JP2017145307A - Heat-resistant silane crosslinked resin molding and heat-resistant silane crosslinkable resin composition and method for producing the same, silane master batch, and heat-resistant product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant silane crosslinked resin molding capable of producing a molded product excellent in appearance and heat resistance even on wide molding and crosslinking conditions and a method for producing the same; a silane master batch and a heat-resistant silane crosslinkable resin composition capable of forming the heat-resistant silane crosslinked resin molding and a method for producing the same; and a heat-resistant product.SOLUTION: There are provided a method for producing a heat-resistant silane crosslinked resin molding which includes a step of mixing at least an inorganic filler and a silane coupling agent containing a specific amount of vinyltrimethoxysilane and vinyltriethoxysilane to prepare a mixture, and a step of melting and mixing the mixture and a base resin in the presence of an organic peroxide at a temperature of a decomposition temperature of the organic peroxide or higher to prepare a silane master batch; a heat-resistant silane crosslinked resin molding and a heat-resistant silane crosslinkable resin composition produced by the same; a silane master batch; and a heat-resistant product.SELECTED DRAWING: None

Description

  The present invention relates to a heat-resistant silane cross-linked resin molded body, a heat-resistant silane cross-linkable resin composition, a production method thereof, a silane masterbatch, and a heat-resistant product using the heat-resistant silane cross-linked resin molded body.

  Insulated wires, cables, cords, optical fiber cores, or optical fiber cords used for internal and external wiring of electrical and electronic equipment have various flame retardancy, mechanical properties (for example, tensile properties), etc. The characteristics are required. Examples of the material used for the coating layer of these wiring materials include a resin composition in which an inorganic filler such as magnesium hydroxide or aluminum hydroxide is blended in a large amount.

In addition, the wiring material may be heated to 80 to 105 ° C. or even 125 ° C. when used for a long time, and heat resistance against this is also required. In order to satisfy such a requirement, a method of crosslinking (crosslinking) the resin composition is taken.
Examples of the crosslinking method include an electron beam crosslinking method and a chemical crosslinking method in which the resin composition is irradiated with an electron beam. Known chemical crosslinking methods include a crosslinking method in which an organic peroxide or the like is thermally decomposed to cause a resin to undergo a crosslinking reaction, and the following silane crosslinking method. Among these crosslinking methods, in particular, the silane crosslinking method often does not require special equipment, and thus can be used in a wide range of fields.

  The silane crosslinking method is a method in which a hydrolyzable silane coupling agent having an unsaturated group is grafted to a resin in the presence of an organic peroxide to obtain a silane graft resin, and then the silane grafting in the presence of a silanol condensation catalyst. In this method, a crosslinked resin is obtained by bringing the resin into contact with moisture.

  As an example of applying the silane cross-linking method, for example, in Patent Document 1, an inorganic filler obtained by surface-treating a resin component obtained by mixing a polyolefin resin and a maleic anhydride resin with a silane coupling agent, a silane coupling agent, There has been proposed a method in which an organic peroxide and a crosslinking catalyst are sufficiently melt-kneaded with a kneader and then molded with a single screw extruder.

  As another method, for example, in Patent Documents 2 to 4, a vinyl aromatic thermoplastic elastomer composition comprising a block copolymer or the like as a base polymer and a non-aromatic rubber softener added as a softener. Has been proposed that is partially cross-linked with an organic peroxide through an inorganic filler having a silane surface treatment.

JP 2001-101928 A JP 2000-143935 A JP 2000-315424 A JP 2001-240719 A

However, in the method described in Patent Document 1, the resin may be crosslinked during melt-kneading with a kneader or the like. Furthermore, silane coupling agents other than the silane coupling agent that is treating the surface of the inorganic filler may volatilize or condense with each other. Therefore, desired heat resistance cannot be imparted to the obtained molded body. In addition, it causes poor appearance in the molded body.
Moreover, even if it is the method described in patent documents 2-4, since resin has not yet sufficient network structure, the bond of resin and an inorganic filler is easy to cut | disconnect at high temperature, and the heat resistance of the obtained molded object Is not enough. The molded body may melt at a high temperature, and for example, the insulating material may melt during soldering of the electric wire. In addition, deformation or foaming may occur during secondary processing.

  In recent years, there has been a demand for a production method capable of obtaining a crosslinked resin molded article having desired heat resistance and appearance even under wide molding conditions and wide crosslinking conditions.

The present invention provides a method for producing a heat-resistant silane cross-linked resin molded article that can produce a heat-resistant silane cross-linked resin molded article excellent in appearance and heat resistance under a wide range of molding and cross-linking conditions, and heat resistance having the above-mentioned excellent characteristics. It is an object to provide a silane cross-linked resin molded article.
Moreover, this invention makes it a subject to provide the silane masterbatch which can form this heat resistant silane crosslinked resin molded object, a heat resistant silane crosslinked resin composition, and its manufacturing method.
Furthermore, this invention makes it a subject to provide the heat resistant product containing the heat resistant silane crosslinked resin molded object obtained with the manufacturing method of the heat resistant silane crosslinked resin molded object.

  The present inventors obtained a mixture obtained by mixing an inorganic filler and a specific combination of silane coupling agents in a silane crosslinking method, and melt-mixed the base resin in the presence of an organic peroxide. By a specific production method of mixing a silane masterbatch with a silanol condensation catalyst or a catalyst masterbatch containing a silanol condensation catalyst, under a wide range of molding conditions, and even when the crosslinking reaction condition of the silane coupling agent is normal temperature (23 ° C.), It has been found that a heat-resistant silane-crosslinked resin molded article having excellent heat resistance in addition to the appearance can be produced. Based on this finding, the present inventors have made further studies and have come up with the present invention.

That is, the subject of this invention was achieved by the following means.
<1>
The following step (1), step (2) and step (3)
Step (1): Melting organic peroxide 0.01 to 0.6 parts by mass, inorganic filler 30 to 300 parts by mass, silane coupling agent, and silanol condensation catalyst with respect to 100 parts by mass of base resin. Step (2) for obtaining a mixture by mixing: Step (3) for obtaining a molded product by molding the mixture obtained in the step (1): The molded product obtained in the step (2) is mixed with water. A method for producing a heat-resistant silane cross-linked resin molded article, comprising a step of obtaining a heat-resistant silane cross-linked resin molded article by contact with the molded article,
The silane coupling agent includes 0.5 to 5 parts by mass of vinyltrimethoxysilane and 1.0 to 15 parts by mass of vinyltriethoxysilane with respect to 100 parts by mass of the base resin.
The step (1) includes the following step (a-1), step (a-2) and step (c), provided that a part of the base resin is melt-mixed in the following step (a-2). The manufacturing method of the heat resistant silane crosslinked resin molding which has the following process (a-1), a process (a-2), a process (b), and a process (c).
Step (a-1): Step of preparing a mixture by mixing at least the inorganic filler and the silane coupling agent Step (a-2): The mixture and all or part of the base resin are mixed with the organic solvent. Step of preparing a silane masterbatch by melting and mixing at a temperature equal to or higher than the decomposition temperature of the organic peroxide in the presence of an oxide Step (b): Melting and mixing the remainder of the base resin and the silanol condensation catalyst Step for preparing catalyst master batch Step (c): Step <2> for melting and mixing the silane master batch and the silanol condensation catalyst or the catalyst master batch.
The manufacturing method of the heat resistant silane crosslinked resin molding as described in <1> whose compounding quantity of the said vinyltrimethoxysilane is 0.5-2 mass parts with respect to 100 mass parts of said base resins.
<3>
The manufacturing method of the heat resistant silane crosslinked resin molding as described in <1> or <2> whose compounding quantity of the said vinyl triethoxysilane is 1.0-5.0 mass parts.
<4>
The base resin contains at least one selected from polyethylene resin, polyolefin copolymer resin having acid copolymerization component or acid ester copolymerization component, ethylene rubber, acrylic rubber, styrene elastomer and chlorinated polyethylene resin, The manufacturing method of the heat resistant silane crosslinked resin molding as described in any one of <1>-<3>.
<5>
To 100 parts by mass of the base resin, 0.01 to 0.6 parts by mass of an organic peroxide, 30 to 300 parts by mass of an inorganic filler, a silane coupling agent, and a silanol condensation catalyst are melt-mixed to obtain a mixture. A method for producing a heat-resistant silane crosslinkable resin composition having the step (1) of obtaining,
The silane coupling agent includes 0.5 to 5 parts by mass of vinyltrimethoxysilane and 1.0 to 15 parts by mass of vinyltriethoxysilane with respect to 100 parts by mass of the base resin.
The step (1) includes the following step (a-1), step (a-2) and step (c), provided that a part of the base resin is melt-mixed in the following step (a-2). The manufacturing method of the heat resistant silane crosslinkable resin composition which has the following process (a-1), a process (a-2), a process (b), and a process (c).
Step (a-1): Step of preparing a mixture by mixing at least the inorganic filler and the silane coupling agent Step (a-2): The mixture and all or part of the base resin are mixed with the organic solvent. Step of preparing a silane masterbatch by melting and mixing at a temperature equal to or higher than the decomposition temperature of the organic peroxide in the presence of an oxide Step (b): Melting and mixing the remainder of the base resin and the silanol condensation catalyst Step for preparing catalyst master batch Step (c): Step <6> for melting and mixing the silane master batch with the silanol condensation catalyst or the catalyst master batch.
A heat resistant silane crosslinkable resin composition produced by the method for producing a heat resistant silane crosslinkable resin composition according to <5>.
<7>
<1>-<5> The heat resistant silane crosslinked resin molded object manufactured by the manufacturing method of the heat resistant silane crosslinked resin molded object as described in any one.
<8>
A heat-resistant product comprising the heat-resistant silane-crosslinked resin molded article according to <7>.
<9>
Heat resistance obtained by melting and mixing 0.01 to 0.6 parts by mass of an organic peroxide, 30 to 300 parts by mass of an inorganic filler, a silane coupling agent, and a silanol condensation catalyst with respect to 100 parts by mass of the base resin. A silane masterbatch used in the production of a functional silane crosslinkable resin composition,
The silane coupling agent includes 0.5 to 5 parts by mass of vinyltrimethoxysilane and 1.0 to 15 parts by mass of vinyltriethoxysilane with respect to 100 parts by mass of the base resin.
At least the inorganic filler and the silane coupling agent are mixed to prepare a mixture, and the resulting mixture and all or part of the base resin are decomposed in the presence of the organic peroxide. A silane masterbatch obtained by melt mixing at a temperature higher than the temperature.

