WO2015002263A1 - Article moulé en résine silane réticulée résistant à la chaleur et son procédé de fabrication, et produit résistant à la chaleur équipé de l'article moulé en résine silane réticulée résistant à la chaleur - Google Patents

Article moulé en résine silane réticulée résistant à la chaleur et son procédé de fabrication, et produit résistant à la chaleur équipé de l'article moulé en résine silane réticulée résistant à la chaleur Download PDF

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Publication number
WO2015002263A1
WO2015002263A1 PCT/JP2014/067768 JP2014067768W WO2015002263A1 WO 2015002263 A1 WO2015002263 A1 WO 2015002263A1 JP 2014067768 W JP2014067768 W JP 2014067768W WO 2015002263 A1 WO2015002263 A1 WO 2015002263A1
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Prior art keywords
heat
mass
inorganic filler
coupling agent
silane coupling
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PCT/JP2014/067768
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English (en)
Japanese (ja)
Inventor
稔 齋藤
西口　雅己
有史 松村
宏樹 千葉
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古河電気工業株式会社
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Priority to JP2015525271A priority Critical patent/JP6329948B2/ja
Priority to CN201480031113.6A priority patent/CN105308102B/zh
Publication of WO2015002263A1 publication Critical patent/WO2015002263A1/fr

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    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2331/04—Homopolymers or copolymers of vinyl acetate

Definitions

  • the present invention relates to a heat-resistant silane cross-linked resin molded body, a method for producing the same, and a heat-resistant product using the heat-resistant silane cross-linked resin molded body, and in particular, excellent heat-resistant silane having mechanical properties, insulation resistance and flame retardancy.
  • the present invention relates to a cross-linked resin molded body, a method for producing the same, and a heat-resistant product using the heat-resistant silane cross-linked resin molded body as an electric wire insulator or sheath.
  • Insulated wires, cables, cords, optical fiber cores and optical fiber cords used for internal and external wiring of electrical and electronic equipment are flame retardant, heat resistant, mechanical properties (for example, tensile properties), and abrasion resistance Various characteristics such as insulation resistance are required.
  • a resin composition containing a large amount of an inorganic filler such as magnesium hydroxide, aluminum hydroxide, or calcium carbonate is usually used.
  • wiring materials used in electric / electronic devices may be heated to 80 to 105 ° C. or even 125 ° C. when used for a long time, and heat resistance against this may be required.
  • a method of bridging also referred to as crosslinking
  • the coating material resin by an electron beam crosslinking method, a chemical crosslinking method, or the like is employed.
  • Silane cross-linking methods are known as a method of crosslinking a polyolefin resin such as polyethylene, an electron beam crosslinking method in which an electron beam is irradiated to crosslink, a chemical crosslinking method in which an organic peroxide is decomposed by applying heat after molding, and a crosslinking reaction is performed.
  • the 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 crosslinking method in particular does not require special equipment, and can be used in a wide range of fields.
  • the silane crosslinking method includes a silane master batch obtained by grafting a silane coupling agent having an unsaturated group to a polyolefin resin, a heat resistant master batch obtained by kneading a polyolefin resin and an inorganic filler, and a silanol condensation catalyst.
  • a method of melt-mixing the contained catalyst master batch There is a method of melt-mixing the contained catalyst master batch.
  • the silane master batch and the heat-resistant master batch are dry-mixed to obtain a single screw extruder or a twin screw extruder.
  • a hydrolyzable silane coupling agent having an unsaturated group is added to the heat-resistant masterbatch obtained by melting and mixing a polyolefin resin and an inorganic filler with a Banbury mixer. And an organic peroxide may be added and graft polymerization may be performed with a single screw extruder.
  • a defective appearance occurs in the molded body due to variation in reaction, and a desired molded body cannot be obtained.
  • the compounding ratio of the inorganic filler in the heat resistant masterbatch must be increased. For this reason, the extrusion load becomes large, the production becomes very difficult, and a desired material or molded product cannot be obtained. Furthermore, this is a two-step process, which is a difficult point in terms of manufacturing 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, the resin is partially crosslinked during melt kneading in a kneader, causing the molded body to have a poor appearance (formation of a large number of protrusions protruding on the surface).
  • most of the silane coupling agents other than the silane coupling agent surface-treated on the inorganic filler may volatilize 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.
  • the resin does not yet have a sufficient network structure, and the bond between the resin and the inorganic filler is released at a high temperature. For this reason, there is a problem that it melts at a high temperature, for example, the insulating material melts during soldering of the electric wire, or deforms or foams when the molded body is secondarily processed.
  • the appearance is remarkably deteriorated or deformed.
  • the present invention solves the above-mentioned problems and is produced by suppressing volatilization of the hydrolyzable silane coupling agent, and has excellent mechanical properties, insulation resistance and flame retardancy, and its molded product It is an object to provide a manufacturing method. Moreover, 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 inventors When using the silane cross-linking method as described above, the present inventors previously mixed a hydrolyzable silane coupling agent that easily volatilizes with an inorganic filler (this is referred to as premixing), and hydrolyzable silane coupling.
  • premixing a hydrolyzable silane coupling agent that easily volatilizes with an inorganic filler
  • hydrolyzable silane coupling When combined with a silane coupling agent premixed inorganic filler bonded to a level that suppresses the volatilization of the agent and a specific amount of brominated flame retardant, insulation is achieved while maintaining the excellent mechanical properties of the heat-resistant silane crosslinked resin molding It has been found that the flame retardancy can be improved to be equal to or higher than that of a molded article obtained by increasing resistance and electron beam crosslinking.
  • step (a), step (b) and step (c) Step (a): 100 parts by mass of resin component (A), 0.01 to 0.6 parts by mass of organic peroxide (P), and 100 parts by mass of inorganic filler (C) including surface-treated inorganic filler (B) 10 to 150 parts by mass of a silane coupling agent premixed inorganic filler (D) obtained by mixing 0.5 to 30.0 parts by mass of a hydrolyzable silane coupling agent (q) with respect to a brominated flame retardant ( h1) Step of melt-mixing 15-60 parts by mass of silanol condensation catalyst (e1) 0.001-0.5 parts by mass
  • the step (a) includes the following step (a1) and step (a3), and further includes the following step (a2) when a part of the resin component (A) is melt-mixed in the following step (a1).
  • Step (a1) Part or all of the resin component (A), the organic peroxide (P), and the silane coupling agent premixed inorganic filler (D) are combined with the organic peroxide (P).
  • the resin component (A) comprises at least (i) 10 to 50% by mass of a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, and (ii) an ethylene- ⁇ -olefin copolymer
  • At least one of the (i) polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component is an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester copolymer.
  • a heat resistant product comprising the heat resistant silane crosslinked resin molded article according to (7).
  • a numerical range represented by using “to” means a range including numerical values described before and after that as a lower limit value and an upper limit value.
  • the heat resistant silane crosslinked resin molding excellent in the mechanical characteristic, the insulation resistance, and the flame retardance manufactured by suppressing volatilization of a hydrolysable silane coupling agent, and its manufacturing method can be provided.
  • 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.
  • the “method for producing a heat-resistant silane-crosslinked resin molded product” of the present invention (hereinafter sometimes referred to as the production method of the present invention) is as described above, and in short, the steps (a), (b) and the steps described above.
  • a method for producing a heat-resistant silane cross-linked resin molded article having (c) The resin component (A) is a specific resin component (A),
  • the step (a) includes the following step (a1) and step (a3), and further includes the following step (a2) when a part of the resin component (A) is melt-mixed in the following step (a1).
  • the brominated flame retardant (h1) is mixed in at least one of the following step (a1) and the following step (a2).
  • the silanol condensation catalyst (e1) is melted in the silane master batch in the step (a3) without performing the step (a2). Can be mixed.
  • the step (a2) and the step (a3) can be performed continuously or all at once (in the same step).
  • the resin component used in the production method of the present invention is “resin component (A)”, the heat-resistant silane crosslinkable resin composition (F) obtained in step (a) and the heat resistance produced by the production method of the present invention.
  • the resin component contained in the functional silane cross-linked resin molded product is referred to as “resin component (G)”.
  • the resin component (G) is synonymous with a mixture of the resin component (A) and the carrier resin (e2). Therefore, in the present invention, the resin component (A), the carrier resin (e2), and the resin component (G) may be simply referred to as a resin component without clearly distinguishing them.
  • the resin component (A) used in the present invention is a crosslinking site that undergoes a crosslinking reaction in the presence of the crosslinking group of the hydrolyzable silane coupling agent (q) and the organic peroxide (P) described below, for example, unsaturated carbon chain.
  • examples thereof include a binding site and a resin, elastomer, rubber, or the like having a carbon atom having a hydrogen atom in the main chain or at the terminal thereof.
  • examples of such resins include polyolefin resins and styrene elastomers.
  • the polyolefin-based resin 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 a known one conventionally used in heat-resistant resin compositions. Can be used. Examples thereof include polyethylene (PE), polypropylene (PP), ethylene- ⁇ -olefin copolymer, polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, and rubbers and elastomers thereof.
  • PE polyethylene
  • PP polypropylene
  • ethylene- ⁇ -olefin copolymer polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component
  • rubbers and elastomers thereof are examples thereof.
  • receptivity to various inorganic fillers including metal hydrates is high, there is an effect of maintaining the mechanical strength even if a large amount of inorganic filler is blended, and withstand voltage while ensuring heat resistance
  • a copolymer having polyethylene (PE), polypropylene (PP), an ethylene- ⁇ -olefin copolymer and an acid copolymer component or an acid ester copolymer component from the viewpoint of suppressing a decrease in withstand voltage characteristics at high temperatures. Etc. are suitable.
