JP5995813B2 - Heat-resistant silane cross-linked resin molded body, method for producing the same, 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, a method for producing the same, and a heat-resistant product using the heat-resistant silane cross-linked resin molded article. The present invention relates to a heat-resistant silane cross-linked resin molded article having excellent flame retardancy, a method for producing the same, and a heat-resistant product using the heat-resistant silane cross-linked resin molded article as an insulator or sheath for electric wires.

Insulated wires, cables, cords and optical fiber cords used for electrical and electronic equipment internal and external wiring, optical fiber cords, flame resistance, heat resistance, mechanical properties (for example, tensile properties), wear resistance Various characteristics such as insulation resistance are required.
As a material used for these wiring materials, a resin composition containing a large amount of an inorganic filler such as magnesium hydroxide, aluminum hydroxide, or calcium carbonate is used.

  In addition, wiring materials used in electrical and electronic equipment may be heated to 80 to 105 ° C. and further to about 125 ° C. when used for a long time, and heat resistance to this is also required. In such a case, for the purpose of imparting high heat resistance to the wiring material, a method of bridging (also referred to as crosslinking) the coating material by an electron beam crosslinking method, a chemical crosslinking method, or the like is employed.

Conventionally, as a method of crosslinking a polyolefin resin such as polyethylene, an electron beam crosslinking method in which an electron beam is irradiated to crosslink, a chemical crosslinking method in which an organic peroxide or the like is decomposed by applying heat after molding, and a crosslinking reaction is performed. Crosslinking methods are known.
The silane crosslinking method is a method in which a hydrolyzable silane coupling agent having an unsaturated group is grafted to a polymer in the presence of an organic peroxide to obtain a silane graft polymer, and then water and moisture in the presence of a silanol condensation catalyst. This is a method of obtaining a cross-linked molded article by contacting them.
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.

  Specifically, a method for producing a heat-resistant silane crosslinked resin includes a silane master batch obtained by grafting a hydrolyzable silane coupling agent having an unsaturated group to a polyolefin resin, and a heat-resistant master obtained by kneading a polyolefin resin and an inorganic filler. There is a method in which a batch and a catalyst master batch 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, the silane masterbatch and the heat-resistant masterbatch are dry-mixed in a single screw extruder or a twin screw extruder. It becomes difficult to melt and knead uniformly. Moreover, in order to perform melt-kneading uniformly when dry-mixing a silane masterbatch and a heat-resistant masterbatch, the ratio of the silane masterbatch is limited as described above. Therefore, it has been difficult to achieve high flame resistance and high heat resistance. Moreover, when manufactured using such a method, it is difficult to impart excellent strength, wear resistance, and reinforcing properties when a crosslinked resin is used.

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 produce a desired silane cross-linked master batch.

Therefore, when producing a heat-resistant silane masterbatch with a Banbury mixer or kneader, a hydrolyzable silane coupling agent having an unsaturated group and an organic peroxidation are added to the heat-resistant masterbatch in which a polyolefin resin and an inorganic filler are melt-mixed. A method may be considered in which a product is added and graft polymerization is carried out using a single screw extruder.
However, in this method, a defective appearance occurs in the molded body due to variation in reaction, and a desired molded body cannot be obtained. In addition, the blending ratio of the inorganic filler in the heat-resistant master batch has to be increased, which increases the extrusion load and makes the production very difficult. As a result, it has been difficult to obtain a desired material or molded body. In addition, this is a two-step process, which is a difficult point in terms of manufacturing cost.

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 technique of partially 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 in a Banbury mixer or kneader, causing the molded body to have poor appearance (forms a number of protrusions protruding on the surface). In addition, most of the silane coupling agent other than the silane coupling agent that is treating the surface of the inorganic filler may be volatilized or condensed. For this reason, desired heat resistance cannot be obtained, and condensation between silane coupling agents may cause deterioration of the appearance of the electric wire.

  Further, even in the methods described in Patent Documents 2 to 4, the resin is not yet in a sufficient network structure, and the bond between the resin and the inorganic filler is broken at a high temperature. For example, the insulating material may melt during soldering of the electric wire, or may be deformed or foamed during secondary processing of the molded body. Furthermore, when heated to about 200 ° C. for a short time, there is a problem that the appearance is remarkably deteriorated or deformed.

  In the method described in Patent Document 5, when a silane cross-linkable flame retardant polyolefin obtained by batch melting and kneading is extruded together with a silanol condensation catalyst, an appearance defect due to rough appearance or unevenness (also referred to as external appearance or simply unevenness) is caused. Prone to occur. In particular, when cleaning the extruder, when changing the setup or when adjusting the eccentricity, once it is stopped, the molded product to be molded is likely to have rough appearance and irregularities, resulting in a remarkable appearance defect. Was confirmed.

The present invention overcomes the problems of conventional silane crosslinking methods, provides a heat-resistant silane crosslinked resin molded article having excellent appearance, mechanical properties and flame retardancy, and a method for producing the same, while suppressing volatilization of the silane coupling agent The task is to do.
Moreover, this invention makes it a subject to provide the heat resistant product using the heat resistant silane crosslinked resin molded object obtained with the manufacturing method of the heat resistant silane crosslinked resin molded object.

That is, the subject of this invention was achieved by the following means.
(1) At least the following step (a), step (b) and step (c)
Step (a): 0.01 to 0.6 parts by mass of organic peroxide (P) and 100 parts by mass of inorganic filler (C) with respect to 100 parts by mass of base resin (A), silane coupling agent (q ) Silane coupling agent premixed inorganic filler (D) formed by mixing 0.5 to 30.0 parts by mass, 10 to 150 parts by mass of brominated flame retardant (h1), and silanol condensation catalyst (E1) Step of melting and mixing 0.001 to 0.5 parts by mass Step (b): Step of molding the heat-resistant silane crosslinkable resin composition (F) obtained in the step (a) Step (c) : A method for producing a heat-resistant silane cross-linked resin molded product comprising a step of bringing the molded product obtained in the step (b) into contact with moisture to cross-link it into a molded product,
The base resin (A) includes a resin comprising a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, a resin comprising a polyethylene resin, a polypropylene resin, an ethylene-α-olefin copolymer, and a styrene elastomer. containing at least one selected from, at that time, of the acid copolymer component and ester copolymer component, the content of the base resin (a) (Z) is 2% by mass or more,
When the step (a) comprises at least the following step ( a 1) and step ( a 3), and a part of the base resin (A) is melt-mixed in the following step ( a 1), at least the following step ( a 1), consisting of step ( a2 ) and step ( a3 ),
Step (a1): All or part of the base resin (A), the organic peroxide (P) and the silane coupling agent premixed inorganic filler (D) are decomposed at the decomposition temperature of the organic peroxide (P). Step of preparing the silane master batch (Dx) by melt mixing as described above Step (a2): Melting and mixing the remainder of the base resin (A) as the carrier resin (e2) and the silanol condensation catalyst (e1) Step for preparing catalyst master batch (Ex) Step (a3): Step for melting and mixing the silane master batch (Dx) and the silanol condensation catalyst (e1) or the catalyst master batch (Ex) The brominated flame retardant ( h1) is mixed in at least one of the step (a1) and the step (a2).
A method for producing a heat-resistant silane cross-linked resin molded article.

(2) In the resin comprising the polyolefin copolymer contained in the silane master batch (Dx), the content of the acid copolymerization component or the acid ester copolymerization component in the resin is 70% by mass or less ( The manufacturing method of the heat resistant silane crosslinked resin molding as described in 1).
(3) Production of the heat-resistant silane-crosslinked resin molded article according to (1) or (2), wherein the brominated flame retardant (h1) is mixed in both steps (a1) and (a2). Method.
(4) The inorganic filler (C) contains 5 to 30 parts by mass of antimony trioxide with respect to 100 parts by mass of the base resin (A), and the content (Z) is 3% by mass or more (1). The manufacturing method of the heat-resistant silane crosslinked resin molding of any one of-(3).
(5) The method for producing a heat-resistant silane-crosslinked resin molded article according to any one of (1) to (4), wherein the base resin (A) contains 0.2 to 20% by mass of a polypropylene resin.
(6) The base resin (A) in the heat-resistant silane crosslinkable resin composition (F) by the method for producing a heat-resistant silane crosslinkable resin molded article according to any one of (1) to (5). A heat-resistant silane cross-linked resin molded product obtained by cross-linking.

(7) A heat-resistant product comprising the heat-resistant silane crosslinked resin molded article according to (6).
(8) The heat-resistant product according to (7), wherein the pre-heat-resistant silane cross-linked resin molded body is provided as a coating for an electric wire or an optical fiber cable.

In the present invention, the “base resin (A)” is a resin for forming a heat-resistant silane crosslinked resin molded product.
In the present invention, the “part of the base resin (A)” is a resin used in the step (a1) of the base resin (A), and a part of the base resin (A) itself (the base resin (A) ), A part of the resin component constituting the base resin (A), a part of the resin component constituting the base resin (A) (for example, the total amount of a specific resin component among a plurality of resin components) ).
The “remaining part of the base resin (A)” is the remaining base resin excluding a part of the base resin (A) used in the step (a1). Specifically, the base resin (A ) Itself (having the same composition as the base resin (A)), the remainder of the resin component constituting the base resin (A), and the remaining resin component constituting the base resin (A).

  The production method of the present invention can overcome the problems of the conventional silane crosslinking method and produce a heat-resistant silane crosslinked resin molded article excellent in appearance, mechanical properties and flame retardancy. Further, according to the present invention, by mixing an inorganic filler and a silane coupling agent before and / or during kneading, volatilization of the silane coupling agent during kneading can be suppressed, and heat-resistant silane A crosslinked resin molded product can be produced efficiently. 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.

  Moreover, according to this invention, the heat resistant product using the heat resistant silane crosslinked resin molding obtained by the manufacturing method of the heat resistant silane crosslinked resin molding of this invention can be provided.

Below, this invention and preferable embodiment in this invention are demonstrated in detail.
The “method for producing a heat-resistant silane-crosslinked resin molded article” of the present invention (hereinafter sometimes referred to as the production method of the present invention) is as described above, and at least the steps (a), (b), and A method for producing a heat-resistant silane cross-linked resin molded article comprising (c),
The base resin (A) is a resin comprising a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, and the acid copolymerization component and acid ester copolymerization component of the resin in the base resin (A) In a ratio that the content (Z) is 2% by mass or more,
When this step (a) melts and mixes all of the base resin (A) in the following step (a1), it comprises at least the following step (a1) and step (a3). In the following step (a1), the base resin ( When a part of A) is melt-mixed, it comprises at least the following step (a1), step (a2) and step (a3),
The brominated flame retardant (h1) is mixed in at least one of the following step (a1) and the following step (a2).

