JP2012149162A - Method of manufacturing silane crosslinking resin molding, and molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing silane crosslinking resin molding of high heat resistance that performs silane crosslinking with one process while suppressing the crosslinking inhibition, and to provide a molding of excellent appearance using the method.SOLUTION: In this method of manufacturing silane crosslinking resin molding, a mixture of carrier resin component (B1) containing organic unsaturated silane compound (B-11) with a specified structure and organic peroxide (B-12), a mixture of carrier resin component (C) containing a silanol condensation catalyst, a mixture of carrier resin component (D) containing an antioxidant are melted, mixed, and made to react with each other at the melting temperature of the carrier resin component (B) or higher, and then are brought into contact with moisture to undergo crosslinking.

Description

  The present invention relates to a method for producing a silane cross-linked resin molded article and a molded article produced by the method.

  Conventionally, methods for cross-linking polyolefin resins such as polyethylene include an electron beam cross-linking method in which an electron beam is used for cross-linking and a chemical cross-linking method in which an organic peroxide is decomposed and cross-linked by applying heat after molding. In addition to these crosslinking methods, silane crosslinking methods are known. The silane cross-linking method is a method of obtaining a cross-linked molded article by reacting an organic unsaturated silane compound in the presence of an organic peroxide to obtain a silane graft polymer, and then contacting with moisture in the presence of a silanol condensation catalyst. is there. Among these crosslinking methods, the silane crosslinking method in particular does not require special equipment and is used in a wide range of fields.

  In the silane crosslinking method, generally, a first step of obtaining a silane graft polymer by reacting an organic unsaturated silane compound in the presence of an organic peroxide and crosslinking by contacting with moisture in the presence of a silanol condensation catalyst. It has two steps of the second step. Since this method requires two steps, a silane cross-linked resin molded product could not be molded at a low cost. Furthermore, after storing the silane graft polymer produced in the first step for a long period of time, if silane crosslinking is performed in the second step, a gelled product is generated on the surface or inside of the molded product, causing problems in the appearance of the crosslinked molded product. .

  Thus, a method has been proposed in which an organic unsaturated silane compound is introduced into a carrier polymer and the reaction is performed in one step (see, for example, Patent Document 1). However, in the case of this method, if a large amount of antioxidant is added to improve heat aging characteristics, the graft reaction and the crosslinking reaction are inhibited by the antioxidant in the grafting step and the crosslinking step. As a result, heat resistance may deteriorate. On the other hand, when the crosslinking reaction is promoted by adding a large amount of a crosslinking agent and a crosslinking aid, the crosslinking proceeds too much and the appearance deteriorates.

Japanese Patent Laid-Open No. 03-167229

  An object of the present invention is to provide a method for producing a silane-crosslinked resin molded article having excellent heat resistance and a molded article using the same.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, the first step of performing silane grafting by adding an antioxidant to the carrier resin, and moisture in the presence of a silanol condensation catalyst. It was found that a silane cross-linked resin molded article excellent in heat resistance and appearance can be obtained by performing the second step of cross-linking by bringing it into contact with each other in one step. The present invention has been made based on this finding.

（式中、Ｒ_ａ１１は不飽和炭化水素基、Ｒ_ｂ１１は脂肪族炭化水素基もしくは水素原子あるいはＹ^１３である。Ｙ^１１、Ｙ^１２及びＹ^１３は加水分解する有機基である。Ｙ^１１、Ｙ^１２及びＹ^１３は互いに同じでも異なっていてもよい。）
＜２＞（Ｂ−２１）下記一般式（２）で表される有機不飽和シラン化合物を含有するキャリア樹脂成分（Ｂ２ａ）の混合物と、

（式中、Ｒ_ａ２１は不飽和炭化水素基、Ｒ_ｂ２１は脂肪族炭化水素基もしくは水素原子あるいはＹ^２３である。Ｙ^２１、Ｙ^２２及びＹ^２３は加水分解する有機基である。Ｙ^２１、Ｙ^２２及びＹ^２３は互いに同じでも異なっていてもよい。）
（Ｂ−２２）有機パーオキサイドを含有するキャリア樹脂成分（Ｂ２ｂ）の混合物と、
シラノール縮合触媒を含有するキャリア樹脂成分（Ｃ）の混合物と、
酸化防止剤を含有するキャリア樹脂成分（Ｄ）の混合物とを、
前記キャリア樹脂成分（Ｂ２ａ）と（Ｂ２ｂ）のうちいずれの溶融温度以上の温度で溶融混合して反応させ、次いで水分と接触させて架橋させることを特徴とするシラン架橋樹脂成形体の製造方法、
＜３＞（Ａ−１）ポリオレフィン樹脂１００〜０質量％及び（Ａ−２）スチレン系エラストマー０〜１００質量％を含有するキャリア樹脂（Ａ）をさらに溶融混合させることを特徴とする＜１＞又は＜２＞に記載のシラン架橋樹脂成形体の製造方法、
＜４＞前記有機不飽和シラン化合物が、全樹脂成分の合計１００質量部に対して、０．２〜４．０質量部含有することを特徴とする＜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＞前記有機パーオキサイドが、全樹脂成分の合計１００質量部に対して、０．０３〜０．８質量部含有することを特徴とする＜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＞前記キャリア樹脂混合物（Ｄ）中の樹脂成分に、他の樹脂成分よりも高い溶融温度のものを含むことを特徴とする＜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＞前記キャリア樹脂混合物（Ｃ）中の樹脂成分に、他の樹脂成分よりも高い溶融温度のものを含むことを特徴とする＜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＞前記酸化防止剤が、全樹脂成分の合計１００質量部に対して、０．３〜７質量部含有されることを特徴とする＜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、
＜９＞前記酸化防止剤が、フェノール系酸化防止剤であることを特徴とする＜１＞〜＜８＞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、及び
＜１０＞＜１＞〜＜９＞のいずれか１項に記載の製造方法により得られることを特徴とするシラン架橋樹脂成形体、
を提供するものである。 That is, the present invention
<1> (B-11) a mixture of an organic unsaturated silane compound represented by the following general formula (1) and a carrier resin component (B1) containing (B-12) an organic peroxide;
A mixture of carrier resin component (C) containing a silanol condensation catalyst;
A mixture of carrier resin component (D) containing an antioxidant,
A method for producing a silane-crosslinked resin molded product, characterized by being melt-mixed at a temperature equal to or higher than the melting temperature of the carrier resin component (B1), reacted and then cross-linked by contacting with moisture.