  • These polyolefin resins may be used alone or in combination of two or more.
  • polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component
  • polyolefin copolymer (i) having an acid copolymerization component or an acid ester copolymerization component
  • the acid copolymerization component or the acid ester copolymerization component include a vinyl acetate component, a (meth) acrylic acid component, an (meth) acrylic acid alkyl component, and the like.
  • examples of the polyolefin copolymer (i) include an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid alkyl copolymer.
  • an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylate copolymer are preferable, and an ethylene-vinyl acetate copolymer is more preferable from the viewpoint of acceptability to an inorganic filler and heat resistance.
  • the alkyl group of the alkyl (meth) acrylate 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.
  • the ethylene-vinyl acetate copolymer may be an alternating copolymer obtained by alternately polymerizing an ethylene component and a vinyl acetate component as long as it is a copolymer of ethylene and vinyl acetate.
  • a block copolymer formed by combining a polymer block and a polymer block of a vinyl acetate component may be used, and further, a random copolymer in which an ethylene component and a vinyl acetate component are randomly polymerized may be used.
  • the ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 17 to 80% by mass, more preferably 20 to 50% by mass, still more preferably 25 to 41% by mass.
  • the vinyl acetate component content can be determined according to JIS K 7192. Two or more copolymers having different vinyl acetate contents may be combined. By using an ethylene-vinyl acetate copolymer having a vinyl acetate content within the above range, sufficient flame retardancy can be ensured.
  • Examples of the ethylene-vinyl acetate copolymer include “Evaflex” (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.) and “Revaprene” (trade name, manufactured by Bayer).
  • the ethylene- (meth) acrylic acid ester copolymer includes both an ethylene-acrylic acid ester copolymer and an ethylene-methacrylic acid ester copolymer.
  • ethylene- (Meth) acrylate copolymer ethylene- (Meth) acrylate copolymer .
  • the ethylene- (meth) acrylic acid ester copolymer is a copolymer of ethylene and (meth) acrylic acid ester, like the above-mentioned ethylene-vinyl acetate copolymer, alternating copolymer, block copolymer. Either a polymer or a random copolymer may be used.
  • the (meth) acrylic acid ester component is not particularly limited, but preferably has an alkyl group having 1 to 4 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, etc. Is mentioned.
  • the content of the (meth) acrylic acid ester component that is a copolymerization component of the ethylene- (meth) acrylic acid ester copolymer is preferably 15 to 80% by mass. When this content is in the above range, sufficient flame retardancy can be ensured.
  • Examples of such ethylene- (meth) acrylic acid ester copolymers include ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, and ethylene-ethyl methacrylate. Examples thereof include a copolymer and an ethylene-butyl acrylate copolymer.
  • Examples of the ethylene- (meth) acrylic acid copolymer include Nucrel (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.). Further, examples of the ethylene-ethyl acrylate copolymer include “Evalroy” (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.). Polyolefin copolymer (i) is used individually by 1 type, or 2 or more types are used together.
  • the ethylene- ⁇ -olefin copolymer (ii) is preferably a copolymer of ethylene and an ⁇ -olefin having 4 to 12 carbon atoms (the polyethylene described later) (Excluding those contained in (PE)).
  • Specific examples of the ⁇ -olefin component include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like.
  • ethylene- ⁇ -olefin copolymer (ii) specifically, an ethylene-butylene copolymer (EBR), an ethylene- ⁇ -olefin copolymer synthesized in the presence of a single site catalyst, a linear chain Type low density polyethylene (LLDPE) and the like.
  • the ethylene- ⁇ -olefin copolymer (ii) may also contain a copolymer containing a diene component, such as an ethylene-propylene rubber (for example, ethylene-propylene-diene rubber).
  • ethylene- ⁇ -olefin copolymer may be used alone, or two or more ethylene- ⁇ -olefin copolymers may be used in combination.
  • Examples of the ethylene- ⁇ -olefin copolymer include Evolue SP0540 (trade name, manufactured by Prime Polymer, LLDPE resin), UE320 (trade name, density 0.922 g / cm 3 , manufactured by Ube Maruzen Polyethylene), UBEC 180 ( trade name, density 0.924 g / cm 3, manufactured by Ube Maruzen polyethylene Co., Ltd.), HI-ZEX 540E (trade name, density 0.956 g / cm 3, manufactured by Prime polymer Co., Ltd.).
  • Evolue SP0540 trade name, manufactured by Prime Polymer, LLDPE resin
  • UE320 trade name, density 0.922 g / cm 3 , manufactured by Ube Maruzen Polyethylene
  • UBEC 180 trade name, density 0.924 g / cm 3, manufactured by Ube Maruzen polyethylene Co., Ltd.
  • HI-ZEX 540E trade name, density 0.956 g / cm 3, manufactured by Prime polymer Co., Ltd.
  • Polypropylene (iii) may be a resin in which one of the polymerization components is a propylene component, and includes random polypropylene and block polypropylene in addition to a homopolymer of propylene (also referred to as homopolypropylene).
  • Random polypropylene as used herein is a copolymer of propylene and ethylene in general, and is a propylene copolymer having an ethylene component content of 1 to 6% by mass, such as ethylene in the propylene chain. It means that the copolymerization component is taken in at random.
  • the “block polypropylene” is a composition containing a homopolypropylene and an ethylene-propylene copolymer, generally having an ethylene component content of about 18% by mass or less, and having a propylene component and a copolymer component. The thing which exists as an independent component.
  • any of these polypropylenes can be used without any particular limitation.
  • Block polypropylene and random polypropylene are preferable in that heat resistance and heat deformation characteristics can be improved.
  • Polypropylene may be used alone or in combination of two or more. Examples of polypropylene include BC8A (trade name, manufactured by Nippon Polypro), PB222A (trade name, manufactured by Sun Allomer), and E150GK (trade name, manufactured by Prime Polymer).
  • the MFR (ASTM-D-1238) of polypropylene is preferably 0.1 to 60 g / 10 minutes, more preferably 0.3 to 25 g / 10 minutes, and further preferably 0.5 to 15 g / 10 minutes. By blending polypropylene in this range, the appearance is improved when the wire is coated.
  • Polyethylene may be a resin in which one of the polymerization components is an ethylene component, and examples thereof include high-density polyethylene (HDPE), high-pressure low-density polyethylene (HPLDPE), and medium-density polyethylene (MDPE). Among these, high pressure low density polyethylene (HPLDPE) is preferable. Polyethylene may be used individually by 1 type, and may use 2 or more types together.
  • HDPE high-density polyethylene
  • HPLDPE high-pressure low-density polyethylene
  • MDPE medium-density polyethylene
  • HPLDPE high pressure low density polyethylene
  • Polyethylene may be used individually by 1 type, and may use 2 or more types together.
  • styrene elastomer examples include block copolymers and random copolymers of conjugated diene compounds and aromatic vinyl compounds, or hydrogenated products thereof.
  • aromatic vinyl compound examples 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.
  • 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.
  • 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.
  • the styrene-based elastomer an elastomer that does not contain a styrene component and contains an aromatic vinyl compound other than styrene may be used.
  • 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.).
  • the resin component (A) may optionally contain an oil as a plasticizer or a mineral oil softener for rubber.
  • oils include paraffinic, naphthenic, and aromatic oils. Paraffin oil has 50% or more of the total number of carbon atoms in the paraffin chain, and naphthenic oil has 30 to 40% naphthenic ring carbon.
  • Aroma oil also called aromatic oil
  • Oils may be used alone or in combination of two or more.
  • the oil is preferably contained in the resin component (A) at a mass ratio of 20% by mass or less.
  • the organic peroxide (P) generates radicals by thermal decomposition and promotes the grafting reaction of the hydrolyzable silane coupling agent to the resin component (A), particularly the hydrolyzable silane coupling agent (q). Acts to promote a grafting reaction by a radical reaction (including a hydrogen radical abstraction reaction from the resin component (A)) between the group and the resin component (A) in the case where contains an ethylenically unsaturated group.
  • 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 4 C ( ⁇ O) —OO (C ⁇ O) R 5 is preferably used.
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represents an alkyl group, an aryl group, or an acyl group.
  • R 1 , R 2 , R 3 , R 4 and R 5 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, 2,5-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- Butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate Diacetyl peroxide, lauroyl peroxide, may benzoyl per
  • 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 hydrolyzable silane coupling agent (q) is mixed with an inorganic filler (C) described later, and surface-treats at least a part of the inorganic filler (C).
  • a hydrolyzable silane coupling agent (q) is not particularly limited, and a hydrolyzable silane coupling agent having an unsaturated group used in the silane crosslinking method can be used.
  • a hydrolyzable silane coupling for example, a hydrolyzable silane coupling agent represented by the following general formula (1) can be suitably 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 each an independently hydrolyzable organic group.
  • Y 11 , Y 12 and Y 13 may be the same as or different from each other.
  • the group R a11 containing an ethylenically unsaturated group is preferably a group containing an ethylenically unsaturated group, and examples thereof include a vinyl group, a (meth) acryloyloxyalkylene group, a p-styryl group, and the like.
  • a vinyl group is preferred.
  • R b11 is an aliphatic hydrocarbon group or a hydrogen atom or Y 13 to be described later.
  • the aliphatic hydrocarbon group is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms excluding the aliphatic unsaturated hydrocarbon group. Can be mentioned. Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include those similar to those having 1 to 8 carbon atoms among alkyl groups of alkyl (meth) acrylate.
