WO2014188925A1 - Article moule en resine reticulable par silane resistant a la chaleur, composition de resine reticulable par silane resistante a la chaleur et procede de fabrication s'y rapportant, produit resistant a la chaleur utilisant un article moule en resine reticulable par silane resistant a la chaleur, ainsi que matiere charge premelangee a base d'agent de couplage silane et matiere de charge la contenant - Google Patents

Article moule en resine reticulable par silane resistant a la chaleur, composition de resine reticulable par silane resistante a la chaleur et procede de fabrication s'y rapportant, produit resistant a la chaleur utilisant un article moule en resine reticulable par silane resistant a la chaleur, ainsi que matiere charge premelangee a base d'agent de couplage silane et matiere de charge la contenant Download PDF

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Publication number
WO2014188925A1
WO2014188925A1 PCT/JP2014/062813 JP2014062813W WO2014188925A1 WO 2014188925 A1 WO2014188925 A1 WO 2014188925A1 JP 2014062813 W JP2014062813 W JP 2014062813W WO 2014188925 A1 WO2014188925 A1 WO 2014188925A1
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Prior art keywords
coupling agent
silane coupling
filler
heat
silane
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PCT/JP2014/062813
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English (en)
Japanese (ja)
Inventor
西口　雅己
有史 松村
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古河電気工業株式会社
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Priority to JP2015518202A priority Critical patent/JP6440613B2/ja
Publication of WO2014188925A1 publication Critical patent/WO2014188925A1/fr

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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
    • H01B3/30—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
    • 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
    • C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
    • 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
    • C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4401—Optical cables
    • G02B6/4429—Means specially adapted for strengthening or protecting the cables
    • G02B6/443—Protective covering
    • 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

Definitions

  • the present invention relates to a heat-resistant silane cross-linked resin molded article and a method for producing the same, a heat-resistant silane cross-linkable resin composition and a method for producing the same, a heat-resistant product using the heat-resistant silane cross-linked resin molded article, and a silane coupling agent premixed filler And a filler containing at least the silane coupling agent mixed filler.
  • the present invention relates to a heat-resistant silane cross-linked resin molded article excellent in mechanical properties, reinforcing properties, heat resistance, flame retardancy and appearance, a method for producing the same, and a heat-resistant silane capable of forming this heat-resistant silane cross-linked resin molded article.
  • the present invention relates to a silane coupling agent pre-mixed filler suitably used in the production method and a filler containing at least the silane coupling agent mixed filler.
  • a resin composition containing a large amount of an inorganic filler such as magnesium hydroxide, aluminum hydroxide, or calcium carbonate is used.
  • wiring materials used in electrical and electronic equipment may be heated to 80 to 105 ° C. and further to about 125 ° C. in continuous use, and heat resistance against this may be required.
  • a method of crosslinking the coating material by an electron beam crosslinking method, a chemical crosslinking method or the like is employed.
  • silane crosslinking method is a method in which a hydrolyzable silane coupling agent having an unsaturated group is grafted to a polymer in the presence of an organic peroxide to obtain a silane graft polymer, and then water and moisture in the presence of a silanol condensation catalyst. This is a method of obtaining a cross-linked molded article by contacting them.
  • the silane cross-linking method in particular does not require special equipment and can be used in a wide range of fields.
  • a method for producing a halogen-free heat-resistant silane cross-linked resin is a heat-resistant kneading silane masterbatch obtained by grafting a hydrolyzable silane coupling agent having an unsaturated group onto a polyolefin resin, with a polyolefin and an inorganic filler. This is a method of melt-mixing a property master batch and a catalyst master batch containing a silanol condensation catalyst.
  • the silane masterbatch and the heat-resistant masterbatch are uniformly mixed in a single screw extruder or a twin screw extruder by dry mixing. It becomes difficult to melt and knead. Moreover, since the ratio including the silane masterbatch is limited, it has been difficult to achieve higher flame resistance and higher heat resistance. Moreover, when such a method is used, excellent strength, wear resistance, and reinforcement cannot be obtained.
  • a hydrolyzable silane coupling agent having a hydrolyzable unsaturated group is added to a heat-resistant masterbatch obtained by melting and mixing a polyolefin resin and a flame retardant.
  • a method of adding an organic peroxide and graft polymerization using a single screw extruder is conceivable.
  • the appearance of the molded product is deteriorated due to variations in the reaction, the amount of inorganic filler in the master batch must be very large, the extrusion load becomes very large, and the production becomes very difficult.
  • a desired material or molded body cannot be obtained.
  • this is a two-step process, which is a problem in terms of cost.
  • Patent Document 1 an inorganic filler surface-treated with a silane coupling agent, a silane coupling agent, an organic peroxide, and a crosslinking catalyst are sufficiently melt-kneaded with a kneader and then molded with a single screw extruder.
  • a method has been proposed. However, in this method, not only does the molded body crosslink during melt kneading in a kneader, but the molded product causes poor appearance (forms protrusions protruding on the surface), and a silane coupling agent surface-treated with an inorganic filler. Most of the silane coupling agents other than those may be volatilized or the silane coupling agents may condense. For this reason, desired heat resistance cannot be obtained, and condensation between silane coupling agents may cause deterioration of the appearance of the electric wire.
  • Patent Documents 2 to 4 disclose a vinyl aromatic thermoplastic elastomer composition having a block copolymer or the like as a base resin and a non-aromatic rubber softener added as a softener.
  • a technique of partially crosslinking using an organic peroxide through a filler has been proposed. Even with such a technique, the resin is not yet in a sufficient network structure, and the bond between the resin and the inorganic filler is dissociated at a high temperature, so it melts at a high temperature, for example, during the soldering of an electric wire
  • the insulating material is melted, deformed when the molded body is secondarily processed, or foamed.
  • when heated to about 200 ° C. for a short time there is a problem that the appearance is remarkably deteriorated or deformed.
  • the present invention solves the above-mentioned problems, suppresses volatilization of the hydrolyzable silane coupling agent, and has excellent mechanical properties, reinforcing properties, heat resistance, flame retardancy, and appearance, and a heat-resistant silane cross-linked resin molded article and its It is an object to provide a manufacturing method. Moreover, this invention makes it a subject to provide the heat resistant silane crosslinkable resin composition which can form this heat resistant silane crosslinked resin molded object, and its manufacturing method. Furthermore, this invention makes it a subject to provide the heat resistant product using the heat resistant silane crosslinked resin molded object obtained with the manufacturing method of the heat resistant silane crosslinked resin molded object.
  • the present invention provides a silane coupling agent premixed filler suitably used in a method for producing a heat-resistant silane cross-linked resin molded article and a method for producing a heat-resistant silane cross-linkable resin composition, and at least the silane coupling agent mixed It is an object to provide a filler containing a filler.
  • the present inventors previously mixed a hydrolyzable silane coupling agent that easily volatilizes with a part of the inorganic filler (this is called premixing), and the inorganic filler and the hydrolyzable silane cup.
  • premixing a hydrolyzable silane coupling agent that easily volatilizes with a part of the inorganic filler
  • the inorganic filler and the hydrolyzable silane cup By preparing a filler part containing a silane coupling agent premixed filler combined to an extent that suppresses volatilization of the ring agent, and a silanol condensation catalyst part, respectively, and by mixing and reacting both, It has been found that the synthesis of the target silane crosslinkable resin can be effectively performed while suppressing the volatilization of the hydrolyzable silane coupling agent.
  • the amount of the hydrolyzable silane coupling agent premixed with the inorganic filler affects the physical properties of the silane crosslinkable resin and the heat-resistant silane crosslinked resin molded product obtained by silane crosslinking thereof. It has also been found that the amount of the hydrolyzable silane coupling agent to be premixed can be set by the heating loss ratio W excluding moisture of the silane coupling agent premixed filler (F).
  • the present inventors have further studied based on these findings, and have come to make the present invention.
  • This is considered to be chemically bonded to the inorganic filler by hydrogen bonding between the silanol group of the hydrolyzable silane coupling agent and the functional group of the inorganic filler.
  • the subject of this invention was achieved by the following means. (1) 0.01 to 0.6 parts by mass of organic peroxide (P) and at least the following silane coupling agent premixed with respect to 100 parts by mass of the resin composition (RC) containing the resin component (R) (A) a step of preparing a silane master batch by melt-mixing 10 to 400 parts by mass of the filler (S) containing the filler (F) at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P); A step (b) of mixing the silane masterbatch and the silanol condensation catalyst (C) to obtain a mixture; Forming the mixture (c); A step (d) of obtaining a heat-resistant silane-crosslinked resin molded body by bringing the molded body into contact with water.
  • ⁇ Silane coupling agent premixed filler (F)> A silane coupling agent premixed filler obtained by mixing a hydrolyzable silane coupling agent with an inorganic filler, when heated at 105 ° C. for 2 hours with respect to the mass of the silane coupling agent premixed filler before heating.
  • Part or all of the organic peroxide (P) is contained in the silane coupling agent premixed filler (F), wherein the heat resistance as described in (1) or (2) For producing a functional silane cross-linked resin molded article.