(Wherein R _a11 is an unsaturated hydrocarbon group, R _b11 is an aliphatic hydrocarbon group, a hydrogen atom or Y ^13. Y ¹¹ , Y ¹² and Y ¹³ are hydrolyzing organic groups. Y ¹¹ , Y ¹² and Y ¹³ may be the same as or different from each other.
<2> (B-21) a mixture of carrier resin component (B2a) containing an organic unsaturated silane compound represented by the following general formula (2);

(In the formula, R _a21 is an unsaturated hydrocarbon group, R _b21 is an aliphatic hydrocarbon group, a hydrogen atom, or Y ^23. Y ²¹ , Y ^22, and Y ²³ are hydrolyzing organic groups. Y ²¹ , Y ²² and Y ²³ may be the same as or different from each other.
(B-22) a mixture of carrier resin component (B2b) containing an organic peroxide;
A mixture of carrier resin component (C) containing a silanol condensation catalyst;
A mixture of carrier resin component (D) containing an antioxidant,
A method for producing a silane-crosslinked resin molded article, characterized by melting and mixing at a temperature equal to or higher than any melting temperature of the carrier resin components (B2a) and (B2b), and then crosslinking by contacting with moisture.
<3> A carrier resin (A) containing (A-1) 100 to 0% by mass of a polyolefin resin and (A-2) 0 to 100% by mass of a styrene elastomer is further melt-mixed. <1> Or the manufacturing method of the silane crosslinked resin molding as described in <2>,
<4> The organic unsaturated silane compound is contained in an amount of 0.2 to 4.0 parts by mass with respect to 100 parts by mass in total of all resin components, and any one of <1> to <3> The method for producing a silane-crosslinked resin molded article according to Item,
<5> The organic peroxide is contained in an amount of 0.03 to 0.8 parts by mass with respect to a total of 100 parts by mass of all resin components. A process for producing the silane-crosslinked resin molded article,
<6> The silane according to any one of <1> to <5>, wherein the resin component in the carrier resin mixture (D) includes one having a higher melting temperature than the other resin components. Production method of crosslinked resin molded body,
<7> The silane according to any one of <1> to <6>, wherein the resin component in the carrier resin mixture (C) includes one having a higher melting temperature than the other resin components. Production method of crosslinked resin molded body,
<8> The antioxidant according to any one of <1> to <7>, wherein the antioxidant is contained in an amount of 0.3 to 7 parts by mass with respect to 100 parts by mass in total of all resin components. A method for producing a silane cross-linked resin molded article,
<9> The method for producing a silane-crosslinked resin molded article according to any one of <1> to <8>, wherein the antioxidant is a phenol-based antioxidant, and <10><1> to <9>, a silane-crosslinked resin molded article obtained by the production method according to any one of
Is to provide.

  According to the method for producing a silane cross-linked resin molded article of the present invention, silane cross-linking can be performed efficiently in one step. Moreover, the silane crosslinked resin molding excellent in heat resistance and appearance can be obtained by the method of the present invention.

（式中、Ｒ_ａ１１は不飽和炭化水素基、Ｒ_ｂ１１は脂肪族炭化水素基もしくは水素原子あるいはＹ^１３である。Ｙ^１１、Ｙ^１２及びＹ^１３は加水分解する有機基である。Ｙ^１１、Ｙ^１２及びＹ^１３は互いに同じでも異なっていてもよい。） The silane cross-linked resin molded article of the present invention is a mixture of (B-11) a carrier resin component (B1) containing an organic unsaturated silane compound represented by the following general formula (1) and (B-12) an organic peroxide. When,
A mixture of carrier resin component (C) containing a silanol condensation catalyst;
A mixture of carrier resin component (D) containing an antioxidant,
The carrier resin component (B1) can be obtained by melting and mixing at a temperature equal to or higher than the melting temperature and then bringing it into contact with moisture to cause crosslinking.

(Wherein R _a11 is an unsaturated hydrocarbon group, R _b11 is an aliphatic hydrocarbon group, a hydrogen atom or Y ^13. Y ¹¹ , Y ¹² and Y ¹³ are hydrolyzing organic groups. Y ¹¹ , Y ¹² and Y ¹³ may be the same as or different from each other.

（式中、Ｒ_ａ２１は不飽和炭化水素基、Ｒ_ｂ２１は脂肪族炭化水素基もしくは水素原子あるいはＹ^２３である。Ｙ^２１、Ｙ^２２及びＹ^２３は加水分解する有機基である。Ｙ^２１、Ｙ^２２及びＹ^２３は互いに同じでも異なっていてもよい。）
（Ｂ−２２）有機パーオキサイドを含有するキャリア樹脂成分（Ｂ２ｂ）の混合物と、
シラノール縮合触媒を含有するキャリア樹脂成分（Ｃ）の混合物と、
酸化防止剤を含有するキャリア樹脂成分（Ｄ）の混合物とを、
前記キャリア樹脂成分（Ｂ２ａ）と（Ｂ２ｂ）のうちいずれの溶融温度以上の温度で溶融混合して反応させ、次いで水分と接触させて架橋させて得ることができる。 Moreover, the silane crosslinked resin molded article of the present invention comprises (B-21) a mixture of carrier resin components (B2a) containing an organic unsaturated silane compound represented by the following general formula (2);

(In the formula, R _a21 is an unsaturated hydrocarbon group, R _b21 is an aliphatic hydrocarbon group, a hydrogen atom, or Y ^23. Y ²¹ , Y ^22, and Y ²³ are hydrolyzing organic groups. Y ²¹ , Y ²² and Y ²³ may be the same as or different from each other.
(B-22) a mixture of carrier resin component (B2b) containing an organic peroxide;
A mixture of carrier resin component (C) containing a silanol condensation catalyst;
A mixture of carrier resin component (D) containing an antioxidant,
The carrier resin components (B2a) and (B2b) can be obtained by melting and mixing at a temperature equal to or higher than the melting temperature, and then bringing them into contact with moisture to cause crosslinking.