  • R b11 is preferably Y 13 .
  • Y 11 , Y 12 and Y 13 are each independently an organic group that can be hydrolyzed, such as an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
  • An acyloxy group is mentioned.
  • an alkoxy group having 1 to 6 carbon atoms is preferable.
  • Specific examples of the alkoxy group having 1 to 6 carbon atoms include, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, and the like. From the viewpoint of hydrolysis reactivity, a methoxy group or An ethoxy group is preferred.
  • the hydrolyzable silane coupling agent represented by the general formula (1) is preferably an unsaturated group-containing silane coupling agent having a high hydrolysis rate, and more preferably R b11 is Y in the general formula (1). 13 and a hydrolyzable silane coupling agent in which Y 11 , Y 12 and Y 13 are the same organic group.
  • Specific preferred hydrolyzable silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxy.
  • Examples include silane, allyltriethoxysilane, vinyltriacetoxysilane, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, (meth) acryloxypropylmethyldimethoxysilane, and the like.
  • a hydrolyzable silane coupling agent having a vinyl group and an alkoxy group at the terminal is more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.
  • a hydrolysable silane coupling agent (q) may be used individually by 1 type, and may use 2 or more types together. Further, the hydrolyzable silane coupling agent (q) may be used alone or as a liquid diluted with a solvent.
  • the inorganic filler used in the present invention is a surface untreated inorganic filler (c1) that has not been surface treated with a surface treatment agent, a surface treated inorganic filler (B) that has been surface treated with a surface treatment agent, and the surface treated inorganic filler (B).
  • the various inorganic fillers used in the present invention preferably have an average particle size of 0.2 to 10 ⁇ m, more preferably 0.3 to 8 ⁇ m, and more preferably 0.35 to 5 ⁇ m, regardless of their form and type. More preferably, it is particularly preferably 0.35 to 3 ⁇ m.
  • the average particle size is in the above range, secondary aggregation is difficult to occur when the hydrolyzable silane coupling agent (q) is mixed, and no fluff is generated, the appearance of the molded article is excellent, and the hydrolyzable silane The resin component (A) is sufficiently crosslinked due to the retention effect of the coupling agent (q).
  • the average particle size is determined by an optical particle size measuring device such as a laser diffraction / scattering type particle size distribution measuring device after being dispersed with alcohol or water.
  • (C1) Surface Untreated Inorganic Filler As the surface untreated inorganic filler (c1) surface-treated in the surface treated inorganic filler (B), and the surface untreated inorganic filler (c1) that can be contained in the inorganic filler (C) If the surface of the inorganic filler has a site capable of forming a hydrogen bond or a reactive site such as a silanol group of a hydrolyzable silane coupling agent, or a site capable of chemical bonding by a covalent bond, it can be used without particular limitation. it can.
  • an OH group hydroxyl, water-containing or water molecule of crystal water, OH group such as carboxyl group), amino group, SH group etc. are mentioned.
  • Such a surface untreated inorganic filler (c1) is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, Magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate, hydrated aluminum silicate, alumina, hydrated magnesium silicate, basic magnesium carbonate, metal hydroxides such as metal compounds having water or crystal water such as hydrotalcite, Metal hydrates, 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 carbo , It can be used zinc borate, hydroxy stannate, zinc stannate and the like.
  • the surface untreated inorganic filler (c1) is preferably a metal hydroxide, calcium carbonate, or silica, and more preferably magnesium hydroxide, aluminum hydroxide, or calcium carbonate, as described above.
  • the surface-treated inorganic filler (B) is obtained by surface-treating the surface untreated inorganic filler (c1) with a surface treatment agent.
  • the surface-treated inorganic filler (B) may be a surface-treated inorganic filler that has already been surface-treated.
  • the surface untreated inorganic filler (c1) or the already surface treated inorganic filler for forming the surface treated inorganic filler (B) is not particularly limited, but the above-described metal hydroxide and metal hydrate are preferable. Furthermore, aluminum hydroxide, magnesium hydroxide and calcium carbonate are preferred.
  • a surface treating agent is not specifically limited, A fatty acid, phosphate ester, polyester, a titanate coupling agent, a silane coupling agent, etc. are mentioned. Of these, fatty acids and silane coupling agents are preferred. Although it does not specifically limit as a fatty acid, A stearic acid, an oleic acid, a lauric acid etc. are preferable. Although it does not specifically limit as a silane coupling agent, The silane coupling agent which has an amino group at the terminal, the silane coupling agent which has double bonds, such as a vinyl group and a methacryloyl group, and the silane which has an epoxy group at the terminal A coupling agent is preferred.
  • the surface-treated inorganic filler (B) may be one that has been surface-treated with one of the aforementioned surface-treating agents, or one that has been surface-treated with two or more.
  • the surface-treated inorganic filler (B) surface-treated with a fatty acid or silane coupling agent is obtained by mixing a surface untreated inorganic filler (c1) and the like with a fatty acid or silane coupling agent.
  • the method of mixing the surface untreated inorganic filler (c1) and the like with the fatty acid or silane coupling agent is not particularly limited, but the surface untreated inorganic filler (c1) or an appropriate surface treatment agent (for example, fatty acid) Or a method in which a fatty acid or a silane coupling agent is added to a surface-treated inorganic filler surface-treated with a silane coupling agent) without heating or heating, and these inorganic fillers are dispersed in a solvent such as water.
  • the amount of these surface treatments is not particularly limited, but it is usually preferably 0.1 to 4% by mass relative to the inorganic filler before the surface treatment such as the untreated inorganic filler (c1).
  • the surface treatment amount is within this range, the mechanical strength and wear resistance can be improved, the elongation and appearance can be improved, and the extrusion load can be reduced.
  • Examples of the surface-treated inorganic filler (B) surface-treated with stearic acid, such as magnesium hydroxide include Kisuma 5AL (trade name, manufactured by Kyowa Chemical Co., Ltd.).
  • Examples of the surface-treated inorganic filler (B) obtained by surface treatment with a silane coupling agent include silane coupling agent surface-treated magnesium hydroxide and silane coupling agent surface-treated aluminum hydroxide.
  • Examples of the silane coupling agent surface-treated magnesium hydroxide include Kisuma 5L, Kisuma 5P (both trade names, manufactured by Kyowa Chemical Co., Ltd.), Magsees S6, Magseeds S4 (both trade names are Kamishima Chemical Co., Ltd.), and the like.
  • Examples of commercially available silane coupling agent surface-treated aluminum hydroxide include Popelite H42-ST-V and Heidilite H42-ST-E (both trade names, Showa Denko KK).
  • the surface treatment inorganic filler (B) may be used alone or in combination of two or more.
  • the inorganic filler (C) used in the present invention is the above-mentioned hydrolyzable silane coupling agent (q) before being melt-mixed with the above-described resin component (A) or the like in the step (a). It is an inorganic filler (C) processed in advance.
  • the inorganic filler (C) may include at least a part of the surface-treated inorganic filler (B), and the whole may be the surface-treated inorganic filler (B), and the remaining part of the surface-untreated inorganic filler (c1) or the like. May be included.
  • inorganic filler (C) contains surface-treated inorganic filler (B)
  • bonding of the hydrolysable silane coupling agent (q) and inorganic filler added later.
  • a hydrolyzable silane coupling agent that binds to the inorganic filler with a certain weak bond can be created.
  • this hydrolyzable silane coupling agent that binds to the inorganic filler with a weak bond it is possible to obtain a heat-resistant silane cross-linked resin molded product having a certain degree of cross-linking, whereby high heat resistance can be obtained.
  • the ratio of the surface-treated inorganic filler (B) in the inorganic filler (C) is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more.
  • the ratio of the surface-treated inorganic filler (B) is preferably 100% by mass or less. When this ratio is 30% by mass or more, the heat resistance of the heat-resistant silane crosslinked resin molded article is improved.
  • the surface-treated inorganic filler (B) and the surface untreated inorganic filler can be used alone or in combination of two or more.
  • silane coupling agent premixed inorganic filler (D) Silane coupling agent premixed inorganic filler
  • the silane coupling agent premixed inorganic filler (D) is prepared by previously mixing the above-mentioned inorganic filler (C) with a hydrolyzable silane coupling agent (q).
  • the inorganic filler (C) is surface-treated with a functional silane coupling agent (q).
  • the silane coupling agent premixed inorganic filler (D) includes the resin component (A), the organic peroxide (P), and the like, as will be described later, and the inorganic filler (C) and the hydrolyzable silane coupling agent (q). And the surface treated by mixing with.
  • the silane coupling agent premixed inorganic filler (D) can also be referred to as a silane coupling agent-containing inorganic filler and a silane coupling agent-treated inorganic filler.
  • the hydrolyzable silane coupling agent (q) for surface-treating the inorganic filler (C) is as described above.
  • the silane coupling agent premixed inorganic filler (D) is obtained by mixing the inorganic filler (C) and the hydrolyzable silane coupling agent (q).
  • a wet process in which the hydrolyzable silane coupling agent (q) and the inorganic filler (C) are mixed in alcohol or water inorganic Examples thereof include a dry treatment for blending the filler (C) and the hydrolyzable silane coupling agent (q), and both.
  • the inorganic filler (C) and the hydrolyzable silane coupling agent (q) are premixed before or simultaneously with the organic peroxide (P) in the step (a) described later, A part of the decomposable silane coupling agent (q) is strongly bonded to the inorganic filler (C) (the reason is, for example, formation of a chemical bond with a hydroxyl group on the surface of the inorganic filler is considered), and silane coupling An agent premixed inorganic filler (D) is prepared.
