JP6265876B2 - Heat-resistant silane cross-linked resin molded body and production method thereof, heat-resistant silane cross-linkable resin composition and production method thereof, silane masterbatch, and heat-resistant product using heat-resistant silane cross-linked resin molded body - Google Patents

Description

The present invention relates to a heat-resistant silane cross-linked resin molded article and a production method thereof, a heat-resistant silane cross-linkable resin composition and a production method thereof, a silane master batch, and a heat-resistant product using the heat-resistant silane cross-linked resin molded article.
More specifically, the heat-resistant silane cross-linked resin molded article having excellent appearance and flame retardancy, and more preferably excellent mechanical properties, a production method with improved moldability, and the heat-resistant silane cross-linked resin molded article The present invention relates to a silane master batch, a heat-resistant silane cross-linkable resin composition and a method for producing the same, and a heat-resistant product using the heat-resistant silane cross-linked resin molded body as an electric wire insulator or sheath.

Insulated wires, cables, cords and optical fiber cores, and optical fiber cords used for electrical and electronic equipment internal and external wiring are flame retardant, heat resistant, and mechanical properties (eg tensile properties, wear resistance) Various characteristics are required.
As a material used for these wiring materials, a resin composition containing a large amount of a metal hydrate such as magnesium hydroxide or aluminum hydroxide is used.

Moreover, wiring materials, such as a flexible rubber electric wire and a rubber cabtyre cable, may be instantaneously exposed to a temperature of 100 ° C. or higher, and heat resistance against this is also required. Furthermore, various characteristics such as characteristics that do not collapse even when pressure is applied from the outside are required.
In order to satisfy such a requirement, a method of crosslinking the coating material by a chemical crosslinking method or the like has been taken for the purpose of imparting high heat resistance and rubber elasticity to the wiring material.

Conventionally, as a method of cross-linking polyolefin resins such as polyethylene and rubbers such as ethylene propylene rubber and chloroprene, an electron beam cross-linking method in which an electron beam is irradiated to form a bridge (also called cross-linking); A chemical crosslinking method and a silane crosslinking method in which a peroxide or the like is decomposed to cause a crosslinking reaction are known.
Of these cross-linking methods, the silane cross-linking method in particular does not require special equipment and can be used in a wide range of fields.

The silane crosslinking method is a method in which a hydrolyzable silane coupling agent having an unsaturated group is grafted to a polymer in the presence of an organic peroxide to obtain a silane graft polymer, and then the silane grafting in the presence of a silanol condensation catalyst. This is a method for obtaining a crosslinked molded article by bringing a polymer into contact with moisture.
Specifically, a method for producing a halogen-free heat-resistant silane crosslinked resin includes, for example, a silane master batch obtained by grafting a hydrolyzable silane coupling agent having an unsaturated group to a polyolefin resin, a polyolefin resin, and an inorganic filler. In this method, a heat-resistant masterbatch obtained by kneading and a catalyst masterbatch containing a silanol condensation catalyst are melt-mixed. However, in this method, when the inorganic filler exceeds 100 parts by mass with respect to 100 parts by mass of the polyolefin resin, after the dry mixing of the silane masterbatch and the heat-resistant masterbatch, uniformly in a single screw extruder or a twin screw extruder It becomes difficult to melt and knead. For this reason, there is a problem that the appearance is deteriorated and the physical properties are greatly reduced. Moreover, the problem that an extrusion load cannot be made high arises.
Therefore, in order to uniformly melt and knead the silane masterbatch and the heat-resistant masterbatch after dry mixing, the proportion of the inorganic filler is limited as described above. Therefore, it has been difficult to achieve high flame resistance and high heat resistance.

Usually, when such inorganic filler exceeds 100 parts by mass with respect to 100 parts by mass of polyolefin resin, it is common to use a continuous mixer, a closed mixer such as a pressure kneader or a Banbury mixer. is there.
On the other hand, when performing silane grafting with a kneader or a Banbury mixer, the hydrolyzable silane coupling agent having an unsaturated group is generally highly volatile and has a problem of volatilizing before the graft reaction. Therefore, it was very difficult to prepare a desired silane cross-linked master batch.

Therefore, when preparing a heat-resistant silane masterbatch with a Banbury mixer or kneader, a hydrolyzable silane coupling agent having an unsaturated group is added to the heat-resistant masterbatch obtained by melting and mixing a polyolefin resin and an inorganic filler. A method of adding an organic peroxide and causing a graft reaction with a single screw extruder is conceivable.
However, in this method, appearance defects may occur in the molded product obtained due to variation in reaction. Moreover, the compounding quantity of the inorganic filler of a masterbatch must be increased very much, and an extrusion load may become remarkably large. As a result, it becomes very difficult to manufacture the molded body. As a result, it has been difficult to obtain a desired material or molded body. In addition, the manufacturing process has two processes, which is a difficulty in manufacturing cost.

  Moreover, even if polyolefin resin, rubber, etc. are cross-linked by the above-described conventional process, the silane cross-linked body has many non-cross-linked parts, and there are cases where a large amount of inorganic filler cannot be blended. Therefore, there has been a problem that sufficient rubber elasticity cannot be imparted and the crosslinked silane is easily crushed when an external force is applied.

In Patent Document 1, an inorganic filler, a silane coupling agent, an organic peroxide, and a cross-linking catalyst that are surface-treated with a silane coupling agent on a resin component obtained by mixing a polyolefin resin and a maleic anhydride resin in a kneader. A method of forming with a single screw extruder after sufficiently melt-kneading has been proposed.
In addition, Patent Documents 2 to 4 describe a vinyl aromatic thermoplastic elastomer composition containing a block copolymer or the like as a base resin and a non-aromatic rubber softener added as a softener, and a silane surface-treated inorganic material. A method of partial crosslinking using an organic peroxide through a filler has been proposed.
Furthermore, in Patent Document 5, an organic peroxide, a silane coupling agent, and a metal hydrate are collectively melt-kneaded with a base material, further melt-molded with a silanol condensation catalyst, and then crosslinked in the presence of water. Thus, a method for easily obtaining a cable having heat resistance has been proposed.

JP 2001-101928 A JP 2000-143935 A JP 2000-315424 A JP 2001-240719 A JP 2012-255077 A

However, in the method described in Patent Document 1, the resin partially cross-links during melt-kneading with a Banbury mixer or kneader, resulting in poor appearance of the resulting molded body (forming a number of protrusions protruding on the surface). ) May occur. Furthermore, most of the silane coupling agent other than the silane coupling agent that is treating the surface of the inorganic filler may be volatilized or condensed. For this reason, desired heat resistance cannot be obtained, and condensation between silane coupling agents may cause deterioration of the appearance of the electric wire.
Moreover, even if it is the method described in patent documents 2-4, since resin has not yet sufficient network structure, the coupling | bonding of resin and an inorganic filler is cut | disconnected at high temperature. Therefore, the molded body melts at a high temperature, and for example, the insulating material sometimes melts during soldering of the electric wire. Further, the molded body may be deformed or foamed during secondary processing. Further, the rubber elasticity is insufficient, and the molded body is easily crushed when an external force is applied, and the molded body is easily deformed at a high temperature.

The method described in Patent Document 5 is liable to cause poor appearance due to rough appearance or unevenness (also referred to as external appearance) when a silane-crosslinkable flame retardant polyolefin obtained by batch melting and kneading is extruded together with a silanol condensation catalyst. In particular, when cleaning the extruder, when changing the setup, or when adjusting the eccentricity, it is confirmed that the molded product formed thereafter is likely to have rough appearance and irregularities, resulting in poor appearance. It was.
In addition, the molded body obtained by the method described in Patent Document 5 is easily crushed when pressure is applied, and cannot solve the problems of conventional chemically crosslinked rubber materials, and can be used as an alternative. There was no problem.

The present invention overcomes the problems of conventional silane cross-linking methods, has excellent appearance and flame retardancy, is easy to mold, and more preferably has a heat-resistant silane cross-linked resin molded article having excellent mechanical properties and production thereof It is an object to provide a method.
Moreover, this invention makes it a subject to provide the silane masterbatch which can form this heat resistant silane crosslinked resin molded object, a heat resistant silane crosslinked resin composition, and its manufacturing method.
Furthermore, this invention makes it a subject to provide the heat resistant product using the heat resistant silane crosslinked resin molded object obtained with the manufacturing method of the heat resistant silane crosslinked resin molded object.

That is, the subject of this invention was achieved by the following means.
<1> ethylene, alpha-olefin and at least Tane含 free base resin _(R B) an ethylene rubber consisting of terpolymers of diene with respect to 100 parts by weight of an organic peroxide 0.01 part by mass or more 0 Step (a) of obtaining a mixture by melting and mixing 6 parts by mass or less, 70 parts by mass or more and 400 parts by mass or less of inorganic filler, 4 parts by mass or more of silane coupling agent and 15.0 parts by mass or less and a silanol condensation catalyst, A method for producing a heat-resistant silane cross-linked resin molded product, comprising the step (b) of obtaining a molded product by molding a mixture and the step (c) of obtaining a heat-resistant silane cross-linked resin molded product by bringing the molded product into contact with water. Because
Wherein step (a) comprises the following steps (1) and step (3), the following step (1) in the case of melt-mixing a part of the base resin in the following step (1) _{(R B),} A method for producing a heat-resistant silane-crosslinked resin molded product, comprising the steps (2) and (3) .
[Step (a)]
Step (1): Melting and mixing all or part of the base resin (R _B ), the organic peroxide, the inorganic filler, and the silane coupling agent at a temperature equal to or higher than the decomposition temperature of the organic peroxide. , step preparing a silane masterbatch (2): the base resin by melt mixing the remainder and the silanol condensation catalyst (R _B), the step step (3) for preparing the catalyst masterbatch: and the silane masterbatch the content of the silanol condensation catalyst or as engineering that mixing the catalyst masterbatch <2> the silane coupling agent is, the base resin (R _B) relative to 100 parts by weight, 15.0 wt than 6 parts by weight <1> The manufacturing method of the heat-resistant silane crosslinked resin molding as described in <1> below.
<3> The method for producing a heat-resistant silane-crosslinked resin molded article according to <1> or <2>, wherein the base resin (R _B ) further contains an organic mineral oil or a styrene-based elastomer .
<4> the base resin (R _B) is, the ethylene rubber and one or both of the styrene-based elastomer containing 50 wt% or less than 2 wt%, containing said organic mineral oil 2 mass% to 40 mass% The manufacturing method of the heat-resistant silane crosslinked resin molding as described in <3>.
<5> the base resin (R _B) is further ethylene - vinyl acetate copolymer and ethylene - of at least one selected from the group consisting of methacrylate ester copolymers, acid copolymers component or ester copolymer <1>-<4> The manufacturing method of the heat resistant silane crosslinked resin molding of any one of <1>-<4> which contains the polyolefin copolymer which has a polymerization component 20 mass% or more and 75 mass% or less.
<6> The base resin (R _B ) is further modified with an acid-modified polyolefin resin modified with an unsaturated carboxylic acid, an acid-modified ethylene rubber modified with an unsaturated carboxylic acid, and an acid modified with an unsaturated carboxylic acid. <1> to <5>, wherein at least one acid-modified resin selected from the group consisting of styrene-based elastomers is contained in an amount of 2% by mass to 30% by mass. Body manufacturing method.
<7> The method for producing a heat-resistant silane crosslinked resin molded article according to any one of <1> to <6>, wherein the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.
<8> The method for producing a heat-resistant silane-crosslinked resin molded article according to any one of <1> to <7>, wherein the melt mixing in the step (a) is performed with a closed mixer.
<9> ethylene, alpha-olefin and at least Tane含 free base resin _(R B) an ethylene rubber consisting of terpolymers of diene with respect to 100 parts by weight of an organic peroxide 0.01 part by mass or more 0 .6 parts by mass or less, 70 parts by mass or more and 400 parts by mass or less of the inorganic filler, more than 4 parts by mass of the silane coupling agent and 15.0 parts by mass or less and a step (a) of obtaining a mixture by melting and mixing the silanol condensation catalyst. A method for producing a heat-resistant silane crosslinkable resin composition,
When the step (a) includes the following step (1) and step (3), and a part of the base resin (R _B ) is melt-mixed in the following step (1), the following step (1) and step (2) The manufacturing method of the heat resistant silane crosslinkable resin composition characterized by having a process (3) .
[Step (a)]
Step (1): Melting and mixing all or part of the base resin (R _B ), the organic peroxide, the inorganic filler, and the silane coupling agent at a temperature equal to or higher than the decomposition temperature of the organic peroxide. , step preparing a silane masterbatch (2): the base resin by melt mixing the remainder and the silanol condensation catalyst (R _B), the step step (3) for preparing the catalyst masterbatch: and the silane masterbatch method of preparing the silanol condensation catalyst or a heat resistant silane crosslinkable resin composition, wherein the <br/> as engineering that mixing the catalyst masterbatch.

