JP6523012B2 - Heat-resistant silane cross-linked resin molded product and heat-resistant silane cross-linkable resin composition, method for producing them, silane master batch, and heat-resistant product - Google Patents

Description

  The present invention relates to a heat-resistant silane cross-linked resin molded product, a heat-resistant silane cross-linkable resin composition, a method for producing them, a silane master batch, and a heat-resistant product using the heat-resistant silane cross-linked resin molded product.

  Various wire materials such as insulated wires, cables, cords, optical fiber core wires or optical fiber cords used for internal wiring or external wiring of electric and electronic devices have various characteristics such as flame resistance and mechanical properties (for example, tensile properties) The characteristics of are required. As a material used for the coating layer of these wiring materials, the resin composition which mix | blended metal hydrates, such as magnesium hydroxide and aluminum hydroxide, with resin in large quantities is mentioned.

In addition, the wiring material may be heated to a temperature of about 80 to 105 ° C., or even about 125 ° C., when used for a long time, and heat resistance to the temperature may also be required. In order to satisfy such a demand, a method is taken to crosslink (crosslink) the resin in the resin composition.
Examples of the method for crosslinking the resin include an electron beam crosslinking method in which the resin composition is irradiated with an electron beam, and a chemical crosslinking method. As a chemical crosslinking method, a crosslinking method in which an organic peroxide or the like is thermally decomposed to cause a crosslinking reaction of a resin, and a silane crosslinking method described below are known. Among these crosslinking methods, in particular, the silane crosslinking method can be used in a wide range of fields because it often does not require special equipment.

In the silane crosslinking method, a hydrolyzable silane coupling agent having an unsaturated group is graft-reacted to a resin in the presence of an organic peroxide to obtain a silane graft resin, and then the silane grafting is performed in the presence of a silanol condensation catalyst. This is a method of obtaining a crosslinked resin by contacting the resin with water.
In order to produce a molded article comprising a halogen-free heat-resistant silane crosslinked resin using a silane crosslinking method, first, a silane graft resin in which a hydrolyzable silane coupling agent is grafted on a resin such as a polyolefin resin is contained. A silane masterbatch, a heat-resistant masterbatch obtained by kneading a resin and an inorganic filler, and a catalyst masterbatch containing a silanol condensation catalyst are respectively prepared. These masterbatches are then melt mixed and shaped and then contacted with moisture.

However, in this method, when an inorganic filler exceeding 100 parts by mass with respect to 100 parts by mass of the resin is mixed, the silane master batch and the heat resistant master batch are dry mixed and then uniform in a single screw extruder or a twin screw extruder. It becomes difficult to melt and knead. As a result, the appearance of the molded body is deteriorated. In addition, the physical properties of the molded body are lowered. Furthermore, the extrusion load at the time of kneading can not be increased.
As described above, the ratio of the inorganic filler is limited as described above in order to melt and knead uniformly after dry mixing of the silane master batch and the heat resistant master batch. Therefore, it was difficult to achieve high flame retardancy and high heat resistance.

  In the first place, when a large amount of inorganic filler is blended as described above, it becomes difficult to prepare a desired silane masterbatch. In the case of blending a large amount of inorganic filler, generally, it is common to use a closed mixer such as a continuous kneader, a pressure kneader, or a Banbury mixer. However, when a kneader or the like is used, the hydrolyzable silane coupling agent volatilizes before the grafting reaction. Therefore, it becomes difficult to prepare a silane masterbatch.

  Then, when using a kneader etc., the method of making it graft-react in a single screw extruder can be considered after mixing a heat resistant masterbatch, a hydrolysable silane coupling agent, and an organic peroxide. However, in this method, appearance defects may occur in the molded product due to variations in grafting reaction and the like. In addition, the number of manufacturing processes is two, and this is a problem in terms of manufacturing cost.

  Moreover, the method of knead | mixing a silane masterbatch and an inorganic filler is also considered. However, in this method, during preparation (during kneading) of the silane-grafted resin, the hydrolyzable silane coupling agent undergoes a hydrolysis and condensation reaction to easily cause appearance defects. Furthermore, if the heating temperature during kneading is not constant, desired physical properties can not be imparted to the molded body. In addition, there are many manufacturing problems, and the number of processes is two, which is a major problem in terms of manufacturing cost.

As a silane crosslinking method other than the above method, for example, Patent Document 1 discloses an inorganic filler surface-treated with a silane coupling agent to a resin component formed by mixing a polyolefin resin and a maleic anhydride resin, a silane coupling agent, A method has been proposed in which the organic peroxide and the crosslinking catalyst are sufficiently melt-kneaded in a kneader and then molded in a single screw extruder.
In Patent Documents 2 to 4, a vinyl aromatic thermoplastic elastomer composition containing a block copolymer or the like as a base polymer and a softening agent for a non-aromatic rubber as a softening agent is inorganic surface-treated with a silane surface. A method of partially crosslinking using an organic peroxide via a filler has been proposed.
Furthermore, Patent Document 5 discloses silane crosslinkability containing a base polymer containing an ethylene vinyl acetate resin having a vinyl acetate content of 33% by mass or 45% by mass, an organic peroxide, a silane coupling agent, and a metal hydrate. A process is described for producing a flame retardant polyolefin component, melt molding it with a silanol condensation catalyst composition, and crosslinking in the presence of water.

JP 2001-101928 A Unexamined-Japanese-Patent No. 2000-143935 JP, 2000-315424, A JP 2001-240719 A JP, 2012-255077, A

In the method described in Patent Document 1, the resin may be crosslinked during melt-kneading with a kneader or the like. Furthermore, silane coupling agents other than the silane coupling agent which is surface-treating the inorganic filler may volatilize or may condense with each other. Therefore, desired heat resistance can not be provided to the molded object obtained. In addition, appearance defects occur in the molded body.
Even in the methods described in Patent Documents 2 to 4, since the resin does not have a sufficient network structure, the bond between the resin and the inorganic filler is easily broken at high temperature, and the heat resistance of the obtained molded article is sufficient. is not. Under high temperature, the molded body may melt, for example, the insulating material may be peeled off during soldering of the wire. In addition, during secondary processing, deformation or foaming may occur.
The method described in Patent Document 5 has a problem that when the silane crosslinkable flame-retardant polyolefin component and the silanol condensation catalyst are melt-formed, the appearance is roughened and the appearance is deteriorated.

  By the way, the wiring material is manufactured in various sizes according to the application and the like. Particularly in the case of a small diameter wiring material, the thickness of the covering layer is reduced. In addition, in general, small diameter wiring materials are molded at a high molding speed (in the case of extrusion molding, extrusion speed). When the coating layer is thinly molded or molded at a high molding speed as described above, appearance defects easily occur in the obtained coating layer (molded body). Even when adopting such a condition that appearance defects are likely to occur, it is desirable to have a method of manufacturing a wiring material while suppressing the occurrence of appearance defects.

An object of the present invention is to overcome the problems of the conventional silane crosslinking method, and to provide a heat-resistant silane-crosslinked resin molded product having an excellent appearance and a method for producing the same.
Another object of the present invention is to provide a silane masterbatch, a heat-resistant silane crosslinkable resin composition, and a method for producing the same, which can form the heat-resistant silane-crosslinked resin molded product.
Furthermore, this invention makes it a subject to provide the heat resistant product containing the heat resistant silane crosslinked resin molded object obtained by the manufacturing method of the heat resistant silane crosslinked resin molded object.

  The present inventors have prepared a silane master batch prepared using a base resin containing only a resin having a vinyl acetate content of 30% by mass or less as an ethylene vinyl acetate resin in a silane crosslinking method, a silanol condensation catalyst or a silanol condensation When a heat-resistant silane cross-linked resin molded product is produced by a specific manufacturing method of mixing with a catalyst master batch containing a catalyst, the heat-resistant silane cross-linked resin molded product obtained is excellent even when adopting conditions which easily cause appearance defects. It has been found that it is possible to give a good appearance. The present inventors have further researched on the basis of this finding and made the present invention.

That is, the object of the present invention is achieved by the following means.
It is a manufacturing method of the heat resistant silane crosslinked resin molded object which has a <1> following process (1), process (2), and process (3) ,
Process (1): 0.01 to 0.6 mass of organic peroxide with respect to 100 mass parts of base resin
Part, 40 to 300 parts by mass of metal hydrate , and the above base in the presence of a radical
A grafting reaction site capable of grafting onto a glass resin, and the metal hydrate
Coupling agent 1 to 15.0 having a reactive site capable of chemically bonding with
Step of melt-mixing parts by mass and silanol condensation catalyst to obtain a mixture Step (2): Step of forming the mixture obtained in the step (1) to obtain a formed body Step (3): Step (2): By bringing the molded body obtained in 2.) into contact with water,
Step of obtaining a fat-molded product The base resin of the step (1) is free of ethylene vinyl acetate resin (EVA-i) having a vinyl acetate content of more than 30% by mass, and has a vinyl acetate content of 30% by mass or less Containing 48 to 85 % by mass of ethylene vinyl acetate resin (EVA-ii), and further containing at least one of ethylene rubber and a styrenic elastomer,
When all the base resin is melt mixed in the following step (a-2) in the above step (1), the above step (1) includes the following step (a-1), step (a-2) and step (a) have c), when a portion of the base resin melt mixing the following step (a-2), wherein step (1) is the following step (a-1), step (a-2), step ( b) and step (c),
A method for producing a heat resistant silane cross-linked resin molded product.
Step (a-1): mixing at least the metal hydrate and the silane coupling agent
A step of preparing a mixture step (a-2): said organic peroxide and said mixture and all or part of said base resin
Dissolved at a temperature above the decomposition temperature of the organic peroxide in the presence of
The silane coupling agent and the base resin are
By shift reaction, Engineering to prepare the silane masterbatch
Step (b): Melt-mixing the remainder of the base resin and the silanol condensation catalyst
Step of preparing a catalyst masterbatch Step (c): the silane masterbatch, the silanol condensation catalyst or the catalyst
Step <2> of the ethylene rubber and the styrene elastomer melt mixing the medium masterbatch, the total content of the base resin, heat resistant silane crosslinkable resin according to Ru der least 5 wt% <1> Method for producing a molded body.
The manufacturing method of the heat resistant silane crosslinked resin molded object as described in <1> or <2> whose vinyl acetate content of <3> above-mentioned ethylene vinyl acetate resin (EVA-ii) is 13-30 mass%.
<4> Any one of <1> to <3>, wherein the silane coupling agent is mixed in an amount of more than 4 parts by mass and 15.0 parts by mass or less with respect to 100 parts by mass of the base resin The manufacturing method of the heat resistant silane crosslinked resin molding as described in 4.
The manufacturing method of the heat resistant silane crosslinked resin molded object as described in any one of <1>-<4> whose <5> silane coupling agent is vinyl trimethoxysilane or vinyl triethoxysilane.
The heat resistant silane crosslinked resin molded object as described in any one of <1>-<5> which does not mix a silanol condensation catalyst substantially in <6> said process (a-1) and process (a-2). Manufacturing method.

