WO2017018091A1 - 電線ケーブル - Google Patents

電線ケーブル Download PDF

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Publication number
WO2017018091A1
WO2017018091A1 PCT/JP2016/068126 JP2016068126W WO2017018091A1 WO 2017018091 A1 WO2017018091 A1 WO 2017018091A1 JP 2016068126 W JP2016068126 W JP 2016068126W WO 2017018091 A1 WO2017018091 A1 WO 2017018091A1
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Prior art keywords
silane
plasticizer
chlorinated polyethylene
crosslinking
mass
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PCT/JP2016/068126
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English (en)
French (fr)
Japanese (ja)
Inventor
新吾 芦原
貴 青山
浩貴 矢▲崎▼
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日立金属株式会社
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Priority to CN201680044052.6A priority Critical patent/CN107924737A/zh
Publication of WO2017018091A1 publication Critical patent/WO2017018091A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/06—Rod-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/154—Coating solid articles, i.e. non-hollow articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/023—On to modified polymers, e.g. chlorinated polymers
    • 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
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/14—Insulating conductors or cables by extrusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
    • H01B13/24—Sheathing; Armouring; Screening; Applying other protective layers by extrusion
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3462—Cables
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to an electric cable.
  • Chlorinated polyethylene is a thermoplastic elastomer that excels in various properties such as heat resistance and wear resistance, and is a material for forming coating layers (eg, insulation layers and sheaths) covering the outer periphery of conductors in electric cables such as electric wires and cables. It is used as.
  • a crosslinking treatment is performed to improve the oil resistance of the coating layer.
  • silane crosslinking using a silane compound silane coupling agent
  • a silane compound is blended with chlorinated polyethylene and kneaded.
  • a silane compound is graft-copolymerized to chlorinated polyethylene by heating to form a silane crosslinkable composition containing silane-grafted chlorinated polyethylene.
  • the silane crosslinkable composition is extruded so as to cover the outer periphery of the conductor and molded into a predetermined shape. Thereafter, the molded body is brought into contact with moisture to advance a crosslinking reaction, thereby forming a silane-crosslinked coating layer.
  • additives are blended in the silane crosslinkable composition forming the coating layer according to the properties required for the coating layer.
  • various additives such as a plasticizer that imparts flexibility to the coating layer, a stabilizer that imparts resistance to the external environment, and carbon black that imparts abrasion resistance are blended.
  • These additives are generally blended at the same time when a silane compound is blended with chlorinated polyethylene from the viewpoint of simplifying the production process. These are kneaded and then heated to graft copolymerize the silane compound with chlorinated polyethylene in the presence of the additive.
  • the silane compound when the silane compound is graft copolymerized with chlorinated polyethylene in the presence of a plasticizer among the additives, the graft copolymerization may be inhibited by the plasticizer.
  • the ratio of graft copolymerization of the silane compound hereinafter also referred to as grafting rate
  • grafting rate the ratio of graft copolymerization of the silane compound
  • graft copolymerization is carried out at a relatively high temperature, it is possible to plasticize a silane crosslinkable composition heated to a high temperature.
  • the plasticizer may volatilize.
  • premature crosslinking occurs, making it difficult to extrude the silane crosslinkable composition and form a coating layer.
  • the formed coating layer has a sufficient degree of crosslinking, but has a low elongation and cannot satisfy the flexibility required for the coating layer.
  • An object of the present invention is to provide an electric cable having a coating layer having a high degree of crosslinking and excellent flexibility.
  • the electric wire cable of one embodiment of the present invention is: Comprising a conductor and a coating layer covering the outer periphery of the conductor;
  • the coating layer is formed by crosslinking a silane crosslinkable composition,
  • the silane crosslinkable composition contains a silane-grafted chlorinated polyethylene obtained by graft copolymerizing a silane compound with chlorinated polyethylene and a non-mineral oil plasticizer.
  • an electric cable having a coating layer having a high degree of crosslinking and excellent flexibility.
  • FIG. 1 is a cross-sectional view showing a schematic structure of a cable according to an embodiment of the present invention.
