WO2015002263A1

WO2015002263A1 - Heat-resistant silane crosslinked resin molded article and method for manufacturing same, and heat-resistant product equipped with heat-resistant silane crosslinked resin molded article

Info

Publication number: WO2015002263A1
Application number: PCT/JP2014/067768
Authority: WO
Inventors: 稔齋藤; 西口　雅己; 有史松村; 宏樹千葉
Original assignee: 古河電気工業株式会社
Priority date: 2013-07-03
Filing date: 2014-07-03
Publication date: 2015-01-08
Also published as: JP6329948B2; CN105308102B; CN105308102A; JPWO2015002263A1

Abstract

A method for manufacturing a heat-resistant silane crosslinked resin molded article, in which a step (a) of melt-mixing a specific resin component, an organic peroxide, an inorganic filler having a silane coupling agent premixed therewith, a bromine-containing flame retardant agent and a silanol condensing catalyst together comprises a step (a1) of melt-mixing a portion or the whole of the resin component, the organic peroxide and the inorganic filler having the silane coupling agent premixed therewith together to prepare a silane MB, a step (a2) of optionally melt-mixing the remainder of the resin component with the silanol condensing catalyst to prepare a catalyst MB, and a step (a3) of melt-mixing the silane MB with the silanol condensing catalyst or the catalyst MB, wherein the bromine-containing flame retardant agent is mixed in step (a1) and/or step (a2); a heat-resistant silane crosslinked resin molded article manufactured by the method; and a heat-resistant product equipped with the heat-resistant silane crosslinked resin molded article.

Description

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

The present invention relates to a heat-resistant silane cross-linked resin molded body, a method for producing the same, and a heat-resistant product using the heat-resistant silane cross-linked resin molded body, and in particular, excellent heat-resistant silane having mechanical properties, insulation resistance and flame retardancy. The present invention relates to a cross-linked resin molded body, a method for producing the same, and a heat-resistant product using the heat-resistant silane cross-linked resin molded body as an electric wire insulator or sheath.

Insulated wires, cables, cords, optical fiber cores and optical fiber cords used for internal and external wiring of electrical and electronic equipment are flame retardant, heat resistant, mechanical properties (for example, tensile properties), and abrasion 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 usually used.

In addition, wiring materials used in electric / electronic devices may be heated to 80 to 105 ° C. or even 125 ° C. when used for a long time, and heat resistance against this may be 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 resin 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 is decomposed by applying heat after molding, and a crosslinking reaction is performed, Silane cross-linking 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.
Among the crosslinking methods described above, the silane crosslinking method in particular does not require special equipment, and can be used in a wide range of fields.

Specifically, the silane crosslinking method includes a silane master batch obtained by grafting a silane coupling agent having an unsaturated group to a polyolefin resin, a heat resistant master batch obtained by kneading a polyolefin resin and an inorganic filler, and a silanol condensation catalyst. There is a method of melt-mixing the contained catalyst master batch. However, in this method, when the amount of the inorganic filler used exceeds 100 parts by mass with respect to 100 parts by mass of the polyolefin resin, the silane master batch and the heat-resistant master batch are dry-mixed to obtain a single screw extruder or a twin screw extruder. It becomes difficult to melt and knead uniformly in the machine. Thus, in order to uniformly melt and knead a silane masterbatch and a heat-resistant masterbatch by dry mixing, the ratio of the silane masterbatch is limited, so that it is possible to achieve higher flame retardancy and higher heat resistance. It was difficult. 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.
However, when silane grafting is carried out with a kneader or Banbury mixer, the hydrolyzable silane coupling agent having an unsaturated group is generally highly volatile and volatilizes before the graft reaction. Therefore, it is 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 is added to the heat-resistant masterbatch obtained by melting and mixing a polyolefin resin and an inorganic filler with a Banbury mixer. And an organic peroxide may be added and graft polymerization may be performed with 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. Moreover, the compounding ratio of the inorganic filler in the heat resistant masterbatch must be increased. For this reason, the extrusion load becomes large, the production becomes very difficult, and a desired material or molded product cannot be obtained. Furthermore, this is a two-step process, which is a difficult point in terms of manufacturing cost.

In Patent Document 1, an inorganic filler surface-treated with a silane coupling agent, a silane coupling agent, an organic peroxide, and a crosslinking catalyst are sufficiently melt-kneaded with a kneader and then molded with a single screw extruder. A method has been proposed.
However, in this method, the resin is partially crosslinked during melt kneading in a kneader, causing the molded body to have a poor appearance (formation of a large number of protrusions protruding on the surface). In addition to this, most of the silane coupling agents other than the silane coupling agent surface-treated on the inorganic filler may volatilize or the silane coupling agents may condense. 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, Patent Documents 2 to 4 disclose a vinyl aromatic thermoplastic elastomer composition having a block copolymer or the like as a base resin and a non-aromatic rubber softener added as a softener. A technique of partially crosslinking using an organic peroxide through a filler has been proposed.
However, even with such a technique, the resin does not yet have a sufficient network structure, and the bond between the resin and the inorganic filler is released at a high temperature. For this reason, there is a problem that it melts at a high temperature, for example, the insulating material melts during soldering of the electric wire, or deforms or foams when the molded body is secondarily processed. Furthermore, when heated to about 200 ° C. for a short time, there is a problem that the appearance is remarkably deteriorated or deformed.

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

The present invention solves the above-mentioned problems and is produced by suppressing volatilization of the hydrolyzable silane coupling agent, and has excellent mechanical properties, insulation resistance and flame retardancy, and its molded product It is an object to provide a manufacturing method.
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.

When using the silane cross-linking method as described above, the present inventors previously mixed a hydrolyzable silane coupling agent that easily volatilizes with an inorganic filler (this is referred to as premixing), and hydrolyzable silane coupling. When combined with a silane coupling agent premixed inorganic filler bonded to a level that suppresses the volatilization of the agent and a specific amount of brominated flame retardant, insulation is achieved while maintaining the excellent mechanical properties of the heat-resistant silane crosslinked resin molding It has been found that the flame retardancy can be improved to be equal to or higher than that of a molded article obtained by increasing resistance and electron beam crosslinking. In addition, it has also been found that when used in combination with a brominated flame retardant, the amount of the silane coupling agent premixed inorganic filler can be reduced.
The present inventors have further studied based on these findings, and have come to make the present invention.

That is, the subject of this invention was achieved by the following means.
(1) The following step (a), step (b) and step (c)
Step (a): 100 parts by mass of resin component (A), 0.01 to 0.6 parts by mass of organic peroxide (P), and 100 parts by mass of inorganic filler (C) including surface-treated inorganic filler (B) 10 to 150 parts by mass of a silane coupling agent premixed inorganic filler (D) obtained by mixing 0.5 to 30.0 parts by mass of a hydrolyzable silane coupling agent (q) with respect to a brominated flame retardant ( h1) Step of melt-mixing 15-60 parts by mass of silanol condensation catalyst (e1) 0.001-0.5 parts by mass Step (b): Heat-resistant silane crosslinkable resin obtained in step (a) A step of molding the composition (F) and a step (c): a heat-resistant silane cross-linked resin molded product having a step of bringing the molded product obtained in the step (b) into contact with moisture to form a molded product A manufacturing method comprising:
The resin component (A) is (i) a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component in an amount of 10 to 90% by mass, and (ii) an ethylene-α-olefin copolymer in an amount of 10 to 90% by mass. %
The step (a) includes the following step (a1) and step (a3), and further includes the following step (a2) when a part of the resin component (A) is melt-mixed in the following step (a1). ,
Step (a1): Part or all of the resin component (A), the organic peroxide (P), and the silane coupling agent premixed inorganic filler (D) are combined with the organic peroxide (P). Step of preparing a silane masterbatch (Dx) by melting and mixing at a temperature equal to or higher than the decomposition temperature of step Step (a2): Melting the remainder of the resin component (A) as the carrier resin (e2) and the silanol condensation catalyst (e1) Step of mixing and preparing a catalyst master batch (Ex) and Step (a3): Melting and mixing the silane master batch (Dx) and the silanol condensation catalyst (e1) or the catalyst master batch (Ex) A method for producing a heat-resistant silane-crosslinked resin molded product, wherein the brominated flame retardant (h1) is mixed in at least one of the step (a1) and the step (a2).

(2) The resin component (A) comprises at least (i) 10 to 50% by mass of a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, and (ii) an ethylene-α-olefin copolymer The method for producing a heat-resistant silane crosslinked resin molded article according to (1), comprising 20 to 80% by mass of the coalescence.
(3) At least one of the (i) polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component is an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester copolymer. (1) The manufacturing method of the heat-resistant silane crosslinked resin molding as described in (2).
(4) The heat-resistant silane cross-linking according to any one of (1) to (3), wherein the brominated flame retardant (h1) is mixed in both steps (a1) and (a2). Manufacturing method of resin molding.
(5) In at least one of the step (a1) and the step (a2), (h3) antimony trioxide is mixed in a total of 5 to 30 parts by mass with respect to 100 parts by mass of the resin component (A). (1) The method for producing a heat-resistant silane crosslinked resin molded article according to any one of (4).
(6) The method for producing a heat-resistant silane crosslinked resin molded article according to any one of (1) to (5), wherein the resin component (A) comprises (iii) 0.2 to 20% by mass of polypropylene.

