed body (also referred to as forming composition) likely produces the concavo-convex point of cross linked gel and spot (baked け), thus degraded appearance.Particularly, in the situation that exceeding 15.0 mass parts, bad order is remarkable.
In addition, silane coupling agent (D) is except meeting above-mentioned consumption, in silane masterbatch, preferably contain with the ratio of 0.5 mass parts～18.0 mass parts with respect to resin combination (A) 100 mass parts, more preferably contain with the ratio of 1.0 mass parts～8.0 mass parts, particularly preferably contain with the ratio of 3.0 mass parts～8.0 mass parts.
The consumption of silane coupling agent (D) is less than in the situation of 0.5 mass parts, crosslinked cannot fully carrying out, and heat-resistant resin composition likely cannot obtain desired thermotolerance and mechanical characteristics.On the other hand, if exceed 18.0 mass parts, there is condensation in silane coupling agent (D) each other, and formed body likely produces the concavo-convex point of cross linked gel and spot, thus degraded appearance.
In silane masterbatch, silane coupling agent (D) more preferably with respect to resin combination (A) 100 mass parts to exceed 4 mass parts and the ratio below 15 mass parts contains, further preferably contain with the ratio of 5 mass parts～12 mass parts, particularly preferably contain with the ratio of 6 mass parts～10 mass parts.
Like this, if more set the content of the silane coupling agent (D) in silane masterbatch, even if forcing machine is stopped also can suppressing for 1 time the generation of crosslinked concavo-convex point, just can obtain the good formed body of outward appearance as long as can only make silane masterbatch residual in forcing machine flow out.
Not yet definite about its details, but can consider as follows.; by adding in a large number silane coupling agent (D); in the grafting reaction being caused by the decomposition of organo-peroxide (B) when mixing; reaction and silane coupling agent (D) reaction each other of fast silane coupling agent (D) and the polyolefin-based resins (A-1) etc. of speed of response are occupied an leading position, and the crosslinking reactions each other such as polyolefin-based resins (A-1) do not occur substantially.Like this, because polyolefin-based resins (A-1) etc. does not react each other substantially, thereby outward appearance is good.On the other hand, silane coupling agent (D) reaction is each other limited by the content of mineral filler (C), the major part of silane coupling agent (D) and mineral filler (C) combination, therefore free silane coupling agent (D) does not also react each other substantially.Therefore, as mentioned above, think and can not had the clean and tidy formed body of outward appearance of the concavo-convex point of gel.
(E) vector resin
Be not particularly limited as vector resin (E), can use with said polyolefins is the same material of resin (A-1), from the viewpoint of good and stable on heating with silanol condensation catalyst (F) affinity, be preferably vinylite.Specifically, as vinylite, can enumerate the above-mentioned polyethylene (PE) such as straight chain type Low Density Polyethylene, Low Density Polyethylene, ultra-low density polyethylene, high density polyethylene(HDPE), ultrahigh molecular weight polyethylene(UHMWPE), preferably straight chain type Low Density Polyethylene, Low Density Polyethylene, ultra-low density polyethylene, high density polyethylene(HDPE), particularly preferably straight chain type Low Density Polyethylene.
The mixture amount of vector resin (E) is preferably 1 mass parts～60 mass parts, more preferably 2 mass parts～50 mass parts, 2 mass parts～40 mass parts more preferably with respect to resin combination (A) 100 mass parts.And can in this vector resin (E), add mineral filler, also can not add mineral filler.Amount to mineral filler is now not particularly limited, and is preferably below 350 mass parts with respect to resinous principle 100 mass parts of vector resin (E).This is because if mineral filler amount is too much, silanol condensation catalyst (F) is difficult to disperse, and is cross-linked and is difficult to carry out.On the other hand, if vector resin (E) is too much, the degree of crosslinking of formed body reduces, and likely cannot obtain suitable thermotolerance.
(F) silanol condensation catalyst
Silanol condensation catalyst (F) in the present invention has the effect of the silane coupling agent with unsaturated group (D) combination that makes grafting by condensation reaction under the existence of moisture.Based on the effect of this silanol condensation catalyst (F), polyolefin-based resins (A-1) etc. is cross-linked by silane coupling agent (D) each other.Its result, can obtain the resin-formed body (also referred to as formed body or heat-resistant resin composition) of excellent heat resistance.
As silanol condensation catalyst (F), use organo-tin compound, metallic soap, platinic compound etc.As general silanol condensation catalyst (F), use such as dibutyl tin laurate, two dioctyltin laurate, two sad dibutyl tins, dibutyltin diacetate, Zinic stearas, lead stearate, barium stearate, calcium stearate, sodium stearate, lead naphthenate, lead sulfate, zinc sulfate, organo-platinic compounds etc., be particularly preferably the organo-tin compounds such as dibutyl tin laurate, two dioctyltin laurate, two sad dibutyl tins, dibutyltin diacetate.
The mixture amount of silanol condensation catalyst (F) is preferably 0.0001 mass parts～0.5 mass parts, 0.001 mass parts～0.1 mass parts more preferably with respect to resin combination (A) 100 mass parts.
If the mixture amount of silanol condensation catalyst (F) is in above-mentioned scope, the condensation reaction of silane coupling agent (D) is promptly carried out, form uniform crosslinking structure, formed body shows flame retardant resistance, and productivity also improves, in addition can suppress gelation, the outward appearance of formed body and the resin characteristics excellence of part.
In addition, not damaging in the scope of object of the present invention, can in heat-resistant resin composition, suitable mixture be generally used for various additives, such as antioxidant, lubricant, metal passivator, fire-retardant (helping) agent or other resin etc. in electric wire, cable, cord, sheet material, foam, pipe, pipe.These additives are advisable to join in vector resin, and especially antioxidant and metal passivator preferably do not hinder the mode of the grafting on polyolefin-based resins (A-1) etc. to join in vector resin (E) with the silane coupling agent (D) being mixed in mineral filler (C).Further preferably wherein do not comprise in fact crosslinking coagent.In operation particularly preferably in making masterbatch, do not comprise in fact crosslinking coagent.If add crosslinking coagent, by organo-peroxide (B), crosslinking coagent is reacted in mixing middle meeting, polyolefin-based resins (A-1) etc. produce crosslinked each other, there is gelation, the outward appearance of formed body significantly reduces, or the grafting of silane coupling agent (D) on polyolefin-based resins (A-1) etc. do not carried out, and possibly cannot obtain thus the thermotolerance of final formed body.Not damaging in the scope of object of the present invention, can in heat-resistant resin composition, import above-mentioned additive.
Herein, crosslinking coagent refer under the existence of organo-peroxide and polyolefin-based resins (A-1) between the material of forming section crosslinking structure, can enumerate the multi-functional compounds such as the allyl group based compounds such as the such as methacrylate ester such as polypropyleneglycol diacrylate, Viscoat 295 compound, triallyl cyanurate, maleimide amine compound, divinyl based compound.