  • FIG. 2 is an explanatory diagram showing a grafting process using a single screw extruder in the example.
  • FIG. 3 is an explanatory view showing the production of the cable in the example.
  • the plasticizer is an additive generally used for enhancing the flexibility of the coating layer.
  • mineral oil refined from crude oil is used.
  • Mineral oils include paraffinic oils, naphthenic oils, and aromatic oils depending on the content ratios of paraffin, naphthene, and aromatic components.
  • these mineral oils greatly inhibit graft copolymerization of silane compounds among plasticizers, so that a sufficient degree of crosslinking cannot be obtained when silane crosslinking is performed.
  • non-mineral oil systems such as chlorinated paraffin and phthalate plasticizers.
  • the plasticizer the grafting rate to chlorinated polyethylene can be increased without inhibiting graft copolymerization of the silane compound. Thereby, a high degree of crosslinking can be obtained when silane crosslinking is performed.
  • the non-mineral oil plasticizer is also excellent in compatibility with the silane-grafted chlorinated polyethylene, it is difficult to elute from the coating layer, and bleed can be suppressed. Therefore, according to the non-mineral oil plasticizer, a coating layer having a high degree of crosslinking and excellent flexibility can be formed.
  • the present invention has been made based on the above findings.
  • silane crosslinkable composition First, the silane crosslinkable composition which forms the coating layer of an electric wire cable is demonstrated.
  • the silane crosslinkable composition contains a silane-grafted chlorinated polyethylene and a non-mineral oil plasticizer.
  • the silane-grafted chlorinated polyethylene is obtained by mixing chlorinated polyethylene, a silane compound, and a peroxide, and graft-copolymerizing the silane compound to the chlorinated polyethylene in the presence of the peroxide.
  • Silane-grafted chlorinated polyethylene has a silane group derived from the graft-copolymerized silane compound in the molecular structure, and when it comes into contact with water, the silane group in the molecular structure is hydrolyzed to form a silanol group.
  • the silanol groups are dehydrated and condensed to form a crosslinked structure, whereby silane crosslinking is performed.
  • Chlorinated polyethylene has a structure in which a part of hydrogen in a hydrocarbon skeleton such as polyethylene is substituted with a chlorine atom having a high electronegativity, and is a highly polar component.
  • the chlorinated polyethylene can be obtained, for example, by blowing chlorine gas into an aqueous suspension obtained by suspending and dispersing linear polyethylene (such as low density polyethylene or high density polyethylene) in water.
  • the degree of chlorination of the chlorinated polyethylene is preferably 25% or more and 45% or less from the viewpoint of obtaining a good balance of various properties such as heat resistance, oil resistance and flame retardancy of the coating layer, and further when forming the coating layer. From the viewpoint of improving workability, it is more preferably 30% or more and 40% or less.
  • the silane compound has an unsaturated bond group and a hydrolyzable silane group.
  • the unsaturated bond group of the silane compound is not limited as long as the silane compound can be graft copolymerized with chlorinated polyethylene, and examples thereof include a vinyl group, a methacryl group, and an acrylic group. Among these, a methacryl group is preferable as the unsaturated bond group.
  • a methacrylic silane compound having a methacrylic group is more compatible with a chlorinated polyethylene than a vinylsilane compound having a vinyl group, and can be easily dispersed in the chlorinated polyethylene.
  • a cross-linked structure can be formed. Furthermore, it is lower in flammability than vinyl silane compounds and is excellent in handleability.
  • hydrolyzable silane group of the silane compound examples include those having a hydrolyzable structure such as a halogen, an alkoxy group, an acyloxy group, and a phenoxy group.
  • silane group having a hydrolyzable structure examples include a halosilyl group, an alkoxysilyl group, an acyloxysilyl group, and a phenoxysilyl group.
  • silane compound examples include methacrylic silanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. Can be used.
  • the amount of silane compound graft copolymerized with chlorinated polyethylene is the degree of crosslinking of the final molded product (coating layer) or the reaction conditions for crosslinking. It may be changed appropriately according to (for example, temperature, time, etc.).
