JPWO2013147148A1 - Method for producing heat resistant resin composition, heat resistant resin composition produced by the production method, and molded article using the heat resistant resin composition - Google Patents

Abstract

(A) A resin composition containing a polyolefin-based resin, 0.01 to 0.6 parts by mass of an organic peroxide and 10 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of the resin composition, and the inorganic filler A step of melt-kneading 0.5 to 15.0 parts by mass of a silane coupling agent with respect to 100 parts by mass above the decomposition temperature of the organic peroxide and preparing a silane masterbatch without mixing a silanol condensation catalyst And (b) a step of molding after melt-kneading the silane masterbatch and the silanol condensation catalyst, and (c) a step of bringing the molded product of the step (b) into contact with moisture and crosslinking. A heat-resistant resin composition produced by the method, a heat-resistant resin composition produced by the method for producing a heat-resistant resin composition, and a molded article comprising a molded product of the heat-resistant resin composition.

Description

  The present invention relates to a method for producing a heat-resistant resin composition, a heat-resistant resin composition produced by the production method, and a molded article using the heat-resistant resin composition. Of a heat-resistant resin composition excellent in heat resistance, a heat-resistant resin composition obtained by the method of producing the heat-resistant resin composition, and molding of an electric wire insulator or sheath using the heat-resistant resin composition It is about goods.

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

  Moreover, the wiring material used for an electric / electronic device may be heated up to 80-105 degreeC and also about 125 degreeC in the state of continuous use, and the heat resistance with respect to this may be requested | required. . In such a case, for the purpose of imparting high heat resistance to the wiring material, a method of crosslinking the coating material by an electron beam crosslinking method or a chemical crosslinking method is employed.

  Conventionally, as a method of crosslinking a polyolefin resin such as polyethylene, an electron beam crosslinking method in which an electron beam is irradiated to crosslink, a chemical crosslinking method in which an organic peroxide or the like is decomposed by applying heat after molding, and a crosslinking reaction is performed. A silane cross-linking method is known. The silane cross-linking method refers to cross-linking molding by reacting a silane coupling agent having an unsaturated group in the presence of an organic peroxide to obtain a silane graft polymer, and then contacting with moisture in the presence of a silanol condensation catalyst. A way to get a body. Of these cross-linking methods, the silane cross-linking method in particular does not require special equipment and can be used in a wide range of fields.

Specifically, for example, a method for producing a halogen-free heat-resistant silane crosslinked resin includes a silane master batch obtained by grafting a silane coupling agent having an unsaturated group to a polyolefin resin, and a heat-resistant master obtained by kneading a polyolefin and an inorganic filler. There is a method of melt-kneading a batch and a catalyst masterbatch containing a silanol condensation catalyst. However, in this method, when the inorganic filler exceeds 100 parts by mass with respect to 100 parts by mass of the polyolefin resin, the silane masterbatch and the heat-resistant masterbatch are dry-mixed and uniformly in a single screw extruder or a twin screw extruder. However, it may be difficult to melt and knead, and the appearance may be deteriorated, the physical properties may be significantly lowered, or the extrusion load may be high and molding may not be possible. Moreover, since the ratio including the silane masterbatch is limited, it has been difficult to achieve higher flame resistance and higher heat resistance.
Usually, for such kneading when the inorganic filler exceeds 100 parts by mass with respect to 100 parts by mass of the polyolefin resin, it is common to use a continuous mixer, a closed mixer such as a pressure kneader or a Banbury mixer. is there.

  On the other hand, when performing silane grafting with a kneader or Banbury mixer, a silane coupling agent having an unsaturated group is generally highly volatile and volatilizes before the grafting reaction. It was very difficult to do.

  Therefore, when producing a heat-resistant silane masterbatch using a Banbury mixer or kneader, a silane coupling agent having a hydrolyzable unsaturated group and an organic peroxide are added to the heat-resistant masterbatch obtained by melting and kneading a polyolefin resin and a flame retardant. A method may be considered in which a product is added and graft polymerization is carried out using a single screw extruder. However, in this method, the appearance of the molded product is deteriorated due to variations in reaction, the amount of inorganic filler in the master batch must be very large, the extrusion load becomes very large, and the production is very difficult. As a result, a desired material or molded body cannot be obtained. In addition, there were two problems, and there was a big problem in cost.

  In Patent Document 1, an inorganic filler surface-treated with a silane coupling agent, a silane coupling agent, an organic peroxide, and a crosslinking catalyst are sufficiently melt-kneaded with a kneader and then molded with a single screw extruder. A method has been proposed.

  In addition, Patent Documents 2 to 4 describe a vinyl aromatic thermoplastic elastomer composition containing a block copolymer or the like as a base resin and a non-aromatic rubber softener added as a softener, and a silane surface-treated inorganic material. A technique of partially crosslinking using an organic peroxide through a filler has been proposed.

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

However, in the method described in Patent Document 1, not only does the molded body crosslink during melt-kneading in a kneader, but the molded product causes poor appearance, and a silane coupling agent other than the silane coupling agent whose surface is treated with an inorganic filler. Most of these may volatilize or the silane coupling agents may condense. For this reason, desired heat resistance cannot be obtained, and condensation between silane coupling agents may cause deterioration of the appearance of the electric wire.
In addition, even with the techniques proposed in Patent Documents 2 to 4, the resin is not yet in a sufficient network structure, and the bond between the resin and the inorganic filler is released at a high temperature. However, for example, there has been a problem that the insulating material is melted during the soldering process of the electric wire, or foaming is generated which is deformed when the forming pair is secondarily processed. Furthermore, when heated to about 200 ° C. for a short time, there is a problem that the appearance is remarkably deteriorated or deformed.