As antioxidant, for example can enumerate 4,4 '-dioctyl diphenylamine, N, the amine such as N '-diphenyl-para-phenylene diamine, 2,2,4 trimethyl 1,2 dihydroquinoline polymer are antioxidant; Four (3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecane alcohol esters; 1,3,5-trimethylammonium-2, the phenol such as 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene are antioxidant; The sulphur such as two (2-methyl-4-(the positive alkylthio propionyl of 3-oxygen base)-5-tert-butyl-phenyl) thioether, 2-mercaptobenzimidazole and zinc salt, tetramethylolmethane-tetra-(3-lauryl-thiopropionate) are antioxidant; Etc..
As metal passivator; can enumerate N; N '-bis-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hydrazine, 3-(N-salicyloyl) amino-1; 2; 4-triazole, 2,2 '-oxalyl amido two (ethyl-3-(3,5 di-tert-butyl-hydroxy phenyl) propionic ester) etc.
With respect to above-mentioned resin combination (A) 100 mass parts, antioxidant can be preferably with 0.1 mass parts～15.0 mass parts, further preferably add with 0.1 mass parts～10 mass parts.
As fire-retardant (helping) agent, weighting agent, can enumerate carbon, clay, zinc oxide, stannic oxide, titanium dioxide, magnesium oxide, molybdenum oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, silicoorganic compound, quartz, talcum, calcium carbonate, magnesiumcarbonate, zinc borate, white carbon black etc.These weighting agents can be used as filler and use in the time of mixed silanes coupling agent, also can join in vector resin.
As lubricant, can enumerate hydrocarbon system, siloxane-based, fatty acid series, fatty acid amide system, ester system, alcohol system, metallic soap system etc.These lubricants are advisable to join in vector resin.
The manufacture method of heat-resistant resin composition of the present invention is described below.
In the manufacture method of heat-resistant resin composition of the present invention, implement following operation (a): not mixed silanes alcohol condensation catalyst (F) and resin combination (A), organo-peroxide (B), mineral filler (C) and silane coupling agent (D) are carried out to melting mixing.
Like this, in operation (a), silanol condensation catalyst (F) does not all mix with any composition." do not mix " and refer to, except not using completely the situation of silanol condensation catalyst (F), also comprise the use as the inevitable use of impurity etc. and degree that can melting mixing in operation described later (b).
In operation (a), preferably in initial operation by mineral filler (C), silane coupling agent (D) and organo-peroxide (B) in the decomposition temperature lower than organo-peroxide, preferably at room temperature carry out dry type or wet mixing and obtain mixture (operation (a-1)).
There is following method to adding silane coupling agent (D) in mineral filler (C): under heating or non-heating, add the processing (dry type) of mixing and mineral filler (C) is scattered in the methods such as the processing (wet type) that adds silane coupling agent (D) under the state in water equal solvent.In the present invention, preferably to adding the processing of mixed silanes coupling agent (D), i.e. dry process in the mode of heating or non-heating in mineral filler (C), preferred dried mineral filler (C).
In the method (wet mixing) that mineral filler (C) is scattered in add silane coupling agent (D) under the state in water equal solvent, silane coupling agent (D) easily securely with mineral filler (C) combination, therefore condensation reaction thereafter is likely difficult to carry out.On the other hand, in mineral filler (C), add in the method (dry type mixing) of mixed silanes coupling agent (D) in the mode of heating or non-heating, mineral filler (C) is more weak with the combination of silane coupling agent (D), is therefore easily cross-linked efficiently.
Now, silane coupling agent (D) and organo-peroxide (B) can be mixed together, be scattered in mineral filler (C), also can disperse respectively, but preferably be mixed together in fact.
The silane coupling agent (D) joining in mineral filler (C) exists in the surperficial mode of surrounding mineral filler (C), its part or all be adsorbed in mineral filler (C), or produce Chemical bond with filler (C) surface.By being such state, the volatilization of the silane coupling agent (D) when kneader or the Banbury etc. after utilizing carries out mixed refining process to main material can significantly reduce, and can make unsaturated group and the polyolefin-based resins (A-1) etc. of silane coupling agent (D) that crosslinking reaction occurs by the organo-peroxide (B) adding simultaneously.Think in addition, in the time of moulding, make silane coupling agent (D) that condensation reaction occur each other by silanol condensation catalyst (F).The mechanism of this reaction is not yet definite, but can consider as follows: in the time of condensation reaction, if mineral filler (C) is excessively strong with the combination of silane coupling agent (D), even if add silanol condensation catalyst (F), also do not depart from from mineral filler (C) with the silane coupling agent (D) of mineral filler (C) combination, silanol condensation reaction (crosslinking reaction) is difficult to carry out.
In addition, according to the difference of working condition, also can only silane coupling agent (D) be mixed in mineral filler (C), in the operation of the manufacture silane masterbatch of subsequent processing, add organo-peroxide (B).It should be noted that, as the method that adds organo-peroxide (B), can be scattered in resin combination (A), for example polyolefin-based resins (A-1), also can add with one matter, or be scattered in wet goods and add, be preferably scattered in resin combination (A).
In subsequent processing, preferably said mixture and resin combination (A) are joined respectively in mixing machine, not mixed silanes alcohol condensation catalyst (F) and heating above in the decomposition temperature of organo-peroxide (B), carry out melting mixing simultaneously, prepare silane masterbatch (operation (a-2)).
More preferably after in silane coupling agent (D) and organo-peroxide (B) are mixed into mineral filler (C), add this mixture and resin combination (A), it is more than the decomposition temperature of organo-peroxide (B) making temperature, mainly make silane coupling agent (D) at the upper graft reaction that occurs of polyolefin-based resins (A-1), prepare silane masterbatch (grafts).
Melting temperature is that the decomposition temperature of organo-peroxide (B) is above, decomposition temperature+25 that are preferably organo-peroxide (B) DEG C～110 DEG C.This decomposition temperature is preferably set after polyolefin-based resins (A-1) melting.In addition, the mixing condition such as mixing time also can suitablely be set.
Under the decomposition temperature that is less than organo-peroxide, carry out when mixing, Silane Grafted reaction does not only occur, cannot obtain desired thermotolerance, and react extruding middle organo-peroxide, sometimes cannot be shaped to desired shape.Preferably not mixing under the state that does not make resin combination (A), for example polyolefin-based resins (A-1) melting, and mixing under the state of melting.
As compounding process, as long as normally used method in rubber, plastics etc. can be used satisfactorily, as device, use such as single screw extrusion machine, twin screw extruder, roller, Banbury or various kneaders etc. according to the amount of mineral filler (C), from the aspect of resin dispersion and crosslinked stability, the hermetic type mixing tanks such as preferred Banbury or various kneaders.
In addition, such mineral filler (C) exceedes in the situation of 100 mass parts with respect to resin combination (A) 100 mass parts conventionally, and general using continuous mixer, adding pressure type kneader, Banbury carry out mixing.
Silane coupling agent (D) does not import separately in silane masterbatch, and preferably and mineral filler (C) carry out importing again after pre-mixing etc.
This be because, silane coupling agent (D) is mixing middle can volatilization, not only uneconomical, and there is condensation and be difficult to carry out melting mixing in the silane coupling agent (D) of absorption, likely cannot obtain desired shape simultaneously in the time of extrusion moulding.
