WO2014084048A1 - 耐熱性シラン架橋性樹脂組成物を用いた成形体の製造方法 - Google Patents
耐熱性シラン架橋性樹脂組成物を用いた成形体の製造方法 Download PDFInfo
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- WO2014084048A1 WO2014084048A1 PCT/JP2013/080669 JP2013080669W WO2014084048A1 WO 2014084048 A1 WO2014084048 A1 WO 2014084048A1 JP 2013080669 W JP2013080669 W JP 2013080669W WO 2014084048 A1 WO2014084048 A1 WO 2014084048A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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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
- C08J3/20—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
- C08J3/241—Preventing premature crosslinking by physical separation of components, e.g. encapsulation
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4401—Optical cables
- G02B6/4429—Means specially adapted for strengthening or protecting the cables
- G02B6/4436—Heat resistant
Definitions
- the present invention relates to a heat-resistant silane cross-linkable resin composition and a method for producing the same, a heat-resistant silane cross-linked resin molded article and a method for producing the same, and a heat-resistant product using the heat-resistant silane cross-linked resin molded article.
- the present invention relates to a heat-resistant product used as an insulator or sheath of an electric wire using the heat-resistant silane crosslinked resin molded product obtained by the method for producing a heat-resistant silane crosslinked resin molded product.
- 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.
- materials used for these wiring materials include resin compositions containing a large amount of inorganic fillers such as magnesium hydroxide, aluminum hydroxide, and calcium carbonate.
- wiring materials used in electrical and electronic equipment may be heated to 80 to 105 ° C. and further to about 125 ° C. in continuous use, and heat resistance against this may be required.
- a method of crosslinking the coating material by an electron beam crosslinking method, a chemical crosslinking method or the like is employed.
- silane crosslinking methods are known.
- the silane cross-linking method in particular does not require special equipment and can be used in a wide range of fields.
- a 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 contacted with moisture in the presence of a silanol condensation catalyst.
- a method for producing a halogen-free heat-resistant silane crosslinked resin is a heat-resistant material in which a silane masterbatch obtained by grafting a silane coupling agent having an unsaturated group onto a polyolefin resin, and a polyolefin and an inorganic filler are kneaded.
- melt-mixing a master batch and a catalyst master batch containing a silanol condensation catalyst.
- an inorganic filler in such a method, it is effective to use a large amount of an inorganic filler in order to achieve high flame resistance, high heat resistance, and excellent strength, wear resistance, and reinforcement.
- an inorganic filler in a proportion exceeding 100 parts by mass with respect to 100 parts by mass of polyolefin it may be difficult to uniformly melt and knead with a single screw extruder or a twin screw extruder. Therefore, when a large amount of inorganic filler is used, it is common to use a closed mixer such as a continuous kneader, a pressure kneader, or a Banbury mixer.
- the silane coupling agent having an unsaturated group is generally highly volatile and often volatilizes before grafting with polyolefin. If volatilization of the silane coupling agent cannot be suppressed, poor appearance occurs and heat resistance tends to be poor.
- a method has been proposed in which a silane coupling agent is suppressed from volatilizing and a polyolefin is grafted with a Banbury mixer or kneader.
- a silane coupling agent having an unsaturated group and an organic peroxide are added to a heat-resistant masterbatch in which a polyolefin and a flame retardant as an inorganic filler are melt-mixed, and graft polymerization is performed using a single screw extruder.
- a method of making it possible is conceivable.
- Patent Document 1 discloses a single-screw extruder after sufficiently melting and kneading an inorganic filler surface-treated with a silane coupling agent, a silane coupling agent, an organic peroxide, and a crosslinking catalyst with a kneader. A method of forming by using a method has been proposed.
- wiring materials used for such electrical equipment, electronic devices, and other wiring cables are also required characteristics of flexibility and elongation characteristics in addition to heat resistance and the like. .
- the present invention solves the above-mentioned problems and the like, suppresses volatilization of the silane coupling agent during mixing or reaction, and has excellent flexibility, heat resistance, elongation characteristics and appearance, and a molded product thereof It is an object to provide a manufacturing method. Moreover, this invention makes it a subject to provide the heat resistant silane crosslinkable resin composition which can form this heat resistant silane crosslinked resin molded object, and its manufacturing method. Furthermore, this invention makes it a subject to provide the heat resistant product using the heat resistant silane crosslinked resin molded object obtained with the manufacturing method of the heat resistant silane crosslinked resin molded object.
- the reason for melting and mixing the silane coupling agent separately from the inorganic filler without using the inorganic filler surface-treated with the silane coupling agent in advance is to add the silane coupling agent using a Banbury mixer or the like.
- the silane coupling agent volatilizes and a sufficient crosslinked product may not be obtained.
- silane coupling agents may be polymerized and gelled, resulting in poor appearance.
- the silane coupling agent may cause a side reaction due to an exothermic reaction that occurs in the graft portion of the resin component, or the silane coupling agents may be polymerized to cause poor appearance.
- the present inventors preliminarily surface the inorganic filler with at least one of fatty acid and phosphate ester in the addition method of the unsaturated group-containing silane coupling agent. If the unsaturated group-containing silane coupling agent is added to the surface-treated inorganic filler after the treatment, the amount of the unsaturated group-containing silane coupling agent that is not easily separated from the inorganic filler not subjected to the crosslinking reaction is suppressed.
- the gelation and volatilization of the unsaturated group-containing silane coupling agent can be effectively suppressed, and the heat-resistant silane cross-linked resin molded article to be produced can be provided with any of flexibility, heat resistance, elongation characteristics and appearance.
- the subject of this invention was achieved by the following means. (1) 0.01 to 0.6 parts by mass of organic peroxide (P) and 100% by mass of untreated surface inorganic filler (F U ) with respect to 100 parts by mass of the resin composition (RC) containing the resin component (R) Of 0.1 to 4.0% by mass of a surface-treated inorganic filler (F T ) obtained by surface-treating the surface-untreated inorganic filler (FU) with at least one of fatty acid and phosphate ester 10 to 400 parts by weight of the filler (F) and 0.5 to 18.0 parts by weight of the unsaturated group-containing silane coupling agent (S) with respect to 100 parts by weight of the surface-treated inorganic filler (F T )
- the surface-treated inorganic filler (F T ) contains at least one kind of the fatty acid and the phosphoric acid ester in an amount of 0.1 to 4.0% by mass, and a hydrolyzable silane coupling agent 0.05 to 1.0.
- the method for producing a heat-resistant silane-crosslinked resin molded product according to (1) which is obtained by surface treatment with mass%.
- the surface-treated inorganic filler (F T ) is obtained by subjecting the surface-treated inorganic filler (F U ) to surface treatment with 0.1 to 1.5% by mass of the fatty acid (1) or ( The manufacturing method of the heat-resistant silane crosslinked resin molding as described in 2).
- the surface-treated inorganic filler (F T) is obtained by surface treatment with surface untreated inorganic filler (F U) the phosphoric acid ester of 0.1 to 2.8 wt% with respect to (1)
- S unsaturated group-containing silane coupling agent
- the inorganic filler (F) contains 30 to 100% by mass of the surface-treated inorganic filler (F T ) based on the total mass of the inorganic filler (F).
- the manufacturing method of the heat-resistant silane crosslinked resin molding of description In any one of (1) to (7), the surface-untreated inorganic filler (F U ) of the surface-treated inorganic filler (F T ) contains at least one metal hydrate.
- the manufacturing method of the heat-resistant silane crosslinked resin molding of description. (9) The method for producing a heat-resistant silane crosslinked resin molded article according to (8), wherein the metal hydrate contains magnesium hydroxide.
- (10) The method for producing a heat-resistant silane cross-linked resin molded article according to (8), wherein the metal hydrate contains calcium carbonate.
- (11) The heat resistant silane crosslinked resin molding according to any one of (1) to (10), wherein the resin component (R) is contained in the resin composition (RC) in an amount of 20 to 100% by mass. Body manufacturing method.
- (12) The step (a) is mixed with the inorganic filler (F) and the unsaturated group-containing silane coupling agent (S), and then the organic peroxide (P) is at a temperature below its decomposition temperature.
- a silane master batch is prepared by melt-mixing the mixture (RC) obtained in the step (a1) of mixing and the resin composition (RC) above the decomposition temperature of the organic peroxide (P).
- the step (b) is a step of mixing the silane master batch with the catalyst master batch containing the silanol condensation catalyst (C) and the carrier resin (E).
- a method for producing a heat-resistant silane crosslinkable resin composition comprising the step (a) and the step (b) and not having at least the step (c).
- the heat resistant silane crosslinked resin molding which was excellent in the softness
- 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 can be provided.
- the “method for producing a heat-resistant silane-crosslinked resin molded product” of the present invention is an organic peroxide (P) of 0.01 to 0 with respect to 100 parts by mass of a resin composition (RC) containing a resin component (R). .6 parts by mass and 0.1 to 4.0% by mass of the surface untreated inorganic filler (F U ), and the surface untreated inorganic filler (FU) is surface treated with at least one of fatty acid and phosphate ester.
- a step (b) preparing a silane masterbatch by melt-mixing the saturated group-containing silane coupling agent (S) at or above the decomposition temperature of the organic peroxide (P), and a silane masterbatch and a silanol condensation catalyst (C)
- the “method for producing a heat-resistant silane crosslinkable resin composition” of the present invention includes the steps (a) and (b), and at least the step (c) and optionally the step (d).
- the “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 are basically the same except for the presence or absence of the step (c). It is. Accordingly, the “method for producing a heat-resistant silane cross-linked resin molded product” of the present invention and the “method for producing a heat-resistant silane cross-linkable resin composition” of the present invention (in the explanation of the common parts of both, The manufacturing method of the present invention is sometimes described below.
- the resin composition (RC) used in the present invention contains a resin component (R) and various oils used as a plasticizer or a softener as required.
- the content of the resin component (R) in the resin composition (RC) is preferably 20% by mass or more with respect to the total mass of the resin composition (RC) in terms of heat resistance performance, crosslinking performance, and strength. More preferably, it is 45% by mass or more, and particularly preferably 60% by mass or more.
- the content of the resin component (R) is 100% by mass at the maximum, but may be, for example, 80% by mass or less.
- the resin composition (RC) is preferably introduced with oil in order to maintain flexibility and maintain a good appearance.
- the oil in the resin composition (RC) is preferably set to 80% by mass, more preferably 55% by mass or less, with respect to the total mass of the resin composition (RC). It is particularly preferably 40% by mass or less.
- the resin composition (RC) may contain other components such as various additives and solvents described later.
- Resin component (R) examples include a polyolefin resin (PO), a polyester resin, a polyamide resin (PA), a polystyrene resin (PS), and a polyol resin, and among them, a polyolefin resin is preferable.
- This resin component (R) may be used individually by 1 type, and may use 2 or more types together.
- the polyolefin-based resin is not particularly limited, and known ones conventionally used for heat-resistant silane crosslinkable resin compositions can be used.
- polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, block copolymer of polypropylene and ethylene- ⁇ -olefin resin, acid copolymer component or acid ester copolymer component (these are collectively referred to as acid copolymer component)
- the receptivity to various inorganic fillers (F) including metal hydrates is high, and even if a large amount of inorganic filler (F) is blended, there is an effect of maintaining mechanical strength, and heat resistance.
- Polyethylene, ethylene- ⁇ -olefin copolymer, polyolefin copolymer resin having acid copolymerization component, styrene elastomer Ethylene-propylene rubber is preferable. These polyolefin resins may be used alone or in combination of two or more.
- 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).
- 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.
- Preferred examples of the ⁇ -olefin component in the ethylene- ⁇ -olefin copolymer include those having 3 to 12 carbon atoms.
- Specific examples of the ⁇ -olefin component include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like.
- the ethylene- ⁇ -olefin copolymer is preferably a copolymer of ethylene and an ⁇ -olefin component having 3 to 12 carbon atoms, specifically, an ethylene-propylene copolymer (EPR), ethylene -Butylene copolymer (EBR), ethylene- ⁇ -olefin copolymer synthesized in the presence of a single site catalyst, and the like.
- EPR ethylene-propylene copolymer
- EBR ethylene -Butylene copolymer
- One ethylene- ⁇ -olefin copolymer may be used alone, or two or more ethylene- ⁇ -olefin copolymers may be used in combination.
- Examples of the block copolymer of polypropylene and ethylene- ⁇ -olefin resin include a copolymer having a polypropylene block and the above-described ethylene- ⁇ -olefin copolymer block.
- Examples of the acid copolymerization component or acid ester copolymerization component in the polyolefin copolymer having an acid copolymerization component include vinyl acetate, (meth) acrylic acid, and alkyl (meth) acrylate.
- the alkyl group of the alkyl (meth) acrylate preferably has 3 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.
- polystyrene resin having an acid copolymer component examples include an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid alkyl copolymer.
- ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer are preferable, and further acceptability to inorganic filler (F).
- an ethylene-vinyl acetate copolymer is preferred.
- the polyolefin copolymer having an acid copolymerization component is used alone or in combination of two or more.
- styrenic elastomer examples include a block copolymer and a random copolymer of a conjugated diene compound and an aromatic vinyl compound, or a hydrogenated product thereof.
- aromatic vinyl compound examples include styrene, p- (tert-butyl) styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethyl.
- examples thereof include styrene, vinyl toluene, p- (tert-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.
- butadiene is preferred.
- This conjugated diene compound is used individually by 1 type, or 2 or more types are used together.
- styrene-based elastomer an elastomer that does not contain a styrene component and contains an aromatic vinyl compound other than styrene may be used by the same manufacturing method.
- styrene-based elastomer examples include, for example, Septon 4077, Septon 4055, Septon 8105 (all trade names, manufactured by Kuraray Co., Ltd.), Dynalon 1320P, Dynalon 4600P, 6200P, 8601P, 9901P (all trade names, JSR Corporation) Manufactured).
- oils examples of the oil optionally contained in the resin composition (RC) include an oil as a plasticizer for the resin component (R) or a mineral oil softener for rubber. Since this oil does not react with the unsaturated group-containing silane coupling agent (S), it is not included in the resin component (R), but may be contained in the resin composition (RC).
- Mineral oil softeners are mixed oils consisting of a combination of aromatic rings, naphthene rings and paraffin chains. Paraffin oils with 50% or more of the total number of carbon atoms in the paraffin chain, naphthenic oils with 30 to 40% naphthenic ring carbons, and aroma oils with 30% or more aromatic carbons (aromatic oils) It is also called oil).
- liquid or low molecular weight synthetic softeners paraffin oil, and naphthene oil are preferably used, and paraffin oil is particularly preferably used.
- paraffin oil examples include Diana Process Oil PW90 and PW380 (both trade names, manufactured by Showa Shell Sekiyu KK), Cosmo Neutral 500 (manufactured by Cosmo Sekiyu KK), and the like.
- Organic peroxide (P) examples include general formulas: R 1 —OO—R 2 , R 1 —OO—C ( ⁇ O) R 3 , R 3 C ( ⁇ O) —OO (C ⁇ O) R 4
- R 1 , R 2 , R 3 and R 4 each independently represents an alkyl group, an aryl group, or an acyl group.
- R 1 , R 2 , R 3 and R 4 are all alkyl groups, or any one is an alkyl group and the rest is an acyl group.
- organic peroxides examples include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, , 5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxy Benzoate, tert-butyl peroxyisopropyl carbonate, dia Chill peroxide, lauroyl peroxide, etc.
- tert- butyl cumyl peroxide and the like.
- dicumyl peroxide 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2 are preferable in terms of odor, colorability, and scorch stability.
- 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 at a rate of temperature increase of 5 ° C./min in a nitrogen gas atmosphere by thermal analysis such as DSC method.
- the inorganic filler (F) used in the step (a) includes a surface-treated inorganic filler (F T ), but can also include an inorganic filler other than the surface-treated inorganic filler (F T ).
- a surface untreated inorganic filler (F U ) not surface-treated with a surface treating agent, an inorganic filler surface-treated with a hydrolyzable silane coupling agent, or the like can be used.
- the surface-treated inorganic filler (F T ) contained in the inorganic filler (F) is at least 30% by mass, more preferably 50% by mass, more preferably 70% by mass with respect to the total mass of the inorganic filler (F). The above is preferable. When the content of the surface-treated inorganic filler (F T ) is 30% by mass or less, at least one of the heat resistance and flexibility of the heat-resistant silane crosslinked resin molded product may be lowered.
- the remainder in the inorganic filler (F) includes other inorganic fillers, for example, an inorganic filler surface-treated with a surface untreated inorganic filler (F U ), a hydrolyzable silane coupling agent, and the like.
- the average particle diameter is preferably 0.2 to 10 ⁇ m
- the thickness is more preferably 0.3 to 8 ⁇ m, further preferably 0.35 to 5 ⁇ m, and further preferably 0.35 to 3 ⁇ m.
- the inorganic filler (F) causes secondary aggregation when the unsaturated group-containing silane coupling agent (S) is mixed, and the heat-resistant silane crosslinked resin molded product. There is a risk that the appearance of the product will be degraded and bumpy.
- the average particle diameter is obtained by dispersing the inorganic filler (F) in alcohol or water and using an optical particle diameter measuring device such as a laser diffraction / scattering particle diameter distribution measuring device.
- the surface untreated inorganic filler (F U ) is an inorganic filler that is not surface-treated and serves as a base of the surface treated inorganic filler (F T ).
- Such surface untreated inorganic filler (F U ) is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, Examples thereof include metal hydrates such as compounds having a hydroxyl group or crystal water, such as aluminum oxide, aluminum nitride, aluminum borate, hydrated aluminum silicate, alumina, hydrated magnesium silicate, basic magnesium carbonate, and hydrotalcite.
- the surface untreated inorganic filler (F U ) for example, 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, zinc hydroxystannate, zinc stannate and the like.
- metal hydrates are preferable, and magnesium hydroxide, calcium carbonate, aluminum hydroxide, magnesium carbonate, and the like are particularly preferable.
- the surface-treated inorganic filler (F T ) is a surface-treated inorganic filler (F U ) that has been surface-treated with at least one of fatty acids and phosphate esters, or at least one of these and a hydrolyzable silane coupling agent. is there.
- the surface-untreated inorganic filler (F U ) is surface-treated in advance, it is possible to suppress a strong bond between the unsaturated group-containing silane coupling agent (S) and the surface-treated inorganic filler (F T ).
- An unsaturated group-containing silane coupling agent (S) that binds to the surface-treated inorganic filler (F T ) with a weak bond can be created.
- the unsaturated group-containing silane coupling agent (S) bonded to the surface-treated inorganic filler (F T ) with this weak bond can provide a heat-resistant silane crosslinked resin molded product having a certain degree of crosslinking.
- flexibility and an elongation characteristic are securable. Therefore, the amount of the surface treatment of at least one of fatty acid and phosphoric acid ester which surface-treats the surface untreated inorganic filler (F U ) in advance is limited.
- the surface-untreated inorganic filler (F U ) is surface-treated with at least one of fatty acid and phosphate ester in an amount of 0.1 to 4.0% by mass with respect to 100 parts by mass as described later. Has been.
- the silane coupling agent strongly bonded to the surface-treated inorganic filler (F T ) is bonded to the surface of the surface-treated inorganic filler (F T ) by chemical bonding (hydrolysis of the silane coupling agent).
- agent refers to a surface-treated inorganic filler (F T)
- weakly binding silane coupling agent refers to a silane coupling agent in the physical adsorption or mixed state on the surface of the surface-treated inorganic filler (F T).
- the fatty acid for surface-treating the surface untreated inorganic filler (F U ) is not particularly limited, and examples thereof include saturated fatty acids having 10 to 22 carbon atoms and unsaturated fatty acids having 10 to 22 carbon atoms.
- saturated fatty acid having 10 to 22 carbon atoms include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, aragdic acid, and behenic acid.
- Examples of the unsaturated fatty acid having 10 to 22 carbon atoms include oleic acid, linolenic acid, and linoleic acid.
- the phosphate ester which surface-treats the surface untreated inorganic filler (F U ) is not particularly limited, and examples thereof include phosphate monoester, phosphate diester, and phosphate triester.
- Examples of the organic group in the phosphate ester include an aliphatic group and an aromatic group.
- Examples of the aliphatic group include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alkynyl group having 2 to 8 carbon atoms.
- Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.
- Examples of the alkenyl group having 2 to 8 carbon atoms include a vinyl group and a propenyl group.
- Examples of the alkynyl group having 2 to 3 carbon atoms include an acetylinyl group and a propynyl group.
- Examples of the aromatic group include a phenyl group.
- the hydrolyzable silane coupling agent for surface-treating the surface-untreated inorganic filler (F U ) is not particularly limited, and has an amino group, vinyl group, (meth) acryloyloxy group, or glycidyl group at the terminal. And more preferably those having a vinyl group and a (meth) acryloyloxy group at the terminal.
- hydrolyzable silane coupling agent having an amino group at the terminal examples include those having an aminoalkyl group, such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Examples include triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and the like.
- aminoalkyl group such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2- (aminoethyl
- What has a vinyl group or a (meth) acryloyloxy group at the terminal includes, for example, an unsaturated group-containing silane coupling agent (S) described later.
- S unsaturated group-containing silane coupling agent
- 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 surface-treated inorganic filler (F T ) is surface-treated with at least one of a fatty acid and a phosphate ester, or at least one of them and a hydrolyzable silane coupling agent.
- a fatty acid and phosphate ester are used individually by 1 type respectively, respectively, 2 or more types may be used together, and at least 1 type of fatty acid and phosphate ester may be used together.
- a hydrolysable silane coupling agent is used individually by 1 type or 2 or more types may be used together, it is used with a fatty acid or phosphate ester.
- the fatty acid, phosphate ester and hydrolyzable silane coupling agent may be used in combination with other surface treatment agents.
- Other surface treatment agents are not particularly limited, and examples thereof include polyesters and titanate coupling agents. These other surface treatment agents are in a ratio that the total amount of fatty acid, phosphate ester and hydrolyzable silane coupling agent is 4.0% by mass or less with respect to the untreated inorganic filler (F U ). Used. If the amount used is too large, the crosslink density is lowered, and the strength and / or heat resistance of the heat resistant silane crosslinked resin molded product may be lowered.
- the surface-treated inorganic filler (F T ) may be appropriately prepared, or a commercially available product may be used.
- a commercially available product for example, as magnesium hydroxide surface-treated with a fatty acid (compound names: stearic acid, oleic acid), Kisuma 5A, Kisuma 5B (both trade names, manufactured by Kyowa Chemical Industry Co., Ltd.), Magsees N6 (trade name, Kamishima Chemical Industries) Etc.).
- examples of aluminum hydroxide surface-treated with a fatty acid include Heidilite H42-S (trade name, manufactured by Showa Denko KK).
- Ryton BSO (trade name, manufactured by Bihoku Flour Industries Co., Ltd.) and the like are exemplified as calcium carbonate surface-treated with a fatty acid (compound name: stearic acid).
- Kisuma 5J (manufactured by Kyowa Chemical Industry Co., Ltd.) and the like are exemplified as magnesium hydroxide surface-treated with a phosphate ester (compound name: stearyl phosphate ester).
- the surface treatment inorganic filler (F T ) surface-treated with a fatty acid and / or phosphate ester and a hydrolyzable silane coupling agent further hydrolyzes the inorganic filler surface-treated with a fatty acid and / or phosphate ester. It can be prepared by surface treatment with a functional silane coupling agent.
- the unsaturated group-containing silane coupling agent (S) is not particularly limited, and a silane coupling agent having an unsaturated group used in the silane crosslinking method can be used.
- an unsaturated group-containing silane coupling agent (S) for example, an unsaturated group-containing silane coupling agent (S) represented by the following general formula (1) can be preferably 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 organic group that hydrolyzes independently.
- Y 11 , Y 12 and Y 13 may be the same as or different from each other.
- Examples of the group R a11 containing an ethylenically unsaturated group include a vinyl group, an alkenyl group having an unsaturated bond at the terminal, a (meth) acryloyloxyalkylene group, a p-styryl group, and the like, more preferably Vinyl group.
- 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 is hydrolyzed, such as an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an acyloxy group having 1 to 4 carbon atoms. Groups. Among these, 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. In terms of hydrolysis reactivity, a methoxy group or An ethoxy group is preferred.
- the unsaturated group-containing silane coupling agent (S) represented by the general formula (1) is preferably a silane coupling agent having an ethylenically unsaturated group and a high hydrolysis rate, more preferably general In the formula (1), R b11 is Y 13 and Y 11 , Y 12 and Y 13 are silane coupling agents each having the same organic group.
- Specific examples of preferable unsaturated group-containing silane coupling agents (S) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, and vinyldiethoxybutoxysilane.
- an unsaturated group-containing silane coupling agent having a vinyl group and an alkoxy group at the terminal is more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.
- the unsaturated group-containing silane coupling agent (S) may be used alone or in a solution diluted with a solvent.
- silanol condensation catalyst (C) functions to bind the unsaturated group-containing silane coupling agent (S) grafted to the resin component (R) in the presence of moisture by a condensation reaction. Based on the action of the silanol condensation catalyst (C), the resin components (R) are cross-linked through the unsaturated group-containing silane coupling agent (S). As a result, a heat-resistant silane cross-linked resin molded article having excellent heat resistance is obtained.
- silanol condensation catalyst (C) an organic tin compound, a metal soap, a platinum compound, or the like is used.
- Common silanol condensation catalysts (C) include, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, zinc stearate, lead stearate, barium stearate, calcium stearate, stearin Sodium acid, lead naphthenate, lead sulfate, zinc sulfate, organic platinum compounds and the like are used.
- organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate are particularly preferable.
- the carrier resin (E) optionally added to the catalyst masterbatch is not particularly limited, but a part of the resin component (R) contained in the resin composition (RC) can also be used. A resin other than R) can also be used. Examples of the carrier resin (E) used separately from the resin component (R) include the same resins as the resin component (R) of the resin composition (RC).
- the carrier resin (E) preferably uses a part of the resin component (R).
- the carrier resin (E) is preferably a polyolefin-based resin, and particularly preferably polyethylene, from the viewpoint of good affinity with the silanol condensation catalyst (C) and excellent heat resistance.
- This carrier resin (E) may be used together with an untreated inorganic filler (F U ) or other filler.
- the inorganic filler used together with the carrier resin (E), that is, added after the unsaturated group-containing silane coupling agent (S) is 350 masses with respect to 100 mass parts of the resin component (R) of the resin composition (RC). Part or less is preferred.
- a silanol condensation catalyst (C) will be hard to disperse
- the heat-resistant silane cross-linked resin molded body and the heat-resistant silane cross-linkable resin composition are various additives commonly used in electric wires, electric cables, electric cords, sheets, foams, tubes, pipes, for example, A crosslinking aid, antioxidant, lubricant, metal deactivator, filler, other resin and the like may be appropriately blended within a range not impairing the object of the present invention.
- These additives may be contained in any component, but may be contained in the catalyst master batch.
- the antioxidant and the metal deactivator are added to the catalyst masterbatch so that the unsaturated group-containing silane coupling agent (S) mixed with the inorganic filler (F) does not inhibit the grafting to the resin component (R).
- a crosslinking aid is not substantially contained.
- the crosslinking aid is not substantially mixed in the step (a) for preparing the silane master batch.
- the crosslinking aid reacts with the organic peroxide (P) during kneading, crosslinking between the resin components (R) occurs, gelation occurs, and the heat resistant silane crosslinked resin molded article is formed. Appearance may deteriorate significantly.
- the graft reaction of the unsaturated group-containing silane coupling agent (S) to the resin component (R) 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 a material that forms a partially crosslinked structure with the resin component (R) in the presence of an organic peroxide.
- a methacrylate compound such as polypropylene glycol diacrylate and trimethylolpropane triacrylate
- examples include allyl compounds such as allyl cyanurate, polyfunctional compounds such as maleimide compounds, and divinyl compounds.
- Antioxidants include amine-based antioxidants such as 4,4′-dioctyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, and a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline.
- Pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, Phenolic antioxidants such as 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (2-methyl-4- (3 -N-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben ⁇ imidazole and its Zinc salts, pentaerythritol - tetrakis (3-lauryl - thiopropionate) and the like sulfur-based antioxidant such.
- Phenolic antioxidants such as 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-
- the antioxidant can be added in an amount of preferably 0.1 to 15.0 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin component (R).
- the lubricant include hydrocarbon, siloxane, fatty acid, fatty amide, ester, alcohol, and metal soap. These lubricants should be added to the carrier resin (E).
- Metal deactivators include N, N′-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and the like.
- the filler including a flame retardant (auxiliary) agent
- examples of the filler include inorganic fillers (F), surface untreated inorganic fillers (F U ), surface treated inorganic fillers (F T ), and other fillers other than inorganic fillers. Can be mentioned. These fillers may be mixed when the unsaturated group-containing silane coupling agent (S) is mixed with the inorganic filler (F), or may be mixed in the catalyst master batch.
- the “method for producing a heat-resistant silane cross-linked resin molded article” of the present invention includes a step (a), a step (b), a step (c), and a step (d).
- the “method for producing a heat-resistant silane crosslinkable resin composition” of the present invention includes the step (a) and the step (b), and at least the step (c), and optionally the step (d). Does not have.
- an inorganic filler containing 0.01 to 0.6 parts by mass of an organic peroxide (P) and a surface-treated inorganic filler (F T ) with respect to 100 parts by mass of the resin composition (RC) (F) 10 to 400 parts by mass and 0.5 to 18.0 parts by mass of an unsaturated group-containing silane coupling agent (S) are melt-mixed at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P), A silane masterbatch is prepared (step a).
- “with respect to 100 parts by mass of the resin composition (RC)” means that “100 parts by mass of the resin composition (RC) and other components are mixed” in step (a). And “a mode in which a part of 100 parts by mass of the resin composition (RC), for example, the resin component (R) is mixed in the step after the step (a), for example, the step (b)”. . Therefore, in the production method of the present invention, it is sufficient that 100 parts by mass of the resin composition (RC) is contained in the “heat-resistant silane crosslinkable resin composition”, and the mixing mode of the resin composition (RC) is particularly It is not limited. Specifically, the resin component (R) contained in the resin composition (RC) may be entirely mixed with other components in the step (a), and a part of the carrier of the catalyst master batch described later. Part or all of the resin (E) may be mixed in the step (b).
- the resin component (R) to be mixed in the step (b) is preferably 1 to 20 parts by mass, particularly 2 to 6 parts by mass, out of 100 parts by mass of the resin composition (RC). Good.
- the resin component (R) mixed in the step (b) is added to the amount of the resin composition (RC) in the step (a). ) Is included.
- the “method for producing a heat-resistant silane crosslinked resin molded product” of the present invention includes a resin composition (RC), an organic peroxide (P),
- the step of preparing the heat-resistant silane crosslinkable resin composition of the present invention by mixing the inorganic filler (F), the unsaturated group-containing silane coupling agent (S) and the silanol condensation catalyst (C), and the above-mentioned step (c ) And step (d), and in the step of preparing the heat-resistant silane crosslinkable resin composition, 80 to 99 parts by mass of the resin composition (RC), the organic peroxide (P), and the inorganic filler (F)
- a step (a ′) of preparing a silane masterbatch by mixing the unsaturated group-containing silane coupling agent (S), and the resulting silane masterbatch, silanol condensation catalyst (C), and resin as the carrier resin (E) Remaining component (R)
- the surface-treated inorganic filler (F T ) used in the step (a) is 0.1 to 4.0% by mass of fatty acid and phosphoric acid with respect to 100 parts by mass of the untreated surface untreated inorganic filler (F U ).
- Surface-treated with at least one ester When the surface treatment amount exceeds 4.0% by mass, the unsaturated group-containing silane coupling agent (S) added later by the fatty acid and the phosphate ester is repelled and completely approaches the surface treatment inorganic filler (F T ).
- Many unsaturated group-containing silane coupling agents (S) that cannot be bonded to the surface-treated inorganic filler (F T ) cannot be formed.
- the unsaturated group-containing silane coupling agent (S) is likely to volatilize, and the crosslinking density of the heat-resistant silane crosslinked resin molded product may be reduced, resulting in a decrease in strength, heat resistance and / or appearance. is there.
- the surface treatment amount of the fatty acid and the phosphate ester is less than 0.1% by mass, not only the effect of the surface treatment with the fatty acid and the phosphate ester, for example, flexibility, elongation characteristics and heat resistance are not sufficiently exhibited.
- the silane coupling agent and the filler cause a strong bond, and many silane coupling agents that are not subjected to the crosslinking reaction are formed. Accordingly, the degree of cross-linking decreases, while the silane coupling agent that has reacted strongly with the filler bonds with the filler and the polymer to form a rigid material.
- This surface treatment amount is that the surface untreated inorganic filler (F U ) is 100 in that the surface untreated inorganic filler (F U ) is excellent in any of flexibility, elongation characteristics and heat resistance of the heat resistant silane crosslinked resin molded product.
- the content is preferably from 0.1 to 3.0% by mass, particularly preferably from 0.15 to 2.0% by mass, based on parts by mass.
- the surface treatment amount of the fatty acid is preferably 0.1 to 1.5% by mass, more preferably 0.15 to 1% by mass, and the surface treatment amount of the phosphate ester is 0.1% by mass. It is preferably 2.8% by mass, more preferably 0.2-2.0% by mass.
- the total amount of the fatty acid, phosphate ester and hydrolyzable silane coupling agent is preferably 0.15 to 5.0% by mass. It is particularly preferably 3 to 2.0% by mass.
- the surface treatment amount of the fatty acid and phosphate ester is selected from the above range, and the surface treatment amount of the hydrolyzable silane coupling agent is in the range of 0.05 to 1.0% by mass, preferably 0.15 to It is selected from the range of 0.8% by mass.
- a predetermined amount of fatty acid, phosphate ester, Mix with hydrolyzable silane coupling agent for example, with respect to 100 parts by mass of the untreated surface untreated inorganic filler (F U ), a predetermined amount of fatty acid, phosphate ester, Mix with hydrolyzable silane coupling agent.
- the mixing method is not particularly limited, and examples thereof include wet processing and dry processing.
- the dry treatment include a method in which a dried surface untreated inorganic filler (F U ) and a fatty acid are added and mixed without heating or heating.
- the wet treatment include a method of adding a fatty acid or the like in a state where a surface untreated inorganic filler (F U ) is dispersed in a solvent such as water. Among these, dry processing is preferable.
- the inorganic filler (F) contains another inorganic filler, such as a surface untreated inorganic filler (F U ), the surface treated inorganic filler (F T ) and the other inorganic filler To prepare an inorganic filler (F).
- another inorganic filler such as a surface untreated inorganic filler (F U )
- the surface treated inorganic filler (F T ) and the other inorganic filler To prepare an inorganic filler (F).
- step (a) the resin composition (RC), the organic peroxide (P), the inorganic filler (F), and the unsaturated group-containing silane coupling agent (S) are decomposed into the organic peroxide (P). Melt and mix above temperature.
- a part of the resin component (R) of the resin composition (RC) is used as the carrier resin (E) described later, as described above, it is mixed in the step (a) and the step (b).
- the total amount of the resin composition (RC) is “100 parts by mass”, and the mixing amount of each component in the step (a) and the step (b) is determined.
- the mixing amount of the organic peroxide (P) is in the range of 0.01 to 0.6 parts by weight, preferably 0.1 to 0.5 parts by weight with respect to 100 parts by weight of the resin composition (RC). Range.
- the resin components (R) can be polymerized within an appropriate range, and extruded without generating agglomerates due to a crosslinked gel or the like.
- a composition having excellent properties can be obtained. That is, when the compounding amount of the organic peroxide (P) is less than 0.010 parts by mass, the crosslinking reaction of the resin component (R) does not proceed or the free silane coupling agents may be bonded to each other. In some cases, sufficient heat resistance and mechanical strength cannot be obtained.
- the resin components (R) may be cross-linked and cannot be molded. Moreover, even if it can be molded, the unsaturated group-containing silane coupling agent (S) is likely to volatilize, and the resin component (R) may be directly cross-linked by a side reaction, which may cause the molded product to be damaged. There is.
- the mixing amount of the inorganic filler (F) is 10 to 400 parts by mass, preferably 30 to 280 parts by mass with respect to 100 parts by mass of the resin composition (RC).
- the blending amount of the inorganic filler (F) is less than 10 parts by mass, the graft reaction of the unsaturated group-containing silane coupling agent (S) becomes non-uniform, and the desired heat resistance cannot be obtained. Appearance may be significantly reduced.
- 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 unsaturated group-containing silane coupling agent (S) is 0.5 to 18.0 parts by mass with respect to 100 parts by mass of the surface-treated inorganic filler (F T ).
- the amount of the unsaturated group-containing silane coupling agent (S) is less than 0.5 parts by mass, the crosslinking reaction does not proceed sufficiently, and the heat resistant silane crosslinkable resin composition and the heat resistant silane crosslinked resin molded article May not exhibit the desired heat resistance, flexibility, or elongation characteristics.
- it exceeds 18.0 parts by mass the entire amount of unsaturated group-containing silane coupling agent (S) may not be adsorbed on the surface of the surface-treated inorganic filler (F T ).
- the unsaturated group-containing silane coupling agent (S) that is not adsorbed volatilizes during kneading.
- sucked may condense, and the heat-resistant silane crosslinked resin molding may have a bridging gel or burnt and deteriorate the appearance.
- the mixing amount of the unsaturated group-containing silane coupling agent (S) is preferably 1.0 to 12.0 parts by mass, and more preferably 2.5 to 8 parts by mass.
- the mixing amount of the unsaturated group-containing silane coupling agent (S) may be within the above range with respect to 100 parts by mass of the surface-treated inorganic filler (F T ), but is further based on 100 parts by mass of the resin component (R).
- the blending amount is preferably within the following range.
- the blending amount with respect to 100 parts by mass of the resin component (R) is preferably 0.5 to 18.0 parts by mass, and more preferably 1.0 to 8.0 parts by mass.
- the resin composition (RC), the organic peroxide (P), the inorganic filler (F), and the unsaturated group-containing silane coupling agent (S) are mixed with the organic peroxide (P). Melt and mix above the decomposition temperature.
- 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 ° C. to 110 ° C. This decomposition temperature is preferably set after the resin component (R) is melted. Further, kneading conditions such as kneading time can be set as appropriate.
- the silane graft reaction When kneading is performed at a temperature lower than the decomposition temperature of the organic peroxide (P), the silane graft reaction, the bond between the surface-treated inorganic filler (F T ) and the resin component (R), and the bond between the inorganic filler (F) do not occur.
- the organic peroxide (P) may react during extrusion and may not be molded into the desired shape.
- the kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic, etc., and the kneading apparatus is appropriately selected according to the amount of the inorganic filler (F).
- the kneading apparatus a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, or various kneaders are used, but a closed mixer such as a Banbury mixer or various kneaders disperses and crosslinks the resin component (R). It is preferable in terms of stability.
- the resin composition (RC), the organic peroxide (P), the inorganic filler (F), and the unsaturated group-containing silane coupling agent (S) can be mixed at a time.
- a mixer-type kneader such as a Banbury mixer or kneader
- the organic peroxide (P), the inorganic filler (F), and the unsaturated group-containing silane cup at the temperature before the resin component (R) melts.
- the ring agent (S) is preferably melt-kneaded after being dispersed in the mixer.
- step (a) If the resin component (R) is first melted, the organic peroxide (P) is first decomposed by heat or kneading and the cross-linking reaction between the resin components (R) proceeds, resulting in poor appearance. End up.
- the organic peroxide (P) is mixed with the inorganic filler (F) and the unsaturated group-containing silane coupling agent (S).
- the inorganic filler (F) and the unsaturated group-containing silane coupling agent (S) are preferably mixed at a temperature lower than the decomposition temperature of the organic peroxide (P), preferably at room temperature.
- the mixing of the inorganic filler (F), the unsaturated group-containing silane coupling agent (S), and the organic peroxide (P) include mixing methods such as wet processing and dry processing.
- the dry treatment and wet treatment at this time are basically the same as the dry treatment and wet method in preparing the surface-treated inorganic filler (F T ) except that the objects to be mixed are different.
- the unsaturated group-containing silane coupling agent (S) is strongly bonded to the surface-treated inorganic filler (F T ), so that the subsequent condensation reaction may be difficult to proceed.
- the bond between the surface-treated inorganic filler (F T ) and the unsaturated group-containing silane coupling agent (S) is relatively weak, crosslinking may easily proceed efficiently.
- the combination of the mixing method in preparing the surface-treated inorganic filler (F T ) and the mixing method in the step (a1) is not particularly limited, but the inorganic filler (F) of the unsaturated group-containing silane coupling agent (S) Surface treatment in that the hydrolyzable silane coupling agent that has been pretreated, that is, a chemical bond with the inorganic filler (F), and the unsaturated group-containing silane coupling agent (S) can be physically bonded.
- Both the mixing method for preparing the inorganic filler (F T ) and the mixing method in the step (a1) are dry processing, or the mixing method for preparing the surface-treated inorganic filler (F T ) is a wet processing and mixing in the step (a1). It is particularly preferred that the method is a dry process.
- the unsaturated group-containing silane coupling agent (S) When the unsaturated group-containing silane coupling agent (S) is added to the surface-treated inorganic filler (F T ) in this way, the unsaturated group-containing silane coupling agent (S) becomes the surface of the surface-treated inorganic filler (F T ). there to surround, a portion thereof or all or adsorbed on the surface-treated inorganic filler (F T), or cause a gradual chemical bond with the surface of the surface-treated inorganic filler (F T). By being in such a state, volatilization of the unsaturated group-containing silane coupling agent (S) during kneading with a subsequent kneader, Banbury mixer or the like is greatly reduced.
- the unsaturated group of the unsaturated group-containing silane coupling agent (S) is combined with the resin component (R) by the organic peroxide (P) added as desired. Further, it is considered that the unsaturated group-containing silane coupling agent (S) undergoes a condensation reaction with the silanol condensation catalyst (C) during molding.
- the mixture prepared in the step (a1) and the resin composition (RC) are melt-mixed at or above the decomposition temperature of the organic peroxide (P). Specifically, each of the mixture and the resin composition (RC) is added to a mixer, melted and kneaded while being heated, and the temperature is set to be equal to or higher than the decomposition temperature of the organic peroxide. Thus, when a mixture and a resin composition (RC) are melt-mixed, a silane masterbatch will be manufactured.
- the organic peroxide (P) may be mixed in the step (a1), may be mixed in the step (a2), or the step (a1) and the step (a2). ). Preferably, it is mixed in step (a1).
- the organic peroxide (P) was mixed with the surface-treated inorganic filler (F T ) together with the unsaturated group-containing silane coupling agent (S). Although it is preferable, it may be mixed alone.
- the mixing amount of the organic peroxide (P) in the step (a1) is appropriately determined in consideration of the mixing amount in the entire step (a), and is, for example, 0 with respect to 100 parts by mass of the resin composition (RC). 0.05 to 0.6 parts by mass, preferably 0.05 to 0.4 parts by mass, and particularly preferably 0.1 to 0.25 parts by mass. More preferably, it is 0.1 to 0.3 parts by mass.
- the organic peroxide (P) is mixed in the step (a1), the organic peroxide is uniformly dispersed in the surface-treated inorganic filler (F T ), and the graft reaction occurs uniformly. An effect that gelled particles hardly occur is obtained.
- the mixture prepared in the step (a1) may be mixed with the resin composition (RC), the resin component (R), or oil, They may be mixed alone.
- the organic peroxide (P) is preferably mixed together with the resin component (R).
- the mixing amount of the organic peroxide (P) in the step (a2) is appropriately determined in consideration of the mixing ratio in the entire step (a), and is set to zero or a part of the planned mixing amount.
- the inorganic filler (F) contains an inorganic filler other than the surface treated inorganic filler (F T ), for example, the surface untreated inorganic filler (F U ), the surface untreated inorganic filler (F U ) Is preferably added after mixing the resin composition (RC), the unsaturated group-containing silane coupling agent (S), and the inorganic filler (F). That is, the surface untreated inorganic filler (F U ) is preferably mixed last in the step (a) and the step (a2). When the surface untreated inorganic filler (F U ) is finally mixed, the unsaturated group-containing silane coupling agent (S) can be bonded to the surface treated inorganic filler (F T ).
- the silane master batch is manufactured by performing the step (a).
- the step (b) is then performed in which the silane master batch and the silanol condensation catalyst (C) are mixed to obtain a mixture.
- the mixing amount of the silanol condensation catalyst (C) is preferably 0.0001 to 0.5 parts by mass, more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the resin component (R).
- the blending amount of the silanol condensation catalyst (C) is less than 0.0001 parts by mass, the crosslinking reaction due to the condensation reaction of the unsaturated group-containing silane coupling agent (S) is difficult to proceed, and the heat resistance of the heat-resistant silane crosslinked resin molded product. Is not sufficiently improved, the productivity is lowered, and the crosslinking reaction may be uneven.
- the silanol condensation reaction proceeds very fast, partial gelation occurs, and the appearance and resin physical properties of the heat-resistant silane crosslinked resin molded product may be deteriorated.
- the compounding quantity of the silanol condensation catalyst (C) in a catalyst masterbatch is suitably set so that the compounding quantity with respect to the resin component (R) may become the said range.
- the silane master batch and the silanol condensation catalyst are mixed.
- the mixing conditions at this time are appropriately selected depending on the mixing method of the silanol condensation catalyst (C). That is, when the silanol condensation catalyst is mixed alone with the silane master batch, the mixing condition is set to the melt mixing condition of the resin component.
- the silanol condensation catalyst when mixing a silanol condensation catalyst as a catalyst masterbatch, it is melt-mixed with a silane masterbatch.
- the melt mixing at this time is basically the same as in step (a).
- the melting temperature is appropriately selected according to the melting temperature of the carrier resin (E).
- the kneading temperature is preferably 80 to 250 ° C., more preferably 100 to 240 ° C.
- the kneading conditions such as kneading time can be set as appropriate.
- This process (b) should just be a process of mixing a silane masterbatch and a silanol condensation catalyst (C), and obtaining a mixture, and may melt-mix these.
- the step (b) is preferably a step in which a catalyst masterbatch containing a silanol condensation catalyst (C) and a carrier resin (E) is melt-mixed with a silane masterbatch.
- the mixing amount of the carrier resin (E) in the catalyst masterbatch can accelerate silane crosslinking quickly, and is less likely to cause gelation during molding, with respect to 100 parts by mass of the resin composition (RC).
- the amount is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 1 to 40 parts by mass.
- the resin composition (RC) is 99 to 80 parts by mass, preferably 98 to 94 parts by mass in the step (a).
- the step (b) 1 to 20 parts by mass, preferably 2 to 6 parts by mass (total 100 parts by mass) are mixed.
- the compounding quantity of the silanol condensation catalyst (C) in a catalyst masterbatch is suitably set so that the compounding quantity with respect to a resin composition (RC) may become the said range.
- the catalyst masterbatch and the silane masterbatch are melt kneaded while heating.
- this melt-kneading there is a resin component (R) whose melting point cannot be measured by DSC or the like, for example, an elastomer.
- the resin component (R) and the organic peroxide (P) is kneaded.
- the carrier resin (E) is preferably melted to disperse the silanol condensation catalyst (C).
- the kneading conditions such as kneading time can be set as appropriate.
- heat silane crosslinkable resin composition of the present invention is a composition obtained by carrying out steps (a) and (b), the resin component (R), a surface-treated inorganic filler (F T ) And an unsaturated group-containing silane coupling agent (S) as a raw material component.
- 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 step (c) may be omitted if a heat-resistant silane cross-linkable resin composition is prepared, and is performed if a heat-resistant silane cross-linked resin molded article is prepared.
- This process (c) should just be able to shape
- 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 (c) can be carried out simultaneously or sequentially with the step (b).
- a series of processes can be employed in which a silane masterbatch and a catalyst masterbatch are melt-kneaded in a coating apparatus and then coated on, for example, an extruded wire or fiber and formed into a desired shape. In this way, a molded body of the heat-resistant silane crosslinkable resin composition of the present invention is obtained.
- the step (d) is then performed in which the obtained molded product is brought into contact with water to obtain a heat-resistant silane cross-linked resin molded product.
- the process itself in this step (d) can be performed by a usual method.
- the hydrolyzable silane coupling agent or unsaturated group-containing silane coupling agent (S) is hydrolyzed, and the hydrolyzable silane coupling agent is passed through the silanol condensation catalyst (C). And / or unsaturated group containing silane coupling agent (S) condenses, and forms a crosslinked structure.
- the condition of contacting with moisture proceeds only by storing at room temperature, but in order to further accelerate the crosslinking, it may be immersed in warm water, placed in a moist heat bath, or exposed to high temperature steam. Moreover, you may apply a pressure in order to permeate
- the manufacturing method of the heat resistant silane crosslinked resin molding of this invention is implemented, and a heat resistant silane crosslinked resin molding is manufactured from the heat resistant silane crosslinking resin composition of this invention. Therefore, the heat-resistant silane cross-linked resin molded product of the present invention is a molded product obtained by carrying out the step (a), the step (b), the step (c) and the step (d), and the resin component (R ), A surface-treated inorganic filler (F T ) and an unsaturated group-containing silane coupling agent (S) as a raw material component.
- the resin component (R) is grafted to the unsaturated group-containing silane coupling agent (S) in the presence of the organic peroxide (P) component when heated and kneaded, and at the same time, the surface-treated inorganic filler (F T 1 ) are bonded to each other via the unsaturated group-containing silane coupling agent (S), or bonded to the resin component (R) via the unsaturated group-containing silane coupling agent (S).
- a large amount of the ring agent (S) is present, and a molded product having a high degree of crosslinking and containing a large amount of the surface-treated inorganic filler (F T ) can be obtained without impairing the extrusion processability during molding. Therefore, it can have both heat resistance, flexibility and appearance while ensuring excellent flame retardancy.
- An unsaturated group-containing silane coupling agent is further added to the surface-treated inorganic filler (F T ) that has been surface-treated with a fatty acid and / or a phosphate ester before and / or during kneading with the resin component (R).
- Mixing (S) suppresses volatilization of the unsaturated group-containing silane coupling agent (S) during kneading and also bonds the unsaturated group-containing silane to the surface-treated inorganic filler (F T ) with a strong bond.
- An unsaturated group-containing silane coupling agent (S) that is bonded to the coupling agent (S) with a weak bond can be formed.
- the resin is obtained by a silane coupling agent having a strong bond with the filler.
- the unsaturated group-containing silane coupling agent (S) can create a bond between the component (R) and the surface-treated inorganic filler (F T ) (reaction k).
- the unsaturated group-containing silane coupling agent (S) having a weak bond with the surface-treated inorganic filler (F T ) is bonded to the resin component (R) by a graft reaction (reaction m).
- the unsaturated group-containing silane coupling agent (S) grafted by such (reaction m) is then mixed with the silanol condensation catalyst (C) and brought into contact with moisture to cause a condensation reaction to cause crosslinking (reaction n). ).
- the unsaturated group-containing silane coupling agent (S) is bound to the surface-treated inorganic filler (F T ) by a strong bond. Inhibits. As a result, there are relatively many unsaturated group-containing silane coupling agents (S) that are bonded to the surface-treated inorganic filler (F T ) by weak bonds.
- the surface treatment inorganic fillers (F T ) through the unsaturated group-containing silane coupling agent (S) can be significantly suppressed
- the surface treatment inorganic can be achieved by (reaction m) and (reaction n).
- Many bonds between the resin components (R) through the filler (F T ) can be created. That is, as described above, it is possible to have both heat resistance, flexibility and appearance while ensuring excellent flame retardancy.
- the presence of the unsaturated group-containing silane coupling agent (S) that is bonded to the surface-treated inorganic filler (F T ) with a strong bond, and the unsaturated group-containing silane that is bonded to the surface-treated inorganic filler (F T ) with a weak bond The abundance of the coupling agent (S) can be adjusted in a well-balanced manner. Thus, by adjusting both the surface treatment amount of the surface-treated inorganic filler (F T ) with the fatty acid and / or phosphate ester and the mixed amount of the unsaturated group-containing silane coupling agent (S) to a specific range.
- reaction k reaction k
- reaction m reaction m
- the inorganic filler (F) is stable even after long-term storage, and can contribute to the stable performance of the heat-resistant silane cross-linked resin molded article and the heat-resistant silane cross-linkable resin composition.
- the unsaturated group-containing silane coupling is weakly bonded to the surface treated inorganic filler (F T ).
- the amount of the agent (S) increases more than necessary. Therefore, when the surface-treated inorganic filler (F U ) is surface-treated with too much hydrolyzable silane coupling agent, the unsaturated group-containing silane coupling agent (S) volatilizes and the heat-resistant silane crosslinked resin molded article is formed. The degree of crosslinking and mechanical strength are reduced.
- the manufacturing method of the present invention is applied to the manufacture of products that require heat resistance (including semi-finished products, parts, and members), products that require strength, products that require short-term heat resistance, and rubber materials. can do.
- 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.
- the production method of the present invention is particularly applied to the production of electric wires and optical cables, and these coatings can be formed.
- the heat-resistant silane crosslinkable resin composition of the present invention is coated in a desired shape while being melt kneaded in an extrusion coating apparatus.
- Such a molded article is a highly heat resistant high temperature non-melting cross-linking composition added with a large amount of inorganic filler, using a general-purpose extrusion coating apparatus without using a special machine such as an electron beam cross-linking machine, It can be produced by extrusion coating around the periphery or around conductors that are longitudinally or twisted with tensile strength fibers.
- any conductor such as an annealed copper single wire or stranded wire can be used as the conductor.
- a conductor plated with tin or an enamel-covered insulating layer may be used as the conductor.
- the thickness of the insulating layer formed around the conductor is not particularly limited, but is usually 0. It is about 15 mm to 8 mm.
- NUC6510 is an ethylene-ethyl acrylate resin (EA content 22 mass%) manufactured by Dow Chemical Japan
- Mitsui 3092EPM is an ethylene-butylene-diene manufactured by Mitsui Chemicals (trade name, ethylene-propylene-diene rubber, ethylene content 66 mass%) It was used.
- “surface treated inorganic filler (FT) 1-27” and “surface untreated inorganic filler (TU) 1” shown in Table 1 were prepared.
- “Surface Treatment Inorganic Filler (FT) 1-27” is a metal hydrate shown in “Type of Filler” in Table 1 in “Silane Treatment Amount (mass%) with respect to Filler (FT)” shown in Table 1.
- Stearic acid behenic acid (also called behenic acid), oleic acid, phosphoric acid ester (compound name: stearyl phosphoric acid ester (manufactured by NOF Corporation) and vinyl methoxysilane (KBM1003 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)) It was prepared by surface treatment in advance with at least one of the above.
- the surface-treated inorganic filler (FT) 23 is a mixture of 67% by mass of magnesium hydroxide that has been surface-treated with 0.5% by mass of stearic acid and 33% by mass of untreated surface calcium carbonate.
- the unsaturated group-containing silane coupling agent (S) “KBM1003” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane) was used.
- the organic peroxide (P) “DCP” (trade name, manufactured by Nippon Kayaku Co., Ltd., dicumyl peroxide (decomposition temperature 151 ° C.)) was used.
- Dioctyltin laurate (“ADK STAB OT-1” (trade name), manufactured by ADEKA) was used as the silanol condensation catalyst (C).
- the carrier resin (E) a part (5 parts by mass) of “UE320” as the resin component (R) was used.
- antioxidant hindered phenol antioxidant
- Irganox 1010 trade name, manufactured by Nagase Sangyo Co., Ltd., pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] Propionate] was used.
- the organic peroxide (P) in the mixing amount (parts by mass) described in “Organic peroxide (P)” in the column is put into a closed ribbon blender and mixed at room temperature for 10 minutes to obtain a mixture. (Step (a1)).
- Example 19 to 23 the inorganic filler (F), the unsaturated group-containing silane coupling agent (S), and the organic peroxide (P) were mixed with a shell mixer at room temperature. The mixture was obtained by mixing with a mixer.
- the treatment amount of the unsaturated group-containing silane coupling agent (S) with respect to the surface-treated inorganic filler (F T ) is substantially 5% by mass.
- Example 22 is 2.5 mass% and Example 23 is 7.5 mass%.
- the calculated values obtained by converting the mixing amount of the organic peroxide (P) mixed in the step (a1) into the mixing amount with respect to 100 parts by mass of the resin composition (RC) are “resin compositions (RC) in Table 2 and Table 3.
- the amount of organic peroxide (P) mixed with (calculated value) ”column.
- silane masterbatch it was confirmed that almost all of the unsaturated group-containing silane coupling agent (S) was grafted to the resin component (R) by decomposition of the organic peroxide (P).
- carrier resin (E) “UE320”, silanol condensation catalyst (C) “dioctyltin laurylate” and antioxidant “Irganox 1010” at a mixing ratio shown in Table 2 and Table 3 at 180 ° C. to Separately melted and mixed at 190 ° C. with a Banbury mixer, and discharged at a material discharge temperature of 180 ° C. to 190 ° C. to obtain a catalyst master batch.
- surface-treated inorganic filler (FT) 1” or “surface-untreated inorganic filler (FU) 1” was added at a ratio shown in Table 2 to prepare a catalyst master batch.
- the silane masterbatch and the catalyst masterbatch are shown in Tables 2 and 3, ie, 95 parts by mass of the resin component (R) of the silane masterbatch and 5 parts by mass of the carrier resin (E) of the catalyst masterbatch.
- the mixture was melt-mixed at 180 ° C. by a Banbury mixer at a ratio of (the total amount of the resin composition (RC) was 100 parts by mass) (step (b)).
- step (b) a heat-resistant silane crosslinkable resin composition was prepared.
- Tables 2 and 3 show “number of blended parts of silane masterbatch” and “number of blended parts of catalyst masterbatch”.
- An electric wire having an outer diameter of 2.8 mm was obtained by covering with 1 mm (step (c)). The electric wire was left in an atmosphere of temperature 80 ° C. and humidity 95% for 24 hours (step (d)).
- cover consisting of a heat resistant silane crosslinked resin molding was manufactured.
- the manufactured wires were evaluated as follows, and the results are shown in Tables 2 and 3. ⁇ Tensile properties> The tensile properties of the wires were evaluated. This tensile test was performed based on UL1581, with a distance between marked lines of 25 mm and a tensile speed of 500 mm / min, and measured elongation at break (%), tensile strength (unit: MPa), and 100% modulus (unit: MPa). In addition, elongation at break evaluates the elongation characteristics, 100 (%) or more was accepted, and tensile strength was 8 (MPa) or more. The 100% modulus is for evaluating flexibility, and 10 (MPa) or less was considered flexible and passed. The 100% modulus is one of the indices for evaluating flexibility, and it can be said that when it is 8 (MPa) or less, the flexibility is excellent, and when it is 7 (MPa) or less, the flexibility is very excellent.
- Heat deformation test was conducted as the heat resistance of the electric wires. This heat deformation test (%) was performed at a measurement temperature of 180 ° C. and a load of 5 N based on UL1581. In this heat deformation test, 70% or less was accepted, but 50% or less is more preferable.
- Extrusion appearance characteristics of electric wire An extrusion appearance test was conducted as an extrusion appearance characteristic of the electric wire.
- Extrusion appearance 1 observed the extrusion appearance when manufacturing an electric wire.
- the appearance was good as “A”
- the appearance was slightly bad as “B”
- “ B ”and above were accepted as product levels.
- Extrusion appearance 2 observed the extrusion appearance when manufacturing the electric wire. Specifically, “A” indicates that the appearance was good when produced with a 65 mm extruder at a linear speed of 80 m, “B” indicates that the appearance was slightly poor, and “C” indicates that the appearance was remarkably poor. It was. Although “B” or higher was accepted as the product level, the extrusion appearance 2 is a severe test in which the linear velocity is increased to 8 times for the purpose of improving productivity, and therefore this test does not necessarily need to pass.
- Examples 1 to 29 were able to satisfy both tensile properties, particularly elongation at break and 100% modulus, heat deformation test, and extrusion appearance. That is, it was found that the heat-resistant silane cross-linked resin molded body according to the present invention provided as a wire covering of Examples 1 to 29 was excellent in all of flexibility, heat resistance, elongation characteristics and appearance. In addition, it can be easily understood that the heat resistance is excellent from the content of the inorganic filler (F). On the other hand, Comparative Examples 1 to 7 were inferior in any of the tensile properties, the heat deformation test, and the 100% modulus, and these could not be juxtaposed.
Abstract
Description
具体的には、例えば、ハロゲンフリーの耐熱性シラン架橋樹脂の製造方法は、ポリオレフィン樹脂に不飽和基を有するシランカップリング剤をグラフトさせたシランマスターバッチと、ポリオレフィン及び無機フィラーを混練した耐熱性マスターバッチと、シラノール縮合触媒を含有した触媒マスターバッチとを溶融混合させる方法がある。
したがって、多量の無機フィラーを用いる場合には、連続混練機、加圧式ニーダー、バンバリーミキサーなどの密閉型ミキサーを用いるのが一般的になっている。
また、本発明は、この耐熱性シラン架橋樹脂成形体を形成可能な耐熱性シラン架橋性樹脂組成物及びその製造方法を提供することを課題とする。
さらに、本発明は、耐熱性シラン架橋樹脂成形体の製造方法で得られた耐熱性シラン架橋樹脂成形体を用いた耐熱性製品を提供することを課題とする。
(1)樹脂成分(R)を含有する樹脂組成物(RC)100質量部に対して、有機過酸化物(P)0.01~0.6質量部と、表面未処理無機フィラー(FU)の0.1~4.0質量%の、脂肪酸及びリン酸エステルの少なくとも1種で前記表面未処理無機フィラー(FU)を表面処理して得られる表面処理無機フィラー(FT)を含む無機フィラー(F)10~400質量部と、表面処理無機フィラー(FT)100質量部に対して0.5~18.0質量部の不飽和基含有シランカップリング剤(S)とを有機過酸化物(P)の分解温度以上で溶融混合してシランマスターバッチを調製する工程(a)と、シランマスターバッチとシラノール縮合触媒(C)とを混合して混合物を得る工程(b)と、前記混合物を成形して成形体を得る工程(c)と、前記成形体を水と接触させて耐熱性シラン架橋樹脂成形体を得る工程(d)とを有する耐熱性シラン架橋樹脂成形体の製造方法。
(2)前記表面処理無機フィラー(FT)が、前記脂肪酸及び前記リン酸エステルの少なくとも1種0.1~4.0質量%と、加水分解性シランカップリング剤0.05~1.0質量%とで表面処理して得られる(1)に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(3)前記表面処理無機フィラー(FT)が、表面未処理無機フィラー(FU)に対して0.1~1.5質量%の前記脂肪酸で表面処理して得られる(1)又は(2)に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(4)前記表面処理無機フィラー(FT)が、表面未処理無機フィラー(FU)に対して0.1~2.8質量%の前記リン酸エステルで表面処理して得られる(1)~(3)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(5)前記加水分解性シランカップリング剤が、不飽和基含有シランカップリング剤(S)である(2)~(4)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(6)前記無機フィラー(F)が、表面処理されていない表面未処理無機フィラー(FU)を含んでいる(1)~(5)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(7)前記無機フィラー(F)が、その全質量に対して30~100質量%の前記表面処理無機フィラー(FT)を含有している(1)~(6)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(8)前記表面処理無機フィラー(FT)の前記表面未処理無機フィラー(FU)が、金属水和物の少なくとも1種を含んでいる(1)~(7)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(9)前記金属水和物が、水酸化マグネシウムを含んでいる(8)に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(10)前記金属水和物が、炭酸カルシウムを含んでいる(8)に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(11)前記樹脂成分(R)が、前記樹脂組成物(RC)中に20~100質量%含有している(1)~(10)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(12)前記工程(a)が、前記無機フィラー(F)と前記不飽和基含有シランカップリング剤(S)と混合し、次いで、有機過酸化物(P)をその分解温度以下の温度で混合して混合物を調製する工程(a1)と、得られた混合物と前記樹脂組成物(RC)とを前記有機過酸化物(P)の分解温度以上で溶融混合して、シランマスターバッチを調製する工程(a2)とを有している(1)~(11)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(13)前記工程(b)が、前記シランマスターバッチと、前記シラノール縮合触媒(C)及びキャリア樹脂(E)を含有する触媒マスターバッチとを混合する工程である(1)~(12)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(14)前記工程(a)が、密閉型のミキサーで溶融混合する(1)~(13)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
(15)前記工程(a)と前記工程(b)とを有し、少なくとも前記工程(c)を有しない耐熱性シラン架橋性樹脂組成物の製造方法。
(16)(15)に記載の耐熱性シラン架橋性樹脂組成物の製造方法により製造された耐熱性シラン架橋性樹脂組成物。
(17)(1)~(14)のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法により製造された耐熱性シラン架橋樹脂成形体。
(18)(17)に記載の耐熱性シラン架橋樹脂成形体を含む耐熱性製品。
(19)前記耐熱性シラン架橋樹脂成形体が、電線又は光ファイバケーブルの被覆として設けられている(18)に記載の耐熱性製品。
本発明の上記及び他の特徴及び利点は、下記の記載からより明らかになるであろう。
本発明に使用される樹脂組成物(RC)は、樹脂成分(R)と、所望により可塑剤又は軟化剤として使用される各種オイルとを含有している。樹脂組成物(RC)における樹脂成分(R)の含有量は、耐熱性能、架橋性能および強度の点で、樹脂組成物(RC)の全質量に対して、20質量%以上であるのが好ましく、45%質量以上であるのがさらに好ましく、60質量%以上であるのが特に好ましい。樹脂成分(R)の含有量は、最大で100質量%であるが、たとえば、80質量%以下にすることもできる。
樹脂組成物(RC)は、柔軟性を保持し、外観を良好に保つためにはオイルの導入が好ましい。その際に樹脂組成物(RC)におけるオイルは、樹脂組成物(RC)の全質量に対して、80質量%を上限に設定されることが好ましく、55質量%以下であるのがより好ましく、40質量%以下であるのが特に好ましい。
なお、樹脂組成物(RC)は樹脂成分(R)及びオイルに加えて他の成分、例えば、後述する各種添加剤、溶媒などを含有していてもよい。
樹脂成分(R)としては、ポリオレフィン系樹脂(PO)、ポリエステル樹脂、ポリアミド系樹脂(PA)、ポリスチレン系樹脂(PS)、ポリオール系樹脂などが挙げられるが、その中でもポリオレフィン樹脂が好ましい。この樹脂成分(R)は、1種単独で使用してもよく、2種以上を併用してもよい。
酸共重合成分を有するポリオレフィン共重合体としては、例えば、エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体、エチレン-(メタ)アクリル酸アルキル共重合体などが挙げられる。この中でもエチレン-酢酸ビニル共重合体、エチレン-アクリル酸メチル共重合体、エチレン-アクリル酸エチル共重合体、エチレン-アクリル酸ブチル共重合体が好ましく、さらには無機フィラー(F)への受容性及び耐熱性の点から、エチレン-酢酸ビニル共重合体が好ましい。酸共重合成分を有するポリオレフィン共重合体は1種単独で使用され、又は2種以上が併用される。
芳香族ビニル化合物としては、例えば、スチレン、p-(tert-ブチル)スチレン、α-メチルスチレン、p-メチルスチレン、ジビニルベンゼン、1,1-ジフェニルスチレン、N,N-ジエチル-p-アミノエチルスチレン、ビニルトルエン、p-(tert-ブチル)スチレンなどが挙げられる。芳香族ビニル化合物は、これらの中でも、スチレンが好ましい。この芳香族ビニル化合物は、1種単独で使用され、又は2種以上が併用される。
共役ジエン化合物としては、例えば、ブタジエン、イソプレン、1,3-ペンタジエン、2,3-ジメチル-1,3-ブタジエンなどが挙げられる。共役ジエン化合物、これらの中でも、ブタジエンが好ましい。この共役ジエン化合物は、1種単独で使用され、又は2種以上が併用される。
樹脂組成物(RC)に所望により含有されるオイルは、樹脂成分(R)の可塑剤又はゴムの鉱物油軟化剤としてのオイルが挙げられる。このオイルは、不飽和基含有シランカップリング剤(S)とは反応しないので、樹脂成分(R)には包含されないが、樹脂組成物(RC)に含有していてもよい。鉱物油軟化剤は、芳香族環、ナフテン環及びパラフィン鎖の三者の組み合わさった炭化水素からなる混合物のオイルである。パラフィン鎖炭素数が全炭素数の50%以上を占めるものをパラフィンオイル、ナフテン環炭素数が30~40%のものはナフテンオイル、芳香族炭素数が30%以上のものはアロマオイル(芳香族オイルともいう)と呼ばれて区別されている。
これらの中でも、液状又は低分子量の合成軟化剤、パラフィンオイル、ナフテンオイルが好適に用いられ、特にパラフィンオイルが好適に用いられる。このようなオイルとして、例えば、ダイアナプロセスオイルPW90、PW380(いずれも商品名、昭和シェル石油社製)、コスモニュートラル500(コスモ石油社製)などが挙げられる。
有機過酸化物(P)としては、一般式:R1-OO-R2、R1-OO-C(=O)R3、R3C(=O)-OO(C=O)R4で表される化合物が好ましい。ここで、R1、R2、R3及びR4は各々独立にアルキル基、アリール基、アシル基を表す。このうち、本発明においては、R1、R2、R3及びR4がいずれもアルキル基であるか、いずれかがアルキル基で残りがアシル基であるものが好ましい。
本発明において、有機過酸化物(P)の分解温度とは、単一組成の有機過酸化物(P)を加熱したとき、ある一定の温度又は温度域でそれ自身が2種類以上の化合物に分解反応を起こす温度を意味し、DSC法などの熱分析により、窒素ガス雰囲気下で5℃/分の昇温速度で、室温から加熱したとき、吸熱又は発熱を開始する温度をいう。
工程(a)で用いる無機フィラー(F)は、表面処理無機フィラー(FT)を含むものであるが、表面処理無機フィラー(FT)以外の無機フィラーを含むこともできる。例えば、本発明では、表面処理剤で表面処理されていない表面未処理無機フィラー(FU)、加水分解性シランカップリング剤などで表面処理された無機フィラーなどを用いることができる。
表面未処理無機フィラー(FU)は、表面処理無機フィラー(FT)のベースとなる、表面処理されていない無機フィラーである。このような表面未処理無機フィラー(FU)としては、特に制限がなく、例えば、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、酸化アルミニウム、窒化アルミニウム、ほう酸アルミニウム、水和珪酸アルミニウム、アルミナ、水和珪酸マグネシウム、塩基性炭酸マグネシウム、ハイドロタルサイトなどの、水酸基又は結晶水を有する化合物のような金属水和物が挙げられる。他にも、表面未処理無機フィラー(FU)として、例えば、窒化ほう素、シリカ(結晶質シリカ、非晶質シリカなど)、カーボン、クレー、酸化亜鉛、酸化錫、酸化チタン、酸化モリブデン、三酸化アンチモン、シリコーン化合物、石英、タルク、ほう酸亜鉛、ホワイトカーボン、硼酸亜鉛、ヒドロキシスズ酸亜鉛、スズ酸亜鉛などが挙げられる。これらの中でも、金属水和物が好ましく、水酸化マグネシウム、炭酸カルシウム、水酸化アルミニウム、炭酸マグネシウムなどが特に好ましい。
表面処理無機フィラー(FT)は、表面未処理無機フィラー(FU)を脂肪酸及びリン酸エステルの少なくとも1種、又は、少なくともこれら1種と加水分解性シランカップリング剤で表面処理したものである。表面未処理無機フィラー(FU)を予め表面処理しておくと、不飽和基含有シランカップリング剤(S)と表面処理無機フィラー(FT)とが強く結合するのを抑えて、ある程度の弱い結合で表面処理無機フィラー(FT)と結合する不飽和基含有シランカップリング剤(S)を作り出すことができる。この弱い結合で表面処理無機フィラー(FT)と結合している不飽和基含有シランカップリング剤(S)によって、ある程度の架橋度を有する耐熱性シラン架橋樹脂成形体を得ることができる。これにより、高い耐熱性が発揮されるにもかかわらず、柔軟性及び伸び特性も確保できる。したがって、表面未処理無機フィラー(FU)を予め表面処理する脂肪酸及びリン酸エステルの少なくとも1種の表面処理量は制限される。具体的には、表面未処理無機フィラー(FU)は、後述するように、その100質量部に対して0.1~4.0質量%の脂肪酸及びリン酸エステルの少なくとも1種で表面処理されている。
末端にアミノ基を有する加水分解性シランカップリング剤としては、アミノアルキル基を有するものが挙げられ、具体的には、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、N-フェニル-3-アミノプロピルトリメトキシシランなどが挙げられる。末端にビニル基又は(メタ)アクリロイルオキシ基を有するものは、例えば、後述する不飽和基含有シランカップリング剤(S)が挙げられる。
末端にグリシジル基を有するものは、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどが挙げられる。
リン酸エステル(化合物名:ステアリルリン酸エステル)で表面処理された水酸化マグネシウムとして、キスマ5J(協和化学工業社製)などが挙げられる。
不飽和基含有シランカップリング剤(S)としては、特に限定されるものではなく、シラン架橋法に用いられる不飽和基を有するシランカップリング剤を使用することができる。このような不飽和基含有シランカップリング剤(S)としては、例えば、下記一般式(1)で表される不飽和基含有シランカップリング剤(S)を好適に用いることができる。
不飽和基含有シランカップリング剤(S)は、単独で用いられてもよく、溶剤で希釈された液で用いられてもよい。
シラノール縮合触媒(C)は、樹脂成分(R)にグラフト化された不飽和基含有シランカップリング剤(S)を縮合反応により水分の存在下で結合させる働きがある。このシラノール縮合触媒(C)の働きに基づき、不飽和基含有シランカップリング剤(S)を介して、樹脂成分(R)同士が架橋される。その結果、耐熱性に優れた耐熱性シラン架橋樹脂成形体が得られる。
触媒マスターバッチに所望により添加されるキャリア樹脂(E)としては、特に限定されないが、樹脂組成物(RC)に含有される樹脂成分(R)の一部を用いることもでき、この樹脂成分(R)とは別の樹脂を用いることもできる。樹脂成分(R)と別に用いるキャリア樹脂(E)としては、樹脂組成物(RC)の樹脂成分(R)と同様の樹脂が挙げられる。キャリア樹脂(E)は樹脂成分(R)の一部を用いるのが好ましい。キャリア樹脂(E)は、シラノール縮合触媒(C)と親和性がよく耐熱性にも優れる点で、ポリオレフィン系樹脂であるのが好ましく、ポリエチレンであるのが特に好ましい。このキャリア樹脂(E)は表面未処理無機フィラー(FU)やその他のフィラーを共に用いてもよい。
キャリア樹脂(E)と共に用いられる、すなわち不飽和基含有シランカップリング剤(S)の後に添加される無機フィラーは、樹脂組成物(RC)の樹脂成分(R)100質量部に対して350質量部以下が好ましい。無機フィラーの添加量が多すぎるとシラノール縮合触媒(C)が分散しにくく、架橋反応が進行しにくくなることがある。
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は、電線、電気ケーブル、電気コード、シート、発泡体、チューブ、パイプにおいて、一般的に使用されている各種の添加剤、例えば、架橋助剤、酸化防止剤、滑剤、金属不活性剤、充填剤、他の樹脂などが本発明の目的を損なわない範囲で適宜配合されていてもよい。これらの添加剤は、いずれの成分に含有されてもよいが、触媒マスターバッチに含有されるのがよい。特に酸化防止剤、金属不活性剤は、無機フィラー(F)に混合された不飽和基含有シランカップリング剤(S)が樹脂成分(R)へのグラフトを阻害しないように、触媒マスターバッチにキャリア樹脂(E)と共に混合されるのが好ましい。このとき、架橋助剤は実質的に含有していないことが好ましい。特に架橋助剤はシランマスターバッチを調製する工程(a)において実質的に混合されないのが好ましい。架橋助剤を加えると、混練り中に有機過酸化物(P)により架橋助剤が反応し、樹脂成分(R)同士の架橋が生じ、ゲル化が生じて耐熱性シラン架橋樹脂成形体の外観が著しく低下することがある。また、不飽和基含有シランカップリング剤(S)の樹脂成分(R)へのグラフト反応が進行しにくく、最終的な耐熱性シラン架橋樹脂成形体の耐熱性が得られなくなるおそれがある。ここで、実質的に含有しない又は混合されないとは、架橋助剤を積極的に添加又は混合しないことを意味し、不可避的に含有又は混合されることを除外するものではない。
滑剤としては、炭化水素系、シロキサン系、脂肪酸系、脂肪酸アミド系、エステル系、アルコール系、金属石けん系などが挙げられる。これらの滑剤はキャリア樹脂(E)に加えた方がよい。