  The present invention solves the above-mentioned problems, suppresses volatilization of the unsaturated group-containing silane coupling agent from the reaction system, and has excellent heat resistance, heat resistance, and mechanical properties, It is another object of the present invention to provide a molded product using the heat resistant resin composition.

That is, the subject of this invention was achieved by the following means.
(1) (a) a resin composition containing a polyolefin-based resin, and 0.01 to 0.6 parts by mass of an organic peroxide and 10 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of the resin composition; Melting and kneading 0.5 to 15.0 parts by mass of a silane coupling agent with respect to 100 parts by mass of the inorganic filler at a temperature equal to or higher than the decomposition temperature of the organic peroxide, and without mixing a silanol condensation catalyst, A step of preparing;
(B) a step of molding after melt-kneading the silane masterbatch and the silanol condensation catalyst;
(C) The manufacturing method of the heat resistant resin composition characterized by including the process of making the molded article of the said (b) process contact with a water | moisture content, and bridge | crosslinking.
(2) (a-1) 0.01 to 0.6 parts by weight of an organic peroxide and 10 to 400 parts by weight of an inorganic filler, and 100 parts by weight of an inorganic peroxide, relative to 100 parts by weight of a resin composition containing a polyolefin resin. Mixing 0.5-15.0 parts by mass of a silane coupling agent with respect to parts by mass to prepare a mixture;
(A-2) melting and kneading the mixture and the resin composition at or above the decomposition temperature of the organic peroxide, and preparing a silane masterbatch without mixing the silanol condensation catalyst;
(B-1) a step of producing a catalyst master batch by mixing a silanol condensation catalyst and a carrier resin;
(B-2) a step of melt-kneading the silane masterbatch and the catalyst masterbatch prepared in the steps (a-2) and (b-1), respectively, and then molding,
(C) The manufacturing method of the heat resistant resin composition as described in (1) characterized by including the process of making the molded product of the said (b-2) process contact with a water | moisture content, and bridge | crosslinking.
(3) (a) a resin composition containing a polyolefin-based resin, 0.01 to 0.6 parts by mass of an organic peroxide and 10 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of the resin composition; Melting and kneading 0.5 to 15.0 parts by mass of a silane coupling agent with respect to 100 parts by mass of the inorganic filler at a temperature equal to or higher than the decomposition temperature of the organic peroxide to prepare a silane masterbatch without mixing the silanol condensation catalyst. Process,
(B-1) a step of producing a catalyst master batch by mixing a silanol condensation catalyst and a carrier resin;
(B-3) a step of melt-kneading and molding the silane masterbatch and the catalyst masterbatch prepared in the steps (a) and (b-1), respectively,
(C) The manufacturing method of the heat resistant resin composition as described in (1) characterized by including the process of making the molded article of the said (b-3) process contact with a water | moisture content, and bridge | crosslinking.

(4) Any one of (1) to (3), wherein 0.5 to 18.0 parts by mass of the silane coupling agent is contained with respect to 100 parts by mass of the resin composition. The manufacturing method of the heat resistant resin composition of description.
(5) The method for producing a flame retardant crosslinking composition according to (4), wherein the silane coupling agent is contained in an amount of more than 4 parts by mass and 15 parts by mass or less.
(6) The method for producing a flame retardant crosslinking composition according to (4), wherein the silane coupling agent is contained in an amount of 5 to 12 parts by mass.
(7) The method for producing a flame retardant crosslinking composition according to (4), wherein the silane coupling agent is contained in an amount of 6 to 10 parts by mass.
(8) The resin composition contains at least one of an ethylene-α-olefin copolymer and a styrene elastomer and a paraffinic oil in a mass ratio of 4 to 70% by mass (1). The manufacturing method of the flame-retardant crosslinked composition of any one of 1)-(7).
(9) The method for producing a flame retardant crosslinked composition according to (8), wherein the mass ratio is 8 to 70 mass%.
(10) The production of the flame retardant crosslinking composition according to (8) or (9), wherein at least one of the ethylene-α-olefin copolymer and the styrene elastomer is the styrene elastomer. Method.
(11) The method for producing a flame retardant crosslinking composition according to any one of (8) to (10), wherein the ethylene-α-olefin copolymer is ethylene-propylene-diene rubber. .
(12) The method for producing a heat-resistant resin composition according to any one of (1) to (11), wherein the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.
(13) The inorganic filler is at least one selected from the group consisting of silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, zinc borate, zinc hydroxystannate and talc ( The manufacturing method of the heat resistant resin composition of any one of 1)-(12).

(14) The method for producing a heat-resistant resin composition according to any one of (1) to (13), wherein the melt-kneading in the production of the silane masterbatch is performed with a closed mixer.
(15) A molded product comprising a molded product of the heat resistant resin composition produced by the method for producing a heat resistant resin composition according to any one of (1) to (14).
(16) The molded product according to (15), wherein the molded product is an electric wire or optical fiber cable coating.
(17) A heat resistant resin composition produced by the method for producing a heat resistant resin composition according to any one of (1) to (14), wherein the polyolefin resin is an inorganic filler via a silanol bond. And a heat-resistant resin composition characterized by being crosslinked.

  The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.