Step (a1): All or part of the base resin (A), the organic peroxide (P), and the silane coupling agent premixed inorganic filler (D) are melt-mixed at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P). Step of preparing silane master batch (Dx) Step (a2): Base resin (A) as carrier resin (e2) when part of base resin (A) is melt-mixed in step (a1) Step of preparing a catalyst master batch (Ex) by melt-mixing the remainder of the catalyst and the silanol condensation catalyst (e1) Step (a3): Silane master batch (Dx) and silanol condensation catalyst (e1) or catalyst master batch (Ex) The process of melt mixing

In the production method of the present invention, when all of the base resin (A) is used in the step (a1), the silanol condensation catalyst (e1) is melted in the silane master batch in the step (a3) without performing the step (a2). Can be mixed.
In addition, the step (a2) and the step (a3) can be performed continuously or all at once (in the same step).

  First, each component used for this invention is demonstrated.

<(A) Base resin and (G) Base resin>
For convenience, the resin used in the production method of the present invention is referred to as “base resin (A)”, the heat-resistant silane crosslinkable resin composition (F) obtained in step (a) and the heat resistance produced by the production method of the present invention. The resin forming the silane cross-linked resin molded product is referred to as “base resin (G)”. As will be described later, the base resin (G) is synonymous with a mixture of the base resin (A) and the carrier resin (e2).

The base resin (A) used in the present invention is a crosslinking site that undergoes a crosslinking reaction in the presence of a crosslinking group of a silane coupling agent (q) and an organic peroxide (P) described below, such as an unsaturated bond site of a carbon chain, And resins, elastomers, rubbers and the like made of a polymer or copolymer having a carbon atom having a hydrogen atom in the main chain or at the terminal thereof. Examples of such resins include polyolefin resins and styrene elastomers. These may be used alone or in combination of two or more.
This base resin (A) contains at least a resin made of a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, which is a kind of polyolefin resin, as a resin component.
In the base resin (A), the content of each component is selected from the following range so that the total of each component is 100% by mass.

Polyolefin resin The polyolefin resin as a resin component 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 thing can be used.
Examples thereof include resins made of polymers such as polyethylene, polypropylene, ethylene-α-olefin copolymers, polyolefin copolymers having acid copolymerization components or acid ester copolymerization components, rubbers and elastomers of these polymers. .
Among these, the receptivity to various inorganic fillers including metal hydrates is high, there is an effect of maintaining mechanical strength even if a large amount of inorganic filler is blended, and withstand voltage while ensuring heat resistance, In particular, a resin comprising polyethylene, polypropylene, an ethylene-α-olefin copolymer, and a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component from the viewpoint of suppressing a decrease in withstand voltage characteristics at high temperatures. Is preferred.
These polyolefin resins may be used individually by 1 type, or may use 2 or more types together.

  In the present invention, polyethylene, polypropylene, an ethylene-α-olefin copolymer, and a resin comprising a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component are respectively represented by polyethylene resin, polypropylene resin, ethylene- It may be called α-olefin copolymer resin and polyolefin copolymer resin.

(I) Polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component Polyolefin copolymer (i) having an acid copolymerization component or an acid ester copolymerization component (simply referred to as a polyolefin copolymer (i)) Examples of the acid copolymerization component or the acid ester copolymerization component include carboxylic acid compounds such as (meth) acrylic acid and acid ester compounds such as vinyl acetate and (meth) acrylic acid esters. . Here, the alkyl group of the (meth) acrylic acid ester 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 (i) include an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid ester copolymer. Among these, an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylic acid ester copolymer are preferable. The polyolefin copolymer (i) may be a block copolymer or a random copolymer. Polyolefin copolymer (i) is used individually by 1 type, or 2 or more types are used together.

  The ethylene- (meth) acrylic acid ester copolymer includes both an ethylene-acrylic acid ester copolymer and an ethylene-methacrylic acid ester copolymer. In the present specification, “ethylene- (Meth) acrylate copolymer ”.

  The content of the acid copolymerization component or the acid ester copolymerization component in the polyolefin copolymer resin is not particularly limited as long as the content (Z) described later is 2% by mass or more.

  Examples of the resin made of an ethylene-vinyl acetate copolymer include EVAFLEX (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.). Examples of the resin made of an ethylene-ethyl acrylate copolymer include EVALROY ( Trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.).

(Ii) Ethylene-α-olefin copolymer The ethylene-α-olefin copolymer (ii) is preferably a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms (in addition, polyethylene described later) Is excluded.). Specific examples of the α-olefin component include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. Specific examples of the ethylene-α-olefin copolymer (ii) include an ethylene-butylene copolymer, an ethylene-α-olefin copolymer synthesized in the presence of a single site catalyst, and a linear low density. A polyethylene (LLDPE) etc. are mentioned. The ethylene-α-olefin copolymer (ii) may contain a copolymer containing a diene component, such as an ethylene-propylene copolymer (for example, an ethylene-propylene-diene copolymer). . An ethylene-alpha-olefin copolymer may be used individually by 1 type, and may use 2 or more types together.
Examples of the ethylene-α-olefin copolymer resin include Engage (trade name, manufactured by Dow) and Evolue (trade name, manufactured by Prime Polymer).

(Iii) Polypropylene Polypropylene (iii) may be a polymer in which one of the polymerization components is a propylene component, and includes random polypropylene and block polypropylene as a copolymer in addition to a homopolymer of propylene.
Here, “random polypropylene” is a copolymer of propylene and ethylene, and is a propylene-based copolymer having an ethylene component content of 1 to 6% by mass, and a copolymer component such as ethylene is contained in the propylene chain. This is taken at random. The “block polypropylene” is a composition containing a homopolypropylene and an ethylene-propylene copolymer, wherein the ethylene component content is about 18% by mass or less, and the propylene component and the copolymer component are independent components. An existing thing.

In the present invention, any of these polypropylenes can be used without any particular limitation. Block polypropylene and random polypropylene are preferable in that heat resistance and heat deformation characteristics can be improved.
Polypropylene may be used alone or in combination of two or more.

  The MFR (ASTM-D-1238) of polypropylene is preferably 0.1 to 60 g / 10 minutes, more preferably 0.3 to 25 g / 10 minutes, and further preferably 0.5 to 15 g / 10 minutes. By blending polypropylene in this range, the appearance is improved when the wire is coated.

  Examples of the polypropylene resin include Novatec (trade name, manufactured by Nippon Polypro Co., Ltd.) and Prime Polypro (trade name, manufactured by Prime Polymer Co., Ltd.).

(Iv) Polyethylene Polyethylene (iv) may be a homopolymer of ethylene, and examples thereof include high-density polyethylene (HDPE), high-pressure low-density polyethylene (HPLDPE), and medium-density polyethylene (MDPE). Among these, high pressure low density polyethylene (HPLDPE) is preferable. Polyethylene may be used individually by 1 type, and may use 2 or more types together.

Styrene Elastomer The styrene elastomer used as a resin component in the present invention refers to a polymer composed of 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.
Examples of such styrenic elastomers include those composed of block copolymers and random copolymers of conjugated diene compounds and aromatic vinyl compounds, or hydrogenated products thereof. Examples of the aromatic vinyl compound include styrene, p- (tert-butyl) styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethyl. Styrene, vinyl toluene, p- (tert-butyl) styrene, etc. are mentioned. Among these, styrene is preferable. This aromatic vinyl compound is used individually by 1 type, or 2 or more types are used together. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Of these, butadiene is preferred. This conjugated diene compound is used individually by 1 type, or 2 or more types are used together. Moreover, you may use the elastomer which does not contain a styrene component but consists of a polymer containing aromatic vinyl compounds other than styrene as a styrene-type elastomer.
Examples of the styrene-based elastomer include Septon (trade name, manufactured by Kuraray Co., Ltd.), Dynaro (trade name, manufactured by JSR Corporation), and the like.

The oil base resin (A) may contain an oil as a plasticizer or a mineral oil softener for rubber, if desired. Examples of such oil include paraffinic, naphthenic, and aromatic oils. These oils are mixed oils including three oils: an oil composed of a hydrocarbon having an aromatic ring, an oil composed of a hydrocarbon having a naphthene ring, and an oil composed of a hydrocarbon having a paraffin chain. Aromatic oils (aromatic oils) refer 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. Naphthenic oil has 30 to 40% of carbon atoms constituting the naphthene ring relative to the total number of carbons, and the number of carbon atoms constituting the paraffin chain is less than 50% relative to the total number of carbons. The carbon atom number which comprises comprises less than 30% with respect to the said total carbon number. Paraffin oil means that the number of carbon atoms constituting the paraffin chain is 50% or more with respect to the total number of carbons and the number of carbon atoms constituting the aromatic ring is less than 30% with respect to the total number of carbons. .
Oils may be used alone or in combination of two or more.

<(P) Organic peroxide>
The organic peroxide (P) generates radicals by at least thermal decomposition, and accelerates the grafting reaction to the resin component of the silane coupling agent, usually the above copolymer, particularly the silane coupling agent (q) is ethylene. It functions to promote the grafting reaction by radical reaction (including hydrogen radical abstraction reaction from the resin component) between the group and the resin component in the case of containing an unsaturated group.
The organic peroxide (P) used in the present invention is not particularly limited as long as it generates radicals. For example, the general formula: R ¹ —OO—R ² , R ¹ —OO—C (= A compound represented by O) R ³ , R ⁴ C (═O) —OO (C═O) R ⁵ is preferably used. 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 an organic peroxide (P) include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy). Hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert- Butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, Acetyl 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 (P) is preferably 80 to 195 ° C, particularly preferably 125 to 180 ° C.
In the present invention, the decomposition temperature of the organic peroxide (P) means that when the organic peroxide (P) having a single composition is heated, the organic peroxide (P) itself becomes two or more kinds of compounds at a certain temperature or temperature range. It means the temperature at which decomposition reaction occurs, and refers to the temperature at which heat absorption or heat generation starts when heated from room temperature in a nitrogen gas atmosphere at a rate of temperature increase of 5 ° C./min by thermal analysis such as DSC method.

<(Q) Silane coupling agent>
The silane coupling agent (q) used for this invention is mixed with the inorganic filler (C) mentioned later, and surface-treats at least one part of an inorganic filler (C).
The silane coupling agent (q) is not particularly limited as long as it has a group that can be grafted to the resin component in the presence of a radical and a group that can be chemically bonded to the inorganic filler. A hydrolyzable silane coupling agent having an unsaturated group used in the silane crosslinking method can be used. As the silane coupling agent (q), those having an amino group, a glycidyl group or an ethylenically unsaturated group and a hydrolyzable group at the terminal are preferable, and more preferably, the terminal is not ethylenic. It is a silane coupling agent having a saturated group and 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 (q), for example, a hydrolyzable silane coupling agent represented by the following general formula (1) can be suitably used.

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

The group R _a11 containing an ethylenically unsaturated group is preferably a group containing an ethylenically unsaturated group, and the group containing an ethylenically unsaturated group is as described above, preferably a vinyl group.

R _b11 is an aliphatic hydrocarbon group, a hydrogen atom or Y ¹³ to be described later, and the aliphatic hydrocarbon group is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms excluding the aliphatic unsaturated hydrocarbon group. Can be mentioned. Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include those similar to those having 1 to 8 carbon atoms among alkyl groups of alkyl (meth) acrylate. R _b11 is preferably Y ¹³ .