In addition, the generation of above-mentioned mixture is not to be different operations from melting mixing operation, but resin combination (A), organo-peroxide (B), silane coupling agent (D) and mineral filler (C) are mixed together more than the decomposition temperature of organo-peroxide, (operation is a) can to prepare silane masterbatch.It should be noted that, due to local being cross-linked may occur, produce concavo-convex point, therefore the generation utilization of the preferred mixture operation different from melting mixing operation carried out.
So in operation (a), the silane masterbatch of preparation at least contains the resolvent of organo-peroxide (B) and is grafted to degree silane coupling agent (D) that can moulding by aftermentioned operation (b) silane grafted polymer that polyolefin-based resins (A-1) etc. obtains.
In the manufacture method of heat-resistant resin composition of the present invention, next implement the operation (b) of carrying out moulding by after silane masterbatch and silanol condensation catalyst (F) melting mixing.This operation (b) is the operation of silane masterbatch and silanol condensation catalyst (F) being carried out to melting mixing, the preferred following mode of operation (b)., comprise the mode of following operation: silanol condensation catalyst (F) is mixed with vector resin (E) and manufacture the operation (b-1) of catalyst masterbatch and by operation (a-2) and operation (b-1) respectively preparation silane masterbatch and catalyst masterbatch melting mixing after carry out moulding operation (b-2); And comprise the mode of following operation: operation (b-1) and by the operation (b-3) of carrying out moulding after the silane masterbatch of preparation and catalyst masterbatch melting mixing respectively in operation (a) and operation (b-1).
Like this, in preferred operation (b), implement vector resin (E) and silanol condensation catalyst (F) to be obtained by mixing the operation (b-1) of catalyst masterbatch.
According to the melt temperature of vector resin (E), can under being the condition of 80 DEG C～250 DEG C, more preferably 100 DEG C～240 DEG C, melting temperature carry out.It should be noted that, the mixing condition such as mixing time can suitablely be set.
Compounding process can utilize the method identical with above-mentioned compounding process to carry out.
Herein, as mentioned above, silanol condensation catalyst (F) is included in catalyst masterbatch, is not included in silane masterbatch.This is because if silanol condensation catalyst (F) is included in silane masterbatch, silane coupling agent (D) condensation occurs and is difficult to carry out melting mixing, and likely cannot obtain desired shape in the time of extrusion moulding.
Next, above-mentioned silane masterbatch and catalyst masterbatch are heated while in coating device melting mixing, be for example coated on and extrude on electric wire or fiber, be shaped to desired shape (operation b-2).It should be noted that, silane masterbatch used can also use by (the silane masterbatch (operation (b-3)) that operation a) obtains.
In melting mixing, also exist elastomerics etc. cannot utilize DSC etc. to measure the resin of fusing point, at least at the temperature of any one melting in polyolefin-based resins (A-1) and organo-peroxide (B), carry out mixing.For silanol condensation catalyst (F) is disperseed, vector resin (E) need to carry out melting.It should be noted that, the mixing condition such as mixing time can suitablely be set.
Compounding process can utilize the method identical with above-mentioned compounding process to carry out.
So implement operation (b).The forming composition obtaining in operation (b) is the mixture (uncrosslinked thing) of silane masterbatch and silanol condensation catalyst (F), at least contains above-mentioned silane grafted polymer.
In the manufacture method of heat-resistant resin composition of the present invention, next implement to make forming composition and contact with moisture and carry out crosslinked operation (c).The above-mentioned processing that makes forming composition and contact with moisture and carry out crosslinked operation (c) itself can utilize usual method to carry out.By making forming composition and contact with moisture, silane coupling agent (D) is hydrolyzed, and silane coupling agent (D) is the condensation by silanol condensation catalyst (F) each other, forms crosslinking structure.
About with the condition of contact with moisture, as long as to preserve and can carry out at normal temperature, but crosslinked in order further accelerating, can also to be immersed in warm water, or to put in damp and hot groove, or be exposed in the water vapour of high temperature.In addition, now, in order to make moisture penetration to inside, can exert pressure.
So implement the manufacture method of heat-resistant resin composition of the present invention, manufacture heat-resistant resin composition of the present invention.In this heat-resistant resin composition, the polyolefin-based resins (A-1) of resin combination (A) is by the organic group Y of silane coupling agent (D) 11, Y 12and Y 13the silanol bonds forming in hydrolysis after condensation is bonded to each other polyolefin-based resins (A-1), thereby is cross-linked.
Polyolefin-based resins (A-1) is for example cross-linked to each other and can, by adding thermal distortion or thermofixation is confirmed, also utilizes the method to confirm to be cross-linked to each other with polyolefin-based resins (A-1) in embodiment described later by silanol bonds and polyolefin-based resins (A-1).
On the other hand, polyolefin-based resins (A-1) is by silanol bonds and mineral filler (C) combination, and mechanical strength and abradability significantly improve.
In the present invention, not yet definite about the details of reaction mechanism, but can consider as follows.
; for the polyolefin-based resins (A-1) of resin combination (A); if mineral filler (C) and silane coupling agent (D) are added to hot milling, be cross-linked with mineral filler (C) by there is the silane coupling agent (D) of graft reaction under the existence at organo-peroxide (B).As long as the silane coupling agent (D) of mixture specified quantitative in resin combination (A), can not damage moulding time, extrude processibility and a large amount of mixture mineral filler (C), can in guaranteeing excellent flame retardant resistance, have thermotolerance and mechanical characteristics concurrently.
The mechanism that acts on polyolefin-based resins (A-1) about the mineral filler (C) mixing with silane coupling agent (D), details is not yet definite, but can consider as follows.; by silane coupling agent (D) is mixed with mineral filler (C); silane coupling agent (D) utilizes alkoxyl group bonding on mineral filler (C) surface; utilization is present in the uncrosslinked part bonding of the ethylenic unsaturated groups such as the vinyl of another end and polyolefin-based resins (A-1), or does not adsorb, is held in hole or the surface of mineral filler (C) in physics and chemistry mode with mineral filler (C) bonding.If it is mixing to add superoxide to carry out under this state, silane coupling agent (D) is substantially non-volatile, polyolefin-based resins (A-1) of the ethylenic unsaturated group of the reactive moieties having as silane coupling agent (D) and resin combination (A) etc. reacts, and causes graft reaction.
Further add wherein vector resin (E), if with contact with moisture, with silane coupling agent (D) hydrolysis of the uncrosslinked part bonding of polyolefin-based resins (A-1) etc. and silanol condensation occurs, polyolefin-based resins (A-1) is each other by silane coupling agent (D) bonding, crosslinked.The resin combination (also referred to as cross-linked composition) obtaining by this reaction or the thermotolerance of formed body are very high, can obtain at high temperature resin combination and the formed body of also not melting.