The mixture containing the carrier resin (B1), (C) and (D) is melt-mixed at a temperature equal to or higher than the melting temperature of the resin component in the carrier resin (B1), so that the organic unsaturated silane in the component (B1) The compound initiates reaction with the organic peroxide. Also, the mixture containing the carrier resin of (B2a) and (B2b), (C) and (D) is melt-mixed at a temperature equal to or higher than any melting temperature of the carrier resin components (B2a) and (B2b). Thus, the organic unsaturated silane compound in the component (B2a) starts to react with the organic peroxide. Thus, you may use the mixture which mix | blended together the organic peroxide and the organic unsaturated silane compound of the specific structure, and used what mixed the organic peroxide and the organic unsaturated silane compound into the separate carrier resin. Also good.
Thereafter, the organic unsaturated silane compound is grafted to the carrier resin component. The grafted functional group can be hydrolyzed in the presence of a silanol catalyst to obtain a silane crosslinked resin molded product. In the present invention, the carrier resin mixture (C) in which the silanol condensation catalyst is mixed with the component (C) and the carrier resin mixture (D) in which the antioxidant is mixed with the component (D) are separated separately. In addition to melt mixing. Thereby, compared with the case where a silanol condensation catalyst and an antioxidant are contained in the same resin component and melt-mixed, crosslinking inhibition can be greatly reduced. For this reason, it is possible to avoid deterioration of the appearance and heat resistance of the molded product due to crosslinking inhibition. By the method of this invention, a silane graft | grafting and bridge | crosslinking can be advanced smoothly and the crosslinked molded object whose gel fraction is about 25-95% can be manufactured efficiently.

The carrier resin used in the above mixture is not particularly limited, and examples thereof include a polyolefin resin described later and a resin component containing a styrene elastomer as necessary. In addition to the carrier resin in the mixture of the components (B1), (B2a), (B2b), (C) and (D), as the optional resin component, the same as the carrier resin in these mixtures, that is, (A- 1) Carrier resin (A) containing 100 to 0% by mass of polyolefin resin and (A-2) 0 to 100% by mass of styrene elastomer may be further melt-mixed.
Further, the resin component in the carrier resin component (D) includes a resin component having a higher melting temperature than the other resin components. Thereby, after the silane grafting is completed and the silane crosslinking proceeds, the antioxidant can be dispersed. For this reason, crosslinking inhibition is reduced and consumption of the antioxidant can be minimized. Therefore, a silane cross-linked resin molded article having excellent appearance and heat resistance can be obtained.
Furthermore, by including the resin component in (C) having a melting temperature higher than that of the other resin components, crosslinking is started after the silane graft has sufficiently progressed. For this reason, a side reaction hardly occurs. As a result, a silane cross-linked resin molded article having an excellent appearance can be obtained.

  Hereinafter, each component used for the manufacturing method of the silane crosslinked resin molding of this invention is demonstrated. In the present invention, a resin in which each component (an organic unsaturated silane compound, an organic peroxide, a silanol condensation catalyst, or an antioxidant) necessary for obtaining a silane-crosslinked resin molded body is mixed is referred to as a carrier resin.

(Carrier resin)
In the method for producing a silane-crosslinked resin molded body of the present invention, the carrier resin used for the components (B1), (B2a), (B2b), (C) and (D) is the following polyolefin resin and / or styrene An elastomer is mentioned. As the carrier resin (A), the same carrier resin used for the components (B1), (B2a), (B2b), (C) and (D) can be used.

Examples of the polyolefin resin used in the present invention include polypropylene resins, ethylene-α-olefin copolymers, and ethylene copolymers other than ethylene-α-olefin copolymers.
Polypropylene resins include propylene homopolymers (homopolypropylene), ethylene-propylene random copolymers, ethylene-propylene block copolymers, propylene and other small amounts of α-olefins (eg, 1-butene, 1-hexene). , 4-methyl-1-pentene, etc.), polypropylene containing atactic propylene as a constituent, and a block copolymer of propylene and ethylene copolymer rubber. In the present specification, the polypropylene resin refers to a copolymer having a propylene component of 85% by mass or more among copolymers having a propylene component and an ethylene component as constituent components in addition to a propylene homopolymer.

  Examples of the ethylene-α-olefin copolymer include LLDPE (linear low density polyethylene, LDPE (low density polyethylene), VLDPE (very low density polyethylene), ethylene-α-olefin copolymer synthesized in the presence of a single site catalyst. In addition to polymers, ethylene components as constituents such as EPR (ethylene-propylene copolymer rubber), EPDM (ethylene-propylene terpolymer rubber), EBR (ethylene-1-butene copolymer rubber), etc. An ethylene copolymer rubber containing 30 to 95% of the ethylene-α-olefin copolymer may be modified with, for example, an unsaturated carboxylic acid such as maleic anhydride.

Examples of the ethylene-based copolymer other than the ethylene-α-olefin copolymer include an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylate alkyl copolymer. It is done.
As the polyolefin resin in the present invention, LLDPE, LDPE, HDPE, VLDPE, an ethylene-α-olefin copolymer synthesized in the presence of a single site catalyst is preferable, and among them, ethylene synthesized in the presence of a single site catalyst is particularly preferable. -Α-olefin copolymers are preferred. Examples of ethylene-α-olefin copolymers synthesized in the presence of a single site catalyst include “AFFINITY” and “ENGAGE” (trade names) from Dow Chemical, “Kernel” from Japan Polyethylene, and Mitsui Chemicals. "Tuffmer" and Prime Polymer's "Evolue" are on the market.