0.01 to 0.6 parts by mass of an organic peroxide, 40 to 300 parts by mass of a metal hydrate, and 100 parts by mass of a <7> base resin, and a graft reaction is performed on the base resin in the presence of a radical Step (1): (1) melt-mixing 1 to 15.0 parts by mass of a silane coupling agent having a possible grafting reaction site and a reaction site capable of chemically bonding with the metal hydrate, and a silanol condensation catalyst; A heat-resistant silane crosslinkable resin composition having
The base resin of the step (1) is an ethylene vinyl acetate resin (EVA having a vinyl acetate content of 30% by mass or less, containing no ethylene vinyl acetate resin (EVA-i) having a vinyl acetate content of more than 30% by mass 48 to 85 % by mass of ii) and further containing at least one of an ethylene rubber and a styrenic elastomer,
When all the base resin is melt mixed in the following step (a-2) in the above step (1), the above step (1) includes the following step (a-1), step (a-2) and step (a) have c), when a portion of the base resin melt mixing the following step (a-2), wherein step (1) is the following step (a-1), step (a-2), step ( b) and step (c),
A method of producing a heat resistant silane crosslinkable resin composition.
Step (a-1): mixing at least the metal hydrate and the silane coupling agent
A step of preparing a mixture step (a-2): said organic peroxide and said mixture and all or part of said base resin
Dissolved at a temperature above the decomposition temperature of the organic peroxide in the presence of
The silane coupling agent and the base resin are
By shift reaction, Engineering to prepare the silane masterbatch
Step (b): Melt-mixing the remainder of the base resin and the silanol condensation catalyst
Step of preparing a catalyst masterbatch Step (c): the silane masterbatch, the silanol condensation catalyst or the catalyst
Process of Melt-mixing with Medium Master Batch <8> A heat-resistant silane crosslinkable resin composition produced by the method of producing a heat-resistant silane crosslinkable resin composition according to <7>.
The heat resistant silane crosslinked resin molded object manufactured with the manufacturing method of the heat resistant silane crosslinked resin molded object of any one of <9> said <1>-<6>.
The heat resistant product containing the heat resistant silane crosslinked resin molded object as described in <10> said <9>.
<11> Vinyl acetate content does not contain ethylene vinyl acetate resin (EVA-i) exceeding 30 mass%, and ethylene vinyl acetate resin (EVA-ii) having vinyl acetate content of 30 mass% or less is 48 to 85 0.01 to 0.6 parts by mass of an organic peroxide and 40 to 300 parts by mass of a metal hydrate with respect to 100 parts by mass of a base resin containing at least one of ethylene rubber and a styrene-based elastomer. And 1 to 15.0 parts by mass of a silane coupling agent having a grafting reaction site capable of grafting to the base resin in the presence of a radical, and a reaction site capable of chemically bonding to the metal hydrate, and silanol condensation A silane masterbatch used for producing a heat-resistant silane crosslinkable resin composition obtained by melt-mixing a catalyst with the catalyst,
A mixture is prepared by mixing at least the metal hydrate and the silane coupling agent, and the obtained mixture and all or a part of the base resin in the presence of the organic peroxide. The silane masterbatch obtained by melt-mixing at the temperature more than decomposition | disassembly temperature, and making the said silane coupling agent and the said base resin graft-react .

  The numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

According to the present invention, a heat-resistant silane-crosslinked resin molded article having an excellent appearance can be produced even if the problem of the conventional silane crosslinking method is overcome and the appearance defect is apt to occur.
Therefore, according to the present invention, it is possible to provide a heat-resistant silane-crosslinked resin molded article having an excellent appearance and a method for producing the same. In addition, it is possible to provide a silane master batch, a heat-resistant silane crosslinkable resin composition, and a method for producing the same, which can form a heat-resistant silane-crosslinked resin molded product excellent in such an appearance. Furthermore, it is possible to provide a heat-resistant product comprising a heat-resistant silane-crosslinked resin molded product excellent in appearance.

First, each component used in the present invention will be described.
<Base resin>
The base resin used in the present invention contains an ethylene vinyl acetate resin (EVA-ii) having a vinyl acetate content of 30% by mass or less, as a resin component having a site to which a silane coupling agent can undergo grafting reaction. It does not contain ethylene vinyl acetate resin (EVA-i) whose content exceeds 30 mass%. In the present invention, not containing EVA-i means not actively using EVA-i.
The base resin may contain a resin other than EVA-ii. As resins other than EVA, a grafting reaction site of a silane coupling agent and a site capable of a grafting reaction in the presence of an organic peroxide, for example, an unsaturated bond site of a carbon chain or a carbon atom having a hydrogen atom are mainly used It is not particularly limited as long as it is a resin or rubber of a polymer having in the chain or at the end thereof.
In addition to the resin component, the base resin may contain an oil component described later.
In the base resin, the content of each component is appropriately determined so that the total amount of each component is 100% by mass, and preferably selected from the following range.

(Resin component)
The base resin contains EVA-ii having a vinyl acetate content (VA content) of 30% by mass or less. Thereby, at least the excellent flame retardancy can be imparted to the heat-resistant silane cross-linked resin molded product.
EVA-ii is not particularly limited as long as it is a resin comprising a copolymer of ethylene and vinyl acetate and having a VA content of 30% by mass or less. In the present invention, the VA content is preferably 13 to 30% by mass. As a result, even under conditions in which appearance defects easily occur, a heat-resistant silane-crosslinked resin molded article having both excellent flame retardancy and an excellent appearance can be produced.
In the present invention, the VA content is a value determined in accordance with JIS K 7192.
Examples of EVA-ii include Evaflex (trade name, manufactured by Mitsui Dupont Polychemicals Co., Ltd.).

  The content of EVA-ii is 5 to 100% by mass in 100% by mass of the base resin. When the content is small, it may not be possible to impart excellent flame retardancy and appearance to the heat-resistant silane cross-linked resin molded article. The content of EVA in the base resin is preferably 45 to 90% by mass, and more preferably 48 to 85% by mass. When the content of EVA-ii is in the above range, reaction between the resins is suppressed during the silane grafting reaction (step (a-2)) even if the condition in which appearance defects easily occur is suppressed, and the flame retardancy is reduced. In addition to, it can give an even better appearance.

  EVA-i is the same as EVA-ii except that the VA content is different.

  As said resin other than EVA-ii which base resin may contain, polyolefin resin etc. are mentioned. The above resins other than EVA-ii may be used alone or in combination of two or more. The same applies to each resin component such as polyethylene.

The polyolefin-based resin is not particularly limited as long as it is a resin comprising a polymer obtained by polymerizing or copolymerizing a compound having an ethylenically unsaturated bond, and those conventionally used in heat-resistant resin compositions It can be used. For example, a resin comprising each polymer such as polyethylene, polypropylene, ethylene-α-olefin copolymer, an acid copolymer component or a polyolefin copolymer having an acid ester copolymer component, or a rubber or elastomer comprising each of the above polymers Etc. Among them, polyethylene, polypropylene, ethylene rubber and styrenic elastomers are preferable.
Although the compounding quantity (content) of polyolefin resin is not specifically limited, It is preferable that it is 0-95 mass% in 100 mass% of base resins, It is more preferable that it is 0-55 mass%, 0-45 More preferably, it is mass%. When the polyolefin resin is contained at the above content, a strong network can be formed, and high heat resistance can be imparted.

Polyethylene is not particularly limited as long as it is a polymer containing an ethylene component as a constituent component, and examples thereof include homopolymers consisting only of ethylene and copolymers containing an ethylene component. The copolymer includes a copolymer of ethylene and 5 mol% or less of α-olefylene (excluding propylene), and ethylene and a non-olefin of 1 mol% or less having only carbon, oxygen and hydrogen atoms as functional groups. Copolymers are included (e.g. JIS K 6748). The above-mentioned .alpha.-olefins and non-olefins can be used without particular limitation, which are conventionally used as copolymer components of polyethylene.
Examples of polyethylene include high density polyethylene (HDPE), low density polyethylene (LDPE), ultra-high molecular weight polyethylene (UHMW-PE), linear low density polyethylene (LLDPE), and ultra low density polyethylene (VLDPE). Among them, linear low density polyethylene and low density polyethylene are preferable.
Although the compounding quantity of resin which consists of polyethylene is not specifically limited, It is more preferable that it is 0-35 mass% in 100 mass% of base resins.

Polypropylene is not particularly limited as long as it is a polymer containing a propylene component as a component. Polypropylene includes homopolymers of propylene (h-PP), random polypropylene (r-PP) which is a copolymer with a small amount of ethylene and / or 1-butene, and rubber components such as ethylene rubber. It contains block polypropylene (b-PP) or the like dispersed in PP or r-PP. Among these, random polypropylene is preferable.
As such PP, for example, Novatec (registered trademark) PP (manufactured by Japan Polypropylene Corporation), Sun Aroma (trade name, manufactured by San Aroma International), Sumitomo Nobrene (registered trademark, manufactured by Sumitomo Chemical Co., Ltd.), and Prime Polypropylene (registered trademark), Prime Polymer Co., Ltd.) and the like.
Although the compounding quantity of resin which consists of polypropylene is not specifically limited, It is preferable that it is 0-35 mass% in 100 mass% of base resins, and it is more preferable that it is 0-25 mass%.

The ethylene-α-olefin copolymer is not particularly limited, but preferably includes a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms (excluding those contained in polyethylene and polypropylene). . The α-olefin is not particularly limited, and examples thereof include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. Specifically, as the ethylene-α-olefin copolymer, ethylene-propylene copolymer (EPR), ethylene-butylene copolymer (EBR), and ethylene-α- synthesized in the presence of a single site catalyst An olefin copolymer etc. are mentioned.
Although the compounding quantity of resin which consists of an ethylene-alpha-olefin copolymer is not specifically limited, It is more preferable that it is 0-35 mass% in 100 mass% of base resins.

The copolymer having the acid copolymerization component or the acid ester copolymerization component is not particularly limited as long as it is a copolymer other than EVA-i and EVA-ii (both may be collectively referred to as EVA). The acid copolymerization component or acid ester copolymerization component is not particularly limited, and includes carboxylic acid compounds such as (meth) acrylic acid and acid ester compounds such as alkyl (meth) acrylate. Here, the alkyl group of the alkyl (meth) acrylate is preferably one having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group. As a polyolefin copolymer (except what is contained in polyethylene) which has an acid copolymerization component or an acid ester copolymerization component, For example, ethylene- (meth) acrylic acid copolymer, ethylene (meth) acrylic acid alkylate Copolymer etc. are mentioned. Among them, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer are preferable.
Although the compounding quantity of resin which consists of a copolymer which has an acid copolymerization component or an acid ester copolymerization component is not specifically limited, It is preferable that it is 0-20 mass% in 100 mass% of base resins, and 0-15 mass. More preferably, it is%.