On the other hand, on mineral filler (C) surface, there is not this hydrolysis reaction in the silane coupling agent (D) of bonding firmly in advance, and the bonding of maintenance and mineral filler (C).Therefore, produce the bonding of polyolefin-based resins (A-1) etc. and mineral filler (C), produce crosslinked by the polyolefin-based resins (A-1) of mineral filler (C) etc.Thus, polyolefin-based resins (A-1) etc. becomes firmly with the adaptation of mineral filler (C), and physical strength and wear resistant are good, can obtain being difficult to impaired heat-resistant resin composition.
Manufacture method of the present invention goes for for example thermotolerance flame-retardant insulating electric wire/heat-proof combustion-resistant cable coating material, other heat-proof combustion-resistant electric wire parts, flame-proof heat-resistant sheet, flame-proof heat-resistant film, other are various has stable on heating formed body, attaching plug specifically, junctor, sleeve (sleeve), casing (box), band base material, pipe, sheet material, wiring material used in the inside and outside distribution of electric/electronic, the isolator of electric wire, the profiled parts such as sheath, the particularly manufacture of electric wire and optical cable.Can carry out coating etc. on one side extruding in coating device melting mixing on one side, thereby be shaped to those shapes.For such products formed, can not use the special machineries such as electron rays cross-linking machine, and utilize the general coating device of extruding to have the cross-linked composition that high-temperature fusion does not occur of the high heat resistance of high amount of inorganic filler to extrude to be coated on conductor around by adding, or extrude the conductor that is coated on longitudinal interpolation or has been twisted into tension stress fiber around, thereby manufacture.For example, as conductor, can use the material arbitrarily such as single line or twisted wire of soft copper.In addition, as conductor, except bare wire, can also use zinc-plated conductor and there is enamel-cover by the conductor of insulating layer coating.Thickness to the insulation layer (coating being made up of heat-resistant resin composition of the present invention) forming around conductor is not particularly limited, and is generally 0.15mm～5mm left and right.
Embodiment
Further describe the present invention based on embodiment below, but the present invention is not limited to these embodiment.It should be noted that, in table 1～table 5, the numeric representation mass parts in each embodiment and comparative example.In table 1～table 5, silane coupling agent (D) is designated as to " conversion amount (C100 mass parts) " with respect to the conversion amount (the 1st of radix point) of mineral filler (C) 100 mass parts.
In embodiment 1～81, comparative example 1～17, use each composition of table 1～table 5, change each specification and make respectively.
It should be noted that, as the each compound shown in table 1～table 5, use following compound.
The composition > of < resin combination (A)
EV180 (trade(brand)name) is the vinyl-vinyl acetate copolymer VA content 33 quality % that chemical company of Mitsui Du Pont manufactures
V-9000 (trade(brand)name) is the vinyl-vinyl acetate copolymer VA content 41 quality % that DU PONT-MITSUI POLYCHEMICALS company manufactures
The ethylene ethyl acrylate resin EA content 22 quality % that NUC6510 (trade(brand)name) manufactures for the Dow Chemical Company
KS240T (trade(brand)name) is the Kernel (registered trademark) (Low Density Polyethylene) that Japanese polyethylene company manufactures
UE320 (trade(brand)name) is that NOVATEC PE (straight chain type Low Density Polyethylene (PE)), oiling company of Mitsubishi manufacture
PB222A (trade(brand)name) is SunAllomer (trade(brand)name), Atactic Polypropelene, the manufacture of SunAllomer Co., Ltd.
Evolue SP0540 (trade(brand)name) is that metallocene LLDPE, PRIME POLYMER Co., Ltd. manufacture
SEPTON 4077 (trade(brand)name) is that styrene-ethylene-ethylene-propylene-styrol copolymer (SEEPS, styrene series elastomer), KURARAY company of Co., Ltd. manufacture, vinylbenzene component content 30%
Mitsui 3092EPM is that terpolymer EP rubber (ethylene content 66%), Mitsui Chemicals, Inc manufacture
EP11 is that terpolymer EP rubber (EPDM), JSR manufacture
Dyna process oil PW90 (trade(brand)name) is that alkane hydrocarbon system oil, Idemitsu Kosen Co., Ltd. manufacture
Admer XE070 (trade(brand)name) is that toxilic acid modified poly ethylene, Mitsui Chemicals, Inc manufacture
< mineral filler (C) >
The wet silicon dioxide (precipitated silica) that Tokusil U (trade(brand)name) manufactures for Tokuyama company
The crystalline silica that CRYSTALITE 5X (trade(brand)name) manufactures for Long Sen company
The non-processor magnesium hydroxide that Kisuma 5 (trade(brand)name) manufactures for consonance chemical company
The calcium carbonate that SOFTON 1200 (trade(brand)name) manufactures for shiraishi calcium company
The calcined kaolin that Glomax LL (trade(brand)name) manufactures for Zhu Yuan chemical industrial company
The zinc borate that Firebrake 290 (trade(brand)name) manufactures for Borax company
The zinc hydroxyl stannate that Alcanex ZHS (trade(brand)name) manufactures for marshy land chemical company
HIGILITE (registered trademark) H42M is clear and the aluminium hydroxide of electrician company manufacture
MV Talc (trade(brand)name) is the talcum that Japanese Misutoron Co., Ltd. manufactures
< silane coupling agent (D) >
The vinyltrimethoxy silane that KBM1003 (trade(brand)name) manufactures for chemical industrial company of SHIN-ETSU HANTOTAI
The vinyltriethoxysilane that KBE1003 (trade(brand)name) manufactures for chemical industrial company of SHIN-ETSU HANTOTAI
< organo-peroxide (B) >
DCP is the dicumyl peroxide (151 DEG C of decomposition temperatures) that Japanese chemical drug company manufactures
PERHEXA 25B (trade(brand)name) is 2 of Nof Corp.'s manufacture, 5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane (149 DEG C of decomposition temperatures)
< silanol condensation catalyst (F) >
The dibutyl tin laurate that ADKSTAB OT-1 (trade(brand)name) manufactures for Asahi Electro-Chemical Co. Ltd
< vector resin (E) >
Above-mentioned UE-320 and above-mentioned EV180
< antioxidant (hindered phenol is antioxidant) >
IRGANOX 1076 (trade(brand)name) is 3-(3,5-di-tert-butyl-hydroxy phenyl) the propionic acid octadecane alcohol ester that Chang Lai industry company manufactures
According to the mass parts ratio of recording in " II " hurdle of table 1～table 5, in the 10L Henschel mixing tank that input Japan essence machines such as (B) such as mineral filler (C), silane coupling agent (D) and organo-peroxides is manufactured, mixing tank, mixed at room temperature 1 hour, is obtained to powder mixture (operation (a-1)).
Next, according to the mass parts ratio of recording in " I " hurdle of table 1～table 5 and " II " hurdle, each composition of above-mentioned powder mixture and resin combination (A) is dropped into Nippon Roll MFG.Co., Ltd. in the 2L Banbury of manufacturing, in this mixing tank with the temperature more than decomposition temperature of organo-peroxide (B), the temperature of 180 DEG C specifically～190 DEG C after mixing approximately 12 minutes, with 180 DEG C～190 DEG C discharges of material outflow temperature, obtain silane masterbatch (operation (a-2)).
It should be noted that, about embodiment 9, do not mix with Henschel mixing tank in advance, but with Banbury by the disposable mixing of each composition (operation (a)) of recording in " I " hurdle of table 1 and " II " hurdle.
According to the mass parts ratio of recording in " III " hurdle of table 1～table 5, by Banbury additionally mixed at the temperature of 180 DEG C～190 DEG C for vector resin (E) and silanol condensation catalyst (F) etc., material outflow temperature is made as to 180 DEG C～190 DEG C and carry out melting mixing, obtains catalyst masterbatch (operation (b-1)).