<10> The heat-resistant silane crosslinkable resin composition comprising been produced by the method according to <9>.
<11> the <1> to heat silane crosslinked resin molded body formed is manufactured by the method according to any one of <8>.
<12> The heat resistant silane crosslinked resin molded product according to <11>, wherein the heat resistant silane crosslinked resin molded product includes a resin formed by crosslinking with an inorganic filler through a silanol bond of a silane coupling agent.
<13> heat-resistant product comprising a heat resistant silane crosslinked resin molded product according to <11> or <12>.
<14> The heat-resistant product according to <13>, wherein the heat-resistant silane-crosslinked resin molded body is provided as a coating for an electric wire or an optical fiber cable.
<15> ethylene, alpha-olefin and at least Tane含 free base resin _(R B) an ethylene rubber consisting of terpolymers of diene with respect to 100 parts by weight of an organic peroxide 0.01 part by mass or more 0 .6 parts by mass or less, 70 parts by mass or more and 400 parts by mass or less of an inorganic filler, more than 4 parts by mass of a silane coupling agent and 15.0 parts by mass or less and a heat-resistant silane crosslinkable resin composition obtained by melt-mixing a silanol condensation catalyst. A silane masterbatch used in the production of
A silane master obtained by melt-mixing all or part of the base resin (R _B ), the organic peroxide, the metal hydrate, and the silane coupling agent at a temperature equal to or higher than the decomposition temperature of the organic peroxide. batch.

In the present invention, the “base resin (R _B )” is a resin for forming a heat-resistant silane cross-linked resin molded product or a heat-resistant silane cross-linkable resin composition.
In the present invention, the term "part of the base resin (R _B)", a resin used in step (1) of the base resin (R _B), the base resin (R _B) portion of itself (base resins having the same composition as the (R _B)), a part of the resin component constituting the base resin (R _B), a part of the resin component constituting the base resin (R _B) (e.g., among the plurality of resin components Specific resin component total amount).
Further, "the rest of the base resin (R _B)", a remainder of the base resin except for a part to be used in the base resin (R _B) Step (1) of, in particular, the base resin (having the same composition as the base resin _{(R B)) (R B} ) itself the remainder, the remainder of the resin component constituting the base resin (R _B), refers to the remaining resin component constituting the base resin (R _B) .
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.

The production method of the present invention overcomes the problems of the conventional silane crosslinking method, has excellent appearance and flame retardancy, and is easy to mold (extrudability is good, especially extrudability after stopping the extruder once is good) ) A heat-resistant silane crosslinked resin molded product can be produced. More preferably, a heat-resistant silane cross-linked resin molded product having excellent mechanical properties can be produced.
According to the present invention, the inorganic filler and the silane coupling agent are mixed before and / or during the kneading with the base resin (R _B ) to thereby volatilize the silane coupling agent during the kneading. Therefore, a heat-resistant silane crosslinked resin molded product can be efficiently produced.
Furthermore, a highly heat-resistant silane cross-linked resin molded body in which a large amount of inorganic filler is added can be produced without using a special machine such as an electron beam cross-linking machine.

According to the present invention, it is possible to provide a silane masterbatch, a heat-resistant silane cross-linkable resin composition, and a method for producing the same, which can form a heat-resistant silane cross-linked resin molded article excellent in appearance and flame retardancy.
Further, according to the present invention, a heat-resistant product using the heat-resistant silane cross-linked resin molded product can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

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 includes at least the steps (1) and (3) below. Step (a) is performed.
Accordingly, the “method for producing a heat-resistant silane cross-linked resin molded product” of the present invention and the “method for producing a heat-resistant silane cross-linkable resin composition” of the present invention (in the explanation of the common parts of both, The manufacturing method of the present invention is sometimes described below.

Step (a): a polyolefin resin, the base resin (R _B) containing at least one selected from the group consisting of ethylene rubber and styrene-based elastomer based on 100 parts by weight of an organic peroxide 0.01 parts by mass or more 0. Step of obtaining a mixture by melting and mixing 6 parts by mass or less, 70 to 400 parts by mass of an inorganic filler, exceeding 4 parts by mass of a silane coupling agent and 15.0 parts by mass or less and a silanol condensation catalyst Step (b): Mixture Step (c): Step of obtaining a heat-resistant silane-crosslinked resin molded body by bringing the molded body into contact with water

Then, the step (a) has at least steps (1) and (3) in the case of melt-mixing all of the base resin (R _B) in the following steps (1), the following step (1) When a part of the base resin (R _B ) is melt-mixed, at least the following steps (1), (2) and (3) are included.
Step (1): All or a part of the base resin (R _B ), an organic peroxide, an inorganic filler, and a silane coupling agent are melt-mixed at a temperature equal to or higher than the decomposition temperature of the organic peroxide, and a silane master batch is prepared. preparation for process step (2) base resin by melt mixing the remainder and silanol condensation catalyst (R _B), the step preparing the catalyst masterbatch (3): silane masterbatch and a silanol condensation catalyst or catalyst masterbatch Here, mixing means obtaining a uniform mixture.

First, each component used in the present invention will be described.
<Base resin _(R B)>
Base resin used in the present invention (R _B) as a resin component, a polyolefin resin contains at least one selected from the group consisting of ethylene rubber and styrene-based elastomer.
In the present invention, the base resin (R _B ) preferably contains a polyolefin resin, and more preferably contains at least one of ethylene rubber and styrene elastomer.
The base resin (R _B ) is an acid-modified polyolefin resin modified with an unsaturated carboxylic acid, an acid-modified ethylene rubber modified with an unsaturated carboxylic acid, and an acid-modified styrene modified with an unsaturated carboxylic acid. It is preferable that at least one acid-modified resin selected from the group consisting of an elastomer is contained as a resin component.
Further, the base resin (R _B ) preferably contains an organic mineral oil as an oil component. In this case, the base resin (R _B ) is at least one selected from the group consisting of polyolefin resin, ethylene rubber and styrene elastomer as the resin component, and organic mineral oil as the oil component as an essential component. Contains the ingredients.

In the base resin (R _B ), the content of each component is appropriately adjusted so that the total of each component is 100% by mass, and is preferably selected from the following range.

(Polyolefin resin)
The polyolefin resin used as the resin component in the present invention is not particularly limited as long as it is a resin composed of a polymer obtained by polymerizing or copolymerizing a compound having an ethylenically unsaturated bond. The well-known thing currently used for the composition can be used.
For example, polymers such as polyethylene, polypropylene, ethylene-α-olefin copolymers, block copolymers of polypropylene and ethylene-α-olefin resins, polyolefin copolymers having acid copolymerization components or acid ester copolymerization components And rubbers of these polymers, elastomers (excluding ethylene rubber and styrene elastomers), and the like.
Among these, polyethylene, polypropylene, and ethylene-α-olefin co-polymers are highly receptive to various inorganic fillers such as metal hydrates and can maintain mechanical strength even when a large amount of inorganic filler is blended. Each resin such as a polyolefin copolymer having a polymer, an acid copolymerization component or an acid ester copolymerization component is suitable.
These polyolefin resins may be used individually by 1 type, or may use 2 or more types together. When two or more types are used in combination, each resin to be combined is not particularly limited, and at least one of polyethylene and polypropylene, and a resin composed of a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component; The combination of is preferable.

Polyethylene is not particularly limited as long as it is a polymer containing an ethylene component as a constituent component. Polyethylene is a homopolymer consisting only of ethylene, a copolymer of ethylene and 5 mol% or less α-olefin (excluding propylene), and 1 mol% or less having only carbon, oxygen and hydrogen atoms in the functional group of ethylene and ethylene. And copolymers with non-olefins (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 polyethylene used in the present invention includes 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). Preferably, linear low density polyethylene and low density polyethylene are mentioned.
Polyethylene may be used individually by 1 type, and may use 2 or more types together.

Polypropylene is not particularly limited as long as it is a polymer containing propylene as a constituent component. Polypropylene includes propylene homopolymer, ethylene-propylene copolymer such as random polypropylene, and block polypropylene as a copolymer.
Here, “random polypropylene” refers to a copolymer of propylene and ethylene having an ethylene component content of 1 to 5% by mass. “Block polypropylene” is a composition containing homopolypropylene and an ethylene-propylene copolymer, with an ethylene component content of about 5 to 15% by mass, and an ethylene component and a propylene component present as independent components. Say what you do.
Polypropylene may be used alone or in combination of two or more.

The ethylene-α-olefin copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms (excluding those contained in polyethylene and polypropylene).
Specific examples of the α-olefin component in the ethylene-α-olefin copolymer include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. These components are mentioned. The ethylene-α-olefin copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms (excluding those contained in polyethylene and polypropylene). Specific examples include ethylene-propylene copolymers (excluding those contained in polypropylene), ethylene-butylene copolymers, and ethylene-α-olefin copolymers synthesized in the presence of a single site catalyst. It is done. An ethylene-alpha-olefin copolymer may be used individually by 1 type, and may use 2 or more types together.

Examples of the acid copolymerization component or acid ester copolymerization component in the polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component include carboxylic acid compounds such as (meth) acrylic acid, and vinyl acetate and (meth) acrylic. Examples include acid ester compounds such as acid alkyls. Here, the alkyl group of the alkyl (meth) acrylate preferably has 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Examples of the polyolefin copolymer (excluding those contained in polyethylene) having an acid copolymerization component or an acid ester copolymerization component include, for example, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, Examples include ethylene- (meth) acrylic acid alkyl copolymers. Among these, an ethylene-vinyl acetate copolymer and an ethylene-alkyl methacrylate copolymer are preferable, and an ethylene-vinyl acetate copolymer is more preferable from the viewpoint of acceptability and heat resistance of the inorganic filler. As the ethylene-alkyl methacrylate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-butyl acrylate copolymer are preferable.
The polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component is used singly or in combination of two or more.