  • the compounding amount of the silane compound is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 1.0 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of chlorinated polyethylene. More preferably. By setting such a blending amount, an appropriate degree of crosslinking can be obtained when silane crosslinking is performed.
  • the peroxide is for graft copolymerizing a silane compound with chlorinated polyethylene. Specifically, the peroxide generates oxy radicals by thermal decomposition. Oxy radicals generate chlorinated polyethylene radicals by extracting hydrogen from chlorinated polyethylene. And the radical of chlorinated polyethylene reacts with the unsaturated bond group (for example, vinyl group, methacryl group, etc.) which a silane compound has, and a silane compound will be graft-copolymerized to chlorinated polyethylene. Thus, the peroxide generates oxy radicals and causes graft copolymerization of the silane compound onto chlorinated polyethylene.
  • the unsaturated bond group for example, vinyl group, methacryl group, etc.
  • an organic peroxide can be used as the peroxide.
  • Organic peroxide has a high hydrogen abstraction ability for extracting hydrogen from chlorinated polyethylene, and can be thermally decomposed at a temperature at which chlorinated polyethylene is hardly deteriorated (it is difficult to dehydrochlorinate) to generate oxy radicals. Since the deterioration start temperature of chlorinated polyethylene is about 200 ° C., it is preferable to use an organic peroxide having a one-minute half-life temperature of 120 ° C. or more and 200 ° C. or less as the peroxide. From the viewpoint of shortening the time required for the grafting reaction, it is better to use an organic peroxide having a one-minute half-life temperature of 150 ° C. or higher and 200 ° C. or lower.
  • the 1-minute half-life temperature is a temperature at which the half-life of the peroxide is 1 minute.
  • dicumyl peroxide 1,1-di (t-butylperoxy) cyclohexane, t-butylperoxyisopropyl carbonate, t-amylperoxyisopropyl carbonate, 2,5 dimethyl 2,5 di (t-butylperoxy) hexane, di-t-butyl peroxide, di-t-amyl peroxide, 1,1-di (t-amylperoxy) cyclohexane, t-butylperoxy 2- Ethyl hexyl carbonate or the like can be used. These may be used alone or in combination of two or more. Among these, dicumyl peroxide having a 1 minute half-life temperature of about 175 ° C. may be used.
  • the compounding amount of the peroxide may be appropriately changed according to the compounding amount of the silane compound, and is preferably 0.03 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the chlorinated polyethylene. By setting such a blending amount, an appropriate degree of crosslinking can be obtained when silane crosslinking is performed.
  • the silane crosslinkable composition is blended with a plasticizer in order to increase the flexibility of the coating layer.
  • a plasticizer in order to increase the flexibility of the coating layer.
  • a non-mineral oil plasticizer is used. Since this plasticizer does not significantly inhibit the graft copolymerization of the silane compound to chlorinated polyethylene, the grafting rate of the silane compound can be increased. And since it is excellent in compatibility with a silane graft chlorinated polyethylene, it is hard to bleed from a silane crosslinkable composition.
  • the non-mineral oil plasticizer is not particularly limited as long as it has an atom with a large electronegativity or a functional group with a large polarity, but at least one of a chlorinated paraffin and a phthalate ester plasticizer may be used.
  • Chlorinated paraffin has the same chemical structure as chlorinated polyethylene and is incorporated into the crosslinked product when silane-grafted chlorinated polyethylene is crosslinked with silane, thereby improving the degree of crosslinking and making the crosslinked product oil resistant. Etc. can be improved.
  • the phthalate ester plasticizer has an ester group and is more polar than the mineral oil plasticizer, the oil resistance of the crosslinked product can be improved. From the viewpoint of further improving the degree of crosslinking of the coating layer, chlorinated polyolefin incorporated in the crosslinked body is more preferable.
  • the blending amount of the non-mineral oil plasticizer is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the chlorinated polyethylene. If it is such a compounding quantity, the bleeding from a coating layer can be suppressed, maintaining the flexibility of a coating layer highly.
