WO2015030055A1 - Objet moulé thermorésistant en résine réticulée par silane et son procédé de production, composition thermorésistante de résine réticulant par silane et son procédé de production, lot-maître de silane et produit thermorésistant produit à l'aide de l'objet moulé thermorésistant en résine réticulée par silane - Google Patents

Objet moulé thermorésistant en résine réticulée par silane et son procédé de production, composition thermorésistante de résine réticulant par silane et son procédé de production, lot-maître de silane et produit thermorésistant produit à l'aide de l'objet moulé thermorésistant en résine réticulée par silane Download PDF

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WO2015030055A1
WO2015030055A1 PCT/JP2014/072443 JP2014072443W WO2015030055A1 WO 2015030055 A1 WO2015030055 A1 WO 2015030055A1 JP 2014072443 W JP2014072443 W JP 2014072443W WO 2015030055 A1 WO2015030055 A1 WO 2015030055A1
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heat
silane
mass
resistant
parts
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PCT/JP2014/072443
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English (en)
Japanese (ja)
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西口　雅己
有史 松村
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古河電気工業株式会社
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Priority to JP2015534260A priority Critical patent/JP6523171B2/ja
Priority to CN201480045774.4A priority patent/CN105473654A/zh
Publication of WO2015030055A1 publication Critical patent/WO2015030055A1/fr

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    • 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
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene

Definitions

  • the present invention relates to a heat-resistant silane cross-linked resin molded article and a production method thereof, a heat-resistant silane cross-linkable resin composition and a production method thereof, a silane master batch, and a heat-resistant product using the heat-resistant silane cross-linked resin molded article.
  • a heat-resistant silane-crosslinked resin molded article having excellent appearance, which is less likely to cause rough appearance and unevenness even when the extruder is temporarily stopped and restarted during molding, and preferably excellent in flame retardancy and mechanical properties, and its production
  • Insulated wires, cables, cords and optical fiber cores, and optical fiber cords used for electrical and electronic equipment internal and external wiring are flame retardant, heat resistant, and mechanical properties (eg tensile properties, wear resistance) Various characteristics are required.
  • a resin composition containing a large amount of a metal hydrate such as magnesium hydroxide or aluminum hydroxide is used.
  • wiring materials used in electrical and electronic equipment may be heated to 80 to 105 ° C. or even 125 ° C. when used for a long time, and heat resistance to this may be required.
  • a method of crosslinking the coating material by an electron beam crosslinking method or a chemical crosslinking method is employed.
  • cross-linking polyolefin resins such as polyethylene
  • electron beam cross-linking by irradiating with an electron beam also referred to as cross-linking
  • organic peroxide and the like are decomposed by applying heat after molding, and cross-linking reaction
  • cross-linking reaction Known are the chemical crosslinking method and the silane crosslinking method.
  • the silane crosslinking method in particular, often does not require special equipment, and thus can be used in a wide range of fields.
  • 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 the silane grafting in the presence of a silanol condensation catalyst. This is a method for obtaining a crosslinked molded article by bringing a polymer into contact with moisture.
  • a method for producing a halogen-free heat-resistant silane crosslinked resin includes, for example, a silane master batch obtained by grafting a hydrolyzable silane coupling agent having an unsaturated group to a polyolefin resin, a polyolefin resin, and an inorganic filler.
  • a heat-resistant masterbatch obtained by kneading and a catalyst masterbatch containing a silanol condensation catalyst are melt-mixed.
  • the silane masterbatch and the heat-resistant masterbatch are uniformly mixed in a single screw extruder or a twin screw extruder after dry mixing. It becomes difficult to melt and knead. For this reason, there is a problem that the appearance is deteriorated and the physical properties are greatly reduced. Further, there arises a problem that the extrusion load is high and molding cannot be performed. Therefore, in order to uniformly melt and knead the silane masterbatch and the heat-resistant masterbatch after dry mixing, the proportion of the inorganic filler is limited as described above. Therefore, it is difficult to achieve higher flame resistance and higher heat resistance.
  • 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.
  • a method of adding an organic peroxide and causing a graft reaction with a single screw extruder is conceivable.
  • appearance defects may occur in the molded product obtained due to variation in reaction.
  • the compounding quantity of the inorganic filler in a masterbatch must be increased very much, and an extrusion load may become remarkably large. As a result, it becomes very difficult to manufacture the molded body. Therefore, a desired material or a molded body could not be obtained.
  • the manufacturing process is two steps, which is also difficult in terms of manufacturing cost.
  • Patent Document 1 an inorganic filler, a silane coupling agent, an organic peroxide, and a cross-linking catalyst that are surface-treated with a silane coupling agent on a resin component obtained by mixing a polyolefin resin and a maleic anhydride resin in a kneader.
  • a method of forming with a single screw extruder after sufficiently melt-kneading has been proposed.
  • 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 method of partial crosslinking using an organic peroxide through a filler has been proposed.
  • Patent Document 5 an organic peroxide, a silane coupling agent, and a metal hydrate are collectively melt-kneaded with a base material, further melt-molded with a silanol condensation catalyst, and then crosslinked in the presence of water.
  • a method for easily obtaining a cable having heat resistance has been proposed.
  • the resin partially cross-links during melt kneading with a Banbury mixer or kneader, resulting in poor appearance of the resulting molded product (a large number of protrusions protruding on the surface). Formation). Further, most of the silane coupling agent other than the silane coupling agent that is treating the surface of the inorganic filler may be volatilized or condensed. 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. Further, even in the methods described in Patent Documents 2 to 4, since the resin has not yet a sufficient network structure, the bond between the resin and the inorganic filler is broken at a high temperature.
  • the molded body melts at a high temperature, and for example, the insulating material sometimes melts during soldering of the electric wire. Further, the molded body may be deformed or foamed during secondary processing. Furthermore, when heated to about 200 ° C. for a short time, the appearance may be significantly deteriorated or deformed.
  • Patent Document 5 can solve the above-described problems of the methods described in Patent Documents 1 to 4 to some extent.
  • this method when the silane cross-linkable flame retardant polyolefin obtained by batch melting and kneading is extruded together with a silanol condensation catalyst, appearance defects due to rough appearance and irregularities (also referred to as irregular appearance) are likely to occur.
  • irregular appearance also referred to as irregular appearance
  • the molded product formed thereafter is likely to have rough appearance and irregularities, resulting in poor appearance. It has been confirmed that this occurs.
  • the present invention solves the above problems, and even if the extruder is stopped and the operation is started again, the appearance is hardly generated and the appearance is hardly generated, and preferably the flame retardancy and mechanical properties are also excellent.
  • PROBLEM TO BE SOLVED To provide a method for producing a heat-resistant silane cross-linked resin molded article, and to provide a heat-resistant silane cross-linked resin molded article that is less likely to cause rough appearance and irregularities and excellent in appearance, and preferably excellent in flame retardancy and mechanical properties. And Moreover, this invention makes it a subject to provide the silane masterbatch which can form this heat resistant silane crosslinked resin molded object, a heat resistant silane crosslinked resin composition, and its manufacturing method. Furthermore, this invention makes it a subject to provide the heat resistant product using the heat resistant silane crosslinked resin molded object obtained with the manufacturing method of the heat resistant silane crosslinked resin molded object.
  • the subject of this invention was achieved by the following means.
  • the organic peroxide is 0.01 to 0.6 parts by mass
  • the inorganic filler is 10 to 400 parts by mass
  • the silane coupling agent exceeds 4 parts by mass.