Y ¹¹ , Y ¹² and Y ¹³ are each independently an organic group that can be hydrolyzed, for example, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An acyloxy group is mentioned. Among these, a C1-C6 alkoxy group is preferable. Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, and the like. From the viewpoint of hydrolysis reactivity, a methoxy group or An ethoxy group is preferred.

The hydrolyzable silane coupling agent represented by the general formula (1) is preferably an unsaturated group-containing silane coupling agent having a high hydrolysis rate, and more preferably R _b11 is Y in the general formula (1). ¹³ and a hydrolyzable silane coupling agent in which Y ¹¹ , Y ¹² and Y ¹³ are the same organic group. More preferably, at least one, particularly preferably all of Y ¹¹ , Y ¹² and Y ¹³ are methoxy groups.

Specific examples of silane coupling agents 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, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltri Examples include ethoxysilane and (meth) acryloxypropylmethyldimethoxysilane. Among these, 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.

  A silane coupling agent (q) may be used individually by 1 type, and may use 2 or more types together. Moreover, a silane coupling agent (q) may be used independently and may be used as a liquid diluted with the solvent.

<Inorganic filler>
The inorganic filler used in the present invention is a surface untreated inorganic filler (c1) that has not been surface treated with a surface treatment agent, a surface treated inorganic filler (c2) that has been surface treated with a surface treatment agent, and a silane coupling agent (q ) And a silane coupling agent premixed inorganic filler (D) or the like.
Below, each inorganic filler used by this invention is demonstrated.

The various inorganic fillers used in the present invention preferably have an average particle size of 0.2 to 10 μm, more preferably 0.3 to 8 μm, regardless of their form and type, and 0.4 to 5 μm. Is more preferable, and it is especially preferable that it is 0.4-3 micrometers. When the average particle size is in the above-mentioned range, secondary aggregation is difficult to occur when the silane coupling agent (q) is mixed, and it is difficult to cause unevenness, the appearance of the molded body is excellent, and the silane coupling agent (q). The resin component is sufficiently cross-linked by the holding effect.
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.

(C) Inorganic filler The inorganic filler (C) used in the present invention is an inorganic filler that is pretreated with the silane coupling agent (q) before being melt-mixed with the base resin (A) or the like in the step (a). (C). This inorganic filler (C) includes any one of a surface untreated inorganic filler (c1) that has not been surface-treated with a surface treatment agent and a surface-treated inorganic filler (c2) that has been surface treated with a surface treatment agent, The whole may be the surface untreated inorganic filler (c1), the surface treated inorganic filler (c2), or a mixture. The inorganic filler (C) preferably contains at least part of the surface-treated inorganic filler (c2), and the balance may contain untreated surface inorganic filler (c1) and the like. Thus, when the inorganic filler (C) contains the surface-treated inorganic filler (c2), in the production method of the present invention, the bonding between the silane coupling agent (q) added later and the inorganic filler is suppressed, A silane coupling agent that binds to the inorganic filler with a certain weak bond can be created. A heat-resistant silane cross-linked resin molded article having a certain degree of cross-linking can be obtained by the silane coupling agent that binds to the inorganic filler with this weak bond, and thereby high heat resistance can be obtained.

The ratio of the surface-treated inorganic filler (c2) in the inorganic filler (C) is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more. The proportion of the surface-treated inorganic filler (c2) is preferably 100% by mass or less. When this ratio is 30% by mass or more, the heat resistance of the heat-resistant silane crosslinked resin molded article is improved.
The surface-treated inorganic filler (c2) and the surface-untreated inorganic filler (c1) may be used alone or in combination of two or more.

  In the present invention, when flame retardancy is particularly improved, it is preferable to use antimony trioxide as a part of the inorganic filler (C), for example, the surface-untreated inorganic filler (c1). When antimony trioxide is used, the flame retardancy of the heat-resistant silane crosslinked resin molded product can be further improved.

(C1) Surface Untreated Inorganic Filler The surface untreated inorganic filler (c1) can be contained in the inorganic filler (C), and can be surface treated to form a surface treated inorganic filler (c2).
The surface-untreated inorganic filler (c1) is not particularly limited as long as it has a site capable of forming a hydrogen bond or the like with a reactive site such as a silanol group of the silane coupling agent or a site capable of chemical bonding by a covalent bond. Can be used. In the surface untreated inorganic filler, the sites capable of chemically bonding with the reaction site of the silane coupling agent include OH groups (hydroxy groups, water molecules containing water or water of crystal water, OH groups such as carboxy groups), amino groups, SH groups, etc. Is mentioned.

  Such a surface untreated inorganic filler (c1) is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, Metal hydroxide and metal water such as magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite and other compounds having hydroxyl group or crystal water Japanese products, 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, hydride Kishisuzu zinc, zinc stannate and the like can be used.

  Among the above-mentioned non-surface treated inorganic fillers (c1), metal hydroxide, calcium carbonate, silica, and antimony trioxide are preferable, and magnesium hydroxide, aluminum hydroxide, calcium carbonate, and antimony trioxide are more preferable.

(C2) Surface-treated inorganic filler The surface-treated inorganic filler (c2) is obtained by surface-treating the surface-untreated inorganic filler (c1) with a surface treatment agent. The surface-treated inorganic filler (c2) includes those obtained by further surface-treating the surface-treated inorganic filler that has already been surface-treated.
The surface untreated inorganic filler (c1) for forming the surface treated inorganic filler (c2) or the surface treated inorganic filler that has already been surface treated is not particularly limited and is exemplified by the surface untreated inorganic filler (c1). The above metal hydroxides and metal hydrates are preferable, and aluminum hydroxide, magnesium hydroxide, and calcium carbonate are more preferable.
Although a surface treating agent is not specifically limited, A fatty acid, phosphate ester, polyester, a titanate coupling agent, a silane coupling agent, etc. are mentioned. Of these, fatty acids and silane coupling agents are preferred. Although it does not specifically limit as a fatty acid, A stearic acid, an oleic acid, a lauric acid etc. are preferable. Although it does not specifically limit as a silane coupling agent, The silane coupling agent which has an amino group at the terminal, the silane coupling agent which has double bonds, such as a vinyl group and a methacryloyl group, and the silane which has an epoxy group at the terminal A coupling agent is preferred. As such a silane coupling agent, the above-mentioned silane coupling agent (q) is mentioned, for example.
The surface-treated inorganic filler (c2) may be one that has been surface-treated with one of the aforementioned surface-treating agents, or one that has been surface-treated with two or more.

  The surface-treated inorganic filler (c2) surface-treated with a fatty acid or a silane coupling agent is obtained by mixing a surface untreated inorganic filler (c1) and the like with a fatty acid or a silane coupling agent. The method of mixing the surface untreated inorganic filler (c1) and the like with the fatty acid or silane coupling agent is not particularly limited, but the surface untreated inorganic filler (c1) or an appropriate surface treatment agent (for example, fatty acid) Or a method in which a fatty acid or a silane coupling agent is added to a surface-treated inorganic filler surface-treated with a silane coupling agent) without heating or heating, and these inorganic fillers are dispersed in a solvent such as water. There is a method of adding a fatty acid or a silane coupling agent in the state. Although the amount of these surface treatments is not particularly limited, it is usually preferably 0.1 to 4% by mass with respect to the inorganic filler before the surface treatment such as the untreated inorganic filler (c1). When the surface treatment amount is within the above range, the mechanical strength and abrasion resistance can be improved, the elongation and appearance can be improved, and the extrusion load can be reduced.

Examples of the surface-treated inorganic filler (c2) surface-treated with stearic acid, such as magnesium hydroxide, include Kisuma 5AL (trade name, manufactured by Kyowa Chemical Co., Ltd.).
Examples of the surface-treated inorganic filler (c2) formed by surface treatment with a silane coupling agent include silane coupling agent surface-treated magnesium hydroxide and silane coupling agent surface-treated aluminum hydroxide. Examples of the silane coupling agent surface-treated magnesium hydroxide include Kisuma 5L, Kisuma 5P (both trade names, manufactured by Kyowa Chemical Co., Ltd.), Magsees S6, Magseeds S4 (both trade names, manufactured by Kamishima Chemical Co., Ltd.), and the like. Examples of commercially available silane coupling agent surface-treated aluminum hydroxide include Heidilite H42-ST-V, Heidilite H42-ST-E (both trade names, Showa Denko).

(D) Silane coupling agent premixed inorganic filler The silane coupling agent premixed inorganic filler (D) is prepared by previously mixing the silane coupling agent (q) with the inorganic filler (C). And the inorganic filler (C) is surface-treated. Therefore, the silane coupling agent premixed inorganic filler (D) can also be referred to as a silane coupling agent-containing inorganic filler and a silane coupling agent-treated inorganic filler. Here, the silane coupling agent (q) for surface-treating the inorganic filler (C) is as described above.

  The silane coupling agent premixed inorganic filler (D) is obtained by mixing the inorganic filler (C) and the silane coupling agent (q). As a method of mixing the silane coupling agent (q) and the inorganic filler (C), a wet treatment in which the silane coupling agent (q) and the inorganic filler (C) are mixed in alcohol or water, an inorganic filler (C) and silane. A dry process of blending with the coupling agent (q) and both are mentioned.

  In this way, when the inorganic filler (C) and the silane coupling agent (q) are premixed before being mixed with the organic peroxide (P) in the step (a) described later, the silane coupling agent (q ) Partly binds strongly to the inorganic filler (C) (the reason is, for example, formation of a chemical bond with a hydroxyl group or the like on the surface of the inorganic filler) or weakly bond (the reason is, for example, mutual bonding by hydrogen bonding) The silane coupling agent premixed inorganic filler (D) is preferably prepared by the action, interaction between ions, partial charges or dipoles, action by adsorption, etc.).

  In this silane coupling agent premixed inorganic filler (D), the silane coupling agent (q) that strongly binds to the inorganic filler (C) and the silane coupling agent (q) that weakly bonds to the inorganic filler (C) are: As will be described later, it exhibits different behavior. Therefore, the effect obtained by the ratio of these silane coupling agents (q) differs. The silane coupling agent (q) that binds weakly to the inorganic filler (C) contributes to the crosslinking between the resin components, and the silane coupling agent (q) that binds strongly to the inorganic filler (C) is the silane coupling agent (q ) Including condensation between the silane coupling agent and the silane coupling agent premixed inorganic filler (D) and the resin component. Therefore, when the ratio of both silane coupling agents is within a specific range, both heat resistance, mechanical properties, flame retardancy, and appearance can be achieved in the silane crosslinking method.

  In the silane coupling agent premixed inorganic filler (D), a method of adjusting the ratio of the silane coupling agent (q) that is weakly bonded to the inorganic filler (C) is, for example, a silane coupling agent (q) and an inorganic filler ( C) and a method of adjusting by mixing at room temperature, a method of storing at room temperature or heating after premixing, or a silane coupling agent (q) by heating the inorganic filler (C) before premixing The method of mixing etc. is mentioned.