  • a silanol condensation catalyst that promotes silane crosslinking
  • a group II element such as magnesium and calcium
  • a group VIII element such as cobalt and iron
  • a metal element such as tin, zinc and titanium
  • metal salts of octylic acid and adipic acid, amine compounds, acids, and the like can be used.
  • dioctyltin dineodecanoate dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctaate, stannous acetate, stannous carbrate, lead naphthenate, zinc caprylate, cobalt naphthenate, etc.
  • Metal salts amine compounds such as ethylamine, dibutylamine, hexylamine and pyridine, inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as toluenesulfonic acid, acetic acid, stearic acid and maleic acid can be used.
  • antioxidants including anti-aging agents
  • fillers such as carbon black, flame retardants, lubricants, copper damage discoloration inhibitors, crosslinking aids, stabilizers, and the like may be used.
  • a non-mineral oil plasticizer is added to chlorinated polyethylene and kneaded. Since the non-mineral oil plasticizer is compatible with the chlorinated polyethylene, the plasticizer can be dispersed in the chlorinated polyethylene.
  • the non-mineral oil plasticizer is preferably blended in the range of 1 to 30 parts by mass with respect to 100 parts by mass of chlorinated polyethylene.
  • a silane compound and a peroxide are added to a mixture in which a plasticizer is dispersed in chlorinated polyethylene and kneaded. Since the non-mineral oil plasticizer having compatibility with the silane compound is dispersed in the mixture, the silane compound can be uniformly dispersed in the mixture without agglomeration.
  • the silane compound ranges from 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of chlorinated polyethylene, and the peroxide ranges from 0.03 parts by weight to 3.0 parts by weight with respect to 100 parts by weight of chlorinated polyethylene. It is preferable to mix with.
  • the mixture to which the silane compound and the peroxide are added is heated and kneaded, whereby the silane compound is graft copolymerized with the chlorinated polyethylene in the presence of the peroxide.
  • a silane-grafted chlorinated polyethylene is formed, and a silane crosslinkable composition containing this and a non-mineral oil plasticizer is obtained.
  • the silane compound is uniformly dispersed without agglomerating in the chlorinated polyethylene and then graft copolymerized, the silane-grafted chlorinated polyethylene has a high silane compound grafting rate, and Silane groups are uniformly introduced.
  • the non-mineral oil plasticizer has compatibility with the silane-grafted chlorinated polyethylene, bleeding is suppressed.
  • the mixture when it is kneaded, it may be kneaded using a kneading reaction apparatus such as a roll machine, an extruder, a kneader, a mixer, or an autoclave.
  • a kneading reaction apparatus such as a roll machine, an extruder, a kneader, a mixer, or an autoclave.
  • kneading conditions and graft reaction conditions are not particularly limited.
  • silane cross-linked product is obtained by bringing the silane cross-linkable composition into contact with water and silane-grafted chlorinated polyethylene by silane cross-linking.
  • silane-grafted chlorinated polyethylene has a high grafting rate and silane groups are uniformly introduced into the chemical structure, the silane crosslinked product obtained therefrom has a high degree of crosslinking and a crosslinked structure. It will be formed homogeneously.
  • the cross-linked silane has a high degree of cross-linking and a gel fraction that is an index of the degree of cross-linking is 70% or more.
  • a gel fraction that is an index of the degree of cross-linking is 70% or more.
  • the upper limit of the gel fraction is not particularly limited, and the higher the gel fraction, the more cross-linked structures are formed in the silane cross-linked product, and the mechanical properties become higher.
  • a gel fraction is calculated
  • the silane cross-linked product contains a non-mineral oil plasticizer. Therefore, the silane cross-linked product is easily stretched and has excellent flexibility. In addition, since the plasticizer is highly compatible, bleeding of the plasticizer is suppressed.
  • FIG. 1 is a cross-sectional view showing a schematic structure of a cable according to an embodiment of the present invention.
  • the cable 1 of this embodiment includes a conductor 10.
  • a conductor 10 As the conductor 10, a copper wire made of low-oxygen copper, oxygen-free copper, or the like, a copper alloy wire, a metal wire made of aluminum, silver, or the like, or a stranded wire formed by twisting metal wires can be used.