The rubber that can be used in the present invention is not particularly limited as long as it is a rubber (including an elastomer) composed of a polymer having a compound having an ethylenically unsaturated bond as a constituent, but ethylene rubber is preferably mentioned. Preferred examples of the ethylene rubber include a copolymer of ethylene and an α-olefin, and a rubber composed of a ternary copolymer of ethylene, an α-olefin and a diene. The diene component of the terpolymer may be a conjugated diene component or a non-conjugated diene component, with a non-conjugated diene component being preferred. That is, examples of the terpolymer include terpolymers of ethylene, α-olefin and conjugated diene, and terpolymers of ethylene, α-olefin and nonconjugated diene, etc. Copolymers with alpha-olefins and terpolymers of ethylene with alpha-olefins and nonconjugated dienes are preferred.
As an alpha-olefin structural component, a C3-C12 alpha-olefin is mentioned suitably, As a specific example, what was mentioned by the ethylene-alpha-olefin copolymer is mentioned. Specific examples of the conjugated diene component include those listed as styrene elastomers, and butadiene and the like are preferable. Specific examples of the non-conjugated diene component include, for example, dicyclopentadiene (DCPD), ethylidene norbornene (ENB), 1,4-hexadiene and the like, with ethylidene norbornene being preferred.
As a rubber which consists of a copolymer of ethylene and an alpha olefin, ethylene propylene rubber, ethylene butene rubber, ethylene octene rubber etc. are mentioned, for example. Examples of the rubber composed of a terpolymer of ethylene, an α-olefin and a 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, and ethylene-propylene rubber and ethylene-propylene-diene rubber are more preferable.

  The amount of ethylene constituent component (referred to as ethylene content) in the copolymer is preferably 20 to 70% by mass, more preferably 25 to 55% by mass, and still more preferably 27 to 52% by mass. Even if the ethylene content is less than 20% by mass or more than 70% by mass, the rubber may be inferior in flexibility and low temperature properties. The ethylene content is measured according to the method described in ASTM D3900.

  Although the compounding quantity of rubber | gum is not specifically limited, 0-40 mass% is preferable in 100 mass% of base resins, 0-25 mass% is more preferable, 3-20 mass% is more preferable. When the blending amount of the rubber is 40% by mass or less, an excellent appearance can be maintained even when the extruder is stopped.

The elastomer that can be used in the present invention is not particularly limited as long as it is composed of a polymer having a compound having an ethylenically unsaturated bond as a constituent, but other than the above, preferably a styrene elastomer is mentioned. . The styrene-based elastomer refers to a polymer composed of an aromatic vinyl compound as a component in its molecule. Therefore, in the present invention, if the polymer contains an ethylene component in its molecule but contains an aromatic vinyl compound component, it is classified as a styrenic elastomer.
As such a styrene-based elastomer, one comprising a block copolymer and a random copolymer of a conjugated diene compound and an aromatic vinyl compound, or a hydrogenated product thereof is preferable. As a component of the aromatic vinyl compound in the polymer, for example, styrene, p- (tert-butyl) styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N- Each component, such as diethyl-p-aminoethyl styrene and vinyl toluene, may be mentioned. Among these, the styrene component is preferable. The components of the aromatic vinyl compound are used singly or in combination of two or more. Examples of the component of the conjugated diene compound include each component such as butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Among these, butadiene component is preferable. The components of the conjugated diene compound are used singly or in combination of two or more. Moreover, as a styrene-type elastomer, you may use the elastomer which does not contain a styrene component and contains an aromatic vinyl compound other than styrene.

As a styrene-type elastomer, it is preferable that content (styrene content) of a styrene structural component is 30 mass% or more. If the styrene content is less than 30% by mass, the oil resistance may decrease or the abrasion resistance may decrease.
Examples of the styrene-based elastomer include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butylene-styrene block copolymer (SBS), styrene -Ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), hydrogenated SBS, hydrogenated SIS, hydrogenated styrene butadiene rubber (HSBR), hydrogen And those made of hydrogenated acrylonitrile butadiene rubber (HNBR) and the like.
As a styrene-type elastomer, it is preferable to use SEPS, SEEPS, SEBS individually or in combination of 2 or more types of these.

  As the styrene-based elastomer, commercially available products can be used. For example, Septon 4077, Septon 4055, Septon 8105 (all trade names, manufactured by Kuraray Co., Ltd.), Dynalon 1320 P, Dynalon 4600 P, 6200 P, 8601 P, 9901 P (All trade names) , Manufactured by JSR Corporation, and the like.

Although the compounding quantity of an elastomer is not specifically limited, It is preferable that it is 0-45 mass% in 100 mass% of base resins, and it is more preferable that it is 0-35 mass%. When the content of the styrene-based elastomer exceeds 45% by mass, heat resistance and long-term heat resistance may be adversely affected.
The blending amount of the styrene-based elastomer and the blending amount of the ethylene rubber are preferably in the above ranges, respectively, but in total, it is more preferably 0 to 50% by mass, and 5 to 50% by mass More preferably, it is particularly preferably 10 to 35% by mass. When the total blending amount of the styrene-based elastomer and the ethylene rubber is in the above range, excellent heat resistance, strength and flexibility can be imparted.

  Each of the above polymers may be acid-modified. The acid used for the acid modification is not particularly limited, and includes unsaturated carboxylic acids or derivatives thereof. Examples of unsaturated carboxylic acids include maleic acid, itaconic acid and fumaric acid. Examples of unsaturated carboxylic acid derivatives include maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, itaconic acid diester, itaconic acid diester, itaconic acid anhydride, fumaric acid monoester, fumaric acid diester, fumaric acid anhydride, etc. be able to. Among these, maleic acid and maleic anhydride are preferable. The amount of acid modification is usually about 0.1 to 7% by mass in one molecule of acid-modified polyolefin resin.

(Oil component)
Although the oil component which the base resin may contain is not particularly limited, an organic oil may be mentioned. When the base resin contains an organic oil, it is possible to produce a silane heat-resistant, silane-crosslinked resin molded article having an excellent appearance by suppressing the generation of bumps (tubes protruding on the surface).
The organic oil is a mixed oil including an oil consisting of a hydrocarbon having an aromatic ring, an oil consisting of a hydrocarbon having a naphthene ring, and an oil consisting of a hydrocarbon having a paraffin chain. Among organic oils, one having 30% or more of the number of carbon atoms constituting an aromatic ring relative to the total number of carbons constituting an aromatic ring, a naphthene ring and a paraffin chain is referred to as an aromatic organic oil. Moreover, the carbon atom number which comprises an aromatic ring says non-aromatic organic oil with less than 30% with respect to the said total carbon number. Specifically, the number of carbon atoms constituting the naphthene ring is 30 to 40% with respect to the total carbon number, and the number of carbon atoms constituting the paraffin chain is less than 50% with respect to the total carbon number Oils and paraffin oils in which the number of carbon atoms constituting the paraffin chain is 50% or more with respect to the total number of carbons are included.
As the organic oil, paraffin oil or naphthenic oil is preferred, and paraffin oil is more preferred in view of mechanical strength. When using the said rubber | gum (ethylene rubber) or a styrene-type elastomer especially as resin, it is preferable to use paraffin oil or naphthene oil together.
Examples of non-aromatic organic oils include Diana Process Oil PW90, PW380 (all trade names, manufactured by Idemitsu Kosan Co., Ltd.), Cosmo Neutral 500 (manufactured by Cosmo Oil Co., Ltd.), and the like.
Although the compounding quantity of oil is not specifically limited, When base resin contains oil, it is preferable that it is 0-30 mass% in 100 mass% of base resins, and it is more preferable that it is 3-25 mass%. When the blending amount of the oil is in the above range, the temperature of the kneaded material rapidly rises during the kneading, and the silane grafting reaction tends to proceed uniformly.

<Organic peroxide>
The organic peroxide generates radicals at least by thermal decomposition, and functions as a catalyst to cause a grafting reaction by a radical reaction on the resin component of the silane coupling agent. In particular, when the silane coupling agent contains an ethylenically unsaturated group, it functions to cause a grafting reaction by a radical reaction between the ethylenically unsaturated group and the resin component (including the extraction of hydrogen radicals from the resin component). .
The organic peroxide is not particularly limited as long as it generates a radical, and for example, general formulas: R ¹ -OO-R ² , R ³ -OO-C (= O) R ⁴ , R ⁵ C (= O) -OO (C = O) compounds represented by ^{R 6} is preferably. Here, R ^{1 to} R ⁶ each independently represent an alkyl group, an aryl group or an acyl group. Among R ^{1 to} R ⁶ of each compound, preferred are those in which all are alkyl groups, or those in which either is an alkyl group and the remainder is an acyl group.

  As such an organic peroxide, for example, dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2 5-Dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxy Benzoate, tert-butyl peroxyisopropyl carbonate, diaceto Peroxide, lauroyl peroxide, may be mentioned tert- butyl cumyl peroxide and the like. Among these, dicumyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2 in terms of odor, color and scorch stability. Preferred is 5-di- (tert-butylperoxy) hexyne-3.

The decomposition temperature of the organic peroxide is preferably 120 to 195 ° C., particularly preferably 125 to 180 ° C.
In the present invention, the decomposition temperature of the organic peroxide means a temperature at which a decomposition reaction occurs in two or more kinds of compounds in a certain temperature or temperature range when heating the organic peroxide of a single composition. means. Specifically, it refers to a temperature at which heat absorption or heat generation starts when heated from room temperature at a temperature rising rate of 5 ° C./minute in a nitrogen gas atmosphere by thermal analysis such as DSC method.

<Metal hydrate>
In the present invention, the metal hydrate is not particularly limited as long as it has a site capable of chemically bonding with a reactive site such as a silanol group of a silane coupling agent by a hydrogen bond or a covalent bond on the surface. Can. In this metal hydrate, as a site which can be chemically bonded to the reactive site of the silane coupling agent, OH group (hydroxyl group, water molecule of hydrous water or water of crystallization, OH group such as carboxy group), amino group, SH group etc. Can be mentioned.

Such metal hydrates include compounds having a hydroxyl group or water of crystallization. For example, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and further calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate etc. In addition, inorganic acid salts or inorganic oxides such as hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite and the like can be mentioned.
Among the metal hydrates, at least one of aluminum hydroxide, magnesium hydroxide, calcium carbonate and magnesium carbonate is preferable, and at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide and calcium carbonate is more preferable. preferable.
The metal hydrate may be used alone or in combination of two or more.

  0.2-10 micrometers is preferable, 0.3-8 micrometers is more preferable, 0.4-5 micrometers is still more preferable, and, as for the average particle diameter of a metal hydrate, 0.4-3 micrometers is especially preferable. When the average particle diameter is in the above range, the effect of holding the silane coupling agent is high, and the heat resistance is excellent. In addition, metal hydrates are less likely to cause secondary aggregation when mixed with a silane coupling agent, and the appearance is excellent. The average particle size is dispersed with alcohol or water, and is determined by an optical particle size measuring apparatus such as a laser diffraction / scattering type particle size distribution measuring apparatus.

  The metal hydrate can use the surface treatment metal hydrate surface-treated by the silane coupling agent etc. For example, as a silane coupling agent surface-treated metal hydrate, Kisuma 5L, Kisuma 5P (all are trade names, magnesium hydroxide, Kyowa Chemical Co., Ltd., etc.), aluminum hydroxide and the like can be mentioned. The surface treatment amount of the metal hydrate with the silane coupling agent is not particularly limited, and is, for example, 3% by mass or less.