<(H1) Brominated flame retardant>
In the present invention, the brominated flame retardant (h1) is used together with the silane coupling agent premixed inorganic filler (D). When the brominated flame retardant (h1) is used, even if the amount of the silane coupling agent premixed inorganic filler (D) is reduced, excellent flame retardancy equivalent to or higher than that of a molded article by electron beam crosslinking is exhibited.

The brominated flame retardant (h1) used in the present invention is not particularly limited as long as it is used as a flame retardant. For example, brominated ethylene bisphthalimide and derivatives thereof, bisbrominated phenylterephthalamide and derivatives thereof, bromine Bisphenols (eg tetrabromobisphenol A) and derivatives thereof, 1,2-bis (bromophenyl) ethane and derivatives thereof, polybromodiphenyl ethers (eg decabromodiphenyl ether) and derivatives thereof, and polybromobiphenyls (eg tribromophenyl) ) And derivatives thereof, organic bromine-containing flame retardants such as hexabromocyclododecane, brominated polystyrene, hexabromobenzene and the like can be used. Here, the “derivative” means one having an organic group such as an alkyl group as a substituent, or one having a different number of bromine atoms.
Among these, in terms of safety, brominated bisphenol (particularly tetrabromobisphenol A), 1,2-bis (bromophenyl) ethane, brominated polystyrene, brominated ethylene bisphthalimide represented by the following structural formula 1 and A 1,2-bis (bromophenyl) ethane derivative represented by the following structural formula 2 is preferable, a brominated ethylene bisphthalimide represented by the following structural formula 1, a 1,2-bis ( More preferred are bromophenyl) ethane derivatives.
In Structural Formula 2, m and n are each independently an integer of 1 to 5, preferably an integer of 3 to 5.

<(E1) Silanol condensation catalyst>
The silanol condensation catalyst (e1) functions to bind the silane coupling agent (q) grafted to the resin component in the presence of moisture by a condensation reaction. Based on the action of the silanol condensation catalyst (e1), the resin components are cross-linked through the silane coupling agent (q). As a result, a heat-resistant silane cross-linked resin molded product having excellent heat resistance can be obtained.

  Examples of the silanol condensation catalyst (e1) used in the present invention include organotin compounds, metal soaps, platinum compounds and the like. Common silanol condensation catalysts (e1) include, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, zinc stearate, lead stearate, barium stearate, calcium stearate, stearin Sodium acid, lead naphthenate, lead sulfate, zinc sulfate, organic platinum compounds and the like are used. Among these, organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate are particularly preferable.

<(E2) Carrier resin>
Although it does not specifically limit as carrier resin (e2), A part of base resin (A) can be used. A part of the base resin (A) may be a part of the resin component constituting the base resin (A) or a part of the resin component constituting the base resin (A). Some resin components are preferred. In this case, the resin component is preferably a polyolefin resin.
In addition, the resin component in case carrier resin is a part of resin component which comprises base resin (A) is not specifically limited.
The carrier resin (e2) may be a resin different from the base resin (A), that is, a resin that does not constitute the base resin (A).

<Other ingredients>
In the present invention, various additives commonly used in electric wires, electric cables, electric cords, sheets, foams, tubes, pipes, such as crosslinking aids, antioxidants, lubricants, metal deactivators, You may use a filler, other resin, etc. suitably in the range which does not impair the objective of this invention.

  These additives may be contained in any component, but may be contained in the catalyst master batch (Mx). In particular, the antioxidant and the metal deactivator are preferably mixed with the carrier resin (e2) of the catalyst masterbatch (Mx) so as not to inhibit the grafting of the silane coupling agent (q) onto the resin component. At this time, it is preferable that a 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 (Dx). When a crosslinking aid is added, the crosslinking aid reacts with the organic peroxide (P) during kneading, causing cross-linking between resin components, resulting in gelation, and reducing the appearance of the heat-resistant silane crosslinked resin molded product. There are things to do. In addition, the graft reaction of the silane coupling agent (q) to the resin component does not proceed easily, and the heat resistance of the final heat-resistant silane crosslinked resin molded article may not be obtained. 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 those that form a partially crosslinked structure with the resin component in the presence of an organic peroxide, such as methacrylate compounds 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 can be added in an amount of preferably 0.1 to 15.0 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the base resin (A).

  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 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 (E).

Next, the production method of the present invention will be specifically described.
As described above, the “method for producing a heat-resistant silane-crosslinked resin molded article” of the present invention comprises at least a step (a) and a step (c).

  In the production method of the present invention, the step (a) comprises 0.01 to 0.6 parts by mass of an organic peroxide (P) and a silane coupling agent premixed inorganic filler (100 parts by mass with respect to 100 parts by mass of the base resin (A). D) 10 to 150 parts by mass, bromine-based flame retardant (h1) 20 to 60 parts by mass and silanol condensation catalyst (e1) 0.001 to 0.5 parts by mass are melt-mixed to obtain a heat-resistant silane crosslinkable resin composition. This is a step of preparing (F).

The base resin (A) used in the step (a) contains at least a polyolefin copolymer resin, and may contain other resin components and oil components. As other resin components, Preferably, the said ethylene-alpha-olefin copolymer resin, a polypropylene resin, a polyethylene resin, a styrene-type elastomer, etc. are mentioned.
When the base resin (A) contains a polyolefin copolymer resin and an ethylene-α-olefin copolymer resin, the insulation resistance, appearance, flexibility, and cold resistance of the heat-resistant silane crosslinked resin molded article are excellent.
In particular, at least one of the polyolefin copolymers (i) is preferably one selected from an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylate copolymer, and an ethylene-α-olefin. The copolymer (ii) is preferably a linear low density polyethylene. At this time, the resin component (A) may consist of a polyolefin copolymer resin and an ethylene-α-olefin copolymer heavy resin, and may contain other resin components.

  The polyolefin copolymer resin is contained in the base resin (A) in such a ratio that the following content (Z) is 2% by mass or more in the base resin (A).

  The content (Z) in the base resin (A) of the acid copolymerization component and the acid ester copolymerization component in the polyolefin copolymer resin is 2% by mass or more, preferably 3% by mass or more. If the content (Z) is less than 2% by mass, desired strength may not be obtained. When the content (Z) is 3% by mass or more, further excellent flame retardancy can be obtained by using it together with antimony trioxide. Although the upper limit of this content rate (Z) is not specifically limited, For example, 35 mass% is preferable.

The content (Z) in the base resin (A) is the total mass ratio of the acid copolymerization component and the acid ester copolymerization component of the polyolefin copolymer resin with respect to the total mass of the base resin (A). ).
Formula (1): Content (Z) = Σ (Ci × Ai) / 100
In formula (1), Ci represents the content (mass%) in the base resin (A) of each component contained in the base resin (A), and Ai is in each component contained in the base resin (A). It represents the content (% by mass) of the acid copolymerization component or acid ester copolymerization component.

Here, Ai is a value obtained by the following method.
That is, when the acid copolymerization component is a vinyl acetate component, the vinyl acetate component content (VA amount) is a value determined in accordance with JIS K 7192.
On the other hand, when the acid copolymerization component is a (meth) acrylic acid component, the amount of (meth) acrylic acid component (Ac amount), and when the acid ester copolymerization component is a (meth) acrylic acid ester component, (meth) acrylic The acid ester component (Ae amount) was obtained from the following formula by preparing a sheet having a thickness of about 0.3 mm with a polyolefin copolymer resin to be measured, measuring an infrared spectrum in a scan range of 500 to 1500 cm ⁻¹ . Value.
Amount of Ac or Ae in polyolefin copolymer resin = A × (absorbance of Bcm ⁻¹ ) / (thickness of test piece (mm)) + C

Here, B is an absorbance specific to the (meth) acrylic acid component and the (meth) acrylic acid ester component, and can be arbitrarily determined unless wrapping with the absorbance of the ethylene component. For example, when the (meth) acrylic acid component is ethyl acrylate, 850 cm ⁻¹ is appropriate.
The values of A and C are values obtained from a calibration curve obtained using a standard sample.

The polyolefin copolymer resin is preferably contained in the base resin (A) used in the step (a1), that is, the silane master batch (Dx) prepared in the step (a1). In this case, in each of the polyolefin copolymer resins contained in the silane masterbatch (Dx), the content of the acid copolymerization component or the acid ester copolymerization component in the resin is preferably 70% by mass or less. That is, in the polyolefin copolymer resin having the largest content of the acid copolymerization component or the acid ester copolymerization component in the polyolefin copolymer resin, the content of the acid copolymerization component or the acid ester copolymerization component is 70% by mass or less. Preferably there is. As for this content, 65 mass% or less is more preferable, and 60 mass% or less is further more preferable. There is a cross-linking reaction between resin components as a side reaction that occurs during the silane grafting reaction. However, if the content exceeds 70% by mass, this side reaction is likely to occur preferentially over the silane grafting reaction, and the appearance deteriorates. Sometimes.
Note that this side reaction is more likely to occur at higher temperatures, so this is not limited as long as the heating temperature of the resin in step (a1) can be accurately controlled.

When the base resin (A) contains a polyolefin copolymer resin and an ethylene-α-olefin copolymer resin, the content of the polyolefin copolymer resin only needs to satisfy the above content (Z). The content of the polyolefin copolymer resin and the content of the ethylene-α-olefin copolymer resin are each selected from the range of 10 to 90% by mass with respect to the entire resin (A). When the content of the polyolefin copolymer resin and the content of the ethylene-α-olefin copolymer resin are within the above ranges, the mechanical properties, insulation resistance, flame resistance, heat resistance and appearance of the heat-resistant silane crosslinked resin molded product At a high level.
In view of combining these at a higher level, the content of the polyolefin copolymer resin is more preferably selected from the range of 10 to 50% by mass relative to the entire base resin (A). The content of the α-olefin copolymer resin is more preferably selected from the range of 20 to 80% by mass with respect to the entire base resin (A).

  The total content of the polyolefin copolymer resin and the ethylene-α-olefin copolymer resin is preferably 30 to 100% by mass, more preferably, based on the entire base resin (A), in terms of excellent mechanical properties and insulation resistance. Each content rate is selected from the above-mentioned range so that it may become 35-98 mass%, More preferably, it is 40-95 mass%.

When the base resin (A) contains a polypropylene resin, the content of the polypropylene resin in the base resin (A) is not particularly limited and is preferably 0.2 to 20% by mass, preferably 0.5 to 15% by mass. Is more preferable. When this content rate is within the above range, both the appearance and flexibility of the heat-resistant silane crosslinked resin molded product can be achieved at a higher level.
In the base resin (A), the content of the polyethylene resin in the base resin (A) is not particularly limited, and is preferably 0 to 30% by mass, and more preferably 0 to 25% by mass.

  In the base resin (A), the content of the styrene elastomer in the base resin (A) is not particularly limited, and is preferably 0 to 30% by mass, and more preferably 0 to 25% by mass.

  In base resin (A), the content rate of oil in base resin (A) is not specifically limited, 20 mass% or less is preferable and 0-15 mass% is more preferable.