Next, utilize Banbury that silane masterbatch and catalyst masterbatch are carried out to melting mixing according to the ratio of 100:5 (mass ratio) at 180 DEG C, import in the 40mm forcing machine (200 DEG C of compression unit extruder temperature 190 DEG C, temperature) of L/D=24, the uncrosslinked heat-resistant resin composition that is 1mm at the outside of 1/0.8mmTA conductor coating thickness, obtains the electric wire that external diameter is 2.8mm (operation (b-2)).Thereafter, this electric wire is placed 24 hours in the atmosphere of 80 DEG C of temperature, humidity 95%, make itself and contact with moisture, obtain having the electric wire (operation (c)) of the coating that makes the crosslinked heat-resistant resin composition forming of uncrosslinked heat-resistant resin composition.
About embodiment 21 and comparative example 17, use as vertical flame retardant test, utilize Banbury that silane masterbatch and catalyst masterbatch are carried out to melting mixing according to the ratio of 100:5 (mass ratio) at 180 DEG C, import in the 40mm forcing machine (200 DEG C of compression unit extruder temperature 190 DEG C, temperature) of L/D=24, the uncrosslinked heat-resistant resin composition that is 1.5mm at the outside of 1/1.6mmTA conductor coating thickness, obtains the electric wire that external diameter is 4.6mm (operation (b-2)).Thereafter, this electric wire is placed 24 hours in the atmosphere of 80 DEG C of temperature, humidity 95%, make itself and contact with moisture, obtain having the electric wire (operation (c)) of the coating that makes the crosslinked heat-resistant resin composition forming of uncrosslinked heat-resistant resin composition.
For obtained each electric wire, measure following adding thermal distortion, thermofixation and extrude outward appearance, the results are shown in table 1～table 5.
It should be noted that, the silane masterbatch in comparative example 9 and the mixture of catalyst masterbatch are dry wizened, cannot carry out extrusion moulding.
Adding the condition of thermal distortion 1 based on JIS C 3005 carries out with 150 DEG C of temperature of mensuration, load 3N.It should be noted that, using below 50% as qualified.
Adding the condition of thermal distortion 2 based on UL1581 carries out with 180 DEG C of temperature of mensuration, load 3N.It should be noted that, be preferably below 50%, illustrate but this test is only for reference.
About thermofixation 1, make the tubular piece of electric wire, after the graticule that installation length is 50mm, the counterweight of 117g is installed in the thermostatic bath of 170 DEG C and is placed 15 minutes, measure the length after placing and obtain elongation.It should be noted that, elongation is as qualified below 120%.
About thermofixation 2, make the tubular piece of electric wire, after the graticule that installation length is 50mm, the counterweight of 180g is installed in the thermostatic bath of 180 DEG C and is placed 15 minutes, measure the length after placing and obtain elongation.It should be noted that, elongation is preferably below 120%, illustrates but this test is only for reference.
About thermofixation 3, make the tubular piece of electric wire, after the graticule that installation length is 50mm, the counterweight of 117g is installed in the thermostatic bath of 220 DEG C and is placed 15 minutes, measure the length after placing and obtain elongation.It should be noted that, elongation is preferably below 120%, illustrates but this test is only for reference.
About extruding outward appearance 1, in the time manufacturing electric wire, observe and extrude outward appearance.It should be noted that, while utilizing 25mm forcing machine to make with linear speed 10m, situation good outward appearance is designated as to " A ", the situation that outward appearance is slightly poor is designated as " B ", and the situation of outward appearance significance difference is designated as to " C ", and by above to " B ", as Product Level, it is qualified to be designated as.
About extruding outward appearance 2, in the time manufacturing electric wire, observe and extrude outward appearance.It should be noted that, while utilizing 65mm forcing machine to make with linear speed 80m, situation good outward appearance is designated as to " A ", the situation that outward appearance is slightly poor is designated as " B ", is permission level but poor situation is designated as " C " by outward appearance.This test is only for reference and illustrate.
About extruding outward appearance 3, in embodiment 10～14 and 51～81, in the time manufacturing electric wire, observe and extrude outward appearance.It should be noted that, after utilizing 65mm forcing machine that the molten mixture of silane masterbatch and catalyst masterbatch is flowed, forcing machine is stopped to 15 minutes, forcing machine again turns round, after the molten mixture of silane masterbatch in forcing machine and catalyst masterbatch is fully flowed, with linear speed 40m/ minute trial-production electric wire.Observe the electric wire of 10m made, situation to concavo-convex point unconfirmed outward appearance is designated as to " A ", the situation that is 1 above (entirety is more than 10) by the concavo-convex point of outward appearance in 1m electric wire is designated as " C ", and the situation that is 1 following (entirety be 10 following) by the concavo-convex point of outward appearance in 1m electric wire is designated as " B ".
" B " is above is qualified as Product Level, but that this test may not need is qualified.
About extruding outward appearance 4, in embodiment 10～14 and 51～81, in the time manufacturing electric wire, observe and extrude outward appearance.It should be noted that, after utilizing 65mm forcing machine that the molten mixture of silane masterbatch and catalyst masterbatch is flowed, forcing machine is stopped to 15 minutes, the forcing machine that again turns round, immediately with linear speed 40m/ minute trial-production electric wire.Observe the electric wire of 5m made, situation to concavo-convex point unconfirmed outward appearance is designated as to " A ", the situation that is 1 above (entirety is more than 10) by the concavo-convex point of outward appearance in 50cm electric wire is designated as " C ", and the situation that is 1 following (entirety be 10 following) by the concavo-convex point of outward appearance in 50cm electric wire is designated as " B ".
" B " is above is qualified as Product Level, but that this test may not need is qualified.
In vertical flame retardant test, use embodiment 21 and the electric wire that is 4.6mm as vertical flame retardant test with the external diameter of made in comparative example 17, the test method based on IEC60332-1 is tested.Test number is n=3.It is qualified that vertical flame retardant test may not need.
About elongation and the tensile strength of isolator, with the tubular piece that embodiment 21 and comparative example 17 are similarly made electric wire, test based on JIS C3005.Tensile strength is that 10MPa is above, elongation is 100% to be qualified when above, but may not need qualified.
Result by table 1～table 5 can be clear and definite, and comparative example 1～17 cannot be taken into account and adds thermal distortion, thermofixation and extrude outward appearance, and on the other hand, embodiment 1～81 can take into account and adds thermal distortion, thermofixation and extrude outward appearance.
The present invention and its embodiment are together illustrated, but applicant thinks, as long as no specifying, the application's invention is not limited to, in any details of explanation, should under the prerequisite of not violating the invention spirit and scope shown in the scope of claims, make wide in range explanation.
The application requires the right of priority based on carried out the Japanese Patent Application 2012-081354 of patent application on March 30th, 2012 in Japan, with the form of reference, its content is introduced as to the part that this specification sheets is recorded.