  According to the present invention, it is excellent in flame retardancy, heat resistance and mechanical properties, and at the time of kneading by mixing the inorganic filler and the silane coupling agent before and / or during kneading with the polyolefin resin. The volatilization of the silane coupling agent can be suppressed, and a heat-resistant resin composition and a molded product of the heat-resistant resin composition can be obtained efficiently. Furthermore, a highly heat-resistant crosslinked composition to which a large amount of an inorganic filler is added can be produced without using a special machine such as an electron beam crosslinking machine.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The method for producing a heat resistant resin composition of the present invention comprises: (a) a resin composition containing a polyolefin-based resin; and 0.01 to 0.6 parts by mass of an organic peroxide based on 100 parts by mass of the resin composition. And 10 to 400 parts by weight of the inorganic filler and 0.5 to 15.0 parts by weight of the silane coupling agent with respect to 100 parts by weight of the inorganic filler are melt-kneaded at a temperature equal to or higher than the decomposition temperature of the organic peroxide, and silanol condensation A step of preparing a silane master batch without mixing the catalyst, (b) a step of melt-kneading the silane master batch and a silanol condensation catalyst, and (c) contacting the molded product of the step with moisture. And crosslinking.

(A) Resin composition containing polyolefin resin The resin composition used in the present invention contains a polyolefin resin as an essential component, and optionally contains a styrene elastomer, paraffin oil, various additives, and the like. doing. When using an ethylene-α-olefin copolymer, which will be described later, as one of the polyolefin resins, or when using a styrene elastomer as one component of the resin composition (A), it contains paraffin oil. In view of excellent flexibility and appearance, it is preferable.
In the present invention, “resin” and “copolymer” are used to include rubber and elastomer. The term “copolymer” is used to include various copolymers such as a random copolymer, a block copolymer, and an alternating copolymer.

The content rate of each component in a resin composition is not specifically limited, The content rate of polyolefin resin may be 100 mass% independently, and may contain the other component in a suitable mass ratio.
For example, the content of the polyolefin resin in the resin composition (A) is 100% by mass at the maximum, but is not limited to this, and the mechanical properties and heat resistance of the entire resin composition (A) are not limited to this. It is preferable that it is 30-100 mass% at a point, and it is more preferable that it is 30-92 mass%. Therefore, in this case, the content of components other than the polyolefin-based resin in the resin composition (A) is preferably 70 to 0% by mass, and 70 to 8% by mass with respect to the entire resin composition (A). It is more preferable that
In the resin composition (A), the total content of the ethylene-α-olefin copolymer, the styrene elastomer, and the paraffinic oil as the polyolefin resin is 4 to 70% by mass. It is preferable in terms of suppressing the occurrence of blisters when stopped and in terms of flexibility, more preferably 8 to 70% by mass, and still more preferably 15 to 70% by mass. Therefore, in this case, the total content of components other than the ethylene-α-olefin copolymer, the styrene elastomer, and the paraffinic oil in the resin composition (A) is 30 to 96 mass with respect to the entire resin composition. %, More preferably 30 to 92% by mass, and even more preferably 30 to 85% by mass.

(A-1) Polyolefin-type resin It does not specifically limit as polyolefin-type resin used in this invention, The well-known thing conventionally used for the heat resistant resin composition can be used. Examples thereof include polyethylene, polypropylene, an ethylene-α-olefin copolymer, a polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component, and rubbers and elastomers thereof. Among these, the receptivity to various inorganic fillers including metal hydrates is high, there is an effect of maintaining mechanical strength even if a large amount of inorganic filler is blended, and withstand voltage while ensuring heat resistance, In particular, polyethylene, an ethylene-α-olefin copolymer, and a copolymer having an acid copolymerization component are preferable from the viewpoint of suppressing a decrease in withstand voltage characteristics at high temperatures. These polyolefin resins may be used alone or in combination of two or more.

  Examples of the polyethylene (PE) include high density polyethylene (HDPE), low density polyethylene (LDPE), ultra high molecular weight polyethylene (UHMW-PE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE). It is done. Among these, linear low density polyethylene (LLDPE) and low density polyethylene (LDPE) are preferable.

  The ethylene-α-olefin copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms. Specific examples of the α-olefin include propylene, 1-butene, 1- Examples include hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. Specific examples of the ethylene-α-olefin copolymer include an ethylene-propylene copolymer (EPR), an ethylene-butylene copolymer (EBR), and an ethylene-α-olefin synthesized in the presence of a single site catalyst. There are copolymers and the like. An ethylene-propylene copolymer is preferable, and examples thereof include an ethylene-propylene-diene copolymer.

  Examples of the polyolefin copolymer having an acid copolymerization component or an acid ester copolymerization component include ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid alkyl copolymer. A polymer etc. are mentioned. Among these, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer are preferable, and further, acceptability to inorganic filler and heat resistance. From the point of view, an ethylene-vinyl acetate copolymer and an ethylene-ethyl acrylate copolymer are particularly preferable.

The content of the polyolefin resin (A-1) in the resin composition (A) is as described above.
When the polyolefin resin (A-1) contains an ethylene-α-olefin copolymer, the content of the ethylene-α-olefin copolymer is the polyolefin resin (A) in the resin composition (A). The content of A-1) is appropriately set so as to be within the above range, and for example, it is preferably 30 to 100% by mass with respect to the resin composition (A).
Moreover, the content rate of an ethylene-alpha-olefin copolymer is a styrene-type elastomer (A-2) and paraffinic oil, when the resin composition (A) contains the paraffinic oil (A-3) mentioned later. It sets suitably so that a total content rate with (A-3) may be in the range mentioned above, for example, it is preferable that it is 4-70 mass% with respect to a resin composition (A). When the content of the ethylene-α-olefin copolymer is in the above range, the appearance of the electric wire is excellent when the flame-retardant crosslinked resin composition of the present invention is used for the electric wire.