  In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

According to the present invention, a heat-resistant silane cross-linked resin molded article having excellent appearance and heat resistance can be produced under a wide range of molding conditions and even when the cross-linking reaction conditions of the silane coupling agent are relaxed to room temperature.
Therefore, according to the present invention, it is possible to provide a heat-resistant silane cross-linked resin molded article having an excellent appearance and heat resistance and a method for producing the same. Moreover, the silane masterbatch which can form the heat-resistant silane crosslinked resin molding excellent in such an external appearance and heat resistance, a heat-resistant silane crosslinkable resin composition, and its manufacturing method can be provided. Furthermore, it is possible to provide a heat-resistant product including a heat-resistant silane-crosslinked resin molded article excellent in appearance and heat resistance.

The manufacturing method of the heat-resistant silane crosslinked resin molding of the present invention includes the following steps (1) to (3). The heat-resistant silane cross-linked resin molded product of the present invention is a molded product obtained by this production method.
Step (1): Melting organic peroxide 0.01 to 0.6 parts by mass, inorganic filler 30 to 300 parts by mass, silane coupling agent, and silanol condensation catalyst with respect to 100 parts by mass of base resin. Step (2) for obtaining a mixture by mixing: Step (3) for obtaining a molded product by molding the mixture obtained in the step (1): The molded product obtained in the step (2) is mixed with water. The process of obtaining a heat-resistant silane crosslinked resin molding by making it contact In the said process (1), the said silane coupling agent is vinyl trimethoxysilane 0.5-5 mass parts with respect to 100 mass parts of base resins, and vinyl. 1.0 to 15 parts by mass of triethoxysilane.

And when this process (1) melt-mixes all of base resin at the following process (a-2), it has a process (a-1), a process (a-2), and a process (c) at least. When a part of the base resin is melt-mixed in the following step (a-2), at least the following step (a-1), step (a-2), step (b) and step (c) are included.
Step (a-1): Step of preparing a mixture by mixing at least the inorganic filler and the silane coupling agent Step (a-2): The mixture and all or part of the base resin are mixed with the organic solvent. Step of preparing a silane masterbatch by melting and mixing at a temperature equal to or higher than the decomposition temperature of the organic peroxide in the presence of an oxide Step (b): Melting and mixing the remainder of the base resin and the silanol condensation catalyst Step of preparing a catalyst master batch Step (c): Step of melt-mixing the silane master batch and the silanol condensation catalyst or the catalyst master batch Here, mixing means obtaining a uniform mixture.
In addition, the mixture obtained in step (1) of the production method of the present invention may hereinafter be referred to as “heat-resistant silane crosslinkable resin composition”.

First, each component used in the present invention will be described.
<Base resin>
The base resin used in the present invention is not particularly limited as long as the resin has a vinyl group of the silane coupling agent and a site capable of graft reaction in the presence of an organic peroxide in the main chain or at the terminal thereof. . Examples of the site capable of graft reaction include a carbon chain unsaturated bond site and a carbon atom having a hydrogen atom. Examples of the base resin include polyolefin resins.
The base resin may contain an oil component described later in addition to the resin component.
This base resin includes a resin component and an arbitrary component such as an oil component. In the present invention, the total of these components is 100% by mass. The compounding amount of each component in the base resin is appropriately determined, and the resins described below are selected from the following ranges, for example.

(Resin component)
The polyolefin resin is not particularly limited as long as it is a resin obtained by polymerizing or copolymerizing a compound having an ethylenically unsaturated bond, and a known resin conventionally used in a heat resistant resin composition is used. can do. For example, polyethylene, polypropylene, ethylene-α-olefin copolymer, block copolymer of polypropylene and ethylene-α-olefin resin, chlorinated polyethylene, polyvinyl chloride, acid copolymerization component or acid ester copolymerization component Each resin of a polyolefin copolymer is mentioned. In addition, rubbers or elastomers of these copolymers are also included. For example, ethylene rubber (for example, ethylene-propylene rubber, ethylene-propylene-diene rubber), acrylic rubber, styrene-based elastomer, and the like can be given.
Among these, at least one selected from polyethylene resins, polyolefin copolymer resins having an acid copolymerization component or an acid ester copolymerization component, ethylene rubber, acrylic rubber, styrene elastomer, and chlorinated polyethylene resin is preferable.
These polyolefin resins may be used individually by 1 type, or may use 2 or more types together.

The polyethylene resin (excluding the chlorinated polyethylene resin) may be a resin having an ethylene component as a main component, and is a homopolymer composed only of ethylene, a copolymer of ethylene and α-olefin (preferably 5 mol% or less). Polymers and copolymers of ethylene and copolymers of non-olefins (preferably having only carbon, oxygen and hydrogen atoms in the functional group, and preferably 1 mol% or less) are included (for example, JIS K 6748). As the above-mentioned α-olefin and non-olefin, known ones conventionally used as a copolymerization component of polyethylene can be used without particular limitation. The α-olefin is preferably one having 4 to 12 carbon atoms, and examples thereof include those described later.
Polyethylene resins that can be used in the present invention 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). ) And the like. Of these, linear low density polyethylene and low density polyethylene are preferable. A polyethylene resin may be used individually by 1 type, and may use 2 or more types together.

The chlorinated polyethylene resin is obtained by replacing at least one hydrogen atom of the above polyethylene with a chlorine atom. As a chlorinated polyethylene resin, what contains a chlorine atom in 20-55 mass% with respect to the total mass of a chlorinated polyethylene resin can be used conveniently. As the chlorinated polyethylene resin, elastane (trade name, manufactured by Showa Denko) or the like can be used.
A chlorinated polyethylene resin may be used individually by 1 type, and may use 2 or more types together.

  As an acid copolymerization component or an acid ester copolymerization component in a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, each component such as vinyl acetate, (meth) acrylic acid, alkyl (meth) acrylate, etc. Is mentioned. Here, the alkyl group of the alkyl (meth) acrylate component preferably has 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Examples of polyolefin copolymer resins (excluding those contained in polyethylene resin) having an acid copolymerization component or an acid ester copolymerization component include ethylene-vinyl acetate copolymer (EVA), ethylene- (meth). Examples of the resins include acrylic acid copolymers and ethylene- (meth) acrylic acid alkyl copolymers. Among these, resins of ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate copolymer are preferable, and inorganic fillers are further used. From the viewpoint of acceptability and heat resistance, ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer resin are preferable. The polyolefin copolymer resin having an acid copolymerization component or an acid ester copolymerization component may be used alone or in combination of two or more.

The ethylene rubber is not particularly limited as long as it is a rubber (including an elastomer) made of a copolymer obtained by copolymerizing a compound having an ethylenically unsaturated bond, and a known rubber can be used. Preferred examples of the ethylene rubber include a copolymer of ethylene and α-olefin, and a rubber made of a terpolymer of ethylene, α-olefin and diene. The diene constituent of the terpolymer may be a conjugated diene constituent or a non-conjugated diene constituent, and a non-conjugated diene constituent is preferred. That is, examples of the ternary copolymer include a ternary copolymer of ethylene, an α-olefin, and a conjugated diene, and a terpolymer of ethylene, an α-olefin, and a nonconjugated diene. As the ethylene rubber, a copolymer of ethylene and α-olefin and a terpolymer of ethylene, α-olefin and non-conjugated diene are preferable.
As the α-olefin, each α-olefin having 3 to 12 carbon atoms is preferable, and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like are preferable. Can be mentioned. Specific examples of the conjugated diene include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like, with butadiene being preferred. Specific examples of the non-conjugated diene include dicyclopentadiene (DCPD), ethylidene norbornene (ENB), 1,4-hexadiene, and the like, and ethylidene norbornene is preferable.
Examples of rubber made of a copolymer of ethylene and α-olefin include ethylene-propylene rubber, ethylene-butene rubber, and ethylene-octene rubber. Examples of the rubber composed of a terpolymer of ethylene, α-olefin and diene include ethylene-propylene-diene rubber and ethylene-butene-diene rubber. Of these, ethylene-propylene rubber, ethylene-butene rubber, ethylene-propylene-diene rubber and ethylene-butene-diene rubber are preferable, and ethylene-propylene rubber and ethylene-propylene-diene rubber are more preferable.

  An ethylene rubber may be used individually by 1 type, and may use 2 or more types together.