  • a part or all of the organic peroxide (P) is not contained in the silane coupling agent premixed filler (F), and is contained in the filler (S). It contains in the premixed filler (S2) which does not contain a silane coupling agent, The manufacturing method of the heat-resistant silane crosslinked resin molding as described in (1) or (2) characterized by the above-mentioned.
  • ⁇ Silane coupling agent premixed filler (F)> A silane coupling agent premixed filler obtained by mixing a hydrolyzable silane coupling agent with an inorganic filler, when heated at 105 ° C. for 2 hours with respect to the mass of the silane coupling agent premixed filler before heating.
  • (8) A heat-resistant product comprising the heat-resistant silane-crosslinked resin molded product according to (7).
  • (11) The silane coupling agent premixed filler (F) according to (10), wherein the heating loss ratio W is 0.2% by mass or more and 2.5% by mass or less.
  • silane crosslinking method when the silane coupling agent premixed filler (F) of the present invention having a predetermined weight loss ratio W is used, volatilization of the hydrolyzable silane coupling agent during kneading can be suppressed.
  • the hydrolyzable silane coupling agent that is relatively strongly bonded to the inorganic filler in the silane coupling agent premixed filler (F) undergoes a condensation reaction so that the network contains the inorganic filler together with the cross-linked sites of the resin components. It becomes possible to obtain very excellent mechanical properties and reinforcement.
  • a hydrolyzable silane coupling agent in the present invention, that is easily volatilized other than the hydrolyzable silane coupling agent that is relatively strongly bonded to the inorganic filler.
  • the hydrolyzable silane coupling agent that is weakly bonded to the inorganic filler is a resin group that crosslinks the resin component by radicals generated by the decomposition of the organic peroxide by desorption from the inorganic filler. After the graft reaction at the site, the hydrolyzable group undergoes a condensation reaction, whereby the resin components are cross-linked with each other, and excellent heat resistance can be exhibited.
  • the heat-resistant silane crosslinked resin molded product can be produced without using a special apparatus such as an electron beam crosslinking apparatus. Therefore, according to the present invention, the volatility of the hydrolyzable silane coupling agent is suppressed, and the heat-resistant silane cross-linked resin molded article excellent in mechanical properties, reinforcing properties, heat resistance, flame retardancy and appearance, and its production method, and The heat-resistant silane crosslinkable resin composition capable of forming the heat-resistant silane-crosslinked resin molded body and a method for producing the same can be provided. Moreover, according to this invention, the heat resistant product using the heat resistant silane crosslinked resin molding obtained by the manufacturing method of the heat resistant silane crosslinked resin molding of this invention can be provided.
  • a silane coupling agent premixed filler suitably used in a method for producing a heat-resistant silane cross-linked resin molded article and a method for producing a heat-resistant silane cross-linkable resin composition, and at least the silane coupling agent Fillers including mixed fillers can be provided.
  • the “method for producing a heat-resistant silane-crosslinked resin molded product” of the present invention is an organic peroxide (P) of 0.01 to 0 with respect to 100 parts by mass of a resin composition (RC) containing a resin component (R). .6 parts by mass and 10 to 400 parts by mass of filler (S) containing a silane coupling agent premixed filler (F) described later are melt-mixed at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P).
  • the manufacturing method of the heat resistant silane crosslinkable resin composition used for the manufacturing method of the heat resistant silane crosslinked resin molding of this invention is based on 100 mass parts of resin compositions (RC) containing the resin component (R).
  • the organic peroxide (P) 0.01 to 0.6 parts by mass and the filler (S) 10 to 400 parts by mass containing the silane coupling agent premixed filler (F) described later are combined with the organic peroxide.
  • the “method for producing a heat-resistant silane cross-linked resin molded product” of the present invention and the “method for producing a heat-resistant silane cross-linkable resin composition” of the present invention are other than the presence or absence of step (c) and step (d) Is basically the same. Accordingly, the “method for producing a heat-resistant silane cross-linked resin molded product” of the present invention and the “method for producing a heat-resistant silane cross-linkable resin composition” of the present invention (in the explanation of the common parts of both, The manufacturing method of the present invention is sometimes described below.
  • the resin composition (RC) used in the present invention contains a resin component (R) and various oils used as a plasticizer or a softener as required.
  • the content of the resin component (R) in the resin composition (RC) is preferably 20% by mass or more based on the total mass of the resin composition (RC) in terms of heat resistance performance, crosslinking performance and strength. More preferably, it is 45% by mass or more, and particularly preferably 60% by mass or more.
  • the content of the resin component (R) is at most 100% by mass, but may be, for example, 80% by mass or less.
  • the resin composition (RC) is preferably mixed with oil as appropriate in order to maintain flexibility and maintain a good appearance.
  • the oil in the resin composition (RC) is preferably set to 80% by mass or less, more preferably 55% by mass or less, based on the total mass of the resin composition (RC). More preferably, it is at most mass%.
  • the oil content is at least 0% by mass, but can be 20% by mass or more, for example.
  • the resin composition (RC) may contain other components such as various additives, a solvent, and an organic peroxide (C) described later.
  • Resin component (R) examples include a crosslinking site that undergoes a crosslinking reaction in the presence of an organic peroxide and a crosslinking group of a hydrolyzable silane coupling agent described later, such as an unsaturated bond site of a carbon chain, or a carbon having a hydrogen atom
  • a crosslinking site that undergoes a crosslinking reaction in the presence of an organic peroxide and a crosslinking group of a hydrolyzable silane coupling agent described later, such as an unsaturated bond site of a carbon chain, or a carbon having a hydrogen atom
  • Any resin having an atom in the main chain or at its terminal may be used, and examples thereof include polyolefin resin (PO), polyester resin, polyamide resin (PA), polystyrene resin (PS), and polyol resin.
  • polyolefin resin (PO) is preferable.
  • This resin component (R) may be used individually by 1 type, and may use 2 or more types together.
  • the polyolefin resin (PO) is not particularly limited as long as it is a resin obtained by polymerizing or copolymerizing a compound having an ethylenically unsaturated bond, and is conventionally known as a heat-resistant resin composition. Can be used.
  • Examples thereof include polymers and rubbers thereof, elastomers, styrene elastomers, ethylene-propylene rubbers (for example, ethylene-propylene-diene rubbers) and the like.
  • elastomers for example, polymers and rubbers thereof
  • styrene elastomers for example, polystyrene elastomers
  • ethylene-propylene rubbers for example, ethylene-propylene-diene rubbers
  • the acceptability with respect to various fillers including metal hydrates is high, and a large amount of the silane coupling agent premixed filler (F) of the present invention (sometimes referred to as filler (F) in the present invention).
  • polyethylene PE
  • polypropylene PP
  • An ethylene- ⁇ -olefin copolymer a polyolefin copolymer having an acid copolymer component, a styrene elastomer, an ethylene-propylene rubber, and the like are suitable.
  • These polyolefin resins (PO) may be used alone or in combination of two or more.
  • Polyethylene may be a resin whose main component is an ethylene component, and is a homopolymer consisting of only ethylene (also referred to as homopolyethylene), a copolymer of ethylene and 5 mol% or less of ⁇ -olefin (excluding propylene). Polymers and copolymers of ethylene and 1 mol% or less non-olefin having only carbon, oxygen and hydrogen atoms in the functional group are included (for example, JIS K 6748). As the above-mentioned ⁇ -olefin and non-olefin, known ones conventionally used as a copolymerization component of polyethylene can be used without particular limitation.
  • PE polyethylene
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • UHMW-PE ultra high molecular weight polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE ultra low density polyethylene
  • LLDPE linear low density polyethylene
  • PE may be used alone or in combination of two or more.
  • Polypropylene (PP) may be a resin whose main component is a propylene component.
  • a propylene homopolymer also referred to as homopolypropylene
  • an ethylene-propylene copolymer such as random polypropylene (referred to as a propylene polymer).
  • block polypropylene block polypropylene.
  • random polypropylene refers to a copolymer of propylene and ethylene, and a propylene-based copolymer having an ethylene component content of 1 to 5% by mass (the ethylene component is randomly bonded).
  • Block polypropylene is a composition comprising homopolypropylene and an ethylene-propylene copolymer, wherein the ethylene component content is about 5 to 15% by mass or less, and the ethylene component and the propylene component are independent components.
  • Polypropylene (PP) may be used alone or in combination of two or more.
  • the ethylene- ⁇ -olefin copolymer is preferably a copolymer of ethylene and an ⁇ -olefin having 3 to 12 carbon atoms (excluding those contained in the above-mentioned polyethylene (PE) and polypropylene (PP)). .).
  • Specific examples of the ⁇ -olefin component in the ethylene- ⁇ -olefin copolymer include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. These components are mentioned.
  • the ethylene- ⁇ -olefin copolymer is preferably a copolymer of ethylene and an ⁇ -olefin having 3 to 12 carbon atoms (excluding those contained in polyethylene (PE) and polypropylene (PP)). Specifically, ethylene-propylene copolymer (EPR, except for those contained in polypropylene (PP)), ethylene-butylene copolymer (EBR), and ethylene-synthesized in the presence of a single site catalyst. Examples include ⁇ -olefin copolymers. One ethylene- ⁇ -olefin copolymer may be used alone, or two or more ethylene- ⁇ -olefin copolymers may be used in combination.