(A-2) Styrene Elastomer In the present invention, a styrene elastomer (A-2) can also be used as a component of the resin composition (A). Styrene-based elastomer (A-2) refers to those having an aromatic vinyl compound such as styrene as a constituent component in the molecule. Therefore, in this invention, even if it contains an ethylene component in a molecule | numerator, if it contains an aromatic vinyl compound component, it will classify | categorize into a styrene-type elastomer (A-2).

Examples of such a styrene elastomer (A-2) include a copolymer of a conjugated diene compound and an aromatic vinyl compound, or a hydrogenated product thereof. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Examples of the aromatic vinyl compound include styrene, p- (t-butyl) styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-. Aminoethyl styrene, vinyl toluene, p- (t-butyl) styrene, etc. are mentioned.
Specific examples of the styrene-based elastomer (A-2) include SEBS (styrene-ethylene-butylene-styrene block copolymer), SIS (styrene-isoprene-styrene block copolymer), hydrogenated SBS, and SEEPS ( Styrene-ethylene-ethylene-propylene-styrene block copolymer), SEPS (styrene-ethylene-propylene-styrene block copolymer), hydrogenated SIS, HSBR (hydrogenated styrene / butadiene rubber), HNBR (hydrogenated acrylonitrile. Butadiene rubber). Examples of commercially available products include Septon (trade name, manufactured by Kuraray Co., Ltd.), Dynalon (trade name, manufactured by JSR Co., Ltd.), and the like.
In addition, as a styrene-type elastomer (A-2), it is preferable to use SEPS, SEEPS, and SEBS whose styrene content is 10 to 40% alone or in combination of two or more thereof.

The content of the styrene-based elastomer (A-2) is appropriately set so that the content of the polyolefin-based resin (A-1) in the resin composition (A) is within the above range. For example, the resin composition It is preferable that it is 2-50 mass% with respect to (A).
The content of the styrene elastomer (A-2) is such that when the resin composition (A) contains a paraffinic oil (A-3) described later, an ethylene-α-olefin copolymer and a paraffinic oil. It sets suitably so that a total content rate with (A-3) may be in the range mentioned above, for example, it is preferable that it is 4-70 mass% with respect to a resin composition (A). When the content of the styrene-based elastomer (A-2) is within this range, the appearance of the electric wire is excellent when the flame-retardant crosslinked resin composition of the present invention is used for the electric wire.

(A-3) Paraffinic oil In the present invention, paraffinic oil (A-3) can also be used as a component of the resin composition (A). As the paraffinic oil (A-3), for example, a non-aromatic mineral oil softener or a liquid or low molecular weight synthetic softener can be used. In general, the mineral oil softener used for rubber is a mixture of an aromatic ring, a naphthene ring and a paraffin chain, and the paraffin chain carbon number accounts for 50% or more of the total carbon number. Paraffinic oils having a naphthenic ring carbon number of 30 to 40% are called naphthenic oils, and those having an aromatic carbon number of 30% or more are called aromatic oils. Of these, paraffinic oil can be used in the present invention.
Examples of commercially available paraffinic oils include Dyna Process Oil (trade name, manufactured by Idemitsu Kosan Co., Ltd.).

The content of the paraffinic oil (A-3) is appropriately set so that the content of the polyolefin resin (A-1) in the resin composition (A) is within the above range. For example, the resin composition It is preferable that it is 2-40 mass% with respect to (A).
Moreover, the content rate of paraffinic oil (A-3) is, when the resin composition (A) contains at least one of an ethylene-alpha-olefin copolymer and a styrene-type elastomer (A-2), The content is appropriately set so that the total content of the ethylene-α-olefin copolymer and the styrene elastomer is within the above-described range. For example, 4 to 70% by mass with respect to the resin composition (A), More preferably, it is 8 to 70% by weight. When the content of the paraffinic oil (A-3) is within this range, the styrene elastomer can be well dispersed during melt-kneading to reduce the occurrence of kneading, and the flame-retardant crosslinked resin composition of the present invention. When the wire is used for an electric wire, the electric wire can be prevented from bleeding at a high temperature.

When the resin composition (A) contains at least one of an ethylene-α-olefin copolymer and a styrene elastomer (A-2), an ethylene-α-olefin copolymer, a styrene elastomer (A-2) The details of the effect that, when the total content of the paraffinic oil (A-3) and the paraffinic oil (A-3) are in the above-mentioned range are excellent in the appearance of the electric wire are not yet clear, they are considered as follows. As a side reaction when the silane coupling agent (D) performs a silane graft reaction on the polyolefin resin (A), a crosslinking reaction between the polyolefin resins (A-1) and a polymerization reaction between the silane coupling agents (D). This is considered to be a cause of the molded product. At this time, by allowing the styrene elastomer to coexist, the crosslinking reaction between the styrene elastomers occurs faster than the crosslinking reaction between the polyolefin resins (A-1). Is less likely to occur. The cross-linking reaction between the styrene-based elastomers (A-2) forms a situation close to the dynamic cross-linking of rubber, and the viscosity is improved. However, since it is difficult to generate blisters, the blisters can be greatly reduced. Furthermore, by adding paraffinic oil (A-3) to the styrene elastomer (A-2), further local reactions between the styrene elastomers (A-2) can be alleviated to reduce waste. Can be considered. Moreover, it is thought that there also exists an effect which suppresses the crosslinking reaction of polyolefin resin (A-1) by carrying out bridge reaction of paraffinic oil (A-3).
On the other hand, the case where the ethylene-α-olefin copolymer is allowed to coexist is considered to be basically the same as the case where the styrene-based elastomer is allowed to coexist.