  The said polyolefin resin is 100-0 mass% in a carrier resin component, Preferably, it is 100-40 mass%, More preferably, it is 100-60 mass%, Most preferably, it is 100-70 mass%. When the amount of the polyolefin resin is too small, the crosslinking does not proceed and the heat resistance is not improved.

The styrene elastomer in the present invention is a copolymer mainly composed of a block and random structure of a conjugated diene compound and an aromatic vinyl compound, or a hydrogenated product thereof.
Examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyltoluene. , P-tert-butylstyrene and the like, and one or more are selected, and styrene is preferred among them.
Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene, and one or more are selected. Of these, butadiene is preferable.
Examples of the styrenic elastomer in the present invention include SBS (styrene / butadiene block copolymer), SIS (styrene / isoprene block copolymer), SEBS (hydrogenated SBS), SEEPS, SEPS (hydrogenated SIS), HSBR (hydrogenated styrene / butadiene). Rubber) and the like. Among these, SEBS and SEPS are preferable.
The amount of the styrene-based elastomer is 0 to 100% by mass, preferably 0 to 40% by mass, and more preferably 0 to 30% by mass. When there is too much quantity of a styrene-type elastomer, bridge | crosslinking does not advance but heat resistance falls.

In addition to the resin component described above, various rubbers such as acrylic rubber or rubber softeners may be used as part of the resin component for imparting strength, imparting flame retardancy, imparting flexibility, etc. good.
In general, mineral oil softeners used as rubber softeners are a combined mixture of aromatic rings, naphthene rings and paraffin chains. Paraffin chain carbon number occupying 50% or more of the total carbon number is called paraffin type, naphthene ring carbon number of 30-40% is naphthene type, aromatic carbon number is 30% or more aromatic type It is called and distinguished.
As the rubber softener of the present invention, liquid or low molecular weight synthetic softeners or paraffinic and naphthenic mineral oils can be used.
In the present invention, in addition to the above resin components, in addition to polyurethane, polyester, nylon resin and elastomers thereof, silicone resins and various rubber resins can be appropriately used as long as the heat resistance of the present invention is not impaired. . Among these, as the carrier resin used in the present invention, the above-described polyolefin resin and, if necessary, a resin component containing a styrene-based elastomer are preferable. The above resin component may be one kind of resin, or two or more kinds of resins may be mixed.

  (A-1) polyolefin resin used as a carrier resin (A) component in this invention can mention the same thing as the above-mentioned polyolefin resin. Moreover, as (A-2) styrene-type elastomer used in this invention, the same thing as the above-mentioned styrene-type elastomer can be mentioned.

(B1), (B2a), (B2b) component (B1) component is a mixture of carrier resin component (B1) containing (B-11) an organic unsaturated silane compound and (B-12) an organic peroxide. . The component (B2a) is a mixture of the carrier resin component (B2a) containing (B-21) an organic unsaturated silane compound.
The organic unsaturated silane compound in the mixture of the carrier resin components (B1) and (B2a) is grafted with each resin component by the action of the organic peroxide.

（式中、Ｒ_ａ１１は不飽和炭化水素基、Ｒ_ｂ１１は脂肪族炭化水素基もしくは水素原子あるいはＹ^１３である。Ｙ^１１、Ｙ^１２及びＹ^１３は加水分解する有機基である。Ｙ^１１、Ｙ^１２及びＹ^１３は互いに同じでも異なっていてもよい。） (B-11), (B-21) Organic unsaturated silane compound (B-11) The organic unsaturated silane compound is represented by the following general formula (1).

(Wherein R _a11 is an unsaturated hydrocarbon group, R _b11 is an aliphatic hydrocarbon group, a hydrogen atom or Y ^13. Y ¹¹ , Y ¹² and Y ¹³ are hydrolyzing organic groups. Y ¹¹ , Y ¹² and Y ¹³ may be the same as or different from each other.

（式中、Ｒ_ａ２１は不飽和炭化水素基、Ｒ_ｂ２１は脂肪族炭化水素基もしくは水素原子あるいはＹ^２３である。Ｙ^２１、Ｙ^２２及びＹ^２３は加水分解する有機基である。Ｙ^２１、Ｙ^２２及びＹ^２３は互いに同じでも異なっていてもよい。）
前記一般式（１）におけるＲ_ａ１１は、一般式（２）におけるＲ_ａ２１と同義であり、一般式（１）におけるＲ_ｂ１１は、一般式（２）におけるＲ_ｂ２１と同義である。また一般式（１）におけるＹ^１１、Ｙ^１２、Ｙ^１３は、それぞれ、一般式（２）におけるＹ^２１、Ｙ^２２、Ｙ^２３と同義である。下記に説明するものであれば、特に制限なく使用することができる。
以下の有機不飽和シラン化合物の説明は、一般式（１）をもって説明し、一般式（２）の有機不飽和シラン化合物の説明は省略する。 (B-21) The organic unsaturated silane compound is represented by the following general formula (2).

(In the formula, R _a21 is an unsaturated hydrocarbon group, R _b21 is an aliphatic hydrocarbon group, a hydrogen atom, or Y ^23. Y ²¹ , Y ^22, and Y ²³ are hydrolyzing organic groups. Y ²¹ , Y ²² and Y ²³ may be the same as or different from each other.
R _a11 in the general formula (1) has the same meaning as R _a21 in the general formula (2), and R _b11 in the general formula (1) has the same _meaning as R _b21 in the general formula (2). Moreover, Y < ¹¹ >, Y < ¹² >, Y < ¹³ > in General formula (1) is synonymous with Y < ²¹ >, Y < ²² >, Y < ²³ > in General formula (2), respectively. Any of those described below can be used without any particular limitation.
The following explanation of the organic unsaturated silane compound will be made with the general formula (1), and explanation of the organic unsaturated silane compound of the general formula (2) will be omitted.