  • the hydrolyzable silane coupling agent (q) which binds strongly to the inorganic filler (C), and the inorganic filler (C) are weakly bonded (interaction by hydrogen bonds, ions And a hydrolyzable silane coupling agent (q) that interacts between partial charges or dipoles, an action by adsorption, etc.), as described later, shows a different behavior. Therefore, the effect obtained by the ratio of these hydrolyzable silane coupling agents (q) differs.
  • a method for adjusting the ratio of the hydrolyzable silane coupling agent (q) that is weakly bonded to the inorganic filler (C) is, for example, a hydrolyzable silane coupling agent ( q) and a method of adjusting by mixing inorganic filler (C) at room temperature, a method of storing at normal temperature or preheated after premixing, or hydrolysis by heating inorganic filler (C) before premixing And a method of mixing with a functional silane coupling agent (q).
  • the brominated flame retardant (h1) is used together with the silane coupling agent premixed inorganic filler (D).
  • the brominated flame retardant (h1) is used, even if the amount of the silane coupling agent premixed inorganic filler (D) is reduced, excellent flame retardancy equivalent to or higher than that of a molded article by electron beam crosslinking is exhibited.
  • the brominated flame retardant (h1) used in the present invention is not particularly limited as long as it is used as a flame retardant.
  • organic bromine-containing flame retardants such as hexabromocyclododecane, brominated polystyrene, hexabromobenzene and the like can be used.
  • the “derivative” means one having an organic group such as an alkyl group as a substituent, or one having a different number of bromine atoms.
  • brominated bisphenol particularly tetrabromobisphenol A
  • 1,2-bis (bromophenyl) ethane 1,2-bis (bromophenyl) ethane
  • brominated polystyrene brominated ethylene bisphthalimide represented by the following structural formula 1
  • a 1,2-bis (bromophenyl) ethane derivative represented by the following structural formula 2 is preferred, a brominated ethylene bisphthalimide represented by the following structural formula 1, a 1,2-bis ( More preferred are bromophenyl) ethane derivatives.
  • each n is independently an integer of 1 to 5, preferably an integer of 3 to 5.
  • silanol condensation catalyst (e1) functions to bind the hydrolyzable silane coupling agent (q) grafted to the resin component (A) in the presence of moisture by a condensation reaction. Based on the function of the silanol condensation catalyst (e1), the resin components (A) are cross-linked through the hydrolyzable silane coupling agent (q). As a result, a heat-resistant silane cross-linked resin molded product having excellent heat resistance can be obtained.
  • silanol condensation catalyst (e1) an organic tin compound, a metal soap, a platinum compound, or the like is used.
  • Common silanol condensation catalysts (e1) 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 (e2) is not particularly limited, but is preferably a polyolefin resin of the resin component (A), and a part of the resin component (A) can be used. What is this resin component (A)? Another resin can also be used.
  • the carrier resin (e2) is preferably an ethylene-vinyl acetate copolymer (i) or polypropylene (iii) in that it has an affinity with the silanol condensation catalyst (e1) and is excellent in heat resistance.
  • a flame retardant aid can be used. It is preferable to use antimony trioxide (h3) as a flame retardant aid. When antimony trioxide is used, the flame retardancy of the heat-resistant silane crosslinked resin molded product can be further improved.
  • additives generally used for electric wires, electric cables, electric cords, sheets, foams, tubes, pipes, etc. for example, crosslinking aids, antioxidants (also referred to as anti-aging agents), Lubricants, metal deactivators, fillers, other resins, and the like may be appropriately used as long as the object of the present invention is not impaired.
  • These additives may be contained in any component, but may be contained in the catalyst master batch (Mx).
  • the antioxidant and the metal deactivator are mixed with the carrier resin (e2) of the catalyst masterbatch (Mx) so as not to inhibit the grafting of the hydrolyzable silane coupling agent (q) to the resin component (A). Preferably it is done.
  • a crosslinking aid is not substantially contained.
  • the crosslinking aid is not substantially mixed in the step (a) for preparing the silane master batch (Dx).
  • the crosslinking aid reacts with the organic peroxide (P) during kneading, crosslinking between the resin components (A) occurs, gelation occurs, and the heat resistant silane crosslinked resin molded article is formed. Appearance may deteriorate. Further, the graft reaction of the hydrolyzable silane coupling agent (q) to the resin component (A) is difficult to proceed, and the heat resistance of the final heat-resistant silane crosslinked resin molded product may not be obtained.
  • 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 one that forms a partially crosslinked structure with the resin component (A) in the presence of an organic peroxide, for example, a methacrylate compound such as polypropylene glycol diacrylate, trimethylolpropane triacrylate, Examples include allyl compounds such as triallyl cyanurate, polyfunctional compounds such as maleimide compounds, and divinyl compounds.
  • an organic peroxide for example, a methacrylate compound such as polypropylene glycol diacrylate, trimethylolpropane triacrylate, Examples include allyl compounds such as triallyl 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 pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Phenol-based antioxidants such as propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben ⁇ imidazole and its zinc salt, penta Risuritoru - tetrakis (3-lauryl - thiopropionate) sulfur-based antioxidants such as and the like.
  • the antioxidant can be added in an amount of preferably 0.1 to 15.0 parts by weight, more preferably 0.1 to 10 parts by
  • 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.
  • lubricant examples include hydrocarbons, siloxanes, fatty acids, fatty acid amides, esters, alcohols, metal soaps and the like. These lubricants should be added to the carrier resin (E).
  • the “method for producing a heat-resistant silane cross-linked resin molded article” of the present invention includes the step (a), the step (b), and the step (c).
  • the step (a) comprises 0.01 to 0.6 parts by mass of an organic peroxide (P), 100 parts by mass of the resin component (A), and a silane coupling agent premixed inorganic.
  • a heat-resistant silane is obtained by melt-mixing 10 to 150 parts by mass of a filler (D), 15 to 60 parts by mass of a brominated flame retardant (h1), and 0.001 to 0.5 parts by mass of a silanol condensation catalyst (e1).
  • This is a step of preparing a crosslinkable resin composition (F).
  • the resin component (A) used in the step (a) is subjected to a crosslinking reaction in the presence of the crosslinking group of the hydrolyzable silane coupling agent (q) and the organic peroxide (P).
  • the resins, elastomers, rubbers, and the like which may contain various oils if desired
  • the polyolefin copolymer (i) and the ethylene- ⁇ -olefin copolymer (ii) are contained.
  • the heat resistance silane crosslinked resin molded article is excellent in insulation resistance, appearance, flexibility, and cold resistance.
  • at least one of the polyolefin copolymers (i) is preferably one selected from an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylic ester copolymer, and an ethylene- ⁇ -olefin.
  • the copolymer (ii) is preferably linear low density polyethylene (LLDPE).
  • the resin component (A) may be composed of the polyolefin copolymer (i) and the ethylene- ⁇ -olefin copolymer (ii), or may contain other resin components.
  • Resin component (A) is selected from the ranges described below for the respective resins and various oils so that the total of the various resins constituting the resin component and various oils is 100% by mass as required.
  • the content of the polyolefin copolymer (i) with respect to the entire resin component (A) And the ethylene- ⁇ -olefin copolymer (ii) content is selected from the range of 10 to 90% by mass.
  • the content of the polyolefin copolymer (i) and the content of the ethylene- ⁇ -olefin copolymer (ii) are within the above ranges, the mechanical properties, insulation resistance, and flame resistance of the heat-resistant silane crosslinked resin molded product High quality, heat resistance and appearance.
  • the content of the polyolefin copolymer (i) is more preferably selected from the range of 10 to 50% by mass with respect to the entire resin component (A).
  • the content of the ethylene- ⁇ -olefin copolymer (ii) is more preferably selected from the range of 20 to 80% by mass with respect to the entire resin component (A).
  • the total content of the polyolefin copolymer (i) and the ethylene- ⁇ -olefin copolymer (ii) is preferably 30 to 100 with respect to the entire resin component (A) in terms of excellent mechanical properties and insulation resistance.
  • Each content is selected from the above-mentioned range so as to be mass%, more preferably 35 to 98 mass%, and still more preferably 40 to 95 mass%.
  • the balance of the resin component (A) is the polyolefin copolymer (i) and the ethylene- ⁇ -olefin.
  • Resin components other than the copolymer (ii) for example, polypropylene (iii), polyethylene (iv), styrene-based elastomer (v), and in some cases, the oil described above may be used.
  • the total amount of the resin component (A) is The content of polypropylene (iii) is preferably selected in the range of 0.2 to 20% by mass, more preferably in the range of 0.5 to 15% by mass. When the content of polypropylene (iii) is within the above range, the appearance and flexibility of the heat-resistant silane crosslinked resin molded article can be achieved at a higher level.
  • resin component (A) contains polyethylene (iv)
  • the content rate of polyethylene (iv) is 30 mass% or less with respect to the whole resin component (A).
  • the resin component (A) contains the styrene elastomer (v)
  • the content of the styrene elastomer (v) is 30% by mass or less based on the entire resin component (A). preferable.
  • the oil content is as described above.
  • the resin component (A) may be used entirely in the step (a1), or a part thereof may be used in the step (a1) and the rest in the step (a2). May be.
  • a part of the resin component (A) is used in the step (a1) and the rest in the step (a2).
  • the mass ratio of the resin component (A) used in the step (a1) and the step (a2) at this time will be described later.