(7) 100 parts by mass of the resin component (A) and 0.01% of the organic peroxide (P) are produced by the method for producing a heat-resistant silane-crosslinked resin molded article according to any one of (1) to (6). 0.5 to 30.0 parts by mass of a hydrolyzable silane coupling agent (q) is mixed with ~ 0.6 parts by mass and 100 parts by mass of the inorganic filler (C) containing the surface-treated inorganic filler (B). Silane coupling agent premixed inorganic filler (D) 10 to 150 parts by mass, brominated flame retardant (h1) 15 to 60 parts by mass, silanol condensation catalyst (e1) 0.001 to 0.5 parts by mass, A heat-resistant silane cross-linked resin molded product obtained by cross-linking the heat-resistant silane cross-linkable resin composition (F) obtained by melting and mixing the above.
(8) A heat resistant product comprising the heat resistant silane crosslinked resin molded article according to (7).
(9) The heat-resistant product according to (8), wherein the pre-heat-resistant silane-crosslinked resin molded body is provided as a coating for an electric wire or an optical fiber cable.

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

ADVANTAGE OF THE INVENTION According to this invention, the heat resistant silane crosslinked resin molding excellent in the mechanical characteristic, the insulation resistance, and the flame retardance manufactured by suppressing volatilization of a hydrolysable silane coupling agent, and its manufacturing method can be provided. 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.
These and other features and advantages of the present invention will become more apparent from the following description.

Below, this invention and preferable embodiment in this invention are demonstrated in detail.
The “method for producing a heat-resistant silane-crosslinked resin molded product” of the present invention (hereinafter sometimes referred to as the production method of the present invention) is as described above, and in short, the steps (a), (b) and the steps described above. A method for producing a heat-resistant silane cross-linked resin molded article having (c),
The resin component (A) is a specific resin component (A),
The step (a) includes the following step (a1) and step (a3), and further includes the following step (a2) when a part of the resin component (A) is melt-mixed in the following step (a1). ,
The brominated flame retardant (h1) is mixed in at least one of the following step (a1) and the following step (a2).
Step (a1): A part or all of the resin component (A), the organic peroxide (P), and the silane coupling agent premixed inorganic filler (D) are at or above the decomposition temperature of the organic peroxide (P). Step (a2) for preparing a silane master batch (Dx) by melting and mixing in step: A resin component as a carrier resin (e2) when part of the resin component (A) is melt-mixed in step (a1) Process step (a3) for preparing catalyst master batch (Ex) by melt-mixing the remainder of (A) and silanol condensation catalyst (e1): Silane master batch (Dx) and silanol condensation catalyst (e1) or catalyst master Process of melt-mixing batch (Ex)

In the production method of the present invention, when all of the resin component (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 in the present invention will be described.

<(A) Resin component and (G) Resin component>
For convenience, the resin component used in the production method of the present invention is “resin component (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 component contained in the functional silane cross-linked resin molded product is referred to as “resin component (G)”. As will be described later, the resin component (G) is synonymous with a mixture of the resin component (A) and the carrier resin (e2). Therefore, in the present invention, the resin component (A), the carrier resin (e2), and the resin component (G) may be simply referred to as a resin component without clearly distinguishing them.

The resin component (A) used in the present invention is a crosslinking site that undergoes a crosslinking reaction in the presence of the crosslinking group of the hydrolyzable silane coupling agent (q) and the organic peroxide (P) described below, for example, unsaturated carbon chain. Examples thereof include a binding site and a resin, elastomer, rubber, or the like 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.

The polyolefin-based resin is not particularly limited as long as it is a resin obtained by polymerizing or copolymerizing a compound having an ethylenically unsaturated bond, and is a known one conventionally used in heat-resistant resin compositions. Can be used. Examples thereof include polyethylene (PE), polypropylene (PP), ethylene-α-olefin copolymer, polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, and rubbers and elastomers thereof. Among these, receptivity to various inorganic fillers including metal hydrates is high, there is an effect of maintaining the mechanical strength even if a large amount of inorganic filler is blended, and withstand voltage while ensuring heat resistance, In particular, a copolymer having polyethylene (PE), polypropylene (PP), an ethylene-α-olefin copolymer and an acid copolymer component or an acid ester copolymer component from the viewpoint of suppressing a decrease in withstand voltage characteristics at high temperatures. Etc. are suitable. These polyolefin resins may be used alone or in combination of two or more.

(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 a vinyl acetate component, a (meth) acrylic acid component, an (meth) acrylic acid alkyl component, and the like. That is, examples of the polyolefin copolymer (i) include an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid alkyl copolymer. Among these, an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylate copolymer are preferable, and an ethylene-vinyl acetate copolymer is more preferable from the viewpoint of acceptability to an inorganic filler and heat resistance. Here, the alkyl group of the alkyl (meth) acrylate preferably has 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.

The ethylene-vinyl acetate copolymer may be an alternating copolymer obtained by alternately polymerizing an ethylene component and a vinyl acetate component as long as it is a copolymer of ethylene and vinyl acetate. A block copolymer formed by combining a polymer block and a polymer block of a vinyl acetate component may be used, and further, a random copolymer in which an ethylene component and a vinyl acetate component are randomly polymerized may be used.

The ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 17 to 80% by mass, more preferably 20 to 50% by mass, still more preferably 25 to 41% by mass. The vinyl acetate component content can be determined according to JIS K 7192. Two or more copolymers having different vinyl acetate contents may be combined. By using an ethylene-vinyl acetate copolymer having a vinyl acetate content within the above range, sufficient flame retardancy can be ensured. Examples of the ethylene-vinyl acetate copolymer include “Evaflex” (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.) and “Revaprene” (trade name, manufactured by Bayer).

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 ethylene- (meth) acrylic acid ester copolymer is a copolymer of ethylene and (meth) acrylic acid ester, like the above-mentioned ethylene-vinyl acetate copolymer, alternating copolymer, block copolymer. Either a polymer or a random copolymer may be used. The (meth) acrylic acid ester component is not particularly limited, but preferably has an alkyl group having 1 to 4 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, etc. Is mentioned.

The content of the (meth) acrylic acid ester component that is a copolymerization component of the ethylene- (meth) acrylic acid ester copolymer is preferably 15 to 80% by mass. When this content is in the above range, sufficient flame retardancy can be ensured.

Examples of such ethylene- (meth) acrylic acid ester copolymers include ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, and ethylene-ethyl methacrylate. Examples thereof include a copolymer and an ethylene-butyl acrylate copolymer. Examples of the ethylene- (meth) acrylic acid copolymer include Nucrel (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.). Further, examples of the ethylene-ethyl acrylate copolymer include “Evalroy” (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.).
Polyolefin copolymer (i) is used individually by 1 type, or 2 or more types are used together.

(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 (the polyethylene described later) (Excluding those contained in (PE)). 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. As the ethylene-α-olefin copolymer (ii), specifically, an ethylene-butylene copolymer (EBR), an ethylene-α-olefin copolymer synthesized in the presence of a single site catalyst, a linear chain Type low density polyethylene (LLDPE) and the like. The ethylene-α-olefin copolymer (ii) may also contain a copolymer containing a diene component, such as an ethylene-propylene rubber (for example, ethylene-propylene-diene rubber). One ethylene-α-olefin copolymer may be used alone, or two or more ethylene-α-olefin copolymers may be used in combination.
Examples of the ethylene-α-olefin copolymer include Evolue SP0540 (trade name, manufactured by Prime Polymer, LLDPE resin), UE320 (trade name, density 0.922 g / cm ³ , manufactured by Ube Maruzen Polyethylene), UBEC 180 ( trade name, density 0.924 g / cm ^3, manufactured by Ube Maruzen polyethylene Co., Ltd.), HI-ZEX 540E (trade name, density 0.956 g / cm ^3, manufactured by Prime polymer Co., Ltd.).

(Iii) Polypropylene (PP)
Polypropylene (iii) may be a resin in which one of the polymerization components is a propylene component, and includes random polypropylene and block polypropylene in addition to a homopolymer of propylene (also referred to as homopolypropylene). “Random polypropylene” as used herein is a copolymer of propylene and ethylene in general, and is a propylene copolymer having an ethylene component content of 1 to 6% by mass, such as ethylene in the propylene chain. It means that the copolymerization component is taken in at random. The “block polypropylene” is a composition containing a homopolypropylene and an ethylene-propylene copolymer, generally having an ethylene component content of about 18% by mass or less, and having a propylene component and a copolymer component. The thing which exists as an independent component.

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.
Examples of polypropylene include BC8A (trade name, manufactured by Nippon Polypro), PB222A (trade name, manufactured by Sun Allomer), and E150GK (trade name, manufactured by Prime Polymer).

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.

(Iv) Polyethylene (PE)
Polyethylene (iv) may be a resin in which one of the polymerization components is an ethylene component, 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.