R _a11 of the organic unsaturated silane compound represented by the general formula (1) is an unsaturated hydrocarbon group, and examples thereof include a vinyl group, a methacryloxy group, and an isocyanate group. As R _a11 , a vinyl group is preferable.
R _b11 is an aliphatic hydrocarbon group, a hydrogen atom, or Y ¹³ described later. Examples of the aliphatic hydrocarbon group include monovalent aliphatic hydrocarbon groups having 1 to 8 carbon atoms excluding the aliphatic unsaturated hydrocarbon group. R _b11 in the present invention is preferably Y ¹³ described later.
Y ¹¹ , Y ¹² and Y ¹³ are organic groups that are hydrolyzed. Y ¹¹ , Y ¹² and Y ¹³ may be the same as or different from each other. These groups are preferably alkoxy groups, and examples thereof include methoxy, ethoxy, butoxy, acetyl and the like. Among these, methoxy or ethoxy is preferable from the viewpoint of reactivity.

As a preferable organic unsaturated silane compound, an organic unsaturated silane compound having a high hydrolysis rate is preferable. In particular, an organic unsaturated silane compound in which R _b11 is Y ¹³ and Y ¹¹ , Y ¹² and Y ¹³ are the same is preferable.
Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, and allyltriethoxysilane. it can.
This organic unsaturated silane compound is preferably contained in an amount of 0.2 to 4.0 parts by mass with respect to 100 parts by mass in total of all resin components. If this amount is too small, grafting of the organic unsaturated silane compound will not proceed sufficiently, and the heat resistance and the degree of crosslinking of the resulting resin molded product will be reduced. Further, the crosslinking at the silane graft portion does not proceed, the crosslinking at the normal polymer main chain occurs, and the appearance of the obtained resin molded product is significantly impaired. Moreover, when there is too much quantity of an organic unsaturated silane compound, superposition | polymerization of organic unsaturated silane compounds will advance and many gelled products will produce | generate. As a result, the appearance of the obtained resin molding is impaired.

(B-12), (B-22) Organic peroxide (B-12) Organic peroxide and (B-22) organic peroxide are synonymous. Any of those described below can be used without any particular limitation.
Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5. -Dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3 5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-Butylperoxyisopropyl carbonate, di Cetyl peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide and the like. Of these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (Tert-Butylperoxy) hexyne-3 is most preferred.
This amount is preferably 0.03 to 0.8 parts by mass in a total of 100 parts by mass of all resin components. If this content is too small, the graft reaction of the organic unsaturated silane compound will not proceed, so the appearance and heat resistance of the resulting resin molded product will be significantly reduced. Moreover, when there is too much content, bridge | crosslinking of polymers will advance and the external appearance of the resin molding obtained will be impaired remarkably.

As a carrier resin containing an organic unsaturated silane compound and an organic peroxide, one type or two or more types may be used. Moreover, you may mix what added the organic unsaturated silane compound and the organic peroxide to two or more resin, respectively.
In addition, when one type of carrier resin is used, the organic unsaturated silane compound and the organic peroxide may be added at the same time or may be mixed after being added separately. When there are two or more types of carrier resins, an organic unsaturated silane compound (B21) is added to one type of resin to form a mixture of carrier resin components (B2a), and organic peroxide (B-22) is added to other resins. In addition, a mixture of the carrier resin component (B2b) may be used and these may be used separately. Moreover, after mixing 2 or more types of resin previously, an organic unsaturated silane compound and an organic peroxide may be added simultaneously or separately, and the obtained mixture may be used.

Further, as the carrier resin of the components (B1), (B2a), and (B2b), when the component (A) is contained, a carrier resin having a melting temperature higher than the melting temperature of the resin component (A) is used. preferable. By using a resin having a temperature equal to or higher than the melting temperature of the component (A) as the components (B1), (B2a), and (B2b), the component (A) is sufficiently melted. Therefore, the organic unsaturated silane compound is efficiently grafted to the carrier resin component (A). As a result, a resin molded body having a good appearance can be obtained.
The component (B1) can be produced by impregnating a carrier resin with (B-11) an organic unsaturated silane compound and (B-12) an organic peroxide and mixing the carrier resin. The component (B2a) can be produced by impregnating the carrier resin with (B-21) an organic unsaturated silane compound and mixing it with the carrier resin. The component (B2b) can be produced by impregnating the carrier resin with (B-22) organic peroxide and mixing it with the carrier resin.

(C) Component As the silanol condensation catalyst in the present invention, an organic tin compound, a metal soap, a platinum compound, or the like is used. Specific silanol condensation catalysts include, specifically, dibutyltin 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.
The silanol condensation catalyst in the present invention has a function of binding the grafted organic unsaturated silane compound in the presence of moisture by a condensation reaction. Based on the action of the silanol condensation catalyst, the polymers are cross-linked through the organic unsaturated silane compound. As a result, a resin molded body having excellent heat resistance can be obtained.
The amount of the silanol condensation catalyst is preferably 0.005 parts by mass to 0.2 parts by mass with respect to 100 parts by mass in total of all resin components. If the content is too small, the heat resistance of the resin molded product obtained without sufficient crosslinking reaction cannot be obtained. Moreover, when there is too much content, since a crosslinking reaction will advance rapidly or reaction will advance partially, the external appearance of the resin molding obtained will fall remarkably.

  In addition, as carrier resin containing a silanol condensation catalyst, you may use said carrier resin 1 type (s) or 2 or more types. When two or more types of carrier resins are used, a silanol condensation catalyst may be added to a certain resin, and other resins may be mixed together, or after mixing two or more types of resins in advance, the silanol condensation catalyst may be added. May be added.