  • the outer diameter of the conductor 10 can be appropriately changed according to the use of the cable 1.
  • An insulating layer 11 is provided so as to cover the outer periphery of the conductor 10.
  • the insulating layer 11 is formed of a conventionally known resin composition, for example, a resin composition containing ethylene propylene rubber.
  • the thickness of the insulating layer 11 can be appropriately changed according to the use of the cable 1.
  • An outer cover layer 12 (sheath 12) is provided so as to cover the outer periphery of the insulating layer 11.
  • the sheath 12 is formed of a silane crosslinked product obtained by crosslinking a silane crosslinkable composition.
  • the sheath 12 has a high degree of crosslinking and is configured so that the gel fraction is 70% or more.
  • the cable 1 is manufactured as follows, for example. First, for example, a copper wire is prepared as the conductor 10. Subsequently, a resin composition containing ethylene propylene rubber is extruded by an extruder so as to cover the outer periphery of the conductor 10 to form the insulating layer 11 having a predetermined thickness. Subsequently, the sheath 12 is formed by extruding the silane crosslinkable composition described above at a predetermined thickness so as to cover the outer periphery of the insulating layer 11. Thereafter, the sheath 12 is exposed to an environment of, for example, a temperature of 80 ° C. and a relative humidity of 90% to react with moisture, whereby the silane crosslinkable composition forming the sheath 12 is crosslinked with silane.
  • a resin composition containing ethylene propylene rubber is extruded by an extruder so as to cover the outer periphery of the conductor 10 to form the insulating layer 11 having a predetermined thickness.
  • the cable 1 is described as an example of the electric cable, but the present invention is not limited to this, and may be configured as an insulated electric wire including an insulating layer as a covering layer.
  • an insulating layer may be formed by extruding the silane crosslinkable composition on the outer periphery of the conductor, and the insulating layer may be brought into contact with water for silane crosslinking.
  • the cable 1 includes one electric wire provided with an insulating layer on the outer periphery of the conductor.
  • the cable 1 is a stranded wire obtained by twisting two or more electric wires. You may prepare.
  • Chlorinated polyethylene (Mooney viscosity at 121 ° C. (ML1 + 4): 55, heat of fusion: less than 1.0 J / g): “CM352L” manufactured by Hangzhou Science & Technology Co., Ltd. -Hydrotalcite: “Mugcellar 1” manufactured by Kyowa Chemical Industry Co., Ltd. Epoxidized soybean oil: “New Sizer 510R” manufactured by Nippon Oil & Fats Co., Ltd. ⁇ Peroxide (Dicumyl peroxide): “DCP” manufactured by NOF Corporation Silane compound (3-methacryloxypropyltrimethoxysilane): “KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Silane compound (3-methacryloxypropyltriethoxysilane): “KBE-503” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Plasticizer chlorinated paraffin: “Empara 40” manufactured by Ajinomoto Fine Techno Co., Ltd.
  • Plasticizer (di-2-ethylhexyl phthalate): Shin Nippon Rika Co., Ltd.
  • “Sanso Sizer Ar DOP” ⁇ Plasticizer (Diisononyl phthalate): Shin Nippon Rika Co., Ltd.
  • Lubricant polyethylene wax (PE wax, molecular weight: 2800): “High Wax NL-200” manufactured by Mitsui Chemicals, Inc.
  • Lubricant ethylenebisoleic acid amide
  • Phenol-based antioxidant (4,4'-thiobis (3-methyl-6-tert-butylphenol)): "NOCRACK 300R” manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Silanol condensation catalyst (dioctyltin dineodecanoate): “Neostan U-830” manufactured by Nitto Kasei Co., Ltd.