If the base resin (R _B) contains a polyolefin resin, the content of the base resin (R _B) in the polyolefin resin is not particularly limited, is possible to form a strong network when the polyolefin resin is contained Yes, high heat resistance can be obtained.
Further, as the polyolefin resin, a resin comprising a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, for example, at least one kind of ethylene-vinyl acetate copolymer and ethylene-alkyl methacrylate copolymer When the resin comprising the copolymer is included, the content of the resin comprising the copolymer in the base resin (R _B ) is not particularly limited, but is preferably 20 to 75% by mass.

(Ethylene rubber)
The ethylene rubber used as the resin component in the present invention 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. 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 component, each α-olefin component having 3 to 12 carbon atoms is preferable, and specific examples thereof include those listed for the olefin copolymer. Specific examples of the conjugated diene constituent component include constituent components such as butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the butadiene constituent component is preferable. Specific examples of the non-conjugated diene component include, for example, dicyclopentadiene (DCPD), ethylidene norbornene (ENB), 1,4-hexadiene, 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.

  As for ethylene rubber, 20-60 mass% is preferable and, as for the ethylene structural-component amount (it is called ethylene amount) in a copolymer, 25-45 mass% is more preferable. The method for measuring the amount of ethylene is a value measured in accordance with the method described in ASTM D3900.

If the base resin _{(R B)} contains ethylene rubber, the content of the base resin _{(R B)} in is not particularly limited, but is preferably 0 to 40 wt%, more preferably from 0 to 25 wt%, 3 20 mass% is more preferable. When the ethylene rubber content exceeds 40% by mass, the appearance may be deteriorated when extrusion is resumed after the extruder is stopped.
Range content of the ethylene rubber has only to meet the above content, but if the base resin (R _B) contains ethylene rubber and styrenic elastomers, the total of the content of the styrene elastomer is below More preferably it is within.

Ethylene rubber has only to meet the above content, but if the base resin (R _B) contains ethylene rubber and organomineral oils, the content of ethylene rubber content of organic mineral oil to be described later The mass ratio (organic mineral oil: ethylene rubber) is preferably 3: 1 to 0.1: 1, more preferably 2.5: 1 to 0.3: 1, and 1.5: 1 to More preferably, it is 0.3: 1. When this mass ratio is in the above range, the organic mineral oil is almost oiled into the ethylene rubber, and the ability to prevent the mixing of moisture is increased, and the oil resistance is increased. In addition, bleeding of organic mineral oil can be prevented even after long-term storage after molding.

(Styrene elastomer)
The styrenic elastomer used as a resin component in the present invention refers to a polymer comprising a polymer having an aromatic vinyl compound as a constituent component in the molecule. Accordingly, in the present invention, if the polymer contains an ethylene constituent component in the molecule but an aromatic vinyl compound constituent component, it is classified as a styrene elastomer.
As such a styrene-based elastomer, a block copolymer and a random copolymer of a conjugated diene compound and an aromatic vinyl compound, or a hydrogenated product thereof is preferable. Examples of the constituent component of the aromatic vinyl compound in the polymer include styrene, p- (tert-butyl) styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N— Examples of the constituent components include diethyl-p-aminoethylstyrene and vinyltoluene. Among these, a styrene constituent component is preferable. The structural component of an aromatic vinyl compound is used individually by 1 type, or 2 or more types are used together. Examples of the constituent component of the conjugated diene compound include those exemplified for ethylene rubber, and among them, a butadiene constituent component is preferable. The structural component of a conjugated diene compound is used individually by 1 type, or 2 or more types are used together. 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.

  As a styrene-type elastomer, it is preferable that content of a styrene structural component is 25% or more. When the styrene content is less than 25% by mass, the oil resistance may be lowered or the wear resistance may be lowered.

Examples of the styrene elastomer include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), hydrogenated SBS, styrene-ethylene-ethylene-propylene-styrene block. Copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), hydrogenated SIS, hydrogenated styrene / butadiene rubber (HSBR), hydrogenated acrylonitrile / butadiene rubber (HNBR), etc. Can be mentioned.
As the styrene elastomer, commercially available products can be used. For example, Septon 4077, Septon 4055, Septon 8105 (all trade names, manufactured by Kuraray Co., Ltd.), Dynalon 1320P, Dynalon 4600P, 6200P, 8601P, 9901P (all trade names) Can be used.

If the base resin _{(R B)} contains a styrene elastomer, the content of the base resin _{(R B)} in is not particularly limited, but is preferably 0 to 50 wt%, preferably from 5 to 35 wt%. When the content rate of a styrene-type elastomer exceeds 50 mass%, it may have a bad influence on heat resistance or long-term heat resistance.

The styrene-based elastomer only needs to satisfy the above content, but when the base resin (R _B ) further contains ethylene rubber, the total content with the ethylene rubber content is preferably 2 to 50% by mass, 5-35 mass% is further more preferable. If the total content of the styrene elastomer and ethylene rubber is within the above range, it may be difficult to cause rough appearance due to resin stagnation in the extruder during long extrusion, or it may be restarted even if the extruder is stopped. In such cases, it is difficult to cause rough appearance, and a molded article having an excellent appearance can be obtained.

The content of the styrene elastomer has only to meet the above content, but if the base resin (R _B) further contains ethylene rubber, and the content of the ethylene rubber and the content of the styrene elastomer The mass ratio (ethylene rubber: styrene elastomer) is preferably 0: 100 to 25:75, more preferably 0: 100 to 50:50, and 0: 100 to 60:40. Further preferred. When this mass ratio is within the above range, even when the extruder is stopped, appearance roughness hardly occurs when it is restarted, and a molded article having an excellent appearance can be obtained.

The content of the styrene elastomer and the ethylene rubber has only to meet the above content, but if the base resin (R _B) is further contain organic mineral oils, and content of organic mineral oil to be described later The mass ratio with respect to the content of the styrene elastomer (organic mineral oil: styrene elastomer) is preferably 4: 1 to 1: 3, more preferably 2: 1 to 1: 2, 1.5 : It is more preferable that it is 1-1: 1.5. When this mass ratio is within the above range, the organic mineral oil is almost oiled into the styrene elastomer, and it is difficult for water to be mixed in and the oil resistance is improved. In addition, bleeding of organic mineral oil can be prevented even after long-term storage after molding.

(Acid-modified resin)
The acid-modified resin used as a resin component in the present invention is an acid-modified polyolefin resin obtained by modifying each polymer of the polyolefin resin with an unsaturated carboxylic acid, and each polymer of the ethylene rubber is modified with an unsaturated carboxylic acid. Acid-modified ethylene rubber, and acid-modified styrene-based elastomers obtained by modifying each polymer of the styrene-based elastomer with an unsaturated carboxylic acid.
Among them, a resin grafted with an unsaturated carboxylic acid and / or a resin grafted with (meth) acrylic acid is preferable. Particularly preferred is a resin grafted with maleic anhydride. Specific examples include maleic anhydride-modified polyolefin resin, maleic anhydride-modified styrene elastomer, maleic anhydride-modified ethylene-propylene-diene rubber, and the like.

  Although it does not specifically limit as an acid used for acid modification, Unsaturated carboxylic acid or its derivative (s) is mentioned. Examples of the unsaturated carboxylic acid include maleic acid, itaconic acid, fumaric acid and the like. Examples of unsaturated carboxylic acid derivatives include maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester, fumaric anhydride, etc. be able to. Of these, maleic acid and maleic anhydride are preferable. The amount of acid modification is usually about 0.1 to 7% by mass in one molecule of the acid-modified polymer.

If the base resin _{(R B)} contains an acid-modified resin, the content of the base resin _{(R B)} is not particularly limited, but is preferably 2 to 30 mass%, more preferably 5 to 25 wt%. When the content of the acid-modified resin is within the above range, a high-strength heat-resistant crosslinked body can be obtained, and an effect that a molded body having an excellent appearance can be obtained can be obtained. If it exceeds 30% by mass, if the extruder is stopped, the appearance will be remarkably deteriorated at the time of restart, or the viscosity of the resin will become very high and extrusion molding will become difficult.

(Organic mineral oil)
The organic mineral oil used as the oil component in the present invention is not particularly limited, but is an oil composed of a hydrocarbon having an aromatic ring, an oil composed of a hydrocarbon having a naphthenic ring, and an oil composed of a hydrocarbon having a paraffin chain. The mixed oil containing the oil is preferable, and the non-aromatic organic oil is more preferable. When the resin contains an organic mineral oil, it is possible to produce a silane-crosslinked resin molded article having an excellent appearance by suppressing the generation of scum.
Aromatic organic oil refers to those having 30% or more of the number of carbon atoms constituting the aromatic ring relative to the total number of carbon atoms constituting the aromatic ring, naphthene ring and paraffin chain. The non-aromatic organic oil preferably used in the present invention refers to a non-aromatic organic oil having less than 30% of the total number of carbon atoms constituting the aromatic ring.
As such a non-aromatic organic oil, the number of carbon atoms constituting the naphthene ring is 30 to 40% of the total number of carbons, and the number of carbon atoms constituting the paraffin chain is based on the total number of carbons. Examples thereof include naphthenic oil that is less than 50% and paraffin oil in which the number of carbon atoms constituting the paraffin chain is 50% or more with respect to the total number of carbons. The non-aromatic organic oil is preferably paraffin oil.

From the viewpoint of preventing swelling at high temperatures, the organic mineral oil preferably has an aniline point of 80 ° C. or higher, and more preferably 100 ° C. or higher. When the aniline point is 80 ° C. or higher, the strength of the heat-resistant silane cross-linked resin molded article at a high temperature can be maintained. Although an aniline point is not specifically limited, 160 degrees C or less is preferable. The aniline point can be measured according to JIS K 2256: 1996.
The kinematic viscosity at 40 ° C. of the organic mineral oil is preferably 30 to 400 mm ² / s. If the kinematic viscosity is too high, the effect of softening the resin may be reduced, and the dispersion of the rubber material may be deteriorated. On the other hand, if the kinematic viscosity is too low, it tends to volatilize during kneading and molding, or it may easily come off from the molded body (blooming). The kinematic viscosity is measured according to JIS K 2283.

  Examples of the non-aromatic organic oil used in the present invention include Diana Process Oil PW90 and PW380 (both trade names, manufactured by Idemitsu Kosan Co., Ltd.), Cosmo Neutral 500 (Cosmo Oil Co., Ltd.), and the like.

If the base resin _{(R B)} contains an organic mineral oil, the content of the base resin _{(R B)} is not particularly limited, but is preferably 2 to 40 wt%, more preferably from 5 to 30 mass%, 5 More preferred is ˜25% by mass. If the content of the organic mineral oil is too small, it may be liable to be generated when the extruder is stopped. On the other hand, when the amount is too large, bloom of non-aromatic organic oil may occur when the heat-resistant silane crosslinked resin molded product is left for a long time.

  In addition to the above-described components, the resin may contain additives described later, or resin components other than the above resin components.

<Organic peroxide>
The organic peroxide functions to generate a radical by at least thermal decomposition and cause a grafting reaction to the resin component of the silane coupling agent as a catalyst. In particular, when the silane coupling agent contains an ethylenically unsaturated group, it acts to cause a grafting reaction due to a radical reaction between the ethylenically unsaturated group and the resin component (including a hydrogen radical abstraction reaction from the resin component). .
The organic peroxide used in the present invention is not particularly limited as long as it generates radicals. For example, a compound represented by the general formula: R ¹ —OO—R ² , R ¹ —OO—C (═O) R ³ , R ⁴ C (═O) —OO (C═O) R ⁵ is preferably used. It is done. Here, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, or an acyl group. Among these, in the present invention, it is preferable that R ¹ , R ² , R ³ , R ⁴ and R ⁵ are all alkyl groups, or any one is an alkyl group and the rest is an acyl group.