  The resin composition (A) contains at least one of ethylene-α olefin rubber and styrene elastomer (A-2) as the polyolefin resin (A-1), and paraffin oil (A-3). As described above, it is preferable in that the appearance of the obtained molded product and the bleed of the electric wire at a high temperature can be prevented. More preferably, the resin composition (A) contains a styrene-based elastomer (A-2) and a paraffinic oil (A-3). Among the above-mentioned ethylene-α-olefin rubbers, ethylene-propylene-diene rubber is preferable.

(B) Organic peroxide The organic peroxide used in the present invention generates radicals by thermal decomposition, and is a radical of an unsaturated group of a silane coupling agent described later and a polyolefin resin (A-1) or the like. It functions to promote the grafting reaction by the reaction (including the reaction of abstracting hydrogen radicals from the polyolefin resin (A-1) and the like). The organic peroxide (B) is not particularly limited as long as it generates radicals. R ¹ —OO—R ² , R—OO—C (═O) R ³ and R ³ C (═O ) -OO (C = O) R ⁴ is preferred. Here, R ¹ , R ² , R ³ and R ⁴ each independently represents an alkyl group, an aryl group, or an acyl group. Among these, in the present invention, it is preferable that R ¹ , R ² , R ³ and R ⁴ are all alkyl groups, or any one is an alkyl group and the other is an acyl group.

  Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2. , 5-Di (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane N-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxide Oxyisopropyl carbonate, diacetyl peroxide, Uronium peroxide, such as tert- butyl cumyl peroxide and the like. Of these, dicumyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2 are preferable in terms of odor, colorability, and scorch stability. , 5-di- (tert-butylperoxy) hexyne-3 is most preferred.

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

  The compounding quantity of an organic peroxide is the range of 0.01-0.6 mass part with respect to 100 mass parts of resin compositions (A), Preferably it is 0.1-0.5 mass part. By setting the organic peroxide within this range, the polymerization can be carried out in an appropriate range, and a composition excellent in extrudability can be obtained without generating an agglomerate due to a crosslinked gel or the like.

  That is, when the blending amount of the organic peroxide is less than 0.01 parts by mass, the crosslinking reaction of the polyolefin resin does not proceed via the silane coupling agent at the time of crosslinking, and the silane coupling agent may be polymerized. . On the other hand, when the amount exceeds 0.6 parts by mass, the silane coupling agent tends to volatilize or there is a risk that the side reaction may cause a flaw.

(C) Inorganic filler As the inorganic filler (C), a site capable of forming a hydrogen bond or the like with a reaction site such as a silanol group of a hydrolyzable silane coupling agent on the surface of the inorganic filler or a site capable of chemical bonding by a covalent bond If it has, it can use without a restriction | limiting in particular. In the inorganic filler, OH groups (OH groups such as hydroxyl groups, water-containing or crystal water molecules, carboxyl groups), amino groups, SH groups, etc., can be chemically bonded to the reaction site of the hydrolyzable silane coupling agent. Is mentioned.

  Such an inorganic filler (C) is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, Metal hydroxide or metal such as aluminum oxide, aluminum nitride, aluminum borate, whisker, hydrated aluminum silicate, alumina, hydrated magnesium silicate, basic magnesium carbonate, metal compound having water or crystal water such as hydrotalcite Hydrates, boron nitride, silica (crystalline silica, amorphous silica, etc.), carbon, clay, zinc oxide, tin oxide, titanium oxide, molybdenum oxide, antimony trioxide, silicone compounds, quartz, talc , Zinc borate, white carbon It can be used zinc borate, hydroxy stannate, zinc stannate.

  Further, the inorganic filler (C) can be used by mixing with a silane coupling agent. The method of mixing the inorganic filler and the silane coupling agent is not particularly limited, but the silane coupling is carried out in an inorganic filler that has not been treated or has been previously surface-treated with stearic acid, oleic acid, phosphate ester, or a part of the silane coupling agent. There are a method of adding and mixing an agent without heating or heating, a method of adding a silane coupling agent in a state where a filler is dispersed in a solvent such as water, and the details will be described later. In this invention, it is preferable to add and mix a silane coupling agent in an inorganic filler, without heating or heating.

  The said inorganic filler (C) can use the inorganic filler surface-treated with the silane coupling agent. Examples of the silane coupling agent surface-treated magnesium hydroxide include magnesium hydroxide commercial products (Kisuma 5L, Kisuma 5P (both trade names, manufactured by Kyowa Chemical Co., Ltd.)), aluminum hydroxide, and the like.

One kind of these inorganic fillers (C) may be blended alone, or two or more kinds may be mixed and used.
Among these inorganic fillers, at least one of silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, zinc borate, zinc hydroxystannate and talc is preferable.

When the inorganic filler (C) is a powder, the average particle size is preferably 0.2 to 10 μm, more preferably 0.3 to 8 μm, 0.4 to 5 μm, 0.4 to More preferably, it is 3 μm.
When the average particle size of the inorganic filler (C) is less than 0.2 μm, the inorganic filler (C) may cause secondary aggregation when mixed with the silane coupling agent in the silane masterbatch, resulting in a decrease in appearance and blisters on the molded body. There is. On the other hand, when it exceeds 10 μm, the appearance may be deteriorated, the retention effect of the silane coupling agent (D) may be lowered, and a problem may be caused in crosslinking.
The average particle size is determined by an optical particle size analyzer such as a laser diffraction / scattering particle size distribution measuring device after being dispersed with alcohol or water.