<Silane coupling agent>
The silane coupling agent used in the present invention is a chemical bond of a metal hydrate with a grafting reaction site (group or atom) capable of grafting to a resin component in the presence of radicals generated by decomposition of organic peroxide. It is sufficient if it has at least a reactive site capable of silanol condensation and a reactive site capable of silanol condensation (including a site formed 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, The hydrolysable silane coupling agent which has a hydrolysable group at the terminal is preferable. The silane coupling agent more preferably has at its terminal a group containing an amino group, a glycidyl group or an ethylenically unsaturated group and a group containing a hydrolysable group, and more preferably ethylene at its terminal. It is a silane coupling agent having a group containing a unsaturated unsaturated group and a group containing a hydrolyzable group. Although it does not specifically limit as group containing an ethylenically unsaturated group, For example, a vinyl group, an allyl group, a (meth) acryloyloxy group, a (meth) acryloyloxy alkylene group, p-styryl group etc. are mentioned. In addition, these silane coupling agents may be used in combination with other terminal coupling groups.

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

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

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

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

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

The silane coupling agent is preferably a silane coupling agent having a high hydrolysis rate, more preferably a silane coupling agent in which R _b11 is Y ¹³ and Y ¹¹ , Y ¹² and Y ¹³ are the same as each other. Or a hydrolyzable silane coupling agent in which at least one of Y ¹¹ , Y ¹² and Y ¹³ is a methoxy group, more preferably R _b11 is Y ¹³ and Y ¹¹ , Y ¹² and Y ¹³ are Silane coupling agents which are identical to one another. Particularly preferred are hydrolyzable silane coupling agents which are all methoxy groups.

Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltrimethoxysilane. Mention may be made of ethoxysilane, vinylsilane such as vinyltriacetoxysilane, and (meth) acryloxysilane such as methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane and methacryloxypropylmethyldimethoxysilane.
3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane as having a glycidyl group at the end And 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
Among the above-mentioned silane coupling agents, silane coupling agents having a vinyl group and an alkoxy group at the end are more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.

  The silane coupling agent may be used alone or in combination of two or more. Further, it may be used as it is or may be used after diluting with a solvent or the like.

<Silanol condensation catalyst>
The silanol condensation catalyst functions to condense the silane coupling agent grafted on the resin component in the presence of water. Based on the function of the silanol condensation catalyst, the resin components are crosslinked via the silane coupling agent. As a result, a heat-resistant silane cross-linked resin molded product having excellent heat resistance is obtained.

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

<Carrier resin>
The silanol condensation catalyst is optionally mixed with the resin and used. The resin (also referred to as a carrier resin) is not particularly limited, but each resin described in the base resin can be used. Among the base resins, the carrier resin is more preferably a resin containing ethylene as a component, and more preferably a resin of polyethylene, because the carrier resin has high affinity to the silanol condensation catalyst and is excellent in heat resistance.

<Additives>
The heat-resistant silane cross-linked resin molded product and the heat-resistant silane cross-linkable resin composition of the present invention comprise various additives generally used in electric wires, electric cables, electric cords, sheets, foams, tubes and pipes. You may contain in the range which does not impair the effect of these. As such an additive, for example, a crosslinking assistant, an antioxidant, a lubricant, a metal deactivator, or a filler (including a flame retardant (co) agent) other than the above metal hydrate and the like can be mentioned. .

  The antioxidant is not particularly limited, and examples thereof include an amine antioxidant, a phenol antioxidant, and a sulfur antioxidant. Examples of amine antioxidants include polymers of 4,4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, and polymers of 2,2,4-trimethyl-1,2-dihydroquinoline. . As a phenol antioxidant, for example, 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 sulfur antioxidants include bis (2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptobenzimidazole and zinc salts thereof, pentaerythritol- Tetrakis (3-lauryl-thiopropionate) and the like can be mentioned. The antioxidant can be added in an amount of preferably 0.1 to 15.0 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the base resin.

Next, the production method of the present invention will be specifically described.
The “method of producing a heat-resistant silane-crosslinked resin molded product” of the present invention and the “method of producing a heat-resistant silane-crosslinkable resin composition” of the present invention each perform at least the following step (1). Therefore, the “method of producing a heat-resistant silane-crosslinked resin molded product” of the present invention and the “method of producing a heat-resistant silane-crosslinkable resin composition” of the present invention will be described together below (in the description common to both production methods) May be referred to as the manufacturing method of the present invention).
Moreover, the "silane masterbatch" of this invention is manufactured by the following process (a-1) and process (a-2) (both processes are put together and it is mentioned process (a)). Therefore, the "method for producing a silane masterbatch" of the present invention will be described in the production method of the present invention.

Step (1): 0.01 to 0.6 parts by mass of organic peroxide, 40 to 300 parts by mass of metal hydrate, and 1 to 15.0 parts of silane coupling agent based on 100 parts by mass of the base resin Step of melt-mixing a part and a silanol condensation catalyst to obtain a mixture step (2): forming a mixture obtained in step (1) to obtain a formed body step (3): obtained in step (2) Contacting the molded body with water to obtain a heat resistant silane crosslinked resin molded body

When this process (1) melt-mixes all of base resin in the following process (a-2), it has a process (a-1), a process (a-2), and a process (c), and the following process When melt-mixing a part of base resin by (a-2), it has a process (a-1), a process (a-2), a process (b), and a process (c).
Step (a-1): A step of mixing at least a metal hydrate and a silane coupling agent to prepare a mixture Step (a-2): a mixture and all or part of a base resin, an organic peroxide Melt mixing in the presence of the organic peroxide at a temperature above the decomposition temperature of the organic peroxide to prepare a silane masterbatch step (b): melt mixing the remainder of the base resin and the silanol condensation catalyst to form a catalyst masterbatch Step (c): Melt mixing of silane masterbatch and silanol condensation catalyst or catalyst masterbatch Here, mixing means obtaining a homogeneous mixture.

  In the production method of the present invention, the “base resin” is a resin for forming a heat-resistant silane cross-linked resin molded product or a heat-resistant 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 the step (1). For example, in the step (a), the “embodiment in which the whole amount (100 parts by mass) of the base resin is blended” and the “embodiment in which a part of the base resin is blended” are included.

In the present invention, “a 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), a base resin A part of the resin component which comprises these, and a part resin component (For example, specific resin component whole quantity among several resin components) which comprises base resin. As for a part of base resin, the one part resin component which comprises base resin is preferable.
Further, “the remainder of the base resin” refers to the remainder of the base resin excluding the portion used in step (a-2), and more specifically, the remainder of the base resin itself (base resin And the rest of the resin component constituting the base resin, and the remaining resin component constituting the base resin.

When a part of the base resin is blended in the step (a-2), 100 parts by mass of the blended amount of the base resin in the step (1) is the amount of the base resin mixed in the step (a-2) and the step (b) It is a total amount.
Here, when the balance of the base resin is blended in the step (b), preferably 80 to 99% by mass, more preferably 94 to 98% by mass is blended in the base resin in the step (a-2), In the step (b), preferably 1 to 20% by mass, more preferably 2 to 6% by mass is blended.

  In the step (1), the blending amount (total blending amount) of EVA-ii is as described above.

  In the step (1), the mixing amount (blending amount) of the organic peroxide is 0.01 to 0.6 parts by mass, and 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the base resin. preferable. When the mixing amount of the organic peroxide is less than 0.01 parts by mass, the grafting reaction does not proceed, and the silane coupling agents are condensed to obtain sufficient heat resistance, in some cases mechanical strength, and reinforcement. There are things I can not do. On the other hand, if the amount is more than 0.6 parts by mass, many of the resin components may be directly crosslinked by side reaction to form bumps, which may cause appearance defects. In particular, appearance defects occur remarkably under conditions where appearance defects are likely to occur. That is, by setting the blending amount of the organic peroxide within this range, it is possible to carry out a grafting reaction within an appropriate range, and to obtain a composition excellent in extrudability without generating gel-like bumps. it can.

  The mixing amount of the metal hydrate is 40 to 300 parts by mass, preferably 80 to 280 parts by mass with respect to 100 parts by mass of the base resin. If the mixing amount of the metal hydrate is less than 40 parts by mass, the grafting reaction of the silane coupling agent may be nonuniform. As a result, sufficient heat resistance may not be obtained, or the appearance may be degraded. Furthermore, there are cases where sufficient flame retardancy can not be obtained. On the other hand, when it exceeds 300 parts by mass, the load at the time of molding or kneading becomes very large, and secondary molding may become difficult.

The mixing amount of the silane coupling agent is 1 to 15.0 parts by mass, preferably more than 4 parts by mass and 15.0 parts by mass or less, and more preferably 6 to 15 with respect to 100 parts by mass of the base resin. .0 parts by mass.
When the mixing amount of the silane coupling agent is less than 1 part by mass, the crosslinking reaction may not proceed sufficiently and may not exhibit excellent heat resistance. In particular, appearance defects tend to occur under conditions where appearance defects are likely to occur. On the other hand, if it exceeds 15 parts by mass, the silane coupling agent can not be adsorbed to the surface of the metal hydrate more than that, and the silane coupling agent volatilizes during kneading, which is not economical. In addition, the non-adsorbing silane coupling agent may be condensed to cause bumps and burns in the molded product, which may deteriorate the appearance. In particular, it is remarkable under conditions where appearance defects easily occur.

If the mixing amount of the silane coupling agent is more than 4.0 parts by mass and not more than 15.0 parts by mass, both the crosslinking reaction between the resin components and the condensation reaction between the silane coupling agents can be suppressed. Thus, it is possible to produce a silane heat-resistant silane cross-linked resin molded product having a clean appearance. In the step (a-2), when the specific amount of the silane coupling agent is used, the grafting reaction of the silane coupling agent and the condensation reaction of the silane coupling agents become dominant. Thereby, it is possible to suppress the cross-linking reaction between the resin components which causes the appearance roughness and unevenness. Further, in the step (a-2), many silane coupling agents are bound or adsorbed to the metal hydrate and immobilized. As a result, the condensation reaction between the silane coupling agents bound or adsorbed to the metal hydrate is less likely to occur.
Thus, by using a specific amount of the silane coupling agent, any of the crosslinking reaction between resin components and the condensation reaction between the silane coupling agents can be suppressed, and the silane heat-resistant silane crosslinked with a beautiful appearance It is believed that resin moldings can be produced.

  The blending 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 mixing amount of the silanol condensation catalyst is within the above range, the crosslinking reaction by the condensation reaction of the silane coupling agent is likely to proceed almost uniformly, and the heat resistance, appearance and physical properties of the heat resistant silane crosslinked resin molding are excellent. Also improves the quality. That is, when the mixing amount of the silanol condensation catalyst is too small, sufficient heat resistance and sometimes mechanical strength may not be obtained. On the other hand, if the amount is too large, the crosslinking reaction due to the condensation reaction of the silane coupling agent may be nonuniform, and the appearance and productivity may be poor.

In the silane masterbatch, all or part of the base resin, the organic peroxide, the metal hydrate, and the silane coupling agent are introduced into the mixer in the above amounts, and the organic peroxide is decomposed. It prepares by the process (a) of melt-kneading heating at the temperature more than temperature.
In the step (a), “melt-mixing all or part of the base resin, organic peroxide, metal hydrate and silane coupling agent” does not specify the order of mixing in melt mixing. It means that you may mix in any order. That is, the order of mixing in step (a) is not particularly limited.
Also, the method of mixing the base resin is not particularly limited. For example, a base resin which is mixed and prepared in advance may be used, or each component, for example, each of the resin component and the oil component may be separately mixed.