(V) Styrene Elastomer Examples of the styrene elastomer (v) include block copolymers and random copolymers of conjugated diene compounds and aromatic vinyl compounds, or hydrogenated products thereof. Examples of the aromatic vinyl compound include styrene, p- (t-butyl) styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethyl. Examples thereof include styrene, vinyl toluene, p- (t-butyl) styrene and the like. Among these, styrene is preferable as the aromatic vinyl compound. This aromatic vinyl compound is used individually by 1 type, or 2 or more types are used together. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Among these, the conjugated diene compound is preferably butadiene. This conjugated diene compound is used individually by 1 type, or 2 or more types are used together. Further, as the styrene-based elastomer, an elastomer that does not contain a styrene component and contains an aromatic vinyl compound other than styrene may be used.
Specific examples of the styrene-based elastomer include, for example, Septon 4077, Septon 4055, Septon 8105 (all trade names, manufactured by Kuraray Co., Ltd.), Dynalon 1320P, Dynalon 4600P, 6200P, 8601P, and 9901P (all trade names, JSR Etc.).

Oil The resin component (A) may optionally contain an oil as a plasticizer or a mineral oil softener for rubber. Examples of such oils include paraffinic, naphthenic, and aromatic oils. Paraffin oil has 50% or more of the total number of carbon atoms in the paraffin chain, and naphthenic oil has 30 to 40% naphthenic ring carbon. Aroma oil (also called aromatic oil) ) Refers to those having an aromatic carbon number of 30% or more. Oils may be used alone or in combination of two or more. The oil is preferably contained in the resin component (A) at a mass ratio of 20% by mass or less.

<(P) Organic peroxide>
The organic peroxide (P) generates radicals by thermal decomposition and promotes the grafting reaction of the hydrolyzable silane coupling agent to the resin component (A), particularly the hydrolyzable silane coupling agent (q). Acts to promote a grafting reaction by a radical reaction (including a hydrogen radical abstraction reaction from the resin component (A)) between the group and the resin component (A) in the case where contains an ethylenically unsaturated group. The organic peroxide (P) is not particularly limited as long as it generates radicals. For example, the general formula: R ¹ —OO—R ² , R ¹ —OO—C (═O) R ³ , A compound represented by 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 organic peroxides (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 Diacetyl peroxide, lauroyl peroxide, may be mentioned tert- butyl cumyl peroxide and the like. Of these, dicumyl peroxide (DCP), 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-in terms of odor, colorability, and scorch stability. Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3 is preferred.

The decomposition temperature of the organic peroxide (P) is preferably from 80 to 195 ° C., particularly preferably from 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) Hydrolyzable silane coupling agent>
The hydrolyzable silane coupling agent (q) is mixed with an inorganic filler (C) described later, and surface-treats at least a part of the inorganic filler (C).
Such a hydrolyzable silane coupling agent (q) is not particularly limited, and a hydrolyzable silane coupling agent having an unsaturated group used in the silane crosslinking method can be used. As such a hydrolyzable silane coupling, 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 examples thereof include a vinyl group, a (meth) acryloyloxyalkylene group, a p-styryl group, and the like. A vinyl group is preferred.

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

Y ¹¹ , Y ¹² and Y ¹³ are each independently an organic group that can be hydrolyzed, such as 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, an alkoxy group having 1 to 6 carbon atoms is preferable. Specific examples of the alkoxy group having 1 to 6 carbon atoms include, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, and the like. 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. Specific preferred hydrolyzable silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxy. Examples include silane, allyltriethoxysilane, vinyltriacetoxysilane, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, (meth) acryloxypropylmethyldimethoxysilane, and the like. Among these, a hydrolyzable silane coupling agent having a vinyl group and an alkoxy group at the terminal is more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.
A hydrolysable silane coupling agent (q) may be used individually by 1 type, and may use 2 or more types together. Further, the hydrolyzable silane coupling agent (q) may be used alone or as a liquid diluted with a 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 (B) that has been surface treated with a surface treatment agent, and the surface treated inorganic filler (B). Silane coupling agent premixed inorganic filler (D) formed by mixing the inorganic filler (C) and the like, and the inorganic filler (C) and the hydrolyzable silane coupling agent (q).
Below, the 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, and more preferably 0.35 to 5 μm, regardless of their form and type. More preferably, it is particularly preferably 0.35 to 3 μm. When the average particle size is in the above range, secondary aggregation is difficult to occur when the hydrolyzable silane coupling agent (q) is mixed, and no fluff is generated, the appearance of the molded article is excellent, and the hydrolyzable silane The resin component (A) is sufficiently crosslinked due to the retention effect of the coupling agent (q).
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.

(C1) Surface Untreated Inorganic Filler As the surface untreated inorganic filler (c1) surface-treated in the surface treated inorganic filler (B), and the surface untreated inorganic filler (c1) that can be contained in the inorganic filler (C) If the surface of the inorganic filler has a site capable of forming a hydrogen bond or a reactive site such as a silanol group of a hydrolyzable silane coupling agent, or a site capable of chemical bonding by a covalent bond, it can be used without particular limitation. it can. In the surface untreated inorganic filler, as the site capable of chemically bonding with the reaction site of the hydrolyzable silane coupling agent, an OH group (hydroxyl, water-containing or water molecule of crystal water, OH group such as carboxyl group), amino group, SH group etc. are 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, Magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate, hydrated aluminum silicate, alumina, hydrated magnesium silicate, basic magnesium carbonate, metal hydroxides such as metal compounds having water or crystal water such as hydrotalcite, Metal hydrates, 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 carbo , It can be used zinc borate, hydroxy stannate, zinc stannate and the like.

The surface untreated inorganic filler (c1) is preferably a metal hydroxide, calcium carbonate, or silica, and more preferably magnesium hydroxide, aluminum hydroxide, or calcium carbonate, as described above.

(B) Surface-treated inorganic filler The surface-treated inorganic filler (B) is obtained by surface-treating the surface untreated inorganic filler (c1) with a surface treatment agent. The surface-treated inorganic filler (B) may be a surface-treated inorganic filler that has already been surface-treated.
The surface untreated inorganic filler (c1) or the already surface treated inorganic filler for forming the surface treated inorganic filler (B) is not particularly limited, but the above-described metal hydroxide and metal hydrate are preferable. Furthermore, aluminum hydroxide, magnesium hydroxide and calcium carbonate are preferred.
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. Examples of such a silane coupling agent include the hydrolyzable silane coupling agent (q) described above.
The surface-treated inorganic filler (B) 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 (B) surface-treated with a fatty acid or silane coupling agent is obtained by mixing a surface untreated inorganic filler (c1) and the like with a fatty acid or 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. The amount of these surface treatments is not particularly limited, but it is usually preferably 0.1 to 4% by mass relative to the inorganic filler before the surface treatment such as the untreated inorganic filler (c1). When the surface treatment amount is within this range, the mechanical strength and wear 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 (B) 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 (B) obtained 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 are Kamishima Chemical Co., Ltd.), and the like. Examples of commercially available silane coupling agent surface-treated aluminum hydroxide include Heidilite H42-ST-V and Heidilite H42-ST-E (both trade names, Showa Denko KK).

The surface treatment inorganic filler (B) may be used alone or in combination of two or more.

(C) Inorganic filler The inorganic filler (C) used in the present invention is the above-mentioned hydrolyzable silane coupling agent (q) before being melt-mixed with the above-described resin component (A) or the like in the step (a). It is an inorganic filler (C) processed in advance. The inorganic filler (C) may include at least a part of the surface-treated inorganic filler (B), and the whole may be the surface-treated inorganic filler (B), and the remaining part of the surface-untreated inorganic filler (c1) or the like. May be included. Thus, when inorganic filler (C) contains surface-treated inorganic filler (B), in the manufacturing method of this invention, the coupling | bonding of the hydrolysable silane coupling agent (q) and inorganic filler added later. And a hydrolyzable silane coupling agent that binds to the inorganic filler with a certain weak bond can be created. With this hydrolyzable silane coupling agent that binds to the inorganic filler with a weak bond, it is possible to obtain a heat-resistant silane cross-linked resin molded product having a certain degree of cross-linking, whereby high heat resistance can be obtained.

The ratio of the surface-treated inorganic filler (B) 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 ratio of the surface-treated inorganic filler (B) 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 (B) and the surface untreated inorganic filler can be used alone or in combination of two or more.

(D) Silane coupling agent premixed inorganic filler The silane coupling agent premixed inorganic filler (D) is prepared by previously mixing the above-mentioned inorganic filler (C) with a hydrolyzable silane coupling agent (q). The inorganic filler (C) is surface-treated with a functional silane coupling agent (q). In addition, the silane coupling agent premixed inorganic filler (D) includes the resin component (A), the organic peroxide (P), and the like, as will be described later, and the inorganic filler (C) and the hydrolyzable silane coupling agent (q). And the surface treated by mixing with. 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 hydrolyzable 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 hydrolyzable silane coupling agent (q). As a method of mixing the hydrolyzable silane coupling agent (q) and the inorganic filler (C), a wet process in which the hydrolyzable silane coupling agent (q) and the inorganic filler (C) are mixed in alcohol or water, inorganic Examples thereof include a dry treatment for blending the filler (C) and the hydrolyzable silane coupling agent (q), and both.

Thus, if the inorganic filler (C) and the hydrolyzable silane coupling agent (q) are premixed before or simultaneously with the organic peroxide (P) in the step (a) described later, A part of the decomposable silane coupling agent (q) is strongly bonded to the inorganic filler (C) (the reason is, for example, formation of a chemical bond with a hydroxyl group on the surface of the inorganic filler is considered), and silane coupling An agent premixed inorganic filler (D) is prepared.

In this silane coupling agent premixed inorganic filler (D), the hydrolyzable silane coupling agent (q), which binds strongly to the inorganic filler (C), and the inorganic filler (C) are weakly bonded (interaction by hydrogen bonds, ions And a hydrolyzable silane coupling agent (q) that interacts between partial charges or dipoles, an action by adsorption, etc.), as described later, shows a different behavior. Therefore, the effect obtained by the ratio of these hydrolyzable silane coupling agents (q) differs. The hydrolyzable silane coupling agent (q) that binds weakly to the inorganic filler (C) contributes to the cross-linking of the resin components (A) and strongly binds to the inorganic filler (C) (q ) Also includes condensation of hydrolyzable silane coupling agents (q), and contributes to bonding between the silane coupling agent premixed inorganic filler (D) and the resin component (A). Therefore, when the ratio of the both hydrolyzable silane coupling agents is set to a specific range, in the silane crosslinking method, both heat resistance, mechanical properties, flame retardancy, and appearance can be achieved.

In the silane coupling agent premixed inorganic filler (D), a method for adjusting the ratio of the hydrolyzable silane coupling agent (q) that is weakly bonded to the inorganic filler (C) is, for example, a hydrolyzable silane coupling agent ( q) and a method of adjusting by mixing inorganic filler (C) at room temperature, a method of storing at normal temperature or preheated after premixing, or hydrolysis by heating inorganic filler (C) before premixing And a method of mixing with a functional silane coupling agent (q).

<(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 preferred, 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, each n is 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 hydrolyzable silane coupling agent (q) grafted to the resin component (A) in the presence of moisture by a condensation reaction. Based on the function of the silanol condensation catalyst (e1), the resin components (A) are cross-linked through the hydrolyzable silane coupling agent (q). As a result, a heat-resistant silane cross-linked resin molded product having excellent heat resistance can be obtained.

As the silanol condensation catalyst (e1), an organic tin compound, a metal soap, a platinum compound, or the like is used. 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>
The carrier resin (e2) is not particularly limited, but is preferably a polyolefin resin of the resin component (A), and a part of the resin component (A) can be used. What is this resin component (A)? Another resin can also be used. The carrier resin (e2) is preferably an ethylene-vinyl acetate copolymer (i) or polypropylene (iii) in that it has an affinity with the silanol condensation catalyst (e1) and is excellent in heat resistance.

<Other ingredients>
In the present invention, a flame retardant aid can be used. It is preferable to use antimony trioxide (h3) as a flame retardant aid. When antimony trioxide is used, the flame retardancy of the heat-resistant silane crosslinked resin molded product can be further improved.

In the present invention, various additives generally used for electric wires, electric cables, electric cords, sheets, foams, tubes, pipes, etc., for example, crosslinking aids, antioxidants (also referred to as anti-aging agents), Lubricants, metal deactivators, fillers, other resins, and the like may be appropriately used as long as the object of the present invention is not impaired. 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 mixed with the carrier resin (e2) of the catalyst masterbatch (Mx) so as not to inhibit the grafting of the hydrolyzable silane coupling agent (q) to the resin component (A). Preferably it is done. 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, crosslinking between the resin components (A) occurs, gelation occurs, and the heat resistant silane crosslinked resin molded article is formed. Appearance may deteriorate. Further, the graft reaction of the hydrolyzable silane coupling agent (q) to the resin component (A) is difficult to proceed, and the heat resistance of the final heat-resistant silane crosslinked resin molded product 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 one that forms a partially crosslinked structure with the resin component (A) in the presence of an organic peroxide, for example, a methacrylate compound such as polypropylene glycol diacrylate, trimethylolpropane triacrylate, Examples include allyl compounds such as triallyl cyanurate, polyfunctional compounds such as maleimide compounds, and divinyl compounds.

Examples of the antioxidant include amine-based oxidation such as a polymer of 4,4′-dioctyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline. Inhibitor, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Phenol-based antioxidants such as propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben ヅ imidazole and its zinc salt, penta Risuritoru - tetrakis (3-lauryl - thiopropionate) sulfur-based antioxidants such as and the like. The antioxidant can be added in an amount of preferably 0.1 to 15.0 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the resin component (A).

Examples of metal deactivators include N, N′-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.

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 cross-linked resin molded article” of the present invention includes the step (a), the step (b), and the 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), 100 parts by mass of the resin component (A), and a silane coupling agent premixed inorganic. A heat-resistant silane is obtained by melt-mixing 10 to 150 parts by mass of a filler (D), 15 to 60 parts by mass of a brominated flame retardant (h1), and 0.001 to 0.5 parts by mass of a silanol condensation catalyst (e1). This is a step of preparing a crosslinkable resin composition (F).

In the production method of the present invention, the resin component (A) used in the step (a) is subjected to a crosslinking reaction in the presence of the crosslinking group of the hydrolyzable silane coupling agent (q) and the organic peroxide (P). Among the resins, elastomers, rubbers, and the like (which may contain various oils if desired), the polyolefin copolymer (i) and the ethylene-α-olefin copolymer (ii) are contained. When the resin component (A) contains the polyolefin copolymer (i) and the ethylene-α-olefin copolymer (ii), the heat resistance silane crosslinked resin molded article is excellent in insulation resistance, appearance, flexibility, and cold resistance. .
In particular, at least one of the polyolefin copolymers (i) is preferably one selected from an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylic ester copolymer, and an ethylene-α-olefin. The copolymer (ii) is preferably linear low density polyethylene (LLDPE). At this time, the resin component (A) may be composed of the polyolefin copolymer (i) and the ethylene-α-olefin copolymer (ii), or may contain other resin components.

Resin component (A) is selected from the ranges described below for the respective resins and various oils so that the total of the various resins constituting the resin component and various oils is 100% by mass as required.

When the resin component (A) contains the polyolefin copolymer (i) and the ethylene-α-olefin copolymer (ii), the content of the polyolefin copolymer (i) with respect to the entire resin component (A) And the ethylene-α-olefin copolymer (ii) content is selected from the range of 10 to 90% by mass. When the content of the polyolefin copolymer (i) and the content of the ethylene-α-olefin copolymer (ii) are within the above ranges, the mechanical properties, insulation resistance, and flame resistance of the heat-resistant silane crosslinked resin molded product High quality, heat resistance and appearance.
In view of combining these at an even higher level, the content of the polyolefin copolymer (i) is more preferably selected from the range of 10 to 50% by mass with respect to the entire resin component (A). The content of the ethylene-α-olefin copolymer (ii) is more preferably selected from the range of 20 to 80% by mass with respect to the entire resin component (A).
The total content of the polyolefin copolymer (i) and the ethylene-α-olefin copolymer (ii) is preferably 30 to 100 with respect to the entire resin component (A) in terms of excellent mechanical properties and insulation resistance. Each content is selected from the above-mentioned range so as to be mass%, more preferably 35 to 98 mass%, and still more preferably 40 to 95 mass%.

When the resin component (A) contains components other than the above-mentioned copolymers (i) and (ii), the balance of the resin component (A) is the polyolefin copolymer (i) and the ethylene-α-olefin. Resin components other than the copolymer (ii), for example, polypropylene (iii), polyethylene (iv), styrene-based elastomer (v), and in some cases, the oil described above may be used.

When the resin component (A) contains polypropylene (iii) in addition to the polyolefin copolymer (i) and the ethylene-α-olefin copolymer (ii), the total amount of the resin component (A) is The content of polypropylene (iii) is preferably selected in the range of 0.2 to 20% by mass, more preferably in the range of 0.5 to 15% by mass. When the content of polypropylene (iii) is within the above range, the appearance and flexibility of the heat-resistant silane crosslinked resin molded article can be achieved at a higher level.
When resin component (A) contains polyethylene (iv), it is preferable that the content rate of polyethylene (iv) is 30 mass% or less with respect to the whole resin component (A).
When the resin component (A) contains the styrene elastomer (v), the content of the styrene elastomer (v) is 30% by mass or less based on the entire resin component (A). preferable.
The oil content is as described above.

In the step (a), as described later, the resin component (A) may be used entirely in the step (a1), or a part thereof may be used in the step (a1) and the rest in the step (a2). May be. In terms of the mixing property of the silanol condensation catalyst (e1), it is preferable that a part of the resin component (A) is used in the step (a1) and the rest in the step (a2). The mass ratio of the resin component (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 weight, preferably 0.03 to 0.00 parts per 100 parts by weight of the resin component (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 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 crosslinking reaction does not proceed at all, or the released silane coupling agents are bonded to each other. Heat resistance, mechanical strength, wear resistance, and reinforcement cannot be obtained sufficiently, and if it exceeds 0.6 parts by mass, many resin components are directly cross-linked by side reaction. In addition, the extrudability deteriorates and there is a risk that bumps will occur.

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 parts by mass with respect to 100 parts by mass of the resin component (A). Part, preferably 20 to 120 parts by weight. When the blending 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 (A) becomes non-uniform, and the desired heat resistance is obtained. It may not be obtained or the appearance may deteriorate 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.

In the step (a), the amount of the brominated flame retardant (h1) is 15 to 60 parts by weight, preferably 20 to 60 parts by weight, more preferably 100 parts by weight of the resin component (A). Is 20 to 40 parts by mass. When the amount of the brominated flame retardant (h1) is less than 15 parts by mass, desired flame retardancy cannot be obtained. On the other hand, when it exceeds 60 mass parts, mechanical strength may fall.

In the step (a), a flame retardant aid such as antimony trioxide, an additive and the like can be mixed. The blending amount of antimony trioxide (h3) 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 resin component (A). When the blending amount of antimony trioxide (h3) is within the above range, desired flame retardancy is obtained and high mechanical properties are exhibited.
The additive is mixed in the above-described amount or an appropriate amount.

In the production method of the present invention, the step (a) has the following step (a1) and step (a3), and when the part of the resin component (A) is melt-mixed in the following step (a1), the following step is further performed. (A2). When the step (a) includes these steps, each component can be uniformly melted and mixed, and the desired effect can be obtained.
Step (a1): A part or all of the resin component (A), the organic peroxide (P), and the silane coupling agent premixed inorganic filler (D) are at or above the decomposition temperature of the organic peroxide (P). Step (a2) for preparing a silane masterbatch (Dx) by melt-mixing in step 2: Melting and mixing the remainder of the resin component (A) as the carrier resin (e2) and the silanol condensation catalyst (e1) Step (a3) of preparing master batch (Ex): Step of melt-mixing silane master batch (Dx) and silanol condensation catalyst (e1) or catalyst master batch (Ex)

In the step (a), the step (a2) is performed when a part of the resin component (A) is melt-mixed in the step (a1), and the whole resin component (A) is melt-mixed in the step (a1). If not done. In this case, in the step (a3), the silanol condensation catalyst (e1) is 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, when antimony trioxide (h3) is used in step (a), it is preferably mixed in either step (a1) or step (a2), and antimony trioxide (h3) is more uniform. It is more preferable to mix at least in the step (a1) from the viewpoint of exhibiting high flame retardancy, and it may be mixed in both the step (a1) and the step (a2).

In the step (a1), part or all of the resin component (A), the organic peroxide (P), the silane coupling agent premixed inorganic filler (D), and preferably the brominated flame retardant (h1) A part or all of the above is put into a mixer and melt-kneaded while being heated above the decomposition temperature of the organic peroxide (P) to prepare a silane masterbatch (Dx).
In step (a), mixing of resin component (A), organic peroxide (P), silane coupling agent premixed inorganic filler (D), brominated flame retardant (h1), antimony trioxide (h3), etc. The method is not particularly limited. For example, the organic peroxide (P) may be mixed alone with the resin component (A) and the silane coupling agent premixed inorganic filler (D). In the present invention, the silane coupling agent premixed inorganic filler is used. It is preferable to be included in (D). That is, in the step (a), a silane coupling agent premixed inorganic filler (D) that does not contain an organic peroxide (P) may be used, but a silane coupling agent that contains an organic peroxide (P). It is preferable to use a premixed inorganic filler (D).

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 hydrolyzable silane coupling agent (q) are mixed by a conventional method or the like, the hydrolyzable silane coupling agent (q) is mixed with the inorganic filler (C) as described above. A silane coupling agent premixed inorganic filler (D) that is strongly or weakly bonded 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, in the preferred step (a1), the hydrolyzable silane coupling agent (q), the organic peroxide (P) and the inorganic filler (C) are mixed, and then the mixture and the resin component (A) are mixed. 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 the preferred step (a1), first, the inorganic filler (C), the hydrolyzable silane coupling agent (q) and the organic peroxide (P) are mixed with the organic peroxide (P) at a predetermined mass ratio. The mixture is prepared by dry or wet mixing at a temperature lower than the decomposition temperature, preferably at room temperature (25 ° C.).

Here, the hydrolyzable silane coupling agent (q) mixed with the inorganic filler (C) is 0.5 to 30.0 parts by mass with respect to 100 parts by mass of the inorganic filler (C), preferably 1.0 to 20.0 parts by mass. When the amount of the hydrolyzable silane coupling agent (q) is less than 0.5 parts by mass, the crosslinking is not sufficient, and the desired heat resistance and mechanical properties can be obtained in the heat-resistant silane crosslinked resin molded product. It may not be possible. On the other hand, if it exceeds 30.0 parts by mass, the hydrolyzable silane coupling agent (q) that does not adsorb on the surface of the inorganic filler (C) increases, and thus volatilizes during kneading, which is not economical. Condensation of the hydrolyzable silane coupling agent (q) that is not adsorbed may result in cross-linked gels and burns in the heat-resistant silane cross-linked resin molded article, and the appearance may deteriorate. In particular, the appearance defect is remarkable when it exceeds 30.0 parts by mass.

The hydrolyzable silane coupling agent (q) is preferably 0.5 to 18.0 parts by weight, and 1.0 to 10.0 parts by weight with respect to 100 parts by weight of the resin component (A). It is more preferable that When the amount of the hydrolyzable silane coupling agent (q) used is less than 0.5 parts by mass, the crosslinking is not sufficiently performed, and desired heat resistance and mechanical properties can be obtained in the heat-resistant silane crosslinked resin molded product. It may not be possible. On the other hand, when it exceeds 18.0 parts by mass, the hydrolyzable silane coupling agents (q) are condensed with each other, and there is a risk that the heat-resistant silane crosslinked resin molded product may be damaged or burnt by the crosslinked gel and the appearance may be deteriorated. is there.

The mixture thus obtained includes a silane coupling agent premixed inorganic filler (D) obtained by mixing an inorganic filler (C) and a hydrolyzable silane coupling agent (q), and an organic peroxide (P). Containing.

Mixing with the inorganic filler (C) and the hydrolyzable silane coupling agent (q) is a state of adding and mixing with heating or non-heating (dry type), or a state in which the inorganic filler (C) is dispersed in a solvent such as water. There is a method of adding a hydrolyzable silane coupling agent (q) (wet). In the present invention, a treatment in which the hydrolyzable silane coupling agent (q) is added to the inorganic filler (C), preferably the dried inorganic filler (C), with heating or non-heating, that is, dry processing is preferable. .

In the method of adding the hydrolyzable silane coupling agent (q) with the inorganic filler (C) dispersed (wet mixing), the hydrolyzable silane coupling agent (q) is strongly bonded to the inorganic filler (C). The subsequent cross-linking reaction may be difficult to proceed. On the other hand, the method of adding and mixing the hydrolyzable silane coupling agent (q) in the inorganic filler (C) with heating or non-heating (dry mixing) is a relatively inorganic filler (C) and hydrolyzable silane coupling. Since the bond of the agent (q) becomes weak, the crosslinking easily proceeds efficiently. At that time, the hydrolyzable silane coupling agent (q) and the organic peroxide (P) may be mixed together and dispersed in the inorganic filler (C), or separately. It is better to mix together substantially.

The hydrolyzable 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 part or all of the hydrolyzable silane coupling agent (q) is adsorbed on the inorganic filler (C) or inorganic. It may cause a loose chemical bond with the filler (C) surface. In such a state, volatilization of the hydrolyzable silane coupling agent (q) during subsequent kneading and processing with a kneader or a Banbury mixer is greatly reduced, and an organic peroxide (P ), The unsaturated group of the hydrolyzable silane coupling agent (q) is considered to undergo a binding reaction with the polyolefin resin. Further, it is considered that the hydrolyzable silane coupling agent (q) undergoes a condensation reaction with the silanol condensation catalyst (e1) during molding.

In step (a1), depending on the production conditions, only the hydrolyzable silane coupling agent (q) can be mixed with the inorganic filler (C), and then the organic peroxide (P) can be added. As a method of adding the organic peroxide (P), the organic peroxide (P) may be dispersed in the resin component (A), or may be added alone or dispersed in oil or the like. Disperse in A).

In the preferred step (a1), the prepared mixture, the resin component (A), preferably the brominated flame retardant (h1), and, if desired, the flame retardant aids and additives are each added to a mixer. In addition, 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 resin component (A) is melted. Also, kneading conditions such as kneading time can be set as appropriate. When kneaded below the decomposition temperature of the organic peroxide (P), a silane graft reaction, a bond between the silane coupling agent premixed inorganic filler (D) and the resin component (A), a silane coupling agent premixed inorganic filler ( The bond between D) 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.