  • the compounding amount of the organic peroxide (P) is 0.01 to 0.6 parts by weight, preferably 0.03 to 0.00 parts per 100 parts by weight of the resin component (A). 5 parts by mass.
  • the organic peroxide (P) within this range, the polymerization can be carried out in an appropriate range, and the heat-resistant silane cross-linking property is excellent in extrudability without generating an agglomerate due to a cross-linked gel or the like.
  • a resin composition (F) can be obtained.
  • the crosslinking reaction does not proceed at the time of crosslinking and the crosslinking reaction does not proceed at all, or the released silane coupling agents are bonded to each other.
  • Heat resistance, mechanical strength, wear resistance, and reinforcement cannot be obtained sufficiently, and if it exceeds 0.6 parts by mass, many resin components are directly cross-linked by side reaction. In addition, the extrudability deteriorates and there is a risk that bumps will occur.
  • the blending amount of the silane coupling agent premixed inorganic filler (D) can be reduced by the combined use with a brominated flame retardant described later, specifically, 10 to 150 parts by mass with respect to 100 parts by mass of the resin component (A). Part, preferably 20 to 120 parts by weight.
  • the blending amount of the silane coupling agent premixed inorganic filler (D) is less than 10 parts by mass, the graft reaction of the silane coupling agent (q) to the resin component (A) becomes non-uniform, and the desired heat resistance is obtained. It may not be obtained or the appearance may deteriorate due to a non-uniform graft reaction.
  • it exceeds 150 parts by mass the load during molding or kneading becomes very large, and secondary molding may be difficult.
  • the amount of the brominated flame retardant (h1) is 15 to 60 parts by weight, preferably 20 to 60 parts by weight, more preferably 100 parts by weight of the resin component (A). Is 20 to 40 parts by mass.
  • the amount of the brominated flame retardant (h1) is less than 15 parts by mass, desired flame retardancy cannot be obtained. On the other hand, when it exceeds 60 mass parts, mechanical strength may fall.
  • a flame retardant aid such as antimony trioxide, an additive and the like can be mixed.
  • the blending amount of antimony trioxide (h3) is preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the resin component (A). When the blending amount of antimony trioxide (h3) is within the above range, desired flame retardancy is obtained and high mechanical properties are exhibited.
  • the additive is mixed in the above-described amount or an appropriate amount.
  • the step (a) has the following step (a1) and step (a3), and when the part of the resin component (A) is melt-mixed in the following step (a1), the following step is further performed. (A2).
  • the step (a) includes these steps, each component can be uniformly melted and mixed, and the desired effect can be obtained.
  • Step (a1) A part or all of the resin component (A), the organic peroxide (P), and the silane coupling agent premixed inorganic filler (D) are at or above the decomposition temperature of the organic peroxide (P).
  • Step (a2) for preparing a silane masterbatch (Dx) by melt-mixing in step 2 Melting and mixing the remainder of the resin component (A) as the carrier resin (e2) and the silanol condensation catalyst (e1)
  • Step (a3) of preparing master batch (Ex) Step of melt-mixing silane master batch (Dx) and silanol condensation catalyst (e1) or catalyst master batch (Ex)
  • the step (a2) is performed when a part of the resin component (A) is melt-mixed in the step (a1), and the whole resin component (A) is melt-mixed in the step (a1). If not done.
  • the silanol condensation catalyst (e1) is used alone instead of the catalyst master batch (Ex).
  • the brominated flame retardant (h1) may be mixed in any one of the steps (a1) and (a2), and the brominated flame retardant (h1) is more uniformly mixed. In view of exhibiting high flame retardancy, it is preferable to mix at least in step (a1), and may be mixed in both step (a1) and step (a2).
  • antimony trioxide (h3) when used in step (a), it is preferably mixed in either step (a1) or step (a2), and antimony trioxide (h3) is more uniform. It is more preferable to mix at least in the step (a1) from the viewpoint of exhibiting high flame retardancy, and it may be mixed in both the step (a1) and the step (a2).
  • step (a1) part or all of the resin component (A), the organic peroxide (P), the silane coupling agent premixed inorganic filler (D), and preferably the brominated flame retardant (h1) A part or all of the above is put into a mixer and melt-kneaded while being heated above the decomposition temperature of the organic peroxide (P) to prepare a silane masterbatch (Dx).
  • step (a) mixing of resin component (A), organic peroxide (P), silane coupling agent premixed inorganic filler (D), brominated flame retardant (h1), antimony trioxide (h3), etc.
  • the method is not particularly limited.
  • the organic peroxide (P) may be mixed alone with the resin component (A) and the silane coupling agent premixed inorganic filler (D).
  • the silane coupling agent premixed inorganic filler is used. It is preferable to be included in (D). That is, in the step (a), a silane coupling agent premixed inorganic filler (D) that does not contain an organic peroxide (P) may be used, but a silane coupling agent that contains an organic peroxide (P). It is preferable to use a premixed inorganic filler (D).
  • the silane coupling agent premixed inorganic filler (D) prior to the step (a1).
  • the hydrolyzable silane coupling agent (q) is mixed with the inorganic filler (C) as described above.
  • a silane coupling agent premixed inorganic filler (D) that is strongly or weakly bonded is obtained.
  • the step of preparing the silane coupling agent premixed inorganic filler (D) is performed prior to the step (a1), it is possible to suppress the occurrence of defects due to local crosslinking.
  • the hydrolyzable silane coupling agent (q), the organic peroxide (P) and the inorganic filler (C) are mixed, and then the mixture and the resin component (A) are mixed.
  • the brominated flame retardant (h1) is melt-kneaded at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P) to prepare a silane masterbatch (graftmer) (Dx).
  • the inorganic filler (C), the hydrolyzable silane coupling agent (q) and the organic peroxide (P) are mixed with the organic peroxide (P) at a predetermined mass ratio.
  • the mixture is prepared by dry or wet mixing at a temperature lower than the decomposition temperature, preferably at room temperature (25 ° C.).
  • the hydrolyzable silane coupling agent (q) mixed with the inorganic filler (C) is 0.5 to 30.0 parts by mass with respect to 100 parts by mass of the inorganic filler (C), preferably 1.0 to 20.0 parts by mass.
  • the amount of the hydrolyzable silane coupling agent (q) is less than 0.5 parts by mass, the crosslinking is not sufficient, and the desired heat resistance and mechanical properties can be obtained in the heat-resistant silane crosslinked resin molded product. It may not be possible.
  • the hydrolyzable silane coupling agent (q) that does not adsorb on the surface of the inorganic filler (C) increases, and thus volatilizes during kneading, which is not economical. Condensation of the hydrolyzable silane coupling agent (q) that is not adsorbed may result in cross-linked gels and burns in the heat-resistant silane cross-linked resin molded article, and the appearance may deteriorate. In particular, the appearance defect is remarkable when it exceeds 30.0 parts by mass.
  • the hydrolyzable silane coupling agent (q) is preferably 0.5 to 18.0 parts by weight, and 1.0 to 10.0 parts by weight with respect to 100 parts by weight of the resin component (A). It is more preferable that When the amount of the hydrolyzable silane coupling agent (q) used is less than 0.5 parts by mass, the crosslinking is not sufficiently performed, and desired heat resistance and mechanical properties can be obtained in the heat-resistant silane crosslinked resin molded product. It may not be possible.
  • the hydrolyzable silane coupling agents (q) are condensed with each other, and there is a risk that the heat-resistant silane crosslinked resin molded product may be damaged or burnt by the crosslinked gel and the appearance may be deteriorated. is there.
  • the mixture thus obtained includes a silane coupling agent premixed inorganic filler (D) obtained by mixing an inorganic filler (C) and a hydrolyzable silane coupling agent (q), and an organic peroxide (P). Containing.
  • D silane coupling agent premixed inorganic filler
  • q hydrolyzable silane coupling agent
  • P organic peroxide
  • Mixing with the inorganic filler (C) and the hydrolyzable silane coupling agent (q) is a state of adding and mixing with heating or non-heating (dry type), or a state in which the inorganic filler (C) is dispersed in a solvent such as water.
  • a method of adding a hydrolyzable silane coupling agent (q) (wet).
  • a treatment in which the hydrolyzable silane coupling agent (q) is added to the inorganic filler (C), preferably the dried inorganic filler (C), with heating or non-heating, that is, dry processing is preferable. .
  • the hydrolyzable silane coupling agent (q) is strongly bonded to the inorganic filler (C).
  • the subsequent cross-linking reaction may be difficult to proceed.
  • the method of adding and mixing the hydrolyzable silane coupling agent (q) in the inorganic filler (C) with heating or non-heating (dry mixing) is a relatively inorganic filler (C) and hydrolyzable silane coupling. Since the bond of the agent (q) becomes weak, the crosslinking easily proceeds efficiently.
  • the hydrolyzable silane coupling agent (q) and the organic peroxide (P) may be mixed together and dispersed in the inorganic filler (C), or separately. It is better to mix together substantially.
  • the hydrolyzable silane coupling agent (q) to be added to the inorganic filler (C) exists so as to surround the surface of the inorganic filler (C), and part or all of the hydrolyzable silane coupling agent (q) is adsorbed on the inorganic filler (C) or inorganic. It may cause a loose chemical bond with the filler (C) surface.
  • step (a1) depending on the production conditions, only the hydrolyzable silane coupling agent (q) can be mixed with the inorganic filler (C), and then the organic peroxide (P) can be added.
  • the organic peroxide (P) may be dispersed in the resin component (A), or may be added alone or dispersed in oil or the like. Disperse in A).