  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-butylperoxy Benzoate, tert-butyl peroxyisopropyl carbonate, diace Peroxide, lauroyl peroxide, may be mentioned tert- butyl cumyl peroxide and the like. Among these, in terms of odor, colorability, and scorch stability, dicumyl peroxide (DCP), 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5- Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3 is preferred.

The decomposition temperature of the organic peroxide is preferably 80 to 195 ° C, particularly preferably 125 to 180 ° C.
In the present invention, the decomposition temperature of an organic peroxide means a temperature at which a decomposition reaction occurs in two or more compounds at a certain temperature or temperature range when an organic peroxide having a single composition is heated. means. Specifically, it refers to a 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>
In the present invention, the inorganic filler is used without particular limitation as long as it has a reactive site such as a silanol group of the silane coupling agent on the surface thereof and a site capable of forming a hydrogen bond or a site capable of chemical bonding by a covalent bond. be able to. 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 aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, and water. Metal hydrates such as compounds with hydroxyl or water of crystallization such as aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, boron nitride, silica (crystalline silica, amorphous silica Etc.), carbon, clay, zinc oxide, tin oxide, titanium oxide, molybdenum oxide, antimony trioxide, silicone compound, quartz, talc, zinc borate, white carbon, zinc borate, zinc hydroxystannate, zinc stannate Can be used.
Among these, the inorganic filler is preferably at least one of silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, zinc borate, zinc hydroxystannate, silica, aluminum hydroxide, magnesium hydroxide and At least one selected from the group consisting of calcium carbonate is more preferable.
One kind of inorganic filler may be blended alone, or two or more kinds may be mixed and used.

  The average particle size of the inorganic filler is preferably 0.2 to 10 μm, more preferably 0.3 to 8 μm, further preferably 0.4 to 5 μm, and particularly preferably 0.4 to 3 μm. When the average particle size of the inorganic filler is less than 0.2 μm, the inorganic filler causes secondary aggregation during mixing with the silane coupling agent, and the appearance of the molded body may be deteriorated or blistered. On the other hand, when it exceeds 10 μm, the appearance may be deteriorated, the retention effect of the silane coupling agent may be lowered, and a problem may be caused in crosslinking. The average particle size is determined by an optical particle size measuring device such as a laser diffraction / scattering type particle size distribution measuring device after being dispersed with alcohol or water.

  As the inorganic filler, an inorganic filler surface-treated with a silane coupling agent or the like can be used. For example, as the silane coupling agent surface-treated metal hydrate, Kisuma 5L, Kisuma 5P (both trade names, magnesium hydroxide, manufactured by Kyowa Chemical Co., Ltd., etc.), aluminum hydroxide and the like can be mentioned. 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>
The silane coupling agent used in the present invention only needs to have a group that can be graft-reacted to the resin component in the presence of a radical and a group that can be chemically bonded to the inorganic filler, and has a hydrolyzable group at the end. A hydrolyzable silane coupling agent is preferred. More preferably, the silane coupling agent has an amino group, a glycidyl group or an ethylenically unsaturated group-containing group and a hydrolyzable group-containing group at the terminal, and more preferably ethylene at the terminal. It is a silane coupling agent having a group containing a polymerizable unsaturated group and a group containing a hydrolyzable group. Although it does not specifically limit as group containing an ethylenically unsaturated group, For example, a vinyl group, an allyl group, a (meth) acryloyloxy group, a (meth) acryloyloxyalkylene group, p-styryl group etc. are mentioned. Moreover, you may use together these silane coupling agents and the silane coupling agent which has another terminal group.

  As such a silane coupling agent, for example, a compound represented by the following general formula (1) can be used.

In general formula (1), R _a11 is a group containing an ethylenically unsaturated group, and R _b11 is an aliphatic hydrocarbon group, a hydrogen atom, or Y ¹³ . Y ¹¹ , Y ¹² and Y ¹³ are hydrolyzable organic groups. Y ¹¹ , Y ¹² and Y ¹³ may be the same as or different from each other.

R _a11 of the silane coupling agent represented by the general formula (1) is preferably a group containing an ethylenically unsaturated group, and the group containing an ethylenically unsaturated group is as described above, preferably vinyl. It is a group.

R _b11 is an aliphatic hydrocarbon group, a hydrogen atom, or Y ¹³ to be described later. The aliphatic hydrocarbon group is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms excluding the aliphatic unsaturated hydrocarbon group. Is mentioned. R _b11 is preferably Y ¹³ described later.

Y ¹¹ , Y ¹² and Y ¹³ are hydrolyzable organic groups such as an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an acyloxy group having 1 to 4 carbon atoms. And an alkoxy group is preferred. Specific examples of the hydrolyzable organic group include methoxy, ethoxy, butoxy, acyloxy and the like. Among these, methoxy or ethoxy is more preferable, and methoxy is particularly preferable from the viewpoint of the reactivity of the silane coupling agent.

The silane coupling agent is preferably a silane coupling agent having a high hydrolysis rate, more preferably a silane coupling agent in which R _b11 is Y ¹³ and Y ¹¹ , Y ¹² and Y ¹³ are the same. . More preferred is a hydrolysable silane coupling agent in which at least one of Y ¹¹ , Y ¹² and Y ¹³ is a methoxy group, and particularly preferred is a hydrolyzable silane coupling agent in which all are methoxy groups.

Specific examples of the silane coupling agent having a vinyl group, (meth) acryloyloxy group or (meth) acryloyloxyalkylene group at the terminal include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, and vinyldimethoxy. Organosilanes such as ethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltriethoxysilane, vinyltriacetoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyl Examples include methyldimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Among such crosslinkable silane coupling agents, a silane coupling agent having a vinyl group and an alkoxy group at the terminal is more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.
Those having a glycidyl group at the terminal are 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

  The silane coupling agent may be used as it is or diluted with a solvent or the like.

<Silanol condensation catalyst>
The silanol condensation catalyst has a function of causing a silane coupling agent grafted to the resin component to undergo a condensation reaction 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 dioctiate, and dibutyltin diacetate are particularly preferable.

<Carrier resin>
The silanol condensation catalyst used in the present invention is mixed with the resin as desired. Such a resin (also referred to as carrier resin) is not particularly limited, but a part of the base resin (R _B ) can be used. The part of the base resin (R _B), may be a part of the resin component constituting the base resin (R _B), but may be part of the resin component constituting the base resin (R _B), the base resin (R Part of the resin component constituting _B ) is preferred. In this case, the resin component is preferably a polyolefin resin. Among the polyolefin resins, a resin containing ethylene as a constituent component is more preferable, and polyethylene is particularly preferable from the viewpoint of good affinity with a 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 are various additives commonly used in electric wires, electric cables, electric cords, sheets, foams, tubes, and pipes. It may be blended appropriately as long as the purpose is not impaired. Examples of such additives include crosslinking aids, antioxidants, lubricants, metal deactivators, fillers, and other resins.
These additives, particularly antioxidants and metal deactivators, may be mixed in any component, but are preferably added to the carrier resin. It is preferable that the crosslinking aid is not substantially contained. In particular, it is preferable that the crosslinking aid is not substantially mixed in the step (a) for preparing the silane master batch. When the crosslinking aid is not substantially mixed, crosslinking between the resin components hardly occurs during kneading, and the appearance and heat resistance of the heat-resistant silane crosslinked resin molded article are excellent. Here, being substantially not contained or not mixed means that a crosslinking aid is not actively added or mixed, and does not exclude inclusion or mixing unavoidably.

  The crosslinking aid refers to a compound that forms a partially crosslinked structure with a resin component in the presence of an organic peroxide. For example, a methacrylate compound such as polypropylene glycol diacrylate and trimethylolpropane triacrylate, triallyl cyanurate, etc. And polyfunctional compounds such as allyl compounds, maleimide compounds, and divinyl compounds.

  Antioxidants such as 4,4′-dioctyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, etc. Agents, pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like, bis (2-methyl-4- (3 -N-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben ヅ imidazole and Zinc salts, pentaerythritol - tetrakis (3-lauryl - thiopropionate) sulfur antioxidant such as and the like. The antioxidant is preferably added in an amount of 0.1 to 15.0 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin.

  Examples of the lubricant include hydrocarbons, siloxanes, fatty acids, fatty acid amides, esters, alcohols, metal soaps, and the like. These lubricants should be added to the carrier resin.

  Examples of metal deactivators include N, N′-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and the like.

  Examples of the filler (including a flame retardant (auxiliary) agent) include fillers other than the various fillers described above.

Next, the production method of the present invention will be specifically described.
In the production method of the present invention, step (a), a polyolefin resin, the base resin (R _B) containing at least one selected from the group consisting of ethylene rubber and styrene-based elastomer based on 100 parts by weight of an organic peroxide Melting and mixing 0.01 part by mass or more and 0.6 part by mass or less, inorganic filler 70 parts by mass or more and 400 parts by mass or less, silane coupling agent exceeding 4 parts by mass and 15.0 parts by mass or less and silanol condensation catalyst. To prepare.

The mixing amount of the organic peroxide is 0.01 to 0.6 parts by mass, preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the base resin (R _B ). When the amount of the organic peroxide is less than 0.01 parts by mass, the crosslinking reaction does not proceed at the time of crosslinking, and the silane coupling agents are condensed with each other to sufficiently obtain heat resistance, mechanical strength, and reinforcement. May not be possible. On the other hand, if it exceeds 0.6 parts by mass, many of the resin components are directly crosslinked by side reactions, and there is a risk that bumps will occur. That is, by setting the mixing amount of the organic peroxide within this range, the composition can be polymerized within an appropriate range, and can be easily molded without generating gel-like spots, that is, a composition having excellent extrudability. Can get.

The mixing amount of the inorganic filler is 70 to 400 parts by mass, preferably 60 to 280 parts by mass with respect to 100 parts by mass of the base resin (R _B ). When the mixing amount of the inorganic filler is less than 70 parts by mass, when the extruder is stopped, or when the rotation speed of the extruder is greatly changed by adjustment or the like, a lot of fluffs may occur, which may cause poor appearance. . On the other hand, if it exceeds 400 parts by mass, the load during molding or kneading becomes very large, and secondary molding may be difficult.

The mixing amount of the silane coupling agent is more than 4 parts by mass and 15.0 parts by mass or less, preferably more than 6 parts by mass and 15.0 parts by mass or less with respect to 100 parts by mass of the base resin (R _B ). is there.
When the amount of the silane coupling agent is 4 parts by mass or less, when molding with the silanol condensation catalyst, a lot of bumps occur when the extruder is stopped or when the number of revolutions of the extruder is greatly changed by adjustment or the like. May cause poor appearance. On the other hand, when the amount exceeds 15 parts by mass, the silane coupling agent cannot be adsorbed on the surface of the inorganic filler beyond that, and the silane coupling agent volatilizes during kneading, which is not economical. Moreover, the silane coupling agent which does not adsorb | suck condenses, and there exists a possibility that a molded object may be fuzzy and burnt and an external appearance may deteriorate.