Claims (17)

1. a manufacture method for heat-resistant resin composition, is characterized in that, described manufacture method comprises following operation:
(a) by the resin combination that contains polyolefin-based resins, be the organo-peroxide of 0.01 mass parts～0.6 mass parts and the mineral filler of 10 mass parts～400 mass parts and be 0.5 mass parts～15.0 mass parts with respect to these mineral filler 100 mass parts silane coupling agent carries out melting mixing more than the decomposition temperature of described organo-peroxide with respect to these resin combination 100 mass parts, not mixed silanes alcohol condensation catalyst and prepare the operation of silane masterbatch;
(b) by the operation of carrying out moulding after described silane masterbatch and silanol condensation catalyst melting mixing; With
(c) make the forming composition of described (b) operation and contact with moisture and carry out crosslinked operation.
2. the manufacture method of heat-resistant resin composition as claimed in claim 1, is characterized in that, described manufacture method comprises following operation:
(a-1) with respect to resin combination 100 mass parts that contain polyolefin-based resins, by the mineral filler of the organo-peroxide of 0.01 mass parts～0.6 mass parts and 10 mass parts～400 mass parts and the silane coupling agent that is 0.5 mass parts～15.0 mass parts with respect to mineral filler 100 mass parts mix the operation of preparing mixture;
(a-2) described mixture and resin combination are carried out to melting mixing more than the decomposition temperature of organo-peroxide, not mixed silanes alcohol condensation catalyst and prepare the operation of silane masterbatch;
(b-1) silanol condensation catalyst and vector resin are mixed and the operation of manufacture catalyst masterbatch;
(b-2) by the operation of carrying out moulding after the silane masterbatch of preparing respectively in described (a-2) and described (b-1) operation and catalyst masterbatch melting mixing; With
(c) make the forming composition of described (b-2) operation and contact with moisture and carry out crosslinked operation.
3. the manufacture method of heat-resistant resin composition as claimed in claim 1, is characterized in that, described manufacture method comprises following operation:
(a) by the resin combination that contains polyolefin-based resins, be the organo-peroxide of 0.01 mass parts～0.6 mass parts and the mineral filler of 10 mass parts～400 mass parts and be 0.5 mass parts～15.0 mass parts with respect to mineral filler 100 mass parts silane coupling agent carries out melting mixing more than the decomposition temperature of organo-peroxide with respect to these resin combination 100 mass parts, not mixed silanes alcohol condensation catalyst and prepare the operation of silane masterbatch;
(b-1) silanol condensation catalyst and vector resin are mixed and the operation of manufacture catalyst masterbatch;
(b-3) by the operation of carrying out moulding after the silane masterbatch of preparing respectively in described (a) and described (b-1) operation and catalyst masterbatch melting mixing; With
(c) make the forming composition of described (b-3) operation and contact with moisture and carry out crosslinked operation.
4. the manufacture method of the heat-resistant resin composition as described in any one in claim 1～3, is characterized in that, with respect to described resin combination 100 mass parts, the described silane coupling agent that contains 0.5 mass parts～18.0 mass parts forms.
5. the manufacture method of flame retardant resistance cross-linked composition as claimed in claim 4, is characterized in that, contains below described silane coupling agent and forms to exceed 4 mass parts and 15 mass parts.
6. the manufacture method of flame retardant resistance cross-linked composition as claimed in claim 4, is characterized in that, contains described silane coupling agent form with 5 mass parts～12 mass parts.
7. the manufacture method of flame retardant resistance cross-linked composition as claimed in claim 4, is characterized in that, contains described silane coupling agent form with 6 mass parts～10 mass parts.
8. the manufacture method of the flame retardant resistance cross-linked composition as described in any one in claim 1～7, it is characterized in that, described resin combination contains at least one and alkane hydrocarbon system oil in ethene-alpha-olefin copolymer and styrene series elastomer with the mass ratio of 4 quality %～70 quality %.
9. the manufacture method of flame retardant resistance cross-linked composition as claimed in claim 8, is characterized in that, described mass ratio is 8 quality %～70 quality %.
10. the manufacture method of flame retardant resistance cross-linked composition as claimed in claim 8 or 9, is characterized in that, at least one in described ethene-alpha-olefin copolymer and styrene series elastomer is described styrene series elastomer.
The manufacture method of 11. flame retardant resistance cross-linked compositions as described in any one in claim 8～10, is characterized in that, described ethene-alpha-olefin copolymer is terpolymer EP rubber.
The manufacture method of 12. heat-resistant resin compositions as described in any one in claim 1～11, is characterized in that, described silane coupling agent is vinyltrimethoxy silane or vinyltriethoxysilane.
The manufacture method of 13. heat-resistant resin compositions as described in any one in claim 1～12, it is characterized in that, described mineral filler is at least one that select in the group of free silicon-dioxide, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, zinc borate, zinc hydroxyl stannate and talcum composition.
The manufacture method of 14. heat-resistant resin compositions as described in any one in claim 1～13, is characterized in that the melting mixing carry out the manufacture of described silane masterbatch in the mixing tank of hermetic type time.
15. 1 kinds of products formeds, is characterized in that, it comprises by the forming composition of the heat-resistant resin composition of the manufacture method manufacturing of the heat-resistant resin composition described in any one in claim 1～14.
16. products formeds as claimed in claim 15, is characterized in that, described products formed is electric wire or optical cable coating body.
17. 1 kinds of heat-resistant resin compositions, it is the heat-resistant resin composition of the manufacture method manufacturing of the heat-resistant resin composition by described in any one in claim 1～14, it is characterized in that, this heat-resistant resin composition is described polyolefin resin by silanol bonds and mineral filler is crosslinked forms.
CN201380018536.XA 2012-03-30 2013-03-29 The manufacture method of heat-resistant resin composition and by the heat-resistant resin composition manufactured by the manufacture method and the products formed of the heat-resistant resin composition is used Active CN104204048B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012-081354 2012-03-30
JP2012081354 2012-03-30
PCT/JP2013/059504 WO2013147148A1 (en) 2012-03-30 2013-03-29 Method for producing heat-resistant resin composition, heat-resistant resin composition produced by method for producing heat-resistant resin composition, and molded article using heat-resistant resin composition