  In the present invention, the silane coupling agent is not introduced alone into the silane masterbatch but is premixed with the metal hydrate. That is, at least a metal hydrate and a silane coupling agent are mixed to prepare a mixture (step (a-1)). The silane coupling agent thus premixed is present so as to surround the surface of the metal hydrate, and a part or all of the silane coupling agent is adsorbed or bonded to the metal hydrate. This can reduce the volatilization of the silane coupling agent during the subsequent melt mixing. Moreover, it can also prevent that the silane coupling agent which is not adsorb | sucked or couple | bonded with a metal hydrate condenses, and melt-kneading becomes difficult. Furthermore, desired shapes can also be obtained during extrusion.

As such mixing method, preferably, organic peroxide, metal hydrate and silane coupling agent are used for several minutes to several hours at a temperature lower than the decomposition temperature of organic peroxide, preferably at room temperature (25.degree. C.) After mixing (dispersing) to a certain extent, dry or wet, a method of melt mixing this mixture and the base resin may be mentioned. This mixing is preferably performed by a mixer-type kneader such as a Banbury mixer or a kneader. In this way, excessive cross-linking reaction between resin components can be prevented, and the appearance becomes excellent.
In this mixing method, a base resin may be present as long as a temperature below the decomposition temperature is maintained. In this case, it is preferable to melt and mix the metal oxide and the silane coupling agent together with the base resin at the above temperature (step (a-1)). In the present invention, the above components can be melt mixed at one time. In this case, part or all of the silane coupling agent is adsorbed or bonded to the metal hydrate during melt mixing.

The method for mixing the metal hydrate and the silane coupling agent is not particularly limited, and even if the organic peroxide is mixed simultaneously with the metal hydrate etc., the metal hydrate and the silane coupling agent are also used. It may be mixed in any of the mixing stages of
For example, the organic peroxide may be mixed with the metal hydrate after being mixed with the silane coupling agent, or may be separately mixed with the metal hydrate separately from the silane coupling agent. In the present invention, the organic peroxide and the silane coupling agent should be substantially mixed together. On the other hand, depending on the production conditions, only the silane coupling agent may be mixed with the metal hydrate and then the organic peroxide may be mixed.
The organic peroxide may be mixed with other components or may be a single substance.

Examples of the method of mixing the metal hydrate, the silane coupling agent and the organic peroxide include mixing methods such as wet processing and dry processing. Specifically, wet processing in which a silane coupling agent is added in a state where metal hydrate is dispersed in solvent such as alcohol and water, dry processing in which both are added and mixed by heating or not heating, and both of them are mentioned. Be In the present invention, a dry treatment is preferable in which the silane coupling agent is added to metal hydrate, preferably dried metal hydrate, with or without heating and mixed.
In wet mixing, since the bonding between the silane coupling agent and the metal hydrate is strong, the volatilization of the silane coupling agent can be effectively suppressed, but it may be difficult for the silanol condensation reaction to proceed. On the other hand, in dry mixing, the silane coupling agent is easily volatilized, but the bonding strength between the metal hydrate and the silane coupling agent is relatively weak, and thus the silanol condensation reaction can be efficiently advanced.

  Next, in the production method of the present invention, the obtained mixture, all or part of the base resin, and the remaining components not mixed in step (a-1) are treated with an organic peroxide in the presence of an organic peroxide. Melt-kneading is carried out while heating 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 (melt-kneaded) is the decomposition temperature of the organic peroxide or higher, preferably the decomposition temperature of the organic peroxide + (25 to 110) ° C. . The decomposition temperature is preferably set after the resin component is melted. If it is the said mixing temperature, the said component will fuse | melt, the organic peroxide will decompose | disassemble and it will act, and the required silane grafting reaction will fully advance in a process (a-2). Other conditions, for example, the mixing time can be set as appropriate.
The mixing method is not particularly limited as long as it is a method commonly used for rubber, plastic and the like. A mixing apparatus is suitably selected according to the mixing amount of a metal hydrate, for example. As a kneading apparatus, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, various kneaders, etc. are used. From the viewpoint of the dispersibility of the resin component and the stability of the crosslinking reaction, a closed mixer such as a Banbury mixer or various kneaders is preferred.
Also, in general, when such metal hydrate is mixed in excess of 100 parts by mass with respect to 100 parts by mass of the base resin, it is preferable to knead with a continuous kneader, a pressure kneader, or a Banbury mixer.

  In the step (a-1) and the step (a-2), particularly in the step (a-2), it is preferable to knead the above-described components without substantially mixing the silanol condensation catalyst. As a result, the condensation reaction of the silane coupling agent can be suppressed, melt mixing can be easily performed, and a desired shape can be obtained during extrusion. Here, "not substantially mixed" does not exclude the unavoidable silanol condensation catalyst, and is present to such an extent that the above-mentioned problems due to silanol condensation of a silane coupling agent do not occur. It also means good. For example, in the step (a-2), the silanol condensation catalyst may be present as long as it is 0.01 parts by mass or less with respect to 100 parts by mass of the base resin.

In the step (1), the blending amounts of the other resins that can be used in addition to the above components and the above additives are appropriately set as long as the object of the present invention is not impaired.
In the step (1), the above-mentioned additives, in particular, the antioxidant and the metal deactivator may be mixed in any of the steps or components, but are preferably mixed in the carrier resin.
In the step (1), particularly in the step (a-1) and the step (a-2), it is preferred that the coagent be substantially not mixed. When the crosslinking aid is not substantially mixed, crosslinking of the resin components does not easily occur during kneading, and the appearance and heat resistance of the heat-resistant silane-crosslinked resin molded product are excellent. Here, "not substantially mixed" means not positively mixing the crosslinking aid, and does not exclude unavoidable mixing.

  Thus, the step (a) consisting of the step (a-1) and the step (a-2) is performed to prepare a silane master batch (also referred to as a silane MB). This silane MB is preferably used together with a silanol condensation catalyst or a catalyst masterbatch described later for producing the mixture (heat-resistant silane crosslinkable resin composition) prepared in the step (1), as described later. Silane MB contains the silane crosslinking resin (silane graft polymer) which the silane coupling agent grafted on the resin component to the extent which can be shape | molded by the below-mentioned process (2).

  Next, in the production method of the present invention, when a portion of the base resin is melt mixed in step (a-2), the remaining portion of the base resin and the silanol condensation catalyst are melt mixed to obtain a catalyst master batch (catalyst MB) Step (b) of preparing Therefore, when melt-mixing the whole base resin at a process (a-2), it is not necessary to perform a process (b), and you may mix another resin and a silanol condensation catalyst.

Although the mixing ratio of the base resin as a carrier resin and the silanol condensation catalyst is not particularly limited, it is preferably set so as to satisfy the above-mentioned compounding amount in the step (1).
The mixing may be any method that allows uniform mixing, and includes mixing (melt mixing) performed under melting of the base resin. Melt mixing can be performed similarly to melt mixing of the said process (a-2). For example, the mixing temperature can be performed at 80 to 250 ° C., more preferably 100 to 240 ° C. Other conditions, for example, the mixing time can be set as appropriate.

In the step (b), another resin can be used as a carrier resin in place of or in addition to the remainder of the base resin. That is, in the step (b), the remaining portion of the base resin in the case of melt-mixing a part of the base resin in the step (a-2), or a resin other than the resin component used in the step (a-2) The catalyst masterbatch may be prepared by melt mixing with a condensation catalyst.
When the carrier resin is another resin, the grafting reaction can be promoted in the step (a-2), and the amount of the other resin compounded is 100 parts by mass of the base resin in that it is difficult to cause bumps during molding. Preferably it is 1-60 mass parts, More preferably, it is 2-50 mass parts, More preferably, it is 2-40 mass parts.

In the step (b), an inorganic filler may be used. In this case, the blending amount of the inorganic filler is not particularly limited, but is preferably 350 parts by mass or less with respect to 100 parts by mass of the carrier resin. If the blending amount of the inorganic filler is large, the silanol condensation catalyst is difficult to disperse, and the crosslinking is difficult to progress. On the other hand, if the blending amount of the inorganic filler is too small, the degree of crosslinking of the molded article may be reduced, and sufficient heat resistance may not be obtained.
In this case, usable inorganic fillers include, in addition to the above metal hydrates, boron nitride, silica (crystalline silica, amorphous silica, etc.), carbon, clay, zinc oxide, tin oxide, titanium oxide, oxide Molybdenum, antimony trioxide, silicone compounds, quartz, talc, zinc borate, white carbon, zinc borate, zinc hydroxystannate, zinc stannate and the like can be mentioned.

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

Next, in the production method of the present invention, step (c) is carried out to obtain a mixture by mixing silane MB and silanol condensation catalyst or catalyst MB.
The mixing method may be any mixing method as long as a homogeneous mixture can be obtained as described above.

  The mixing is basically similar to the melt mixing of step (a-2). Although there are also resin components whose melting point can not be measured by DSC or the like, such as an elastomer, kneading is carried out at a temperature at which at least either the resin component or the like and the organic peroxide melt. The melting temperature is appropriately selected according to the melting temperature of the base resin or the carrier resin, and is, for example, preferably 80 to 250 ° C., more preferably 100 to 240 ° C. Other conditions, for example, mixing (kneading) time can be set appropriately.

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

  This step (c) may be a step of mixing a silane masterbatch and a silanol condensation catalyst to obtain a mixture, and a step of melt mixing a catalyst masterbatch containing a silanol condensation catalyst and a carrier resin with a silane masterbatch. Is preferred.

Thus, the steps (a) to (c) (step (1)), that is, the method for producing the heat-resistant silane crosslinkable resin composition of the present invention is performed, and the mixture is the heat-resistant silane crosslinkable resin of the present invention A composition is manufactured. The heat resistant 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 bound or adsorbed to the metal hydrate, but it is not silanol condensed as described later. Therefore, the silane crosslinkable resin is a crosslinkable resin in which a silane coupling agent bonded or adsorbed to a metal hydrate is grafted onto a base resin, and a silane coupling agent not bonded or adsorbed to a metal hydrate is a base resin And at least a crosslinkable resin grafted thereto. In addition, the silane crosslinkable resin may have a silane coupling agent to which metal hydrate is bound or adsorbed, and a silane coupling agent to which metal hydrate is not bound or adsorbed. Furthermore, it may contain a silane coupling agent and an unreacted resin component.
As described above, the silane crosslinkable resin is an uncrosslinked product in which the silane coupling agent is not silanol condensed. In practice, partial cross-linking (partial cross-linking) is unavoidable when melt-blended in step (c), but the heat-resistant silane crosslinkable resin composition obtained is obtained at least in the molding in step (2) It is assumed that formability is maintained.

  In the step (1), the steps (a) to (c) can be performed simultaneously or successively.

Next, the method for producing a heat-resistant silane-crosslinked resin molded product of the present invention performs step (2) and step (3).
In the method for producing a heat-resistant silane cross-linked resin molded article of the present invention, the step (2) of obtaining a molded article by molding the obtained mixture is performed. In this step (2), it is sufficient if the mixture can be formed, and the forming method and the forming conditions are appropriately selected according to the form of the heat resistant product of the present invention. The molding method includes extrusion molding using an extruder, extrusion molding using an injection molding machine, and molding using another molding machine. Extrusion is preferred when the heat resistant product of the present invention is a wire or fiber optic cable.