  In the step (a), as described later, the base resin (A) may be used entirely in the step (a1), partly used in the step (a1), and the rest in the step (a2). May be. In terms of the mixing properties of the silanol condensation catalyst (e1), it is preferable that a part of the base resin (A) is used in the step (a1) and the rest is used in the step (a2). The mass ratio of the base resin (A) used in the step (a1) and the step (a2) at this time will be described later.

In the step (a), the compounding amount of the organic peroxide (P) is 0.01 to 0.6 parts by mass, preferably 0.03 to 0.03 parts, per 100 parts by mass of the base resin (A). 5 parts by mass. By making the organic peroxide (P) within this range, the polymerization can be carried out in an appropriate range, and the heat-resistant silane cross-linking property is excellent in extrudability without generating an agglomerate due to a cross-linked gel or the like. A resin composition (F) can be obtained.
That is, when the blending amount of the organic peroxide (P) is less than 0.01 parts by mass, the crosslinking reaction does not proceed at the time of crosslinking, and the free silane coupling agents are bonded to each other, resulting in heat resistance, mechanical strength, Abrasion resistance, reinforcement can not be sufficiently obtained, on the other hand, if it exceeds 0.6 parts by mass, many of the resin components are directly cross-linked by a side reaction, extrudability is reduced, There is a risk of bumps.

  The blending amount of the silane coupling agent premixed inorganic filler (D) can be reduced by the combined use with a brominated flame retardant described later, specifically, 10 to 150 mass with respect to 100 mass parts of the base resin (A). Part, preferably 20 to 120 parts by weight. When the compounding amount of the silane coupling agent premixed inorganic filler (D) is less than 10 parts by mass, the graft reaction of the silane coupling agent (q) to the resin component becomes non-uniform, and the desired heat resistance cannot be obtained. Or, the appearance may be deteriorated due to a non-uniform graft reaction. On the other hand, if it exceeds 150 parts by mass, the load during molding or kneading becomes very large, and secondary molding may be difficult.

  As described above, when high flame retardancy is required, it is preferable to use antimony trioxide as a part of the inorganic filler (C). The blending amount of antimony trioxide is preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the base resin (A) in terms of flame retardancy. Even if 30 parts by mass or more of antimony trioxide is blended, not only the desired flame retardancy is not improved, but also the specific gravity of the heat-resistant silane-crosslinked resin molded product is increased.

  In the step (a), the blending amount of the brominated flame retardant (h1) is 20 to 60 parts by mass, preferably 20 to 40 parts by mass with respect to 100 parts by mass of the base resin (A). A desired flame retardance is not acquired as the compounding quantity of a brominated flame retardant (h1) is less than 20 mass parts. On the other hand, when it exceeds 60 mass parts, mechanical strength may fall.

  In the step (a), the additive is mixed in the above-described amount or an appropriate amount.

In the production method of the present invention, the step (a) comprises at least the step ( a 1) and the step ( a 3) when the entire base resin (A) is melt-mixed in the following step (a1). When a part of (A) is melt-mixed, it comprises at least steps ( a1 ) to ( a3 ). When step (a) comprises at least these steps, each component can be uniformly melted and mixed, and the desired effect can be obtained.
Step (a1): All or part of the base resin (A), the organic peroxide (P), and the silane coupling agent premixed inorganic filler (D) are melt-mixed at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P). Step of preparing the silane masterbatch (Dx) Step (a2): The remainder of the base resin (A) as the carrier resin (e2) and the silanol condensation catalyst (e1) are melt-mixed to obtain a catalyst masterbatch (Ex Step (a3): Melting and mixing silane masterbatch (Dx) and silanol condensation catalyst (e1) or catalyst masterbatch (Ex)

In the step (a), the step (a2) is performed when a part of the base resin (A) is melt-mixed in the step (a1), and the whole base resin (A) is melt-mixed in the step (a1). If not done. In this case, in the step (a3), the silanol condensation catalyst (e1) can be used alone instead of the catalyst master batch (Ex).
In the step (a), the brominated flame retardant (h1) may be mixed in any one of the steps (a1) and (a2), and the brominated flame retardant (h1) is more uniformly mixed. In view of exhibiting high flame retardancy, it is preferable to mix at least in step (a1), and may be mixed in both step (a1) and step (a2).
Furthermore, it may be mixed in both steps (a1) and (a2) only when the inorganic filler (C) is 20 parts by mass or more. In that case, the filler used in the step (a1) is 10 parts by mass or more, preferably 20 parts by mass or more.

  In the step (a1), all or a part of the base resin (A), the organic peroxide (P), the silane coupling agent premixed inorganic filler (D), preferably all or the brominated flame retardant (h1) A part is put into a mixer and melt-kneaded while heating to a temperature higher than the decomposition temperature of the organic peroxide (P) to prepare a silane masterbatch (Dx).

In step (a) and step (a1), base resin (A), organic peroxide (P), silane coupling agent premixed inorganic filler (D), preferably brominated flame retardant (h1), etc. are melt mixed. Then, it does not specify the mixing order at the time of melt mixing, but it means that mixing may be performed in any order. That is, the mixing order in the step (a) and the step (a1) is not particularly limited.
Further, the mixing method of the base resin (A) is not particularly limited. For example, the base resin (A) mixed and prepared in advance may be used, and each component, for example, a resin component and an oil component may be used separately.

For example, the organic peroxide (P) may be mixed with the base resin (A) or the silane coupling agent premixed inorganic filler (D). In the present invention, the organic peroxide (P) is mixed with the base resin (A). Is preferred. That is, a silane coupling agent premixed inorganic filler (D) containing an organic peroxide (P) may be used, but a silane coupling agent premixed inorganic filler (D) containing no organic peroxide (P). ) Is preferably used.
The organic peroxide (P) may be dispersed in the base resin (A), or may be added alone or dispersed in oil or the like.

  Here, it is preferable to prepare or prepare the silane coupling agent premixed inorganic filler (D) prior to the step (a1). For example, when the inorganic filler (C) and the silane coupling agent (q) are mixed by a conventional method or the like, the silane coupling agent premixed inorganic filler (D) is obtained. As described above, when the step of preparing the silane coupling agent premixed inorganic filler (D) is performed prior to the step (a1), it is possible to suppress the occurrence of defects due to local crosslinking.

  Specifically, the suitable step (a1) comprises mixing the silane coupling agent (q) and the inorganic filler (C), then the mixture, the base resin (A), the organic peroxide (P) and preferably The brominated flame retardant (h1) is melt-kneaded at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P) to prepare a silane masterbatch (graftmer) (Dx).

  In a suitable step (a1), first, the inorganic filler (C) and the silane coupling agent (q) are dry-mixed or wet-mixed at a predetermined mass ratio, preferably at room temperature (25 ° C.), to obtain a mixture. Prepare.

  Here, the silane coupling agent (q) mixed with the inorganic filler (C) is 0.5 to 30.0 parts by mass, preferably 1.0 with respect to 100 parts by mass of the inorganic filler (C). -20.0 mass parts. When the mixing amount of the silane coupling agent (q) is less than 0.5 parts by mass, the crosslinking is not sufficiently performed, and there is a possibility that desired flame resistance and mechanical properties cannot be obtained in the heat resistant silane crosslinked resin molded product. is there. On the other hand, when the amount exceeds 30.0 parts by mass, the amount of the silane coupling agent (q) that does not adsorb on the surface of the inorganic filler (C) increases, and thus volatilizes during kneading. Condensation of the coupling agent (q) may cause cross-linked gels and burns in the heat-resistant silane cross-linked resin molded article, resulting in a deterioration in appearance. In particular, the appearance defect is remarkable when it exceeds 30.0 parts by mass.

  Moreover, it is preferable that a silane coupling agent (q) is 0.5-18.0 mass parts with respect to 100 mass parts of base resin (A), and is 1.0-15.0 mass parts. Is more preferable, and it is still more preferable that it is 4.0-12.0. When the amount of the silane coupling agent (q) used is less than 0.5 parts by mass, the crosslinking is not sufficiently performed, and there is a possibility that desired flame resistance and mechanical properties cannot be obtained in the heat-resistant silane crosslinked resin molded product. is there. On the other hand, when it exceeds 18.0 parts by mass, the silane coupling agents (q) are condensed with each other, and the heat-resistant silane cross-linked resin molded product may be brittle or burnt in the cross-linked gel, which may deteriorate the appearance.

  The mixture thus obtained contains a silane coupling agent premixed inorganic filler (D) obtained by mixing an inorganic filler (C) and a silane coupling agent (q).

  Mixing with the inorganic filler (C) and the silane coupling agent (q) is performed by heating or non-heating and mixing (dry type), or in a state where the inorganic filler (C) is dispersed in a solvent such as water. There exist methods, such as a process (wet process) which adds a ring agent (q). In this invention, the process which adds and mixes a silane coupling agent (q) in an inorganic filler (C), preferably the dried inorganic filler (C) with heating or non-heating, that is, a dry process is preferable.

  In the method of adding the silane coupling agent (q) in a state where the inorganic filler (C) is dispersed (wet mixing), the silane coupling agent (q) tends to be strongly bonded to the inorganic filler (C), and the subsequent crosslinking reaction. May be difficult to advance. On the other hand, the method of adding and mixing the silane coupling agent (q) in the inorganic filler (C) with or without heating (dry mixing) is a relatively bond between the inorganic filler (C) and the silane coupling agent (q). Since it becomes weak, it becomes easy to crosslink efficiently. At that time, the silane coupling agent (q) and the organic peroxide (P) may be mixed together and dispersed in the inorganic filler (C) or separately.

  The silane coupling agent (q) to be added to the inorganic filler (C) exists so as to surround the surface of the inorganic filler (C), and all or a part of the silane coupling agent (q) is adsorbed to the inorganic filler (C) or the inorganic filler (C ) It may cause a loose chemical bond with the surface. By entering such a state, it is considered that the volatilization of the silane coupling agent (q) during kneading with a subsequent kneader or Banbury mixer is greatly reduced. Further, it is considered that the silane coupling agent (q) undergoes a condensation reaction with the silanol condensation catalyst (e1) 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. This is probably because the silanol condensation reaction (crosslinking reaction) is difficult to proceed.

  In a suitable step (a1), each of the prepared mixture, the base resin (A), the organic peroxide (P), preferably the brominated flame retardant (h1), and optionally an additive, is then added. In addition to the mixer, they are melt-kneaded while heating to prepare a silane masterbatch (Dx).

  In the step (a1), the kneading temperature is not less than the decomposition temperature of the organic peroxide (P), preferably the decomposition temperature of the organic peroxide (P) + (25 to 110) ° C. This decomposition temperature is preferably set after the base resin (A) is 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 (P), the silane grafting reaction, the bond between the silane coupling agent premixed inorganic filler (D) and the resin component, and between the silane coupling agent premixed inorganic filler (D) Bonding does not occur and the desired heat resistance cannot be obtained, and the organic peroxide (P) reacts during the extrusion, and may not be molded into a desired shape.

  The kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic and the like, and the kneading apparatus is appropriately selected depending on the amount of the silane coupling agent premixed inorganic filler (D), for example. As a kneading apparatus, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer or various kneaders are used, and a closed mixer such as a Banbury mixer or various kneaders is capable of dispersing resin components and stabilizing the crosslinking reaction. In terms of surface.