  • the prepared mixture, the resin component (A), preferably the brominated flame retardant (h1), and, if desired, the flame retardant aids and additives are each added to a mixer. In addition, they are melt-kneaded while heating to prepare a silane masterbatch (Dx).
  • 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 (A) is melted.
  • kneading conditions such as kneading time can be set as appropriate.
  • the kneading method any method usually used for rubber, plastic, etc. can be used, and the kneading apparatus is appropriately selected according to the amount of the silane coupling agent premixed inorganic filler (D), for example.
  • a kneading apparatus a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, or various kneaders are used.
  • a closed mixer such as a Banbury mixer or various kneaders is used for the dispersibility of the resin component (A) and the crosslinking reaction. It is preferable in terms of stability.
  • the step of preparing the silane coupling agent premixed inorganic filler (D) as in the preferred step (a1) in advance, but when the above components are kneaded in the above blending amounts, local crosslinking is performed. Can be suppressed. Therefore, the step (a1) can also be carried out without making the preparation step separate from the melt-kneading step. That is, the silane master batch (Dx) can be prepared by mixing the above-described components together at a temperature higher than the decomposition temperature of the organic peroxide (P).
  • step (a1) is performed to prepare a silane master batch (also referred to as silane MB) (Dx).
  • the silane masterbatch prepared in step (a1) is a decomposition product of an organic peroxide (P), preferably a brominated flame retardant (h1), a resin component (A) and a silane coupling agent premixed inorganic filler. It is a reaction mixture of (D), and contains a silane crosslinkable resin in which a hydrolyzable silane coupling agent (q) is grafted to the resin component (A) to such an extent that it can be molded by the step (b) described later.
  • step (a2) is performed.
  • Step (a2) is a step of preparing a catalyst master batch (Ex) by melting and mixing the remainder of the resin component (A) as the carrier resin (e2) and the silanol condensation catalyst (e1).
  • the compounding amount of the silanol condensation catalyst (e1) is 0.001 to 0.5 parts by mass, preferably 0.003 to 0.1 parts per 100 parts by mass of the resin component (A) used in the step (a). Part by mass.
  • the blending amount of the silanol condensation catalyst (e1) is less than 0.001 part by mass, crosslinking due to the condensation reaction of the hydrolyzable silane coupling agent (q) is difficult to proceed, and the heat resistance of the heat-resistant silane crosslinked resin molded article is sufficient. However, the productivity may be reduced, and the crosslinking may be uneven.
  • the silanol condensation reaction proceeds very rapidly, resulting in partial gelation and the appearance of the heat-resistant silane crosslinked resin molded product being reduced, or heat-resistant silane crosslinked resin molding Physical properties of the body may be reduced.
  • the blending amount of the carrier resin (e2) is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and further preferably 2 to 40 parts by mass with respect to 100 parts by mass of the resin component (A) in the step (a). Part by mass.
  • the carrier resin (e2) it is preferable to use a part of the resin component (A) within the range satisfying the above-mentioned blending amount. In this case, the resin component (A) and the carrier resin (e2) are added so that the total of the resin component (A) used in the step (a1) and the carrier resin (e2) used in the step (a2) is 100 parts by mass. The usage amount of is appropriately set.
  • the carrier resin (e2) is preferably 5 to 40 parts by mass, particularly preferably 10 to 30 parts by mass, out of a total of 100 parts by mass with the resin component (A).
  • the resin component (A) used in the step (a1) is 60 to 95 parts by mass, and the total amount of the resin component (A) and the carrier resin (e2) is a reference for the blending amount of each component. .
  • the catalyst master batch (Ex) may contain other components in addition to the silanol condensation catalyst (e1) and the carrier resin (e2).
  • you may contain the inorganic filler.
  • content of an inorganic filler is not specifically limited, 350 mass parts or less are preferable with respect to 100 mass parts of carrier resin (e2). This is because if the amount of the inorganic filler is too large, the silanol condensation catalyst (e1) is difficult to disperse and the crosslinking is difficult to proceed.
  • carrier resin (e2) there exists a possibility that the crosslinking degree of a molded object may fall and appropriate heat resistance may not be acquired.
  • a resin other than the resin component (A) can be used as the carrier resin (e2).
  • the melt mixing conditions with the silanol condensation catalyst (e1) and the carrier resin (e2) are appropriately set according to the melting temperature of the carrier resin (e2).
  • the kneading temperature can be 80 to 250 ° C., more preferably 100 to 240 ° C.
  • the kneading conditions such as kneading time can be set as appropriate.
  • the kneading method can be performed by the same method as the kneading method in the step (a1).
  • the catalyst master batch (Ex) (also referred to as catalyst MB) thus obtained is a mixture of a silanol condensation catalyst (e1), a carrier resin (e2), and a filler that is added as desired.
  • the process (a3) which melt-mixes a silane masterbatch (Dx), a silanol condensation catalyst (e1), or a catalyst masterbatch (Ex) is performed.
  • the catalyst master batch (Ex) prepared in the step (a2) is used, and when the step (a2) is not performed, the silanol condensation catalyst (e1) is used.
  • step (a3) the silane master batch (Dx), the catalyst master batch (Ex), and the like are melt-kneaded while heating.
  • this melt-kneading there is a resin component (A) whose melting point cannot be measured by DSC or the like, for example, an elastomer, but kneading is performed at a temperature at which at least one of the resin component (A) and the organic peroxide (P) is melted.
  • the carrier resin (e2) is preferably melted to disperse the silanol condensation catalyst (e2).
  • the kneading conditions such as kneading time can be set as appropriate.
  • the melt-kneading method can be performed by the same method as the kneading method in the step (a1).
  • a heat-resistant silane crosslinkable resin composition (F) containing at least two different silane crosslinkable resins with different crosslinking methods is prepared.
  • This heat-resistant silane crosslinkable resin composition (F) is a composition prepared by the step (a), and is a resin component (A), a silane coupling agent premixed inorganic filler (D), preferably bromine It is considered as a mixture of the silane masterbatch (Dx) and the silanol condensation catalyst (e1) or the catalyst masterbatch (Ex) containing the flame retardant (h1) as a raw material component.
  • the step (b) of molding the heat-resistant silane crosslinkable resin composition (F) is then performed to obtain a molded product.
  • the molding method only needs to mold the heat-resistant silane crosslinkable resin composition (F), and the molding method and molding conditions are appropriately selected according to the form of the heat-resistant product of the present invention. For example, when the heat-resistant product of the present invention is an electric wire or an optical fiber cable, extrusion molding or the like is selected.
  • This step (b) can be performed simultaneously or continuously with the mixing of the silane masterbatch (Dx) and the catalyst masterbatch (Ex).
  • a silane masterbatch (Dx) and a catalyst masterbatch (Ex) are melt-kneaded in a coating apparatus (step (a)), and then covered with, for example, an extruded wire or fiber and formed into a desired shape (step (b) )) Can be adopted.
  • the step (c) is then performed in which the molded product (uncrosslinked product) obtained in the step (b) is brought into contact with water to be crosslinked.
  • the hydrolyzable group of the hydrolyzable silane coupling agent is hydrolyzed into silanol by bringing the molded product into contact with water, and the silanol condensation catalyst (e2) present in the resin.
  • the hydroxyl groups of silanol are condensed to each other to cause a crosslinking reaction, thereby obtaining a heat-resistant silane-crosslinked resin molded body in which the heat-resistant silane-crosslinkable resin composition (F) is crosslinked.
  • the process itself of this process (c) can be performed by a normal 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 only by storage at room temperature, but in order to further accelerate the cross-linking, when contacting with moisture, water is immersed in warm water, put into a wet heat tank, For example, exposure to water vapor. In this case, pressure may be applied to allow moisture to penetrate inside.
  • the production method of the present invention is carried out, and a heat-resistant silane cross-linked resin molded product is produced from the heat-resistant silane cross-linkable resin composition (F). Therefore, the heat-resistant silane cross-linked resin molded product of the present invention is a molded product obtained by performing the step (a) and, if desired, the step (b) and the step (c).
  • the resin component (A) is heated and kneaded at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P) together with the silane coupling agent premixed inorganic filler (D) in the presence of the organic peroxide (P) component. And grafted with a hydrolyzable silane coupling agent by radicals generated by the decomposition of the organic peroxide (P).
  • resin component (A) couple
  • An agent can be formed.
  • the hydrolyzable silane coupling agent having a strong bond with the inorganic filler (C) is an ethylenically unsaturated group which is a cross-linking group.
  • the hydrolyzable silane coupling agent having a weak bond with the inorganic filler (C) is from the surface of the inorganic filler (C).
  • the ethylenically unsaturated group, which is a crosslinkable group of the hydrolyzable silane coupling agent, was released by hydrogen radical abstraction by radicals generated by decomposition of the organic peroxide (P) of the resin component (A).
  • a graft reaction occurs by reacting with a resin radical. It is considered that 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 to cause a crosslinking reaction by a condensation reaction.
  • hydrolysis reaction in which a hydroxyl group on the surface of the inorganic filler is chemically bonded by a covalent bond by 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 cross-linking reaction by condensation using a silanol condensation catalyst in the presence of water is performed after forming the formed body, whereby the formed body is obtained after the conventional final cross-linking reaction.
  • it is excellent in workability in the process up to forming the molded body, and can bind a plurality of hydrolyzable silane coupling agents on the surface of one inorganic filler particle, and has higher heat resistance than before, For example, it becomes possible to obtain solder heat resistance at 380 ° C., which will be described later, and to obtain high mechanical strength, insulation resistance and flame retardancy.