  Thus, when the amount of the silane coupling agent mixed exceeds 4.0 parts by mass and is 15.0 parts by mass or less, the appearance is excellent. Although the details of the mechanism are not yet clear, it is thought as follows. That is, in the step (a), the reaction due to the decomposition of the organic peroxide when the silane coupling agent is silane-grafted to the resin component has a fast reaction rate, the graft reaction between the silane coupling agent and the resin component, The condensation reaction between the ring agents becomes dominant. Therefore, the cross-linking reaction between resin components, particularly polyolefin resins, which cause rough appearance and appearance fouling is very difficult to occur. Thus, the cross-linking reaction between the resin components is effectively suppressed by the mixing amount of the silane coupling agent. Thereby, the external appearance at the time of shaping | molding becomes favorable. Moreover, since the said defect by the crosslinking reaction of resin components decreases, even if it restarts after stopping an extruder, it becomes difficult to generate | occur | produce an appearance defect. Thus, the cross-linking reaction between the resin components can be suppressed, and a silane cross-linked resin molded article having a good appearance can be produced.

On the other hand, in the step (a), many silane coupling agents are immobilized by binding or adsorption to an inorganic filler. Therefore, the condensation reaction between the silane coupling agents bonded or adsorbed to the inorganic filler hardly occurs. In addition, it does not bind or adsorb to the inorganic filler, hardly causes the condensation reaction between the free silane coupling agents, and suppresses the formation of gel-like spots due to the condensation reaction between the free silane coupling agents. be able to.
Thus, by using a specific amount of the silane coupling agent, both the crosslinking reaction between the resin components and the condensation reaction between the silane coupling agents can be suppressed, and the silane crosslinked resin molded article having a clean appearance. It is thought that can be manufactured.

In the production method of the present invention, the step (a) includes, for the base resin (R _B ), “a total amount of the base resin (R _B ), that is, an aspect in which 100 parts by mass” is blended, and “base resin (R _B )”. A mode in which a part of is blended. Therefore, in the production method of the present invention, it is only necessary that 100 parts by mass of the base resin (R _B ) is contained in the mixture obtained in the step (a), and the total amount of the base resin (R _B ) will be described later. may be mixed with (1), also a part are mixed in step (1), admixed as a carrier resin in step (2) the balance being described later, i.e. the base resin (R _B) is a step (1) You may mix in both processes of a process (2).
When a part of the base resin (R _B ) is blended in the step (2), the mixing amount of 100 parts by mass of the base resin (R _B ) in the step (a) is mixed in the steps (1) and (2). It is the total amount of base resin (R _B ).
Here, when the remainder of the base resin (R _B ) is blended in step (2), the base resin (R _B ) is preferably 80 to 99 parts by mass, more preferably 94 to 98 parts by mass in step (1). In the step (2), preferably 1 to 20 parts by mass, more preferably 2 to 6 parts by mass are blended.

This step (a) includes at least step (1) and step (3), and in specific cases, includes at least step (1) to step (3). When step (a) comprises at least these steps, each component can be uniformly melted and mixed, and the desired effect can be obtained.
Step (1): All or a part of the base resin (R _B ), an organic peroxide, an inorganic filler, and a silane coupling agent are melt-mixed at a temperature equal to or higher than the decomposition temperature of the organic peroxide, and a silane master batch is prepared. preparation for process step (2) base resin by melt mixing the remainder and silanol condensation catalyst (R _B), the step preparing the catalyst masterbatch (3): a silane masterbatch and silanol condensation catalyst or catalyst masterbatch Mixing process

In step (1), the base resin (R _B ), organic peroxide, inorganic filler, and silane coupling agent are charged into a mixer, and melt kneaded while heating to a temperature equal to or higher than the decomposition temperature of the organic peroxide. A silane master batch is prepared.

  In the step (1), the kneading temperature for melting and mixing the above-described components is equal to or higher than the decomposition temperature of the organic peroxide, preferably the decomposition temperature of the organic peroxide + (25 to 110) ° C. This decomposition temperature is preferably set after the resin component has melted. Also, kneading conditions such as kneading time can be set as appropriate. When kneaded at a temperature lower than the decomposition temperature of the organic peroxide, the graft reaction of the silane coupling agent does not occur and the desired heat resistance cannot be obtained, and the organic peroxide reacts during the extrusion. Therefore, it may be impossible to form the desired shape.

As a kneading method, any method usually used for rubber, plastic, etc. can be used satisfactorily, and the kneading apparatus is appropriately selected according to, for example, the amount of inorganic filler mixed. As the kneading apparatus, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, or various kneaders are used. In terms of surface.
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 (R _B ), it is preferably kneaded with a continuous kneader, a pressure kneader, or a Banbury mixer. .

In the present invention, “all or part of the base resin (R _B ), the organic peroxide, the inorganic filler, and the silane coupling agent are melt-mixed” does not specify the mixing order at the time of melt-mixing. , Which means that they can be mixed in any order. That is, the mixing order in the step (1) is not particularly limited.
Further, the mixing method of the base resin (R _B ) is not particularly limited. For example, may be used premixed prepared base resin (R _B), the components, for example, each resin component and the oil component may be used separately.

In the step (1), for example, a base resin (R _B ), an organic peroxide, an inorganic filler, and a silane coupling agent can be melt-mixed at a time.
Preferably, the silane coupling agent is not introduced into the silane master batch alone, but is introduced by premixing with an inorganic filler. Thereby, it becomes difficult for the silane coupling agent to volatilize during kneading, and it is possible to prevent the silane coupling agent not adsorbed on the inorganic filler from condensing and making melt kneading difficult. Moreover, a desired shape can also be obtained at the time of extrusion molding.
As such a mixing method, preferably, a mixer type kneader such as a Banbury mixer or a kneader is used, and the organic peroxide, the inorganic filler, and the silane coupling agent are mixed or dispersed at a temperature lower than the decomposition temperature of the organic peroxide. A method of melting and mixing the mixture and the base resin (R _B ) after the mixing is performed. If it does in this way, the excessive crosslinking reaction of resin components can be prevented, and an external appearance is excellent.

  The inorganic filler, the silane coupling agent, and the organic peroxide are mixed at a temperature lower than the decomposition temperature of the organic peroxide, preferably at room temperature (25 ° C.). The method for mixing the inorganic filler, the silane coupling agent, and the organic peroxide is not particularly limited, and the organic peroxide may be mixed with the inorganic filler or the like, or the inorganic filler and the silane coupling agent may be mixed. They may be mixed in any of the mixing stages. Examples of the mixing method of the inorganic filler, the silane coupling agent, and the organic peroxide include mixing methods such as wet processing and dry processing.

As a method of mixing the inorganic filler and the silane coupling agent, a wet process in which the silane coupling agent is added in a state where the inorganic filler is dispersed in a solvent such as alcohol or water, and a dry process in which both are added by heating or non-heating. Treatment and both. 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 the above-described wet mixing, the silane coupling agent tends to be strongly chemically bonded to the inorganic filler, so that the subsequent silanol condensation reaction may be difficult to proceed. On the other hand, in dry mixing, since the bond between the inorganic filler and the silane coupling agent is relatively weak, the silanol condensation reaction easily proceeds efficiently.

  The silane coupling agent added to the inorganic filler exists so as to surround the surface of the inorganic filler, and part or all of the silane coupling agent is adsorbed by the inorganic filler or chemically bonded to the surface of the inorganic filler. By being in such a state, the volatilization of the silane coupling agent during kneading with a subsequent kneader or Banbury mixer is greatly reduced, and the unsaturated group of the silane coupling agent is reduced by the organic peroxide. It is considered that a crosslinking reaction occurs with the resin component. In addition, it is considered that the silane coupling agent undergoes a condensation reaction with a silanol condensation catalyst during molding. Although the mechanism of this reaction is not clear, if the bond between the inorganic filler and the silane coupling agent is too strong during the condensation reaction, the silane coupling agent bonded to the inorganic filler will be removed from the inorganic filler even if a silanol condensation catalyst is added. It is considered that the silanol condensation reaction (crosslinking reaction) is difficult to proceed.

In step (1), the organic peroxide may be mixed with the silane coupling agent and then dispersed in the inorganic filler, or separately from the silane coupling agent and dispersed separately in the inorganic filler. In the present invention, the organic peroxide and the silane coupling agent should be mixed substantially together.
In the present invention, depending on production conditions, only the silane coupling agent may be mixed with the inorganic filler, and then the organic peroxide may be added. That is, in the step (1), an inorganic filler previously mixed with a silane coupling agent can be used. As a method of adding the organic peroxide, it may be dispersed in other components or may be added alone.

In a preferred mixing method, a mixture of an inorganic filler, a silane coupling agent and an organic peroxide and a base resin (R _B ) are then melt-kneaded while being heated to a temperature higher than the decomposition temperature of the organic peroxide, A silane masterbatch is prepared.

  In step (1), no silanol condensation catalyst is used. That is, in the step (1), the above-described components are kneaded without substantially mixing the silanol condensation catalyst. Thereby, the silane coupling agent is easy to melt and mix without condensing, and a desired shape can be obtained during extrusion molding. 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), 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 resin.

Thus, a process (1) is performed and a silane masterbatch is prepared.
The silane master batch (also referred to as silane MB) prepared in the step (1) is preferably used for the production of the mixture (heat-resistant silane crosslinkable resin composition) prepared in the step (a), as will be described later. It is used together with a silanol condensation catalyst or a catalyst master batch described later. This silane MB is a mixture prepared by melt-mixing the above components in step (1).

  The silane masterbatch prepared in step (1) contains a decomposition product of an organic peroxide, a resin component, a reaction mixture of an inorganic filler and a silane coupling agent, and an organic mineral oil. The silane coupling agent contains two types of silane crosslinkable resins (silane graft polymer) grafted to the resin component to such an extent that they can be molded.

In the production method of the present invention, then, in the case of melt-mixing a part of the base resin (R _B) in step (1), and the remainder of the base resin (R _B) and the silanol condensation catalyst is melt-mixed, Step (2) of preparing a catalyst master batch is performed. Therefore, when all the base resin (R _B ) is melt-mixed in the step (1), the step (2) may not be performed, and other resins described later may be used.

The mixing ratio of the base resin (R _B ) and the silanol condensation catalyst in the step (2) is set so as to satisfy the mixing ratio with the base resin (R _B ) of the silane masterbatch in the step (3) described later. . The base resin (R _B ) is mixed with a silanol condensation catalyst as a carrier resin, and the remainder of the base resin (R _B ) mixed in the step (1) is used.
The mixing of the base resin (R _B ) and the silanol condensation catalyst is appropriately determined according to the melting temperature of the base resin (R _B ). For example, the kneading temperature can be 80 to 250 ° C, more preferably 100 to 240 ° C. Kneading conditions such as kneading time can be set as appropriate. The kneading method can be performed by the same method as the above kneading method.

The silanol condensation catalyst may be mixed with another carrier resin instead of or in addition to the remainder of the base resin (R _B ). That is, in the step (2), the remainder of the base resin (R _B ) when a part of the base resin (R _B ) is melt-mixed in the step (1), or the resin components other than the resin components used in the step (1) A catalyst master batch may be prepared by melt-mixing a resin and a silanol condensation catalyst. Other carrier resins are not particularly limited, and various resins can be used.
When the carrier resin is another resin, the silane crosslinking can be accelerated quickly in the step (b), and the carrier resin is blended in the base resin (R _B ) in that it is less likely to cause blistering during molding. Preferably it is 1-60 mass parts with respect to 100 mass parts, More preferably, it is 2-50 mass parts, More preferably, it is 2-40 mass parts.