Furthermore, as the carrier resin of the component (C), when it contains the component (A), it has a melting temperature higher than the melting temperature of the component (A) and the resin components of the components (B1), (B2a), and (B2b). It is preferable to use a carrier resin. When the component (A) is not contained, it is preferable to use a carrier resin having a melting temperature higher than the melting temperature of the resin components (B1), (B2a), and (B2b). Thereby, the organounsaturated silane compound can be sufficiently grafted to the resin of the component (A) and the components (B1), (B2a), and (B2b). After the grafting is sufficiently advanced, the resin component (C) is melted and the silanol condensation catalyst starts to work. Therefore, it is possible to suppress incomplete crosslinking reaction and generation of a silane condensate that is not grafted. As a result, a silane-crosslinked flame-retardant resin molded article having good heat resistance and appearance can be obtained.
(C) The carrier resin containing a silanol condensation catalyst can be produced by mixing it with the carrier resin component (C) using a kneading apparatus that normally uses a silanol condensation catalyst.

Component (D) As an antioxidant in the present invention, polymerization of 4,4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline Amine-based antioxidants such as pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl) Phenolic antioxidants such as -4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis ( 2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptobenzimidazole and Zinc salts, pentaerythritol - tetrakis (3-lauryl - thiopropionate) and sulfur-based antioxidants and the like. Among these, a phenolic antioxidant is preferable, and specifically, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) is preferable.
From the viewpoint of heat aging characteristics, the content of the antioxidant in a total of 100 parts by mass of all resin components is preferably 0.3 to 7 parts by mass. More preferably, it is 0.4-6 mass parts, and 0.5-5 mass parts is especially preferable.

In addition, as carrier resin containing antioxidant, you may use said carrier resin 1 type (s) or 2 or more types. Moreover, you may add antioxidant to two or more resin, respectively.
(D) component can be manufactured by mixing with carrier resin component (D) using the kneading apparatus which uses antioxidant normally.

In the present invention, in addition to the above components, a metal deactivator, a weathering agent, a flame retardant (auxiliary) agent, a filler, a lubricant and other additives may be appropriately blended within a range not impairing the object of the present invention. it can. The procedure for adding these additives is not particularly limited, but it is preferable to add them to the component (D) or to add them before or while adding the component (D) to the molding machine.
Examples of metal deactivators include N, N′-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.
Examples of the weathering agent to be added include general weathering agents such as a light stabilizer (for example, a hindered amine-based light stabilizer) and an ultraviolet absorber (for example, a benzotriazole-based ultraviolet absorber, carbon black).
Flame retardants (auxiliaries) and fillers include magnesium hydroxide, aluminum hydroxide, carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compounds, quartz, talc, Examples include calcium carbonate, magnesium carbonate, and white carbon.
Examples of the lubricant include hydrocarbon-based, fatty acid-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based, and silicone-based materials. Among these, hydrocarbon-based and silicone-based materials are preferable.

Although the silane crosslinked resin molding of this invention is not specifically limited, For example, it can manufacture with the following method.
(B1), (C) and (D) component, or (B2a), (B2b), (C) and (D) component mixture, if necessary, further blending (A) component with, for example, a blender The resin composition can be obtained by melt-kneading with a kneading apparatus usually used such as a uniaxial kneading extruder, a biaxial kneading extruder, a Banbury mixer, a kneader, or a roll. The melt kneading is performed at a temperature equal to or higher than the melting temperature of the components (B1), (B2a) and (B2b), and if necessary, the component (A). Furthermore, it is preferable to knead at a melting temperature higher than the resins of the components (B1) and (C) or the components (B2a), (B2b) and (C). Here, when the resin component has a melting point, the melting temperature refers to the melting point measured by DSC (differential scanning calorimeter), and since the styrene-based elastomer does not have a melting point, the temperature at which the hard segment polystyrene melts. Let it be the melting temperature. The resin composition thus obtained can be allowed to stand at room temperature, or left in warm water, water, or moist heat to cause contact with moisture to advance the crosslinking reaction, thereby obtaining a silane crosslinked resin molded product.

The component (A) and the components (B1), (C), and (D), or the mixture of the components (B2a), (B2b), (C), and (D) can be produced by the following method.
(A) A component can be manufactured by melt-kneading each component using kneading apparatuses normally used, such as a uniaxial kneading extruder, a biaxial kneading extruder, a Banbury mixer, a kneader, and a roll. The kneading temperature is preferably 150 ° C to 240 ° C. As the component (A), one kind of material may be used as it is, or two or more kinds of materials may be mixed and used in a blender or the like.
The mixture of the component (B1) can be obtained by impregnating a carrier resin with an organic unsaturated silane compound and an organic peroxide. The impregnation method is not particularly limited, but a mixer capable of heating is preferable, and examples thereof include a super mixer and a Henschel mixer. The impregnation temperature is not particularly limited, but the impregnation is preferably performed at a temperature lower by about 10 to 40 ° C. than the melting point of the carrier resin. Note that a carrier resin may be impregnated with a mixed solution in which an organic peroxide is dissolved in an organic unsaturated silane compound.
The mixture of the component (B2a) can be obtained by impregnating a carrier resin with an organic unsaturated silane compound. Although the impregnation method is not particularly limited, it can be carried out in the same manner as the mixture of the component (B1). Moreover, the mixture of the component (B2b) can be obtained by impregnating a carrier resin with an organic organic peroxide. Although the impregnation method is not particularly limited, it can be carried out in the same manner as the mixture of the component (B1).
(C) Component mixture and (D) component mixture are prepared by melting each component using a commonly used kneading apparatus such as a single-screw kneading extruder, twin-screw kneading extruder, Banbury mixer, kneader, or roll. What is necessary is just to knead | mix. The kneading temperature is preferably 150 ° C to 240 ° C.

When adding other components in addition to the above-mentioned components, a blender that is obtained by melt kneading using a kneading apparatus commonly used such as a uniaxial kneading extruder, a biaxial kneading extruder, a Banbury mixer, a kneader, or a roll in advance. It is preferable to blend with.
In addition, when storing the above components, it is preferable to store at least the component (D) separately from other components. The components (B1) and (B2a) are preferably sealed and stored in order to suppress volatilization of the organic unsaturated silane compound.