充填剤(難燃(助)剤を含む。)としては、無機フィラー(F)、表面未処理無機フィラー(FU)、表面処理無機フィラー(FT)及びその他の無機フィラー以外の充填剤が挙げられる。これらの充填剤は、無機フィラー(F)と共に不飽和基含有シランカップリング剤(S)を混合させる際に混合されてもよく、触媒マスターバッチに混合されてもよい。
本発明の「耐熱性シラン架橋樹脂成形体の製造方法」は、上記の通り、工程(a)と工程(b)と工程(c)と工程(d)とを有している。一方、本発明の「耐熱性シラン架橋性樹脂組成物の製造方法」は、上記の通り、工程(a)と工程(b)とを有し、少なくとも工程(c)、所望により工程(d)を有していない。
特に、脂肪酸の表面処理量は、0.1~1.5質量%であるのが好ましく、0.15~1質量%であるのがさらに好ましく、リン酸エステルの表面処理量は、0.1~2.8質量%であるのが好ましく、0.2~2.0質量%であるのがさらに好ましい。
工程(a)は、局所的な架橋反応によるブツの発生を防止できる点で、無機フィラー(F)と不飽和基含有シランカップリング剤(S)と混合し、有機過酸化物(P)をその分解温度以下の温度で有機過酸化物(P)をさらに混合、分散して混合物を調製する工程(a1)と、得られた混合物と樹脂成分(R)とを有機過酸化物(P)の分解温度以上の温度で溶融してシランマスターバッチを調製する工程(a2)とを有しているのが好ましい。
このときの乾式処理及び湿式処理は混合対象物が異なること以外は表面処理無機フィラー(FT)を調製する際の乾式処理及び湿式方法と基本的に同様である。湿式処理では、不飽和基含有シランカップリング剤(S)が強く表面処理無機フィラー(FT)と結合しやすくなるため、その後の縮合反応が進みにくくなることがある。一方、乾式処理は、表面処理無機フィラー(FT)と不飽和基含有シランカップリング剤(S)との結合が比較的弱いため効率的に架橋が進みやすくなることがある。
工程(a1)において有機過酸化物(P)を混合する場合は、有機過酸化物(P)は、不飽和基含有シランカップリング剤(S)と共に表面処理無機フィラー(FT)に混合した方が好ましいが、単独で混合されてもよい。
この工程(b)は、シランマスターバッチとシラノール縮合触媒(C)とを混合して混合物を得る工程であればよく、これらを溶融混合してもよい。本発明の製造方法において、工程(b)はシラノール縮合触媒(C)及びキャリア樹脂(E)を含有する触媒マスターバッチとシランマスターバッチとを溶融混合する工程であるのが好ましい。
なお、触媒マスターバッチにおけるシラノール縮合触媒(C)の配合量は、樹脂組成物(RC)に対する配合量が前記範囲となるように適宜に設定される。
水分と接触させる条件は、常温で保管するだけで進行するが、架橋をさらに加速させるために、温水に浸水させたり、湿熱槽に入れたり、高温の水蒸気にさらしてもよい。また、その際に水分を内部に浸透させるために圧力を掛けてもよい。
すなわち、上述のように、優れた難燃性を確保しながらも耐熱性、柔軟性及び外観を併せ持つことができる。
したがって、本発明のように、脂肪酸及び/又はリン酸エステルの表面処理量、並びに、脂肪酸及び/又はリン酸エステルと共に使用する加水分解性シランカップリング剤の表面処理量を特定の範囲に設定することによって、表面処理無機フィラー(FT)と強い結合で結びつく不飽和基含有シランカップリング剤(S)の存在量と、表面処理無機フィラー(FT)と弱い結合で結びつく不飽和基含有シランカップリング剤(S)の存在量とをバランスよく調整できる。このように、表面処理無機フィラー(FT)の脂肪酸及び/又はリン酸エステルでの表面処理量及び不飽和基含有シランカップリング剤(S)の混合量を共に特定の範囲に調整することによって、これら(反応k)、(反応m)が互いにバランスよく相俟って、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に、高い耐熱性に加えて、優れた柔軟性、伸び特性及び外観をも付与することができる。また、無機フィラー(F)は、長期保管されても安定しており、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が安定した特性を発揮するのに貢献できる。
樹脂組成物(RC)の樹脂成分(R)として、
「エンゲージ7256」はダウケミカル日本社製の直鎖低密度ポリエチレン、
「UE320」は日本ポリエチレン社製のノバテックPE(商品名、直鎖低密度ポリエチレン)、
「EV180」は三井デュポンポリケミカル社製のエチレン-酢酸ビニル共重合樹脂(VA含有量33質量%)、
「セプトン4077」はクラレ社製のスチレン系エラストマー(スチレン含有量40%)、
「ダイアナプロセスオイルPW-90」は出光興産社製のパラフィンオイル、
「NUC6510」はダウケミカル日本社製のエチレン-エチルアクリレート樹脂(EA含有量22質量%)、
「三井3092EPM」は三井化学社製のエチレン-ブチレン-ジエン(商品名、エチレン-プロピレン-ジエンゴム、エチレン量66質量%)
を使用した。
「表面処理無機フィラー(FT) 1~27」は、表1の「フィラーの種類」に示す金属水和物を、表1に示す「フィラー(FT)に対するシラン処理量(質量%)」で、ステアリン酸、ベヘン酸(ベヘニン酸ともいう。)、オレイン酸、リン酸エステル(化合物名:ステアリルリン酸エステル(日油社製)及びビニルメトキシシラン(KBM1003(商品名、信越化学工業社製))の少なくとも1種により、予め表面処理して調製されたものである。
有機過酸化物(P)としては、「DCP」(商品名、日本化薬社製、ジクミルパーオキサイド(分解温度151℃))を使用した。
シラノール縮合触媒(C)として、ジオクチルスズラウリレート(「アデカスタブOT-1」(商品名)、ADEKA社製)を使用した。
キャリア樹脂(E)としては、樹脂成分(R)としての「UE320」の一部(5質量部)を使用した。
酸化防止剤(ヒンダードフェノール系酸化防止剤)として、「イルガノックス1010」(商品名、長瀬産業社製、ペンタエリトリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]を使用した。
まず、表1に記載の質量部の表面処理無機フィラー(FT)と、この表面処理無機フィラー(FT)100質量部に対して表2及び表3に示す「工程(a1)での混合量」欄の「(S)のフィラーに対する混合量」(質量%)で不飽和基含有シランカップリング剤(S)「KBM1003」とを東洋精機製10Lリボンブレンダーに投入して混合し、次いで、有機過酸化物(P)の分解温度以下の温度、具体的には室温で表面処理無機フィラー(FT)100質量部に対して表2及び表3に示す「工程(a1)での混合量」欄の「有機過酸化物(P)に記載の混合量(質量部)の有機過酸化物(P)を密閉型のリボンブレンダーに投入して、室温で10分混合して混合物を得た(工程(a1))。
得られたシランマスターバッチにおいて、有機過酸化物(P)の分解により不飽和基含有シランカップリング剤(S)はそのほぼ全量が樹脂成分(R)にグラフトしていることを確認した。
実施例28及び29は、「表面処理無機フィラー(FT) 1」又は「表面未処理無機フィラー(FU) 1」を表2に示す割合で添加して、触媒マスターバッチ調製した。
<引張特性>
電線の引張特性を評価した。この引張試験は、UL1581に基づき、標線間25mm、引張速度500mm/分で行い、破断時伸び(%)、引張強さ(単位:MPa)及び100%モジュラス(単位:MPa)を測定した。なお、破断時伸びは伸び特性を評価するものであり、100(%)以上を合格とし、引張強さは8(MPa)以上で合格とした。100%モジュラスは柔軟性を評価するものであり、10(MPa)以下を柔軟で合格とした。100%モジュラスは、柔軟性を評価する指標の1つで有り、8(MPa)以下であると柔軟性に優れ、7(MPa)以下であると柔軟性に非常に優れているといえる。
電線を加熱しても変形しにくい特性としての補強性を加熱変形試験によって評価した。この加熱変形試験(%)は、UL1581に基づいて、測定温度121℃、荷重5Nで行った。この加熱変形試験1は70%以下を合格としたが、50%以下がより好ましい。
電線の耐熱性として加熱変形試験を行った。この加熱変形試験(%)は、UL1581に基づいて、測定温度180℃、荷重5Nで行った。この加熱変形試験は70%以下を合格としたが、50%以下がより好ましい。
電線の押出外観特性として押出外観試験を行った。押出外観1は、電線を製造する際に押出外観を観察した。なお、25mm押出機にて線速10mで作成した際に外観が良好だったものを「A」、外観がやや悪かったものを「B」、外観が著しく悪かったものを「C」とし、「B」以上は製品レベルとして合格とした。
一方、比較例1~7は引張特性、加熱変形試験及び100%モジュラスのいずれかが劣り、これらを並立することができなかった。
Claims (19)
- 樹脂成分(R)を含有する樹脂組成物(RC)100質量部に対して、有機過酸化物(P)0.01~0.6質量部と、表面未処理無機フィラー(FU)の0.1~4.0質量%の、脂肪酸及びリン酸エステルの少なくとも1種で前記表面未処理無機フィラー(FU)を表面処理して得られる表面処理無機フィラー(FT)を含む無機フィラー(F)10~400質量部と、前記表面処理無機フィラー(FT)100質量部に対して0.5~18.0質量部の不飽和基含有シランカップリング剤(S)とを前記有機過酸化物(P)の分解温度以上で溶融混合して、シランマスターバッチを調製する工程(a)と、
前記シランマスターバッチとシラノール縮合触媒(C)とを混合して混合物を得る工程(b)と、
前記混合物を成形して成形体を得る工程(c)と、
前記成形体を水と接触させて耐熱性シラン架橋樹脂成形体を得る工程(d)とを有する耐熱性シラン架橋樹脂成形体の製造方法。 - 前記表面処理無機フィラー(FT)が、前記脂肪酸及び前記リン酸エステルの少なくとも1種0.1~4.0質量%と、加水分解性シランカップリング剤0.05~1.0質量%とで表面処理して得られる請求項1に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記表面処理無機フィラー(FT)が、表面未処理無機フィラー(FU)に対して0.1~1.5質量%の前記脂肪酸で表面処理して得られる請求項1又は請求項2に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記表面処理無機フィラー(FT)が、表面未処理無機フィラー(FU)に対して0.1~2.8質量%の前記リン酸エステルで表面処理して得られる請求項1~3のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記加水分解性シランカップリング剤が、不飽和基含有シランカップリング剤(S)である請求項2~4のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記無機フィラー(F)が、表面処理されていない表面未処理無機フィラー(FU)を含んでいる請求項1~5のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記無機フィラー(F)が、その全質量に対して30~100質量%の前記表面処理無機フィラー(FT)を含有している請求項1~6のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記表面処理無機フィラー(FT)の前記表面未処理無機フィラー(FU)が、金属水和物の少なくとも1種を含んでいる請求項1~7のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記金属水和物が、水酸化マグネシウムを含んでいる請求項8に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記金属水和物が、炭酸カルシウムを含んでいる請求項8に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記樹脂成分(R)が、前記樹脂組成物(RC)中に20~100質量%含有している請求項1~10のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記工程(a)が、前記無機フィラー(F)と前記不飽和基含有シランカップリング剤(S)と混合し、次いで、有機過酸化物(P)をその分解温度以下の温度で混合して混合物を調製する工程(a1)と、得られた混合物と前記樹脂組成物(RC)とを前記有機過酸化物(P)の分解温度以上で溶融混合して、シランマスターバッチを調製する工程(a2)とを有している請求項1~11のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記工程(b)が、前記シランマスターバッチと、前記シラノール縮合触媒(C)及びキャリア樹脂(E)を含有する触媒マスターバッチとを混合する工程である請求項1~12のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記工程(a)が、密閉型のミキサーで溶融混合する請求項1~13のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法。
- 前記工程(a)と前記工程(b)とを有し、少なくとも前記工程(c)を有しない耐熱性シラン架橋性樹脂組成物の製造方法。
- 請求項15に記載の耐熱性シラン架橋性樹脂組成物の製造方法により製造された耐熱性シラン架橋性樹脂組成物。
- 請求項1~14のいずれか1項に記載の耐熱性シラン架橋樹脂成形体の製造方法により製造された耐熱性シラン架橋樹脂成形体。
- 請求項17に記載の耐熱性シラン架橋樹脂成形体を含む耐熱性製品。
- 前記耐熱性シラン架橋樹脂成形体が、電線又は光ファイバケーブルの被覆として設けられている請求項18に記載の耐熱性製品。
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JP6219307B2 (ja) | 2017-10-25 |
EP2927268A4 (en) | 2016-08-10 |
CN104822744A (zh) | 2015-08-05 |
JPWO2014084048A1 (ja) | 2017-01-05 |
CN104822744B (zh) | 2018-03-20 |
EP2927268A1 (en) | 2015-10-07 |
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