Publications (2)

Publication Number Publication Date
CN104204048A true CN104204048A (en) 2014-12-10
CN104204048B CN104204048B (en) 2018-03-16

Family

ID=49260390

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380018536.XA Active CN104204048B (en) 2012-03-30 2013-03-29 The manufacture method of heat-resistant resin composition and by the heat-resistant resin composition manufactured by the manufacture method and the products formed of the heat-resistant resin composition is used

Country Status (3)

Country Link
JP (1) JP6219268B2 (en)
CN (1) CN104204048B (en)
WO (1) WO2013147148A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109790339A (en) * 2016-10-12 2019-05-21 理研科技株式会社 Elastic composition, water crosslinking elastic composition and its manufacturing method
CN112321930A (en) * 2016-07-12 2021-02-05 日立Ge核能株式会社 Polyethylene resin composition, and pipe material, pipe, and joint each comprising same

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2927268A4 (en) * 2012-11-30 2016-08-10 Furukawa Electric Co Ltd Production method for moulded body using heat-resistant silane-cross-linkable resin composition
JP6329907B2 (en) * 2012-11-30 2018-05-23 古河電気工業株式会社 Method for producing molded article using heat-resistant silane crosslinkable resin composition
WO2014188925A1 (en) * 2013-05-20 2014-11-27 古河電気工業株式会社 Heat-resistant silane-cross-linkable resin-molded article, heat-resistant silane-cross-linkable resin composition and manufacturing method therefor, heat-resistant product using heat-resistant silane-cross-linkable resin-molded article, as well as silane coupling agent premixed filler and filler containing same
CN105308102B (en) * 2013-07-03 2018-05-29 古河电气工业株式会社 Heat resistance crosslinked with silicane resin-formed body and its manufacturing method and the heat resistance product for having used heat resistance crosslinked with silicane resin-formed body
JP6523171B2 (en) * 2013-08-27 2019-05-29 古河電気工業株式会社 Heat resistant silane cross-linked resin molded article and method for producing the same, heat resistant silane cross-linkable resin composition and method for producing the same, silane master batch, and heat resistant product using heat resistant silane cross-linked resin molded article
CN105473645B (en) 2013-09-27 2019-01-15 古河电气工业株式会社 Heat resistance crosslinked with silicane resin-formed body and its manufacturing method, heat resistance crosslinked with silicane resin combination and its manufacturing method
WO2015046478A1 (en) 2013-09-27 2015-04-02 古河電気工業株式会社 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
JP6452610B2 (en) * 2013-09-27 2019-01-16 古河電気工業株式会社 Heat-resistant silane cross-linked resin molded body and production method thereof, heat-resistant silane cross-linkable resin composition and production method thereof, silane masterbatch, and heat-resistant product using heat-resistant silane cross-linked resin molded body
JPWO2016056634A1 (en) * 2014-10-08 2017-07-27 古河電気工業株式会社 Flame-retardant crosslinked resin molded body, flame-retardant crosslinked resin composition and production method thereof, flame-retardant silane masterbatch, and molded article
JP6325413B2 (en) * 2014-10-08 2018-05-16 古河電気工業株式会社 Crosslinked resin molded body, crosslinkable resin composition and production method thereof, silane masterbatch, and molded article
JP6782164B2 (en) 2014-10-08 2020-11-11 古河電気工業株式会社 Crosslinked resin molded article and crosslinkable resin composition and their production method, silane masterbatch, and molded article
JP6140140B2 (en) * 2014-12-24 2017-05-31 古河電気工業株式会社 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
JP2016148002A (en) * 2015-02-13 2016-08-18 古河電気工業株式会社 Polyolefin crosslinked foam molded body, polyolefin crosslinking foam molded body and manufacturing method thereof, and polyolefin crosslinked foam product
JP6598474B2 (en) * 2015-03-03 2019-10-30 古河電気工業株式会社 Silane-crosslinkable rubber composition, silane-crosslinked rubber molded article, production method thereof, and silane-crosslinked rubber molded article
JP6688634B2 (en) * 2015-03-03 2020-04-28 古河電気工業株式会社 SILANE CROSSLINKABLE RUBBER COMPOSITION, SILANE CROSSLINKED RUBBER MOLDED BODY, PROCESS FOR PRODUCING THEM, AND SILANE CROSSLINKED RUBBER MOLDED ARTICLE
JP6559996B2 (en) * 2015-03-30 2019-08-14 古河電気工業株式会社 Heat-resistant silane cross-linked resin molded body, heat-resistant silane cross-linkable resin composition and production method thereof, silane masterbatch, and heat-resistant product
CN105175934A (en) * 2015-07-15 2015-12-23 安徽鸿海电缆有限公司 High-strength wear-resistant waterproof cable
CN105006286A (en) * 2015-07-15 2015-10-28 安徽鸿海电缆有限公司 High-flame-retardation, electricity-resistant and aging-resistant cable
JP6706858B2 (en) * 2016-03-31 2020-06-10 古河電気工業株式会社 Heat-resistant chlorine-containing crosslinked resin molded product and its manufacturing method, silane masterbatch, masterbatch mixture and its molded product, and heat-resistant product
JP6706855B2 (en) * 2016-02-12 2020-06-10 古河電気工業株式会社 Heat-resistant chlorine-containing crosslinked resin molded body, method for producing the same, and heat-resistant product
JP6706854B2 (en) * 2016-02-12 2020-06-10 古河電気工業株式会社 Heat-resistant cross-linked resin molded product and its manufacturing method, and heat-resistant product
WO2017138641A1 (en) * 2016-02-12 2017-08-17 古河電気工業株式会社 Molded body of chlorine-containing heat-resistant crosslinked resin, production method therefor, silane masterbatch, masterbatch mixture, molded body thereof, and heat-resistant product
JP6204632B1 (en) * 2016-03-07 2017-09-27 株式会社フジクラ Silane crosslinkable resin composition, and cable manufacturing method using the same
JP6490618B2 (en) * 2016-03-31 2019-03-27 古河電気工業株式会社 Flame-retardant crosslinked resin molded body, flame-retardant crosslinked resin composition and production method thereof, flame-retardant silane masterbatch, and flame-retardant molded article
JP2018083937A (en) * 2016-11-14 2018-05-31 Ｍｃｐｐイノベーション合同会社 Silane crosslinked polyvinyl chloride resin and method for producing molding thereof
JP6523513B2 (en) * 2018-04-10 2019-06-05 古河電気工業株式会社 Crosslinked resin molded article and crosslinkable resin composition, method for producing them, silane master batch, and molded article
KR102090256B1 (en) 2018-06-12 2020-03-17 주식회사 엘지화학 Crosslinked polyolefin separator and manufacturing method thereof
JP7097318B2 (en) * 2019-03-04 2022-07-07 古河電気工業株式会社 Method for manufacturing silane crosslinked resin molded product

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55129551A (en) * 1979-03-28 1980-10-07 Taku Yamada Bed for wall
JPS5749109A (en) * 1980-09-09 1982-03-20 Fujikura Ltd Method of producing crosslinked polyolefin rubber insulated wire
JP2000133048A (en) * 1998-10-30 2000-05-12 Yazaki Corp Tracking-resistant insulated electric wire and tracking- resistant insulated cable
JP2001101928A (en) * 1999-09-29 2001-04-13 Yazaki Corp Flame-retardant resin composition
CN1923879A (en) * 2006-09-19 2007-03-07 上海电缆研究所 Silicane crosslinking flame retardant polyolefin cable material with low smoke halogen and preparation technology thereof
CN101633754A (en) * 2009-05-22 2010-01-27 上海凯波特种电缆料厂有限公司 Oil resistant type silane natural cross-linking low smoke halogen-free flame retardant polyolefin cable material and preparation method thereof
CN101679717A (en) * 2007-05-31 2010-03-24 株式会社自动网络技术研究所 Process for producing flame retardant silane-crosslinked olefin resin, electric insulated wire, and process for manufacturing electric insulated wire
CN101688046A (en) * 2007-07-12 2010-03-31 株式会社自动网络技术研究所 Flame-retardant silane-crosslinked olefin resin composition, insulated wire, and method for production of flame-retardant silane-crosslinked olefin resin
JP2012255077A (en) * 2011-06-08 2012-12-27 Riken Technos Corp Method for manufacturing electric wire-molded body including silane-crosslinking flame retardant polyolefin and silanol catalyst resin composition

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52108462A (en) * 1976-03-09 1977-09-10 Showa Electric Wire & Cable Co Method of producing bridged polyolefin formed article
JPS55129441A (en) * 1979-03-28 1980-10-07 Furukawa Electric Co Ltd:The Method of crosslinking poly-alpha-olefin resin
JPS57172925A (en) * 1981-04-16 1982-10-25 Shin Etsu Chem Co Ltd High-filling of organic polymer with inorganic filler
JPS58129044A (en) * 1982-01-28 1983-08-01 Showa Electric Wire & Cable Co Ltd Preparation of flame-retardant crosslinked polyolefin composition
JPS61204245A (en) * 1985-03-07 1986-09-10 Toa Nenryo Kogyo Kk Polyolefin composition
JPH02185549A (en) * 1989-01-12 1990-07-19 Showa Electric Wire & Cable Co Ltd Preparation of silane-crosslinked polyolefin
DE4437465A1 (en) * 1994-10-19 1996-04-25 Peroxid Chemie Gmbh Organic peroxide-containing masterbatch composition
JP3486105B2 (en) * 1998-06-17 2004-01-13 矢崎総業株式会社 Flame-retardant crosslinked olefin resin composition and method for producing flame-retardant crosslinked olefin resin
JP4050570B2 (en) * 2001-08-13 2008-02-20 リケンテクノス株式会社 Flame retardant thermoplastic elastomer composition
JP3989306B2 (en) * 2002-06-11 2007-10-10 日本ユニカー株式会社 Water crosslinkable resin composition excellent in tracking resistance and weather resistance, and power cable having an insulating coating layer comprising the same
JP5577600B2 (en) * 2009-02-03 2014-08-27 Ｎｏｋ株式会社 EPDM composition
JP5598843B2 (en) * 2010-03-17 2014-10-01 古河電気工業株式会社 Multilayer electric wire and manufacturing method thereof
JP5594185B2 (en) * 2011-02-25 2014-09-24 三菱化学株式会社 Molded product and electric wire coated with the molded product