  • a method for producing a heat-resistant silane cross-linked resin molded article (5) The method for producing a heat-resistant silane-crosslinked resin molded article according to any one of (1) to (4), wherein the melt-mixing in the step (a) is performed with a closed mixer. (6) The method for producing a heat-resistant silane-crosslinked resin molded article according to any one of (1) to (5), wherein a silanol condensation catalyst is not substantially mixed in the step (a).
  • the organic peroxide is 0.01 parts by mass or more and 0.6 parts by mass or less
  • the inorganic filler is 10 parts by mass or more and 400 parts by mass or less, and exceeds 4 parts by mass of the silane coupling agent.
  • a method for producing a heat-resistant silane crosslinkable resin composition comprising the step (b) of mixing the silane master batch and a silanol condensation catalyst to obtain a mixture.
  • (11) A heat resistant product comprising the heat resistant silane crosslinked resin molded article according to (9) or (10).
  • the organic peroxide is 0.01 to 0.6 parts by mass
  • the inorganic filler is 10 to 400 parts by mass
  • the silane coupling agent exceeds 4 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • a silane master batch obtained by melt-kneading 15.0 parts by mass or less at a temperature not lower than the decomposition temperature of the organic peroxide.
  • the method for producing a heat-resistant silane-crosslinked resin molded article of the present invention comprises a silane coupling agent of more than 4 parts by mass and less than 15 parts by mass with respect to 100 parts by mass of a polyolefin resin in the presence of an inorganic filler and an organic peroxide.
  • both the cross-linking reaction between polyolefin resins and the condensation reaction between silane coupling agents can be suppressed, and the silane cross-linked resin having a clean appearance can be obtained.
  • a molded body can be produced.
  • an inorganic filler and a silane coupling agent are mixed at a predetermined ratio before and / or during kneading with a polyolefin resin.
  • mixing can be suppressed, and a heat resistant silane crosslinked resin molding can be manufactured efficiently.
  • excellent flame retardancy and mechanical properties can be imparted to the heat-resistant silane-crosslinked resin molded article.
  • the highly heat-resistant silane crosslinked resin molding which added the inorganic filler in large quantities can be manufactured, without using special machines, such as an electron beam crosslinking machine.
  • heat-resistant silane cross-linked resin molding that is less likely to cause rough appearance and irregularities and is excellent in appearance, and preferably excellent in flame retardancy and mechanical properties.
  • the manufacturing method of a body, and the heat-resistant silane crosslinked resin molding obtained by this manufacturing method can be provided.
  • the silane masterbatch which can form this heat-resistant silane crosslinked resin molded object, a heat-resistant silane crosslinkable resin composition, and its manufacturing method can be provided.
  • a heat-resistant product using the heat-resistant silane cross-linked resin molded product obtained by the method for producing a heat-resistant silane cross-linked resin molded product can be provided.
  • the “method for producing a heat-resistant silane-crosslinked resin molded article” of the present invention includes the following steps (a) to (d).
  • the “method for producing a heat-resistant silane crosslinkable resin composition” of the present invention has the following steps (a) and (b), and does not make the steps (c) and (d) essential steps.
  • the “method for producing a heat-resistant silane-crosslinked resin molded product” of the present invention and the “method for producing a heat-resistant silane-crosslinked resin composition” of the present invention include the following steps (c) and (d). Other than that is basically the same.
  • the polyolefin resin is not particularly limited as long as it is a resin made of a polymer obtained by polymerizing or copolymerizing a compound having an ethylenically unsaturated bond, and is conventionally known as a heat-resistant resin composition. Can be used.
  • Examples thereof include resins and resins made of polymers such as rubbers, elastomers, styrene elastomers, ethylene-propylene rubbers (for example, ethylene-propylene-diene rubbers).
  • polyethylene, polypropylene, and ethylene- ⁇ -olefin co-polymers are highly receptive to various inorganic fillers such as metal hydrates and can maintain mechanical strength even when a large amount of inorganic fillers are blended.
  • a resin such as a polymer, a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, a styrene elastomer, and an ethylene-propylene rubber is preferred.
  • These polyolefin resins may be used individually by 1 type, or may use 2 or more types together.
  • the polyethylene is not particularly limited as long as it is a polymer mainly composed of an ethylene component.
  • Polyethylene is a homopolymer consisting only of ethylene, a copolymer of ethylene and 5 mol% or less ⁇ -olefin (excluding propylene), and 1 mol% or less having only ethylene, carbon, oxygen and hydrogen atoms in the functional group.
  • copolymers with non-olefins for example, JIS K 6748.
  • known ones conventionally used as a copolymerization component of polyethylene can be used without any particular limitation.
  • polyethylene examples include high density polyethylene (HDPE), low density polyethylene (LDPE), ultra high molecular weight polyethylene (UHMW-PE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE). Is mentioned. Of these, linear low density polyethylene (LLDPE) and low density polyethylene (LDPE) are preferable. Polyethylene may be used individually by 1 type, and may use 2 or more types together.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • UHMW-PE ultra high molecular weight polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • Polyethylene may be used individually by 1 type, and may use 2 or more types together.
  • Polypropylene is not particularly limited as long as it is a polymer mainly composed of a propylene component.
  • Polypropylene includes propylene homopolymers, ethylene-propylene copolymers such as random polypropylene, and block polypropylene as copolymers.
  • random polypropylene refers to a copolymer of propylene and ethylene having an ethylene component content of 1 to 5 mass%.
  • Block polypropylene is a composition containing a homopolypropylene and an ethylene-propylene copolymer, having an ethylene component content of about 5 to 15% by mass, and an ethylene component and a propylene component existing as independent components. Say what you do. Polypropylene may be used alone or in combination of two or more.
  • the ethylene- ⁇ -olefin copolymer is preferably a copolymer of ethylene and an ⁇ -olefin having 3 to 12 carbon atoms (except for those contained in the above-mentioned polyethylene and polypropylene).
  • Specific examples of the ⁇ -olefin component in the ethylene- ⁇ -olefin copolymer include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. These components are mentioned.
  • the ethylene- ⁇ -olefin copolymer is preferably a copolymer of ethylene and an ⁇ -olefin having 3 to 12 carbon atoms (excluding those contained in polyethylene and polypropylene). Specifically, an ethylene-propylene copolymer (excluding those contained in polypropylene), an ethylene-butylene copolymer, an ethylene- ⁇ -olefin copolymer synthesized in the presence of a single site catalyst, etc. Can be mentioned.
  • One ethylene- ⁇ -olefin copolymer may be used alone, or two or more ethylene- ⁇ -olefin copolymers may be used in combination.
  • Examples of the acid copolymerization component or acid ester copolymerization component in the polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component include carboxylic acid compounds such as (meth) acrylic acid, and vinyl acetate and (meth) acrylic.
  • Examples include acid ester compounds such as acid alkyls.
  • 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.
  • polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component examples include, for example, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene -Alkyl (meth) acrylate copolymer and the like.
  • ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer are preferable.
  • acceptability and heat resistance of inorganic fillers are preferred.
  • an ethylene-vinyl acetate copolymer and an ethylene-ethyl acrylate copolymer are preferable.
  • the polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component is used singly or in combination of two or more.
  • Styrenic elastomers are those having an aromatic vinyl compound as a constituent component in the molecule. Therefore, in this invention, even if it contains an ethylene component in a molecule
  • 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 and vinyl toluene. Among these, styrene is preferable as the aromatic vinyl compound. This aromatic vinyl compound is used individually by 1 type, or 2 or more types are used together.
  • conjugated diene compound examples 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.
  • a styrene-based elastomer an elastomer containing an aromatic vinyl compound other than styrene, which does not contain a styrene component, may be used by a similar production method.
  • styrene elastomer examples include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), hydrogenated SBS, styrene-ethylene-ethylene-propylene-styrene block. Copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), hydrogenated SIS, hydrogenated styrene / butadiene rubber (HSBR), hydrogenated acrylonitrile / butadiene rubber (HNBR), etc. it can.
  • SEEPS styrene-ethylene-butylene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEPS styrene-ethylene-ethylene-propylene-styrene
  • styrene elastomer As the styrene elastomer, it is preferable to use SEPS, SEEPS or SEBS having a styrene constituent content of 10 to 40% alone or in combination of two or more thereof.
  • SEPS polystyrene elastomer
  • SEEPS polystyrene elastomer
  • SEBS polystyrene elastomer
  • commercially available products can be used. For example, Septon 4077, Septon 4055, Septon 8105 (all trade names, manufactured by Kuraray Co., Ltd.), Dynalon 1320P, Dynalon 4600P, 6200P, 8601P, 9901P (all Product name, manufactured by JSR).
  • the polyolefin resin that is, the polymer may be acid-modified.
  • Unsaturated carboxylic acid or its derivative (s) is mentioned.
  • the unsaturated carboxylic acid include maleic acid, itaconic acid, fumaric acid and the like.
  • unsaturated carboxylic acid derivatives include maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester, fumaric anhydride, etc. It is done. Among these, maleic acid or maleic anhydride is preferable.
  • the amount of acid modification is usually about 0.1 to 7% by mass in one molecule of the acid-modified polyolefin resin.
  • the polyolefin resin may contain various oils used as a plasticizer or a softener as desired.
  • oils include oils as plasticizers used in polyolefin resins or mineral oil softeners for rubber.
  • the mineral oil softener is a mixed oil including three oils: an oil composed of a hydrocarbon having an aromatic ring, an oil composed of a hydrocarbon having a naphthene ring, and an oil composed of a hydrocarbon having a paraffin chain.
  • Paraffin oil is the one that occupies 50% or more of the total carbon number of hydrocarbons having paraffin chains, and naphthenic oil or aromatic ones that have 30 to 40% carbon atoms that constitute hydrocarbons having a naphthene ring.
  • aroma oils Those having 30% or more carbon atoms constituting hydrocarbons having a ring are called aroma oils and are distinguished.
  • liquid or low molecular weight synthetic softeners, paraffin oil, and naphthene oil are preferably used, and paraffin oil is particularly preferably used.
  • paraffin oil is particularly preferably used.
  • oils include Diana Process Oil PW90 and PW380 (both are trade names, manufactured by Idemitsu Kosan Co., Ltd.), Cosmo Neutral 500 (Cosmo Oil Co., Ltd.), and the like.
  • the oil is preferably 80% by mass or less with respect to the total mass of the polymer and the oil contained in the polyolefin resin in terms of heat resistance performance, crosslinking performance, and strength. It is more preferably at most 40% by mass, and even more preferably at most 40% by mass.
  • the oil content is at least 0% by mass, but can be 20% by mass or more, for example. That is, the polyolefin resin is preferably 20% by mass or more, more preferably 45% by mass or more, and further preferably 60% by mass or more with respect to the total mass.
  • the content of the polyolefin resin is at most 100% by mass, but may be, for example, 80% by mass or less.
  • Organic peroxide functions to generate radicals by thermal decomposition and promote the grafting reaction of the silane coupling agent to the polyolefin resin.
  • the silane coupling agent contains an ethylenically unsaturated group, it works to promote the grafting reaction by radical reaction between the ethylenically unsaturated group and the polyolefin resin (including hydrogen radical abstraction reaction from the polyolefin resin).
  • the organic peroxide is not particularly limited as long as it generates radicals.
  • R 1 —OO—R 2 , R 1 —OO—C ( ⁇ O) R 3 , R 4 C ( ⁇ O) —OO (C ⁇ O) R 5 is preferably used. It is done.
  • 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, , 5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxy Benzoate, tert-butyl peroxyisopropyl carbonate, dia Chill peroxide, lauroyl peroxide, may be mentioned
  • DCP dicumyl peroxide
  • 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane 2,5-in terms of odor, colorability, and scorch stability.
  • Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3 is preferred.
  • the decomposition temperature of the organic peroxide is preferably from 80 to 195 ° C., particularly preferably from 125 to 180 ° C.
  • the decomposition temperature of an organic peroxide means a temperature at which a decomposition reaction occurs in two or more compounds at a certain temperature or temperature range when an organic peroxide having a single composition is heated. means. Specifically, it 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 inorganic filler can be used without particular limitation as long as it has a site capable of forming a hydrogen bond or the like with a reactive site such as a silanol group of the silane coupling agent on the surface or a site capable of chemical bonding by a covalent bond.
  • a reactive site such as a silanol group of the silane coupling agent on the surface or a site capable of chemical bonding by a covalent bond.
  • Examples of the site that can be chemically bonded to the reaction site of the silane coupling agent in this inorganic filler include OH groups (hydroxy groups, water molecules containing water or water of crystal water, OH groups such as carboxy groups), amino groups, and SH groups. It is done.
  • inorganic fillers examples include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate, whisker, and water.
  • Metal hydrates such as compounds having hydroxyl or water of crystallization such as aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, boron nitride, silica (crystalline silica, amorphous Silica, etc.), carbon, clay, zinc oxide, tin oxide, titanium oxide, molybdenum oxide, antimony trioxide, silicone compound, quartz, talc, zinc borate, white carbon, zinc borate, hydroxy hydroxystannate, zinc stannate can do.
  • the inorganic filler is preferably at least one of silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, zinc borate, and zinc hydroxystannate.
  • Silica, aluminum hydroxide, magnesium hydroxide, carbonate More preferred is at least one selected from the group consisting of calcium and antimony trioxide.
  • an inorganic filler may be mix
  • the average particle diameter of the inorganic filler is preferably 0.2 to 10 ⁇ m, more preferably 0.3 to 8 ⁇ m, further preferably 0.4 to 5 ⁇ m, and particularly preferably 0.4 to 3 ⁇ m.
  • the average particle size of the inorganic filler is less than 0.2 ⁇ m, the inorganic filler causes secondary aggregation during mixing with the silane coupling agent, and the appearance of the molded body may be deteriorated or blistered.
  • it exceeds 10 ⁇ m the appearance may be deteriorated, the retention effect of the silane coupling agent may be decreased, and a problem may be caused in crosslinking.
  • 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.
  • an inorganic filler surface-treated with a silane coupling agent can be used.
  • the silane coupling agent surface-treated magnesium hydroxide include magnesium hydroxide commercial products (Kisuma 5L, Kisuma 5P (both trade names, manufactured by Kyowa Chemical Co., Ltd.)) and aluminum hydroxide.
  • silane coupling agent Any silane coupling agent may be used as long as it has a group that can be graft-reacted to a polyolefin resin in the presence of a radical and a group that can be chemically bonded to an inorganic filler.
  • a coupling agent is preferred. More preferably, the silane coupling agent has an amino group, a glycidyl group or an ethylenically unsaturated group-containing group and a hydrolyzable group-containing group at the terminal, and more preferably ethylene at the terminal. It is a silane coupling agent having a group containing a polymerizable unsaturated group and a group containing a hydrolyzable group.
  • the group containing an ethylenically unsaturated group is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth) acryloyloxy group, a (meth) acryloyloxyalkylene group, and a p-styryl group. Moreover, you may use together these silane coupling agents and the silane coupling agent which has another terminal group.
  • silane coupling agent for example, a compound represented by the following general formula (1) can be used.
  • R a11 is a group containing an ethylenically unsaturated group
  • R b11 is an aliphatic hydrocarbon group, a hydrogen atom, or Y 13 .
  • Y 11 , Y 12 and Y 13 are hydrolyzable organic groups. Y 11 , Y 12 and Y 13 may be the same as or different from each other.
  • R a11 of the silane coupling agent represented by the general formula (1) is preferably a group containing an ethylenically unsaturated group, and the group containing an ethylenically unsaturated group is as described above, preferably vinyl. It is a group.
  • R b11 is an aliphatic hydrocarbon group, a hydrogen atom, or Y 13 described later, and the aliphatic hydrocarbon group is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms excluding the aliphatic unsaturated hydrocarbon group. and the like, preferably below Y 13.
  • Y 11 , Y 12 and Y 13 are hydrolyzable organic groups such as an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an acyloxy group having 1 to 4 carbon atoms. And an alkoxy group is preferred.
  • Specific examples of the hydrolyzable organic group include methoxy, ethoxy, butoxy, acyloxy and the like. Among these, methoxy or ethoxy is more preferable, and methoxy is particularly preferable from the viewpoint of the reactivity of the silane coupling agent.
  • the silane coupling agent is preferably a silane coupling agent having a high hydrolysis rate, more preferably a silane coupling agent in which R b11 is Y 13 and Y 11 , Y 12 and Y 13 are the same. . More preferred is a hydrolysable silane coupling agent in which at least one of Y 11 , Y 12 and Y 13 is a methoxy group, and particularly preferred is a hydrolyzable silane coupling agent in which all are methoxy groups.
  • silane coupling agent having a vinyl group, (meth) acryloyloxy group or (meth) acryloyloxyalkylene group at the terminal include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, and vinyldimethoxy.
  • Organosilanes such as ethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltriethoxysilane, vinyltriacetoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyl Examples include methyldimethoxysilane. These silane coupling agents may be used alone or in combination of two or more.
  • a silane coupling agent having a vinyl group and an alkoxy group at the terminal is more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.
  • Those having a glycidyl group at the terminal are 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
  • the silane coupling agent may be used as it is or diluted with a solvent or the like.
  • the silanol condensation catalyst has a function of subjecting a silane coupling agent grafted to a polyolefin resin to a condensation reaction in the presence of moisture. Based on the action of this silanol condensation catalyst, polyolefin resins are cross-linked through a silane coupling agent. As a result, a heat-resistant silane cross-linked resin molded article having excellent heat resistance is obtained.
  • silanol condensation catalyst an organic tin compound, a metal soap, a platinum compound, or the like is used.
  • Common silanol condensation catalysts include, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, zinc stearate, lead stearate, barium stearate, calcium stearate, sodium stearate, 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 silanol condensation catalyst is used by mixing with a resin if desired.
  • a resin also referred to as carrier resin
  • Such a resin is not particularly limited, and examples thereof include resins similar to polyolefin resins.
  • a part of the above-mentioned polyolefin resin can also be used as the carrier resin.
  • a resin made of polyethylene is preferred in that it has good affinity with the silanol condensation catalyst and is excellent in heat resistance.
  • the heat-resistant silane cross-linked resin molded body and the heat-resistant silane cross-linkable resin composition are various additives commonly used in electric wires, electric cables, electric cords, sheets, foams, tubes, and pipes. It may be blended appropriately as long as the purpose is not impaired.
  • additives include crosslinking aids, antioxidants, lubricants, metal deactivators, fillers, and other resins. These additives, particularly antioxidants and metal deactivators, may be mixed in any component, but are preferably added to the carrier resin. It is preferable that the crosslinking aid is not substantially contained. In particular, it is preferable that the crosslinking aid is not substantially mixed in the step (a) for preparing the silane master batch.
  • crosslinking aid When the crosslinking aid is not substantially mixed, crosslinking between polyolefin resins hardly occurs during kneading, and the appearance and heat resistance of the heat-resistant silane crosslinked resin molded article are excellent.
  • 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 assistant refers to a compound that forms a partially crosslinked structure with a polyolefin resin in the presence of an organic peroxide.
  • polyfunctional compounds such as methacrylate compounds such as polypropylene glycol diacrylate and trimethylolpropane triacrylate, allyl compounds such as triallyl cyanurate, maleimide compounds, and divinyl compounds can be used.
  • Antioxidants such as 4,4′-dioctyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, etc.
  • Agents pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like, bis (2-methyl-4- (3 -N-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptobenzimidazole and its zinc salt, pentaerythrine Lithol - tetrakis (3-lau
  • Lubricants 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).
  • 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.
  • Fillers include fillers other than the various fillers described above.
  • the step (a) comprises 0.01 parts by mass or more and 0.6 parts by mass or less of the organic peroxide and 10 parts by mass or more and 400 parts by mass or less of the inorganic filler with respect to 100 parts by mass of the polyolefin resin.
  • the silane coupling agent is melt-kneaded in excess of 4 parts by mass and 15.0 parts by mass at a temperature equal to or higher than the decomposition temperature of the organic peroxide. Thereby, a silane masterbatch is prepared.
  • the mixing amount of the organic peroxide is 0.01 to 0.6 parts by mass, preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the amount of the organic peroxide is less than 0.01 parts by mass, the crosslinking reaction does not proceed at the time of crosslinking, and the silane coupling agents are condensed with each other to sufficiently obtain heat resistance, mechanical strength, and reinforcement. May not be possible.
  • it exceeds 0.6 parts by mass many of the polyolefin resins are directly cross-linked by a side reaction, and there is a risk of causing scum. That is, by setting the mixing amount of the organic peroxide within this range, the polymerization can be carried out in an appropriate range, and the extrudability is excellent without causing agglomerates due to the crosslinked gel or the like. A composition can be obtained.
  • the mixing amount of the inorganic filler is 10 to 400 parts by mass, preferably 30 to 280 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the mixing amount of the inorganic filler is less than 10 parts by mass, the graft reaction of the silane coupling agent becomes nonuniform, and the desired heat resistance cannot be obtained, or the appearance may deteriorate due to the nonuniform reaction.
  • it exceeds 400 parts by mass the load during molding or kneading becomes very large, and secondary molding may be difficult.
  • the mixing amount of the silane coupling agent is more than 4.0 parts by mass and not more than 15.0 parts by mass, preferably 6 to 15.0 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • amount of the silane coupling agent mixed is 4.0 parts by mass or less, when molding with the silanol condensation catalyst, if the extruder is stopped or the rotational speed of the extruder is greatly changed by adjustment, etc. There is a possibility that it will occur many times, resulting in poor appearance.
  • the silane coupling agent when the amount exceeds 15.0 parts by mass, the silane coupling agent cannot be completely adsorbed on the surface of the inorganic filler, and the silane coupling agent volatilizes during kneading, which is not economical. Moreover, the silane coupling agent which does not adsorb
  • the usage-amount of a silane coupling agent exceeds 4.0 mass parts and is 15.0 mass parts or less, it is excellent in an external appearance.
  • the reaction due to the decomposition of the organic peroxide when the silane coupling agent is silane-grafted onto the polyolefin resin is a graft reaction between the silane coupling agent and the polyolefin resin having a high reaction rate, or a silane coupling agent.
  • the condensation reaction between them becomes dominant. Therefore, the cross-linking reaction between the polyolefin resins that causes rough appearance and rough appearance hardly occurs.
  • the cross-linking reaction between polyolefin resins can be effectively suppressed by the mixing amount of the silane coupling agent.
  • molding becomes favorable.
  • the said defect by the crosslinking reaction of polyolefin resin decreases, even if an extruder is stopped, it becomes difficult to generate
  • a cross-linking reaction between polyolefin resins can be suppressed, and a silane cross-linked resin molded article having a good appearance can be produced.
  • in the step (a) many silane coupling agents are bonded and fixed to the inorganic filler.
  • the condensation reaction between the silane coupling agents bonded to the inorganic filler hardly occurs.
  • the condensation reaction between the free silane coupling agents does not occur without binding to the inorganic filler, and the occurrence of gel spots due to the condensation reaction between the free silane coupling agents can be suppressed.
  • both the crosslinking reaction between the polyolefin resins and the condensation reaction between the silane coupling agents can be suppressed, and the silane crosslinked resin molded article having a clean appearance. It is thought that can be manufactured.
  • the kneading temperature for melting and mixing the above-mentioned components is not less than the decomposition temperature of the organic peroxide, preferably the decomposition temperature of the organic peroxide + (25 to 110) ° C.
  • This decomposition temperature is preferably set after the polyolefin resin is melted.
  • kneading conditions such as kneading time can be set as appropriate.
  • a kneading method any method usually used for rubber, plastic, etc. can be used satisfactorily, and the kneading apparatus is appropriately selected according to, for example, the amount of inorganic filler mixed.
  • a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, or various kneaders are used, and a closed mixer such as a Banbury mixer or various kneaders is used to disperse the polyolefin resin and stabilize the crosslinking reaction. In terms of surface.
  • such an inorganic filler when such an inorganic filler is mixed in an amount exceeding 100 parts by mass with respect to 100 parts by mass of the polyolefin resin, it is preferably kneaded with a continuous kneader, a pressure kneader, or a Banbury mixer.
  • the order of mixing is not specified, and the components may be mixed in any order as long as the mixing ratio is within the above range. That is, in the step (a), the mixing order is not particularly limited.
  • the above components can be melted and mixed at a time.
  • the silane coupling agent is not introduced into the silane master batch alone, but is introduced by premixing with an inorganic filler.
  • the silane coupling agent is not introduced into the silane master batch alone, but is introduced by premixing with an inorganic filler.
  • a desired shape can be obtained during extrusion molding.
  • a mixing method preferably, a mixer type kneader such as a Banbury mixer or a kneader is used, and the organic peroxide, the inorganic filler, and the silane coupling agent are mixed or dispersed at a temperature lower than the decomposition temperature of the organic peroxide.
  • a method of melt-mixing the mixture and the polyolefin resin after the mixing is performed. If it does in this way, the excessive crosslinking reaction of polyolefin resin can be prevented, and it is excellent in an external appearance.
  • the inorganic filler, the silane coupling agent and the organic peroxide are mixed at a temperature lower than the decomposition temperature of the organic peroxide, preferably at room temperature (25 ° C.).
  • the method for mixing the inorganic filler, the silane coupling agent, and the organic peroxide is not particularly limited, and the organic peroxide may be mixed with the inorganic filler or the like, or the inorganic filler and the silane coupling agent may be mixed. They may be mixed in any of the mixing stages. Examples of the mixing method of the inorganic filler, the silane coupling agent, and the organic peroxide include mixing methods such as wet processing and dry processing.
  • a wet process in which the silane coupling agent is added in a state where the inorganic filler is dispersed in a solvent such as water a dry process in which both are added by heating or non-heating, and mixed. And both.
  • dry processing is preferred in which a silane coupling agent is added to an inorganic filler, preferably a dried inorganic filler, with heating or non-heating and mixed.
  • the silane coupling agent tends to be strongly bonded to the inorganic filler, so that the subsequent silanol condensation reaction may be difficult to proceed.
  • dry mixing since the bond between the inorganic filler and the silane coupling agent is relatively weak, the silanol condensation reaction easily proceeds efficiently.
  • the silane coupling agent added to the inorganic filler exists so as to surround the surface of the inorganic filler, and part or all of the silane coupling agent is adsorbed by the inorganic filler or chemically bonded to the surface of the inorganic filler.
  • the volatilization of the silane coupling agent during kneading with a subsequent kneader or Banbury mixer is greatly reduced, and the unsaturated group of the silane coupling agent is reduced by the organic peroxide. It is thought that it crosslinks with polyolefin resin.
  • the silane coupling agent undergoes a condensation reaction with a silanol condensation catalyst during molding.
  • the organic peroxide may be mixed with the silane coupling agent and then dispersed in the inorganic filler, or separately from the silane coupling agent and dispersed separately in the inorganic filler.
  • the organic peroxide and the silane coupling agent should be mixed substantially together.
  • only the silane coupling agent may be mixed with the inorganic filler, and then the organic peroxide may be added. That is, in the step (a), an inorganic filler previously mixed with a silane coupling agent can be used.
  • the organic peroxide As a method of adding the organic peroxide, it may be dispersed in a polyolefin resin, may be added alone, or may be added after being dispersed in oil or the like, and is preferably added after being dispersed in a polyolefin resin.
  • a mixture of an inorganic filler, a silane coupling agent and an organic peroxide, and a polyolefin resin are then melt-kneaded while heating to a temperature higher than the decomposition temperature of the organic peroxide to obtain a silane master batch.
  • step (a) no silanol condensation catalyst is used. That is, in the step (a), the above-described components are kneaded without substantially mixing the silanol condensation catalyst. Thereby, the silane coupling agent is easy to melt and mix without condensing, and a desired shape can be obtained during extrusion molding.
  • substantially not mixed does not exclude the unavoidably existing silanol condensation catalyst, and is present to such an extent that the above-mentioned problem due to silanol condensation of the silane coupling agent does not occur. Means good.
  • step (a) is performed to prepare a silane master batch.
  • the silane masterbatch prepared in the step (a) contains a reaction mixture of an organic peroxide decomposition product, a polyolefin resin, an inorganic filler and a silane coupling agent, and can be molded by the step (b) described later.
  • the silane coupling agent contains two types of silane crosslinkable resins (silane graft polymer) grafted onto the polyolefin resin.
  • the step (b) of obtaining a mixture by mixing the silane master batch and the silanol condensation catalyst is performed.
  • the mixing method may be any mixing method as long as a uniform mixture can be obtained as described above.
  • pellets such as dry blends may be mixed and introduced into a molding machine at room temperature or high temperature, or may be mixed and melted and mixed, pelletized again, and then introduced into the molding machine.
  • the silane master batch and the silanol condensation catalyst are not maintained at a high temperature for a long time in a mixed state.
  • about the obtained mixture let it be the mixture with which the moldability in the shaping
  • the silanol condensation catalyst is preferably used together with a carrier resin. That is, the step (b) may be a step of mixing the silane master batch and the silanol condensation catalyst, and a step of melt mixing the catalyst master batch containing the silanol condensation catalyst and the carrier resin and the silane master batch is preferable. Therefore, preferably, in performing step (b), the carrier resin and the silanol condensation catalyst are melt-mixed to prepare a catalyst master batch.
  • the mixing ratio of the carrier resin and the silanol condensation catalyst in the catalyst master batch is set so as to satisfy the mixing ratio with the polyolefin resin of the silane master batch in the step (b) described later.
  • the mixing of the carrier resin and the silanol condensation catalyst is appropriately determined according to the melting temperature of the carrier resin.
  • 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 above kneading method.
  • the catalyst masterbatch prepared in this way is a mixture of a silanol condensation catalyst, a carrier resin, and a filler that is optionally added.
  • the compounding amount of the silanol condensation catalyst is preferably 0.0001 to 0.5 parts by mass, more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the mixing amount of the silanol condensation catalyst is within the above range, the crosslinking reaction by the condensation reaction of the silane coupling agent is likely to proceed almost uniformly, and the heat-resistant silane crosslinked resin molded article has excellent heat resistance, appearance and physical properties, and is produced. Also improves.
  • the amount of the carrier resin 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 polyolefin resin.
  • an inorganic filler may or may not be added to this carrier resin.
  • the amount of the inorganic filler is not particularly limited, but is preferably 350 parts by mass or less with respect to 100 parts by mass of the polyolefin resin as the carrier resin. This is because if the amount of filler is too large, the silanol condensation catalyst is difficult to disperse and crosslinking is difficult to proceed. On the other hand, if the carrier resin is too much, the degree of cross-linking of the molded article is lowered, and there is a possibility that proper heat resistance cannot be obtained.
  • step (b) the mixing conditions of the silane masterbatch and the silanol condensation catalyst or catalyst masterbatch are appropriately selected. That is, when the silanol condensation catalyst is mixed alone with the silane master batch, the mixing condition is set to an appropriate melt mixing condition depending on the polyolefin resin.
  • melt mixing is preferable in terms of dispersion of the silanol condensation catalyst, which is basically the same as the melt mixing in step (1).
  • polyolefin resins whose melting points cannot be measured by DSC or the like, such as elastomers, but they are kneaded at a temperature at which at least one of the polyolefin resin and the organic peroxide is melted.
  • the melting temperature is appropriately selected according to the melting temperature of the carrier resin, and is preferably 80 to 250 ° C., more preferably 100 to 240 ° C., for example.
  • the kneading conditions such as kneading time can be set as appropriate.
  • the steps (a) and (b) of the present invention that is, the method for producing the heat-resistant silane crosslinkable resin composition of the present invention is carried out, and silanes having at least two different crosslinking methods as described later.
  • a heat-resistant silane crosslinkable resin composition containing a crosslinkable resin is produced. Therefore, the heat-resistant silane crosslinkable resin composition of the present invention is a composition obtained by carrying out step (a) and step (b), and is a mixture of a silane masterbatch and a silanol condensation catalyst or a catalyst masterbatch. It is considered a thing.
  • the components are basically the same as the silane masterbatch and silanol condensation catalyst or catalyst masterbatch.
  • the step (c) and the step (d) are then performed. That is, in the method for producing a heat-resistant silane cross-linked resin molded article of the present invention, the step (c) of molding the obtained mixture, that is, the heat-resistant silane cross-linkable resin composition of the present invention to obtain a molded article is performed.
  • This process (c) should just be able to shape
  • step (c) the operation of the extruder can be temporarily stopped and restarted without problems due to reasons such as cleaning of the extruder, changeover, eccentricity adjustment, and production interruption.
  • the temperature at this time is not particularly limited as long as the polyolefin resin is softened or melted, and is 200 ° C., for example.
  • step (c) can be carried out simultaneously or sequentially with step (b).
  • a series of steps in which a silane masterbatch and a silanol condensation catalyst (C) or a catalyst masterbatch are melt-kneaded in a coating apparatus and then coated on, for example, an extruded electric wire or fiber and formed into a desired shape can be employed.
  • the heat-resistant silane crosslinkable resin composition of the present invention is molded, and the molded body of the heat-resistant silane crosslinkable resin composition obtained in steps (a) to (c) is an uncrosslinked body. Therefore, the heat-resistant silane crosslinked resin molded product of the present invention is a molded product that is crosslinked or finally crosslinked by performing the following step (d) after the step (c).
  • a step of bringing the molded product (uncrosslinked product) obtained in the step (c) into contact with water is performed.
  • the hydrolyzable group of the silane coupling agent is hydrolyzed into silanol, and the silanol condensation catalyst present in the resin condenses the hydroxyl groups of the silanol to cause a crosslinking reaction, resulting in a heat-resistant molded article.
  • the process itself in this step (d) can be performed by a usual method.
  • the hydrolyzable group of the silane coupling agent is hydrolyzed and the silane coupling agents are condensed to form a crosslinked structure.
  • Condensation between silane coupling agents proceeds just by storing at room temperature. Therefore, in the step (d), it is not necessary to positively contact the molded body (uncrosslinked body) with water. It can also be contacted with moisture to further accelerate the crosslinking.
  • a method of positively contacting water such as immersion in warm water, charging into a wet heat tank, exposure to high-temperature steam, and the like. In this case, pressure may be applied to allow moisture to penetrate inside.
  • the method for producing a heat-resistant silane crosslinked resin molded product of the present invention is carried out, and a heat-resistant silane crosslinked resin molded product is produced from the heat-resistant silane crosslinked resin composition of the present invention. Therefore, the heat-resistant silane cross-linked resin molded product of the present invention is a molded product obtained by carrying out steps (a) to (d). And this molded object contains the polyolefin resin formed by bridge
  • reaction mechanism in the production method of the present invention is not yet clear, but are considered as follows. That is, when a polyolefin resin is heated and kneaded at a temperature equal to or higher than the decomposition temperature of the organic peroxide together with an inorganic filler and a silane coupling agent in the presence of the organic peroxide component, the organic peroxide is decomposed to generate radicals. On the other hand, grafting occurs with a silane coupling agent. In addition, the heating reaction at this time partially promotes a chemical bond formation reaction by a covalent bond between a silane coupling agent and a group such as a hydroxyl group on the surface of the inorganic filler.
  • the final cross-linking reaction may be performed in the step (d), and when a specific amount of the silane coupling agent is blended with the polyolefin resin as described above, the inorganic filler is obtained without impairing the extrusion processability at the time of molding. Can be blended in a large amount, and both heat resistance and mechanical properties can be obtained while ensuring excellent flame retardancy.
  • the mechanism of action of the above process of the present invention is not yet clear, but is estimated as follows. That is, by using an inorganic filler and a silane coupling agent before and / or during kneading with a polyolefin resin, the silane coupling agent is bonded to the inorganic filler with an alkoxy group and is present at the other end. It binds to an uncrosslinked portion of the polyolefin resin with an ethylenically unsaturated group such as a group, or is physically and chemically adsorbed and held in the hole or surface of the inorganic filler without being bonded to the inorganic filler.
  • a silane coupling agent that binds to an inorganic filler with a strong bond for example, a chemical bond with a hydroxyl group on the surface of the inorganic filler may be considered
  • a silane coupling agent that binds to a weak bond for example, The reason can be, for example, an interaction by hydrogen bond, an interaction between ions, partial charges or dipoles, an action by adsorption, etc.
  • the reason can be, for example, an interaction by hydrogen bond, an interaction between ions, partial charges or dipoles, an action by adsorption, etc.
  • the silane coupling agent having a strong bond with the inorganic filler among the silane coupling agents undergoes a graft reaction with the cross-linked site of the polyolefin resin.
  • a plurality of silane coupling agents are bonded to the surface of one inorganic filler particle through a strong bond, a plurality of polyolefin resins are bonded through the inorganic filler particle.
  • the silane coupling agent having a weak bond with the inorganic filler is detached from the surface of the inorganic filler, and the ethylenically unsaturated group, which is a crosslinking group of the silane coupling agent, is A graft reaction occurs by reacting with a resin radical generated by abstraction of a hydrogen radical by a radical generated by decomposition of an organic peroxide.
  • the 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 condensation reaction (crosslinking reaction).
  • the crosslinking reaction by condensation using a silanol condensation catalyst in the presence of water in this step (d) is performed after forming the molded body.
  • a plurality of silane coupling agents can be bonded to the surface of one inorganic filler particle, so that higher heat resistance than before can be obtained and high mechanical strength can be obtained.
  • the silane crosslinkable resin formed by graft reaction of the silane coupling agent bonded to the inorganic filler with a strong bond to the polyolefin resin comes into contact with moisture, the inorganic filler is bonded via the silanol bond of the silane coupling agent.
  • a crosslinked silane-crosslinked polyolefin resin is formed.
  • a silane coupling agent bonded to an inorganic filler with a strong bond is considered to contribute to high mechanical properties, in some cases, abrasion resistance, scratch resistance, and the like.
  • the silane crosslinkable resin formed by graft reaction of the silane coupling agent bonded to the inorganic filler with a weak bond on the polyolefin resin comes into contact with moisture
  • the polyolefin resin is cross-linked through the silanol bond of the silane coupling agent.
  • a silane-crosslinked polyolefin resin is formed.
  • a silane coupling agent bonded to an inorganic filler with a weak bond is considered to contribute to an improvement in the degree of crosslinking, that is, an improvement in heat resistance.
  • a silane coupling agent exceeding 4.0 parts by mass and 15.0 parts by mass or less is mixed with the inorganic filler, and as described above, the polyolefin at the time of melt-kneading in the step (a)
  • the cross-linking reaction between the resins can be effectively suppressed.
  • the degree is different, the silane coupling agent is bonded to the inorganic filler, and is not easily volatilized during the melt kneading in the step (a), and the reaction between the free silane coupling agents is also effective. Can be suppressed. Therefore, even if the extruder is stopped, it is considered that poor appearance is unlikely to occur and a silane-crosslinked resin molded article with good appearance can be produced.
  • the manufacturing method of the present invention can be applied to the manufacture of products (including semi-finished products, parts, and members) that require heat resistance, products that require strength, component parts of products such as rubber materials, or members thereof.
  • 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. Can be applied.
  • the manufacturing method of the present invention is particularly suitably applied to the manufacture of the insulators and sheaths of electric wires and optical cables among the components of the above-described products, and can be formed as a covering thereof.
  • Insulators, sheaths, and the like can be formed by coating them in such a shape while melt-kneading them in an extrusion coating apparatus.
  • a general-purpose extrusion coating apparatus is used without using a special machine such as an electron beam cross-linking machine, which is a high heat resistant high temperature non-melting cross-linked composition to which a large amount of inorganic filler is added.
  • any conductor such as an annealed copper single wire or stranded wire can be used as the conductor.
  • the conductor may be tin-plated or an enamel-covered insulating layer.
  • the thickness of the insulating layer (the coating layer made of the heat resistant resin composition of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 to 5 mm.
  • Examples 1 to 18 and Comparative Examples 1 to 5 were carried out using the components shown in Tables 1 and 2 while changing the respective specifications or manufacturing conditions.
  • ⁇ Organic peroxide> “Perhexa 25B” (trade name, manufactured by NOF Corporation, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, decomposition temperature 149 ° C.)
  • ⁇ Inorganic filler> (1) Magnesium hydroxide (trade name: Kisuma 5, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.8 ⁇ m) (2) Aluminum hydroxide (trade name: Heidilite H42M, Showa Denko, average particle size 1.2 ⁇ m) (3) Calcium carbonate (trade name: Softon 1200, manufactured by Bihoku Flour Chemical Co., Ltd., average particle size 1.5 ⁇ m) (4) Antimony trioxide (trade name: PATOX-C, manufactured by Nippon Seiko Co., Ltd., average particle size of 3.5 ⁇ m) (5) Silica (trade name: Crystallite 5X, manufactured by Tatsumori, average particle size 1.2 ⁇ m)
  • Examples 1 to 15 and Comparative Examples 1 to 5 First, an organic peroxide, an inorganic filler, and a silane coupling agent are put into a 10 L Henschel mixer manufactured by Toyo Seiki at a mass ratio shown in Table 1, and mixed at room temperature (25 ° C.) for 1 hour to obtain a powder mixture. Got. Next, the powder mixture thus obtained and the polyolefin resin were charged into a 2 L Banbury mixer manufactured by Nippon Roll at a mass ratio shown in Table 1, and the decomposition temperature of the organic peroxide (P) or higher was exceeded. After kneading at a temperature, specifically 180 to 190 ° C.
  • silane master batch also referred to as silane MB
  • step (a) The obtained silane MB contains at least two silane crosslinkable resins obtained by graft-reacting a silane coupling agent to an olefin resin.
  • the carrier resin “UE320”, the silanol condensation catalyst, and the antioxidant are separately melt-mixed by a Banbury mixer at a mass ratio shown in Table 1 at 180 to 190 ° C., and discharged at a material discharge temperature of 180 to 190 ° C.
  • a catalyst master batch (also referred to as catalyst MB) was obtained.
  • This catalyst masterbatch is a mixture of a carrier resin, a silanol condensation catalyst and an antioxidant.
  • silane MB and catalyst MB were melted at 180 ° C. by a Banbury mixer at a mass ratio shown in Table 1, that is, 100 parts by mass of polyolefin resin of silane SM and 5 parts by mass of carrier resin of catalyst MB. Mixed (step (b)).
  • a heat-resistant silane crosslinkable resin composition was prepared.
  • This heat-resistant silane crosslinkable resin composition is a mixture of silane MB and catalyst MB, and contains at least two types of silane crosslinkable resins described above.
  • this heat-resistant silane cross-linked resin molded product contains the above-described silane cross-linked resin obtained by cross-linking the silane cross-linkable resin by a condensation reaction of a hydrolyzable group of the silane coupling agent.
  • Silane MB (step (a)) and catalyst MB were prepared in the same manner as in Example 1, using the components shown in Table 2 in the mass ratio (parts by mass) shown in the same table. Subsequently, the obtained silane MB and catalyst MB were put into a closed ribbon blender, and dry blended at room temperature (25 ° C.) for 5 minutes to obtain a dry blend. At this time, the mixing ratio of the silane MB and the catalyst MB was such that the polyolefin resin of silane SM was 100 parts by mass and the carrier resin of catalyst MB was 5 parts by mass (see Table 2).
  • the outside of the conductor was coated with a thickness of 1 mm to obtain an electric wire (uncrosslinked) having an outer diameter of 2.8 mm (step (b) and step (c)).
  • the obtained electric wire (uncrosslinked) was left in an atmosphere of a temperature of 80 ° C. and a humidity of 95% for 24 hours (step (d)).
  • cover consisting of a heat resistant silane crosslinked resin molding was manufactured.
  • Example 17 Each component shown in Table 2 was used at a mass ratio (parts by mass) shown in the same table, and in the same manner as in Example 1 above, an electric wire (outer diameter 2. 8 mm, uncrosslinked) was obtained (step (a), step (b) and step (c)). The obtained electric wire was left in an atmosphere of a temperature of 23 ° C. and a humidity of 50% for 72 hours (step (d)). Thus, the electric wire which has the coating
  • Silane MB was prepared in the same manner as in Example 1 above using the components shown in Table 2 in the mass ratio (parts by mass) shown in the same table (step (a)).