  • the hydrolyzable silane coupling agent bonded to the inorganic filler (C) with a strong bond contributes to high mechanical strength, insulation resistance and flame retardancy, and has a weak bond to the inorganic filler (C).
  • the bonded hydrolyzable silane coupling agent contributes to the improvement of the degree of crosslinking.
  • the inorganic filler (C) when a surface-treated inorganic filler that has been slightly surface-treated with a silane coupling agent or other surface treatment agent in advance is used, a pre-treated silane coupling agent or a post-added hydrolyzable silane A large amount of the silane coupling agent premixed inorganic filler (D) to which the coupling agent (q) is strongly bonded is formed, and a molded article having high mechanical properties (for example, mechanical strength), insulation resistance and flame retardancy can be obtained.
  • a surface-treated inorganic filler that has been slightly surface-treated with a silane coupling agent or other surface treatment agent in advance when used, a pre-treated silane coupling agent or a post-added hydrolyzable silane A large amount of the silane coupling agent premixed inorganic filler (D) to which the coupling agent (q) is strongly bonded is formed, and a molded article having high mechanical properties (for example, mechanical strength), insulation resistance and flame retardancy
  • the hydrolyzable silane coupling agent added later is weakly bonded.
  • a large amount of the silane coupling agent premixed inorganic filler (D) is formed and the mechanical strength is not greatly improved, a molded article having excellent flexibility and the like can be obtained.
  • the brominated flame retardant (h1) contains a large amount of bromine having a high electronegativity and has a high polarity. Therefore, the brominated flame retardant (h1) is further incorporated into the strong network between the resin component (A) and the silane coupling agent premixed inorganic filler (D) via the hydrolyzable silane coupling agent (q). Therefore, it is considered that the interaction is increased and the flame retardancy is improved.
  • 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, components 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 heat-resistant product of the present invention is the above-mentioned various heat-resistant products including a heat-resistant silane cross-linked resin molded article, and a heat-resistant product containing the heat-resistant silane cross-linked resin molded article as a coating for an insulator or a sheath, for example, an electric wire And optical cables.
  • Insulators, sheaths, and the like can be formed by coating them in such a shape while melt-kneading them in an extrusion coating apparatus.
  • Such a molded body such as an insulator or a sheath is a general-purpose extrusion coating apparatus that uses a large amount of an inorganic filler and a highly heat-resistant and non-melting crosslinked composition without using a special machine such as an electron beam crosslinking machine.
  • 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 formed around the conductor is not particularly limited, but is usually about 0.15 to 8 mm.
  • EVA1 EV360, ethylene-vinyl acetate copolymer resin “Evaflex” (trade name) manufactured by Mitsui DuPont Chemical Co., Ltd., VA content 25% by mass
  • EVA2 EV180 Ethylene-vinyl acetate copolymer resin “Evaflex” (trade name) manufactured by Mitsui DuPont Chemical Co., Ltd., VA content 33% by mass
  • LLDPE “Evolue SP0540” (trade name), LLDPE resin manufactured by Prime Polymer Co.
  • Random polypropylene “PB222A” (trade name), random PP resin manufactured by Sun Allomer (v) Styrene "Septon 4077” (trade name) as a base elastomer, "Diana Process Oil PW90” (trade name) as a process oil made by Kuraray, "XP650” (trade name) as a silane graft polyethylene made by Idemitsu Kosan, manufactured by Hyundai Silane grafted polyethylene
  • DCP decomposition temperature 151 ° C.
  • antimony trioxide As antimony trioxide, as an antimony trioxide crosslinking aid manufactured by Toyota Tsusho Corporation, “Ogmont T200” (trade name), manufactured by Shin-Nakamura Chemical Co., Ltd., or trimethylolpropane trimethacrylate as an anti-aging agent, “Irganox 1010” (trade name), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by BASF as a lubricant, “NS-M” (trade name), Magnesium stearate, manufactured by Nippon Oil & Fats, or “X21-3043” (trade name), polyorganosiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 1 First, the inorganic filler (B), hydrolyzable silane coupling agent (q) and organic peroxide (P) shown in the “Silane MB (D1)” column of Table 1 are blended in the amounts shown in Table 1, The mixture was put into a Toyo Seiki 10 L Henschel mixer and mixed at room temperature for 10 minutes to obtain a powder mixture containing an organic peroxide (P) and a silane coupling agent premixed inorganic filler (D). Next, this powder mixture, resin component (A), brominated flame retardant (h1), antimony trioxide (h3) and lubricant shown in the “Silane MB (D1)” column of Table 1 are manufactured by Nippon Roll.
  • the mixture was put into a 2 L Banbury mixer, kneaded in the mixer for about 12 minutes, and then discharged at a material discharge temperature of 180 to 190 ° C. to obtain a silane master batch (D1) (step (a1)).
  • the mixture Prior to discharge, the mixture was kneaded at a temperature not lower than the decomposition temperature of the organic peroxide (P), specifically 180 to 190 ° C. for 5 minutes.
  • P organic peroxide
  • the blending amount (part by mass) of the hydrolyzable silane coupling agent (q) with respect to 100 parts by mass of the inorganic filler (C) at this time is shown in the “Silane MB (D1)” column of Table 1. Indicated.
  • the carrier resin (e2), the silanol condensation catalyst (e1) and the anti-aging agent shown in the “Catalyst MB (E1)” column of Table 1 are separately mixed with a Banbury mixer at 120 to 160 ° C., and a material discharge temperature of 120 to The mixture was melted and mixed at 180 ° C. to obtain a catalyst master batch (E1) (step (a2)).
  • the temperature was introduced at a temperature of 180 ° C. and melted and mixed at 180 ° C., and the outside of the 21 / 0.18TA conductor was coated with a wall thickness of 0.84 mm to obtain an electric wire having an outer diameter of 2.63 mm (step (a3) and Step (b)).
  • This electric wire was left in an atmosphere of a temperature of 60 ° C. and a humidity of 95% for 48 hours (step (c)). In this way, an insulated wire having a coating (insulating layer) made of a heat-resistant silane cross-linked resin molded article was produced.
  • Table 1 shows the blending ratio (mixing ratio) of each component used in Example 1, that is, the raw material composition ratio of the heat-resistant silane cross-linked resin molded article, as “heat-resistant silane cross-linkable resin composition (F)”.
  • Examples 2 to 15, Comparative Examples 1 and 2 A silane masterbatch (Dx) and a catalyst masterbatch (Ex) were prepared in the same manner as in Example 1 with the formulations shown in Tables 1 to 4 (step (a1) and step (a2)), and the respective blending ratios are shown. Except for the mass ratios shown in Tables 1 to 4, the outside of the 21 / 0.18 TA conductor was coated with a thickness of 0.84 mm in the same manner as in Example 1 to obtain an electric wire with an outer diameter of 2.63 mm (step ( a3) and step (b)). The electric wire was left in an atmosphere of temperature 60 ° C. and humidity 95% for 48 hours (step (c)) to produce an insulated electric wire having a coating (insulating layer) made of a heat-resistant silane crosslinked resin molded product.
  • Example 2 brominated flame retardant (h1) and antimony trioxide (h3) were melt-kneaded in step (a2).
  • Example 13 the brominated flame retardant (h1) was melt-kneaded in the step (a2), and antimony trioxide (h3) was melt-kneaded in the step (a1).
  • Example 11 and 12 brominated flame retardant (h1) was melt-kneaded in both steps (a1) and (a2), and antimony trioxide (h3) was melt-kneaded in step (a2).
  • inorganic filler (C), hydrolyzable silane coupling agent (q), organic peroxide (P), resin component (A), brominated flame retardant (h1), antimony trioxide ( h3) and the lubricant were put into a 2 L Banbury mixer made by Nippon Roll, then kneaded for about 12 minutes with the mixer, and then discharged at a material discharge temperature of 180 to 190 ° C. to obtain a silane master batch (D16 to 20) ( Step (a1)). Prior to discharge, the mixture was kneaded at a temperature not lower than the decomposition temperature of the organic peroxide (P), specifically 180 to 190 ° C. for 5 minutes.
  • Catalyst master batches (E16 to 20) were prepared in the same manner as in Example 1 with the formulation shown in Table 3.
  • Example 1 except that the silane master batch (D16-20) and the catalyst master batch (E16-20) were used in the mass ratios shown in Table 3 instead of the silane master batch (D1) and the catalyst master batch (E1).
  • the outside of the 21 / 0.18 TA conductor was coated with a thickness of 0.84 mm to obtain an electric wire with an outer diameter of 2.63 mm (step (a3) and step (b)).
  • the electric wire was left in an atmosphere of temperature 60 ° C. and humidity 95% for 48 hours (step (c)) to produce an insulated electric wire having a coating (insulating layer) made of a heat-resistant silane crosslinked resin molded product.
  • Comparative Examples 3 to 6 silane cross-linked resin molded articles were produced by a silane cross-linking method different from that of the present invention.
  • Tables 1 to 4 the silane crosslinking method of the present invention using the resin component (A), the silane coupling agent premixed inorganic filler (D) and the organic peroxide (P) is referred to as “silane crosslinking 1”,
  • silane crosslinking 2 The silane crosslinking method of Comparative Examples 3 to 6 using a resin grafted with a coupling agent was designated as “silane crosslinking 2”.
  • Silanol condensation catalyst (e1), anti-aging agent and lubricant are mixed with a Banbury mixer at 120 to 180 ° C., and melt mixed at a material discharge temperature of 180 to 190 ° C. to obtain catalyst master batches (E23) to (E26).