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55129551A (en) * 1979-03-28 1980-10-07 Taku Yamada Bed for wall
JPS5749109A (en) * 1980-09-09 1982-03-20 Fujikura Ltd Method of producing crosslinked polyolefin rubber insulated wire
JP2000133048A (en) * 1998-10-30 2000-05-12 Yazaki Corp Tracking-resistant insulated electric wire and tracking- resistant insulated cable
JP2001101928A (en) * 1999-09-29 2001-04-13 Yazaki Corp Flame-retardant resin composition
CN1923879A (en) * 2006-09-19 2007-03-07 上海电缆研究所 Silicane crosslinking flame retardant polyolefin cable material with low smoke halogen and preparation technology thereof
CN101679717A (en) * 2007-05-31 2010-03-24 株式会社自动网络技术研究所 Process for producing flame retardant silane-crosslinked olefin resin, electric insulated wire, and process for manufacturing electric insulated wire
CN101688046A (en) * 2007-07-12 2010-03-31 株式会社自动网络技术研究所 Flame-retardant silane-crosslinked olefin resin composition, insulated wire, and method for production of flame-retardant silane-crosslinked olefin resin
CN101633754A (en) * 2009-05-22 2010-01-27 上海凯波特种电缆料厂有限公司 Oil resistant type silane natural cross-linking low smoke halogen-free flame retardant polyolefin cable material and preparation method thereof
JP2012255077A (en) * 2011-06-08 2012-12-27 Riken Technos Corp Method for manufacturing electric wire-molded body including silane-crosslinking flame retardant polyolefin and silanol catalyst resin composition
CN103890865A (en) * 2011-06-08 2014-06-25 理研科技株式会社 Method for manufacturing molded body for electrical wire

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112321930A (en) * 2016-07-12 2021-02-05 日立Ge核能株式会社 Polyethylene resin composition, and pipe material, pipe, and joint each comprising same
CN112321930B (en) * 2016-07-12 2023-08-25 日立Ge核能株式会社 Polyethylene resin composition, and pipe material, pipe and joint containing the same
CN109790339A (en) * 2016-10-12 2019-05-21 理研科技株式会社 Elastic composition, water crosslinking elastic composition and its manufacturing method
CN109790339B (en) * 2016-10-12 2022-06-14 理研科技株式会社 Elastomer composition, water-crosslinkable elastomer composition, and method for producing same

Also Published As

Publication number Publication date
WO2013147148A1 (en) 2013-10-03
CN104204048B (en) 2018-03-16
JP6219268B2 (en) 2017-10-25
JPWO2013147148A1 (en) 2015-12-14

Similar Documents

Publication Publication Date Title
CN104204048A (en) Method for producing heat-resistant resin composition, heat-resistant resin composition produced by method for producing heat-resistant resin composition, and molded article using heat-resistant resin composition
JP6767438B2 (en) Heat-resistant silane cross-linked resin molded body and its manufacturing method, heat-resistant silane cross-linked resin composition and its manufacturing method, silane masterbatch, and heat-resistant product using heat-resistant silane cross-linked resin molded body
CN105473645B (en) Heat resistance crosslinked with silicane resin-formed body and its manufacturing method, heat resistance crosslinked with silicane resin combination and its manufacturing method
JP6265875B2 (en) Heat-resistant silane cross-linked resin molded body and production method thereof, heat-resistant silane cross-linkable resin composition and production method thereof, silane masterbatch, and heat-resistant product using heat-resistant silane cross-linked resin molded body
US10438718B2 (en) Heat-resistant silane crosslinked resin molded body and method of producing the same, heat-resistant silane crosslinkable resin composition and method of producing the same, silane master batch, and heat-resistant product using heat-resistant silane crosslinked resin molded body
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
JP6858115B2 (en) Method for Producing Silane Crosslinkable Rubber Composition and Silane Crosslinkable Rubber Mold
CN104812813A (en) Production method for moulded body using heat-resistant silane-cross-linkable resin composition
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
JP5989419B2 (en) Heat resistant resin composition, method for producing the heat resistant resin composition, wiring material having the heat resistant resin composition, cable and molded article
JP6395745B2 (en) Silane-crosslinked resin molded body, silane-crosslinkable resin composition and production method thereof, silane masterbatch, and molded article
JP6667474B2 (en) Silane crosslinked resin molded article and method for producing the same, silane masterbatch, masterbatch mixture and molded article thereof, and heat-resistant product
JP6706870B2 (en) SILANE CROSSLINKABLE RUBBER COMPOSITION, SILANE CROSSLINKED RUBBER MOLDED BODY, PROCESS FOR PRODUCING THE SAME, AND SILANE CROSSLINKED RUBBER MOLDED ARTICLE
CN104822744A (en) Production method for moulded body using heat-resistant silane-cross-linkable resin composition
JP6462606B2 (en) Heat-resistant silane cross-linked resin molded body, heat-resistant silane cross-linkable resin composition and production method thereof, silane masterbatch, and heat-resistant product
JP6688634B2 (en) SILANE CROSSLINKABLE RUBBER COMPOSITION, SILANE CROSSLINKED RUBBER MOLDED BODY, PROCESS FOR PRODUCING THEM, AND SILANE CROSSLINKED RUBBER MOLDED ARTICLE
JP6559996B2 (en) Heat-resistant silane cross-linked resin molded body, heat-resistant silane cross-linkable resin composition and production method thereof, silane masterbatch, and heat-resistant product
JP6895920B2 (en) Method for manufacturing heat-resistant silane-crosslinked polyolefin resin molded product, silane-crosslinked polyolefin resin composition, heat-resistant silane-crosslinked polyolefin resin molded product, heat-resistant product, electric wire and optical fiber cable
JP6567311B2 (en) Heat-resistant silane cross-linked resin molded body, heat-resistant silane cross-linkable resin composition and production method thereof, silane masterbatch, and heat-resistant product
JP2023107031A (en) Heat-resistant silane crosslinked resin molded body, silane crosslinked resin composition and methods for producing them, and wiring material
JP6490618B2 (en) Flame-retardant crosslinked resin molded body, flame-retardant crosslinked resin composition and production method thereof, flame-retardant silane masterbatch, and flame-retardant molded article
JP2022153156A (en) Silane crosslinked resin molded body and method for producing the same, silane crosslinkable resin composition and method for producing the same and product
JP2022155042A (en) Silane-crosslinked acrylic rubber molding and method for manufacturing the same, silane-crosslinkable acrylic rubber composition, and silane-crosslinked acrylic rubber molded article
JP2022152948A (en) Silane-crosslinked rubber molding and method for manufacturing the same, silane-crosslinkable rubber composition, and silane-crosslinked rubber molded article
JP2016188306A (en) Heat-resistant silane crosslinked resin molding and heat-resistant silane crosslinkable resin composition and method for producing them, silane master batch and heat-resistant product

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant