JP6395745B2 - Silane-crosslinked resin molded body, silane-crosslinkable resin composition and production method thereof, silane masterbatch, and molded article - Google Patents

Description

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

  Insulation wires, cables, cords, optical fiber core wires, or optical fiber cords (fiber optic cables) used for internal or external wiring of electrical / electronic equipment have flame resistance, mechanical properties, insulation or heat resistance. Various characteristics such as these are required. These wiring materials are used outdoors, or may be used by being immersed in oil (in a state where they can be in contact with machine oil or the like). Examples of wiring materials used in this manner include automotive wiring materials, natural resource drilling cables, or mining cables. These wiring materials and the like are also required to have a property that is difficult to be damaged (scratch resistance), flexibility, oil resistance, and the like because they come into contact with other cables or members during manufacture or use.

  Examples of the material for forming the outermost layer of the wiring material include a composition containing a resin such as engineering plastic (engineering plastic) or a chlorinated polyethylene resin, or a rubber such as chloroprene rubber (for example, patents). References 1 and 2).

International Publication No. 2005/121244 JP-A-5-93093

However, the wiring material having the outermost layer formed using engineering plastics is excellent in heat resistance and scratch resistance, but is inferior in flexibility and is not suitable for applications such as wiring materials that require flexibility in the outermost layer. . Engineering plastics are not versatile, and there is room for improvement in application to wiring materials. On the other hand, a wiring material having an outermost layer formed using chloroprene rubber has flexibility and oil resistance, but is inferior in scratch resistance. In addition, the electrical properties of the outermost layer are poor, and there is room for improvement in insulation for application to wiring materials that require insulation.
Even under such circumstances, each of the above-mentioned wiring materials has a wide range of uses and a wide range of usage environments, and even if it is an insulating wiring material, both flexibility and scratch resistance are achieved. However, it is required to exhibit higher oil resistance.

An object of the present invention is to overcome the problems of conventional wiring materials, to provide a silane-crosslinked resin molded article that exhibits both high flexibility and scratch resistance and high oil resistance, and a method for producing the same.
Moreover, this invention makes it a subject to provide the silane masterbatch which can form this silane crosslinked resin molded object, a silane crosslinkable resin composition, and its manufacturing method.
Furthermore, this invention makes it a subject to provide the molded article containing the silane crosslinked resin molded object obtained with the manufacturing method of the silane crosslinked resin molded object.

  The present inventors have obtained a base resin obtained by graft-bonding a silane coupling agent obtained by a specific mixing method using a base resin containing a specific amount of a specific ethylene-α-olefin rubber and polyolefin resin and a silane coupling agent. It has been found that when a silane cross-linked resin molded product is produced by a specific silane cross-linking method using a silane, the resulting silane cross-linked resin molded product can be imparted with excellent flexibility, scratch resistance and high oil resistance. Based on this finding, the present inventors have made further studies and have come up with the present invention.

一般式（１）中、Ｒ _ａ１１ はエチレン性不飽和基を含有する基、Ｒ _ｂ１１ は脂肪族炭
化水素基、水素原子又はＹ ^１３ を示す。Ｙ ^１１ 、Ｙ ^１２ 及びＹ ^１３ は加水分解しうる
有機基を示す。
前記工程（１）を行うに当たり、
前記ベース樹脂が、エチレン含有量が４５〜６５質量％であるエチレン−αオレフ
ィンゴム１５〜５８質量％とポリオレフィン樹脂８５〜４２質量％とを含有し、
下記工程（ａ−２）でベース樹脂の全部を溶融混合する場合には、前記工程（１）
が下記工程（ａ−１）、工程（ａ−２）及び工程（ｃ）を有し、下記工程（ａ−２）
でベース樹脂の一部を溶融混合する場合には、前記工程（１）が下記工程（ａ−１）
、工程（ａ−２）、工程（ｂ）及び工程（ｃ）を有する、シラン架橋樹脂成形体の製
造方法。
工程（ａ−１）：少なくとも前記無機フィラー及び前記シランカップリング剤を混
合して混合物を調製する工程
工程（ａ−２）：前記混合物と前記ベース樹脂の全部又は一部とを、前記有機過酸
化物の存在下で前記有機過酸化物の分解温度以上の温度において
溶融混合して、前記有機過酸化物から発生したラジカルによって
前記エチレン性不飽和基を含有する基と前記ベース樹脂とをグラ
フト化反応させることにより、シランマスターバッチを調製する
工程
工程（ｂ）：前記ベース樹脂の残部及び前記シラノール縮合触媒を溶融混合して、
触媒マスターバッチを調製する工程
工程（ｃ）：前記シランマスターバッチと、前記シラノール縮合触媒又は前記触媒
マスターバッチとを溶融混合する工程
＜２＞前記ベース樹脂が、前記エチレン−αオレフィンゴム２５〜５８質量％と、前記ポリオレフィン樹脂７５〜４２質量％とを含有する＜１＞に記載のシラン架橋樹脂成形体の製造方法。
＜３＞前記エチレン−αオレフィンゴムのエチレン含有量が４５〜６５質量％であり、かつジエン含有量が０〜４．５質量％である＜１＞又は＜２＞に記載のシラン架橋樹脂成形体の製造方法。
＜４＞前記無機フィラーの配合量が、前記ベース樹脂１００質量部に対して、３０〜１００質量部である＜１＞〜＜３＞のいずれか１項に記載のシラン架橋樹脂成形体の製造方法。
＜５＞前記シランカップリング剤が、ベース樹脂１００質量部に対して、３〜１２質量部の配合量で混合される＜１＞〜＜４＞のいずれか１項に記載のシラン架橋樹脂成形体の製造方法。
＜６＞前記シランカップリング剤が、ビニルトリメトキシシラン又はビニルトリエトキシシランである＜１＞〜＜５＞のいずれか１項に記載のシラン架橋樹脂成形体の製造方法。
＜７＞前記工程（ａ−１）及び工程（ａ−２）において、シラノール縮合触媒を実質的に混合しない＜１＞〜＜６＞のいずれか１項に記載のシラン架橋樹脂成形体の製造方法。
＜８＞ベース樹脂１００質量部に対して、有機過酸化物０．０１〜０．６質量部と、無機フィラー２５〜１２０質量部と、下記一般式（１）で表されるシランカップリング剤１〜１５．０質量部と、シラノール縮合触媒とを溶融混合して混合物を得る工程（１）を有するシラン架橋性樹脂組成物の製造方法であって、

一般式（１）中、Ｒ _ａ１１ はエチレン性不飽和基を含有する基、Ｒ _ｂ１１ は脂肪族炭
化水素基、水素原子又はＹ ^１３ を示す。Ｙ ^１１ 、Ｙ ^１２ 及びＹ ^１３ は加水分解しうる
有機基を示す。
前記工程（１）を行うに当たり、
前記ベース樹脂が、エチレン含有量が４５〜６５質量％であるエチレン−αオレフ
ィンゴム１５〜５８質量％とポリオレフィン樹脂８５〜４２質量％とを含有し、
下記工程（ａ−２）でベース樹脂の全部を溶融混合する場合には、前記工程（１）
が下記工程（ａ−１）、工程（ａ−２）及び工程（ｃ）を有し、下記工程（ａ−２）
でベース樹脂の一部を溶融混合する場合には、前記工程（１）が下記工程（ａ−１）
、工程（ａ−２）、工程（ｂ）及び工程（ｃ）を有する、シラン架橋樹脂成形体の製
造方法。
工程（ａ−１）：少なくとも前記無機フィラー及び前記シランカップリング剤を混
合して混合物を調製する工程
工程（ａ−２）：前記混合物と前記ベース樹脂の全部又は一部とを、前記有機過酸
化物の存在下で前記有機過酸化物の分解温度以上の温度において
溶融混合して、前記有機過酸化物から発生したラジカルによって
前記エチレン性不飽和基を含有する基と前記ベース樹脂とをグラ
フト化反応させることにより、シランマスターバッチを調製する
工程
工程（ｂ）：前記ベース樹脂の残部及び前記シラノール縮合触媒を溶融混合して、
触媒マスターバッチを調製する工程
工程（ｃ）：前記シランマスターバッチと、前記シラノール縮合触媒又は前記触媒
マスターバッチとを溶融混合する工程
＜９＞上記＜８＞に記載のシラン架橋性樹脂組成物の製造方法により製造されてなるシラン架橋性樹脂組成物。
＜１０＞上記＜１＞〜＜７＞のいずれか１項に記載のシラン架橋樹脂成形体の製造方法により製造されてなるシラン架橋樹脂成形体。
＜１１＞上記＜１０＞に記載のシラン架橋樹脂成形体を含む成形品。
＜１２＞前記シラン架橋樹脂成形体が、電線あるいは光ファイバーケーブルの被覆層である＜１１＞に記載の成形品。
＜１３＞エチレン含有量が４５〜６５質量％であるエチレン−αオレフィンゴム１５〜５８質量％とポリオレフィン樹脂８５〜４２質量％とを含有するベース樹脂１００質量部に対して、有機過酸化物０．０１〜０．６質量部と、無機フィラー２５〜１２０質量部と、下記一般式（１）で表されるシランカップリング剤１〜１５．０質量部と、シラノール縮合触媒とを溶融混合してなるシラン架橋性樹脂組成物の製造に用いられるシランマスターバッチであって、

一般式（１）中、Ｒ _ａ１１ はエチレン性不飽和基を含有する基、Ｒ _ｂ１１ は脂肪族炭
化水素基、水素原子又はＹ ^１３ を示す。Ｙ ^１１ 、Ｙ ^１２ 及びＹ ^１３ は加水分解しうる
有機基を示す。
少なくとも前記無機フィラー及び前記シランカップリング剤を混合して混合物を調製し、得られた混合物と前記ベース樹脂の全部又は一部とを前記有機過酸化物の存在下で前記有機過酸化物の分解温度以上の温度において溶融混合して、前記有機過酸化物から発生したラジカルによって前記エチレン性不飽和基を含有する基と前記ベース樹脂とをグラフト化反応させることにより、得られるシランマスターバッチ。 That is, the subject of this invention was achieved by the following means.
<1> A method for producing a silane-crosslinked resin molded article having the following step (1), step (2) and step (3) ,
Step (1): 0.01 to 0.6 mass of organic peroxide with respect to 100 mass parts of the base resin
Part, 25 to 120 parts by mass of inorganic filler, and the following general formula (1)
1 to 15.0 parts by mass of a silane coupling agent and a silanol condensation catalyst
Step of obtaining a mixture by melting and mixing Step (2): Step of obtaining a molded body by molding the mixture obtained in Step (1) Step (3): Forming the molded body obtained in Step (2) Process of obtaining a silane cross-linked resin molded product by contacting with water

In general formula (1), R _a11 is a group containing an ethylenically unsaturated group, and R _b11 is an aliphatic carbon.
Hydrocarbon group, a hydrogen atom or ^{Y 13.} Y ¹¹ , Y ¹² and Y ¹³ can be hydrolyzed
An organic group is shown.
In performing the step (1),
The base resin contains 15 to 58% by mass of an ethylene-α olefin rubber having an ethylene content of 45 to 65% by mass and 85 to 42% by mass of a polyolefin resin,
When all of the base resin is melt-mixed in the following step (a-2), the step (1)
Has the following step (a-1), step (a-2) and step (c), and the following step (a-2)
In the case of melting and mixing a part of the base resin in step (1), the step (1) is the following step (a-1).
, Production of a silane cross-linked resin molded article having the step (a-2), the step (b) and the step (c)
Manufacturing method.
Step (a-1): mixing at least the inorganic filler and the silane coupling agent
Step of combining to prepare a mixture Step (a-2): The mixture and all or part of the base resin are combined with the organic peracid.
At a temperature above the decomposition temperature of the organic peroxide in the presence of
By melt mixing and radicals generated from the organic peroxide
The group containing the ethylenically unsaturated group and the base resin are mixed together.
Prepare silane masterbatch by phthalating reaction
Step Step (b): Melt and mix the remainder of the base resin and the silanol condensation catalyst,
Step of preparing a catalyst master batch Step (c): The silane master batch and the silanol condensation catalyst or the catalyst
<2> The step of melt mixing the masterbatch <2> The base resin includes 25 to 58% by mass of the ethylene-α-olefin rubber and 75 to 42% by mass of the polyolefin resin. Manufacturing method of a molded object.
<3> The silane-crosslinked resin molding according to <1> or <2>, wherein the ethylene-α-olefin rubber has an ethylene content of 45 to 65% by mass and a diene content of 0 to 4.5% by mass. Body manufacturing method.
<4> Manufacture of the silane crosslinked resin molding of any one of <1>-<3> whose compounding quantity of the said inorganic filler is 30-100 mass parts with respect to 100 mass parts of said base resins. Method.
<5> The silane cross-linking resin molding according to any one of <1> to <4>, wherein the silane coupling agent is mixed in an amount of 3 to 12 parts by mass with respect to 100 parts by mass of the base resin. Body manufacturing method.
<6> The method for producing a silane-crosslinked resin molded article according to any one of <1> to <5>, wherein the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.
<7> Production of a silane-crosslinked resin molded article according to any one of <1> to <6>, wherein the silanol condensation catalyst is not substantially mixed in the step (a-1) and the step (a-2). Method.
<8> 0.01 to 0.6 parts by mass of an organic peroxide, 25 to 120 parts by mass of an inorganic filler, and a silane coupling agent represented by the following general formula (1) with respect to 100 parts by mass of the base resin It is a manufacturing method of the silane crosslinkable resin composition which has the process (1) which melt-mixes 1-15.0 mass parts and a silanol condensation catalyst, and obtains a mixture,

In general formula (1), R _a11 is a group containing an ethylenically unsaturated group, and R _b11 is an aliphatic carbon.
Hydrocarbon group, a hydrogen atom or ^{Y 13.} Y ¹¹ , Y ¹² and Y ¹³ can be hydrolyzed
An organic group is shown.
In performing the step (1),
The base resin contains 15 to 58% by mass of an ethylene-α olefin rubber having an ethylene content of 45 to 65% by mass and 85 to 42% by mass of a polyolefin resin,
When all of the base resin is melt-mixed in the following step (a-2), the step (1)
Has the following step (a-1), step (a-2) and step (c), and the following step (a-2)
In the case of melting and mixing a part of the base resin in step (1), the step (1) is the following step (a-1).
, Production of a silane cross-linked resin molded article having the step (a-2), the step (b) and the step (c)
Manufacturing method.
Step (a-1): mixing at least the inorganic filler and the silane coupling agent
Step of combining to prepare a mixture Step (a-2): The mixture and all or part of the base resin are combined with the organic peracid.
At a temperature above the decomposition temperature of the organic peroxide in the presence of
By melt mixing and radicals generated from the organic peroxide
The group containing the ethylenically unsaturated group and the base resin are mixed together.
Prepare silane masterbatch by phthalating reaction
Step Step (b): Melt and mix the remainder of the base resin and the silanol condensation catalyst,
Step of preparing a catalyst master batch Step (c): The silane master batch and the silanol condensation catalyst or the catalyst
Step 9 for melt-mixing with master batch <9> A silane crosslinkable resin composition produced by the method for producing a silane crosslinkable resin composition according to <8> above.
<10> A silane cross-linked resin molded product produced by the method for producing a silane cross-linked resin molded product according to any one of <1> to <7>.
<11> A molded article comprising the silane crosslinked resin molded article according to <10>.
<12> The molded article according to <11>, wherein the silane-crosslinked resin molded body is a coating layer of an electric wire or an optical fiber cable.
<13> The organic peroxide is 0 with respect to 100 parts by mass of the base resin containing 15 to 58% by mass of the ethylene-α-olefin rubber having an ethylene content of 45 to 65% by mass and 85 to 42% by mass of the polyolefin resin. .01 to 0.6 parts by mass, 25 to 120 parts by mass of an inorganic filler, 1 to 15.0 parts by mass of a silane coupling agent represented by the following general formula (1), and a silanol condensation catalyst are melt-mixed. A silane masterbatch used for the production of a silane crosslinkable resin composition comprising:

In general formula (1), R _a11 is a group containing an ethylenically unsaturated group, and R _b11 is an aliphatic carbon.
Hydrocarbon group, a hydrogen atom or ^{Y 13.} Y ¹¹ , Y ¹² and Y ¹³ can be hydrolyzed
An organic group is shown.
At least the inorganic filler and the silane coupling agent are mixed to prepare a mixture, and the resulting mixture and all or part of the base resin are decomposed in the presence of the organic peroxide. A silane masterbatch obtained by melting and mixing at a temperature equal to or higher than the temperature, and grafting reaction of the group containing the ethylenically unsaturated group and the base resin with radicals generated from the organic peroxide .

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

According to the present invention, a silane cross-linked resin molded article that overcomes the problems of conventional wiring materials and has excellent flexibility, scratch resistance and oil resistance can be produced.
Therefore, according to the present invention, it is possible to provide a silane-crosslinked resin molded article having both flexibility and scratch resistance and higher oil resistance and a method for producing the same. Moreover, the silane masterbatch which can form the silane crosslinked resin molding which shows such an outstanding characteristic, a silane crosslinkable resin composition, and its manufacturing method can be provided. Furthermore, it is possible to provide a molded product including a silane cross-linked resin molded product exhibiting excellent characteristics.

First, each component used in the present invention will be described.
<Base resin>
The base resin used in the present invention contains an ethylene-α olefin rubber and a polyolefin resin at a content rate described later. Both the ethylene-α olefin rubber and the polyolefin resin (also referred to as a resin component) have a site where a silane coupling agent described later can be grafted.

(Ethylene-α olefin rubber)
The ethylene-α olefin rubber is a copolymer of ethylene, α-olefin, and, if necessary, diene, and ethylene-α having an ethylene constituent amount (referred to as ethylene content) in the copolymer of 45 to 65% by mass. Olefin rubber. When the ethylene content is less than 45% by mass, the flexibility may be inferior. On the other hand, when ethylene content exceeds 65 mass%, it may be inferior to at least one of a softness | flexibility and oil resistance. The ethylene content is preferably 45 to 62% by mass, and more preferably 48 to 55% by mass in terms of having excellent flexibility, scratch resistance and oil resistance. The ethylene content is a value measured according to the method described in ASTM D3900.

As for ethylene-alpha olefin rubber, 0-4.5 mass% is preferable, and, as for the amount of diene components (it is called diene content) in a copolymer, 0-2.5 mass% is more preferable. When the diene content is 2.5% by mass or less, steric hindrance is reduced during silane grafting, cross-linking becomes dense, and the oil resistance of the silane cross-linked resin molded product can be further improved. The diene content can be measured by, for example, infrared absorption spectroscopy (FT-IR), proton NMR ( ¹ H-NMR) method or the like.

The ethylene-α olefin rubber is a rubber made of an ethylene-α olefin copolymer, preferably a rubber made of a binary copolymer of ethylene and α-olefin, and ethylene, α-olefin and diene. Examples thereof include rubber made of a terpolymer. The diene of the terpolymer may be a conjugated diene or a non-conjugated diene, and is preferably a non-conjugated diene. That is, examples of the ternary copolymer include a ternary copolymer of ethylene, an α-olefin, and a conjugated diene, and a terpolymer of ethylene, an α-olefin, and a nonconjugated diene. Preferred are binary copolymers of ethylene and α-olefins and terpolymers of ethylene, α-olefins and non-conjugated dienes.
Preferred examples of the α-olefin include α-olefins having 3 to 12 carbon atoms. The α-olefin is not particularly limited, and examples thereof include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene.
Examples of the conjugated diene include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like, and butadiene is preferable. Non-conjugated dienes include, for example, dicyclopentadiene (DCPD), ethylidene norbornene (ENB), 1,4-hexadiene, and ethylidene norbornene is preferred. Each component of a conjugated diene compound and a non-conjugated diene is used individually by 1 type, or can use 2 or more types together.

  Examples of the rubber composed of a binary copolymer of ethylene and α-olefin include ethylene-propylene rubber, ethylene-butene rubber, and ethylene-octene rubber. Examples of the rubber made of a terpolymer of ethylene, α-olefin and diene include ethylene-propylene-diene rubber and ethylene-butene-diene rubber. Among them, ethylene-propylene rubber, ethylene-butene rubber, ethylene-propylene-diene rubber and ethylene-butene-diene rubber are preferable, ethylene-propylene rubber and ethylene-propylene-diene rubber are more preferable, ethylene-propylene rubber or ethylene-propylene-ethylidene norbornene. Rubber is particularly preferred.

  The content rate of ethylene-alpha olefin rubber is 15-58 mass% in 100 mass% of base resins. When the content of the ethylene-α-olefin rubber is less than 15% by mass, the flexibility may be inferior. On the other hand, when the content of the ethylene-α-olefin rubber exceeds 58% by mass, the scratch resistance may be inferior. The content of the ethylene-α olefin rubber is preferably 22 to 58 parts by mass, and more preferably 25 to 53% by mass in terms of achieving both flexibility and scratch resistance while maintaining oil resistance.

  One type of ethylene-α-olefin rubber may be used alone, or two or more types may be used in combination. When two or more ethylene-α olefin rubbers are used in combination, in the present invention, the ethylene content may be within the above range as the whole ethylene-α olefin rubber, and the ethylene content of each ethylene-α olefin rubber is the above. It is preferable to be within the range.

(Polyolefin resin)
The polyolefin resin is not particularly limited as long as it is a resin made of a polymer obtained by polymerizing or copolymerizing a compound having an ethylenically unsaturated bond, and is a known one conventionally used in resin compositions. Can be used. Examples thereof include resins such as polyethylene, polypropylene, ethylene-α-olefin copolymers, polyolefin copolymers having an acid copolymerization component or an acid ester copolymerization component, and polymers such as these rubbers or elastomers. .
These polyolefin resins may be used individually by 1 type, or may use 2 or more types together.

The polyethylene may be a polymer resin containing an ethylene component, and is a homopolymer composed of only ethylene, or a copolymer of ethylene and α-olefin (preferably 5 mol% or less) (except for those corresponding to polypropylene). And a resin comprising a copolymer of ethylene and a non-olefin (preferably 1 mol% or less) having only carbon, oxygen and hydrogen atoms in the functional group. In addition, the above-mentioned α-olefin and non-olefin can be used without particular limitation as well-known ones conventionally used as a copolymerization component of polyethylene.
Examples of polyethylene that can be used in the present invention include high density polyethylene, low density polyethylene, ultra high molecular weight polyethylene (UHMW-PE), linear low density polyethylene, and very low density polyethylene (VLDPE). Among these, high-density polyethylene, low-density polyethylene, and linear low-density polyethylene are preferable, and linear low-density polyethylene (LLDPE) or low-density polyethylene (LDPE) is more preferable. Polyethylene may be used individually by 1 type, and may use 2 or more types together.

The polypropylene may be a polymer whose main component contains a propylene constituent component, and includes a propylene homopolymer, an ethylene-propylene copolymer such as random polypropylene, and a block polypropylene as a copolymer.
Here, “random polypropylene” refers to a copolymer of propylene and ethylene having an ethylene component content of 1 to 5% by mass. “Block polypropylene” is a composition containing homopolypropylene and an ethylene-propylene copolymer, with an ethylene component content of about 5 to 15% by mass, and an ethylene component and a propylene component present as independent components. Say what you do.
Polypropylene may be used alone or in combination of two or more.

  The ethylene-α-olefin copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms (excluding those corresponding to the above polyethylene and polypropylene). The α-olefin component is as described above. An ethylene-alpha-olefin copolymer may be used individually by 1 type, and may use 2 or more types together.

  Examples of the acid copolymerization component in the polyolefin copolymer having an acid copolymerization component include carboxylic acid compounds such as (meth) acrylic acid, and acid ester compounds such as vinyl acetate and alkyl (meth) acrylate. Here, the alkyl group of the alkyl (meth) acrylate preferably has 1 to 12 carbon atoms. Examples of the polyolefin copolymer having an acid copolymer component include an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid alkyl copolymer. The polyolefin copolymer having an acid copolymerization component may be used alone or in combination of two or more.

  Styrenic elastomers are those having an aromatic vinyl compound as a constituent component in the molecule. Examples of such styrenic elastomers include block copolymers and random copolymers of conjugated diene compounds and aromatic vinyl compounds, or hydrogenated products thereof. Examples of such styrenic elastomer include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-butadiene-styrene block copolymer. (Hydrogenated SBS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butadiene rubber (SBR), hydrogenated SIS, Examples thereof include hydrogenated styrene-butadiene rubber (HSBR). Styrenic elastomers may be used alone or in combination of two or more.

  The polyolefin resin, that is, the polymer may be acid-modified. It does not specifically limit as an acid used for acid modification, The unsaturated carboxylic acid etc. which are used normally are mentioned.

As the polyolefin resin, among them, a resin such as polyethylene, polypropylene, ethylene-α-olefin copolymer, polyolefin copolymer having an acid copolymerization component, or a styrene-based elastomer is preferable because of its high acceptability for inorganic fillers. More preferred is polyethylene or polypropylene.
In addition to the ethylene-α olefin rubber, the polyolefin resin is a low-density polyethylene (low-density polyethylene) in terms of being able to impart excellent flexibility, scratch resistance and oil resistance to the silane crosslinkable resin molding. LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), or polypropylene are preferred, and the density is particularly 0.91 g / cm ² or more in that excellent electrical properties and excellent oil resistance can be imparted. The linear low-density polyethylene or low-density polyethylene is preferred.

  The content of the polyolefin resin is 42 to 85% by mass in 100% by mass of the base resin. When the content of the polyolefin resin is less than 42% by mass, the scratch resistance may be inferior. On the other hand, when the content of the polyolefin resin exceeds 85% by mass, the flexibility may be inferior. 42-78 mass% is preferable and 47-75 mass% is preferable at the point which can make a softness | flexibility and scratch resistance compatible, maintaining oil resistance.

  The base rubber contains the above-described ethylene-α olefin rubber and the above-described polyolefin resin, and may contain other components. Examples of other components include resins other than the base resin, and various oils used as plasticizers or softeners. Examples of the resin other than the base resin include natural rubber, chloroprene rubber, acrylic rubber, and silicone rubber. Examples of the oil include mineral oil softeners (paraffin oil, naphthenic oil and aroma oil). In the present invention, the base resin includes an embodiment containing oil and an embodiment not containing oil.

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

  Examples of such organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, , 5-Dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxy Benzoate, tert-butyl peroxyisopropyl carbonate, diace Peroxide, lauroyl peroxide, may be mentioned tert- butyl cumyl peroxide and the like. Of these, dicumyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2 are preferable in terms of odor, colorability, and scorch stability. , 5-Di- (tert-butylperoxy) hexyne-3 is preferred.

The decomposition temperature of the organic peroxide is preferably 80 to 195 ° C, particularly preferably 125 to 180 ° C.
In the present invention, the decomposition temperature of an organic peroxide means a temperature at which a decomposition reaction occurs in two or more compounds at a certain temperature or temperature range when an organic peroxide having a single composition is heated. means. Specifically, it refers to the temperature at which heat absorption or heat generation starts when heated from room temperature in a nitrogen gas atmosphere at a rate of temperature increase of 5 ° C./min by thermal analysis such as DSC method.

<Inorganic filler>
In the present invention, the inorganic filler is not particularly limited as long as the inorganic filler has a site capable of chemically bonding with a reactive site such as a silanol group of the silane coupling agent and a hydrogen bond or a covalent bond, or an intermolecular bond. Can be used. Examples of the site that can be chemically bonded to the reaction site of the silane coupling agent in this inorganic filler include OH groups (hydroxy groups, water molecules containing water or water of crystal water, OH groups such as carboxy groups), amino groups, and SH groups. It is done.

  The inorganic filler is not particularly limited, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, Examples thereof include metal hydrates such as hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, talc and other compounds having hydroxyl groups or crystal water. Boron nitride, silica (crystalline silica, amorphous silica, etc.), carbon, clay, zinc oxide, tin oxide, titanium oxide, molybdenum oxide, antimony trioxide, silicone compound, quartz, zinc borate, zinc borate, Examples thereof include zinc hydroxystannate and zinc stannate.

  As the inorganic filler, a surface-treated inorganic filler surface-treated with a silane coupling agent or the like can be used. For example, Kisuma 5L, Kisuma 5P (both trade names, magnesium hydroxide, manufactured by Kyowa Chemical Industry Co., Ltd., etc.) and the like are exemplified as the silane coupling agent surface treatment inorganic filler. The surface treatment amount of the inorganic filler by the silane coupling agent is not particularly limited, but is, for example, 3% by mass or less.

Of these inorganic fillers, at least one selected from the group consisting of silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, and silica is preferable.
An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

  When the inorganic filler is a powder, the average particle size of the inorganic filler is preferably 0.2 to 10 μm, more preferably 0.3 to 8 μm, further preferably 0.4 to 5 μm, particularly 0.4 to 3 μm. preferable. When the average particle size is within the above range, the retention effect of the silane coupling agent is high and the heat resistance is excellent. Further, the inorganic filler hardly aggregates when mixed with the silane coupling agent, and the appearance is excellent. The average particle size is obtained by an optical particle size measuring device such as a laser diffraction / scattering type particle size distribution measuring device in which an inorganic filler is dispersed with alcohol or water.

<Silane coupling agent>
The silane coupling agent used in the present invention can chemically bond a grafting reaction site (group or atom) capable of grafting to a resin component in the presence of radicals generated by the decomposition of an organic peroxide and an inorganic filler. It is sufficient to have at least a reactive site capable of reacting with a site and capable of silanol condensation (including a site generated by hydrolysis, such as a silyl ester group). As such a silane coupling agent, the silane coupling agent conventionally used for the silane crosslinking method is mentioned.

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

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

R _a11 is a grafting reaction site and is preferably a group containing an ethylenically unsaturated group. Examples of the group containing an ethylenically unsaturated group include a vinyl group, a (meth) acryloyloxyalkylene group, and a p-styryl group. Among these, a vinyl group is preferable.

Examples of the aliphatic hydrocarbon group that can be taken by R _b11 include _C 1-8 monovalent aliphatic hydrocarbon groups excluding an aliphatic unsaturated hydrocarbon group. R _b11 is preferably Y ¹³ described later.

Y ¹¹ , Y ¹² and Y ¹³ are silanol-condensable reaction sites (hydrolyzable organic groups), for example, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and a carbon number The acyloxy group of 1-4 is mentioned, An alkoxy group is preferable. Specific examples of the hydrolyzable organic group include methoxy, ethoxy, butoxy, acyloxy and the like. Among these, methoxy or ethoxy is more preferable, and methoxy is particularly preferable from the viewpoint of the reactivity of the silane coupling agent.

The silane coupling agent is preferably a silane coupling agent having a high hydrolysis rate, more preferably a silane cup in which R _b11 is Y ¹³ and Y ¹¹ , Y ¹² and Y ¹³ are the same. A ring agent or a hydrolyzable silane coupling agent in which at least one of Y ¹¹ , Y ¹² and Y ¹³ is a methoxy group.

Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltrimethoxysilane. Examples thereof include vinyl silanes such as ethoxysilane and vinyltriacetoxysilane, and (meth) acryloxysilanes such as methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, and methacryloxypropylmethyldimethoxysilane.
Among the silane coupling agents, a silane coupling agent having a vinyl group and an alkoxy group at the terminal is more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.

  A silane coupling agent may be used individually by 1 type, and may use 2 or more types together. Further, it may be used as it is or diluted with a solvent or the like.

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

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

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

<Additives>
In the present invention, various additives generally used in electric wires, electric cables, electric cords, sheets, foams, tubes, and pipes may be used as long as the effects of the present invention are not impaired. Examples of such additives include crosslinking aids, antioxidants, lubricants, metal deactivators, and fillers (including flame retardant (auxiliary) agents) other than the above inorganic fillers.
Although it does not specifically limit as antioxidant, For example, amine antioxidant, phenol antioxidant, sulfur antioxidant, etc. are mentioned. Examples of the amine antioxidant include a polymer of 4,4′-dioctyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline, and the like. . Examples of the phenol antioxidant include pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like. Examples of the sulfur antioxidant include bis (2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptobenzimidazole and its zinc salt, pentaerythritol-tetrakis. (3-lauryl-thiopropionate) and the like. The antioxidant can be added in an amount of preferably 0.1 to 15.0 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the halogen-containing resin.

Next, the production method of the present invention will be specifically described.
Both the manufacturing method of the silane cross-linked resin molding of the present invention and the manufacturing method of the silane cross-linking resin composition of the present invention perform at least the following step (1). Therefore, these manufacturing methods will be described below together (in the description common to both manufacturing methods, there are cases where they are referred to as the manufacturing method of the present invention).
The “silane masterbatch” of the present invention is produced by the following step (a-1) and step (a-2) (both steps are collectively referred to as step (a)). Therefore, the “manufacturing method of silane masterbatch” of the present invention will be described in the manufacturing method of the present invention.

Step (1): 0.01 to 0.6 parts by mass of an organic peroxide, 25 to 120 parts by mass of an inorganic filler, and 1 to 15.0 parts by mass of a silane coupling agent with respect to 100 parts by mass of the base resin Step of obtaining a mixture by melting and mixing with a silanol condensation catalyst Step (2): Step of obtaining a molded body by molding the mixture obtained in Step (1) Step (3): Obtained in Step (2) A process of obtaining a silane cross-linked resin molded product by bringing the molded product into contact with water

When this step (1) melts and mixes all of the base resin in the following step (a-2), the step (a-1), the step (a-2) and the step (c) are included. When a part of the base resin is melt-mixed in (a-2), the process includes steps (a-1), (a-2), (b), and (c).
Step (a-1): Step of preparing a mixture by mixing at least an inorganic filler and a silane coupling agent Step (a-2): Presence of organic peroxide in the mixture and all or part of the base resin Step of preparing a silane masterbatch by melting and mixing at a temperature equal to or higher than the decomposition temperature of the organic peroxide Step (b): Melting and mixing the remainder of the base resin and the silanol condensation catalyst to prepare a catalyst masterbatch Step to perform Step (c): Step of melt mixing silane masterbatch and silanol condensation catalyst or catalyst masterbatch Here, mixing means obtaining a uniform mixture.

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

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

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

  In the step (1), the blending amount (content ratio) of the ethylene-α olefin rubber and the polyolefin resin in the base resin is as described above.

  In the step (1), the compounding amount of the organic peroxide is 0.01 to 0.6 parts by mass, preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the base resin. When the blending amount of the organic peroxide is less than 0.01 parts by mass, the graft reaction does not proceed, the unreacted silane coupling agents are condensed with each other, or the unreacted silane coupling agent is volatilized, and heat resistance, Depending on the condition, mechanical strength and reinforcement may not be sufficiently obtained. On the other hand, when it exceeds 0.6 parts by mass, many of the resin components are directly cross-linked by a side reaction to form a defect, which may cause poor appearance. That is, by setting the blending amount of the organic peroxide within this range, the graft reaction can be carried out within an appropriate range, and a silane master excellent in extrudability without causing gel-like lumps (agglomerates). Batch etc. can be obtained.

  The compounding quantity of an inorganic filler is 25-120 mass parts with respect to 100 mass parts of base resins, 30-100 mass parts is preferable and its 35-95 mass parts is more preferable. If the blending amount of the inorganic filler is less than 25 parts by mass, it may not be possible to impart excellent heat resistance to the silane crosslinked resin molded article. On the other hand, when it exceeds 120 parts by mass, it may not be possible to impart excellent oil resistance.

The compounding quantity of a silane coupling agent is 1-15.0 mass parts with respect to 100 mass parts of base resins. When the blending amount of the silane coupling agent is less than 1 part by mass, the crosslinking reaction does not proceed sufficiently, and excellent scratch resistance or oil resistance, and further heat resistance may not be exhibited. On the other hand, when it exceeds 15 parts by mass, the silane coupling agent cannot be completely adsorbed on the surface of the inorganic filler, and the silane coupling agent volatilizes during kneading, which is not economical. Moreover, the silane coupling agent which does not adsorb | suck condenses, and there exists a possibility that an external appearance may deteriorate by producing a spot and burning in a molded object.
From the above viewpoint, the blending amount of the silane coupling agent is preferably 3 to 12 parts by mass, more preferably 4 to 12 parts by mass with respect to 100 parts by mass of the resin.

  The compounding amount of the silanol condensation catalyst is not particularly limited, and is preferably 0.0001 to 0.5 parts by mass, more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the base resin. When the blending amount of the silanol condensation catalyst is within the above range, the crosslinking reaction by the condensation reaction of the silane coupling agent tends to proceed almost uniformly, the appearance and physical properties of the silane crosslinked resin molded article are excellent, and the productivity is also improved. . That is, if the amount of the silanol condensation catalyst is too small, crosslinking due to the condensation reaction of the silane coupling agent is difficult to proceed, the scratch resistance and heat resistance, and further the heat resistance is not improved, the productivity is reduced, Or the cross-linking may be non-uniform. On the other hand, if the amount is too large, the crosslinking reaction due to the condensation reaction of the silane coupling agent becomes uneven, and the appearance and productivity may be inferior.

In the production method of the present invention, step (1) is performed.
In this step (1), all or part of the base resin, the organic peroxide, the inorganic filler, the silane coupling agent, and the silanol condensation catalyst are melt-mixed in a specific mixing order. In the present invention, first, at least an inorganic filler and a silane coupling agent are mixed to prepare a mixture (step (a-1)). That is, the silane coupling agent is premixed with the inorganic filler as described above.
A method of mixing the inorganic filler and the silane coupling agent is not particularly limited, and examples thereof include a mixing method such as a wet process and a dry process. Specifically, a wet treatment in which an inorganic filler is dispersed in a solvent such as alcohol or water, a wet treatment in which a silane coupling agent is added, an untreated inorganic filler, or stearic acid, oleic acid, phosphate ester or Examples thereof include a dry treatment in which a silane coupling agent is heated or non-heated and mixed in an inorganic filler whose surface is treated with a silane coupling agent, and both. In the present invention, dry processing is preferred in which a silane coupling agent is added to an inorganic filler, preferably a dried inorganic filler, with heating or non-heating and mixed.
The silane coupling agent premixed in this manner exists so as to surround the surface of the inorganic filler, and a part or all of the silane coupling agent is adsorbed or bonded to the inorganic filler. Thereby, volatilization of the silane coupling agent can be reduced during subsequent melt mixing. Moreover, it is possible to prevent the silane coupling agent that is not adsorbed or bonded to the inorganic filler from condensing and making melt kneading difficult. Furthermore, a desired shape can be obtained during extrusion molding.

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

In the step (1), the method of mixing the organic peroxide is not particularly limited, and may be present when the mixture and the base resin are melt-mixed. The organic peroxide, for example, may be mixed simultaneously with the inorganic filler or the like, or may be mixed in any of the mixing stages of the inorganic filler and the silane coupling agent, to form a mixture of the inorganic filler and the silane coupling agent. It may be mixed. For example, the organic peroxide may be mixed with the inorganic filler after being mixed with the silane coupling agent, or may be separately mixed with the inorganic filler separately from the silane coupling agent. Depending on production conditions, only the silane coupling agent may be mixed with the inorganic filler, and then the organic peroxide may be mixed.
The organic peroxide may be mixed with other components or may be a simple substance.

  In the mixing method of the inorganic filler and the silane coupling agent, in the wet mixing, since the bonding force between the silane coupling agent and the inorganic filler becomes strong, volatilization of the silane coupling agent can be effectively suppressed. The condensation reaction may be difficult to proceed. On the other hand, in dry mixing, the silane coupling agent tends to volatilize, but since the bonding strength between the inorganic filler and the silane coupling agent becomes relatively weak, the silanol condensation reaction easily proceeds efficiently.

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

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

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

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

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

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

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

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

Moreover, you may use an inorganic filler in a process (b). In this case, although the compounding quantity of an inorganic filler is not specifically limited, 120 mass parts or less are preferable with respect to 100 mass parts of carrier resins. This is because if the blending amount of the inorganic filler is large, the silanol condensation catalyst is difficult to disperse and the crosslinking is difficult to proceed. On the other hand, when there are too few compounding quantities of an inorganic filler, the crosslinking degree of a molded object will fall and sufficient heat resistance may not be obtained.
In this case, examples of usable inorganic fillers include the above inorganic fillers.

The catalyst MB thus prepared is a mixture of a silanol condensation catalyst, a carrier resin, and a filler that is optionally added.
The catalyst MB is used as a master batch set together with the silane MB in the production of the silane crosslinkable resin composition prepared in the step (1).

In the production method of the present invention, the step (c) is then performed in which the silane MB and the silanol condensation catalyst or catalyst MB are mixed to obtain a mixture.
The mixing method may be any mixing method as long as a uniform mixture can be obtained as described above, but is preferably basically the same as the melt mixing in step (a-2). There are resin components such as elastomers whose melting points cannot be measured by DSC or the like, but they are kneaded at a temperature at which at least one of the resin components and the organic peroxide is melted. The melting temperature is appropriately selected according to the melting temperature of the base resin or the carrier resin, and is preferably 80 to 250 ° C., more preferably 100 to 240 ° C., for example. Other conditions such as mixing (kneading) time can be set as appropriate.

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

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

Thus, the process (a)-(c) (process (1)), ie, the manufacturing method of the silane crosslinkable resin composition of this invention is performed, and the silane crosslinkable resin composition of this invention is manufactured as a mixture. Is done. This silane crosslinkable resin composition contains silane crosslinkable resins having different crosslinking methods. In this silane crosslinkable resin, the reaction site of the silane coupling agent may be bonded or adsorbed to the inorganic filler, but is not silanol condensed as described later. Therefore, the silane crosslinkable resin includes a crosslinkable resin in which a silane coupling agent bonded or adsorbed to an inorganic filler is grafted to the base resin, and a crosslink in which a silane coupling agent not bonded to or adsorbed to the inorganic filler is grafted to the base resin. At least. The silane crosslinkable resin may be grafted with a silane coupling agent to which an inorganic filler is bonded or adsorbed and a silane coupling agent to which an inorganic filler is not bonded or adsorbed. Furthermore, a silane coupling agent and an unreacted resin component may be included.
As described above, the silane crosslinkable resin is an uncrosslinked product in which the silane coupling agent is not silanol condensed. Actually, when melt-mixed in step (c), partial cross-linking (partial cross-linking) is unavoidable, but at least the moldability in the molding in step (2) is obtained for the resulting silane cross-linkable resin composition. Is held.