  Moreover, normally, when such a silane coupling agent premixed inorganic filler (D) is mixed in excess of 100 parts by mass with respect to 100 parts by mass of the base resin (A), a continuous kneader, a pressure kneader, a Banbury. Kneading with a mixer is common.

  In addition, it is preferable to perform the step of preparing the silane coupling agent premixed inorganic filler (D) in advance, as in the preferred step (a1), but if the local crosslinking can be suppressed, the step (a1) ) Can be carried out continuously in the kneading apparatus without making the preparation step separate from the melt-kneading step, and the above-mentioned components can be combined together at a temperature higher than the decomposition temperature of the organic peroxide (P). A silane masterbatch (Dx) can also be prepared by mixing.

  Thus, the step (a1) is carried out to prepare a silane master batch (also referred to as silane MB) (Dx).

  The silane masterbatch prepared in step (a1) is a decomposition product of an organic peroxide (P), preferably a brominated flame retardant (h1), a base resin (A) and a silane coupling agent premixed inorganic filler. It is a reaction mixture of (D), and contains the silane crosslinkable resin in which the silane coupling agent (q) is grafted to the resin component to such an extent that it can be molded by the step (b) described later.

  In step (a) in the production method of the present invention, when part of the base resin (A) is melt-mixed in step (a1), step (a2) is performed. Step (a2) is a step of preparing a catalyst master batch (Ex) by melting and mixing the remainder of the base resin (A) as the carrier resin (e2) and the silanol condensation catalyst (e1).

The compounding quantity of a silanol condensation catalyst (e1) is 0.001-0.5 mass part with respect to 100 mass parts of base resin (A) used at a process (a), Preferably it is 0.003-0.1. Part by mass.
When the blending amount of the silanol condensation catalyst (e1) is less than 0.001 part by mass, crosslinking due to the condensation reaction of the silane coupling agent (q) is difficult to proceed, and the heat resistance of the heat-resistant silane crosslinked resin molded article is sufficiently improved. Therefore, there is a risk that productivity may be reduced and cross-linking may be uneven. On the other hand, if it exceeds 0.5 parts by mass, the silanol condensation reaction proceeds very rapidly, resulting in partial gelation and the appearance of the heat-resistant silane crosslinked resin molded product being reduced, or heat-resistant silane crosslinked resin molding Physical properties of the body may be reduced.

  It is preferable to use a part of the base resin (A) as the carrier resin (e2). In this case, the base resin (A) and the carrier resin (e2) are adjusted so that the total of the base resin (A) used in the step (a1) and the carrier resin (e2) used in the step (a2) is 100 parts by mass. The usage amount of is appropriately set. Specifically, the carrier resin (e2) may be 5 to 40 parts by mass, particularly 10 to 30 parts by mass, out of a total of 100 parts by mass with the base resin (A). In this case, the base resin (A) used in the step (a1) is 60 to 95 parts by mass, and the total amount of the base resin (A) and the carrier resin (e2) is a reference for the blending amount of each component. .

  In the step (a1), for example, when the entire base resin (A) is used, a resin other than the base resin (A) can be used as the carrier resin (e2). In this case, the blending amount of the other resin is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and further preferably 2 to 2 parts by mass with respect to 100 parts by mass of the base resin (A) in the step (a). 40 parts by mass. It is preferable to perform a step of melt-mixing the other resin and the silanol condensation catalyst (e1).

The catalyst master batch (Ex) may contain other components in addition to the silanol condensation catalyst (e1) and the carrier resin (e2). For example, you may contain the inorganic filler. The inorganic filler that may be contained is not particularly limited, and examples thereof include the above inorganic fillers.
Although content of an inorganic filler is not specifically limited, 350 mass parts or less are preferable with respect to 100 mass parts of carrier resin (e2). This is because if the amount of the inorganic filler is too large, the silanol condensation catalyst (e1) is difficult to disperse and the crosslinking is difficult to proceed. Moreover, when there is too much carrier resin (e2), there exists a possibility that the crosslinking degree of a molded object may fall and appropriate heat resistance may not be acquired.

  The melt mixing conditions with the silanol condensation catalyst (e1) and the carrier resin (e2) are appropriately set according to the melting temperature of the carrier resin (e2). For example, the kneading temperature can be 80 to 250 ° C, more preferably 100 to 240 ° C. The kneading conditions such as kneading time can be set as appropriate. The kneading method can be performed by the same method as the kneading method in the step (a1).

  The catalyst master batch (Ex) (also referred to as catalyst MB) thus obtained is a mixture of a silanol condensation catalyst (e1), a carrier resin (e2), and a filler that is optionally added.

In the process (a) in the manufacturing method of this invention, the process (a3) which melt-mixes a silane masterbatch (Dx), a silanol condensation catalyst (e1), or a catalyst masterbatch (Ex) is performed.
In the step (a3), the catalyst master batch (Ex) prepared in the step (a2) is used, and when the step (a2) is not performed, the silanol condensation catalyst (e1) is used.

  In the step (a3), the silane master batch (Dx), the catalyst master batch (Ex), and the like are melt-kneaded while heating. In this melt-kneading, there are resin components such as elastomers whose melting points cannot be measured by DSC or the like, but kneading is performed at a temperature at which at least one of the resin component and the organic peroxide (P) is melted. The carrier resin (e2) is preferably melted to disperse the silanol condensation catalyst (e2). The kneading conditions such as kneading time can be set as appropriate. The melt-kneading method can be performed by the same method as the kneading method in the step (a1).

  In this way, a heat-resistant silane crosslinkable resin composition (F) containing at least two silane crosslinkable resins having different crosslinking methods is prepared. This heat-resistant silane crosslinkable resin composition (F) is a composition prepared by the step (a), and is a base resin (A), a silane coupling agent premixed inorganic filler (D), preferably bromine It is considered to be a mixture of the silane masterbatch (Dx) containing the flame retardant (h1) as a raw material component and the silanol condensation catalyst (e1) or the catalyst masterbatch (Ex).

  Next, in the production method of the present invention, a step (b) of molding the heat-resistant silane crosslinkable resin composition (F) is performed to obtain a molded product. The molding method only needs to mold the heat-resistant silane crosslinkable resin composition (F), and the molding method and molding conditions are appropriately selected according to the form of the heat-resistant product of the present invention. For example, when the heat-resistant product of the present invention is an electric wire or an optical fiber cable, extrusion molding or the like is selected.

  This step (b) can be performed simultaneously or continuously with the mixing of the silane masterbatch (Dx) and the catalyst masterbatch (Ex). For example, a silane masterbatch (Dx) and a catalyst masterbatch (Ex) are melt-kneaded in a coating apparatus (step (a)), and then covered with, for example, an extruded wire or fiber and formed into a desired shape (step (b) )) Can be adopted.

  In this way, a molded product of the uncrosslinked heat-resistant silane crosslinkable resin composition (F) is obtained. 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).

  Next, in the production method of the present invention, the step (c) is carried out by bringing the molded product (uncrosslinked product) obtained in the step (b) into contact with water for crosslinking. In this step (c), the hydrolyzable group of the silane coupling agent is hydrolyzed into silanol by bringing the molded product into contact with water, and the silanol is converted by silanol condensation catalyst (e2) present in the resin. These hydroxyl groups are condensed to each other to cause a crosslinking reaction to obtain a crosslinked heat-resistant silane crosslinked resin molded product. The process itself of this process (c) can be performed by a normal method. By bringing moisture into contact with the molded product, the hydrolyzable group of the silane coupling agent is hydrolyzed and the silane coupling agents are condensed with each other to form a crosslinked structure.

  Condensation between silane coupling agents proceeds only by storage at room temperature, but in order to further accelerate the crosslinking, when contacting with moisture, it is immersed in warm water, put into a moist heat bath, heated to high-temperature steam. Exposure and the like. In this case, pressure may be applied to allow moisture to penetrate inside.

  Thus, the manufacturing method of this invention is implemented and a heat resistant silane crosslinked resin molded object is manufactured from a heat resistant silane crosslinked resin composition (F). Therefore, the heat-resistant silane cross-linked resin molded product of the present invention is a molded product obtained by performing the step (a) and, if desired, the step (b) and the step (c).

The details of the reaction mechanism of the production method of the present invention are not yet clear, but are considered as follows.
That is, the resin component, particularly the above-mentioned copolymer, is heated in the presence of the organic peroxide (P) component together with the silane coupling agent premixed inorganic filler (D) above the decomposition temperature of the organic peroxide (P). When kneaded, the radicals generated by the decomposition of the organic peroxide (P) are grafted with a silane coupling agent. Thereby, the resin components are bonded (crosslinked), and the resin component and the silane coupling agent premixed inorganic filler (D) are bonded.
In the present invention, the final cross-linking reaction may be performed in step (c), and it becomes possible to mix a large amount of inorganic filler without impairing the extrusion processability at the time of molding. While ensuring, it can have both heat resistance and mechanical properties.

  Moreover, although the mechanism of the operation of the above process of the present invention is not yet clear, it is estimated as follows.

That is, the silane coupling agent premixed inorganic filler (D) in which the silane coupling agent is bonded to the inorganic filler to such an extent that volatilization is suppressed before and / or during kneading with the base resin (A) is used. Thus, volatilization of the silane coupling agent at the time of kneading can be suppressed, and a silane coupling agent that can be bonded to the inorganic filler by a strong bond and a silane coupling agent that can be bonded by a weak bond can be formed.
When such a silane coupling agent premixed inorganic filler (D) is kneaded at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P) together with the base resin (A) in the presence of the organic peroxide (P), Of the silane coupling agents of the silane coupling agent premixed inorganic filler (D), the silane coupling agent having a strong bond with the inorganic filler (C) retains the bond with the inorganic filler and is a crosslinking group thereof. Ethylenically unsaturated groups and the like are grafted with the cross-linked sites of the resin component, particularly when a plurality of silane coupling agents are present on the surface of one inorganic filler particle through a strong bond, the resin passes through the inorganic filler particle. It is thought that a plurality of polymer molecules of the component are bonded to each other, and the crosslinked network with the inorganic filler is expanded. Thus, 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 causes the silane coupling agent chemically bonded by a covalent bond to a hydroxyl group on the surface of the inorganic filler, A hydrolyzable group that is not bonded to the filler causes a condensation reaction to further expand the cross-linking network.

  On the other hand, among the silane coupling agents of the silane coupling agent premixed inorganic filler (D), the silane coupling agent having a weak bond with the inorganic filler (C) is detached from the surface of the inorganic filler (C), and the silane cup The grafting reaction occurs when the ethylenically unsaturated group, which is a crosslinking group of the ring agent, reacts with the radical of the resin component generated by the extraction of the hydrogen radical by the radical generated by the decomposition of the organic peroxide (P) of the resin component. . It is considered that the silane coupling agent in the graft portion generated in such a manner is then mixed with a silanol condensation catalyst and brought into contact with moisture to cause a condensation reaction (crosslinking reaction).