As the kneading method, any method usually used for rubber, plastic, etc. can be used, and the kneading apparatus is appropriately selected according to 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. A closed mixer such as a Banbury mixer or various kneaders is used for the dispersibility of the resin component (A) and the crosslinking reaction. It is preferable in terms of stability.

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 resin component (A), a continuous kneader, a pressure kneader, Kneading with a Banbury mixer is common.

In addition, it is preferable to perform the step of preparing the silane coupling agent premixed inorganic filler (D) as in the preferred step (a1) in advance, but when the above components are kneaded in the above blending amounts, local crosslinking is performed. Can be suppressed. Therefore, the step (a1) can also be carried out without making the preparation step separate from the melt-kneading step. That is, the silane master batch (Dx) can be prepared by mixing the above-described components together at a temperature higher than the decomposition temperature of the organic peroxide (P).

Thus, the step (a1) is performed 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 resin component (A) and a silane coupling agent premixed inorganic filler. It is a reaction mixture of (D), and contains a silane crosslinkable resin in which a hydrolyzable silane coupling agent (q) is grafted to the resin component (A) 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 resin component (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 resin component (A) as the carrier resin (e2) and the silanol condensation catalyst (e1).

The compounding amount of the silanol condensation catalyst (e1) is 0.001 to 0.5 parts by mass, preferably 0.003 to 0.1 parts per 100 parts by mass of the resin component (A) used in the step (a). 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 hydrolyzable silane coupling agent (q) is difficult to proceed, and the heat resistance of the heat-resistant silane crosslinked resin molded article is sufficient. However, the productivity may be reduced, and the crosslinking 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.

The blending amount of the carrier resin (e2) is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and further preferably 2 to 40 parts by mass with respect to 100 parts by mass of the resin component (A) in the step (a). Part by mass.
As the carrier resin (e2), it is preferable to use a part of the resin component (A) within the range satisfying the above-mentioned blending amount. In this case, the resin component (A) and the carrier resin (e2) are added so that the total of the resin component (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) is preferably 5 to 40 parts by mass, particularly preferably 10 to 30 parts by mass, out of a total of 100 parts by mass with the resin component (A). In this case, the resin component (A) used in the step (a1) is 60 to 95 parts by mass, and the total amount of the resin component (A) and the carrier resin (e2) is a reference for the blending amount of each component. .

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. 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.
When all of the resin component (A) is used in the step (a1), a resin other than the resin component (A) can be used as the carrier resin (e2). In this case, it is preferable to perform a step of melt-mixing the other resin and the silanol condensation catalyst (e1).

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 added as desired.

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 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 is a resin component (A) whose melting point cannot be measured by DSC or the like, for example, an elastomer, but kneading is performed at a temperature at which at least one of the resin component (A) 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).

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

In the production method of the present invention, the step (b) of molding the heat-resistant silane crosslinkable resin composition (F) is then 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 an uncrosslinked heat-resistant silane crosslinkable resin composition (F) is obtained.

In the production method of the present invention, the step (c) is then performed in which the molded product (uncrosslinked product) obtained in the step (b) is brought into contact with water to be crosslinked. In this step (c), the hydrolyzable group of the hydrolyzable silane coupling agent is hydrolyzed into silanol by bringing the molded product into contact with water, and the silanol condensation catalyst (e2) present in the resin. As a result, the hydroxyl groups of silanol are condensed to each other to cause a crosslinking reaction, thereby obtaining a heat-resistant silane-crosslinked resin molded body in which the heat-resistant silane-crosslinkable resin composition (F) is crosslinked. 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 hydrolyzable silane coupling agent is hydrolyzed, and the hydrolyzable silane coupling agents are condensed to form a crosslinked structure.

Condensation between hydrolyzable silane coupling agents proceeds only by storage at room temperature, but in order to further accelerate the cross-linking, when contacting with moisture, water is immersed in warm water, put into a wet heat tank, For example, exposure to water vapor. In this case, pressure may be applied to allow moisture to penetrate inside.

Thus, the production method of the present invention is carried out, and a heat-resistant silane cross-linked resin molded product is produced from the heat-resistant silane cross-linkable 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 (A) is heated and kneaded at a temperature equal to or higher than the decomposition temperature of the organic peroxide (P) together with the silane coupling agent premixed inorganic filler (D) in the presence of the organic peroxide (P) component. And grafted with a hydrolyzable silane coupling agent by radicals generated by the decomposition of the organic peroxide (P). Thereby, resin component (A) couple | bonds together (bridge | crosslinking), and a resin component (A) and a silane coupling agent premixed inorganic filler (D) couple | bond together.

Also, the reason why these reactions occur is not clear yet, but is estimated as follows.

That is, a silane coupling agent premixed inorganic filler (D) in which a hydrolyzable silane coupling agent is bonded to an inorganic filler to such an extent that volatilization is suppressed before and / or during kneading with the resin component (A). ) Suppresses volatilization of the hydrolyzable silane coupling agent during kneading, and hydrolyzable silane coupling that binds to the inorganic filler with a strong bond and a weak bond. An agent can be formed.
When such a silane coupling agent premixed inorganic filler (D) is kneaded with the resin component (A) in the presence of the organic peroxide (P) above the decomposition temperature of the organic peroxide (P), Among hydrolyzable silane coupling agents of the silane coupling agent premixed inorganic filler (D), the hydrolyzable silane coupling agent having a strong bond with the inorganic filler (C) is an ethylenically unsaturated group which is a cross-linking group. When a plurality of hydrolyzable silane coupling agents are present on the surface of one inorganic filler (C) particle through a strong bond, such as the crosslinking site of the resin component (A) and the graft reaction, C) It is considered that a plurality of polymer molecules of the resin component (A) are bonded through the particles, and a crosslinked network with the inorganic filler is expanded.

On the other hand, among the hydrolyzable silane coupling agents of the silane coupling agent premixed inorganic filler (D), the hydrolyzable silane coupling agent having a weak bond with the inorganic filler (C) is from the surface of the inorganic filler (C). The ethylenically unsaturated group, which is a crosslinkable group of the hydrolyzable silane coupling agent, was released by hydrogen radical abstraction by radicals generated by decomposition of the organic peroxide (P) of the resin component (A). A graft reaction occurs by reacting with a resin radical. It is considered that the hydrolyzable silane coupling agent in the graft portion thus produced is then mixed with a silanol condensation catalyst and brought into contact with moisture to cause a crosslinking reaction by a condensation reaction.

In the case of a hydrolyzable silane coupling agent having a strong bond with the above-mentioned inorganic filler, a hydrolysis reaction in which a hydroxyl group on the surface of the inorganic filler is chemically bonded by a covalent bond by a condensation reaction in the presence of water by this silanol condensation catalyst. Decomposable silane coupling agents also undergo a condensation reaction to further expand the cross-linking network.

In particular, in the present invention, in this step (c), the cross-linking reaction by condensation using a silanol condensation catalyst in the presence of water is performed after forming the formed body, whereby the formed body is obtained after the conventional final cross-linking reaction. Compared to the method of forming, it is excellent in workability in the process up to forming the molded body, and can bind a plurality of hydrolyzable silane coupling agents on the surface of one inorganic filler particle, and has higher heat resistance than before, For example, it becomes possible to obtain solder heat resistance at 380 ° C., which will be described later, and to obtain high mechanical strength, insulation resistance and flame retardancy.

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

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 hydrolyzable silane A large amount of the silane coupling agent premixed inorganic filler (D) to which the coupling agent (q) is strongly bonded 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 other surface treatment agent is used as the inorganic filler (C), the hydrolyzable silane coupling agent added later is weakly bonded. Although a large amount of the silane coupling 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 the silane coupling agent premixed inorganic filler (D) in which the hydrolyzable 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 is obtained. In addition, by controlling the formation amount of the silane coupling agent premixed inorganic filler (D) to which the hydrolyzable silane coupling agent is weakly bonded, the degree of cross-linking is lowered and a material that can be recycled can be obtained. It becomes possible.

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 (A) and the silane coupling agent premixed inorganic filler (D) via the hydrolyzable silane coupling agent (q). Therefore, it is considered that the interaction is increased and the flame retardancy is improved.

The manufacturing method of the present invention can be applied to the manufacture of components (including semi-finished products, parts, and members) that require heat resistance, products that require strength, components of products such as rubber materials, or members thereof. it can. Examples of such products include electric wires such as heat-resistant flame-retardant insulated wires, heat-resistant and flame-resistant cable coating materials, rubber substitute electric wires and cable materials, other heat-resistant and flame-resistant electric wire components, flame-resistant and heat-resistant sheets, and flame-resistant and heat-resistant films. Can be mentioned. 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 formed around the conductor (the coating layer made of the heat-resistant silane crosslinked resin molding of the present invention) 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.
In Tables 1 to 4, the numerical values in Examples and Comparative Examples represent parts by mass unless otherwise specified, and are indicated by “0” when clearly indicating that the components are 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 (A) and carrier resin (e2)>
As (i), EVA1: EV360, ethylene-vinyl acetate copolymer resin “Evaflex” (trade name) manufactured by Mitsui DuPont Chemical Co., Ltd., VA content 25% by mass
EVA2: EV180 Ethylene-vinyl acetate copolymer resin “Evaflex” (trade name) manufactured by Mitsui DuPont Chemical Co., Ltd., VA content 33% by mass
(Ii) LLDPE: “Evolue SP0540” (trade name), LLDPE resin manufactured by Prime Polymer Co. (iii) Random polypropylene: “PB222A” (trade name), random PP resin manufactured by Sun Allomer (v) Styrene "Septon 4077" (trade name) as a base elastomer, "Diana Process Oil PW90" (trade name) as a process oil made by Kuraray, "XP650" (trade name) as a silane graft polyethylene made by Idemitsu Kosan, manufactured by Hyundai Silane grafted polyethylene

<Surface treatment inorganic filler (B)>
Magnesium hydroxide pretreated with stearic acid: “Kisuma 5AL” (trade name), manufactured by Kyowa Chemical Industry Co., Ltd. <hydrolyzable silane coupling agent (q)>
“KBM1003” (trade name), vinyltrimethoxysilane <organic peroxide (P)> manufactured by Shin-Etsu Chemical Co., Ltd.
Dicumyl peroxide (DCP, decomposition temperature 151 ° C.), manufactured by Nippon Kayaku Co., Ltd. <silanol condensation catalyst (e1)>
Dioctyltin laurate: “ADK STAB OT-1” (trade name), ADEKA silanol condensation catalyst <brominated flame retardant (h1)>
“Cytex 8010” (trade name), 1,2-bis (bromophenyl) ethane, manufactured by Albemarle

<Others>
(H3) As antimony trioxide, as an antimony trioxide crosslinking aid manufactured by Toyota Tsusho Corporation, “Ogmont T200” (trade name), manufactured by Shin-Nakamura Chemical Co., Ltd., or trimethylolpropane trimethacrylate as an anti-aging agent, “Irganox 1010” (trade name), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by BASF as a lubricant, “NS-M” (trade name), Magnesium stearate, manufactured by Nippon Oil & Fats, or “X21-3043” (trade name), polyorganosiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.

Example 1
First, the inorganic filler (B), hydrolyzable silane coupling agent (q) and organic peroxide (P) shown in the “Silane MB (D1)” column of Table 1 are blended in the amounts shown in Table 1, The mixture was put into a Toyo Seiki 10 L Henschel mixer and mixed at room temperature for 10 minutes to obtain a powder mixture containing an organic peroxide (P) and a silane coupling agent premixed inorganic filler (D).
Next, this powder mixture, resin component (A), brominated flame retardant (h1), antimony trioxide (h3) and lubricant shown in the “Silane MB (D1)” column of Table 1 are manufactured by Nippon Roll. The mixture was put into a 2 L Banbury mixer, kneaded in 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)). Prior to discharge, the mixture was kneaded at a temperature not lower than the decomposition temperature of the organic peroxide (P), specifically 180 to 190 ° C. for 5 minutes.
For reference, the blending amount (part by mass) of the hydrolyzable 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. Indicated.

On the other hand, the carrier resin (e2), the silanol condensation catalyst (e1) and the anti-aging agent shown in the “Catalyst MB (E1)” column of Table 1 are separately mixed with a Banbury mixer at 120 to 160 ° C., and a material discharge temperature of 120 to The mixture was melted and mixed at 180 ° C. to obtain a catalyst master batch (E1) (step (a2)).

Next, the silane masterbatch (D1) and the catalyst masterbatch (E1) were dry blended at a mass ratio of 168.2: 24.050, and an L / D = 24 40 mm extruder (compressor screw temperature 170 ° C., head) The temperature was introduced at a temperature of 180 ° C. and melted and mixed at 180 ° C., and the outside of the 21 / 0.18TA conductor was coated with a wall thickness of 0.84 mm to obtain an electric wire having an outer diameter of 2.63 mm (step (a3) and Step (b)).
This electric wire was left in an atmosphere of a temperature of 60 ° C. and a humidity of 95% for 48 hours (step (c)).
In this way, an insulated wire having a coating (insulating layer) made of a heat-resistant silane cross-linked resin molded article was produced.

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 to 15, Comparative Examples 1 and 2)
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 to 4 (step (a1) and step (a2)), and the respective blending ratios are shown. Except for the mass ratios shown in Tables 1 to 4, the outside of the 21 / 0.18 TA conductor was coated with a thickness of 0.84 mm 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 temperature 60 ° C. and humidity 95% for 48 hours (step (c)) to produce an insulated electric wire having a coating (insulating layer) made of a heat-resistant silane crosslinked resin molded product.

In Example 2, brominated flame retardant (h1) and antimony trioxide (h3) were melt-kneaded in step (a2). In Example 13, the brominated flame retardant (h1) was melt-kneaded in the step (a2), and antimony trioxide (h3) was melt-kneaded in the step (a1).
In Examples 11 and 12, brominated flame retardant (h1) was melt-kneaded in both steps (a1) and (a2), and antimony trioxide (h3) was melt-kneaded in step (a2).

(Examples 16 to 20)
In the formulation shown in Table 3, inorganic filler (C), hydrolyzable silane coupling agent (q), organic peroxide (P), resin component (A), brominated flame retardant (h1), antimony trioxide ( h3) and the lubricant were put into a 2 L Banbury mixer made by Nippon Roll, then kneaded for about 12 minutes with the mixer, and then discharged at a material discharge temperature of 180 to 190 ° C. to obtain a silane master batch (D16 to 20) ( Step (a1)). Prior to discharge, the mixture was kneaded at a temperature not lower than the decomposition temperature of the organic peroxide (P), specifically 180 to 190 ° C. for 5 minutes.
Catalyst master batches (E16 to 20) were prepared in the same manner as in Example 1 with the formulation shown in Table 3.
Example 1 except that the silane master batch (D16-20) and the catalyst master batch (E16-20) were used in the mass ratios shown in Table 3 instead of the silane master batch (D1) and the catalyst master batch (E1). Similarly, the outside of the 21 / 0.18 TA conductor was coated with a thickness of 0.84 mm 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 temperature 60 ° C. and humidity 95% for 48 hours (step (c)) to produce an insulated electric wire having a coating (insulating layer) made of a heat-resistant silane crosslinked resin molded product.

(Comparative Examples 3 to 6)
In Comparative Examples 3 to 6, silane cross-linked resin molded articles were produced by a silane cross-linking method different from that of the present invention. In Tables 1 to 4, the silane crosslinking method of the present invention using the resin component (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 Examples 3 to 6 using a resin grafted with a coupling agent was designated as “silane crosslinking 2”.
That is, carrier resin (e2), surface-treated inorganic filler (B), brominated flame retardant (h1), antimony trioxide described in the “catalyst MB (E23)” column to “catalyst MB (E26)” column of Table 4 (H3) Silanol condensation catalyst (e1), anti-aging agent and lubricant are mixed with a Banbury mixer at 120 to 180 ° C., and melt mixed at a material discharge temperature of 180 to 190 ° C. to obtain catalyst master batches (E23) to (E26). Got.
Next, silane-grafted polyethylene and catalyst master batches (E23) to (E26) were dry blended at the “blending ratio” shown in Table 4 as silane masterbatches (D23) to (D26), and L / D = 24. Introduced into a 40 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 wall thickness of 0.84 mm. A 63 mm wire was obtained. 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.

(Reference example)
As a reference example, the resin component (A), surface treatment inorganic filler (B), brominated flame retardant (h1), antimony trioxide (h3), crosslinking aid, anti-aging agent and lubricant shown in Table 4 are banbury. The mixture was mixed at 120 to 180 ° C. with a mixer, and melt mixed at a material discharge temperature of 120 to 180 ° C. to obtain a resin composition.
This resin composition was introduced into a 40 mm extruder with L / D = 24 (compressor screw temperature 170 ° C., head temperature 180 ° C.), melted and mixed at 180 ° C., and thickened outside the 21 / 0.18 TA conductor. A wire having an outer diameter of 2.63 mm was obtained by coating with 0.84 mm. The obtained electric wire was subjected to electron beam irradiation (15 Mrad) to crosslink the coating resin layer to produce an insulated electric wire.
In Table 4, the “crosslinking method” of the reference example was “electron beam”.

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 gap between marked lines of 25 mm and a pulling speed of 500 mm / min, tensile strength (indicated as “TS” in Tables 1 to 4) (MPa) and elongation at break ( In Tables 1 to 4, “EL” (%) was measured. The tensile strength was 13.8 MPa or more, and the elongation at break was 300% or more.

(Insulation resistance)
As for the insulation resistance, the initial value (after 1 hour in water) of the insulation resistance defined in JISC3005 was measured. 2500 MΩ · km or more was regarded as acceptable.

(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, the test is accepted. In Tables 1 to 4, “○” is indicated, and if there is an abnormality such as melting or foaming of the coating layer, the test is rejected. ".