  In step (1), steps (a) to (c) can be performed continuously.

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

Moreover, a process (2) can be performed simultaneously with a process (c) or continuously. That is, as one embodiment of the melt mixing in the step (c), there is an embodiment in which the forming raw material is melt-mixed at the time of melt-molding, for example, at the time of extrusion molding or just before that. For example, pellets such as dry blends may be mixed together at room temperature or high temperature and introduced into a molding machine (melt mixing), or mixed and then melt mixed, pelletized again, and then introduced into the molding machine. Also good. More specifically, a mixture (molding material) of silane MB and silanol condensation catalyst or catalyst MB is melt-kneaded in a coating apparatus, and then extrusion coated on the outer peripheral surface of a conductor or the like to be molded into a desired shape. A series of processes can be adopted.
In this way, a molded body of the silane crosslinkable resin composition is obtained. Similar to the silane crosslinkable resin composition, this molded body is partially crosslinked, but is in a partially crosslinked state that retains the moldability that can be molded in the step (2). Therefore, the silane cross-linked resin molded body of the present invention is formed into a cross-linked or finally cross-linked molded body by performing the step (3).

In the manufacturing method of the silane crosslinked resin molding of this invention, the process (3) which contacts the molded object obtained at the process (2) with water is performed. Thereby, the reaction site of the silane coupling agent is hydrolyzed to become silanol, and the hydroxyl groups of silanol are condensed with each other by the silanol condensation catalyst present in the molded article, thereby causing a crosslinking reaction. Thus, a silane cross-linked resin molded product in which the silane coupling agent is cross-linked by silanol condensation can be obtained.
The process itself in this step (3) can be performed by a normal method. Condensation between silane coupling agents proceeds only by storage at room temperature. Therefore, in the step (3), it is not necessary to positively contact the molded body with water. In order to promote this crosslinking reaction, the molded body can be brought into contact with moisture. For example, it is possible to employ a method of positively contacting water, such as immersion in warm water, charging into a wet heat tank, exposure to high-temperature steam, and the like. In this case, pressure may be applied to allow moisture to penetrate inside.

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

The details of the reaction mechanism in the production method of the present invention are not yet clear, but are considered as follows.
That is, by using (mixing) an inorganic filler and a silane coupling agent before and / or during kneading with the base resin, the silane coupling agent binds to the inorganic filler with a group capable of chemically bonding, It is bonded to the uncrosslinked portion of the resin component with a group capable of graft reaction existing at the other end and held. Alternatively, the silane coupling agent is a group that can be chemically bonded to a hole or surface of the inorganic filler without bonding to the inorganic filler, and can be grafted to the resin component without bonding to the inorganic filler. Bonded with the uncrosslinked portion and retained. Thus, a silane coupling agent that binds to an inorganic filler with a strong bond (for example, a chemical bond with a hydroxyl group on the surface of the inorganic filler may be considered) and a silane coupling agent that binds to a weak bond (for example, The reason can be, for example, an interaction by hydrogen bond, an interaction between ions, partial charges or dipoles, an action by adsorption, etc.). In this state, by adding an organic peroxide and kneading with the base resin, the silane coupling agent is hardly volatilized as described above, and condensation between the silane coupling agents is suppressed, and the inorganic filler and A silane crosslinkable resin is formed by graft reaction of silane coupling agents having different bonds to the resin component.

Even by the kneading described above, among the silane coupling agents, the silane coupling agent having a strong bond with the inorganic filler retains the bond with the inorganic filler, and the crosslinkable group that can undergo a graft reaction is present in the crosslinkable portion of the resin component. Graft reaction. In particular, when a plurality of silane coupling agents are bonded to the surface of one inorganic filler particle through a strong bond, a plurality of resin components are bonded through the inorganic filler particle. By these reactions or bonds, the crosslinked network via the inorganic filler is expanded. That is, a silane crosslinkable resin formed by graft reaction of the silane coupling agent bonded to the inorganic filler onto the resin component is formed.
The silane coupling agent having a strong bond with the inorganic filler hardly causes a condensation reaction in the presence of water by the silanol condensation catalyst, and the bond with the inorganic filler is maintained. The reason why the silanol condensation reaction hardly occurs is considered to be that the binding energy between the inorganic filler and the silane coupling agent is very high and the condensation reaction does not occur even under the silanol condensation catalyst. Thus, the resin component and the inorganic filler are bonded, and the resin component is cross-linked through the silane coupling agent. As a result, the adhesiveness between the resin component and the inorganic filler is strengthened, and a molded article having good mechanical strength and wear resistance and hardly scratched is obtained. In particular, a plurality of silane coupling agents can be bonded to the surface of one inorganic filler particle, and high mechanical strength can be obtained. Thus, the silane coupling agent bonded with a strong bond to the inorganic filler is considered to contribute to the development or improvement of scratch resistance, mechanical properties, and in some cases, wear resistance.

  On the other hand, among the silane coupling agents, the silane coupling agent having a weak bond with the inorganic filler is separated from the surface of the inorganic filler by the kneading described above, and is a group capable of undergoing a graft reaction, which is a crosslinking group of the silane coupling agent. However, it reacts with the radicals of the resin component generated by the extraction of hydrogen radicals by radicals generated by the decomposition of the organic peroxide to cause a graft reaction. That is, a silane crosslinkable resin is formed by graft reaction of the silane coupling agent released from the inorganic filler to the resin component. The silane coupling agent in the graft portion thus produced is then mixed with a silanol condensation catalyst and brought into contact with moisture to cause a condensation reaction (crosslinking reaction). The heat resistance of the silane cross-linked resin molded product obtained by this cross-linking reaction is increased. Thus, it is considered that the silane coupling agent bonded to the inorganic filler with a weak bond contributes to an improvement in the degree of crosslinking, that is, an improvement in heat resistance.

  Furthermore, when the silane coupling agent is previously mixed with the inorganic filler by the production method of the present invention, the appearance is excellent because the condensation between the silane coupling agents is suppressed as described above.

In the production method of the present invention, when an ethylene-α olefin rubber having a specific ethylene content and a polyolefin resin are used in a specific ratio as a base resin, the silane crosslinked resin molded article has excellent flexibility and scratch resistance. And high oil resistance can be imparted. Although it is not yet certain about the details that such excellent characteristics can be imparted to the silane cross-linked resin molded article, it is considered as follows.
That is, when the above-mentioned specific resin component is used in a specific ratio, the crystallinity of the resin component is reduced, and the graft reaction with the grafting reaction site of the silane coupling agent in the resin component is possible due to the crystallinity reduction. More parts. In addition, the reaction energy required for the graft reaction between the resin component and the silane coupling agent is reduced due to the reduction in steric hindrance due to the decrease in crystallinity. By these, a silane coupling agent becomes easy to carry out a graft reaction to a resin component, and the crosslinking density of a resin component becomes high. Therefore, the freedom degree of a resin component falls, it becomes difficult for oil to penetrate | invade or mix, and it is thought that high oil resistance is expressed even at high temperature.
Moreover, the softness | flexibility of ethylene-alpha olefin rubber can be maintained by using together ethylene-alpha olefin rubber with specific ethylene content and polyolefin resin as a base resin in a specific ratio.
Moreover, when a resin containing a specific amount of specific ethylene-α olefin rubber and polyolefin resin is used as the base resin, it is considered that the above-mentioned scratch resistance improving effect by the silane coupling agent having a strong bond with the inorganic filler is enhanced. .
In the present invention, when these are exhibited in a well-balanced manner, excellent flexibility and scratch resistance and high oil resistance can be imparted to the silane crosslinked resin molded product.

The production method of the present invention includes products that require oil resistance, flexibility, and scratch resistance (including semi-finished products, parts, and members), products that require heat resistance, products that require strength, The present invention can be applied to the manufacture of product components such as products that require flame retardancy, rubber materials, or components thereof. Therefore, the molded article of the present invention is such a product. At this time, the molded product may be a product including a silane cross-linked resin molded body, or may be a product including only a silane cross-linked resin molded body.
Examples of the molded article of the present invention include a coating material for an electric wire such as an insulated wire or a heat-resistant cable, a rubber wire / cable material, a heat-resistant electric wire component, a heat-resistant sheet, and a heat-resistant film. Also, power supply plugs, connectors, sleeves, boxes, tape base materials, tubes, sheets, packing materials, cushioning materials, anti-vibration materials, wiring materials used for internal and external wiring of electrical and electronic equipment, especially electric wires and optical fiber cables. Can be mentioned.