  In the step (2), when the mixing amount of the silane coupling agent exceeds 4 parts by mass, cleaning of the extruder, change of stage, eccentricity adjustment and middle stage without lowering the excellent appearance of the molded body It can be resumed after being stopped once due to reasons such as.

Further, the step (2) can be performed simultaneously with or sequentially to the step (c). That is, as an embodiment of the melt mixing in the step (c), there is a mode in which the molding raw material is melt mixed in the melt molding, for example, in the extrusion molding or immediately before that. For example, pellets such as dry blend may be mixed at normal temperature or high temperature and introduced into a molding machine (melt mixing), mixed and then melt mixed, pelletized again, and introduced into a molding machine It is also good. More specifically, a molding material which is a mixture 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 form a desired shape. A series of steps can be employed.
Thus, a molded article of the heat resistant silane crosslinkable resin composition is obtained. Like the heat-resistant silane-crosslinkable resin composition, this molded article is in a partially crosslinked state in which partial crosslinking is unavoidable but the moldability in the step (2) is maintained. Therefore, the heat-resistant silane cross-linked resin molded article of the present invention is made into a cross-linked or final cross-linked molded article by carrying out the step (3).

In the method for producing a heat-resistant silane cross-linked resin molded article of the present invention, the step (3) of bringing the molded article obtained in the step (2) into contact with water is performed. As a result, the hydrolyzable group of the silane coupling agent is hydrolyzed to form silanol, and the hydroxyl group of silanol is condensed by the silanol condensation catalyst present in the molded product to cause a crosslinking reaction. Thus, a heat-resistant silane-crosslinked resin molded product in which the silane coupling agent is crosslinked by silanol condensation can be obtained.
The process itself of this process (3) can be performed by a normal method. The condensation between the silane coupling agents proceeds only by storage at normal temperature. Therefore, in the step (3), it is not necessary to positively contact the molded body with water. In order to accelerate this crosslinking reaction, the shaped bodies can also be contacted with moisture. For example, it is possible to adopt a method in which water is actively brought into contact such as water immersion in warm water, charging to a moist heat tank, exposure to high temperature water vapor and the like. In addition, pressure may be applied to allow water to permeate inside.

  Thus, the method for producing a heat-resistant silane-crosslinked resin molded article of the present invention is carried out, and a heat-resistant silane-crosslinked resin molded article is produced from the heat-resistant silane crosslinkable resin composition of the present invention. The heat-resistant silane cross-linked resin molded product contains a cross-linked resin in which a silane cross-linkable resin is condensed via a siloxane bond, as described later. One form of the silane cross-linked resin molded product contains a silane cross-linked resin and a metal hydrate. Here, the metal hydrate may be bound to the silane coupling agent of the silane crosslinking resin. Therefore, in this silane cross-linked resin, a cross-linked resin in which a plurality of cross-linked resins are bonded or adsorbed to a metal hydrate by a silane coupling agent to bond (cross-link) via a metal hydrate and a silane coupling agent; The reaction site of the silane coupling agent of the crosslinkable resin is hydrolyzed and mutually subjected to a silanol condensation reaction, thereby including at least a crosslinked resin crosslinked via the silane coupling agent. In the silane crosslinking resin, bonding (crosslinking) via a metal hydrate and a silane coupling agent may be mixed with crosslinking via a silane coupling agent. Further, it may contain a silane coupling agent, an unreacted resin component and / or a non-crosslinked silane crosslinkable resin.

  Although the details of the reaction mechanism in the production method of the present invention are not clear yet, it is considered as follows. That is, when the resin component is heated and kneaded in the presence of the organic peroxide together with the metal hydrate and the silane coupling agent above the decomposition temperature of the organic peroxide, the organic peroxide is decomposed to generate radicals, and the resin Grafting of the silane coupling agent occurs to the components.

By the heating in the step (a-2), a reaction of formation of a chemical bond by a covalent bond between a silane coupling agent and a group such as a hydroxyl group on the surface of the metal hydrate also partially occurs.
In the present invention, the final crosslinking reaction may be carried out in the step (c), and when the silane coupling agent is compounded in a specific amount as described above to the base resin, the metal water is not impaired without impairing the extrusion processability at the time of molding. It becomes possible to blend a large amount of the hydrate, and while having excellent flame retardancy, it can have heat resistance, mechanical properties and the like.

  Also, the mechanism of action of the above process of the present invention is not clear yet, but is presumed as follows. That is, by using a metal hydrate and a silane coupling agent before and / or at the time of kneading with the base resin, the silane coupling agent is bonded to the metal hydrate through a group capable of chemically bonding, The graftable group present at the other end is bonded to the uncrosslinked portion of the resin component and retained. Alternatively, they are physically or chemically adsorbed and held in the holes or surface of the metal hydrate without binding to the metal hydrate. Thus, a silane that is weakly bonded to a silane coupling agent that is strongly bonded to metal hydrate (the reason may be, for example, the formation of a chemical bond with a hydroxyl group on the surface of metal hydrate) A coupling agent (for example, interaction by hydrogen bond, interaction between ions, partial charge or dipole, action by adsorption, etc. can be considered) can be formed. In this state, when an organic peroxide is added and kneading is performed, as described later, a silane coupling agent having a different bond with the metal hydrate is grafted to the resin component, with the silane coupling agent hardly evaporating as described later. A reacted silane crosslinkable resin is formed.

  Among the silane coupling agents, the silane coupling agent having a strong bond with the metal hydrate is held in the bond with the metal hydrate and the graftable group which is a crosslinking group is It grafts with the crosslinking site of the resin component. In particular, when a plurality of silane coupling agents are bonded to the surface of one metal hydrate particle through a strong bond, a plurality of resin components are bonded through the metal hydrate particle. These reactions or bonds broaden the cross-linked network via this metal hydrate. That is, a silane crosslinkable resin is formed in which the silane coupling agent bonded to the metal hydrate is grafted to the resin component.

  In the case of a silane coupling agent having a strong bond with a metal hydrate, a condensation reaction in the presence of water by this silanol condensation catalyst is unlikely to occur, and the bond with the metal hydrate is maintained. The reason why the silanol condensation reaction hardly occurs is considered to be that the binding energy of the metal hydrate and the silane coupling agent is very high, and the condensation reaction does not occur even under the silanol condensation catalyst. Thus, bonding between the resin component and the metal hydrate occurs, and crosslinking of the resin component via the silane coupling agent occurs. As a result, the adhesion between the resin component and the metal hydrate is strengthened, and a molded article which is excellent in mechanical strength and abrasion resistance and hard to be scratched is obtained. In particular, a plurality of silane coupling agents can be bonded to one metal hydrate particle surface, and high mechanical strength can be obtained. Thus, it is considered that the silane coupling agent bonded to the metal hydrate by a strong bond contributes to high mechanical properties, in some cases abrasion resistance, scratch resistance and the like.

  On the other hand, among the silane coupling agents, the silane coupling agent having a weak bond with the metal hydrate is separated from the surface of the metal hydrate, and a graftable group which is a crosslinking group of the silane coupling agent is It reacts with the radical of the resin component which arose by the hydrogen radical abstraction by the radical which arose by decomposition of organic peroxide, and a grafting reaction occurs. That is, a silane crosslinkable resin is formed in which the silane coupling agent separated from the metal hydrate graft-reacts with the resin component. The silane coupling agent of the graft portion thus produced is then mixed with a silanol condensation catalyst and brought into contact with moisture to cause a condensation reaction (crosslinking reaction). The heat resistance of the heat-resistant silane-crosslinked resin molded product obtained by this crosslinking reaction is enhanced, and it becomes possible to obtain a heat-resistant silane-crosslinked resin molded product which does not melt even at high temperatures. Thus, it is considered that the silane coupling agent bound by a weak bond to the metal hydrate contributes to the improvement of the degree of crosslinking, that is, the improvement of the heat resistance.

  In the present invention, in particular, the crosslinking reaction by condensation using a silanol condensation catalyst in the presence of water in the step (c) is carried out after forming the molded body. As a result, compared with the conventional method of forming a molded product after the final cross-linking reaction, it is possible to obtain excellent heat resistance higher than that of the conventional one, as well as excellent workability in the steps until the molded product formation.

Furthermore, when the silane coupling agent is mixed with the metal hydrate according to the production method of the present invention, as described above, the condensation between the silane coupling agents can be suppressed and the like, whereby the appearance becomes excellent. Moreover, in the present invention, when mixing more than 4.0 parts by mass and 15.0 parts by mass or less of the silane coupling agent into the metal hydrate, as described above, the step (1), particularly the step (1) The crosslinking reaction between the resin components at the time of melt-kneading in a-2) can be effectively suppressed. In addition, the silane coupling agent is bound to the metal hydrate, and it is difficult to volatilize during the melt-kneading in the step (1), particularly in the step (a-2), and the free silane coupling agents The reaction can also be effectively suppressed. Therefore, it is thought that appearance defects are less likely to occur even if the extruder is restarted after stopping the extruder, and a silane-resistant silane-crosslinked resin molded article having a good appearance can be produced.
Here, resuming after stopping temporarily depends on the composition of the base resin, processing conditions, etc. and can not be described uniquely, but for example, it can be resumed at 190 ° C., with an interval of up to 30 minutes, preferably up to 90 minutes. Say.

  In the production method of the present invention, when EVA-ii is used as the base resin, excellent flame retardancy can be imparted to the heat resistant silane cross-linked resin molded product. And when base resin contains EVA-ii by the said compounding quantity, an appearance defect can be prevented effectively, without reducing the outstanding flame retardance. Furthermore, excellent flame retardancy can be maintained even under conditions where appearance defects are likely to occur. The details are not clear yet, but are considered as follows.

In step (a-2), EVA is likely to liberate a carbonyl oxygen of an acetate group (CH ₃ C () O) O—) by a radical generated by the decomposition of an organic peroxide. When the part where the oxygen is released and the other resin component are combined, the molecular weight increases, and the resin does not melt even at the time of molding, resulting in gel-like bumps. However, by blending EVA-ii having a VA content of 30% by mass or less in a blending amount within the above range, generation of bumps due to an increase in molecular weight can be suppressed, and an excellent appearance can be imparted.
Moreover, EVA-ii with small VA content has high crystallinity. This is considered to be difficult to absorb moisture and to reduce the water content in the base resin. As a result, silane coupling agents do not easily undergo a silanol condensation reaction, and an excellent appearance can be imparted.
In particular, in the case of forming a coating layer having a thin layer thickness, in the case of increasing the extrusion speed of the heat-resistant silane crosslinkable resin composition, the appearance of the heat-resistant silane crosslinkable resin composition is not high enough. Is triggered. However, in the present invention, the increase in the molecular weight and the condensation reaction of the silane coupling agent can be sufficiently suppressed by blending the EVA-ii in the compounding amount in the above range. Therefore, the fluidity of the heat-resistant silane crosslinkable resin composition is high, and an excellent appearance can be provided even under such conditions where appearance defects are likely to occur.