Next, various molded articles can be mentioned as the silane cross-linked resin molded product obtained by the production method of the present invention. For example, an insulated wire, a cable, an optical cord, etc. can be obtained by the manufacturing method of the present invention.
Insulated electric wires and cables can be produced by subjecting conductors, optical fibers, aggregated insulated wires, and other molded bodies to extrusion coating by the above-described method and silane crosslinking using an ordinary extruder.
Although there is no restriction | limiting in particular in the thickness of an insulated wire, Preferably, a 0.15-3 mm thing can be obtained. The covering layer may have a multilayer structure.
Also, by the production method of the present invention, a conductor is extrusion-coated to form a coating layer, and then left at room temperature, or left in warm water, water, or moist heat to have a heat-resistant silane crosslinked coating layer A wiring material can be obtained. Furthermore, in order to improve heat resistance, the coating layer after extrusion can be further crosslinked by other methods.

Further, as a method for crosslinking, an electron beam irradiation crosslinking method can be employed.
In the case of the electron beam crosslinking method, the resin composition is extruded to form a coating layer, and then crosslinked by irradiating an electron beam by a conventional method. The electron beam dose is appropriately 1 to 30 Mrad, and in order to efficiently crosslink, the resin composition constituting the coating layer includes a methacrylate compound such as trimethylolpropane triacrylate, and an allyl group such as triallyl cyanurate. You may contain polyfunctional compounds, such as a compound, a maleimide type compound, and a divinyl type compound, as a crosslinking adjuvant.

  The molded article of the present invention is not particularly limited in size and shape, for example, in addition to the above-described insulated wires, cables, optical cords, etc., power plugs, connectors, sleeves, boxes, tape base materials, Various molded bodies such as tubes and sheets can be produced. By the production method of the present invention, a crosslinked product can be obtained by a conventional molding method such as injection molding. Sheets, tubes, and the like can also be manufactured in the same manner as the electric wire coating, and if necessary, further crosslinking can be performed as in the case of the wiring material.

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

[Examples 1 to 16]
As for the content of each component of Examples 1 to 16 in Table 1-1 and Table 1-2, the numerical values in the tables are parts by mass except for “ratio of resin components”.
Regarding the component (A), Example 8 was dry blended with a blender, Example 10 was mixed with a Banbury mixer (BM), and other examples were obtained by using resin pellets as they were.
For the component (B), Examples 1 to 12 were prepared by impregnating the carrier resin with this mixed solution after dissolving the (B-12) organic peroxide in the (B-11) organic unsaturated silane compound. , (B1) component mixture was obtained.
For Examples 15 and 16, (B-21) an organic unsaturated silane compound was impregnated into a carrier resin (engage 7256 or kernel KF360) to obtain a mixture of components (B2a). In addition, (B-22) organic peroxide was impregnated into the carrier resin (UE320) to obtain a mixture of components (B2b).
The components (C) and (D) were obtained by melt-kneading each component using a Banbury mixer.
Each resin component was blended at a ratio shown in “Ratio (%) of resin component” in Table 1-1 and Table 1-2, and blended with a blender to obtain a resin mixture. For example, in Example 1, the resin component of component (A) is 55%, the resin component of component (B1) is 20%, the resin component of component (C) is 5%, and the resin component of component (D) is 20%. The composition as shown in “Composition after mixing” in Table 1 was obtained.

Next, the above-mentioned resin mixture was coated on a conductor (tin-plated annealed copper single wire having a conductor diameter of 0.8 mmφ) by an extrusion method using an extrusion coating apparatus for producing an electric wire, thereby producing an insulated wire. The outer diameter was 2.4 mm (coating layer thickness 0.8 mm).
Extrusion was carried out at a cylinder temperature of 180 ° C. and a head temperature of 190 ° C. The obtained electric wire was used after being left in a thermostatic chamber at 60 ° C. and 90% for 24 hours.

[Comparative Examples 1 to 7]
The content of each component of Comparative Examples 1 to 7 in Table 2 is “parts by mass” except for the “ratio of resin component”.
Components (A), (B1), and (F) shown in Table 2 were prepared by the following method.
The component (A) in Table 2 was obtained by using resin pellets as they were.
About the (B1) component of Table 2, the liquid mixture which melt | dissolved the organic peroxide in the organic unsaturated silane compound was prepared. The resin component (B1) was obtained by impregnating this mixed liquid into a carrier resin.
The component (F) shown in Table 2 was melt kneaded using a Banbury mixer to produce each resin composition.
Next, resin components (A), (B1), and (F) components were blended as shown in Table 2, and blended with a blender to obtain a resin composition.
(A), (B1), and (F) component were mix | blended in the ratio shown in "ratio (%) of the resin component" of Table 2, and it blended with the blender, and obtained the resin mixture. For example, in Comparative Example 1, the resin component of component (A) is 60%, the resin component of component (B1) is 20%, and the resin component of component (C) is 20%. The composition as “composition after mixing” was obtained.

Next, the above resin composition resin composition is coated on the conductor (tin-plated annealed copper single wire having a conductor diameter of 0.8 mmφ) by an extrusion method using an extrusion coating apparatus for producing an electric wire, Manufactured. The outer diameter was 2.4 mm (coating layer thickness 0.8 mm).
Extrusion was carried out at a cylinder temperature of 180 ° C. and a head temperature of 190 ° C. The obtained electric wire was used after being left in a thermostat bath of 90% at 60 ° C. for 24 hours.