  In addition, a filler may or may not be added to this carrier resin. The amount of the filler at that time is not particularly limited, but is preferably 350 parts by mass or less with respect to 100 parts by mass of the carrier resin. This is because if the amount of filler is too large, the silanol condensation catalyst is difficult to disperse and crosslinking is difficult to proceed. On the other hand, if the carrier resin is too much, the degree of cross-linking of the molded article is lowered, and there is a possibility that proper heat resistance cannot be obtained.

The catalyst masterbatch thus prepared is a mixture of a silanol condensation catalyst and a carrier resin, and optionally added filler.
The prepared catalyst masterbatch (also referred to as catalyst MB) is used for the production of the heat-resistant silane crosslinkable resin composition prepared in step (a) together with silane MB.

Next, in the production method of the present invention, the silane master batch and the silanol condensation catalyst or the catalyst master batch prepared in step (2) are mixed to perform step (3) of obtaining a mixture.
The mixing method may be any mixing method as long as a uniform mixture can be obtained as described above. For example, pellets such as dry blends may be mixed and introduced into the molding machine at room temperature or high temperature, or may be mixed and melted and mixed, pelletized again, and then introduced into the molding machine.
In any mixing, in order to avoid the silanol condensation reaction, it is preferable that the silane master batch and the silanol condensation catalyst are not maintained at a high temperature for a long time in a mixed state. About the obtained mixture, it is set as the mixture with which the moldability in the shaping | molding in a process (b) was hold | maintained.

The blending amount of the silanol condensation catalyst is preferably 0.0001 to 0.5 parts by mass, more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the base resin (R _B ). When the mixing amount of the silanol condensation catalyst is within the above range, the crosslinking reaction by the condensation reaction of the silane coupling agent is likely to proceed almost uniformly, and the heat resistance, appearance and physical properties of the heat-resistant silane crosslinked resin molded product are excellent, and production Also improves.

  In the step (b), the mixing conditions of the silane master batch and the silanol condensation catalyst or catalyst master batch are appropriately selected. That is, when the silanol condensation catalyst is mixed alone with the silane master batch, the mixing conditions are set to appropriate melt mixing conditions depending on the resin.

  On the other hand, when a catalyst master batch containing a silanol condensation catalyst is mixed with a silane master batch, melt mixing is preferable in terms of dispersion of the silanol condensation catalyst, which is basically the same as the melt mixing in step (1). 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 carrier resin, and is preferably 80 to 250 ° C., more preferably 100 to 240 ° C., for example. Kneading conditions such as kneading time can be set as appropriate.

  This step (3) may be a step in which a silane master batch and a silanol condensation catalyst (C) are mixed to obtain a mixture, and a catalyst master batch and a silane master batch containing the silanol condensation catalyst (C) and a carrier resin. It is preferable that the step is a melt-mixing step.

In this way, the process (a), that is, the method for producing the heat-resistant silane crosslinkable resin composition of the present invention is carried out, and the heat resistance contains at least two different silane crosslinkable resins as described later. A silane crosslinkable resin composition (also referred to as a flame retardant silane crosslinkable resin composition) is produced. Therefore, the heat-resistant silane crosslinkable resin composition of the present invention is a composition obtained by carrying out the step (a), and is considered to be a mixture of a silane masterbatch and a silanol condensation catalyst or a catalyst masterbatch. The components are basically the same as the silane masterbatch and silanol condensation catalyst or catalyst masterbatch.
As described above, the silane MB and the silanol condensation catalyst or catalyst master batch are used as a batch set for producing a heat-resistant silane crosslinkable resin composition.

Next, the manufacturing method of the heat-resistant silane crosslinked resin molding of this invention performs a process (b) and a process (c). That is, in the method for producing a heat-resistant silane cross-linked resin molded product of the present invention, the step (b) of obtaining the molded product by molding the obtained mixture, that is, the heat-resistant silane cross-linkable resin composition of the present invention is performed. This process (b) 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. For example, when the heat-resistant product of the present invention is an electric wire or an optical fiber cable, extrusion molding or the like is selected.
The step (b) can be resumed after being temporarily stopped due to reasons such as cleaning of the extruder, changing the position, adjusting the eccentricity, and the middle stage of production without deteriorating the excellent appearance of the molded body.
Moreover, it can implement simultaneously or continuously with the process (3) of a process (a). For example, a series of processes in which a silane masterbatch and a silanol condensation catalyst or a catalyst masterbatch are melt-kneaded in a coating apparatus and then coated on, for example, an extruded electric wire or fiber and formed into a desired shape can be employed.
Thus, the heat-resistant silane crosslinkable resin composition of the present invention is molded, and the molded body of the heat-resistant silane crosslinkable resin composition obtained in the steps (a) and (b) is an uncrosslinked body. Therefore, the heat-resistant silane crosslinked resin molded product of the present invention is a molded product that is crosslinked or finally crosslinked by performing the following step (c) after the step (a) and the step (b).

  In the manufacturing method of the heat-resistant silane crosslinked resin molding of this invention, the process which makes the molded object (non-crosslinked body) obtained at the process (b) contact with water is performed. As a result, the hydrolyzable group of the silane coupling agent is hydrolyzed into silanol, and the silanol condensation catalyst present in the resin condenses the hydroxyl groups of the silanol to cause a crosslinking reaction, resulting in a heat-resistant molded article. Can be obtained. The process itself of this process (c) can be performed by a normal method. By bringing moisture into contact with the molded body, the hydrolyzable group of the silane coupling agent is hydrolyzed and the silane coupling agents are condensed to form a crosslinked structure.

  Condensation between silane coupling agents proceeds only by storage at room temperature. Therefore, in the step (c), it is not necessary to positively contact the molded body (uncrosslinked body) with water. It can also be contacted with moisture to further accelerate the crosslinking. For example, it is possible to employ a method of positively contacting water, such as immersion in warm water, charging into a wet heat tank, exposure to high-temperature steam, and the like. In this case, pressure may be applied to allow moisture to penetrate inside.

  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. Therefore, the heat-resistant silane cross-linked resin molded product of the present invention is a molded product obtained by carrying out the steps (a) to (c). And this molded object contains the resin component formed by bridge | crosslinking with an inorganic filler through a silanol bond so that it may mention later.

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, if the resin component is heated and kneaded at a temperature 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 component, the organic peroxide decomposes to generate radicals, and the resin component On the other hand, grafting occurs with a silane coupling agent. Further, the heating at this time also causes a chemical bond formation reaction due to a covalent bond between the silane coupling agent and the inorganic filler, particularly a group such as a hydroxyl group on the surface of the metal hydrate.
In the present invention, in step (c), there is also possible to perform the final crosslinking reaction, when the specific amount of the base resin (R _B) a silane coupling agent as described above, impairs the extrudability in molding It becomes possible to mix | blend an inorganic filler in large quantities, and it can have heat resistance, a mechanical characteristic, etc., ensuring the outstanding flame retardance.

Moreover, the mechanism of the action of the above process of the present invention is not yet clear, but is estimated as follows. That is, by using an inorganic filler and a silane coupling agent before and / or during kneading with the base resin (R _B ), the silane coupling agent is bonded to the inorganic filler with an alkoxy group, and the other Bonded to the uncrosslinked portion of the resin component with an ethylenically unsaturated group such as a vinyl group present at the end, or physically and chemically adsorbed to the hole or surface of the inorganic filler without binding to the inorganic filler. , Retained. 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 an organic peroxide is added and kneaded, the silane coupling agent is hardly volatilized as described later, and the bond with the inorganic filler is different. The silane coupling agent is grafted to the resin component. Thus, at least two kinds of silane crosslinkable resins are 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 ethylenically unsaturated group as a crosslinking group is a resin component. It undergoes a graft reaction with the crosslinking site. 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, a 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 inorganic filler and the silane coupling agent are bonded by a strong hydrogen bond, and this bond does not shift by heat or shear. 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.

  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 ethylenically unsaturated group, which is a crosslinking group of the silane coupling agent, is organically oxidized. A graft reaction occurs by reacting with radicals of the resin component generated by abstraction of hydrogen radicals by radicals generated by decomposition of the product. 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 becomes very high, and it becomes possible to obtain a heat-resistant silane cross-linked resin molded product that does not melt even at high temperatures.

  In particular, in the present invention, the cross-linking reaction by condensation using a silanol condensation catalyst in the presence of water in the step (c) is performed after forming the formed 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. Further, a plurality of silane coupling agents can be bonded to the surface of one inorganic filler particle, and high mechanical strength can be obtained.

As described above, when the silane crosslinkable resin formed by graft reaction of the silane coupling agent bonded to the inorganic filler with a strong bond to the resin component comes into contact with moisture, the inorganic filler is bonded via the silanol bond of the silane coupling agent. A crosslinked silane crosslinked resin is formed. A silane coupling agent bonded to an inorganic filler with a strong bond is considered to contribute to high mechanical properties, in some cases, abrasion resistance, scratch resistance, and the like.
Moreover, when the silane crosslinkable resin formed by graft reaction of the silane coupling agent bonded to the inorganic filler with a weak bond to the resin component comes into contact with moisture, the resin components are cross-linked via the silanol bond of the silane coupling agent. A silane cross-linked resin is formed. A silane coupling agent bonded to an inorganic filler with a weak bond is considered to contribute to an improvement in the degree of crosslinking, that is, an improvement in heat resistance.

At this time, when the step (a) having at least the above steps (1) and (3) is performed using a base resin (R _B ) containing ethylene rubber, cross-linking is formed by bonding ethylene rubber and an inorganic filler. The silane crosslinkable resin molded body that is highly crushed and exhibits high rubber elasticity is obtained by contacting the water-soluble resin with moisture. In particular, since ethylene rubber has higher reactivity than other resins such as polyolefin resin, it is considered that a silane coupling agent bonded with a strong bond to an inorganic filler selectively grafts to ethylene rubber. Thus, it is considered that a crosslinked rubber molded network bonded with an inorganic filler is formed, and a silane crosslinkable resin molded body having high heat resistance, reinforcement, and the like and being hard to be crushed is obtained.

Further, the resin using a base resin (R _B) containing a resin composed of polyolefin copolymer having an acid copolymer component or ester copolymer component, the step of at least the step (1) and (3) ( When a) is performed, it does not melt at high temperature, has high heat resistance, and can achieve both excellent strength, wear resistance and flame retardancy.

By the way, when a large amount of inorganic filler is added, radicals are easily generated in the resin component. Therefore, when heating and mixing the base resin (R _B) component and an organic peroxide in a state blended with inorganic fillers in large quantities, the addition reaction of the silane coupling agent and a resin component also, for example, between the resin component reactive Reaction between silane coupling agents occurs as a side reaction. When such a side reaction occurs, the resulting silane crosslinkable resin molded article has a poor appearance, and when the extruder is stopped, the appearance is remarkably impaired, and further flaws may occur.

In particular, a resin made of a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component has a higher reactivity than a polyolefin resin and is easily reacted with an organic peroxide. When this resin is present, the above side reaction tends to occur.
The reaction between silane coupling agents and the reaction between the silane coupling agent and the resin component is faster than the reaction of a resin or the like made of a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component.