The manufacturing method of the present invention is a product requiring heat resistance (including semi-finished products, parts and members), a product requiring strength, a product requiring flame retardancy, a component of a product such as a rubber material or the like It can apply to manufacture of the member. Therefore, the heat resistant product of the present invention is such a product. At this time, the heat-resistant product may be a product containing a heat-resistant silane cross-linked resin molded product or a product consisting of only the heat-resistant silane cross-linked resin molded product.
As the heat resistant product of the present invention, for example, covering material of electric wire such as heat resistant flame retardant insulated wire or heat resistant flame retardant cable, material of rubber alternative electric wire / cable, other, heat resistant flame retardant electric wire parts, flame retardant heat resistant sheet, flame resistant A heat resistant film etc. are mentioned. In addition, power plugs, connectors, sleeves, boxes, tape substrates, tubes, sheets, packings, cushioning materials, vibration-proof materials, wiring materials used for internal and external wiring of electric and electronic devices, particularly electric wires and optical cables may be mentioned. .

Among the above-mentioned products, the production method of the present invention is suitably applied particularly to the production of electric wires and optical cables, and can be formed as a covering material (insulator, sheath) thereof.
When the heat-resistant product of the present invention is an extrusion-molded article such as an electric wire or cable, preferably, the molding material is melt-kneaded in an extruder (extrusion coating apparatus) to prepare a heat-resistant silane crosslinkable resin composition. The heat-resistant silane crosslinkable resin composition can be extruded to the outer periphery of a conductor or the like to coat the conductor or the like (step (c) and step (2)). Such a heat-resistant product is a conductor using a general-purpose extrusion coating apparatus without using a special machine such as an electron beam crosslinking machine and a heat-resistant silane crosslinkable resin composition to which a large amount of metal hydrate is added. Can be molded by extrusion coating on the periphery of the above or around the conductor having the tensile strength fibers longitudinally or twisted. For example, a single wire or a stranded wire of soft copper can be used as the conductor. In addition to the bare wire, a conductor having a tin-plated one or an enamel-coated insulating layer can also be used as the conductor. The thickness of the insulating layer (coating layer made of the heat resistant silane crosslinkable resin composition of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 to 5 mm.

  In particular, according to the present invention, even in the molding step (2), even when the condition in which appearance defects easily occur is adopted, the occurrence of appearance defects can be prevented, and excellent flame retardancy can be maintained. Therefore, in the present invention, the diameter of the electric wire, the cable or the like can be made small.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
In Table 1, the numerical values relating to the compounding amount of each example represent parts by mass unless otherwise specified.

In Examples 1 to 3 and Reference Examples 1 to 5 and Comparative Examples 1 to 9, the following components are used, the respective specifications are set to the conditions shown in Table 1, and evaluation results to be described later are shown in Table 1. It showed together.

Details of each compound shown in Table 1 are shown below.
<Base resin>
(EVA-ii)
"Evaflex EV 560" (brand name, Mitsui-DuPont Chemical Co., Ltd., VA content: 14% by mass)
"Evaflex EV360" (brand name, Mitsui-DuPont Chemical Co., Ltd. make, VA content 25 mass%)
"Evaflex EV260" (brand name, Mitsui-DuPont Chemical Co., Ltd. make, VA content 28 mass%)
(EVA-i)
"Evaflex EV170" (brand name, Mitsui-DuPont Chemical Co., Ltd. make, VA content 33 mass%)
"V9000" (trade name, manufactured by Mitsui / Dupont Chemical, VA content: 40% by mass)
"REVAPREN 600 HV" (trade name, manufactured by LANXESS, VA content: 60% by mass)
(Polyethylene resin)
"UE320" (Novatec PE (trade name), manufactured by Japan Polyethylene Corporation, linear low density polyethylene (LLDPE))
"Hyzex 5305E" (trade name, manufactured by Prime Polymer, high density polyethylene (HDPE))
(Polypropylene resin)
"PB222A" (trade name, manufactured by Sun Aroma, random polypropylene)
(Ethylene-propylene-diene rubber: EPDM)
"Nodel IP-4760P" (trade name, manufactured by Dow Chemical Co., ethylene content: 67% by mass)
"Nodel IP-4520P" (trade name, manufactured by Dow Chemical Co., ethylene content 50% by mass)
(Styrenic elastomer: SEPS)
"Septon 4077" (trade name, manufactured by Kuraray, SEPS, styrene content: 30% by mass)
(Oil: OIL)
"Diana Process Oil PW-90" (brand name, Idemitsu Kosan, paraffin oil)

<Metal hydrate>
(Aluminum hydroxide)
"Hi-Dilight H42M" (trade name, manufactured by Showa Denko, surface-untreated aluminum hydroxide)
(Magnesium hydroxide)
"Kisuma 5A" (trade name, manufactured by Kyowa Chemical Co., Ltd., fatty acid pretreated magnesium hydroxide)
"Kisuma 5" (trade name, manufactured by Kyowa Chemical Co., Ltd., surface untreated magnesium hydroxide)
"Kisuma 5L" (trade name, manufactured by Kyowa Chemical Co., Ltd., silane coupling agent pretreated magnesium hydroxide)
Each metal hydrate was used after conditioning for 1 week in an environment of 23 ° C. and 50% relative humidity.

<Silane coupling agent>
"KBM 1003" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane)
<Organic peroxide>
"Park Mill D" (trade name, manufactured by NOF Corporation, dicumyl peroxide, decomposition temperature 151 ° C))
<Silanol condensation catalyst>
Adekastab OT-1 (trade name, manufactured by ADEKA, dioctyl tin dilaurate)

<Antioxidant>
“Irganox 1076” (trade name, manufactured by BASF, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)

(Examples 1 to 3, Reference Examples 1 to 5 and Comparative Examples 1 to 9)
In Examples 1 to 3 and Reference Examples 1 to 5 and Comparative Examples 1 to 9, a part of resin components constituting the base resin was used as a carrier resin of the catalyst MB. Specifically, in Examples 1 and 2 and Reference Examples 1 and 2 and Comparative Examples 4 to 9, a part (5 parts by mass) of PE which is one of the resin components constituting the base resin was used. In Example 3 and Reference Example 3 and Comparative Examples 1 to 3, all (5 parts by mass) of PE which is one of resin components constituting the base resin was used. Moreover, in the reference examples 4 and 5 , a part (5 mass parts) of EVA-ii which is one of the resin components which comprise base resin was used.

  First, an organic peroxide, a metal hydrate, a silane coupling agent and an antioxidant are introduced into a Toyo Seiki 10 L Henschel mixer at a mass ratio shown in Table 1 and mixed at room temperature (25 ° C.) for 1 hour The powder mixture was obtained (step (a-1)). Next, the powder mixture thus obtained, and the resin component and oil shown in the base resin column of Table 1 are introduced into a 2L Banbury mixer made by Nippon Roll Co., Ltd. in a mass ratio shown in Table 1, and organic After kneading for 10 minutes at a temperature higher than the decomposition temperature of the peroxide, specifically 190 ° C., the material was discharged at a temperature of 190 ° C. to obtain a silane MB (step (a-2)). In the obtained silane MB, a silane coupling agent graft-reacts with the resin component to contain a silane crosslinkable resin.

On the other hand, carrier resin, silanol condensation catalyst and antioxidant are melted and mixed by a Banbury mixer at 180 to 190 ° C. in a mass ratio shown in Table 1, and discharged at a material discharge temperature of 180 to 190 ° C. (Step (b)).
Then, Silane MB and Catalyst MB were charged into a closed ribbon blender, and dry blending was performed for 5 minutes at room temperature (25 ° C.) to obtain a dry blending. At this time, the mixing ratio of the silane MB and the catalyst MB is a mass ratio shown in Table 1, and specifically, the base resin of the silane MB is 95 parts by mass in Examples , Reference Examples and Comparative Examples. The proportion of carrier resin of MB was 5 parts by mass.

Next, the obtained dried blend was melt mixed and molded under the following extrusion molding conditions (1) to (4), respectively, to obtain coated conductors (step (c) and step (2)).
<Extrusion molding conditions (1)>
The obtained dried blend was introduced into an extruder (cylinder temperature 180 ° C., head temperature 200 ° C.) equipped with a screw with L / D (ratio of screw effective length L to diameter D) = 23 and screw diameter 90 mm. . While melt-blending the dried blend in this extruder, extrude at a linear velocity of 7 m / min so that the thickness becomes 2.0 mm around the 7/34 / 0.45A stranded wire (conductor diameter 8.4 mm). Then, a coated conductor having an outer diameter of 12.4 mm was obtained (step (c) and step (2)).
<Extrusion molding conditions (2)>
The obtained dried blend was introduced into an extruder (cylinder temperature 180 ° C., head temperature 200 ° C.) equipped with a screw with L / D (ratio of screw effective length L to diameter D) = 23 and screw diameter 90 mm. . While melt-blending the dried blend in this extruder, extrude at a linear velocity of 20 m / min so that the thickness becomes 2.0 mm around the 7/34 / 0.45A stranded wire (conductor diameter 8.4 mm) Then, a coated conductor having an outer diameter of 12.4 mm was obtained (step (c) and step (2)).
<Extrusion molding conditions (3)>
The obtained dried blend was put into an extruder (cylinder temperature 180 ° C., head temperature 200 ° C.) equipped with a screw with L / D (ratio of screw effective length L to diameter D) = 24 and screw diameter 50 mm. . While melt-blending the dried blend in this extruder, extrude at a linear velocity of 50 m / min so that the thickness becomes 0.4 mm around the 7 / 0.16 A stranded wire (conductor diameter 0.48 mm). A coated conductor with a diameter of 1.28 mm was obtained (step (c) and step (2)).
<Extrusion molding conditions (4)>
The obtained dried blend was put into an extruder (cylinder temperature 180 ° C., head temperature 200 ° C.) equipped with a screw with L / D (ratio of screw effective length L to diameter D) = 24 and screw diameter 50 mm. . While melt-blending the dried blend in this extruder, extrude at a linear velocity of 200 m / min so that the thickness becomes 0.4 mm around the 7 / 0.16 A stranded wire (conductor diameter 0.48 mm). A coated conductor with a diameter of 1.28 mm was obtained (step (c) and step (2)).

  The heat-resistant silane crosslinkable resin composition was prepared by melt-mixing the above-mentioned dry blend in an extruder before extrusion. This heat resistant silane crosslinkable resin composition is a mixture of silane MB and catalyst MB, and contains the above-mentioned silane crosslinkable resin.

  The resulting coated conductors were left in an atmosphere at a temperature of 80 ° C. and a relative humidity of 95% for 24 hours (step (3)). Thus, each electric wire which covered the said twisted wire with the heat resistant silane crosslinked resin molded object according to the said extrusion molding conditions (1)-(4) was manufactured. The heat-resistant silane-crosslinked resin molded product as a coating has the above-mentioned silane cross-linked resin.

  The following tests were conducted for each of the manufactured electric wires and the like, and the results are shown in Table 1.