The acrylic rubber (ACM) is not particularly limited, but is obtained by copolymerizing an alkyl acrylate such as ethyl acrylate or butyl acrylate and a monomer having an unsaturated hydrocarbon or various functional groups as a constituent component. A rubber elastic body made of a copolymer is preferable. Although it does not specifically limit as a monomer copolymerized with alkyl acrylate, Ethylene, 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, acrylonitrile, a butadiene etc. can be mentioned.
Examples of the acrylic rubber obtained by copolymerizing an alkyl acrylate and a monomer having a functional group include Nipol AR (trade name, manufactured by Nippon Zeon), JSR AR (trade name, manufactured by JSR), and the like. .
The acrylic rubber particularly preferably contains methyl acrylate as a constituent component. Such an acrylic rubber comprises a copolymer such as a binary copolymer with ethylene and a terpolymer obtained by further copolymerizing an unsaturated hydrocarbon having a carboxy group in the side chain. Rubber (also referred to as ethylene acrylic rubber) can be particularly preferably used. Examples of the ethylene acrylic rubber made of a binary copolymer include Baymac DP and Baymac DLS. Examples of the ethylene acrylic rubber made of a terpolymer include Baymac G, Baymac HG, Baymac LS, and Baymac GLS (trade names, all manufactured by Mitsui DuPont Polychemical Co., Ltd.).

Examples of the styrenic elastomer include block copolymers and random copolymers of conjugated diene compounds and aromatic vinyl compounds, or hydrogenated products thereof. Examples of the aromatic vinyl compound include styrene, p- (t-butyl) styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethyl. Styrene, vinyl toluene, p- (t-butyl) styrene, etc. are mentioned. Among these, styrene is preferable as the aromatic vinyl compound. These aromatic vinyl compounds may be used alone or in combination of two or more. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Among these, the conjugated diene compound is preferably butadiene. This conjugated diene compound may be used alone or in combination of two or more. In addition, as a styrene-based elastomer, an elastomer containing an aromatic vinyl compound other than styrene, which does not contain a styrene component, may be used by a similar production method.
Examples of the styrene elastomer include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butylene-styrene block copolymer (SBS), and styrene. -Ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), hydrogenated SBS, hydrogenated SIS, hydrogenated styrene-butadiene rubber (HSBR), hydrogen And acrylonitrile-butadiene rubber (HNBR).
Styrenic elastomers may be used alone or in combination of two or more.

Polypropylene resin should just be resin which has a propylene component as a main component, In addition to the homopolymer of propylene, ethylene-propylene copolymers, such as random polypropylene, and block polypropylene are included as a copolymer.
The ethylene-α-olefin copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms (except for those contained in the polyethylene and polypropylene).
The compounding quantity of a polypropylene resin and an ethylene-alpha-olefin copolymer is not specifically limited, It sets suitably.

As the base resin, the above resins and the like can be used alone or in appropriate combination. For example, in the present invention, a group consisting of a polyethylene resin, a polyolefin copolymer resin having an acid copolymerization component or an acid ester copolymerization component, an ethylene rubber, an acrylic rubber, a styrene elastomer, and a chlorinated polyethylene resin (referred to as group I). It is preferable that 40-100 mass% is included at least 1 sort (s) selected from. The base resin contains 40 to 100% by mass of at least one selected from the group consisting of a polyethylene resin and a polyolefin copolymer resin having an acid copolymerization component or an acid ester copolymerization component (referred to as group II). Those are more preferred.
In particular, it is preferable that 70-100 mass% of at least 1 type of resin selected from the said group I or group II is included.
The balance is an oil component, various additives, a solvent, and the like, which will be described later.

(Oil component)
Although the oil component which a base resin can contain is not specifically limited, Organic oil or mineral oil is mentioned. When the base resin contains an organic oil, it is possible to produce a silane heat-resistant silane cross-linked resin molded article having an excellent appearance by suppressing the occurrence of bumps (the protrusions protruding on the surface).
As the organic oil or mineral oil, paraffin oil or naphthenic oil is preferable, and paraffin oil is more preferable in terms of mechanical strength.
Although content of oil is not specifically limited, It is preferable that it is 30 mass% or less in 100 mass% of base resin. When base resin contains oil, it is more preferable that it is 2-30 mass% in 100 mass% of base resin, it is further more preferable that it is 3-25 mass%, and 5-20 mass% is especially preferable. When the oil content is within the above range, the temperature of the kneaded product quickly rises during kneading, and the silane graft reaction easily proceeds uniformly.

  In addition to the oil, the base resin may contain other components such as various additives and solvents described later.

<Organic peroxide>
The organic peroxide generates radicals by at least thermal decomposition, and serves as a catalyst to cause a graft reaction by radical reaction to the resin component of the silane coupling agent. In particular, it functions to cause a graft reaction by a radical reaction between the vinyl group of the silane coupling agent and the resin component (including a hydrogen radical abstraction reaction from the resin component).
The organic peroxide is not particularly limited as long as it generates radicals. For example, the general formula: R ¹ —OO—R ² , R ³ —OO—C (═O) R ⁴ , R ⁵ C A compound represented by (═O) —OO (C═O) R ⁶ is preferred. Here, R ^{1 to} R ⁶ each independently represents an alkyl group, an aryl group, or an acyl group. Among R ^{1 to} R ⁶ of each compound, those in which all are alkyl groups or those in which any one is an alkyl group and the remainder is an acyl group are preferable.

  Examples of such organic peroxides 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-butyl peroxide Oxybenzoate, tert-butyl peroxyisopropyl carbonate, diace Peroxide, lauroyl peroxide, may be mentioned tert- butyl cumyl peroxide and the like. Of these, 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 is preferably from 80 to 195 ° C, particularly preferably from 125 to 180 ° C.
In the present invention, the decomposition temperature of an organic peroxide means that when an organic peroxide having a single composition is heated, it is itself half decomposed into two or more compounds at a certain temperature or temperature range for 1 minute. It means the temperature at which the reaction takes place (1 minute half-life temperature). Specifically, it refers to the temperature at which heat absorption or heat generation starts when heated from room temperature in a nitrogen gas atmosphere at a rate of temperature increase of 5 ° C./min by thermal analysis such as DSC method.

<Inorganic filler>
The inorganic filler used in the present invention is chemically bonded to the reaction site of the silane coupling agent (the trialkoxysilyl group and the triethoxysilyl group are collectively referred to as trialkoxysilyl group) on the surface by hydrogen bonding or covalent bonding. As long as it has a possible site, it can be used without particular limitation. Examples of the site that can be chemically bonded to the reaction site of the silane coupling agent in this inorganic filler include OH groups (hydroxy groups, water molecules containing water or water of crystal water, OH groups such as carboxy groups), amino groups, and SH groups. It is done.

Examples of such inorganic fillers include metal hydrates such as compounds having hydrated water, hydroxyl groups or crystal water. Examples of the metal hydrate include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and talc, and further calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, In addition to aluminum nitride, aluminum borate whisker, etc., inorganic acid salts or inorganic oxides such as hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, etc. having hydrated water and the like can be mentioned. .
In addition to metal hydrates, examples of the inorganic filler include boron nitride, silica (crystalline silica, amorphous silica, etc.), carbon black, clay, zinc oxide, tin oxide, titanium oxide, molybdenum oxide, three Examples thereof include antimony oxide, silicone compound, quartz, zinc borate, white carbon, zinc borate, zinc hydroxystannate, and zinc stannate.
Among these, the inorganic filler is preferably at least one selected from the group consisting of metal hydrate, clay, silica, and carbon black.
An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

  The average primary particle size of the inorganic filler is preferably 0.001 to 10 μm, more preferably 0.005 to 5 μm, still more preferably 0.01 to 2 μm, and particularly preferably 0.015 to 1 μm. When the average primary particle size is within the above range, the retention effect of the silane coupling agent is high, and the tensile strength and compression set are excellent. Further, the inorganic filler hardly aggregates when mixed with the silane coupling agent, and the appearance is excellent. The average primary particle size is determined by an optical particle size analyzer such as a laser diffraction / scattering particle size distribution measuring device after being dispersed with alcohol or water.

  As the inorganic filler, a surface-treated inorganic filler surface-treated with a silane coupling agent or the like can be used. Examples of the silane coupling agent surface treatment inorganic filler include Kisuma 5L and Kisuma 5P (both trade names, magnesium hydroxide, manufactured by Kyowa Chemical Co., Ltd.) and the like. The surface treatment amount of the inorganic filler with the silane coupling agent is not particularly limited, but is, for example, 2% by mass or less.

<Silane coupling agent>
In the present invention, as the silane coupling agent, at least a specific amount of vinyltrimethoxysilane and vinyltriethoxysilane are used in combination.
These silane coupling agents undergo a graft reaction on the resin component in the presence of radicals generated by the decomposition of the organic peroxide. Moreover, it reacts with the site | part which can be chemically bonded of an inorganic filler, and it couple | bonds with the surface of an inorganic filler, or adsorb | sucks to an inorganic filler.
By using the two types of silane coupling agents in combination, volatilization of the free silane coupling agent is further suppressed during the melt mixing in the step (a-2) and during the molding of the crosslinked resin molded body in the step (2). It is thought. Thereby, even if it is a case where it is a case where it is a case where it is a case where it is a case where it is a case where it continuously extrudes by high-temperature extrusion molding and a molded object, it can suppress generation | occurrence | production of the fuzz by foaming and the crosslinking reaction of resin components. Foaming is not preferable because it not only impairs the appearance of the resulting molded article, but can also cause a decrease in strength and the occurrence of sparks. Further, since hydrolysis of the silane coupling agent occurs even at room temperature, a molded article having a desired degree of crosslinking can be obtained even when left at room temperature without being treated with warm water.
The silane coupling agent may be used as it is or diluted with a solvent or the like.

<Silanol condensation catalyst>
The silanol condensation catalyst functions to cause a condensation reaction of the silane coupling agent grafted to the resin component in the presence of moisture. Based on the action of this silanol condensation catalyst, the resin components are cross-linked through a silane coupling agent. As a result, a heat-resistant silane cross-linked resin molded article having excellent heat resistance is obtained.