However, in the present invention, the silane coupling agent is added to more than 4 parts by mass and up to 15 parts by mass with respect to 100 parts by mass of the base resin (R _B ). The silane coupling agent that is being reacted reacts predominantly fast, suppresses the occurrence of the side reaction, and a silane-crosslinked resin molded article having a good appearance can be obtained.
In addition, the silane coupling agent is bonded or adsorbed to the inorganic filler, and is less likely to volatilize during melt kneading in the step (a), effectively suppressing the reaction between the free silane coupling agents. it can.

Further, by using the base resin (R _B) containing the ethylene rubber or styrene elastomers, when carrying out process (a) having at least the steps (1) and (3) are highly reactive ethylene rubber or Side reactions concentrate on styrene elastomers. If it does so, the reaction between resin components and the side reaction between silane coupling agents will be suppressed, and also ethylene rubber or a styrene system elastomer will be in a dynamic crosslinked state. As described above, when the ethylene rubber or the styrene elastomer is in a dynamically cross-linked state, the cross-linked state in the ethylene rubber or the styrene elastomer is made uniform, and it is difficult to cause irregularities and poor appearance.
Furthermore, when the resin contains a non-aromatic organic oils, the base resin (R _B) and the ethylene rubber are compatible, and more rubber microdispersed of is considered that the appearance is improved.

Therefore, a heat-resistant silane cross-linked resin molded article having an excellent appearance and a heat-resistant silane cross-linked resin molded article having excellent flame resistance (also referred to as a flame retardant silane cross-linked resin molded article having excellent heat resistance) are obtained. In addition to the moldability when the extruder is not stopped (extrusion moldability), as well as the moldability when the extruder is restarted after being stopped (extrusion moldability after the extruder is temporarily stopped) Can be manufactured.
Here, once restarting after restarting, it cannot be stated uniquely depending on the resin composition, processing conditions, etc., but for example, at intervals of up to 5 minutes, preferably up to 10 minutes, more preferably up to 15 minutes. Say what you can do. The temperature at this time is not particularly limited as long as the resin component is softened or melted, and is 200 ° C., for example.

The manufacturing method of the present invention is used to manufacture components (including semi-finished products, parts, and members) that require heat resistance or flame retardancy, products that require strength, component parts of products such as rubber materials, or members thereof. Can be applied. Examples of such heat-resistant products or flame-retardant products include electric wires such as heat-resistant flame-retardant insulated wires, heat-resistant and flame-retardant cable coating materials, rubber substitute wires and cable materials, other heat-resistant and flame-resistant electric wire components, and flame-resistant and heat-resistant sheets. And flame retardant heat resistant film. Also for the production of power plugs, connectors, sleeves, boxes, tape substrates, tubes, sheets, packing materials, cushioning materials, anti-vibration materials, electrical and electronic equipment, and wiring materials, especially electric wires and optical cables. Can be applied. The manufacturing method of the present invention is particularly suitably applied to the manufacture of the insulators and sheaths of electric wires and optical cables among the components of the above-described products, and can be formed as a covering thereof.
Insulators, sheaths, and the like can be formed by coating them in such a shape while melt-kneading them in an extrusion coating apparatus. For such molded products such as insulators and sheaths, a general-purpose extrusion coating apparatus is used without using a special machine such as an electron beam cross-linking machine, which is a high heat resistant high temperature non-melting cross-linked composition to which a large amount of inorganic filler is added. Can be formed by extrusion coating around the conductor, or around the conductor that has been stretched or twisted with tensile strength fibers. For example, any conductor such as an annealed copper single wire or stranded wire can be used as the conductor. In addition to the bare wire, the conductor may be tin-plated or an enamel-covered insulating layer. The thickness of the insulating layer (the coating layer made of the heat resistant resin composition of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 to 5 mm.

  EXAMPLES 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 of the examples and comparative examples represent parts by mass.

Examples 1 to 3, Reference Examples 1 to 15 and Comparative Examples 1 to 4 were carried out using the components shown in Tables 1 and 2 by changing the respective specifications or manufacturing conditions, etc. Also shown.

The following compounds were used as the components shown in Tables 1 and 2.
<Base resin _(R B)>
(1) Resin component As a polyolefin resin, “EV180” (trade name, manufactured by Mitsui DuPont Chemical Co., Ltd., ethylene / vinyl acetate copolymer resin (EVA), VA content 33% by mass)
“EV523” (trade name, manufactured by Mitsui DuPont Chemical Co., Ltd., ethylene / vinyl acetate copolymer resin (EVA), VA content 33% by mass)
“NUC6510” (trade name, manufactured by Nippon Unicar Company, ethylene-ethyl acrylate resin, EA content 23 mass%, density 0.93 g / cm ³ )
“Engage 7256” (trade name, manufactured by Dow Chemical Company, linear low density polyethylene (LLDPE), density 0.885 g / cm ³ )
"Kernel (registered trademark) KS240T" (manufactured by Nippon Polyethylene Co., Ltd., low density polyethylene (LLDPE))
"PB222A" (trade name, manufactured by Sun Allomer, random polypropylene)
Ethylene rubber “Mitsui 3092M” (trade name, manufactured by Mitsui Chemicals, ethylene-propylene-diene rubber, ethylene content 65%, diene content 4.6%)
"Mitsui 0045" (trade name, manufactured by Mitsui Chemicals, ethylene-propylene rubber, ethylene content 51% by mass)
“Septon 4077” as a styrene elastomer (trade name, manufactured by Kuraray Co., Ltd., SEPS, styrene content 30% by mass)
As an acid-modified resin, “Admer XE-070” (trade name, manufactured by Mitsui Chemicals, maleic anhydride-modified ethylene-α-olefin copolymer)
“Adtex L6100M” (trade name, manufactured by Nippon Polyethylene Co., Ltd., maleic anhydride-modified ethylene-α-olefin copolymer)
“Clayton 1901FG” (trade name, manufactured by Kraton Chemical Co., Ltd., maleic anhydride-modified styrene elastomer (styrene-ethylene-butylene copolymer))

(2) “Diana Process Oil PW90” as an organic mineral oil (trade name, manufactured by Idemitsu Kosan Co., Ltd., paraffin oil, aniline point 127.7 ° C., kinematic viscosity 92 mm ² / s (40 ° C.))

<Organic peroxide>
“Perhexa 25B” (trade name, manufactured by NOF Corporation, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, decomposition temperature 149 ° C.)
<Inorganic filler>
Magnesium hydroxide (trade name: Kisuma 5, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.8 μm)
Aluminum hydroxide (trade name: Heidilite H42M, manufactured by Showa Denko KK, average particle size 1.2 μm)
<Silane coupling agent>
"KBM-1003" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane)
<Silanol condensation catalyst>
“ADK STAB OT-1” (trade name, manufactured by ADEKA, dioctyltin dilaurate)
<Carrier resin (resin component constituting the base resin _{(R B))>}
"UE320" (Nippon Polyethylene, Novatec PE (trade name), linear low density polyethylene (LLDPE))

<Antioxidant>
“Irganox 1010” (trade name, manufactured by BASF, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate])

(Examples 1-3, Reference Examples 1-12 and Comparative Examples 1-4)
In these examples and comparative examples, a part of the resin components constituting the base resin (R _B ) was used as the carrier resin for the catalyst master batch. Specifically, the total amount of LLDPE (UE320) which is one of the resin components constituting the base resin (R _B ) (Examples 1 and 2, Reference Examples 1 to 12 and Comparative Examples 1 to 4 is 5 parts by mass, Example 3 used 10 parts by mass).

First, an organic peroxide, an inorganic filler, and a silane coupling agent are put into a 10 L Henschel mixer manufactured by Toyo Seiki at a mass ratio shown in Table 1, and mixed at room temperature (25 ° C.) for 1 hour to obtain a powder mixture. Got.
Next, the powder mixture obtained in this manner and the resin component and oil component shown in Table 1 were introduced into a 2 L Banbury mixer made by Nippon Roll at a mass ratio shown in Table 1, and an organic peroxide was added. After being kneaded for 12 minutes at a rotation speed of 35 rpm at 180 to 190 ° C., the material was discharged at a material discharge temperature of 180 to 190 ° C. to obtain a silane master batch (also referred to as silane MB) ( Step (1)). The obtained silane MB contains at least two silane crosslinkable resins 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 are separately melt-mixed by a Banbury mixer at a mass ratio shown in Table 1 at 180 to 190 ° C, and discharged at a material discharge temperature of 180 to 190 ° C. A batch (also referred to as catalyst MB) was obtained (step (2)). This catalyst masterbatch is a mixture of a carrier resin and a silanol condensation catalyst.
Then, the silane MB and catalyst MB, the mass ratio shown in Table 1, i.e., a silane MB base resin _{(R B)} is 95 parts by mass or 90 parts by weight, the carrier resin catalyst MB 5 mass parts or 10 parts by weight The mixture was melt-mixed at 180 ° C. by a Banbury mixer at a ratio (step (3)).
Thus, the process (a) was performed and the heat-resistant silane crosslinkable resin composition was prepared. This heat-resistant silane crosslinkable resin composition is a mixture of silane MB and catalyst MB, and contains at least two types of silane crosslinkable resins described above.

  Subsequently, this heat-resistant silane crosslinkable resin composition was subjected to L / D (ratio of screw effective length L and diameter D) = 24, 65 (screw diameter) mm extruder (compressor screw temperature 190 ° C., head temperature 200). And the outside of the 1 / 0.8 TA conductor was coated with a thickness of 1 mm to obtain an electric wire (uncrosslinked) having an outer diameter of 2.8 mm (step (b)).

The obtained electric wire was left in an atmosphere of 80 ° C. and 95% humidity for 24 hours to polycondensate silanol (step (c)).
Thus, the electric wire coat | covered with the heat resistant silane crosslinked resin molding was manufactured.
As described above, this heat-resistant silane cross-linked resin molded product is converted into the above-mentioned silane cross-linked resin in which the silane coupling agent of the silane cross-linkable resin is converted to silanol and the hydroxyl groups of silanol are cross-linked by a condensation reaction.

( Reference Example 13 )
Silane MB (step (1)) and catalyst MB (step (2)) were prepared in the same manner as in Reference Example 1 using the components shown in Table 2 in the mass ratio (parts by mass) shown in the same table. .
Subsequently, the obtained silane MB and catalyst MB were put into a closed ribbon blender, and dry blended at room temperature (25 ° C.) for 5 minutes to obtain a dry blend. In this case, the mixing ratio of the silane MB and the catalyst MB, the silane MB of the base resin (R _B) is 95 parts by mass, and the mass ratio of the carrier resin catalyst MB is 5 parts by weight (see Table 2). Next, this dried blend was put into a 40 mm extruder (compressor screw temperature 190 ° C., head temperature 200 ° C.) with L / D = 24, and 1 / 0.8 TA while melt mixing in the extruder screw. The outside of the conductor was coated with a thickness of 1 mm to obtain an electric wire (uncrosslinked) having an outer diameter of 2.8 mm (step (3) and step (b)).
The obtained electric wire (uncrosslinked) was left in an atmosphere of a temperature of 80 ° C. and a humidity of 95% for 24 hours (step (c)).
Thus, the electric wire which has the coating | cover consisting of a heat resistant silane crosslinked resin molding was manufactured.