  • Examples of the acid copolymerization component in the polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component include vinyl acetate, (meth) acrylic acid, alkyl (meth) acrylate, and the like.
  • the alkyl group of the alkyl (meth) acrylate component preferably has 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.
  • polyethylene (PE) examples include, for example, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer. Examples thereof include a polymer and an ethylene-alkyl (meth) acrylate copolymer. Of these, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer are preferable. Furthermore, acceptability and heat resistance of filler (F) are preferred. From the viewpoint of properties, an ethylene-vinyl acetate copolymer is preferable.
  • the polyolefin copolymer having an acid copolymerization component is used alone or in combination of two or more.
  • Examples of the styrenic elastomer include block copolymers and random copolymers of conjugated diene compounds and aromatic vinyl compounds, or hydrogenated products thereof.
  • Examples of the aromatic vinyl compound include styrene, p- (t-butyl) styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethyl.
  • Examples thereof include styrene, vinyl toluene, p- (t-butyl) styrene and the like. Among these, styrene is preferable as the aromatic vinyl compound.
  • This aromatic vinyl compound is used individually by 1 type, or 2 or more types are used together.
  • the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Among these, the conjugated diene compound is preferably butadiene.
  • This conjugated diene compound is used individually by 1 type, or 2 or more types are used together.
  • a styrene-based elastomer an elastomer containing an aromatic vinyl compound other than styrene, which does not contain a styrene component, may be used by a similar production method.
  • styrene-based elastomer examples include, for example, Septon 4077, Septon 4055, Septon 8105 (all trade names, manufactured by Kuraray Co., Ltd.), Dynalon 1320P, Dynalon 4600P, 6200P, 8601P, and 9901P (all trade names, JSR Etc.).
  • oils examples of the oil optionally contained in the resin composition (RC) include an oil as a plasticizer for the resin component (R) or a mineral oil softener for rubber.
  • a mineral oil softening agent is a mixture of an aromatic ring, a naphthene ring, and a paraffin chain, and a paraffinic oil whose paraffin chain carbon number accounts for 50% or more of the total carbon number, Those having a naphthene ring carbon number of 30 to 40% are called naphthenic oils, and those having an aromatic carbon number of 30% or more are called aroma oils (also called aromatic oils).
  • liquid or low molecular weight synthetic softeners, paraffinic oils, and naphthenic oils are preferably used, and paraffinic oils are particularly preferably used.
  • paraffinic oils are particularly preferably used.
  • examples of such oil include Diana Process Oil PW90 and PW380 (both trade names, manufactured by Idemitsu Kosan Co., Ltd.), Cosmo Neutral 500 (manufactured by Cosmo Oil Co., Ltd.), and the like.
  • Organic peroxide (P) generates radicals by thermal decomposition, and promotes the grafting reaction of the hydrolyzable silane coupling agent to the resin component (R).
  • the hydrolyzable silane coupling agent is ethylenic.
  • an unsaturated group When an unsaturated group is contained, it serves to promote a grafting reaction by a radical reaction (including a hydrogen radical abstraction reaction from the resin component) between the group and the resin component (R).
  • the organic peroxide (P) is not particularly limited as long as it generates radicals.
  • R 1 —OO—R 2 , R 1 —OO—C ( ⁇ O) R 3 , A compound represented by R 3 C ( ⁇ O) —OO (C ⁇ O) R 4 is preferably used.
  • R 1 , R 2 , R 3 and R 4 each independently represents an alkyl group, an aryl group, or an acyl group.
  • R 1 , R 2 , R 3 and R 4 are all alkyl groups, or any one is an alkyl group and the rest is an acyl group.
  • organic peroxides examples include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, , 5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxy Benzoate, tert-butyl peroxyisopropyl carbonate, dia Chill peroxide, lauroyl peroxide, may be mentioned
  • DCP dicumyl peroxide
  • 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane 2,5-in terms of odor, colorability, and scorch stability.
  • Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3 is preferred.
  • the decomposition temperature of the organic peroxide (P) is preferably from 80 to 195 ° C., particularly preferably from 125 to 180 ° C.
  • the decomposition temperature of the organic peroxide (P) means that when the organic peroxide (P) having a single composition is heated, the organic peroxide (P) itself becomes two or more kinds of compounds at a certain temperature or temperature range. It means the temperature at which decomposition reaction occurs, and refers to the temperature at which heat absorption or heat generation starts when heated from room temperature in a nitrogen gas atmosphere at a rate of temperature increase of 5 ° C./min by thermal analysis such as DSC method.
  • the filler (S) used in the step (a) of the present invention includes a silane coupling agent premixed filler (F), and optionally hydrolyzable silane coupling other than the silane coupling agent premixed filler (F).
  • the other filler (S2) which does not contain an agent may be included.
  • the surface is treated with an inorganic filler not treated with a hydrolyzable silane coupling agent or a treatment agent other than the hydrolyzable silane coupling agent.
  • Treated inorganic filler sometimes called untreated inorganic filler
  • filler formed by mixing this untreated inorganic filler with organic peroxide (P) sometimes called peroxide premixed filler
  • P organic peroxide
  • the filler (S2) and the silane coupling agent premixed filler (F) can be used alone or in combination of two or more.
  • Each of the various fillers that can be used in the step (a) of the present invention preferably has an average particle size of 0.2 to 10 ⁇ m, more preferably 0.3 to 8 ⁇ m, and 0.35 More preferably, it is ⁇ 5 ⁇ m and 0.35 to 3 ⁇ m. If the average particle size is less than 0.2 ⁇ m, secondary aggregation may occur during mixing of the hydrolyzable silane coupling agent, and the appearance of the molded article may be deteriorated or blistered. On the other hand, when the thickness exceeds 10 ⁇ m, the appearance may be deteriorated, or the retention effect of the hydrolyzable silane coupling agent may be reduced, causing a problem in crosslinking.
  • the average particle size is determined by an optical particle size analyzer such as a laser diffraction / scattering particle size distribution measuring device after being dispersed with alcohol or water.
  • the surface of the inorganic filler is hydrolyzable.
  • Any reaction site such as a silanol group of the silane coupling agent and a site capable of forming a hydrogen bond or a site capable of chemical bonding by a covalent bond can be used without particular limitation.
  • the sites capable of chemically bonding with the reaction site of the hydrolyzable silane coupling agent include OH groups (hydroxy groups, hydrated or water molecules of crystal water, OH groups such as carboxyl groups), amino groups, and SH groups. Etc.
  • Such an untreated inorganic filler is not particularly limited, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, oxidation Metal hydroxides and metal hydrates such as aluminum, aluminum nitride, aluminum borate, hydrated aluminum silicate, alumina, hydrated magnesium silicate, basic magnesium carbonate, and metal compounds having crystal water such as hydrotalcite Boron nitride, silica (crystalline silica, amorphous silica, etc.), carbon, clay, zinc oxide, tin oxide, titanium oxide, molybdenum oxide, antimony trioxide, silicone compound, quartz, talc, zinc borate , White carbon, boric acid , Hydroxy zinc stannate, zinc stannate and the like can be used.
  • aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, oxidation Metal hydroxides and metal hydrates such as
  • metal hydroxide, calcium carbonate, and silica are preferable, and magnesium hydroxide, aluminum hydroxide, and calcium carbonate are more preferable.
  • This inorganic filler may be previously treated with a surface treatment agent other than the hydrolyzable silane coupling agent.
  • a surface treatment agent other than the hydrolyzable silane coupling agent.
  • fatty acids such as a stearic acid, an oleic acid, a lauric acid, phosphate ester, polyester, a titanate coupling agent, etc. are mentioned.
  • the surface treatment amount is preferably 1.0% by mass or less with respect to the inorganic filler. When this amount is too large, the crosslinking density is lowered, and the heat resistance and heat deformability may be significantly lowered.
  • the silane coupling agent premixed filler (F) is obtained by previously mixing a hydrolyzable silane coupling agent with the above-described untreated inorganic filler and surface-treating the inorganic filler with this hydrolyzable silane coupling agent. Therefore, the silane coupling agent premixed filler (F) can also be referred to as a silane coupling agent-containing filler and a silane coupling agent-treated filler.
  • the silane coupling agent premixed filler (F) has a weight loss ratio W excluding moisture when heated at 105 ° C. for 2 hours, as will be described later, of 0.15 mass% or more and 3.0 mass% or less. It is.
  • the silane coupling agent premixed filler (F) having such a weight loss ratio W is suitably used for a silane crosslinking method including condensation of silanols.
  • This silane coupling agent premixed filler (F) can be used in addition to the silane crosslinking method by utilizing its stability and reactivity.
  • the hydrolyzable silane coupling agent only needs to have a group capable of grafting to the resin component (R) in the presence of a radical and a group capable of chemically bonding to the untreated inorganic filler.
  • Preferred are those having a group containing a group, a glycidyl group or an ethylenically unsaturated group and hydrolyzable, and more preferably having an ethylenically unsaturated group and a group containing hydrolyzable at the terminal. It is a hydrolyzable silane coupling agent.