  Examples of the silanol condensation catalyst used in the present invention include organotin compounds, metal soaps, platinum compounds and the like. Common silanol condensation catalysts include, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, zinc stearate, lead stearate, barium stearate, calcium stearate, sodium stearate, lead naphthenate, Lead sulfate, zinc sulfate, organic platinum compounds and the like are used. Among these, organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and dibutyltin diacetate are particularly preferable.

<Carrier resin>
The silanol condensation catalyst is used by mixing with a resin if desired. Such a resin (also referred to as carrier resin) is not particularly limited, and each resin described in the base resin can be used. Of the base resins, the carrier resin is more preferably a resin containing ethylene as a constituent component, and more preferably a polyethylene resin, because the carrier resin has good affinity with the silanol condensation catalyst and excellent heat resistance.

<Additives>
The heat-resistant silane cross-linked resin molded body and the heat-resistant silane cross-linkable resin composition include various additives generally used in electric wires, electric cables, electric cords, sheets, foams, tubes, and pipes. You may contain in the range which does not impair the effect of. Examples of such additives include crosslinking aids, antioxidants, lubricants, metal deactivators, and fillers (including flame retardant (auxiliary) agents) other than the above inorganic fillers.

Although it does not specifically limit as antioxidant, For example, amine antioxidant, phenol antioxidant, sulfur antioxidant, etc. are mentioned. Examples of the amine antioxidant include a polymer of 4,4′-dioctyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline, and the like. . Examples of the phenol antioxidant include pentaerythritol-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like. Examples of the sulfur antioxidant include bis (2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben プ ト imidazole and its zinc salt, pentaerythritol- And tetrakis (3-lauryl-thiopropionate).
The antioxidant is preferably added in an amount of 0.1 to 15.0 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the base resin.

Next, the production method of the present invention will be specifically described.
Each of 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-linked resin composition” of the present invention performs at least the step (1) described above. Therefore, 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 will be described together (in the description common to both production methods). May be referred to as the production method of the present invention).
In addition, the “silane masterbatch” of the present invention is produced by the above-described step (a-1) and step (a-2) (both steps are collectively referred to as step (a)). Therefore, the “manufacturing method of silane masterbatch” of the present invention will be described in the manufacturing method of the present invention.

  In the production method of the present invention, the “base resin” is a resin for forming a heat-resistant silane cross-linked resin molded product or a heat-resistant silane cross-linkable resin composition. Therefore, in the production method of the present invention, 100 parts by mass of the base resin may be contained in the mixture obtained in step (1). For example, in the step (a-2), “a mode in which the total amount (100 parts by mass) of the base resin is blended” and “a mode in which a part of the base resin is blended” are included.

In the present invention, the “part of the base resin” is a resin used in the step (a-2) of the base resin, and a part of the base resin itself (having the same composition as the base resin), the base resin And a part of resin components constituting the base resin (for example, the total amount of specific resin components among the plurality of resin components). A part of the base resin is preferably a part of the resin component constituting the base resin.
Further, the “base resin balance” is the remaining base resin excluding a part of the base resin used in the step (a-2), specifically, the base resin itself (base resin itself). The rest of the resin components constituting the base resin and the remaining resin components constituting the base resin.

When a part of the base resin is blended in the step (a-2), the blending amount of 100 parts by mass of the base resin in the step (1) is that of the base resin mixed in the step (a-2) and the step (b). Total amount.
Here, when the remainder of the base resin is blended in the step (b), the base resin is blended in the step (a-2), preferably 80 to 99% by mass, more preferably 94 to 98% by mass, In a process (b), Preferably 1-20 mass%, More preferably, 2-6 mass% is mix | blended.

  In the step (1), the compounding amount of the organic peroxide is 0.01 to 0.6 parts by mass, preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the base resin. When the blending amount of the organic peroxide is less than 0.01 parts by mass, the graft reaction does not proceed, and the silane coupling agents condense with each other to sufficiently obtain heat resistance, and in some cases, mechanical strength and reinforcement. There are times when you can't. On the other hand, when it exceeds 0.6 parts by mass, many of the resin components are directly cross-linked by a side reaction to form a defect, which may cause poor appearance. In particular, the appearance defect is remarkably generated under the condition where the appearance defect is likely to occur. That is, by setting the blending amount of the organic peroxide within this range, a graft reaction can be performed within an appropriate range, and a composition excellent in extrudability can be obtained without generating gel-like spots. it can.

  The compounding quantity of an inorganic filler is 30-300 mass parts with respect to 100 mass parts of base resins. When the blending amount of the inorganic filler is less than 30 parts by mass, it may not be possible to impart excellent flame retardancy to the heat-resistant silane crosslinked resin molded article. In addition, the graft reaction of the silane coupling agent may become non-uniform. Thereby, sufficient heat resistance may not be obtained or the appearance may be deteriorated. On the other hand, if it exceeds 300 parts by mass, the load during molding or kneading becomes very large, and secondary molding may be difficult.

The compounding quantity of vinyltrimethoxysilane is 0.5-5 mass parts with respect to 100 mass parts of base resins, Preferably it is 0.5-2 mass parts.
If the blending amount of vinyltrimethoxysilane is less than 0.5 parts by mass, the crosslinking reaction does not normally proceed sufficiently at room temperature and does not exhibit excellent heat resistance, although it depends on the blending amount of vinyltriethoxysilane. is there. On the other hand, if it exceeds 5 parts by mass, the vinyltrimethoxysilane may volatilize during molding and the appearance may deteriorate. This is particularly noticeable under conditions where appearance defects tend to occur. The normal temperature here means 15 to 25 ° C. and a humidity of 30 to 65%.

The compounding quantity of vinyltriethoxysilane is 1.0-15 mass parts with respect to 100 mass parts of base resins, Preferably it is 1.0-5.0 mass parts.
When the amount of vinyltriethoxysilane is less than 1.0 part by mass, although it depends on the amount of vinyltrimethoxysilane, the crosslinking reaction usually does not proceed sufficiently at room temperature and does not exhibit excellent heat resistance. is there. In addition, poor appearance tends to occur during high temperature extrusion. On the other hand, when the amount exceeds 15 parts by mass, no further improvement in the effect is observed, which is not economical. Moreover, vinyl triethoxysilane which is not adsorbed on the inorganic filler may condense, and the molded product may be fuzzy or burnt to deteriorate the appearance. This is particularly noticeable under conditions where appearance defects tend to occur.

The total blending amount of vinyltrimethoxysilane and vinyltriethoxysilane is preferably 1.5 to 20 parts by mass and more preferably 1.5 to 6 parts by mass with respect to 100 parts by mass of the base resin. preferable. Conventionally, depending on the silane coupling agent to be used, if the blending amount is too large, it may become impossible to mold, but according to the present invention, the volatilization amount of the entire silane coupling agent is reduced. Even if it is blended in a larger amount than the conventional amount, it can be molded.
The ratio of the amount of vinyltrimethoxysilane and vinyltriethoxysilane (vinyltrimethoxysilane / vinyltriethoxysilane) is preferably 0.035 to 2, more preferably 0.2 to 1.5. preferable.

  The compounding amount of the silanol condensation catalyst is not particularly limited, and 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 base resin. When the amount of the silanol condensation catalyst is within the above range, the crosslinking reaction due to the condensation reaction of the silane coupling agent is likely to proceed almost uniformly, and the heat resistance, appearance and physical properties of the heat-resistant silane crosslinked resin molded product are excellent, producing Also improves. That is, if the amount of the silanol condensation catalyst is too small, sufficient heat resistance and sometimes mechanical strength may not be obtained. On the other hand, if the amount is too large, the crosslinking reaction due to the condensation reaction of the silane coupling agent becomes uneven, and the appearance and productivity may be inferior.

The silane masterbatch is prepared by adding all or part of the base resin, the organic peroxide, the inorganic filler, and the silane coupling agent in the above blending amounts, for example, into a mixer, and then decomposing the organic peroxide. It is prepared by the step (a) of melt kneading while heating to the above temperature.
In the present invention, “all or part of the base resin, organic peroxide, inorganic filler and silane coupling agent are melt-mixed” means at least a mixture of the inorganic filler and silane coupling agent and the base resin are melt-mixed. If so, the order of mixing the components is not specified, which means that they may be mixed in any order.
Moreover, the mixing method of the base resin is not particularly limited. For example, a base resin mixed and prepared in advance may be used, and each component, for example, a resin component and an oil component may be mixed separately.

  In the present invention, the silane coupling agent is not introduced alone into the silane masterbatch but is premixed with an inorganic filler. That is, at least an inorganic filler and a silane coupling agent are mixed to prepare a mixture (step (a-1)). The silane coupling agent premixed in this manner exists so as to surround the surface of the inorganic filler, and a part or all of the silane coupling agent is adsorbed or bonded to the inorganic filler. Thereby, volatilization of the silane coupling agent can be reduced during subsequent melt mixing. Moreover, it is possible to prevent the silane coupling agent that is not adsorbed or bonded to the inorganic filler from condensing and making melt kneading difficult. Furthermore, a desired shape can be obtained during extrusion molding.

As such a mixing method, the inorganic filler and the silane coupling agent are preferably about several minutes to several hours at an arbitrary temperature, for example, a temperature lower than the decomposition temperature of the organic peroxide, preferably room temperature (25 ° C.). There is a method in which after mixing (dispersing) in a dry or wet manner, this mixture, a base resin and an organic peroxide are melt-mixed. This mixing is preferably performed with a mixer-type kneader such as a Banbury mixer or a kneader. If it does in this way, the excessive crosslinking reaction of resin components can be prevented, and the external appearance will be excellent.
In the mixing method of the inorganic filler and the silane coupling agent, a base resin may be present, and when the organic peroxide coexists, a temperature lower than the decomposition temperature is maintained. In this case, it is preferable that the metal oxide and the silane coupling agent are mixed with the base resin at the above temperature (step (a-1)) and then melt mixed.