  • the resin component (A), surface treatment inorganic filler (B), brominated flame retardant (h1), antimony trioxide (h3), crosslinking aid, anti-aging agent and lubricant shown in Table 4 are banbury.
  • the mixture was mixed at 120 to 180 ° C. with a mixer, and melt mixed at a material discharge temperature of 120 to 180 ° C. to obtain a resin composition.
  • a wire having an outer diameter of 2.63 mm was obtained by coating with 0.84 mm.
  • the obtained electric wire was subjected to electron beam irradiation (15 Mrad) to crosslink the coating resin layer to produce an insulated electric wire.
  • the “crosslinking method” of the reference example was “electron beam”.
  • Insulation resistance As for the insulation resistance, the initial value (after 1 hour in water) of the insulation resistance defined in JISC3005 was measured. 2500 M ⁇ ⁇ km or more was regarded as acceptable.
  • solder heat resistance test was performed as a heat resistance test of the insulated wires. Specifically, one layer of aluminum foil was wound around the outer periphery of the insulated wire, and a portion of 3 cm in length was immersed in a solder bath set at 380 ° C. and held for 5 seconds. Thereafter, the insulated wire was pulled from the solder bath, and the presence or absence of melting of the outer periphery of the insulated wire and the presence of foaming inside the coating layer were confirmed except for the aluminum foil. As a result, if there is no abnormality such as melting or foaming of the coating layer, the test is accepted. In Tables 1 to 4, “ ⁇ ” is indicated, and if there is an abnormality such as melting or foaming of the coating layer, the test is rejected. ".
  • This VW-1 test is an evaluation method in which a combustion level is confirmed by holding a sample vertically and applying a burner, and is a test method that requires a higher flame retardant level than a horizontal flame retardant test. Therefore, this VW-1 test is a severe test and was evaluated for reference, and it is not always necessary to pass all the tests.
  • Extruded appearance also called electric wire appearance
  • An extrusion appearance test was conducted as an extrusion appearance characteristic of the insulated wire. The extrusion appearance was observed when the insulated wire was manufactured. Extrusion appearance was as follows: “ ⁇ ” when the appearance of the extrudate was good when produced with a 40 mm extruder at a linear speed of 10 m, “ ⁇ ” when the appearance was slightly bad, “ ⁇ ”, and “ ⁇ ” or higher was regarded as a product level.
  • Comparative Examples 3 to 6 Silane cross-linking 2) using silane-grafted polyethylene without using the silane coupling agent premixed inorganic filler (D) and organic peroxide (P) are both insulation resistance and solder. It was inferior in heat resistance.
  • the comparative example 3 which reduced the compounding quantity of the surface treatment inorganic filler (B) and increased the compounding quantity of antimony trioxide (h3) has a material price in order to mix
  • Comparative Examples 4 and 5 in which the blending amount of the surface-treated inorganic filler (B) was increased and the blending amount of antimony trioxide (h3) was decreased, in addition to the insulation resistance and the solder heat resistance, although the material price decreased. Also inferior in tensile strength.
  • Comparative Example 6 in which the amount of the surface-treated inorganic filler (B) was increased as compared with Comparative Example 5, in addition to insulation resistance, tensile strength and solder heat resistance, the elongation at break was inferior.
  • the specific resin component (A) is crosslinked, and by blending an appropriate amount of the silane coupling agent premixed inorganic filler (D) and the brominated flame retardant (h1), A heat-resistant silane-crosslinked resin molded article having superior tensile strength, elongation, insulation resistance, and heat resistance compared to the silane-crosslinking method “silane-crosslinked 2 (Comparative Examples 3 to 6)” using silane-grafted polyethylene. Can be obtained.
  • the heat-resistant silane cross-linked resin molded article is more excellent in flame retardancy that is comparable to or surpassing electron beam cross-linking (reference example). Can be obtained.
  • the polyolefin copolymer (i) is 10 to 50% by mass and the ethylene- ⁇ -olefin copolymer (ii) is 20% with respect to the entire resin component (A).
  • an insulation resistance value of 3000 M ⁇ ⁇ km or more is exhibited, and the insulation resistance is further improved, which is preferable.
  • Examples 1 to 6 and 11 to 20 when 5 parts by mass or more of antimony trioxide (h3) is blended, both the horizontal flame retardant test and the VW-1 test pass all, and further excellent flame retardant It is preferable because it exhibits its properties. Further, as in Examples 1 to 5 and 11 to 20, it is preferable to add 0.2 to 15% by mass or more of polypropylene (iii) with respect to the entire resin component (A) because the appearance of the electric wire is good.
  • the step of preparing the silane coupling agent premixed inorganic filler (D) in advance is omitted, and when the respective components are mixed in the mixer, By adsorbing the silane coupling agent (q) to the inorganic filler (C), the silane coupling agent premixed inorganic filler (D) is prepared, and then each of the above-described temperatures above the decomposition temperature of the organic peroxide (P).
  • a silane masterbatch (Dx) can also be prepared by mixing the components.

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Abstract

Cette invention concerne un procédé de fabrication d'un article moulé en résine silane réticulée résistant à la chaleur comprenant une étape (a) de mélange à l'état fondu d'un composant de résine spécifique, d'un peroxyde organique, d'une charge inorganique contenant un agent de couplage silane avec lequel elle a été prémélangée, d'un agent ignifugeant contenant du brome et d'un catalyseur de condensation de type silanol, ladite étape (a) comprenant une étape (a1) de mélange à l'état fondu de tout ou partie du composant de résine, du peroxyde organique et de la charge inorganique contenant l'agent de couplage silane avec lequel elle a été prémélangée pour préparer un MB silane, une étape (a2) facultative de mélange à l'état fondu du reste du composant de résine avec le catalyseur de condensation de type silanol pour préparer un MB catalyseur et une étape (a3) de mélange à l'état fondu du MB silane avec le catalyseur de condensation de type silanol ou le MB catalyseur, l'agent ignifugeant contenant du brome étant mélangé dans l'étape (a1) et/ou l'étape (a2) ; un article moulé en résine silane réticulée résistant à la chaleur fabriqué par ledit procédé ; et un produit résistant à la chaleur équipé de l'article moulé en résine silane réticulée résistant à la chaleur selon l'invention.
PCT/JP2014/067768 2013-07-03 2014-07-03 Article moulé en résine silane réticulée résistant à la chaleur et son procédé de fabrication, et produit résistant à la chaleur équipé de l'article moulé en résine silane réticulée résistant à la chaleur WO2015002263A1 (fr)

Priority Applications (2)

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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
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
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
JP2016188306A (ja) * 2015-03-30 2016-11-04 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
JP2017186416A (ja) * 2016-04-04 2017-10-12 日立金属株式会社 難燃性バッチ、それを用いて形成される電線・ケーブルおよびその製造方法
JP2018044032A (ja) * 2016-09-12 2018-03-22 日立金属株式会社 触媒バッチ、それを用いて形成される電線・ケーブルおよびその製造方法
WO2018070491A1 (fr) * 2016-10-12 2018-04-19 リケンテクノス株式会社 Composition élastomère, composition élastomère réticulable à l'eau, et procédé de production de composition élastomère
JP2019026692A (ja) * 2017-07-27 2019-02-21 矢崎総業株式会社 樹脂組成物、並びにこれを用いた被覆電線及びワイヤーハーネス
JP2021028366A (ja) * 2019-08-09 2021-02-25 古河電気工業株式会社 電線・ケーブルの製造方法及び電線・ケーブル
CN116715920A (zh) * 2023-08-10 2023-09-08 广东永鑫华新型材料有限公司 一种电器用高强度耐高温阻燃聚丙烯材料及其制备方法

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EP3248510A4 (fr) * 2015-01-23 2018-08-22 Pacific Wave Co., Ltd. Coussin en forme de treillis tridimensionnel ignifuge
WO2016117704A1 (fr) * 2015-01-23 2016-07-28 株式会社パシフィックウエーブ Coussin en forme de treillis tridimensionnel ignifuge
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
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
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
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
JP2016188306A (ja) * 2015-03-30 2016-11-04 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
JP2017186416A (ja) * 2016-04-04 2017-10-12 日立金属株式会社 難燃性バッチ、それを用いて形成される電線・ケーブルおよびその製造方法
JP2018044032A (ja) * 2016-09-12 2018-03-22 日立金属株式会社 触媒バッチ、それを用いて形成される電線・ケーブルおよびその製造方法
WO2018070491A1 (fr) * 2016-10-12 2018-04-19 リケンテクノス株式会社 Composition élastomère, composition élastomère réticulable à l'eau, et procédé de production de composition élastomère
JPWO2018070491A1 (ja) * 2016-10-12 2019-07-25 リケンテクノス株式会社 エラストマー組成物、水架橋性エラストマー組成物、及びその製造方法
JP2019026692A (ja) * 2017-07-27 2019-02-21 矢崎総業株式会社 樹脂組成物、並びにこれを用いた被覆電線及びワイヤーハーネス
JP2021028366A (ja) * 2019-08-09 2021-02-25 古河電気工業株式会社 電線・ケーブルの製造方法及び電線・ケーブル
JP7157717B2 (ja) 2019-08-09 2022-10-20 古河電気工業株式会社 電線・ケーブルの製造方法
CN116715920A (zh) * 2023-08-10 2023-09-08 广东永鑫华新型材料有限公司 一种电器用高强度耐高温阻燃聚丙烯材料及其制备方法
CN116715920B (zh) * 2023-08-10 2023-10-20 广东永鑫华新型材料有限公司 一种电器用高强度耐高温阻燃聚丙烯材料及其制备方法

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