  • the group containing an ethylenically unsaturated group is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth) acryloyloxy group, a (meth) acryloyloxyalkylene group, and a p-styryl group. Moreover, you may use together these hydrolysable silane coupling agents and the hydrolysable silane coupling agent which has another terminal group.
  • hydrolyzable silane coupling agent for example, a compound represented by the following general formula (1) can be used.
  • R a11 is a group containing an ethylenically unsaturated group
  • R b11 is an aliphatic hydrocarbon group, a hydrogen atom or Y 13.
  • Y 11 , Y 12 and Y 13 are hydrolyzable organic groups. Y 11 , Y 12 and Y 13 may be the same or different from each other.
  • R a11 of the hydrolyzable silane coupling agent represented by the general formula (1) is preferably a group containing an ethylenically unsaturated group, and the group containing an ethylenically unsaturated group is as described above. Preferably, it is a vinyl group.
  • R b11 is an aliphatic hydrocarbon group, a hydrogen atom, or Y 13 described later, and the aliphatic hydrocarbon group is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms excluding the aliphatic unsaturated hydrocarbon group. and the like, preferably below Y 13.
  • Y 11 , Y 12 and Y 13 are hydrolyzable organic groups such as an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an acyloxy group having 1 to 4 carbon atoms.
  • An alkoxy group is preferred.
  • Specific examples of the hydrolyzable organic group include methoxy, ethoxy, butoxy, acyloxy and the like.
  • the hydrolyzable silane coupling agent is preferably volatile at 100 ° C., and methoxy or ethoxy is more preferable, and methoxy is particularly preferable from the viewpoint of volatility and reactivity of the hydrolyzable silane coupling agent.
  • “having volatility” means that at least a part thereof is volatilized when left at normal pressure at 100 ° C.
  • the hydrolyzable silane coupling agent is preferably a hydrolyzable silane coupling agent having a high hydrolysis rate, more preferably R b11 is Y 13 , and Y 11 , Y 12 and Y 13 are the same as each other.
  • a hydrolyzable silane coupling agent, more preferably at least one of Y 11 , Y 12 and Y 13 , particularly preferably all are methoxy groups.
  • hydrolyzable silane coupling agents having a vinyl group, (meth) acryloyloxy group, or (meth) acryloyloxyalkylene group at the terminal include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltributoxysilane.
  • hydrolyzable silane coupling agents having a vinyl group and an alkoxy group at the terminal are more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.
  • Those having a glycidyl group at the terminal are 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • the silane coupling agent premixed filler (F) of the present invention is obtained by mixing the above-mentioned untreated inorganic filler and a hydrolyzable silane coupling agent.
  • a wet treatment in which the hydrolyzable silane coupling agent and the untreated inorganic filler are mixed in alcohol or water, an untreated inorganic filler and the hydrolyzable silane are mixed.
  • an untreated inorganic filler is uniformly dispersed in a solvent such as water, a hydrolyzable silane coupling agent is added thereto, and after sufficient mixing, the slurry mixture is dried.
  • a solvent such as water
  • a hydrolyzable silane coupling agent is added thereto, and after sufficient mixing, the slurry mixture is dried.
  • an untreated inorganic filler is charged into, for example, a ribbon blender, and a hydrolyzable silane coupling agent is added thereto and stirred.
  • Conditions in these wet processing and dry processing are not particularly limited and are appropriately selected.
  • the hydrolyzable silane cup is obtained as described above.
  • a part of the ring agent is strongly bonded to the inorganic filler (for the reason, for example, formation of a chemical bond with a hydroxyl group or the like on the surface of the inorganic filler is considered), and the silane coupling agent premixed filler (F) is prepared.
  • the hydrolyzable silane coupling agent that binds strongly to the inorganic filler and the inorganic filler are weakly bonded (interaction by hydrogen bonding, between ions, partial charges, or dipoles).
  • the hydrolyzable silane coupling agent that weakly bonds with the inorganic filler is used for crosslinking between the resin components (R).
  • the hydrolyzable silane coupling agent that contributes and binds strongly to the inorganic filler includes the condensation of hydrolyzable silane coupling agents, such as bonding of the silane coupling agent premixed filler (F) and the resin component (R), etc. Contribute to.
  • the hydrolyzable silane that binds weakly to the inorganic filler by setting the ratio of the hydrolyzable silane coupling agent that weakly binds to the inorganic filler.
  • the function of the hydrolyzable silane coupling agent that strongly binds to the coupling agent and the inorganic filler can be adjusted. For example, by adjusting the ratio of both hydrolyzable silane coupling agents, it is possible to achieve both heat resistance, mechanical properties, reinforcement, flame retardancy, and appearance in the silane crosslinking method.
  • the ratio of the hydrolyzable silane coupling agent that binds weakly to the inorganic filler can be quantified by the heating loss ratio W. That is, the silane coupling agent premixed filler (F) of the present invention contains a hydrolyzable silane coupling agent that weakly binds to the inorganic filler in an amount satisfying the heating loss ratio W in the following range.
  • the silane coupling agent premixed filler (F) of the present invention is a weight loss by heating excluding moisture when heated at 105 ° C. for 2 hours with respect to the mass of the silane coupling agent premixed filler before heating.
  • the ratio W is 0.15 mass% or more and 3.0 mass% or less.
  • the ratio of the hydrolyzable silane coupling agent that binds weakly to the inorganic filler is optimized, and the desired effect is exhibited.
  • the silane coupling agent pre-mixed filler (F) of the present invention is used as a filler for the silane crosslinking method, if the ratio W of heat loss is less than 0.15% by mass, the resin components (R) are crosslinked with each other. Is not performed sufficiently and heat resistance cannot be maintained sufficiently.
  • the hydrolyzable silane coupling agents are cross-linked with each other, causing scumming or the hydrolyzable silane coupling agent volatilizes in large quantities during compound production.
  • the obtained physical properties may not be stable, or problems in the production environment may occur.
  • the ratio W of heat loss of the silane coupling agent premixed filler (F) of the present invention is, for example, when used as a filler for the silane crosslinking method, it has heat resistance, mechanical properties, reinforcing properties, flame retardancy and appearance. In terms of achieving a good balance, it is preferably 0.2% by mass or more and 2.5% by mass or less, and more preferably 0.5% by mass or more and 2.0% by mass or less.
  • the heating loss ratio W of the silane coupling agent premixed filler (F) of the present invention can be measured as follows. That is, about 10 g of the silane coupling agent premixed filler (F) is accurately weighed and placed on a petri dish and heated at 105 ° C. for 2 hours. Measure the mass accurately immediately after heating. On the other hand, approximately 1 g of silane coupling agent pre-mixed filler (F) before heating is accurately weighed, and the silane coupling agent pre-mixed filler (F) is heated to 160 ° C. by Karl Fischer titration to dry nitrogen gas. Moisture collected in is automatically titrated with electrochemically generated iodine and the water content is measured.
  • the heating loss ratio W of the silane coupling agent premixed filler (F) is calculated from the mass and moisture content thus measured by the following equation.
  • W [(Whp ⁇ Wha) / Wha ⁇ 100] ⁇ water content (%)
  • Whp represents the mass of the silane coupling agent premixed filler (F) before heating
  • Wha represents the mass of the silane coupling agent premixed filler (F) after heating.
  • the silane coupling agent premixed filler (F) may be appropriately prepared, or a commercially available product may be used.
  • a hydrolyzable silane coupling agent for example, as magnesium hydroxide premixed with a hydrolyzable silane coupling agent, Kisuma 5L, Kisuma 5P (both trade names, manufactured by Kyowa Chemical Co., Ltd.), Magseeds S6, Magseeds HV-6F (both trade names Kanjima) Chemical Industry Co., Ltd., Hydrite H42-ST-V, Hydrite H42-ST-E (both trade names, Showa Denko Co., Ltd.) as aluminum hydroxides premixed with hydrolyzable silane coupling agents )).
  • the method of adjusting the heating loss ratio W of the silane coupling agent premixed filler (F) of the present invention is, for example, a method of adjusting by mixing a hydrolyzable silane coupling agent and an inorganic filler at room temperature, or the like.
  • the ratio W of the weight loss after mixing or the commercial product is within the above-described range, the method of adjusting the ratio W of the weight loss by heating may not be performed.
  • the hydrolyzable silane coupling mixed with the inorganic filler is used to adjust the heating loss ratio W to 0.15 mass% or more and 3.0 mass% or less.
  • the mixing amount of the agent is preferably 0.3 to 10% by mass with respect to the inorganic filler.
  • the silanol condensation catalyst (C) has a function of subjecting the hydrolyzable silane coupling agent grafted to the resin component (R) to a condensation reaction in the presence of moisture. Based on the action of the silanol condensation catalyst (C), the resin components (R) are cross-linked through a hydrolyzable silane coupling agent. As a result, a heat-resistant silane cross-linked resin molded article having excellent heat resistance is obtained.
  • silanol condensation catalyst (C) an organic tin compound, a metal soap, a platinum compound, or the like is used.
  • Common silanol condensation catalysts (C) include, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, zinc stearate, lead stearate, barium stearate, calcium stearate, stearin Sodium acid, lead naphthenate, lead sulfate, zinc sulfate, organic platinum compounds and the like are used.
  • organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate are particularly preferable.