Examples of the mixing method of the inorganic filler and the silane coupling agent include a mixing method such as a wet process and a dry process. Specifically, a wet process in which a silane coupling agent is added in a state where an inorganic filler is dispersed in a solvent such as alcohol or water, a dry process in which both are added by heating or non-heating, and both are mentioned. In the present invention, dry processing is preferred in which a silane coupling agent is added to an inorganic filler, preferably a dried inorganic filler, with heating or non-heating and mixed.
In wet mixing, since the cohesion between the silane coupling agent and the inorganic filler becomes strong, volatilization of the silane coupling agent can be effectively suppressed, but the silanol condensation reaction may be difficult to proceed. On the other hand, in dry mixing, the silane coupling agent tends to volatilize, but since the bonding strength between the inorganic filler and the silane coupling agent becomes relatively weak, the silanol condensation reaction easily proceeds efficiently.

When the organic peroxide is mixed with the silane coupling agent, the mixing method is not particularly limited, and the organic peroxide may be mixed at the same time as the inorganic filler or at the mixing stage of the inorganic filler and the silane coupling agent. May be.
For example, the organic peroxide may be mixed with the inorganic filler after being mixed with the silane coupling agent, or may be separately mixed with the inorganic filler separately from the silane coupling agent. When mixing an organic peroxide with a silane coupling agent, it is better to mix the organic peroxide and the silane coupling agent substantially together. On the other hand, depending on production conditions, only the silane coupling agent may be mixed with the inorganic filler, and then the organic peroxide may be mixed.
The organic peroxide may be mixed with other components or may be a simple substance.

  Next, in the production method of the present invention, all or a part of the obtained mixture and the base resin, and the remaining components not mixed in step (a-1) are organically added in the presence of an organic peroxide. Melting and kneading while heating to a temperature above the decomposition temperature of the peroxide (step (a-2)).

In step (a-2), the temperature at which the above components are melt-mixed (also referred to as melt kneading or kneading) (also referred to as mixing temperature) is equal to or higher than the decomposition temperature of the organic peroxide, preferably the decomposition temperature of the organic peroxide. The temperature is + (25 to 110) ° C. This mixing temperature is preferably set after the resin component has melted. If it is the said mixing temperature, the said component will melt | dissolve and an organic peroxide will decompose | disassemble and act and a required silane grafting reaction will fully advance in a process (a-2). Other conditions such as the mixing time can be set as appropriate.
The mixing method is not particularly limited as long as it is a method usually used for rubber, plastic and the like. The mixing device is appropriately selected according to, for example, the blending amount of the inorganic filler. As the kneading apparatus, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, various kneaders, or the like is used. A closed mixer such as a Banbury mixer or various kneaders is preferable in terms of the dispersibility of the resin component and the stability of the crosslinking reaction.
In general, when such an inorganic filler is mixed in an amount exceeding 100 parts by mass with respect to 100 parts by mass of the base resin, it is preferably kneaded with a continuous kneader, a pressure kneader, or a Banbury mixer.

  In the step (a-1) and the step (a-2), particularly in the step (a-2), it is preferable to knead the above-mentioned components without substantially mixing the silanol condensation catalyst. Thereby, the condensation reaction of a silane coupling agent can be suppressed, it is easy to melt and mix, and a desired shape can be obtained during extrusion molding. Here, “substantially not mixed” does not exclude the unavoidably existing silanol condensation catalyst, and is present to such an extent that the above-mentioned problem due to silanol condensation of the silane coupling agent does not occur. Means good. For example, in the step (a-2), the silanol condensation catalyst may be present as long as it is 0.01 part by mass or less with respect to 100 parts by mass of the base resin.

In the step (1), the amount of other resins that can be used in addition to the above components and the additive are appropriately set within a range that does not impair the object of the present invention. In the step (1), the additives, particularly the antioxidant and the metal deactivator may be mixed in any step and may be mixed in any component, but are mixed in the carrier resin. Is good.
In the step (1), particularly in the step (a-1) and the step (a-2), it is preferable that the crosslinking assistant is not substantially mixed. If the crosslinking aid is not substantially mixed, crosslinking between the resin components hardly occurs during the melt mixing, and the appearance and heat resistance of the heat-resistant silane crosslinked resin molded article are excellent. Here, being substantially not mixed means that the crosslinking aid is not actively mixed, and does not exclude unavoidable mixing.

  Thus, a process (a-1) and a process (a-2) are performed and a silane masterbatch (it is also called silane MB) is prepared. As will be described later, this silane MB is preferably used together with a silanol condensation catalyst or a catalyst master batch described later in the production of the mixture (heat-resistant silane crosslinkable resin composition) prepared in step (1). Silane MB contains a silane crosslinkable resin (silane graft polymer) in which a silane coupling agent is grafted to a resin component to such an extent that it can be molded by the step (2) described later.

  Next, in the production method of the present invention, when a part of the base resin is melt-mixed in the step (a-2), the remainder of the base resin and the silanol condensation catalyst are melt-mixed to obtain a catalyst master batch (catalyst MB). (B) is also performed. Therefore, when all the base resin is melt-mixed in the step (a-2), the step (b) may not be performed, and another resin and a silanol condensation catalyst may be mixed.

The mixing ratio of the base resin as the carrier resin and the silanol condensation catalyst is not particularly limited, but is preferably set so as to satisfy the above blending amount in the step (1).
The mixing may be a method capable of uniformly mixing, and includes mixing (melting mixing) performed under melting of the base resin. The melt mixing can be performed in the same manner as the melt mixing in the step (a-2). For example, the mixing temperature can be 80 to 250 ° C, more preferably 100 to 240 ° C. Other conditions such as the mixing time can be set as appropriate.

In the step (b), another resin can be used as the carrier resin in place of or in addition to the remainder of the base resin. That is, in the step (b), the remainder of the base resin when a part of the base resin is melt-mixed in the step (a-2), or a resin other than the resin component used in the step (a-2), and silanol A catalyst master batch may be prepared by melt-mixing with a condensation catalyst.
When the carrier resin is another resin, the graft reaction can be promoted in the step (a-2), and it is difficult for the carrier resin to form during molding. The blending amount of the other resin is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and further preferably 2 to 40 parts by mass with respect to 100 parts by mass of the base resin.

Moreover, you may use an inorganic filler in a process (b). In this case, although the compounding quantity of an inorganic filler is not specifically limited, 350 mass parts or less are preferable with respect to 100 mass parts of carrier resins. This is because if the blending amount of the inorganic filler is large, the silanol condensation catalyst is difficult to disperse and the crosslinking is difficult to proceed. On the other hand, when there are too few compounding quantities of an inorganic filler, the crosslinking degree of a molded object will fall and sufficient heat resistance may not be obtained.
In this case, examples of usable inorganic fillers include the above inorganic fillers.

The catalyst MB prepared in this way is a mixture of a silanol condensation catalyst and a carrier resin, a filler to be added as desired.
The catalyst MB is used as a master batch set in the production of the heat-resistant silane crosslinkable resin composition prepared in the step (1) together with the silane MB.

In the production method of the present invention, the step (c) is then performed in which the silane MB and the silanol condensation catalyst or catalyst MB are mixed to obtain a mixture.
The mixing method may be any mixing method as long as a uniform mixture can be obtained as described above.

  The mixing in the step (c) is basically the same as the melt mixing in the step (a-2). There are resin components such as elastomers whose melting points cannot be measured by DSC or the like, but they are kneaded at a temperature at which at least one of the resin components and the organic peroxide melts. The melting temperature is appropriately selected according to the melting temperature of the base resin or the carrier resin, and is preferably 80 to 250 ° C., more preferably 100 to 240 ° C., for example. Other conditions such as mixing (kneading) time can be set as appropriate.

  In the step (c), in order to avoid silanol condensation reaction, it is preferable that the silane MB and the silanol condensation catalyst are not mixed and kept at a high temperature for a long time.

  The step (c) may be any step as long as the mixture is obtained by mixing the silane masterbatch and the silanol condensation catalyst, and the step of melt mixing the catalyst masterbatch containing the silanol condensation catalyst and the carrier resin and the silane masterbatch. It is.

In this way, the steps (a) to (c) (step (1)), that is, the method for producing the heat-resistant silane crosslinkable resin composition of the present invention is performed, and the heat-resistant silane crosslinkable resin of the present invention is used as a mixture. A composition is produced. This heat-resistant silane crosslinkable resin composition contains silane crosslinkable resins having different crosslinking methods. In this silane crosslinkable resin, the trialkoxysilyl group of the silane coupling agent may be bonded or adsorbed to the inorganic filler, but is not silanol condensed as described later. Therefore, in the silane crosslinkable resin, the silane coupling agent bonded or adsorbed to the inorganic filler is grafted to the base resin, and the silane coupling agent not bonded to or adsorbed to the inorganic filler is grafted to the base resin. And at least a crosslinkable resin. The silane crosslinkable resin may have a silane coupling agent to which an inorganic filler is bonded or adsorbed and a silane coupling agent to which an inorganic filler is not bonded or adsorbed. Furthermore, a silane coupling agent and an unreacted resin component may be included.
As described above, the silane crosslinkable resin is an uncrosslinked product in which the silane coupling agent is not silanol condensed. In practice, when melt-mixed in step (c), partial cross-linking (partial cross-linking) is unavoidable, but the resulting heat-resistant silane cross-linking resin composition is at least in the molding in step (2). Assume that moldability is maintained.

  In step (1), steps (a) to (c) can be performed simultaneously or sequentially.