  In particular, in the present invention, the molded body is formed after the conventional final cross-linking reaction by performing the cross-linking reaction by condensation using the silanol condensation catalyst in the presence of water in the step (c) after forming the molded body. Compared with the method, it is excellent in workability in the process up to the formation of the molded body, and higher heat resistance than conventional, for example, solder heat resistance at 380 ° C. described later can be obtained. Also, a plurality of silane coupling agents can be bonded to the surface of one inorganic filler particle, and high mechanical strength, insulation resistance and flame retardancy can be obtained.

  Thus, the silane coupling agent bonded to the inorganic filler (C) with a strong bond contributes to high mechanical strength, insulation resistance and flame retardancy, and bonded to the inorganic filler (C) with a weak bond. The silane coupling agent contributes to the improvement of the degree of crosslinking.

  In the present invention, when the base resin (A) contains a polyolefin copolymer resin and the content (Z) in the base resin (A) is 2% by mass or more, the mechanical strength can be further improved. . Although the details are not yet clear, it is thought as follows. That is, it is presumed that the mechanical strength is improved by forming a stronger network between the inorganic filler (C) and the resin component because the resin component has polarity. Although the reason is not clear, the mechanical strength is improved regardless of whether the resin component itself is silane-modified.

  Particularly in the present invention, in the base resin (A) used in the step (a1), when the content of the acid copolymerization component or the acid ester copolymerization component in the polyolefin copolymer resin is 70% by mass or less, The crosslinking reaction can be suppressed, and a more excellent appearance can be obtained.

  As the inorganic filler (C), when a surface-treated inorganic filler that has been slightly surface-treated with a silane coupling agent or other surface treatment agent in advance is used, a pre-treated silane coupling agent or a post-added silane coupling agent A large amount of the silane coupling agent premixed inorganic filler (D) strongly bonded with (q) is formed, and a molded article having high mechanical properties (for example, mechanical strength), insulation resistance and flame retardancy can be obtained. On the other hand, when a surface-treated inorganic filler that has been surface-treated in advance with a silane coupling agent or another surface treatment agent is used as the inorganic filler (C), the silane coupling agent added later is weakly bonded. Although a large amount of the agent premixed inorganic filler (D) is formed and the mechanical strength is not greatly improved, a molded article having excellent flexibility and the like can be obtained. Further, when a large amount of silane coupling agent premixed inorganic filler (D) in which the silane coupling agent is weakly bonded to the surface-treated inorganic filler or inorganic filler (C), a molded article having a high degree of crosslinking can be obtained. Further, by controlling the formation amount of the silane coupling agent premixed inorganic filler (D) in which the silane coupling agent is weakly bonded, the degree of cross-linking is lowered and a material that can be recycled can be obtained.

  When the silane coupling agent premixed inorganic filler (D) and the brominated flame retardant (h1) exhibiting such actions are used in combination, it is difficult to reduce the amount of the silane coupling agent premixed inorganic filler (D) used. Excellent flammability. The reason why such flame retardancy is excellent is not yet clear, but is considered as follows. That is, the brominated flame retardant (h1) contains a large amount of bromine having a high electronegativity and has a high polarity. Therefore, the brominated flame retardant (h1) is further incorporated into the strong network between the resin component and the silane coupling agent premixed inorganic filler (D) via the silane coupling agent (q), thereby allowing interaction. It is thought that the increased flame retardancy was improved.

  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.

The heat-resistant product of the present invention is the above-mentioned various heat-resistant products including a heat-resistant silane cross-linked resin molded article, and a heat-resistant product containing the heat-resistant silane cross-linked resin molded article as a coating for an insulator or a sheath, for example, an electric wire And optical cables.
Insulators, sheaths, and the like can be formed by coating them in such a shape while melt-kneading them in an extrusion coating apparatus. Such a molded body such as an insulator or a sheath is a general-purpose extrusion coating apparatus that uses a large amount of an inorganic filler and a highly heat-resistant and non-melting crosslinked composition without using a special machine such as an electron beam crosslinking machine. 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 silane cross-linked resin molded body of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 to 8 mm.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

The Examples and Comparative Examples were carried out using the following components with the respective specifications set to the conditions shown in Tables 1 and 2, and the evaluations described later were also shown.
In Examples and Comparative Examples, the silane crosslinking method of the present invention using the base resin (A), the silane coupling agent premixed inorganic filler (D), and the organic peroxide (P) is referred to as “silane crosslinking 1” The silane crosslinking method of Comparative Example 4 using a resin grafted with a coupling agent was designated as “silane crosslinking 2”.
In Tables 1 and 2, the numerical values in each Example and Comparative Example represent parts by mass unless otherwise specified, and are indicated by “0” when clearly indicating that the component is not contained. A blank also indicates that the corresponding component is not contained.

The following compounds were used as the compounds shown in Table 1.
<Resin component of base resin (A)>
In addition, the code | symbol of the copolymer to contain was attached | subjected to each resin component.
As a polyolefin copolymer resin (i-1) “Evaflex EV460” (trade name, manufactured by Mitsui DuPont Chemical Co., Ltd., a resin comprising an ethylene-vinyl acetate copolymer, VA content 19% by mass)
(I-2) “Evaflex EV170” (trade name, manufactured by Mitsui DuPont Chemical Co., Ltd., resin comprising ethylene-vinyl acetate copolymer, VA content 33% by mass)
(I-3) “Evaflex EV45XL” (trade name, manufactured by Mitsui DuPont Chemical Co., Ltd., resin comprising ethylene-vinyl acetate copolymer, VA content 46% by mass)
(I-4) "Revaprene 700HV" (trade name, manufactured by LANXESS, resin made of ethylene-vinyl acetate copolymer, VA content 70 mass%)
(I-5) “NUC6520” (trade name, manufactured by Nippon Unicar Co., Ltd., resin composed of ethylene ethyl acrylate, EA content 24 mass%)

As an ethylene-α-olefin copolymer resin (ii-1) “Evolue SP0540” (trade name, manufactured by Prime Polymer, LLDPE resin)
(Ii-2) “Engage 7256” (trade name, manufactured by Dow Chemical Company, linear low-density polyethylene resin)
As polypropylene (iii) (iii-1) “PB222A” (trade name, manufactured by Sun Allomer, random polypropylene resin)
(Iii-2) “BC8A” (trade name, manufactured by Nippon Polypro Co., Ltd., block polypropylene resin)

As a styrene-based elastomer, “Septon 4033” (trade name, manufactured by Kuraray)
As oil, “Diana Process Oil PW90” (trade name, Idemitsu Kosan Co., Ltd., paraffin oil)
As a silane cross-linked resin, “LINKRON XCF730N” (trade name, manufactured by Mitsubishi Chemical Corporation, silane cross-linked polyethylene)

<Inorganic filler>
As the surface-treated inorganic filler (c2) (c2-1) “Kisuma 5AL” (trade name, manufactured by Kyowa Chemical Industry, magnesium hydroxide surface-treated with stearic acid)
(C2-2) “Kisuma 5L” (trade name, manufactured by Kyowa Chemical Industry Co., Ltd., magnesium hydroxide surface-treated with a silane coupling agent, treatment amount 1% by mass)
As surface untreated inorganic filler (c1) (c1-1) “Hijilite 42M” (trade name, manufactured by Showa Denko KK, surface untreated aluminum hydroxide)
(C1-2) “Softon 1200” (trade name, manufactured by Shiraishi Calcium Co., Ltd., surface untreated calcium carbonate)
(C1-3) “PATOX-C” (trade name, manufactured by NSK Ltd., antimony trioxide)

<Silane coupling agent (q)>
"KBM1003" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane)
<Organic peroxide (P)>
“Park Mill D” (trade name, manufactured by NOF Corporation, dicumyl peroxide (DCP), decomposition temperature 151 ° C.))
<Silanol condensation catalyst (e1)>
(E1-1) “ADK STAB OT-1” (trade name, manufactured by ADEKA, dioctyltin laurate)
<Brominated flame retardant (h1)>
(H1-1) “Cytex 8010” (trade name, manufactured by Albemarle, 1,2-bis (bromophenyl) ethane)

<Others>
As an antioxidant, “Irganox 1010” (trade name, manufactured by BASF, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate])
As a lubricant, “X-21-3043” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., silicone gum)

  In Examples and Comparative Examples, a part of the resin component constituting the base resin (A) (for example, (iii-1) of Example 1) or a part of the resin component (for example, (( ii-1)) was used as carrier resin (e2) for the catalyst masterbatch.

Example 1
First, the inorganic filler (c2-2) and the silane coupling agent (q) shown in the “Silane MB (D1)” column of Table 1 are charged into a 10 L Henschel mixer manufactured by Toyo Seiki at the blending amounts shown in Table 1. The mixture was mixed at room temperature for 10 minutes to obtain a powder mixture containing the silane coupling agent premixed inorganic filler (D).
Next, this powder mixture and the resin component, organic peroxide (P) and brominated flame retardant (h1) shown in the “Silane MB (D1)” column of Table 1 are placed in a 2 L Banbury mixer manufactured by Nippon Roll. The mixture was kneaded with the mixer for about 12 minutes and then discharged at a material discharge temperature of 180 to 190 ° C. to obtain a silane master batch (D1) (step (a1)). In addition, before discharge | emission, it knead | mixed for 5 minutes at the rotation speed of 35 rpm in the temperature more than the decomposition temperature of organic peroxide (P), specifically 180-190 degreeC. The obtained silane masterbatch (D1) contains at least two types of silane crosslinkable resins in which a silane coupling agent is graft-reacted to the resin component.
For reference, the compounding amount (parts by mass) of the silane coupling agent (q) with respect to 100 parts by mass of the inorganic filler (C) at this time is shown in the “Silane MB (D1)” column of Table 1.
Table 1 shows the maximum content of the acid copolymerization component or the acid ester copolymerization component in the polyolefin copolymer resin contained in the silane masterbatch (Dx).

  Meanwhile, the carrier resin (e2), the silanol condensation catalyst (e1-1) and the antioxidant shown in the column of “Catalyst MB (E1)” in Table 1 were separately mixed at 120 to 160 ° C. with a Banbury mixer, and the material discharge temperature was It melt-mixed at 120-180 degreeC, and obtained the catalyst masterbatch (E1) (process (a2)).

Next, the silane masterbatch (D1) and the catalyst masterbatch (E1) were dry blended at a blending ratio (mass ratio) shown in Table 1, and L / D (ratio of screw effective length L to diameter D) = 24 Introduced into a 40 mm (screw diameter) mm extruder (compressor screw temperature 170 ° C., head temperature 180 ° C.), melted and mixed at 180 ° C., and coated on the outside of the 21 / 0.18 TA conductor with a thickness of 0.84 mm. Then, an electric wire having an outer diameter of 2.63 mm was obtained (step (a3) and step (b)).
This electric wire was left in an atmosphere of 60 ° C. and 95% humidity for 48 hours to polycondensate silanol (step (c)).
Thus, the insulated wire coat | covered with the heat resistant silane crosslinked resin molding (insulating layer) was manufactured. In this heat-resistant silane cross-linked resin molded article, as described above, the silane coupling agent of the silane cross-linkable resin is converted to silanol, and the hydroxyl group of silanol is converted into the above-mentioned silane cross-linked resin cross-linked by a condensation reaction.