<Appearance test (1)>
In each electric wire manufactured using the coated conductor obtained by the above extrusion molding condition (1), the one having excellent appearance is “A”, the one having no problem in the appearance as the electric wire is “B” as the electric wire When there was a problem with the appearance, there was a problem of "B". The evaluation is "B" or higher is the pass level of this test.
<Appearance test (2)>
In each electric wire manufactured using the coated conductor obtained under the above extrusion molding condition (2), the one having excellent appearance is “A”, the one having no problem in appearance as a wire is “B” as a wire When there was a problem with the appearance, there was a problem of "B". The evaluation is "B" or higher is the pass level of this test. This appearance test (2) is a reference test.
<Appearance test (3)>
In each electric wire manufactured using the coated conductor obtained under the above extrusion molding condition (3), the one having excellent appearance is “A”, the one having no problem in the appearance as a wire is “B” as a wire When there was a problem with the appearance, there was a problem of "B". The evaluation is "B" or higher is the pass level of this test.
<Appearance test (4)>
In each electric wire manufactured using the coated conductor obtained under the above extrusion molding condition (4), the one having excellent appearance is “A”, the one having no problem in the appearance as the electric wire is “B” as the electric wire When there was a problem with the appearance, there was a problem of "B". The evaluation is "B" or higher is the pass level of this test. This appearance test (4) is a reference test.

<Hot set test (heat resistance test)>
The hot set test was performed using the tubular piece manufactured similarly to each electric wire manufactured using the coated conductor obtained by the said extrusion molding conditions (1). The hot set test was performed according to the method described in IEC (International Electronic Standards Commission: 60811-2-1). The test condition is 200 ° C., the heating time is 15 minutes, the load is 20 N / cm ² , the elongation after heating is 100% or less, and the elongation after heating and removal of load is 25% or less. The pass level of “A” was indicated as a pass level, and the other was indicated as “C” as a failure level of this test.

<Flame retardancy test (1)>
For each electric wire manufactured using the coated conductor obtained under the above extrusion molding conditions (1), the "one-wire test of cable" described in IEC 60332-1 and the "60 degree inclined flame retardant test" described in JIS C 3005 Did.
In the evaluation of the flame retardancy test (1), a case where both the "one-wire cable test" and the "60 degree inclined flame retardant test" pass is represented as "A" as a desirable level of this test, and only one of the tests passed. The case was represented by "B" as a pass level of this test, and when both failed, it was represented by "C" as a fail level of this test.

<Flame retardancy test (2)>
For each electric wire manufactured using the coated conductor obtained under the above extrusion molding conditions (3), in the same manner as in the flame retardancy test (1), the "one-wire test of cable" described in IEC 60332-1, and JIS C The “60 degree inclination flame retardant test” described in 3005 was conducted.
In the evaluation of the flame retardancy test (2), a case where both the "one-wire cable test" and the "60 degree inclined flame retardant test" pass is represented as "A" as a desirable level of this test, and only one of the tests passed. The case was represented by "B" as a pass level of this test, and when both failed, it was represented by "C" as a fail level of this test.

<Tensile characteristics (mechanical characteristics)>
The tensile test was performed about the coating (tubular piece) extracted from each electric wire manufactured using the coated conductor obtained by the said extrusion molding conditions (1).
In this tensile test, tensile strength (MPa) and tensile elongation (%) were measured according to JIS C 3005 under conditions of 25 mm between marked lines and a tensile speed of 200 mm / min.
As for tensile strength, what was 10 MPa or more was represented by "A" as a pass level of this test, and what was less than 10 MPa was represented by "C" as a rejection level of this test. As for tensile elongation, what was 200% or more was represented by "A" as a pass level of this test, and what was less than 200% was represented by "C" as a failure level of this test.

As is clear from the results shown in Table 1, all of Examples 1 to 3 passed the appearance test (3) in addition to the appearance tests (1) and (2). As described above, according to the embodiment of the present invention, the appearance is excellent even if a thin wire is manufactured by extruding a thin coating layer at a high linear velocity.
In particular, Examples 1 to 3 containing 45 to 90% by mass of EVA-ii also passed the appearance test (4) and the flame retardancy test (2).
Furthermore, Examples 1 to 3 also passed the hot set test, flame retardancy and tensile properties.
As described above, in the present invention, even when the condition in which appearance defects easily occur is adopted, the appearance can be made excellent. Specifically, even if the outer diameter of the manufactured wire is 12.4 mm, further 1.28 mm, and the coating thickness is 2.0 mm, further 0.4 mm, an excellent appearance can be given. The Moreover, even when the extrusion speed was increased to 20 m / min, 50 m / min, and further 200 m / min, an excellent appearance could be provided.

  On the other hand, in Comparative Examples 1 to 3 in which the base resin contains EVA-i, the appearance test (3) failed, regardless of the content. Moreover, the appearance test (3) failed in Comparative Example 4 which contains EVA-i and does not contain EVA-ii. In addition, Comparative Example 5 in which the compounding amount of the organic peroxide was small and Comparative Example 9 in which the silanol catalyst was not compounded failed in the hot setting test and were inferior in heat resistance. In Comparative Example 6 in which the compounding amount of the organic peroxide was large, both of the appearance tests (1) and (3) failed. The appearance test (3) and the heat resistance fail in Comparative Example 7 where the compounding amount of the silane coupling agent is small, and the appearance test (1) and (3) fail in Comparative Example 8 where the content is large. The

Claims (11)

A method for producing a heat-resistant silane-crosslinked resin molded article, comprising the following steps (1), (2) and (3) ,
Process (1): 0.01 to 0.6 mass of organic peroxide with respect to 100 mass parts of base resin
Part, 40 to 300 parts by mass of metal hydrate , and the above base in the presence of a radical
A grafting reaction site capable of grafting onto a glass resin, and the metal hydrate
Coupling agent 1 to 15.0 having a reactive site capable of chemically bonding with
Step of melt-mixing parts by mass and silanol condensation catalyst to obtain a mixture Step (2): Step of forming the mixture obtained in the step (1) to obtain a formed body Step (3): Step (2): By bringing the molded body obtained in 2.) into contact with water,
Step of obtaining a fat-molded product The base resin of the step (1) is free of ethylene vinyl acetate resin (EVA-i) having a vinyl acetate content of more than 30% by mass, and has a vinyl acetate content of 30% by mass or less Containing 48 to 85 % by mass of ethylene vinyl acetate resin (EVA-ii), and further containing at least one of ethylene rubber and a styrenic elastomer,
When all the base resin is melt mixed in the following step (a-2) in the above step (1), the above step (1) includes the following step (a-1), step (a-2) and step (a) have c), when a portion of the base resin melt mixing the following step (a-2), wherein step (1) is the following step (a-1), step (a-2), step ( b) and step (c),
A method for producing a heat resistant silane cross-linked resin molded product.
Step (a-1): mixing at least the metal hydrate and the silane coupling agent
A step of preparing a mixture step (a-2): said organic peroxide and said mixture and all or part of said base resin
Dissolved at a temperature above the decomposition temperature of the organic peroxide in the presence of
The silane coupling agent and the base resin are
By shift reaction, Engineering to prepare the silane masterbatch
Step (b): Melt-mixing the remainder of the base resin and the silanol condensation catalyst
Step of preparing a catalyst masterbatch Step (c): the silane masterbatch, the silanol condensation catalyst or the catalyst
Process of melt mixing with medium master batch The ethylene rubber and the styrene elastomer, the total content of the base resin, the manufacturing method of heat resistant silane crosslinkable resin molded article according to Ru der least 5 wt% claim 1.   The method according to claim 1 or 2, wherein the vinyl acetate content of the ethylene vinyl acetate resin (EVA-ii) is 13 to 30% by mass.   The heat resistance according to any one of claims 1 to 3, wherein the silane coupling agent is mixed in an amount of more than 4 parts by mass and 15.0 parts by mass or less with respect to 100 parts by mass of the base resin. The manufacturing method of a silane crosslinked resin molding.   The method for producing a heat-resistant silane-crosslinked resin molded product according to any one of claims 1 to 4, wherein the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.   The method for producing a heat-resistant silane-crosslinked resin molded product according to any one of claims 1 to 5, wherein the silanol condensation catalyst is not substantially mixed in the steps (a-1) and (a-2). 0.01 to 0.6 parts by mass of organic peroxide, 40 to 300 parts by mass of metal hydrate, and grafting capable of grafting onto the base resin in the presence of radicals based on 100 parts by mass of the base resin Heat resistance having a step (1) of obtaining a mixture by melt mixing 1 to 15.0 parts by mass of a silane coupling agent having a reactive site and a reactive site capable of chemically bonding with the metal hydrate, and a silanol condensation catalyst It is a manufacturing method of water-soluble silane crosslinkable resin composition,
The base resin of the step (1) is an ethylene vinyl acetate resin (EVA having a vinyl acetate content of 30% by mass or less, containing no ethylene vinyl acetate resin (EVA-i) having a vinyl acetate content of more than 30% by mass 48 to 85 % by mass of ii) and further containing at least one of an ethylene rubber and a styrenic elastomer,
When all the base resin is melt mixed in the following step (a-2) in the above step (1), the above step (1) includes the following step (a-1), step (a-2) and step (a) have c), when a portion of the base resin melt mixing the following step (a-2), wherein step (1) is the following step (a-1), step (a-2), step ( b) and step (c),
A method of producing a heat resistant silane crosslinkable resin composition.
Step (a-1): mixing at least the metal hydrate and the silane coupling agent
A step of preparing a mixture step (a-2): said organic peroxide and said mixture and all or part of said base resin
Dissolved at a temperature above the decomposition temperature of the organic peroxide in the presence of
The silane coupling agent and the base resin are
By shift reaction, Engineering to prepare the silane masterbatch
Step (b): Melt-mixing the remainder of the base resin and the silanol condensation catalyst
Step of preparing a catalyst masterbatch Step (c): the silane masterbatch, the silanol condensation catalyst or the catalyst
Process of melt mixing with medium master batch   A heat-resistant silane crosslinkable resin composition produced by the method for producing a heat-resistant silane crosslinkable resin composition according to claim 7.   The heat resistant silane crosslinked resin molded object manufactured with the manufacturing method of the heat resistant silane crosslinked resin molded object of any one of Claims 1-6.   A heat resistant product comprising the heat resistant silane cross-linked resin molded product according to claim 9. Containing ethylene vinyl acetate resin (EVA-i) with a vinyl acetate content exceeding 30% by mass and containing 48 to 85 % by mass of an ethylene vinyl acetate resin (EVA-ii) having a vinyl acetate content of 30% by mass or less and, further the base resin 100 parts by weight containing at least one ethylene rubber and styrene-based elastomer, and an organic peroxide 0.01 to 0.6 parts by weight, and the metal hydrate 40 to 300 parts by weight, the radical 1 to 15.0 parts by mass of a silane coupling agent having a grafting reaction site capable of grafting onto the base resin in the presence of the above, and a reaction site capable of chemically bonding to the metal hydrate, and a silanol condensation catalyst A silane masterbatch used for producing a heat resistant silane crosslinkable resin composition formed by melt mixing,
A mixture is prepared by mixing at least the metal hydrate and the silane coupling agent, and the obtained mixture and all or a part of the base resin in the presence of the organic peroxide. The silane masterbatch obtained by melt-mixing at the temperature more than decomposition | disassembly temperature, and making the said silane coupling agent and the said base resin graft-react .