Next, the manufacturing method of the heat-resistant silane crosslinked resin molding of this invention performs a process (2) and a process (3).
In the method for producing a heat-resistant silane-crosslinked resin molded product of the present invention, the step (2) of molding the obtained mixture to obtain a molded product is performed. This process (2) should just be able to shape | mold a mixture, and according to the form of the heat resistant product of this invention, a shaping | molding method and shaping | molding conditions are selected suitably. Examples of the molding method include extrusion molding using an extruder, extrusion molding using an injection molding machine, and molding using other molding machines. Extrusion molding is preferred when the heat-resistant product of the present invention is an electric wire or an optical fiber cable.

  Moreover, a process (2) can be performed simultaneously with a process (c) or continuously. That is, as one embodiment of the melt mixing in the step (c), there is an embodiment in which each molding material is melt-mixed during melt molding, for example, during extrusion molding, or immediately before. For example, pellets such as dry blends may be mixed together at room temperature or high temperature and introduced into a molding machine (melt mixing), or mixed and then melt mixed, pelletized again, and then introduced into the molding machine. Also good. More specifically, a molding material that is a mixture of silane MB and silanol condensation catalyst or catalyst MB is melt-kneaded in a coating apparatus, and then extrusion coated on the outer peripheral surface of a conductor or the like to be molded into a desired shape. A series of processes can be adopted.

In the present invention, molding conditions are not particularly limited, and conventionally employed conditions can be employed. Moreover, according to the production method of the present invention, for example, in extrusion molding, extrusion molding at a higher temperature (for example, resin temperature of 220 ° C. or more), long extrusion (for example, continuous extrusion for 24 hours or more), etc. Even under molding conditions where appearance defects tend to occur, a molded article having the above-described excellent characteristics can be produced.
In this way, a molded body of the heat-resistant silane crosslinkable resin composition is obtained. Similar to the heat-resistant silane crosslinkable resin composition, this molded body is partially crosslinked, but is in a partially crosslinked state that retains moldability that can be molded in the step (2). Therefore, the heat-resistant silane cross-linked resin molded product of the present invention is formed into a cross-linked or finally cross-linked molded product by performing the step (3).

In the manufacturing method of the heat-resistant silane crosslinked resin molding of the present invention, the step (3) of bringing the molded body obtained in the step (2) into contact with water is performed. Thereby, the trialkoxysilyl group of the silane coupling agent is hydrolyzed to become silanol, and the hydroxyl groups of silanol are condensed with each other by the silanol condensation catalyst present in the molded article, thereby causing a crosslinking reaction. In this way, a heat-resistant silane crosslinked resin molded product in which the silane coupling agent is crosslinked by silanol condensation can be obtained.
The process itself in this step (3) can be performed by a normal method. Condensation between silane coupling agents proceeds only by storage at room temperature in the presence of moisture. In particular, in the present invention, a sufficient degree of cross-linking can be obtained simply by storing the molded body at room temperature. Therefore, in the step (3), it is not necessary to positively contact the molded body with water, which contributes to energy saving.
In order to promote this cross-linking reaction, the molded body can be positively brought into contact with moisture. For example, immersion in room temperature water, storage in a high humidity environment, and the like can be mentioned. Furthermore, in order to advance the condensation reaction promptly, contact with water as necessary, such as immersion in warm water (for example, 50 to 90 ° C.), injection into a wet heat bath, exposure to high-temperature steam, etc. Can be adopted. In this case, pressure may be applied to allow moisture to penetrate inside.

  Thus, 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. As will be described later, this heat-resistant silane cross-linked resin molded product contains a cross-linked resin obtained by condensing a silane cross-linkable resin via a siloxane bond. One form of this silane crosslinked resin molding contains a silane crosslinked resin and an inorganic filler. Here, the inorganic filler may be bonded to the silane coupling agent of the silane cross-linked resin. Therefore, this silane cross-linked resin includes a cross-linked resin in which a plurality of cross-linked resins are bonded or adsorbed to an inorganic filler by a silane coupling agent and bonded (cross-linked) through the inorganic filler and the silane coupling agent, and the above cross-linkable resin. The trialkoxysilyl group of the silane coupling agent hydrolyzes and undergoes silanol condensation reaction with each other, thereby containing at least a crosslinked resin crosslinked via the silane coupling agent. Moreover, as for the silane crosslinking resin, a bond (crosslinking) via an inorganic filler and a silane coupling agent and a crosslinking via a silane coupling agent may be mixed. Furthermore, the silane coupling agent and the unreacted resin component and / or the silane crosslinkable resin which is not bridge | crosslinked may be included.

  The details of the reaction mechanism in the production method of the present invention are not yet clear, but are considered as follows. That is, when the resin component is heated and kneaded at a temperature equal to or higher than the decomposition temperature of the organic peroxide together with the inorganic filler and the silane coupling agent in the presence of the organic peroxide, the organic peroxide is decomposed to generate radicals, On the other hand, a graft reaction of the silane coupling agent occurs.

Due to the heating in the step (a-2), a chemical bond forming reaction is also caused by a covalent bond between the silane coupling agent and a site capable of chemical bonding such as a hydroxyl group on the surface of the inorganic filler.
In the present invention, the final cross-linking reaction may be performed in step (c). When a specific amount of the silane coupling agent is blended in the base resin as described above, the inorganic filler is not impaired without impairing the extrusion processability at the time of molding. Can be blended in a large amount, and while ensuring excellent flame retardancy, it can have both heat resistance and mechanical properties.

  Moreover, although the mechanism of the operation of the above process of the present invention is not yet clear, it is estimated as follows. That is, by using an inorganic filler and a silane coupling agent before and / or during kneading with the base resin, the silane coupling agent binds to the inorganic filler with a trialkoxysilyl group and is attached to the other end. The existing vinyl group is bonded to the uncrosslinked portion of the resin component and retained. Alternatively, it is physically or chemically adsorbed on the hole or surface of the inorganic filler without being bonded to the inorganic filler, and is held by being bonded to the resin component with the vinyl group present at the other end. Thus, a silane coupling agent that binds to an inorganic filler with a strong bond (for example, a chemical bond with a hydroxyl group on the surface of the inorganic filler may be considered) and a silane coupling agent that binds to a weak bond (for example, The reason can be, for example, an interaction by hydrogen bond, an interaction between ions, partial charges or dipoles, an action by adsorption, etc.). In this state, when the organic peroxide was added and kneaded, the silane coupling agent was hardly volatilized as described later, and the silane coupling agent having a different bond with the inorganic filler grafted to the resin component. A silane crosslinkable resin is formed.

  By the kneading described above, among the silane coupling agents, the silane coupling agent having a strong bond with the inorganic filler retains the bond with the inorganic filler, and the vinyl group which is a cross-linking group is grafted to the cross-linked site of the resin component. react. In particular, when a plurality of silane coupling agents are bonded to the surface of one inorganic filler particle through a strong bond, a plurality of resin components are bonded through the inorganic filler particle. By these reactions or bonds, the crosslinked network via the inorganic filler is expanded. That is, a silane crosslinkable resin formed by graft reaction of the silane coupling agent bonded to the inorganic filler onto the resin component is formed.

  In the case of a silane coupling agent having a strong bond with an inorganic filler, the condensation reaction in the presence of water by this silanol condensation catalyst is unlikely to occur, and the bond with the inorganic filler is retained. The reason why the silanol condensation reaction hardly occurs is considered to be that the binding energy between the inorganic filler and the silane coupling agent is very high and the condensation reaction does not occur even under the silanol condensation catalyst. Thus, the resin component and the inorganic filler are bonded, and the resin component is cross-linked through the silane coupling agent. As a result, the adhesiveness between the resin component and the inorganic filler is strengthened, and a molded article having good mechanical strength and wear resistance and hardly scratching is obtained. In particular, a plurality of silane coupling agents can be bonded to the surface of one inorganic filler particle, and high mechanical strength can be obtained. Thus, the silane coupling agent bonded with a strong bond to the inorganic filler is considered to contribute to high mechanical properties, and in some cases, wear resistance, scratch resistance, and the like.

On the other hand, among the silane coupling agents, the silane coupling agent having a weak bond with the inorganic filler is detached from the surface of the inorganic filler, and the vinyl group which is a crosslinking group of the silane coupling agent is decomposed by the organic peroxide. The graft reaction occurs by reacting with the radicals of the resin component generated by the extraction of hydrogen radicals by the generated radicals. That is, a silane crosslinkable resin is formed by graft reaction of the silane coupling agent released from the inorganic filler to the resin component. The silane coupling agent in the graft portion thus produced is then mixed with a silanol condensation catalyst and brought into contact with moisture to cause a condensation reaction (crosslinking reaction). The heat resistance of the heat-resistant silane cross-linked resin molded product obtained by this cross-linking reaction is increased, and a heat-resistant silane cross-linked resin molded product that does not melt even at high temperatures can be obtained. Thus, it is considered that the silane coupling agent bonded to the inorganic filler with a weak bond contributes to an improvement in the degree of crosslinking, that is, an improvement in heat resistance.
In particular, in the present invention, among the two types of silane coupling agents separated from the inorganic filler, vinyltrimethoxysilane having a small molecular weight and a small steric hindrance preferentially undergoes a graft reaction to the resin component. It is considered that vinyltriethoxysilane will later undergo a graft reaction at a site where vinyltrimethoxysilane is not grafted. Thereby, the silane coupling agent desorbed from the inorganic filler can be rapidly grafted to the resin component (before volatilization).
On the other hand, the triethoxysilyl group of vinyltriethoxysilane graft-reacted on the resin component has a relatively mild hydrolyzability, and the crosslinking reaction does not easily proceed in the molding process.
In the present invention, by using vinyltrimethoxysilane and vinyltriethoxysilane in a specific ratio as the silane coupling agent, the above-described action (grafting reactivity and crosslinking reactivity to the resin component) as the silane coupling agent is achieved. Both can be achieved at a high level. Therefore, according to this invention, the volatilization amount of the whole silane coupling agent can be reduced, and the coupling | bonding of resin components can also be suppressed. Furthermore, the silane coupling agent can undergo a crosslinking reaction under a wide range of conditions. As a result, it is considered that even if the molding conditions are widened, poor appearance hardly occurs, and sufficient heat resistance can be obtained by a crosslinking reaction at room temperature.