  • the carrier resin (E) to be added to the catalyst master batch as desired is not particularly limited.
  • the carrier resin (E) include the same resins as the resin component (R) of the resin composition (RC).
  • the carrier resin (E) is preferably a polyolefin-based resin (PO), particularly preferably polyethylene (PE), because it has a good affinity with the silanol condensation catalyst (C) and excellent heat resistance.
  • the heat-resistant silane cross-linked resin molded body and the heat-resistant silane cross-linkable resin composition are various additives commonly used in electric wires, electric cables, electric cords, sheets, foams, tubes, pipes, for example,
  • a crosslinking aid, antioxidant, lubricant, metal deactivator, filler, other resin and the like may be appropriately blended within a range not impairing the object of the present invention.
  • These additives may be contained in any component, but it is better to add them to the carrier resin (E).
  • the antioxidant and the metal deactivator are hydrolysable mixed in the filler (F). It is better to add to the carrier resin (E) so that the silane coupling agent does not inhibit the grafting to the resin component (R).
  • a crosslinking aid is not substantially contained.
  • the crosslinking aid is not substantially mixed in the step (a) for preparing the silane master batch.
  • the crosslinking aid reacts with the organic peroxide (P) during kneading, crosslinking between the resin components (R) occurs, gelation occurs, and the heat resistant silane crosslinked resin molded article is formed.
  • P organic peroxide
  • the crosslinking aid reacts with the organic peroxide (P) during kneading, crosslinking between the resin components (R) occurs, gelation occurs, and the heat resistant silane crosslinked resin molded article is formed.
  • the appearance is remarkably lowered or the final heat resistance of the molded article cannot be obtained due to the grafting of the hydrolyzable silane coupling agent to the resin component (R) not progressing.
  • being substantially not contained or not mixed means that a crosslinking aid is not actively added or mixed, and does not exclude inclusion or mixing unavoidably.
  • the crosslinking aid refers to a compound that forms a partially crosslinked structure with the resin component (R) in the presence of an organic peroxide.
  • a methacrylate compound such as polypropylene glycol diacrylate or trimethylolpropane triacrylate
  • examples include allyl compounds such as allyl cyanurate, polyfunctional compounds such as maleimide compounds, and divinyl compounds.
  • antioxidants examples include amine-based oxidation such as a polymer of 4,4′-dioctyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline.
  • Inhibitor pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, a phenolic antioxidant, bis (2-methyl-4- ( 3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben ⁇ imidazole and its zinc salt, Pentaerythritol - tetrakis (3-lauryl - thiopropionate) and the like sulfur-based antioxidant such.
  • the antioxidant can be added in an amount of preferably 0.1 to 15.0 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to
  • lubricant examples include hydrocarbon, siloxane, fatty acid, fatty amide, ester, alcohol, and metal soap. These lubricants should be added to the carrier resin (E).
  • metal deactivators examples include N, N′-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.
  • filler including a flame retardant (auxiliary) agent
  • examples of the filler include fillers other than the various fillers described above.
  • the “method for producing a heat-resistant silane cross-linked resin molded article” of the present invention includes a step (a), a step (b), a step (c), and a step (d).
  • the “method for producing a heat-resistant silane crosslinkable resin composition” of the present invention includes the steps (a) and (b), and at least the step (c) and optionally the step (d). .
  • the step (a) includes 0.01 to 0.6 parts by mass of an organic peroxide (P) and a filler (F) with respect to 100 parts by mass of the resin composition (RC).
  • 10 to 400 parts by mass of the filler (S) is melt-mixed at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P) to prepare a silane master batch.
  • the blending amount of the filler (S) is 10 to 400 parts by mass, preferably 30 to 280 parts by mass with respect to 100 parts by mass of the resin composition (RC).
  • the blending amount of the filler (S) is less than 10 parts by mass, the graft reaction of the hydrolyzable silane coupling agent becomes non-uniform, the desired heat resistance cannot be obtained, or the appearance deteriorates due to the non-uniform reaction. There is a risk.
  • it exceeds 400 parts by mass the load during molding or kneading becomes very large, and secondary molding may be difficult.
  • the filler (S) contains the silane coupling agent premixed filler (F) described above.
  • the amount of the silane coupling agent premixed filler (F) is preferably included in such an amount as to satisfy the relationship satisfying the formula (1) described later. For example, it is preferably at least 30% by mass or more, more preferably 50% by mass or more preferably 70% by mass or more in the filler (S). When the amount of the filler (F) is less than 30% by mass, the mechanical strength, wear resistance, and reinforcement may be inferior.
  • the silane coupling agent premixed filler (F) is expressed by the following formula (1) in relation to the heat loss (X ⁇ W) excluding moisture when heated at 105 ° C. for 2 hours. It is preferable that the silane coupling agent premixed filler (F) is melt-mixed so that Z to be at least 0.15.
  • X is the blending amount (parts by mass) of the silane coupling agent premixed filler (F)
  • W is the above-described heating loss ratio (mass%)
  • Y is the blending of the resin composition (RC). Amount (parts by mass).
  • the amount of the silane coupling agent premixed filler (F) in step (a) is a content that satisfies the above Z, and this Z is preferably at least 0.15 or more. By setting it as this range, a bridge
  • Z is more preferably 0.3 to 4.5, more preferably 0.3 to 2.0, and more preferably 0.5 to 1.5 in terms of heat resistance and appearance. Is particularly preferred.
  • the compounding amount of the organic peroxide (P) is in the range of 0.01 to 0.6 parts by weight, preferably 0.1 to 0.5 parts by weight with respect to 100 parts by weight of the resin composition (RC). It is. By setting the blending amount of the organic peroxide (P) within this range, the resin components (R) can be polymerized within an appropriate range and extruded without generating aggregates due to cross-linked gels or the like. A composition having excellent properties can be obtained. That is, when the blending amount of the organic peroxide (P) is less than 0.01 parts by mass, the crosslinking reaction does not proceed at the time of crosslinking and the crosslinking reaction does not proceed at all, or the free hydrolyzable silane coupling agents are bonded to each other.
  • the hydrolyzable silane coupling agent is likely to volatilize, and the resin component (R) may be directly cross-linked by a side reaction, and there is a possibility that a scum may be generated.
  • step (a) the resin composition (RC), the organic peroxide (P), and the filler (S) are charged into a mixer and melted while being heated to a temperature higher than the decomposition temperature of the organic peroxide (P). Knead to prepare a silane masterbatch.
  • the mixing method of the resin composition (RC), the organic peroxide (P), and the filler (S) is not particularly limited.
  • the organic peroxide (P) may be mixed alone with the resin composition (RC) and the filler (S), but in the present invention, the organic peroxide (P) is preferably contained in the filler (S).
  • part or all of the silane coupling agent premixed filler (F) may be mixed in advance, or not mixed with the silane coupling agent premixed filler (F), and the filler (S). You may mix with the other pre-mixed filler (S2) which does not contain the hydrolysable silane coupling agent contained. That is, in the step (a), a silane coupling agent premixed filler (F) containing no organic peroxide (P) may be used, or a silane coupling agent preparatory containing an organic peroxide (P). A mixed filler (F) may be used.
  • the organic peroxide (P) in any form in the filler (S), and the so-called peroxide premixed filler containing the organic peroxide (P). May be used, or a filler containing no organic peroxide (P) may be used.
  • the filler (S) containing the organic peroxide (P) and the resin composition (RC) in any method.
  • the organic peroxide (P) is mixed at a temperature lower than the decomposition temperature of the organic peroxide (P).
  • the silane coupling agent premixed filler (F) and the filler (S) containing the filler are prepared or prepared prior to the step (a).
  • the hydrolyzable silane coupling agent is strongly or weakly bonded to the inorganic filler.
  • An agent premixed filler (F) is obtained.
  • a hydrolyzable silane coupling agent in addition to the silane coupling agent premixed filler (F), a hydrolyzable silane coupling agent can be additionally added depending on production conditions.
  • a hydrolyzable silane coupling agent it can mix with a silane coupling agent premix filler (F), a filler (S), etc., for example.
  • the silane coupling agent premixed filler (F) is satisfied. Is preferably set in consideration of Z or the like in the formula (1).
  • the kneading temperature is not less than the decomposition temperature of the organic peroxide (P), preferably the decomposition temperature of the organic peroxide (P) + (25 to 110) ° C.
  • This decomposition temperature is preferably set after the resin component (R) is melted.
  • kneading conditions such as kneading time can be set as appropriate.
  • silane graft reaction, silane coupling agent premixed filler (F) and resin component (R) bond, silane coupling agent premixed filler (F) Bonding between them does not occur, and the desired heat resistance cannot be obtained.
  • the organic peroxide (P) may react during extrusion, and may not be molded into a desired shape.
  • the kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic and the like.
  • a kneading apparatus a single screw extruder, a twin screw extruder, a roll, a Banbury mixer or various kneaders are used, and a closed mixer such as a Banbury mixer or various kneaders is used for dispersibility of the resin component (R) and crosslinking reaction. It is preferable in terms of stability.