The manufacturing method of the present invention is suitably applied to electric wires and manufacturing among the products described above, and is used in particular outdoors, and may be used by being immersed in oil. It is suitably applied to a cable for natural resource drilling (heat-resistant cable coating material) or a mine cable (heat-resistant cable coating material). Thereby, coating materials (insulator or sheath), such as these electric wires, can be formed.
When the molded product of the present invention is an extrusion molded product such as an electric wire or cable, preferably, the silane crosslinkable resin composition is prepared by melt-kneading the molding material in an extruder (extrusion coating apparatus). The crosslinkable resin composition can be produced by extruding the outer periphery of a conductor or the like to cover the conductor or the like. Even if such a molded article adds a large amount of an inorganic filler, the silane crosslinkable resin composition is used around a conductor using a general-purpose extrusion coating apparatus without using a special machine such as an electron beam crosslinking machine. Or it can shape | mold by carrying out the extrusion coating of the circumference | surroundings of the conductor to which the tensile strength fiber was added or twisted together. For example, a soft copper single wire or a stranded wire can be used as the conductor. In addition to the bare wire, a conductor plated with tin or an enameled insulating layer can be used as the conductor. The thickness of the insulating layer (the coating layer made of the silane cross-linked resin molded body of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 to 5 mm.

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

  In Examples 1 to 13 and Comparative Examples 1 to 6, the following components were used and the respective specifications were set to the conditions shown in Tables 1 and 2, and the evaluation results described later in Tables 1 and 2 are shown. Also shown.

The detail of each compound shown in Table 1 and Table 2 is shown below.
<Resin component>
(Ethylene-α olefin rubber)
EP rubber 1: EPT0045 (trade name), manufactured by Mitsui Chemicals, ethylene-propylene rubber, ethylene content 51 mass%, diene content 0 mass%
EP rubber 2: Nodel 3640 (trade name), manufactured by Dow Chemical Company, ethylene-propylene-ethylidene norbornene rubber, ethylene content 60 mass%, diene content 1.8 mass%
EP rubber 3: Nodel 3670 (trade name), ethylene-propylene-ethylidene norbornene rubber, manufactured by Dow Chemical Company, ethylene content 70% by mass, diene content 0.5% by mass
EP rubber 4: Nodel 4520 (trade name), ethylene-propylene-ethylidene norbornene rubber, manufactured by Dow Chemical Co., ethylene content 50 mass%, diene content 4.9 mass%
(Polyolefin resin)
PO1: NUC7641 (trade name), manufactured by Japan Unica, linear low density polyethylene PO2: UBEC180 (trade name), manufactured by Ube Maruzen Polyethylene, low density polyethylene PO3: PB222A (trade name), manufactured by Sun Allomer, polypropylene

<Inorganic filler>
Calcium carbonate: Softon 1200 (trade name), Silica: Crystallite 5X (trade name) manufactured by Bihoku Powder Chemical Co., Ltd., Magnesium hydroxide manufactured by Tatsumori Co., Ltd .: Kisuma 5 (trade name, surface untreated magnesium hydroxide), Kyowa Chemical <Silane coupling agent>
"KBM1003" (trade name, manufactured by Shin-Etsu Silicone, vinyltrimethoxysilane)
<Organic peroxide>
“Perkadox BC-FF” (trade name): manufactured by Kayaku Akzo, di-α-cumyl peroxide (decomposition temperature 151 ° C.)
<Antioxidant (hindered phenol antioxidant)>
“Irganox 1010” (trade name, manufactured by BASF, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate])
<Silanol condensation catalyst>
“ADK STAB OT-1” (trade name, manufactured by ADEKA, dioctyltin dilaurate)

(Examples 1-13 and Comparative Examples 1-6)
In Examples 1 to 13 and Comparative Examples 1 to 6, 5% by mass (PO1) of the base resin was used as a carrier resin for the catalyst MB.

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

  On the other hand, the carrier resin, the silanol condensation catalyst, and the antioxidant were melt mixed at 180 ° C. with a Banbury mixer at the mass ratio shown in Tables 1 and 2 to obtain catalyst MB (step (b)). The catalyst MB is a mixture of a carrier resin and a silanol condensation catalyst.

Next, silane MB and catalyst MB were charged into a closed ribbon blender and dry blended at room temperature (25 ° C.) for 3 minutes to obtain a dry blend. In each example, the mixing ratio of silane MB and catalyst MB was such that the base resin of silane MB was 95 parts by mass and the carrier resin of catalyst MB was 5 parts by mass.
Next, the obtained dry blend was subjected to L / D (ratio of effective screw length L to diameter D) = 24, screw having a screw diameter of 40 mm (feed portion screw temperature 160 ° C., compression portion screw temperature). 190 ° C., head temperature 200 ° C.). While melt-mixing the dry blend in this extruder, the outer diameter of the 1 / 0.8 TA conductor (conductor diameter 0.8 mm) was extruded at a linear speed of 5 m / min so as to have a coating thickness of 0.8 mm. A 2.4 mm coated conductor was obtained (step (c) and step (2)). A heat-resistant silane crosslinkable resin composition was prepared by melt-mixing the dry blend in an extruder before extrusion molding.

Each of the obtained coated conductors was left in an atmosphere at a temperature of 70 ° C. and a relative humidity of 90% for 1 day (step (3)).
Thus, the electric wire which has the coating layer which consists of a silane crosslinked resin molding on the outer peripheral surface of the said conductor was manufactured. The silane cross-linked resin molding as the coating layer has the above-mentioned silane cross-linked resin.

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

<Flexibility test (tensile test)>
About the tubular piece (coating layer) produced by extracting the conductor from each manufactured electric wire, the tensile test was done and the flexibility of the tubular piece was evaluated based on 100% modulus.
In this tensile test, according to JIS C 3005, the tensile strength at 100% elongation was measured under the conditions of a distance between marked lines of 20 mm and a tensile speed of 200 mm / min, and the obtained value was 100% modulus (unit: MPa). It was. The evaluation of flexibility is expressed by “A” as an excellent level when the 100% modulus was 10 MPa or less, and expressed as “B” when it was over 10 MPa and 12 MPa or less, and exceeded 12 MPa. Was represented by “C” as a failure level of this test.

<Scratch resistance test>
In accordance with JASO D 618, a scrape wear test was performed on each manufactured electric wire. The conditions were a needle diameter of 0.45 mm and a test load of 10N. The number of times until the needle reached the conductor was counted. The evaluation of the scratch resistance is expressed as “A” as an excellent level when the number of times until the needle reaches the conductor is 100 times or more, and as a rejection level of this test when it is less than 100 times. C ”.

<Oil resistance test (A)>
About each manufactured electric wire, the "oil resistance test" as described in JISC3005 was done. In the oil resistance test (A), the oil immersion temperature was 100 ° C., the oil immersion time was 18 hours, and ASTM No. 2 oil was used as the oil.
In the evaluation of the oil resistance test (A), the residual ratio before and after the oil resistance test was “A” when the strength and elongation were 70% or more, and those with 60% or more and less than 70% “ B ”, and“ C ”was less than 60% in either strength or elongation. An evaluation “B” or higher is a passing level of this test.

<Oil resistance test (B)>
In the oil resistance test (A), ASTM No. 2 oil was used as the oil, and the oil resistance test (B) was performed in the same manner as the oil resistance test (A) except that the oil immersion temperature was changed to 120 ° C.
In the evaluation of the oil resistance test (B), the residual ratio before and after the oil resistance test was “A” when the strength and elongation were 70% or more, and those when the residual ratio was 60% or more and less than 70%. B ”, and“ C ”was less than 60% in either strength or elongation. This test is a reference test, but the pass level is "B" or higher.

<Measurement of volume resistivity (volume resistivity)>
The dry blend obtained in the production of each electric wire was press-molded (170 ° C., 10 minutes) to obtain a sheet sample having a thickness of 1 mm. The sheet was applied according to JIS K 6271, 500 V was applied between the electrodes, and the volume resistivity after 1 minute was measured.
The evaluation of the volume resistivity is expressed as “A” in which the measured volume resistivity is 1 × 10 ¹⁵ (Ω · cm) or more as a pass, and is 1 × 10 ¹⁴ (Ω · cm) or more and 1 × 10. Those less than ¹⁵ (Ω · cm) were expressed as “B” and those less than 1 × 10 ¹⁴ (Ω · cm) as “C” as rejected.