  In particular, in the present invention, the crosslinking reaction by the condensation using the silanol condensation catalyst in the presence of water in the step (c) is performed after forming the molded body. Thereby, as compared with the conventional method of forming a molded body after the final cross-linking reaction, the workability in the process up to the formation of the molded body is excellent, and higher heat resistance than before can be obtained.

  Furthermore, when the silane coupling agent is mixed with the inorganic filler by the production method of the present invention, the appearance is excellent because the condensation of the silane coupling agents is suppressed as described above. Moreover, the silane coupling agent is bonded to the inorganic filler, and is not easily volatilized during the melt kneading in the step (1), particularly the step (a-2), and the reaction between the free silane coupling agents is also possible. It can be effectively suppressed. Therefore, when the material stays in a high temperature state, for example, it is considered that a poor-appearance silane heat-resistant silane cross-linked resin molded article can be produced even when the extruder is temporarily stopped and restarted. . Here, once restarting after stopping, it cannot be unambiguously described depending on the composition of the base resin, processing conditions, etc., but for example, it can be restarted at 190 ° C. for an interval of 30 minutes, preferably 90 minutes. Say.

The production method of the present invention is a component of products such as products requiring heat resistance (including semi-finished products, parts, and members), products requiring strength, products requiring flame retardancy, rubber materials, etc. It can be applied to manufacture of the member. Therefore, the heat-resistant product of the present invention is such a product. At this time, the heat-resistant product may be a product including a heat-resistant silane cross-linked resin molded body, or may be a product composed only of a heat-resistant silane cross-linked resin molded body.
Examples of the heat-resistant product of the present invention include, for example, a coating material for a heat-resistant flame-retardant insulated wire or a heat-resistant flame-retardant cable, a rubber substitute wire / cable material, a heat-resistant flame-retardant electric wire component, a flame-resistant heat-resistant sheet, Examples include a flame-resistant heat-resistant film. Also included are power plugs, connectors, sleeves, boxes, tape substrates, tubes, sheets, packing materials, cushioning materials, anti-vibration materials, wiring materials used for internal and external wiring of electrical and electronic equipment, especially electric wires and optical cables. It is done.

The manufacturing method of the present invention is preferably applied particularly to the manufacture of electric wires and optical cables among the above products, and these coating materials (insulators and sheaths) can be formed under a wide range of molding and crosslinking conditions.
When the heat-resistant product of the present invention is an extrusion-molded product such as an electric wire or cable, preferably, the molding material is melt-kneaded in an extruder (extrusion coating apparatus) to prepare a heat-resistant silane crosslinkable resin composition. The heat-resistant silane crosslinkable resin composition can be produced by a method of extruding the outer periphery of a conductor or the like to coat the conductor or the like and then causing a crosslinking reaction. In this method, a heat-resistant silane crosslinkable resin composition to which a large amount of an inorganic filler has been added is used around a conductor, using a general-purpose extrusion coating apparatus without using a special machine such as an electron beam crosslinking machine, or It can be formed by extrusion coating around a conductor in which tensile strength fibers are vertically attached or twisted together. For example, a soft copper single wire or a stranded wire can be used as the conductor. In addition to the bare wire, a conductor plated with tin or an enameled insulating layer can be used as the conductor. The thickness of the insulating layer (the coating layer made of the heat-resistant silane crosslinkable resin molded body of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 to 5 mm.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.
In Tables 1 and 2, the numerical values related to the blending amounts in each example represent parts by mass unless otherwise specified.

  In Examples 1 to 15 and Comparative Examples 1 to 9, the following components were used and the respective specifications were set to the conditions shown in Tables 1 and 2, and the evaluation results described later in Tables 1 and 2 are shown. Also shown.

The detail of each compound shown in Table 1 and Table 2 is shown below.
<Base resin>
PE: “UE320” (Nippon Polyethylene Co., Ltd., Novatec PE (trade name), linear low density polyethylene resin (LLDPE), density 0.92 g / cm ³ )
EVA: “EV170” (trade name, manufactured by Mitsui DuPont Chemical Co., Ltd., ethylene-vinyl acetate copolymer resin (EVA), VA content 33 mass%, density 0.96 g / cm ³ )
EEA: “NUC6510” (trade name, manufactured by Nippon Unicar Company, ethylene-ethyl acrylate copolymer resin, EA content 23 mass%, density 0.93 g / cm ³ )
Styrene elastomer: “Septon 4077” (trade name, manufactured by Kuraray Co., Ltd., SEPS, styrene content: 30% by mass)
Oil: “Cosmo Neutral 500” (trade name, manufactured by Cosmo Oil Lubricants, paraffin oil)
Ethylene rubber: “EPT0045” (trade name, manufactured by Mitsui Chemicals, ethylene-propylene rubber, diene content 0 mass%, ethylene content 51 mass%)
Acrylic rubber: “Bay Mac DP” (trade name, manufactured by DuPont, acrylic rubber)
<Inorganic filler>
Magnesium hydroxide 1: “Kisuma 5” (trade name, manufactured by Kyowa Chemical Co., Ltd., surface untreated magnesium hydroxide)
Magnesium hydroxide 2: “Kisuma 5L” (trade name, manufactured by Kyowa Chemical Co., Ltd., silane coupling agent pretreated magnesium hydroxide, treatment amount 1 mass%)
Aluminum hydroxide: “Hijilite 42M” (trade name, manufactured by Showa Denko KK, surface untreated aluminum hydroxide)
Calcium carbonate: “Softon 1200” (trade name, manufactured by Shiraishi Calcium Co., Ltd., surface untreated calcium carbonate)
<Silane coupling agent>
KBM: “KBM-1003” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane)
KBE: “KBE-1003” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., vinyltriethoxysilane)
<Organic peroxide>
"Perkadox BC-FF" (trade name, Dicumyl peroxide (DCP) from Kayaku Akzo, decomposition temperature 149 ° C)
<Antioxidant>
"Irganox 1010" (trade name, manufactured by BASF, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate])
<Silanol condensation catalyst>
“ADK STAB OT-1” (trade name, manufactured by ADEKA, dioctyltin dilaurate)

(Examples 1-15 and Comparative Examples 1-9)
In Examples 1 to 15 and Comparative Examples 1 to 9, 5% by mass (PE) of the resin component constituting the base resin was used as a carrier resin for the catalyst MB.

  First, an inorganic filler and a silane coupling agent were put into a 10 L Henschel mixer manufactured by Toyo Seiki at a mass ratio shown in Table 1 or Table 2, and mixed at room temperature (25 ° C.) for 5 minutes to obtain a powder mixture. (Step (a-1)). Next, the mass shown in Table 1 or Table 2 is the powder mixture thus obtained, the resin component shown in the silane MB column of Table 1 or Table 2, the organic peroxide, and the antioxidant. The silane MB was obtained by introducing into a 2 L Banbury mixer manufactured by Nippon Roll Co., Ltd. and kneading for 5 minutes at a temperature equal to or higher than the decomposition temperature of the organic peroxide, specifically 200 ° C. (step (a-2)) ). The obtained silane MB contains a silane crosslinkable resin obtained by graft reaction of a silane coupling agent to the resin component.

On the other hand, the carrier resin, the silanol condensation catalyst, and the antioxidant were melt-mixed with a Banbury mixer at a mass ratio shown in Table 1 or Table 2 at 180 ° C. to obtain catalyst MB (step (b)). The catalyst MB is a mixture of a carrier resin and a silanol condensation catalyst.
Next, silane MB and catalyst MB were charged into a closed ribbon blender and dry blended at room temperature (25 ° C.) for 3 minutes to obtain a dry blend. In each example, the mixing ratio of silane MB and catalyst MB was such that the base resin of silane MB was 95 parts by mass and the carrier resin of catalyst MB was 5 parts by mass.

Next, the obtained dry blend was melt-mixed and molded under the following extrusion molding conditions (1) or (2) to obtain coated conductors (step (c) and step (2)), respectively.
<Extrusion conditions (1)>
The obtained dry blend was subjected to L / D (ratio between screw effective length L and diameter D) = 24 and screw having a screw diameter of 40 mm (feed portion screw temperature 160 ° C., compression portion screw temperature 190 ° C. The head temperature was 200 ° C.). While melt-mixing the dry blend in this extruder, the outer circumference of 1 / 0.8 A (conductor diameter 0.8 mm) was extruded at a linear speed of 5 m / min so as to have a coating thickness of 0.8 mm. A 4 mm coated conductor was obtained (step (c) and step (2)).

<Extrusion conditions (2)>
In the extrusion molding condition (1), a coated conductor was obtained in the same manner as in the extrusion molding condition (1) except that the compression part screw temperature was 220 ° C. and the head temperature was 240 ° C. (step (c) and step) (2)).

  The coated conductor obtained by the extrusion molding condition (1) or (2) was allowed to stand for 48 hours in an atmosphere of 23 ° C. and 50% humidity to produce an electric wire (step (3)). Thus, the electric wire was manufactured from the covering conductor which coat | covered the said conductor with the heat resistant silane crosslinked resin molded object by the said extrusion molding conditions (1) and (2). The heat-resistant silane cross-linked resin molding as the coating has the above-mentioned silane cross-linked resin.