  • the mixing of the resin composition (RC), the organic peroxide (P), and the filler (S) is not performed separately from the melt-kneading step, and the resin composition (RC) and the organic peroxide (P ) And filler (S) can be mixed together above the decomposition temperature of the organic peroxide (P) to produce a silane masterbatch.
  • step (a) is carried out to prepare a silane master batch.
  • the silane masterbatch prepared in the step (a) is a reaction mixture of a decomposition product of an organic peroxide (P), a resin composition (RC), and a silane coupling agent premixed filler (F), which will be described later.
  • the hydrolyzable silane coupling agent contains a silane crosslinkable resin grafted to the resin component (R) to the extent that it can be molded by the step (c).
  • the step (b) is then performed in which the silane master batch and the silanol condensation catalyst (C) are mixed to obtain a mixture.
  • the mixing amount of the silanol condensation catalyst (C) is preferably 0.0001 to 0.5 parts by mass, more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the resin component (R).
  • the blending amount of the silanol condensation catalyst (C) is less than 0.0001 part by mass, the crosslinking reaction due to the condensation reaction of the hydrolyzable silane coupling agent is difficult to proceed, and the heat resistance of the heat resistant silane crosslinked resin molding is sufficiently improved. Otherwise, the productivity may be reduced and the cross-linking reaction may become uneven.
  • the silanol condensation reaction proceeds very fast, partial gelation occurs, and the appearance and resin physical properties of the heat-resistant silane crosslinked resin molded product may be deteriorated.
  • the compounding quantity of the silanol condensation catalyst (C) in a catalyst masterbatch is suitably set so that the compounding quantity with respect to the resin component (R) may become the said range.
  • step (b) a silane master batch and a silanol condensation catalyst are mixed.
  • the mixing conditions at this time are appropriately selected depending on the mixing method of the silanol condensation catalyst (C). That is, when the silanol condensation catalyst (C) is mixed alone with the silane master batch, the mixing condition is set to the melt mixing condition of the resin component (R). On the other hand, when mixing a silanol condensation catalyst (C) as a catalyst masterbatch, it is melt-mixed with a silane masterbatch.
  • the melt mixing at this time is basically the same as in step (a).
  • the melting temperature is appropriately selected according to the melting temperature of the carrier resin (E).
  • the kneading temperature is preferably 80 to 250 ° C., more preferably 100 to 240 ° C.
  • the kneading conditions such as kneading time can be set as appropriate.
  • This step (b) may be any step in which a silane master batch and a silanol condensation catalyst (C) are mixed to obtain a mixture, and these may be melt-mixed.
  • the step (b) is preferably a step in which a catalyst masterbatch containing a silanol condensation catalyst (C) and a carrier resin (E) and a silane masterbatch are melt-mixed.
  • the mixing amount of the carrier resin (E) in the catalyst masterbatch can accelerate silane crosslinking in the step (d), and the resin composition (RC) is 100 masses in that gelation is less likely to occur during molding.
  • the amount is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and still more preferably 2 to 40 parts by mass with respect to parts.
  • a filler may or may not be added to this carrier resin (E).
  • the quantity of the filler in that case is not specifically limited, 350 mass parts or less are preferable with respect to 100 mass parts of resin components of carrier resin (E). This is because if the amount of filler is too large, the silanol condensation catalyst is difficult to disperse and crosslinking is difficult to proceed. On the other hand, if the carrier resin is too much, the degree of cross-linking of the molded article is lowered, and there is a possibility that proper heat resistance cannot be obtained.
  • the compounding quantity of the silanol condensation catalyst (C) in a catalyst masterbatch is suitably set so that the compounding quantity with respect to the resin component (R) may become the said range.
  • the catalyst master batch is a mixture of a silanol condensation catalyst (C) and a carrier resin (E), and a filler added as desired.
  • the catalyst masterbatch and the silane masterbatch are melt kneaded while heating.
  • this melt-kneading there is a resin component (R) whose melting point cannot be measured by DSC or the like, for example, an elastomer.
  • the resin component (R) and the organic peroxide (P) is kneaded.
  • the carrier resin (E) is preferably melted to disperse the silanol condensation catalyst (C).
  • the kneading conditions such as kneading time can be set as appropriate.
  • the method for producing a heat-resistant silane crosslinkable resin composition of the invention is carried out, and a heat-resistant silane crosslinkable resin composition containing silane crosslinkable resins having different crosslinking methods is produced. Therefore, the heat-resistant silane crosslinkable resin composition of the present invention is a composition obtained by carrying out steps (a) and (b), and is a resin component (R), a silane coupling agent premixed filler It is considered to be a mixture of a silane masterbatch and a silanol condensation catalyst (C) or a catalyst masterbatch containing (F) and filler (S) as raw material components.
  • the components are basically the same as the silane masterbatch and silanol condensation catalyst (C) or catalyst masterbatch.
  • step (c) and step (d) are then performed. That is, in the method for producing a heat-resistant silane cross-linked resin molded article of the present invention, the step (c) of molding the obtained mixture, that is, the heat-resistant silane cross-linkable resin composition of the present invention to obtain a molded article is performed.
  • This process (c) should just be able to shape
  • Step (c) can be performed simultaneously or sequentially with step (b).
  • a series of processes can be employed in which a silane masterbatch and a catalyst masterbatch are melt-kneaded in a coating apparatus and then coated on, for example, an extruded wire or fiber and formed into a desired shape.
  • the heat-resistant silane crosslinkable resin composition of the present invention is molded, and the molded body of the heat-resistant silane crosslinkable resin composition obtained in the steps (a), (b) and (c) is not yet formed. It is a cross-linked product. Therefore, the heat-resistant silane cross-linked resin molded product of the present invention includes a molded product that has been cross-linked or finally cross-linked by performing the following step (d) after step (a), step (b), and step (c). To do.
  • the hydrolyzable group of the hydrolyzable silane coupling agent by bringing the molded product (uncrosslinked product) obtained in step (c) into contact with water. Is hydrolyzed to form silanol, and the silanol condensation catalyst (C) present in the resin condenses the hydroxyl groups of silanol to cause a crosslinking reaction, thereby obtaining a heat-resistant silane crosslinked resin molded body of the crosslinked molded body ( d) is carried out.
  • the process itself in this step (d) can be performed by a usual method.
  • the hydrolyzable group of the hydrolyzable silane coupling agent is hydrolyzed, and the hydrolyzable silane coupling agents are condensed to form a crosslinked structure.
  • Condensation between hydrolyzable silane coupling agents proceeds just by storing at room temperature. Therefore, in the step (d), it is not necessary to positively contact the molded body (uncrosslinked body) with water. However, in order to further accelerate the crosslinking, when contacting with moisture, it is immersed in warm water, a moist heat bath. It is possible to adopt a method of positively contacting with water, such as charging to water or exposure to high-temperature water vapor. In this case, pressure may be applied to allow moisture to penetrate inside.
  • the method for producing a heat-resistant silane crosslinked resin molded product of the present invention is carried out, and a heat-resistant silane crosslinked resin molded product is produced from the heat-resistant silane crosslinked resin composition of the present invention. Therefore, the heat-resistant silane cross-linked resin molded product of the present invention is a molded product obtained by carrying out the step (a), the step (b), the step (c) and the step (d).
  • the resin component (R) is not less than the decomposition temperature of the organic peroxide (P) together with the filler (S) containing the silane coupling agent premixed filler (F) in the presence of the organic peroxide (P) component.
  • the organic peroxide (P) is decomposed to generate radicals, and the resin component (R) is grafted by the hydrolyzable silane coupling agent.
  • the chemical reaction for forming a chemical bond by a covalent bond between the hydrolyzable silane coupling agent and a group such as a hydroxyl group on the surface of the inorganic filler is also partially promoted by the heating at this time.
  • a final cross-linking reaction may be performed, and the hydrolyzable silane coupling agent is blended in the resin component (R) in a specific amount as described above, and the extrusion processability at the time of molding is increased. It becomes possible to mix
  • the mechanism of action of the above process of the present invention is not yet clear, but is estimated as follows. That is, by using the silane coupling agent premixed filler (F) of the present invention before and / or during kneading with the resin component (R), volatilization of the hydrolyzable silane coupling agent during kneading can be achieved. In addition to being suppressed, it is possible to form a hydrolyzable silane coupling agent that binds to the filler with a strong bond and a hydrolyzable silane coupling agent that binds with a weak bond.
  • a hydrolyzable silane coupling agent having a strong bond with an inorganic filler has an ethylenically unsaturated group or the like as its cross-linking group and a graft reaction with the cross-linking site of the resin component (R), particularly 1
  • a plurality of hydrolyzable silane coupling agents exist on the surface of one inorganic filler particle through a strong bond, a plurality of resin components (R) are bonded through the inorganic filler particle.
  • the cross-linking network expands.
  • the hydrolyzable silane coupling agent having a weak bond with the inorganic filler is detached from the surface of the inorganic filler to crosslink the hydrolyzable silane coupling agent.
  • the ethylenically unsaturated group which is a group, reacts with a resin radical generated by abstraction of a hydrogen radical by a radical generated by the decomposition of the organic peroxide (P) of the resin component (R) to cause a graft reaction.
  • the hydrolyzable silane coupling agent in the graft portion thus produced is then mixed with a silanol condensation catalyst and brought into contact with moisture, thereby causing a crosslinking reaction by a condensation reaction.