  • the carrier resin “UE320”, the silanol condensation catalyst, and the antioxidant were melt-mixed by a twin screw extruder at a mass ratio shown in Table 2 to obtain a catalyst MB.
  • the screw diameter of the twin screw extruder was set to 35 mm, and the cylinder temperature was set to 180 to 190 ° C.
  • the obtained catalyst MB is a mixture of a carrier resin, a silanol condensation catalyst and an antioxidant. Subsequently, the obtained silane MB and catalyst MB were melt-mixed at 180 ° C.
  • step (b) The mixing ratio of silane MB and catalyst MB was such that the polyolefin resin of silane SM was 100 parts by mass and the carrier resin of catalyst MB was 5 parts by mass (see Table 2).
  • This heat-resistant silane crosslinkable resin composition is a mixture of silane MB and catalyst MB, and contains at least two types of silane crosslinkable resins described above.
  • an electric wire (uncrosslinked) having an outer diameter of 2.8 mm was obtained (step (c)).
  • the obtained electric wire (uncrosslinked) was left in a state of being immersed in warm water at a temperature of 50 ° C. for 10 hours (step (d)).
  • cover consisting of a heat resistant silane crosslinked resin molding was manufactured.
  • a tensile test was conducted as a mechanical property of the electric wire. This tensile test was performed according to JIS C 3005. Using the wire tubular piece from which the conductor was extracted from the wire, the tensile strength (MPa) and the tensile elongation (%) were measured at 25 mm between the marked lines and at a pulling speed of 500 mm / min. A tensile strength of 8 MPa or more is accepted, and a tensile elongation of 100% or more is accepted.
  • Heat deformation test was conducted as the heat resistance of the electric wires. The heat deformation test was performed at a measurement temperature of 150 ° C. and a load of 5 N based on UL1581. A measured value of 50% or less was accepted.
  • Hot set test 1 is to make a tubular piece of electric wire, mark it with a length of 50mm, attach a weight of 117g in a constant temperature bath at 170 ° C, leave it for 15 minutes, and measure the length after leaving Then, the elongation was determined (hot set test 1). Next, the length after standing after the load was removed was measured to determine the elongation (hot set test 2). In the hot set test 1, an elongation rate of 100% or less was accepted, and in the hot set test 2, an elongation rate of 80% or less was accepted.
  • Extrusion appearance test 1 was conducted as an extrusion appearance characteristic of the electric wire.
  • the extrusion appearance test 1 was evaluated by observing the extrusion appearance when manufacturing the electric wire. Specifically, when the wire was extruded with a 65 mm extruder at a line speed of 50 m / min, “A” indicates that the appearance of the wire was good, “B” indicates that the appearance was slightly bad, and “B” indicates that the appearance was remarkably bad. Was “C”, and “B” or higher was accepted as a product level.
  • Extrusion appearance 2 is that when producing an electric wire, the wire speed is set to 50 m / min with a 65 mm extruder, the electric wire is produced, the extruder is stopped once in the middle, and the extruder is again operated under the same conditions after 10 minutes. It evaluated by observing the external appearance of the manufactured electric wire by operating and manufacturing an electric wire. Specifically, the wire speed was set again at 50 m / min, the extruder was restarted, and the appearance of the electric wire extruded after 5 minutes was observed.
  • the evaluation was “A” when the wire speed was good and no more than 2 pieces per 1 m when observed 5 minutes after setting the line speed to 50 m / min. Or, “B” means that 3 to 10 bumps are confirmed in 1 m, “C” means that the appearance is remarkably bad, or 11 or more bumps are confirmed in 1 m, and “B” or more.
  • the product level was accepted.
  • Examples 1 to 18 all passed the extrusion appearance test 2. Even if the extruder was stopped and restarted, rough appearance and irregularities occurred. This makes it possible to produce electric wires that are difficult to handle and have an excellent appearance.
  • Examples 1 to 4, 6 to 10, 12 to 14, and 16 to 18 in which the silane coupling agent was used in an amount of 6 parts by mass or more with respect to the polyolefin resin in the extrusion appearance test 2, no more than 2 pieces per 1 m
  • the heat-resistant silane crosslinked resin moldings according to the present invention provided as the coatings for the wires of Examples 1 to 18 were excellent in appearance even when the extruder was stopped and then restarted. Moreover, it was excellent in mechanical properties, heat resistance and appearance. In addition, it can be easily understood that flame retardancy is superior from the amount of inorganic filler mixed.
  • Comparative Example 4 in which the amount of organic peroxide used is small the heat deformation test and hot set test 1 failed and the heat resistance was poor, and in Comparative Example 5 where the amount of organic peroxide used was large, even extrusion molding could not be performed. .

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Abstract

L'invention concerne un procédé de production comprenant l'étape (a) de malaxage en masse fondue de 100 parties en masse d'une résine de polyoléfine avec 0,01 à 0,6 partie en masse, valeurs extrêmes comprises, d'un peroxyde organique, 10 à 400 parties en masse, valeurs extrêmes comprises, d'une charge inorganique et plus de 4 parties en masse et 15,0 parties en masse ou moins d'un agent de couplage de type silane à une température qui est égale ou supérieure à la température de décomposition du peroxyde organique pour préparer un lot-maître de silane ; un lot-maître de silane produit par le procédé de production ; un objet moulé thermorésistant en résine réticulée par silane ; une composition thermorésistante de résine réticulant par silane ; et un produit thermorésistant.
PCT/JP2014/072443 2013-08-27 2014-08-27 Objet moulé thermorésistant en résine réticulée par silane et son procédé de production, composition thermorésistante de résine réticulant par silane et son procédé de production, lot-maître de silane et produit thermorésistant produit à l'aide de l'objet moulé thermorésistant en résine réticulée par silane WO2015030055A1 (fr)

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CN201480045774.4A CN105473654A (zh) 2013-08-27 2014-08-27 耐热性硅烷交联树脂成型体及其制造方法、耐热性硅烷交联性树脂组合物及其制造方法、硅烷母料、以及使用了耐热性硅烷交联树脂成型体的耐热性产品

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WO2016140251A1 (fr) * 2015-03-03 2016-09-09 古河電気工業株式会社 Composition de caoutchouc réticulable au silane ainsi que corps moulé en caoutchouc réticulé au silane, procédé de fabrication de ceux-ci, et article moulé en caoutchouc réticulé au silane
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
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KR102103953B1 (ko) * 2019-04-09 2020-04-23 한국신발피혁연구원 내열성과 영구압축줄음율이 우수한 epdm 고무 조성물
JP2021155592A (ja) * 2020-03-27 2021-10-07 古河電気工業株式会社 耐熱性難燃架橋フッ素ゴム成形体及びその製造方法、並びに耐熱性製品
JP7203783B2 (ja) 2020-03-27 2023-01-13 古河電気工業株式会社 耐熱性難燃架橋フッ素ゴム成形体及びその製造方法、並びに耐熱性製品
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JP7416288B2 (ja) 2021-01-29 2024-01-17 住友電気工業株式会社 電力ケーブル
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WO2022196432A1 (fr) * 2021-03-17 2022-09-22 株式会社Tbm Composition de résine chargée de poudre de substance inorganique et article moulé
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