(Horizontal flame retardant test)
For each of the five specimens (N = 5) prepared for each insulated wire, UL1581 Horizon Flame Test was performed and the number of passing was shown (passing number / N number). All the passes are “5/5”.

(VW-1 test)
Each of the 5 specimens (N = 5) prepared for each insulated wire was subjected to UL1581 Vertical Flame Test to indicate the number of passing (passing number / N number). Pass is all pass. This VW-1 test is an evaluation method in which a combustion level is confirmed by holding a sample vertically and applying a burner, and is a test method that requires a higher flame retardant level than a horizontal flame retardant test. Therefore, this VW-1 test is a severe test and was evaluated for reference, and it is not always necessary to pass all the tests.

(Extruded appearance (also called electric wire appearance))
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 as follows: “○” when the appearance of the extrudate was good when produced with a 40 mm extruder at a linear speed of 10 m, “△” when the appearance was slightly bad, “×”, and “△” or higher was regarded as a product level.

As shown in Tables 1 to 3, all of the insulated wires of Examples 1 to 20 produced by the production method of the present invention were tensile strength, elongation at break, insulation resistance, horizontal flame test and extrusion appearance. In addition, both the solder heat resistance test passed. That is, all of the insulated wires of Examples 1 to 20 were excellent in mechanical properties, insulation resistance, flame retardancy and appearance, and heat resistance.
Thus, according to the present invention, volatilization of the hydrolyzable silane coupling agent can be suppressed even when melt-mixed with a Henschel mixer or a Banbury mixer, and the heat resistance has excellent mechanical properties, insulation resistance and flame retardancy. It turned out that a silane crosslinked resin molding can be manufactured.

In contrast, as shown in Table 4, in Comparative Example 1 using only LLDPE (ii) as the resin component (A), the tensile strength was unacceptable. Moreover, in Comparative Example 2 using only EVA1 (i) as the resin component (A), the elongation at break and the insulation resistance were unacceptable.

On the other hand, Comparative Examples 3 to 6 (Silane cross-linking 2) using silane-grafted polyethylene without using the silane coupling agent premixed inorganic filler (D) and organic peroxide (P) are both insulation resistance and solder. It was inferior in heat resistance.
Moreover, the comparative example 3 which reduced the compounding quantity of the surface treatment inorganic filler (B) and increased the compounding quantity of antimony trioxide (h3) has a material price in order to mix | blend expensive antimony trioxide (h3) in large quantities. It will be high.
In Comparative Examples 4 and 5, in which the blending amount of the surface-treated inorganic filler (B) was increased and the blending amount of antimony trioxide (h3) was decreased, in addition to the insulation resistance and the solder heat resistance, although the material price decreased. Also inferior in tensile strength.
In Comparative Example 6, in which the amount of the surface-treated inorganic filler (B) was increased as compared with Comparative Example 5, in addition to insulation resistance, tensile strength and solder heat resistance, the elongation at break was inferior.

From the above, by using the silane crosslinking method according to the present invention, the specific resin component (A) is crosslinked, and by blending an appropriate amount of the silane coupling agent premixed inorganic filler (D) and the brominated flame retardant (h1), A heat-resistant silane-crosslinked resin molded article having superior tensile strength, elongation, insulation resistance, and heat resistance compared to the silane-crosslinking method “silane-crosslinked 2 (Comparative Examples 3 to 6)” using silane-grafted polyethylene. Can be obtained.
Further, by using the silane cross-linking method “silane cross-linking 1” of the present invention, the heat-resistant silane cross-linked resin molded article is more excellent in flame retardancy that is comparable to or surpassing electron beam cross-linking (reference example). Can be obtained.
Further, as in Examples 1 to 9 and 11 to 20, the polyolefin copolymer (i) is 10 to 50% by mass and the ethylene-α-olefin copolymer (ii) is 20% with respect to the entire resin component (A). When blended in an amount of ˜80% by mass, an insulation resistance value of 3000 MΩ · km or more is exhibited, and the insulation resistance is further improved, which is preferable.
In addition, as in Examples 1 to 6 and 11 to 20, when 5 parts by mass or more of antimony trioxide (h3) is blended, both the horizontal flame retardant test and the VW-1 test pass all, and further excellent flame retardant It is preferable because it exhibits its properties.
Further, as in Examples 1 to 5 and 11 to 20, it is preferable to add 0.2 to 15% by mass or more of polypropylene (iii) with respect to the entire resin component (A) because the appearance of the electric wire is good.
Further, as shown in Examples 16 to 20, in the step (a), the step of preparing the silane coupling agent premixed inorganic filler (D) in advance is omitted, and when the respective components are mixed in the mixer, By adsorbing the silane coupling agent (q) to the inorganic filler (C), the silane coupling agent premixed inorganic filler (D) is prepared, and then each of the above-described temperatures above the decomposition temperature of the organic peroxide (P). A silane masterbatch (Dx) can also be prepared by mixing the components.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims priority based on Japanese Patent Application No. 2013-139551 filed in Japan on July 3, 2013, the contents of which are hereby incorporated by reference. Capture as part.

Claims

The following step (a), step (b) and step (c)
Step (a): 100 parts by mass of resin component (A), 0.01 to 0.6 parts by mass of organic peroxide (P), and 100 parts by mass of inorganic filler (C) including surface-treated inorganic filler (B) 10 to 150 parts by mass of a silane coupling agent premixed inorganic filler (D) obtained by mixing 0.5 to 30.0 parts by mass of a hydrolyzable silane coupling agent (q) with respect to a brominated flame retardant ( h1) Step of melt-mixing 15-60 parts by mass of silanol condensation catalyst (e1) 0.001-0.5 parts by mass Step (b): Heat-resistant silane crosslinkable resin obtained in step (a) A step of molding the composition (F) and a step (c): a heat-resistant silane cross-linked resin molded product having a step of bringing the molded product obtained in the step (b) into contact with moisture to form a molded product A manufacturing method comprising:
The resin component (A) is (i) a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component in an amount of 10 to 90% by mass, and (ii) an ethylene-α-olefin copolymer in an amount of 10 to 90% by mass. %
The step (a) includes the following step (a1) and step (a3), and further includes the following step (a2) when a part of the resin component (A) is melt-mixed in the following step (a1). ,
Step (a1): Part or all of the resin component (A), the organic peroxide (P), and the silane coupling agent premixed inorganic filler (D) are combined with the organic peroxide (P). Step of preparing a silane masterbatch (Dx) by melting and mixing at a temperature equal to or higher than the decomposition temperature of step Step (a2): Melting the remainder of the resin component (A) as the carrier resin (e2) and the silanol condensation catalyst (e1) Step of mixing and preparing a catalyst master batch (Ex) and Step (a3): Melting and mixing the silane master batch (Dx) and the silanol condensation catalyst (e1) or the catalyst master batch (Ex) A method for producing a heat-resistant silane-crosslinked resin molded product, wherein the brominated flame retardant (h1) is mixed in at least one of the step (a1) and the step (a2).
The resin component (A) contains at least (i) a polyolefin copolymer having an acid copolymer component or an acid ester copolymer component in an amount of 10 to 50% by mass, and (ii) an ethylene-α-olefin copolymer 20 to The manufacturing method of the heat resistant silane crosslinked resin molding of Claim 1 containing 80 mass%.
2. The polyolefin copolymer having (i) an acid copolymerization component or an acid ester copolymerization component is an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester copolymer. Or the manufacturing method of the heat-resistant silane crosslinked resin molding of 2.
The production of the heat-resistant silane-crosslinked resin molded article according to any one of claims 1 to 3, wherein the brominated flame retardant (h1) is mixed in both the steps (a1) and (a2). Method.
2. In at least one of the step (a1) and the step (a2), (h3) antimony trioxide is mixed in a total of 5 to 30 parts by mass with respect to 100 parts by mass of the resin component (A). 5. A method for producing a heat-resistant silane crosslinked resin molded article according to any one of items 1 to 4.
The method for producing a heat-resistant silane-crosslinked resin molded article according to any one of claims 1 to 5, wherein the resin component (A) contains (iii) 0.2 to 20% by mass of polypropylene.
By the method for producing a heat-resistant silane cross-linked resin molded article according to any one of claims 1 to 6,
Hydrolysis with respect to 100 parts by mass of resin component (A), 0.01 to 0.6 parts by mass of organic peroxide (P), and 100 parts by mass of inorganic filler (C) containing surface-treated inorganic filler (B) 10 to 150 parts by mass of a silane coupling agent premixed inorganic filler (D) obtained by mixing 0.5 to 30.0 parts by mass of a functional silane coupling agent (q), and a brominated flame retardant (h1) 15 to 60 parts A heat-resistant silane cross-linked resin molded product obtained by crosslinking a heat-resistant silane cross-linkable resin composition (F) obtained by melting and mixing parts by mass and 0.001 to 0.5 parts by mass of a silanol condensation catalyst (e1).
A heat-resistant product comprising the heat-resistant silane cross-linked resin molded article according to claim 7.
The heat-resistant product according to claim 8, wherein the pre-heat-resistant silane cross-linked resin molded product is provided as a coating for an electric wire or an optical fiber cable.