  • a hydrolyzable silane coupling agent having a strong bond with the above inorganic filler a hydrolytic bond chemically bonded to the hydroxyl group on the surface of the inorganic filler by a covalent reaction in a condensation reaction in the presence of water by this silanol condensation catalyst.
  • Decomposable silane coupling agents also undergo a condensation reaction to further expand the cross-linking network.
  • the molded body is formed after the conventional final cross-linking reaction by performing the cross-linking reaction by condensation using a silanol condensation catalyst in the presence of water in the step (d) after forming the molded body.
  • it is excellent in workability in the process up to the formation of a molded body and can bind a plurality of hydrolyzable silane coupling agents to the surface of one inorganic filler particle, thereby obtaining higher heat resistance than before.
  • high mechanical strength, wear resistance, and trauma resistance can be obtained.
  • the hydrolyzable silane coupling agent bonded with a strong bond to the untreated inorganic filler contributes to high mechanical strength, abrasion resistance, trauma resistance, and reinforcement, and to the untreated inorganic filler. It is considered that the hydrolyzable silane coupling agent bonded with a weak bond contributes to the improvement of the degree of crosslinking.
  • silane coupling agent premixed filler (F) when the silane coupling agent premixed filler (F) in which the ratio W of heating loss is adjusted to a small value is used, or a hydrolyzable silane coupling agent is used later.
  • a large amount of a hydrolyzable silane coupling agent having a strong bond with the untreated inorganic filler is formed, and a molded article having high mechanical properties, abrasion resistance, and trauma resistance can be obtained.
  • the silane coupling agent premixed filler (F) in which the ratio W of the weight loss by heating is adjusted to a large value is used, the hydrolyzable silane coupling agent having a strong bond with the untreated inorganic filler is not so much. Since it is not formed, the strength is not improved, but it is considered that a molded article having excellent flexibility and the like can be obtained.
  • a hydrolyzable silane coupling agent having a weak bond with an untreated inorganic filler when produced, a molded article having a high degree of crosslinking can be obtained, and a hydrolyzable silane having a weak bond.
  • the amount of the coupling agent By controlling the amount of the coupling agent to be small, it is possible to obtain a molded article having a low degree of crosslinking and a high flexibility.
  • hydrolyzable silane coupling agent when a large amount of untreated inorganic filler is pretreated with a hydrolyzable silane coupling agent, many hydrolyzable silane coupling agents having a strong bond with the untreated inorganic filler are formed. Furthermore, when a post-treatment hydrolyzable silane coupling agent is added, it reacts with the hydrolyzable silane coupling agent added in advance to form a hydrolyzable silane coupling agent having a strong bond with the untreated inorganic filler. . Therefore, if too much hydrolyzable silane coupling agent is pretreated, it is difficult to increase the crosslink density of the molded product.
  • the hydrolyzable silane coupling agent has a strong bond with the untreated inorganic filler.
  • a hydrolyzable silane coupling agent having a weak bond with the degradable silane coupling agent is formed in a well-balanced manner, and the degree of crosslinking and strength can be easily controlled by adjusting the amount of pretreatment.
  • the hydrolyzable silane coupling agent when the hydrolyzable silane coupling agent is mixed with the filler that has been treated in advance with a large amount of the hydrolyzable silane coupling agent, the hydrolyzable silane coupling agent mixed later is pre-coated. Since it bonds with the decomposable silane coupling agent, it becomes impossible to form a hydrolyzable silane coupling agent that binds to the filler with a weak bond. Therefore, when a hydrolyzable silane coupling agent is mixed with a filler that has been treated with a large amount of a hydrolyzable silane coupling agent in advance, the degree of cross-linking with the resulting resin composition and molded product is reduced, and heat resistance is improved. I can't let you.
  • the amount of the strong bond hydrolyzable silane coupling agent bonded to the untreated inorganic filler and the ratio of the weak bond hydrolyzable silane coupling agent are determined by the heating loss of the filler (F). This can be confirmed by measuring the ratio W. That is, as described above, when the filler (F) is heated to about 100 ° C., the weakly bond hydrolyzable silane coupling agent volatilizes, and only the strong bond hydrolyzable silane coupling agent is present. It has been found that it remains (that is, cannot be volatilized by a chemical bond by a covalent bond with a hydroxyl group or the like on the surface of the filler).
  • a hydrolyzable silane coupling having a strong bond to the untreated inorganic filler depending on the content W of the silane coupling agent premixed filler (F) and the heating loss ratio W of the silane coupling agent premixed filler (F). It becomes possible to confirm the amount of the hydrolyzable silane coupling agent having a weak bond with the agent.
  • the ratio W of the heat loss of the silane coupling agent premixed filler (F) is as described above.
  • the manufacturing method of the present invention can be applied to the manufacture of components (including semi-finished products, parts, and members) that require heat resistance, products that require strength, component parts of products such as rubber materials, or members thereof. it can.
  • Examples of such products include electric wires such as heat-resistant flame-retardant insulated wires, heat-resistant and flame-resistant cable coating materials, rubber substitute electric wires and cable materials, other heat-resistant and flame-resistant electric wire components, flame-resistant and heat-resistant sheets, and flame-resistant and heat-resistant films.
  • Electric wires such as heat-resistant flame-retardant insulated wires, heat-resistant and flame-resistant cable coating materials, rubber substitute electric wires and cable materials, other heat-resistant and flame-resistant electric wire components, flame-resistant and heat-resistant sheets, and flame-resistant and heat-resistant films.
  • power plugs, connectors, sleeves, boxes, tape substrates, tubes, sheets, packing materials, cushioning materials, anti-vibration materials, electrical and electronic equipment, and wiring materials especially electric wires and optical cables.
  • the manufacturing method of the present invention is suitably applied particularly to the manufacture of the insulators and sheaths of electric wires and optical cables among the components of the above-described products, and can be formed as a covering thereof.
  • Insulators, sheaths, and the like can be formed by coating them into their shapes while melt-kneading them in an extrusion coating apparatus. Molded products such as insulators and sheaths can be used for general-purpose extrusion coating equipment without using a special machine such as an electron beam cross-linking machine. Can be formed by extrusion coating around the conductor, or around the conductor that has been stretched or twisted with tensile strength fibers.
  • any conductor such as an annealed copper single wire or stranded wire can be used as the conductor.
  • the conductor may be tin-plated or an enamel-covered insulating layer.
  • the thickness of the insulating layer (the coating layer made of the heat-resistant resin composition of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 to 8 mm.
  • styrene elastomer (styrene content 40%)
  • “Diana Process PW90” (trade name): Paraffin oil “NUC6510” (trade name) manufactured by Idemitsu Kosan Co., Ltd .: Ethylene ethyl acrylate resin (EA content 22 mass%) manufactured by Dow Chemical Japan Co., Ltd.
  • “Mitsui 3092 EPM” (trade name): Ethylene-propylene-diene rubber manufactured by Mitsui Chemicals, Inc. (ethylene content 66%)
  • (A) Preparation of silane coupling agent premixed filler (F) (including peroxide-containing filler) Silane coupling agent premixed fillers (F) (f1) to (f25) are untreated inorganic fillers.
  • organic peroxide (P) with a hydrolyzable silane coupling agent and, if desired, organic peroxide (P) in an amount (part by mass) shown in Table 1 with respect to 100 parts by mass of untreated inorganic filler.
  • the mixture was introduced into a 10 L Henschel mixer manufactured by Toyo Seiki at a temperature lower than the temperature, specifically at room temperature, and mixed for 10 minutes to prepare a powder mixture.
  • the obtained silane coupling agent premixed filler (F) is a mixture of an untreated inorganic filler, a hydrolyzable silane coupling agent, and optionally an organic peroxide (P), and is hydrolyzable silane coupling.
  • the agent has a mixture of a strong bond and a weak bond to the untreated inorganic filler.
  • the obtained silane coupling agent premixed filler (F) was used after the conditions or treatment described in the “Remarks” column of Table 1, respectively.
  • premixed filler S2
  • S2-A and S2-B represent untreated inorganic filler and organic peroxide (P) with respect to 100 parts by mass of untreated inorganic filler. It was prepared in the same manner as the silane coupling agent premixed filler (F) with the blending amount (part by mass) shown in 1.
  • the obtained premixed filler (also referred to as a peroxide premixed filler) is a mixture of an untreated inorganic filler and an organic peroxide.
  • untreated filler S2-C
  • calcium carbonate (“Softon 1500” (trade name, manufactured by Bihoku Flour Chemical Co., Ltd.) was used as it was.
  • magnesium hydroxide “Kisuma 5” (trade name, manufactured by Kyowa Chemical Industry), calcium carbonate “Softon 1500” (trade name, manufactured by Bihoku Powdered Industries Co., Ltd.), Aluminum hydroxide “BF013” (trade name, manufactured by Nippon Light Metal Co., Ltd.) and silica “Crystallite 5X” (trade name, manufactured by Tatsumori Co., Ltd.) were used.
  • Antioxidant hindered phenolic antioxidant
  • “Irganox 1010” (trade name): pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] manufactured by Nagase & Co., Ltd.