  • silane crosslinkable composition ⁇ Example 1>
  • an additive such as a plasticizer was added to the base polymer. Specifically, first, as shown in Table 1 below, in a pressure type kneader, 100 parts by mass of chlorinated polyethylene, 6 parts by mass of hydrotalcite as a stabilizer, and epoxidized soybean oil as a stabilizer 6 parts by weight, 3 parts by weight of PE wax as a lubricant, 1 part by weight of ethylenebisoleic acid amide as a lubricant, 40 parts by weight of carbon, and non-mineral oil-based chlorinated paraffin as a plasticizer 10 parts by mass were added and kneaded for 5 minutes at a blade rotation number of 20 rpm. At this time, the kneader tank was not particularly heated, and the temperature of the kneaded product was raised to about 100 ° C. due to heat generation of the rubber component.
  • a silane compound and a peroxide were added to the kneaded product.
  • the kneaded product was subjected to silane grafting treatment using a single screw extruder 100 shown in FIG. Specifically, the kneaded material was continuously supplied into the cylinder 103a from the hopper 101 of the single screw extruder 100, and sent out from the cylinder 103a to the cylinder 103b by the rotation of the screw 102. At this time, the kneaded material was heated and softened and kneaded by the cylinders 103a and 103b to graft copolymerize the chlorinated polyethylene with the silane compound. Thereby, the silane graft
  • the silane crosslinkable composition was sent to the head part 104 of the extruder 100, and the strand 20 (length 150 cm) of the silane crosslinkable composition was extruded from the die 105. Then, the strand 20 was introduced into the water tank 106, cooled with water, and drained with an air wiper 107. Then, the strand 20 was pelletized with the pelletizer 108, and the pellet 21 which consists of a silane crosslinkable composition was formed. And in order to prevent the mutual adhesion of the pellet 21, the talc 1 mass part was applied to the pellet 21, and the compound of Example 1 was obtained. In the silane grafting process, a 40 mm single screw single screw extruder 100 was used.
  • the ratio L / D between the screw diameter D and the screw length L was 25. Further, the temperature of the cylinder 103a was 80 ° C., the temperature of the cylinder 103b was 200 ° C., and the temperature of the head portion 104 was 200 ° C. Further, as the screw 102, a full flight shape with a compression ratio of 2.0 was used. The rotation speed of the screw 102 was 20 rpm. Further, a die having a hole diameter of 5 mm and three holes was used as the die 105.
  • a masterbatch containing an antioxidant and a silanol condensation catalyst was prepared separately from the above compound. Specifically, in a pressure kneader, 100 parts by mass of chlorinated polyethylene, 6 parts by mass of hydrotalcite as a stabilizer, 6 parts by mass of epoxidized soybean oil as a stabilizer, phenolic antioxidant 0.08 parts by mass of the agent, 1.5 parts by mass of the amine-based antioxidant, and 2 parts by mass of the silanol condensation catalyst were added and kneaded for 10 minutes at a blade rotation number of 20 rpm. And this kneaded material was continuously supplied to the single screw extruder 100 shown in FIG.
  • the silane crosslinkable composition of Example 1 was prepared by adding the pellet master batch to the pellet compound and dry blending. At this time, the master batch was added to the compound at a ratio such that the master batch was 2.5 parts by mass with respect to 100 parts by mass of the chlorinated polyethylene in the compound.
  • Examples 2 and 3 In Examples 2 and 3, as shown in Table 1, except that the kind of plasticizer contained in the silane crosslinkable composition was changed from chlorinated paraffin to di-2-ethylhexyl phthalate or diisononyl phthalate. A silane crosslinkable composition was prepared in the same manner as in Example 1 to prepare a cable.
  • Example 4 In Example 4, the type of the silane compound was changed from 3-methacryloxypropyltrimethoxysilane to 3-methacryloxypropyltriethoxysilane, and the blending amount was changed from 3.35 parts by mass to 3.92 parts by mass.
  • a silane crosslinkable composition was prepared in the same manner as in Example 1 to produce a cable.
  • Comparative Example 1 a silane crosslinkable composition was prepared and a cable was prepared in the same manner as in Example 1 except that no plasticizer was added.
  • Comparative Examples 2 to 4 silane crosslinkable compositions were prepared and cables were prepared in the same manner as in Example 1 except that the type of plasticizer was changed from a non-mineral oil type to a mineral oil type.
  • mineral oil plasticizer paraffinic process oil was used in Comparative Example 2, naphthenic process oil was used in Comparative Example 3, and aromatic process oil was used in Comparative Example 4.