The compounding quantity of an inorganic filler (C) is 10-400 mass parts with respect to 100 mass parts of resin compositions (A), Preferably it is 30-280 mass parts, More preferably, it is 30-200 mass parts.
When the blending amount of the inorganic filler (C) is less than 10 parts by mass, the graft reaction of the silane coupling agent (D) becomes non-uniform and the desired heat resistance cannot be obtained, or the appearance deteriorates due to the non-uniform reaction. There is a risk. On the other hand, if it exceeds 400 parts by mass, the load during molding or kneading becomes very large, and secondary molding may be difficult.

(D) Silane Coupling Agent The silane coupling agent (D) is not particularly limited as long as it has a group that can be grafted to the polyolefin resin (A) in the presence of a radical and a group that can be hydrolyzed. However, conventionally, a silane coupling agent having an unsaturated group used for silane crosslinking can be used. For example, a compound represented by the following general formula (1) can be used.

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

R _a11 of the silane coupling agent represented by the general formula (1) is preferably a group containing an ethylenically unsaturated group, such as a vinyl group, an allyl group, a (meth) acryloyloxyalkylene group, or p-styryl. Group, etc. can be mentioned, More preferably, it is a vinyl group.

R _b11 represents an aliphatic hydrocarbon group, a hydrogen atom, or Y ¹³ described later, and the aliphatic hydrocarbon group is an aliphatic hydrocarbon group other than an aliphatic unsaturated hydrocarbon group, preferably having 1 to 1 carbon atoms. 8 monovalent aliphatic hydrocarbon groups. R _b11 is preferably Y ¹³ described later.

Y ¹¹ , Y ¹² and Y ¹³ represent an organic group to be hydrolyzed, and examples thereof include an alkoxy group having 1 to 4 carbon atoms, an aryloxy group having 6 to 8 carbon atoms, and an acyloxy group having 1 to 4 carbon atoms, Among them, an alkoxy group having 1 to 4 carbon atoms, preferably an acyloxy group having 1 carbon atom (OCOCH ₃ ), and more preferably an alkoxy group having 1 to 2 carbon atoms. Specific examples of the organic group to be hydrolyzed include a methoxy group, an ethoxy group, a butoxy group, an acetyloxy group, and a (meth) acrylooxy group. Among these, a methoxy group or an ethoxy group is preferable from the viewpoint of reactivity.

The silane coupling agent is preferably a silane coupling agent having an unsaturated group with a high hydrolysis rate, more preferably R _b11 is Y ¹³ and Y ¹¹ , Y ¹² and Y ¹³ are the same. Silane coupling agent. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, vinyltriacetoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, Examples thereof include a silane coupling agent having an ethylenic double bond at the end, such as methacryloxypropylmethyldimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Among such crosslinkable silane coupling agents, a silane coupling agent having a vinyl group and an alkoxy group at the terminal is more preferable, and vinyltrimethoxysilane and vinyltriethoxysilane are particularly preferable.

  A silane coupling agent (D) is 0.5-15.0 mass parts with respect to 100 mass parts of inorganic fillers (C), Preferably it is 1.0-12.0 mass parts. The silane coupling agent (D) itself may be used, or one diluted with a solvent may be used.

  When the usage-amount of a silane coupling agent (D) is less than 0.5 mass part, bridge | crosslinking is not fully performed but there exists a possibility that desired heat resistance and a mechanical characteristic cannot be acquired to a heat resistant resin composition. On the other hand, when the amount exceeds 15.0 parts by mass, no more silane coupling agent is adsorbed on the surface of the inorganic filler (C) and volatilizes during kneading, which is not economical and condenses. The body (also referred to as a molded product) may be cross-linked gel burned or burned to deteriorate the appearance. In particular, the appearance defect is remarkable when the content exceeds 15.0 parts by mass.

  Moreover, in addition to satisfy | filling the above-mentioned usage-amount, a silane coupling agent (D) is 0.5-18.0 mass parts with respect to 100 mass parts of resin compositions (A) in a silane masterbatch. Is preferably contained in a proportion of 1.0 to 8.0 parts by mass, more preferably in a proportion of 3.0 to 8.0 parts by mass. Particularly preferred.

  When the usage-amount of a silane coupling agent (D) is less than 0.5 mass part, bridge | crosslinking is not fully performed but there exists a possibility that desired heat resistance and a mechanical characteristic cannot be acquired to a heat resistant resin composition. On the other hand, when the amount exceeds 18.0 parts by mass, the silane coupling agents (D) are condensed with each other, and the molded article may be brittle or burnt in the crosslinked gel, resulting in a poor appearance.