  • the prepared silane coupling agent premixed filler (F), peroxide premixed filler (S2) or untreated inorganic filler (S2-C) and the resin composition (RC) shown in Tables 2 and 3 were used.
  • a mass ratio shown in Table 2 and Table 3 it is put into a 2 L Banbury mixer made by Nippon Roll, and the temperature is higher than the decomposition temperature of the organic peroxide (P), specifically at 180 to 190 ° C. for about 12 minutes. After kneading, the material was discharged at a material discharge temperature of 180 to 190 ° C.
  • Example 25 without mixing perhexa 25B with an untreated inorganic filler and a Henschel mixer beforehand, it poured with the Banbury mixer separately from the untreated inorganic filler, and mixed with the resin composition (RC).
  • Example 26 DCP0.06 mass part was supplied with the Banbury mixer separately from the silane coupling agent premixed filler (f15) which mixed DCP previously.
  • This catalyst masterbatch is a mixture of a carrier resin (E), a silanol condensation catalyst (C) and an antioxidant.
  • silane masterbatch and the catalyst masterbatch are shown in Tables 2 and 3, ie, 100 parts by mass of the resin composition (RC) of the silane masterbatch and 5% by mass of the carrier resin (E) of the catalyst masterbatch.
  • the mixture was melt-mixed at 180 ° C. by a Banbury mixer at a ratio of parts (step (b)).
  • a heat-resistant silane crosslinkable resin composition was prepared.
  • This heat-resistant silane crosslinkable resin composition is a mixture of a silane masterbatch and a catalyst masterbatch, and contains at least two kinds of silane crosslinkable resins described above.
  • An electric wire having an outer diameter of 2.8 mm was obtained by covering with 1 mm (step (c)). The obtained electric wire was left in an atmosphere of temperature 80 ° C. and humidity 95% for 24 hours (step (d)).
  • cover consisting of a heat resistant silane crosslinked resin molding was manufactured.
  • this heat-resistant silane cross-linked resin molded product contains the above-mentioned various silane cross-linked products in which the silane cross-linkable resin is cross-linked by the condensation reaction of the hydrolyzable group of the hydrolyzable silane coupling agent. .
  • a tensile test was conducted as a mechanical property of the electric wire. This tensile test was performed based on UL1581, with a gap between marked lines of 25 mm and a tensile speed of 500 mm / min, and measured tensile strength (unit: MPa) and elongation at break (%). The elongation at break is 100 (%) or more, and the tensile strength is 10 (MPa) or more.
  • a hot set test (high temperature thermal deformation characteristics) was conducted as the heat resistance of the electric wires.
  • a tubular piece of electric wire was prepared in the same manner as in each of the examples and comparative examples, and after a rating of 50 mm in length, a 117 g weight was attached in a thermostatic bath at 200 ° C. and left for 15 minutes. The length after standing was measured to determine the elongation (%). Next, the load was removed and the length after standing was measured to obtain the elongation percentage (%).
  • the hot set at the time of holding the load was regarded as acceptable when the elongation was 100% or less, and the hot set after weight removal was regarded as acceptable when the elongation was 80% or less.
  • Extrusion appearance characteristics of electric wire An extrusion appearance test was conducted as an extrusion appearance characteristic of the electric wire.
  • Extrusion appearance 1 observed the extrusion appearance when manufacturing an electric wire.
  • B ”and above were accepted as product levels.
  • Extrusion appearance 2 observed the extrusion appearance when manufacturing the electric wire. Specifically, “A” indicates that the appearance was good when produced with a 65 mm extruder at a linear speed of 80 m, “B” indicates that the appearance was slightly poor, and “C” indicates that the appearance was remarkably poor. It was. Although “B” or higher was accepted as the product level, the extrusion appearance 2 is a severe test in which the linear velocity is increased to 8 times for the purpose of improving productivity, and therefore this test does not necessarily need to pass.
  • Examples 1 to 26 were able to achieve all of mechanical properties, reinforcement properties, heat resistance, and extrusion appearance. That is, it was found that the heat-resistant silane cross-linked resin moldings according to the present invention provided as the wire coatings of Examples 1 to 26 were excellent in all of mechanical properties, reinforcement properties and appearance. In addition, it can be easily estimated that the flame retardancy is excellent from the content of the inorganic filler (S). On the other hand, Comparative Examples 1 to 7 were inferior in at least one of mechanical properties, reinforcing properties, heat resistance and appearance, and could not satisfy all of them.

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Abstract

　L'invention porte sur un procédé de fabrication comprenant une étape (a) consistant à faire fondre et mélanger 0,01 à 0,6 partie en poids d'un peroxyde organique (P) pour 100 parties en masse d'une composition de résine (RC) et 100 à 400 parties en masse d'une matière de charge (S) contenant une matière de charge prémélangée à base d'agent de couplage silane (F), le taux de perte à la chaleur (W) sans compter l'humidité lorsqu'elle est chauffée pendant deux heures à 105 °C étant de 0,15 à 3,0 % en masse, à une température supérieure ou égale à la température de dissolution du peroxyde organique (P) pour préparer un mélange maître de silane ; sur un article moulé en résine réticulable par silane résistant à la chaleur et une composition de résine réticulable par silane résistante à la chaleur fabriqués à l'aide de ce procédé de fabrication ; sur un produit résistant à la chaleur qui utilise l'article moulé en résine réticulable par silane résistant à la chaleur ; sur une matière de charge prémélangée à base d'agent de couplage silane ; et sur une matière de charge la contenant.
PCT/JP2014/062813 2013-05-20 2014-05-14 Article moule en resine reticulable par silane resistant a la chaleur, composition de resine reticulable par silane resistante a la chaleur et procede de fabrication s'y rapportant, produit resistant a la chaleur utilisant un article moule en resine reticulable par silane resistant a la chaleur, ainsi que matiere charge premelangee a base d'agent de couplage silane et matiere de charge la contenant WO2014188925A1 (fr)

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WO2016140251A1 (fr) * 2015-03-03 2016-09-09 古河電気工業株式会社 Composition de caoutchouc réticulable au silane ainsi que corps moulé en caoutchouc réticulé au silane, procédé de fabrication de ceux-ci, et article moulé en caoutchouc réticulé au silane
WO2016140253A1 (fr) * 2015-03-03 2016-09-09 古河電気工業株式会社 Composition de caoutchouc réticulable au silane ainsi que corps moulé en caoutchouc réticulé au silane, procédé de fabrication de ceux-ci, et article moulé en caoutchouc réticulé au silane
JP2017145307A (ja) * 2016-02-16 2017-08-24 古河電気工業株式会社 耐熱性シラン架橋樹脂成形体及び耐熱性シラン架橋性樹脂組成物とそれらの製造方法、シランマスターバッチ、並びに、耐熱性製品
JP2017179235A (ja) * 2016-03-31 2017-10-05 古河電気工業株式会社 難燃性架橋樹脂成形体及び難燃性架橋性樹脂組成物とそれらの製造方法、難燃性シランマスターバッチ、並びに、難燃性成形品

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JP2013227559A (ja) * 2012-03-30 2013-11-07 Furukawa Electric Co Ltd:The 難燃性樹脂組成物の製造方法、並びに、その製造方法で製造された耐熱性樹脂組成物及び該耐熱性樹脂組成物を用いた成形品

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WO2016140252A1 (fr) * 2015-03-03 2016-09-09 古河電気工業株式会社 Composition de caoutchouc réticulable au silane ainsi que corps moulé en caoutchouc réticulé au silane, procédé de fabrication de ceux-ci, et article moulé en caoutchouc réticulé au silane
WO2016140251A1 (fr) * 2015-03-03 2016-09-09 古河電気工業株式会社 Composition de caoutchouc réticulable au silane ainsi que corps moulé en caoutchouc réticulé au silane, procédé de fabrication de ceux-ci, et article moulé en caoutchouc réticulé au silane
WO2016140253A1 (fr) * 2015-03-03 2016-09-09 古河電気工業株式会社 Composition de caoutchouc réticulable au silane ainsi que corps moulé en caoutchouc réticulé au silane, procédé de fabrication de ceux-ci, et article moulé en caoutchouc réticulé au silane
JPWO2016140253A1 (ja) * 2015-03-03 2017-12-14 古河電気工業株式会社 シラン架橋性ゴム組成物及びシラン架橋ゴム成形体とそれらの製造方法、並びに、シラン架橋ゴム成形品
JPWO2016140251A1 (ja) * 2015-03-03 2017-12-14 古河電気工業株式会社 シラン架橋性ゴム組成物及びシラン架橋ゴム成形体とそれらの製造方法、並びに、シラン架橋ゴム成形品
JP2017145307A (ja) * 2016-02-16 2017-08-24 古河電気工業株式会社 耐熱性シラン架橋樹脂成形体及び耐熱性シラン架橋性樹脂組成物とそれらの製造方法、シランマスターバッチ、並びに、耐熱性製品
JP2017179235A (ja) * 2016-03-31 2017-10-05 古河電気工業株式会社 難燃性架橋樹脂成形体及び難燃性架橋性樹脂組成物とそれらの製造方法、難燃性シランマスターバッチ、並びに、難燃性成形品

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