  Table 1 shows the blending ratio (mixing ratio) of each component used in Example 1, that is, the raw material composition ratio of the heat-resistant silane cross-linked resin molded article, as “heat-resistant silane cross-linkable resin composition (F)”.

(Examples 2-15, 17 and 18 and Comparative Examples 1-3)
A silane masterbatch (Dx) and a catalyst masterbatch (Ex) were prepared in the same manner as in Example 1 with the formulations shown in Tables 1 and 2, respectively, except that they were blended at the blending ratios (mass ratios) shown in Tables 1 and 2. Was coated with a thickness of 0.84 mm on the outside of the 21 / 0.18 TA conductor in the same manner as in Example 1 to obtain an electric wire with an outer diameter of 2.63 mm (step (a3) and step (b)). The electric wire was left in an atmosphere of 60 ° C. and 95% humidity for 48 hours (step (c)) to produce an insulated electric wire covered with a heat-resistant silane crosslinked resin molded product (insulating layer).

  In Examples 9 and 11, the brominated flame retardant (h1) was melt-kneaded in the step (a2).

(Example 16)
In the step (a1) of Example 1, the powder mixture containing the silane coupling agent premixed inorganic filler (D) was prepared in a separate step, and each of those shown in the “Silane MB (D1)” column of Table 1 was prepared. Except that the ingredients were mixed with a Nippon Roll 2L Banbury mixer before mixing with an inorganic filler (c2-2) and a silane coupling agent (q) for 10 minutes at a rotation speed of 3 rpm to prepare a silane masterbatch (D19). Produced an insulated wire in the same manner as in Example 1.

(Comparative Example 4)
In Comparative Example 4, a silane cross-linked resin molded product was produced by a silane cross-linking method 2 different from the present invention.
In the same manner as in Example 1, a resin component such as a silane crosslinked resin, a surface-treated inorganic filler (c2), antimony trioxide and a brominated flame retardant (h1) shown in the column “Silane MB (D20)” in Table 2 were mixed. Thus, a silane master batch (D20) was obtained.
In the same manner as in Example 1, the resin component, silanol condensation catalyst (e1) and antioxidant shown in the column “Catalyst MB (E20)” in Table 2 were melted and mixed to obtain a catalyst master batch (E20). It was.
The silane masterbatch (D20) and the catalyst masterbatch (E20) were dry blended at the “blending ratio” shown in Table 2, and a 40 mm extruder with L / D = 24 (compressor screw temperature 170 ° C., head temperature 180 ° C. And the outer side of the 21 / 0.18 TA conductor was coated with a thickness of 0.84 mm to obtain an electric wire having an outer diameter of 2.63 mm. The electric wire was left in an atmosphere of a temperature of 60 ° C. and a humidity of 95% for 48 hours to produce an insulated wire having an insulating layer.

The following evaluation was performed about each manufactured insulated wire.
(Mechanical properties)
A tensile test was conducted as a mechanical property of the insulated wire. The tensile test of this insulated wire was performed based on UL1581, with a distance between marked lines of 25 mm and a tensile speed of 500 mm / min, and measured tensile strength (MPa) and elongation at break (%).
The tensile strength of 13.8 MPa or more was an acceptable level, expressed as “A”, and expressed as “C” when less than 13.8 MPa. Further, the elongation at break is an acceptable level of 300% or more, expressed as “A”, and less than 300% as “C”.

(Solder heat resistance)
A solder heat resistance test was performed as a heat resistance test of the insulated wires. Specifically, one layer of aluminum foil was wound around the outer periphery of the insulated wire, and a portion of 3 cm in length was immersed in a solder bath set at 380 ° C. and held for 5 seconds. Thereafter, the insulated wire was pulled from the solder bath, and the presence or absence of melting of the outer periphery of the insulated wire and the presence of foaming inside the coating layer were confirmed except for the aluminum foil. As a result, if there is no abnormality such as melting or foaming of the coating layer, it is an acceptable level. In Tables 1 and 2, it is indicated by “A”, and “C” when there is abnormality such as melting or foaming of the coating layer. The notation.

(Horizontal flame retardant test)
For each of the five specimens (N = 5) prepared for each insulated wire, UL1581 Horizon Flame Test was performed. The case where the number of specimens that passed this test was all 5 specimens was the “accepted level”, represented by “A”, and the specimen that did not pass even one specimen was represented by “C”.

(VW-1 test)
A UL 1581 vertical flame test was performed on each of five samples (N = 5) prepared for each insulated wire. The case where the number of specimens that passed this test was all 5 specimens was the “desirable level”, represented by “A”, and the specimen that did not pass even one specimen was represented by “C”.
The VW-1 test is an evaluation method in which a sample is held vertically and a burner is applied to check the combustion level, and is a test method that requires a higher flame retardant level than the horizontal flame retardant test. Therefore, this VW-1 test is a severe test and is evaluated for reference, and does not necessarily pass.

(Appearance test 1: Extrusion appearance (also referred to as wire appearance) test)
An extrusion appearance test was conducted as an extrusion appearance characteristic of the insulated wire. The extrusion appearance was observed when the insulated wire was manufactured. Extrusion appearance was "A" when the appearance of the electric wire extruded at 10 m / min with a screw diameter of 40 mm was good, "B" when the appearance was slightly bad, and remarkably bad appearance Is “C”, and “A” and “B” are acceptable levels as products.

(Appearance test 2: Extrusion test (also called cross-linking test))
An extrusion test was conducted as an extrusion appearance characteristic of the insulated wire. Extruded material measured and observed the manufactured electric wire using a bump inspection device. In the extrusion test, “C”, 100 μm was obtained in which 100 μm or more bumps (cross-linked protrusions protruding on the surface) were confirmed on the electric wire extruded at a line speed of 10 m / min with an extruder having a screw diameter of 40 mm. Although the above-mentioned bumps could not be confirmed, “B” indicates that the bumps could be confirmed with a microscope, and “A” indicates that the bumps could not be confirmed even with a microscope. “A” and “B” are acceptable levels as products.

As shown in Table 1 and Table 2, the insulated wires of Examples 1 to 18 manufactured by the manufacturing method of the present invention were tensile strength, elongation at break, solder heat resistance test, horizontal flame resistance test, appearance test ( Both the extrusion appearance and the extrusion protrusion test) passed. That is, all the insulated wires of Examples 1 to 18 were excellent in appearance, mechanical properties, and flame retardancy.
In particular, those containing 5 to 30 parts by mass of antimony trioxide with respect to 100 parts by mass of the base resin (A) and having a content (Z) of 3% by mass or more pass the VW-1 test, and are difficult. The flammability was excellent.
Thus, according to the present invention, it is possible to suppress the volatilization of the silane coupling agent even when melt-mixed with a Henschel mixer or a Banbury mixer, and to produce a heat-resistant silane crosslinked resin molded article having excellent appearance, mechanical properties, and flame retardancy. It turns out that it can be manufactured.

On the other hand, Comparative Example 1 with a small content of brominated flame retardant (h1) failed even in the horizontal flame retardant test and was inferior in flame retardancy.
Comparative Example 2 in which the content (Z) of the polyolefin copolymer resin was 0.95% by mass had insufficient tensile strength.
In Comparative Example 3 in which the silane coupling agent premixed inorganic filler (D) could not be prepared, the solder heat resistance test, the extrusion appearance, and the extrusion flutter test failed.
In Comparative Example 4 using the silane cross-linked resin, the solder heat resistance test was inferior.

Claims (8)

At least the following step (a), step (b) and step (c)
Step (a): 0.01 to 0.6 parts by mass of organic peroxide (P) and 100 parts by mass of inorganic filler (C) with respect to 100 parts by mass of base resin (A), silane coupling agent (q ) Silane coupling agent premixed inorganic filler (D) formed by mixing 0.5 to 30.0 parts by mass, 10 to 150 parts by mass of brominated flame retardant (h1), and silanol condensation catalyst (E1) Step of melting and mixing 0.001 to 0.5 parts by mass Step (b): Step of molding the heat-resistant silane crosslinkable resin composition (F) obtained in the step (a) Step (c) : A method for producing a heat-resistant silane cross-linked resin molded product comprising a step of bringing the molded product obtained in the step (b) into contact with moisture to cross-link it into a molded product,
The base resin (A) includes a resin comprising a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, a resin comprising a polyethylene resin, a polypropylene resin, an ethylene-α-olefin copolymer, and a styrene elastomer. containing at least one selected from, at that time, of the acid copolymer component and ester copolymer component, the content of the base resin (a) (Z) is 2% by mass or more,
When the step (a) comprises at least the following step ( a 1) and step ( a 3), and a part of the base resin (A) is melt-mixed in the following step ( a 1), at least the following step ( a 1), consisting of step ( a2 ) and step ( a3 ),
Step (a1): All or part of the base resin (A), the organic peroxide (P) and the silane coupling agent premixed inorganic filler (D) are decomposed at the decomposition temperature of the organic peroxide (P). Step of preparing the silane master batch (Dx) by melt mixing as described above Step (a2): Melting and mixing the remainder of the base resin (A) as the carrier resin (e2) and the silanol condensation catalyst (e1) Step for preparing catalyst master batch (Ex) Step (a3): Step for melting and mixing the silane master batch (Dx) and the silanol condensation catalyst (e1) or the catalyst master batch (Ex) The brominated flame retardant ( h1) is mixed in at least one of the step (a1) and the step (a2).
A method for producing a heat-resistant silane cross-linked resin molded article.   The resin comprising the polyolefin copolymer contained in the silane master batch (Dx), wherein the content of the acid copolymerization component or the acid ester copolymerization component in the resin is 70% by mass or less. The manufacturing method of the heat-resistant silane crosslinked resin molding of description.   The method for producing a heat-resistant silane-crosslinked resin molded article according to claim 1 or 2, wherein the brominated flame retardant (h1) is mixed in both the step (a1) and the step (a2).   The inorganic filler (C) contains 5 to 30 parts by mass of antimony trioxide with respect to 100 parts by mass of the base resin (A), and the content (Z) is 3% by mass or more. The manufacturing method of the heat-resistant silane crosslinked resin molding of any one of Claims 1.   The manufacturing method of the heat-resistant silane crosslinked resin molding of any one of Claims 1-4 in which the said base resin (A) contains 0.2-20 mass% of polypropylene resins.   The base resin (A) in the heat-resistant silane cross-linkable resin composition (F) is cross-linked by the method for producing a heat-resistant silane cross-linked resin molded article according to any one of claims 1 to 5. Heat-resistant silane cross-linked resin molding.   A heat-resistant product comprising the heat-resistant silane-crosslinked resin molded article according to claim 6.   The heat-resistant product according to claim 7, wherein the pre-heat-resistant silane cross-linked resin molded body is provided as a coating for an electric wire or an optical fiber cable.