In the silane masterbatch, the silane coupling agent (D) is more preferably contained in a proportion of more than 4 parts by mass and 15 parts by mass or less with respect to 100 parts by mass of the resin composition (A). More preferably, it is contained in a proportion of 5 to 12 parts by mass, particularly preferably 6 to 10 parts by mass.
In this way, when the content of the silane coupling agent (D) in the silane master batch is set to be large, the occurrence of cross-linking flaws can be suppressed even if the extruder is stopped once, and the silane master batch remaining in the extruder If only this is poured out, a molded article having a good appearance can be obtained.
Although the details are not yet clear, it is thought as follows. That is, by adding a large amount of the silane coupling agent (D), the grafting reaction due to the decomposition of the organic peroxide (B) during kneading causes the silane coupling agent (D) and the polyolefin resin (A) having a high reaction rate. The reaction with -1) and the like and the reaction between the silane coupling agents (D) are dominant, and the crosslinking reaction between the polyolefin resins (A-1) and the like hardly occurs. Thus, since polyolefin resin (A-1) etc. hardly react, external appearance becomes favorable. On the other hand, the reaction between the silane coupling agents (D) is limited by the content of the inorganic filler (C), and most of the silane coupling agents (D) are bonded to the inorganic filler (C). The reaction between the free silane coupling agents (D) hardly occurs. Therefore, as described above, it is considered that a molded article having a clean appearance free from gel spots can be obtained.

(E) Carrier resin Although it does not specifically limit as carrier resin (E), The thing similar to the said polyolefin resin (A-1) can be used, Preferably affinity with silanol condensation catalyst (F) is good. It is an ethylene-based resin in terms of heat resistance. Specifically, examples of the ethylene-based resin include the above-mentioned polyethylene (PE) such as linear low density polyethylene, low density polyethylene, ultra low density polyethylene, high density polyethylene, and ultra high molecular weight polyethylene. Density polyethylene, low density polyethylene, ultra-low density polyethylene, and high density polyethylene are preferred, and linear low density polyethylene is particularly preferred.

  The amount of the carrier resin (E) is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and further preferably 2 to 40 parts by mass with respect to 100 parts by mass of the resin composition (A). . Further, an inorganic filler may or may not be added to this carrier resin (E). The amount of the inorganic filler at that time is not particularly limited, but is preferably 350 parts by mass or less with respect to 100 parts by mass of the resin component of the carrier resin (E). This is because if the amount of the inorganic filler is too large, the silanol condensation catalyst (F) is difficult to disperse and the crosslinking is difficult to proceed. On the other hand, when there is too much carrier resin (E), there exists a possibility that the crosslinking degree of a molded object may fall and appropriate heat resistance may not be obtained.

(F) Silanol condensation catalyst The silanol condensation catalyst (F) in the present invention has a function of binding a silane coupling agent (D) having a grafted unsaturated group in the presence of moisture by a condensation reaction. Based on the action of the silanol condensation catalyst (F), the polyolefin resin (A-1) and the like are cross-linked through the silane coupling agent (D). As a result, a resin molded body excellent in heat resistance (also simply referred to as a molded body or a heat resistant resin composition) can be obtained.

  As the silanol condensation catalyst (F), organotin compounds, metal soaps, platinum compounds and the like are used. Common silanol condensation catalysts (F) include, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, zinc stearate, lead stearate, barium stearate, calcium stearate, stearin Sodium acid, lead naphthenate, lead sulfate, zinc sulfate, organic platinum compounds, etc. are used, but particularly preferred are organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctiate, dibutyltin diacetate, etc. is there.

  The amount of the silanol condensation catalyst (F) 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 resin composition (A). .

  When the blending amount of the silanol condensation catalyst (F) is within the above range, the condensation reaction of the silane coupling agent (D) proceeds rapidly to form a uniform cross-linked structure, and the molded product has flame retardancy. In addition to improving the productivity and productivity, it is possible to suppress partial gelation and to improve the appearance and resin physical properties of the molded product.

  In addition, the heat-resistant resin composition includes various additives commonly used in electric wires, electric cables, electric cords, sheets, foams, tubes, and pipes, such as antioxidants, lubricants, metal additives, and the like. An activator, a flame retardant (auxiliary) agent, other resins, and the like can be appropriately blended within a range not impairing the object of the present invention. These additives should be added to the carrier resin. In particular, the antioxidant and the metal deactivator are the silane coupling agent (D) mixed with the inorganic filler (C) and the polyolefin resin (A-1). It is better to add to the carrier resin (E) so as not to hinder grafting onto the carrier resin. Furthermore, it is preferable that a crosslinking adjuvant is not included substantially among them. In particular, it is preferable that the crosslinking aid is not substantially contained in the step of preparing the master batch. When the cross-linking aid is added, the cross-linking aid reacts with the organic peroxide (B) during kneading, cross-linking of the polyolefin resin (A-1) and the like occurs, gelation occurs, and the appearance of the molded product If the silane coupling agent (D) is not markedly lowered or grafted to the polyolefin resin (A-1) or the like, the final molded article may not have heat resistance. The additive can be introduced into the heat resistant resin composition as long as the object of the present invention is not impaired.

  Here, the crosslinking aid refers to a material that forms a partially crosslinked structure with the polyolefin resin (A-1) in the presence of an organic peroxide, such as polypropylene glycol diacrylate, trimethylolpropane triacrylate. And polyfunctional compounds such as methacrylate compounds, allyl compounds such as triallyl cyanurate, maleimide compounds, and divinyl compounds.

Examples of the antioxidant include amine-based oxidation such as a polymer of 4,4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline. Inhibitor, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Phenol-based antioxidants such as propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben ヅ imidazole and its zinc salt, pentae Suritoru - tetrakis (3-lauryl - thiopropionate) and the like sulfur-based antioxidant such.
Examples of metal deactivators include N, N′-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.

  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 resin composition (A).

  Flame retardant (auxiliary) and filler include carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compound, quartz, talc, calcium carbonate, magnesium carbonate, zinc borate And white carbon. These fillers may be used when a silane coupling agent is mixed as a filler, or may be added to a carrier resin.