  • the cables 1 of Examples 1 to 4 and Comparative Examples 1 to 4 were produced by extruding the prepared silane crosslinkable composition with a single screw extruder 100 shown in FIG. Specifically, a copper conductor having a cross-sectional area of 8 mm 2 is inserted as the conductor 10 into the die 105 of the single-screw extruder 100, and ethylene propylene rubber (EP rubber) is extruded on the outer periphery thereof to have a thickness of 1.0 mm.
  • the cable 1 was produced by forming the insulating layer 11 and extruding the silane crosslinkable composition described above on the outer periphery of the insulating layer 11 to form a sheath 12 having a thickness of 1.7 mm.
  • the cable 1 was stored in a constant temperature and humidity chamber at a temperature of 60 ° C. and a relative humidity of 95% for 24 hours, and subjected to silane crosslinking treatment.
  • a 20 mm single-screw single-screw extruder 100 was used.
  • the ratio L / D between the screw diameter D and the screw length L was 15.
  • the temperature of the cylinder 103a was 120 ° C.
  • the temperature of the cylinder 103b was 150 ° C.
  • the temperature of the crosshead portion 110 was 150 ° C.
  • the temperature of the neck 109 was 150 ° C.
  • the temperature of the die 105 was 130 ° C.
  • the rotation speed of the screw 102 was 15 rpm, and the screw 102 having a full flight shape and a compression ratio of 2.0 was used.
  • the gel fraction of the sheath after silane crosslinking was measured. First, 0.5 g of a sample was taken from the sheath after silane crosslinking, and this sample was put in a 40 mesh brass wire mesh. Subsequently, the sample was extracted with xylene in a 110 ° C. oil bath. After the extraction treatment, the remaining sample was taken out from xylene and vacuum-dried at 80 ° C. for 4 hours.
  • the mass of the remaining sample after drying was weighed, and the gel fraction R of the sample was calculated from the following equation using the mass a of the sample before xylene extraction and the mass b of the remaining sample after xylene extraction.
  • R (%) b / a ⁇ 100
  • the case where the gel fraction after cross-linking is 70% or more was regarded as acceptable “ ⁇ ”
  • the case where the gel fraction was less than 70% was regarded as unacceptable “x”.
  • the tensile elongation of the sheath was measured. First, the sheath was peeled off from the cable, and the sheath was punched with a No. 6 dumbbell to prepare a test sample. The test sample was pulled at a tensile speed of 500 mm / min, and the tensile elongation was measured. In this example, if the tensile elongation was 350% or more, it was judged as acceptable “ ⁇ ”, and if it was less than 350%, it was judged as unacceptable “x”.
  • the oil resistance of the sheath is the test lubricating oil No. specified in JIS K6258. 2 (IRM902 oil) was used to heat the sheath in oil at 120 ° C. for 18 hours, and the residual ratio of tensile strength before and after heating was determined. In this example, if the residual tensile strength of the sheath after the oil resistance test was 60% or more, it was judged as “good”, and if it was less than that, it was judged as “bad”.
  • Table 1 shows the evaluation results for the examples and comparative examples.
  • a conductor Comprising a conductor and a coating layer covering the outer periphery of the conductor;
  • the coating layer is formed by crosslinking a silane crosslinkable composition,
  • the silane crosslinkable composition provides an electric wire cable containing a silane-grafted chlorinated polyethylene obtained by graft copolymerization of a silane compound with chlorinated polyethylene and a non-mineral oil plasticizer.
  • the non-mineral oil plasticizer is at least one of a chlorinated paraffin and a phthalate ester plasticizer.
  • the blending amount of the non-mineral oil plasticizer is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the chlorinated polyethylene.
  • the silane compound has a methacryl group.
  • the silane compound is at least one of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane.
  • the gel fraction after crosslinking of the coating layer is 70% or more.

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CA2190050A1 (en) * 1996-11-12 1998-05-12 G. Ronald Brown Moisture cross-linking of vinyl chloride homopolymers and copolymers
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