<Hot set test>
A hot set test was performed using a tubular piece prepared by extracting a conductor from each manufactured electric wire. The hot set test was conducted in accordance with the method described in IEC60811-2-1. The test conditions were 200 ° C, heating time was 15 minutes, load was 20 N / cm ² , elongation after heating was 100% or less, and elongation after heating and removal of load was 25% or less. The pass level was represented by “A”, and the others were represented by “C” as fail levels of the test. The hot set test is a test for evaluating and confirming the heat resistance of the silane cross-linked resin molded article, and is a reference test in the present invention.

As is clear from the results shown in Tables 1 and 2, Examples 1 to 13 all passed the flexibility test, the scratch resistance test, and the oil resistance test (A). Thus, according to the present invention, it was possible to manufacture an electric wire having a silane cross-linked resin molded article having both flexibility and scratch resistance and higher oil resistance as a coating layer.
Furthermore, all of Examples 1 to 13 passed the volume resistivity test and the hot set test. According to the present invention, in addition to the above-mentioned excellent characteristics, an electric wire having a silane cross-linked resin molded article having excellent insulation and / or heat resistance as a coating layer can be produced.

On the other hand, Comparative Example 1 in which the base resin does not contain a polyolefin resin and Comparative Example 2 in which an EP rubber is excessively contained failed the scratch resistance test. Further, Comparative Example 3 in which the content of EP rubber in the base resin was too small and Comparative Example 4 in which no EP rubber was contained failed the flexibility test. Comparative Example 5 using an ethylene-α-olefin rubber rubber having an ethylene content that was too high and Comparative Example 6 having an excessive amount of inorganic filler failed the oil resistance test (A).

Claims (13)

A method for producing a silane-crosslinked resin molded article having the following step (1), step (2) and step (3) ,
Step (1): 0.01 to 0.6 mass of organic peroxide with respect to 100 mass parts of the base resin
Part, 25 to 120 parts by mass of inorganic filler, and the following general formula (1)
1 to 15.0 parts by mass of a silane coupling agent and a silanol condensation catalyst
Step of obtaining a mixture by melting and mixing Step (2): Step of obtaining a molded body by molding the mixture obtained in Step (1) Step (3): Forming the molded body obtained in Step (2) Process of obtaining a silane cross-linked resin molded product by contacting with water

In general formula (1), R _a11 is a group containing an ethylenically unsaturated group, and R _b11 is an aliphatic carbon.
Hydrocarbon group, a hydrogen atom or ^{Y 13.} Y ¹¹ , Y ¹² and Y ¹³ can be hydrolyzed
An organic group is shown.
In performing the step (1),
The base resin contains 15 to 58% by mass of an ethylene-α olefin rubber having an ethylene content of 45 to 65% by mass and 85 to 42% by mass of a polyolefin resin,
When all of the base resin is melt-mixed in the following step (a-2), the step (1)
Has the following step (a-1), step (a-2) and step (c), and the following step (a-2)
In the case of melting and mixing a part of the base resin in step (1), the step (1) is the following step (a-1).
, Production of a silane cross-linked resin molded article having the step (a-2), the step (b) and the step (c)
Manufacturing method.
Step (a-1): mixing at least the inorganic filler and the silane coupling agent
Step of combining to prepare a mixture Step (a-2): The mixture and all or part of the base resin are combined with the organic peracid.
At a temperature above the decomposition temperature of the organic peroxide in the presence of
By melt mixing and radicals generated from the organic peroxide
The group containing the ethylenically unsaturated group and the base resin are mixed together.
Prepare silane masterbatch by phthalating reaction
Step Step (b): Melt and mix the remainder of the base resin and the silanol condensation catalyst,
Step of preparing a catalyst master batch Step (c): The silane master batch and the silanol condensation catalyst or the catalyst
Process of melt mixing with master batch   The method for producing a silane-crosslinked resin molded article according to claim 1, wherein the base resin contains 25 to 58 mass% of the ethylene-α-olefin rubber and 75 to 42 mass% of the polyolefin resin.   The method for producing a silane-crosslinked resin molded article according to claim 1 or 2, wherein the ethylene-α-olefin rubber has an ethylene content of 45 to 65 mass% and a diene content of 0 to 4.5 mass%.   The method for producing a silane-crosslinked resin molded body according to any one of claims 1 to 3, wherein a blending amount of the inorganic filler is 30 to 100 parts by mass with respect to 100 parts by mass of the base resin.   The manufacturing method of the silane crosslinked resin molded object of any one of Claims 1-4 with which the said silane coupling agent is mixed with the compounding quantity of 3-12 mass parts with respect to 100 mass parts of base resins.   The method for producing a silane-crosslinked resin molded article according to any one of claims 1 to 5, wherein the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.   The method for producing a silane-crosslinked resin molded article according to any one of claims 1 to 6, wherein a silanol condensation catalyst is not substantially mixed in the step (a-1) and the step (a-2). Silane coupling agents 1 to 15 represented by the following general formula (1) with respect to 100 parts by mass of the base resin: 0.01 to 0.6 parts by mass of the organic peroxide, 25 to 120 parts by mass of the inorganic filler. A method for producing a silane crosslinkable resin composition comprising a step (1) of melting and mixing 0.0 part by mass and a silanol condensation catalyst to obtain a mixture,

In general formula (1), R _a11 is a group containing an ethylenically unsaturated group, and R _b11 is an aliphatic carbon.
Hydrocarbon group, a hydrogen atom or ^{Y 13.} Y ¹¹ , Y ¹² and Y ¹³ can be hydrolyzed
An organic group is shown.
In performing the step (1),
The base resin contains 15 to 58% by mass of an ethylene-α olefin rubber having an ethylene content of 45 to 65% by mass and 85 to 42% by mass of a polyolefin resin,
When all of the base resin is melt-mixed in the following step (a-2), the step (1)
Has the following step (a-1), step (a-2) and step (c), and the following step (a-2)
In the case of melting and mixing a part of the base resin in step (1), the step (1) is the following step (a-1).
, Production of a silane cross-linked resin molded article having the step (a-2), the step (b) and the step (c)
Manufacturing method.
Step (a-1): mixing at least the inorganic filler and the silane coupling agent
Step of combining to prepare a mixture Step (a-2): The mixture and all or part of the base resin are combined with the organic peracid.
At a temperature above the decomposition temperature of the organic peroxide in the presence of
By melt mixing and radicals generated from the organic peroxide
The group containing the ethylenically unsaturated group and the base resin are mixed together.
Prepare silane masterbatch by phthalating reaction
Step Step (b): Melt and mix the remainder of the base resin and the silanol condensation catalyst,
Step of preparing a catalyst master batch Step (c): The silane master batch and the silanol condensation catalyst or the catalyst
Process of melt mixing with master batch   The silane crosslinkable resin composition manufactured by the manufacturing method of the silane crosslinkable resin composition of Claim 8.   A silane cross-linked resin molded product produced by the method for producing a silane cross-linked resin molded product according to any one of claims 1 to 7.   A molded article comprising the silane crosslinked resin molded article according to claim 10.   The molded article according to claim 11, wherein the silane crosslinked resin molded body is a coating layer of an electric wire or an optical fiber cable. With respect to 100 parts by mass of base resin containing 15 to 58% by mass of ethylene-α olefin rubber having an ethylene content of 45 to 65% by mass and 85 to 42% by mass of polyolefin resin, 0.01 to Silane obtained by melt-mixing 0.6 parts by mass, 25 to 120 parts by mass of an inorganic filler, 1 to 15.0 parts by mass of a silane coupling agent represented by the following general formula (1), and a silanol condensation catalyst. A silane masterbatch used for the production of a crosslinkable resin composition,

In general formula (1), R _a11 is a group containing an ethylenically unsaturated group, and R _b11 is an aliphatic carbon.
Hydrocarbon group, a hydrogen atom or ^{Y 13.} Y ¹¹ , Y ¹² and Y ¹³ can be hydrolyzed
An organic group is shown.
At least the inorganic filler and the silane coupling agent are mixed to prepare a mixture, and the resulting mixture and all or part of the base resin are decomposed in the presence of the organic peroxide. A silane masterbatch obtained by melting and mixing at a temperature equal to or higher than the temperature, and grafting reaction of the group containing the ethylenically unsaturated group and the base resin with radicals generated from the organic peroxide .