( Reference Example 14 )
Each component shown in Table 2 was used in the mass ratio (parts by mass) shown in the same table, and in the same manner as in Reference Example 1, the outer periphery of the conductor was coated with a heat-resistant silane crosslinkable resin composition (outer diameter 2. 8 mm, uncrosslinked) was obtained (step (a) and step (b)).
The obtained electric wire was left in an atmosphere at a temperature of 23 ° C. and a humidity of 50% for 72 hours (step (c)).
Thus, the electric wire which has the coating | cover consisting of a heat resistant silane crosslinked resin molding was manufactured.

( Reference Example 15 )
Silane MB was prepared in the same manner as in Reference Example 1 using each component shown in Table 2 in the mass ratio (parts by mass) shown in the same table (step (a)).
On the other hand, the carrier resin “UE320”, the silanol condensation catalyst, and the antioxidant were melt-mixed by a twin screw extruder at a mass ratio shown in Table 2 to obtain a catalyst MB. The screw diameter of the twin screw extruder was set to 35 mm, and the cylinder temperature was set to 180 to 190 ° C. The obtained catalyst MB is a mixture of a carrier resin, a silanol condensation catalyst and an antioxidant.
Subsequently, the obtained silane MB and catalyst MB were melt-mixed at 180 ° C. by a Banbury mixer (step (b)). The mixing ratio of silane MB and catalyst MB was such that the polyolefin resin of silane MB was 95 parts by mass and the carrier resin of catalyst MB was 5 parts by mass (see Table 2). In this way, a heat-resistant silane crosslinkable resin composition was prepared. This heat-resistant silane crosslinkable resin composition is a mixture of silane MB and catalyst MB, and contains at least two types of silane crosslinkable resins described above.
Next, this heat-resistant silane crosslinkable resin composition was introduced into a 40 mm extruder (compressor screw temperature 190 ° C., head temperature 200 ° C.) with L / D = 24, and the thickness was increased outside the 1 / 0.8 TA conductor. An electric wire (uncrosslinked) having an outer diameter of 2.8 mm was obtained by coating with 1 mm (step (b)).
The obtained electric wire (uncrosslinked) was left in a state of being immersed in warm water at a temperature of 50 ° C. for 10 hours (step (c)).
Thus, the electric wire which has the coating | cover consisting of a heat resistant silane crosslinked resin molding was manufactured.

  The manufactured wires were evaluated as follows, and the results are shown in Tables 1 and 2.

<Mechanical properties>
A tensile test was conducted as a mechanical property of the electric wire.
This tensile test was performed at a measurement temperature of 20 ° C., a gap between marked lines of 25 mm, and a tensile speed of 500 mm / min, using a wire tubular piece obtained by extracting a conductor from an electric wire, based on UL1581, tensile strength (MPa) and tensile elongation ( %).
In the evaluation of the tensile strength, 8 MPa or more is an acceptable level, but 10 MPa or more is a desirable level.
In the evaluation of elongation, 100% or more is an acceptable level, but 150% or more is a desirable level.

<Heating deformation test>
A heat deformation test was performed as a heat resistance test.
The heat deformation test was performed based on UL1581 at a measurement temperature of 121 ° C. and a load of 5N.
In the evaluation, a measured value of 50% or less is an acceptable level.

<Flame retardance test>
The flame retardant test 1 was a 60 degree inclined flame retardant test based on JIS C 3005.
At the same time, the fire is removed and the fire extinguishes spontaneously.
In the flame retardancy test 2, three samples of each electric wire were prepared, and the UL1581 VW-1 test was performed. 3 when the sample all have passed is the desired level as electrostatic line.
This test is shown for reference only, and the result of this flame retardant test 2 does not necessarily have to reach the desired level.

<Extrusion appearance characteristics of electric wire>
The extrusion appearance characteristics of the electric wires were evaluated by observing the extrusion appearance when manufacturing the electric wires.
Specifically, the external appearance characteristic 1 of the electric wire was “A” when the external appearance of the electric wire was good when extruded at 120 m / min with an extruder having a screw diameter of 65 mm, and the external appearance was slightly bad. "B", the appearance of which is remarkably bad is "C", and "A" and "B" are acceptable levels as products.

The extrusion appearance characteristic 2 of the electric wire was performed after the extruder was temporarily stopped and restarted.
Specifically, when producing an electric wire, the wire speed is set to 50 m / min with an extruder having a screw diameter of 65 mm, the electric wire is produced, the extruder is stopped once in the middle, and again under the same conditions after 10 minutes. The electric wire was manufactured by operating an extruder, and it evaluated by observing the external appearance of the manufactured electric wire. The observation was made to be the appearance of the electric wire extruded 5 minutes after setting the linear velocity again to 50 m / min and restarting the extruder.
The evaluation was “A” when the wire speed was good and no more than 2 pieces per 1 m when observed 5 minutes after setting the line speed to 50 m / min. Alternatively, “B” indicates that 3 to 9 bumps were confirmed in 1 m, “C” indicates that the appearance was remarkably poor, or 10 or more bumps were confirmed in 1 m, and “A” and “ “B” is an acceptable level as a product.

As is clear from the results of Tables 1 and 2, Examples 1 to 3 all passed the heat deformation test, the flame retardancy test and the extrusion appearance characteristics, and were excellent in appearance, heat resistance and flame retardancy. The electric wire could be manufactured with good extrudability. In particular, it was possible to produce with good extrudability even after the extruder was stopped. Also, the mechanical properties were excellent.

On the other hand, although the comparative example 1 with little content of a silane coupling agent passed the heat deformation test, the flame retardancy test, and the extrusion appearance characteristic 1, the extrusion appearance characteristic 2 failed.
Moreover, the comparative example 2 with little content of an organic peroxide was inferior to heat resistance because the heat deformation test failed.
Comparative Example 3 having a high silane coupling agent content failed in the extrusion appearance characteristics.
In Comparative Example 4 in which the content of the inorganic filler is small, the flame retardancy test 1 and the extrusion appearance characteristic 2 were unacceptable.

Claims (15)

Ethylene, alpha-olefin and at least Tane含 free base resin _(R B) relative to 100 parts by weight of an organic peroxide 0.01 parts by mass or more 0.6 mass ethylene rubber consisting of terpolymers of dienes Part (a) of obtaining a mixture by melting and mixing 70 parts by weight or less, inorganic filler 70 parts by weight or more and 400 parts by weight or less, exceeding 4 parts by weight of the silane coupling agent and 15.0 parts by weight or less and a silanol condensation catalyst, and molding the mixture A step (b) for obtaining a molded body and a step (c) for obtaining a heat-resistant silane crosslinked resin molded body by bringing the molded body into contact with water. ,
Wherein step (a) comprises the following steps (1) and step (3), the following step (1) in the case of melt-mixing a part of the base resin in the following step (1) _{(R B),} A method for producing a heat-resistant silane-crosslinked resin molded product, comprising the steps (2) and (3) .
[Step (a)]
Step (1): Melting and mixing all or part of the base resin (R _B ), the organic peroxide, the inorganic filler, and the silane coupling agent at a temperature equal to or higher than the decomposition temperature of the organic peroxide. , step preparing a silane masterbatch (2): the base resin by melt mixing the remainder and the silanol condensation catalyst (R _B), the step step (3) for preparing the catalyst masterbatch: and the silane masterbatch the silanol condensation catalyst or as engineering that mixing the catalyst masterbatch The content of the silane coupling agent is more than 6 parts by mass and not more than 15.0 parts by mass with respect to 100 parts by mass of the base resin (R _B ). Production method. Wherein the base resin (R _B) further method for producing a heat resistant silane crosslinked resin molded product according to claim 1 or 2 comprising an organic mineral oil or a styrene elastomer. The base resin (R _B ) contains 2% by mass or more and 50% by mass or less of one or both of the ethylene rubber and the styrene elastomer, and contains 2% by mass or more and 40% by mass or less of the organic mineral oil. The manufacturing method of the heat-resistant silane crosslinked resin molding as described in 2. Wherein the base resin (R _B) is further ethylene - vinyl acetate copolymer and ethylene - of at least one selected from the group consisting of methacrylate ester copolymers, the acid copolymer component or ester copolymer component The manufacturing method of the heat-resistant silane crosslinked resin molding of any one of Claims 1-4 which contains the polyolefin copolymer which has 20 to 75 mass%. Wherein the base resin (R _B) is further unsaturated carboxylic acid-modified acid-modified polyolefin resin, modified acid-modified styrene-based elastomer modified with acid-modified ethylene rubber and unsaturated carboxylic acids with unsaturated carboxylic acids The method for producing a heat-resistant silane-crosslinked resin molded article according to any one of claims 1 to 5, comprising at least one acid-modified resin selected from the group consisting of 2 mass% and 30 mass%.   The method for producing a heat-resistant silane-crosslinked resin molded article according to any one of claims 1 to 6, wherein the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.   The manufacturing method of the heat-resistant silane crosslinked resin molding of any one of Claims 1-7 with which the melt mixing of the said process (a) is performed with an airtight mixer. Ethylene, alpha-olefin and at least Tane含 free base resin _(R B) relative to 100 parts by weight of an organic peroxide 0.01 parts by mass or more 0.6 mass ethylene rubber consisting of terpolymers of dienes Part or less, inorganic filler 70 parts by weight or more and 400 parts by weight or less, silane coupling agent 4 parts by weight and 15.0 parts by weight or less and heat-resistant silane having step (a) of obtaining a mixture by melting and mixing a silanol condensation catalyst A method for producing a crosslinkable resin composition, comprising:
When the step (a) includes the following step (1) and step (3), and a part of the base resin (R _B ) is melt-mixed in the following step (1), the following step (1) and step (2) The manufacturing method of the heat resistant silane crosslinkable resin composition characterized by having a process (3) .
[Step (a)]
Step (1): Melting and mixing all or part of the base resin (R _B ), the organic peroxide, the inorganic filler, and the silane coupling agent at a temperature equal to or higher than the decomposition temperature of the organic peroxide. , step preparing a silane masterbatch (2): the base resin by melt mixing the remainder and the silanol condensation catalyst (R _B), the step step (3) for preparing the catalyst masterbatch: and the silane masterbatch the silanol condensation catalyst or as engineering that mixing the catalyst masterbatch   A heat-resistant silane crosslinkable resin composition produced by the production method according to claim 9.   A heat-resistant silane cross-linked resin molded product produced by the production method according to claim 1.   The heat-resistant silane cross-linked resin molded article according to claim 11, wherein the heat-resistant silane cross-linked resin molded article contains a resin formed by crosslinking with an inorganic filler through a silanol bond of a silane coupling agent.   A heat-resistant product comprising the heat-resistant silane-crosslinked resin molded article according to claim 11 or 12.   The heat-resistant product according to claim 13, wherein the heat-resistant silane cross-linked resin molded body is provided as a coating for an electric wire or an optical fiber cable. Ethylene, alpha-olefin and at least Tane含 free base resin _(R B) relative to 100 parts by weight of an organic peroxide 0.01 parts by mass or more 0.6 mass ethylene rubber consisting of terpolymers of dienes Part or less, 70 parts by weight or more and 400 parts by weight or less of an inorganic filler, more than 4 parts by weight of a silane coupling agent and 15.0 parts by weight or less A silane masterbatch used,
A silane master obtained by melt-mixing all or part of the base resin (R _B ), the organic peroxide, the metal hydrate, and the silane coupling agent at a temperature equal to or higher than the decomposition temperature of the organic peroxide. batch.