Each component material shown in the table is as follows.
(A) Component (A-1) Component Among the following materials, when it has a melting point, the melting temperature refers to the melting point measured by DSC (differential scanning calorimeter). Since the styrene-based elastomer does not have a melting point, the melting temperature is the temperature at which the hard segment polystyrene melts.
・ Polyethylene Product name: Engage 7256, Manufacturer: Dow Chemical, Melting temperature: 75 ° C
Product Name: Engage 8842, Manufacturer: Dow Chemical, Melting Temperature: 38 ° C
Product name: Kernel KF360, manufacturer: Nippon Polychem Co., Ltd., melting temperature: 91 ° C
・ Linear low density polyethylene Product name: UE320, Manufacturer: Nippon Polyethylene Co., Ltd., Melting temperature: 121 ° C
-Ethylene-ethyl acrylate copolymer Product name: NUC6510, manufacturer: Nippon Unicar Co., Ltd., melting temperature: 94 ° C
-Block polypropylene Product name: BC8A, manufacturer: Nippon Polypropylene Co., Ltd., melting temperature: 162 ° C
(A-2) Component / Styrene Elastomer (SEEPS)
Product name: Septon 4077, manufacturer: Kuraray Co., Ltd., melting temperature: 80-100 ° C

(B) Component (B-11), (B-21)
・ Organic unsaturated silane compounds (vinyltrimethoxysilane)
Product Name: Dynasylan, Manufacturer: Evonik Degussa (B-12), (B-22)
・ Organic peroxide Product name: Park Mill D, Manufacturer: Nippon Oil & Fat Co., Ltd.
Product name: Perhexa 25B, Manufacturer: Nippon Oil & Fat Co., Ltd.

(C) Silanol condensation catalyst / dibutyltin dilaurate Product name: TN-12, Manufacturer: Sakai Chemical Industry (D) Antioxidant / phenolic antioxidant Product name: Irganox 1010, Manufacturer: BASF Japan Product name: Irga Knox MD1024, Manufacturer: BASF Japan

The following evaluation was performed on each of the obtained insulated wires, and the obtained results are shown in Table 2.
(1) Heat deformation Heat deformation was measured according to the method of UL1581. The measurement temperature was 160 ° C., and the load was 3N. 50% or less is acceptable.
(2) Appearance The appearance of the electric wires was confirmed visually. Samples with no problem in appearance were marked with ◯, samples with slight defects but no problem on the product were marked with △, and samples with many defects and poor appearance were marked with x. Δ or more is acceptable.
(3) Gel fraction About 0.1 g was collected from the coating layer of the electric wire and immersed in xylene at 120 ° C. for 20 hours, and the gel fraction was calculated from the mass change rate before and after immersion (mass after immersion / mass before immersion). Asked. The values are shown in Table 1-1 and Table 2.

From the results of Table 1-1, Table 1-2, and Table 2, Comparative Examples 1 to 7 all had inferior heat deformation and appearance. This is thought to be because crosslinking inhibition by the antioxidant occurred because the silanol condensation catalyst and the antioxidant were added to the same carrier resin component and mixed.
On the other hand, Examples 1-16 of this invention were able to obtain the molded article excellent in the external appearance without a heat deformation.

Claims (10)

(B-11) a mixture of a carrier resin component (B1) containing an organic unsaturated silane compound represented by the following general formula (1) and (B-12) an organic peroxide;
A mixture of carrier resin component (C) containing a silanol condensation catalyst;
A mixture of carrier resin component (D) containing an antioxidant,
A method for producing a silane-crosslinked resin molded article, characterized by melting and mixing at a temperature equal to or higher than the melting temperature of the carrier resin component (B1), allowing the mixture to react, and then bringing it into contact with moisture for crosslinking.

(Wherein R _a11 is an unsaturated hydrocarbon group, R _b11 is an aliphatic hydrocarbon group, a hydrogen atom or Y ^13. Y ¹¹ , Y ¹² and Y ¹³ are hydrolyzing organic groups. Y ¹¹ , Y ¹² and Y ¹³ may be the same as or different from each other. (B-21) a mixture of carrier resin component (B2a) containing an organic unsaturated silane compound represented by the following general formula (2);

(In the formula, R _a21 is an unsaturated hydrocarbon group, R _b21 is an aliphatic hydrocarbon group, a hydrogen atom, or Y ^23. Y ²¹ , Y ^22, and Y ²³ are hydrolyzing organic groups. Y ²¹ , Y ²² and Y ²³ may be the same as or different from each other.
(B-22) a mixture of carrier resin component (B2b) containing an organic peroxide;
A mixture of carrier resin component (C) containing a silanol condensation catalyst;
A mixture of carrier resin component (D) containing an antioxidant,
A method for producing a silane-crosslinked resin molded article, characterized in that the carrier resin components (B2a) and (B2b) are melt-mixed and reacted at a temperature equal to or higher than any melting temperature, and then contacted with moisture to crosslink.   The carrier resin (A) containing (A-1) 100 to 0% by mass of a polyolefin resin and (A-2) 0 to 100% by mass of a styrene elastomer is further melt-mixed. The manufacturing method of the silane crosslinked resin molded object of description.   The said organic unsaturated silane compound contains 0.2-4.0 mass parts with respect to a total of 100 mass parts of all the resin components, The silane of any one of Claims 1-3 characterized by the above-mentioned. A method for producing a crosslinked resin molded article.   The said organic peroxide contains 0.03-0.8 mass part with respect to a total of 100 mass parts of all the resin components, The silane crosslinked resin of any one of Claims 1-4 characterized by the above-mentioned. Manufacturing method of a molded object.   The resin component in the carrier resin mixture (D) includes a resin component having a melting temperature higher than that of other resin components. The silane-crosslinked resin molded product according to any one of claims 1 to 5, Production method.   The resin component in the carrier resin mixture (C) includes a resin component having a higher melting temperature than the other resin components. The silane-crosslinked resin molded article according to any one of claims 1 to 6, Production method.   The said antioxidant is contained 0.3-7 mass parts with respect to a total of 100 mass parts of all the resin components, The silane crosslinked resin molding of any one of Claims 1-7 characterized by the above-mentioned. Body manufacturing method.   The method for producing a silane-crosslinked resin molded article according to any one of claims 1 to 8, wherein the antioxidant is a phenol-based antioxidant. A silane cross-linked resin molded article obtained by the production method according to any one of claims 1 to 9.