  Each manufactured electric wire was subjected to the following test, and the results are shown in Tables 1 and 2.

<Appearance test 1>
In each electric wire manufactured using the coated conductor obtained under the extrusion molding condition (1), the appearance of a portion where 20 minutes had passed after the dry blend was extruded from the extruder was observed. “A” indicates that the wire appearance is excellent, “B” indicates that there is no problem in the wire appearance (acceptable extent as the wire appearance), and “C” indicates that the wire appearance is problematic. It was. An evaluation of “B” or higher is a passing level of this test.
<Appearance test 2>
Appearance test 2 is a test on an electric wire manufactured under long extrusion conditions.
In each electric wire manufactured using the coated conductor obtained under the above extrusion molding condition (1), the appearance of a portion where 3 hours had elapsed after the dry blend was extruded from the extruder was observed. The case where the appearance as an electric wire was excellent was designated as “A”, the case where there was no problem in the appearance as an electric wire was designated as “B”, and the case where the appearance as an electric wire was problematic was designated as “C”. An evaluation of “B” or higher is a passing level of this test.
<Appearance test 3>
Appearance test 3 is a test on an electric wire manufactured under high temperature extrusion conditions.
In each electric wire manufactured using the coated conductor obtained under the above extrusion molding condition (2), the appearance of a portion where 20 minutes had elapsed after extrusion of the dry blend from the extruder was observed. The case where the appearance as an electric wire was excellent was designated as “A”, the case where there was no problem in the appearance as an electric wire was designated as “B”, and the case where the appearance as an electric wire was problematic was designated as “C”. An evaluation of “B” or higher is a passing level of this test.
In addition, the electric wires used in the appearance test 3 were visually observed for foaming inside the electric wires.

<Heat resistance 1 hot water conditions>
The coated conductor obtained by the extrusion molding condition (1) was immersed in warm water at 70 ° C. for 12 hours to produce an electric wire (state A) (step (3)).
A hot set test was performed on the electric wire in state A according to the method described in IEC60881-2-1. A tubular piece was prepared from the electric wire, and a marked line with a length of 20 mm was attached. Then, a 20 N / cm ² weight was attached in a constant temperature bath at 200 ° C. and left for 15 minutes. Then, the length of the tubular piece was measured, and elongation rate (%) = elongation (mm) / 20 mm × 100 was obtained. The elongation rate is 50% or less as “A”, 50% to 100% or less as “B”, 100% or more elongation or breakage during the test as “C”, “B” The above was regarded as passing.

<Heat resistance 2 room temperature conditions>
The coated conductor obtained by the extrusion molding condition (1) was allowed to stand for 48 hours in an atmosphere of 23 ° C. and 50% humidity to produce an electric wire (state B). (Process (3))
A hot set test was conducted on the electric wire in state B in accordance with the method described in IEC60881-2-1. A tubular piece was prepared from the electric wire, and a marked line with a length of 20 mm was attached. Then, a 20 N / cm ² weight was attached in a constant temperature bath at 200 ° C. and left for 15 minutes. Then, the length of the tubular piece was measured, and elongation rate (%) = elongation (mm) / 20 mm × 100 was obtained. The elongation rate is 50% or less as “A”, 50% to 100% or less as “B”, 100% or more elongation or breakage during the test as “C”, “B” The above was regarded as passing.

Examples 1 to 15 all passed heat resistance 1, heat resistance 2, appearance test 1, appearance test 2 and appearance test 3. In Example 14, fine foaming was observed in the appearance test 3, but it was a pass. According to the production method of the present invention, a heat-resistant silane crosslinked molded article excellent in appearance and heat resistance was obtained without being influenced by molding conditions and crosslinking conditions.
In Comparative Example 1 which did not contain vinyltriethoxysilane and contained a small amount of vinyltrimethoxysilane, all of heat resistance 1, heat resistance 2, appearance test 1 and appearance test 3 failed. In Comparative Example 2 containing no vinyltriethoxysilane, the heat resistance 2 was not acceptable. In Comparative Example 3 with a small amount of vinyltriethoxysilane, the heat resistance 2 was not acceptable. In Comparative Examples 4 and 5, which did not contain vinyltrimethoxysilane, the heat resistance 2 failed. Comparative Example 6 containing no vinyltriethoxysilane failed in the appearance test 3, and foaming inside the electric wire was observed. In Comparative Example 7 in which the amount of the organic peroxide was too small, the heat resistances 1 and 2 were not acceptable. In Comparative Example 8 in which the amount of the organic peroxide was too large, the appearance tests 1 to 3 failed. In Comparative Example 9 having a large amount of vinyltrimethoxysilane, the appearance test 3 failed.
In Comparative Examples 4 to 6 and 9, the heat resistance 2 or the appearance test 3 does not reach the acceptance criteria of the present invention, but the heat resistance 1 and the appearance test 1 corresponding to the conventional evaluation criteria are acceptable levels.

Claims (9)

The following step (1), step (2) and step (3)
Step (1): Melting organic peroxide 0.01 to 0.6 parts by mass, inorganic filler 30 to 300 parts by mass, silane coupling agent, and silanol condensation catalyst with respect to 100 parts by mass of base resin. Step (2) for obtaining a mixture by mixing: Step (3) for obtaining a molded product by molding the mixture obtained in the step (1): The molded product obtained in the step (2) is mixed with water. A method for producing a heat-resistant silane cross-linked resin molded article, comprising a step of obtaining a heat-resistant silane cross-linked resin molded article by contact with the molded article,
The silane coupling agent includes 0.5 to 5 parts by mass of vinyltrimethoxysilane and 1.0 to 15 parts by mass of vinyltriethoxysilane with respect to 100 parts by mass of the base resin.
The step (1) includes the following step (a-1), step (a-2) and step (c), provided that a part of the base resin is melt-mixed in the following step (a-2). The manufacturing method of the heat resistant silane crosslinked resin molding which has the following process (a-1), a process (a-2), a process (b), and a process (c).
Step (a-1): Step of preparing a mixture by mixing at least the inorganic filler and the silane coupling agent Step (a-2): The mixture and all or part of the base resin are mixed with the organic solvent. Step of preparing a silane masterbatch by melting and mixing at a temperature equal to or higher than the decomposition temperature of the organic peroxide in the presence of an oxide Step (b): Melting and mixing the remainder of the base resin and the silanol condensation catalyst Step of preparing a catalyst master batch Step (c): Melting and mixing the silane master batch and the silanol condensation catalyst or the catalyst master batch   The manufacturing method of the heat resistant silane crosslinked resin molding of Claim 1 whose compounding quantity of the said vinyltrimethoxysilane is 0.5-2 mass parts with respect to 100 mass parts of said base resins.   The manufacturing method of the heat resistant silane crosslinked resin molding of Claim 1 or 2 whose compounding quantity of the said vinyl triethoxysilane is 1.0-5.0 mass parts.   The base resin contains at least one selected from polyethylene resin, polyolefin copolymer resin having acid copolymerization component or acid ester copolymerization component, ethylene rubber, acrylic rubber, styrene elastomer and chlorinated polyethylene resin, The manufacturing method of the heat-resistant silane crosslinked resin molding of any one of Claims 1-3. To 100 parts by mass of the base resin, 0.01 to 0.6 parts by mass of an organic peroxide, 30 to 300 parts by mass of an inorganic filler, a silane coupling agent, and a silanol condensation catalyst are melt-mixed to obtain a mixture. A method for producing a heat-resistant silane crosslinkable resin composition having the step (1) of obtaining,
The silane coupling agent includes 0.5 to 5 parts by mass of vinyltrimethoxysilane and 1.0 to 15 parts by mass of vinyltriethoxysilane with respect to 100 parts by mass of the base resin.
The step (1) includes the following step (a-1), step (a-2) and step (c), provided that a part of the base resin is melt-mixed in the following step (a-2). The manufacturing method of the heat resistant silane crosslinkable resin composition which has the following process (a-1), a process (a-2), a process (b), and a process (c).
Step (a-1): Step of preparing a mixture by mixing at least the inorganic filler and the silane coupling agent Step (a-2): The mixture and all or part of the base resin are mixed with the organic solvent. Step of preparing a silane masterbatch by melting and mixing at a temperature equal to or higher than the decomposition temperature of the organic peroxide in the presence of an oxide Step (b): Melting and mixing the remainder of the base resin and the silanol condensation catalyst Step of preparing a catalyst master batch Step (c): Melting and mixing the silane master batch and the silanol condensation catalyst or the catalyst master batch   A heat-resistant silane crosslinkable resin composition produced by the method for producing a heat-resistant silane crosslinkable resin composition according to claim 5.   A heat-resistant silane crosslinked resin molded product produced by the method for producing a heat-resistant silane crosslinked resin molded product according to any one of claims 1 to 5.   A heat-resistant product comprising the heat-resistant silane-crosslinked resin molded article according to claim 7. Heat resistance obtained by melting and mixing 0.01 to 0.6 parts by mass of an organic peroxide, 30 to 300 parts by mass of an inorganic filler, a silane coupling agent, and a silanol condensation catalyst with respect to 100 parts by mass of the base resin. A silane masterbatch used in the production of a functional silane crosslinkable resin composition,
The silane coupling agent includes 0.5 to 5 parts by mass of vinyltrimethoxysilane and 1.0 to 15 parts by mass of vinyltriethoxysilane with respect to 100 parts by mass of the base resin.
At least the inorganic filler and the silane coupling agent are mixed to prepare a mixture, and the resulting mixture and all or part of the base resin are decomposed in the presence of the organic peroxide. A silane masterbatch obtained by melt mixing at a temperature higher than the temperature.