  Examples of the lubricant include hydrocarbon, siloxane, fatty acid, fatty amide, ester, alcohol, and metal soap. These lubricants should be added to the carrier resin.

Hereinafter, the manufacturing method of the heat resistant resin composition of this invention is demonstrated.
In the method for producing a heat resistant resin composition of the present invention, a resin composition (A), an organic peroxide (B), an inorganic filler (C) and a silane coupling agent (D) are mixed with a silanol condensation catalyst (F). The step (a) of melt-mixing without mixing is carried out.
Thus, in the step (a), the silanol condensation catalyst (F) is not mixed with any component. “Not mixed” includes not only the case where the silanol condensation catalyst (F) is not completely used, but also the inevitable use as impurities and the use that can be melt-mixed in the step (b) described later. Meaning.

  In the step (a), in the first step, the inorganic filler (C), the silane coupling agent (D) and the organic peroxide (B) are dried at a temperature below the decomposition temperature of the organic peroxide, preferably at room temperature. It is preferable to obtain a mixture by wet mixing (step (a-1)).

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

In the method of adding the silane coupling agent (D) in a state where the inorganic filler (C) is dispersed in a solvent such as water (wet mixing), the silane coupling agent (D) is strongly bonded to the inorganic filler (C). Therefore, the subsequent condensation reaction may be difficult to proceed. On the other hand, the method of adding and mixing the silane coupling agent (D) in the inorganic filler (C) with heating or non-heating (dry mixing) is relatively binding of the inorganic filler (C) and the silane coupling agent (D). Since it is weak, the cross-linking easily proceeds efficiently.
At that time, the silane coupling agent (D) and the organic peroxide (B) may be mixed together and dispersed in the inorganic filler (C) or may be dispersed separately. It is better to mix together.

  The silane coupling agent (D) added to the inorganic filler (C) exists so as to surround the surface of the inorganic filler (C), and part or all of the silane coupling agent (D) is adsorbed to the inorganic filler (C) or filled with the filler (C ) It may chemically bond with the surface. In such a state, volatilization of the silane coupling agent (D) when kneading and processing the material in a subsequent kneader or Banbury mixer is greatly reduced, and an organic peroxide ( By B), the unsaturated group of the silane coupling agent (D) is considered to undergo a crosslinking reaction with the polyolefin resin (A-1) and the like. Further, it is considered that the silane coupling agent (D) undergoes a condensation reaction with the silanol condensation catalyst (F) during molding. Although the mechanism of this reaction is not clear, if the bond between the inorganic filler (C) and the silane coupling agent (D) is too strong during the condensation reaction, the inorganic filler (C) can be added even if the silanol condensation catalyst (F) is added. It is considered that the silane coupling agent (D) bonded to the silane coupling agent does not come off from the inorganic filler (C), and the silanol condensation reaction (crosslinking reaction) is difficult to proceed.

  Depending on the production conditions, only the silane coupling agent (D) may be mixed with the inorganic filler (C), and the organic peroxide (B) may be added in the step of producing the silane master batch in the next step. In addition, as a method of adding organic peroxide (B), what was disperse | distributed to the resin composition (A), for example, polyolefin-type resin (A-1), may be added alone, or it may disperse | distribute to oil etc. Although it may be added, it is preferable to be dispersed in the resin composition (A).

In the next step, each of the mixture and the resin composition (A) is added to a mixer, and melt kneading while heating above the decomposition temperature of the organic peroxide (B) without mixing the silanol condensation catalyst (F). And it is preferable to prepare a silane masterbatch (process (a-2)).
More preferably, after the silane coupling agent (D) and the organic peroxide (B) are mixed with the inorganic filler (C), the mixture and the resin composition (A) are added to the organic peroxide (B The silane masterbatch (graftmer) is prepared by grafting the silane coupling agent (D) to the polyolefin resin (A-1) mainly at a decomposition temperature of).

The kneading temperature is not less than the decomposition temperature of the organic peroxide (B), preferably the decomposition temperature of the organic peroxide (B) + 25 ° C. to 110 ° C. This decomposition temperature is preferably set after the polyolefin resin (A-1) is melted. Also, kneading conditions such as kneading time can be set as appropriate.
When kneading at a temperature lower than the decomposition temperature of the organic peroxide, the silane graft reaction does not occur and the desired heat resistance cannot be obtained, and the organic peroxide reacts during the extrusion, resulting in a desired shape. In some cases, it cannot be molded. Preferably, the resin composition (A), for example, the polyolefin resin (A-1) is kneaded in a melted state without being kneaded in a melted state.

The kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastics, etc., and as the apparatus, for example, a single screw extruder, a twin screw extruder, a roll, a banbury depending on the amount of the inorganic filler (C). A mixer or various kneaders are used, but a closed mixer such as a Banbury mixer or various kneaders is preferable in terms of resin dispersion and crosslinking stability.
Usually, when such inorganic filler (C) exceeds 100 parts by mass with respect to 100 parts by mass of the resin composition (A), kneading with a continuous kneader, a pressure kneader or a Banbury mixer is common. .

The silane coupling agent (D) is preferably not introduced into the silane masterbatch alone, but introduced by premixing with the inorganic filler (C).
This is because the silane coupling agent (D) volatilizes during kneading and is not economical, and the non-adsorbing silane coupling agent (D) is condensed to make melting and kneading difficult, and is desirable during extrusion molding. This is because the shape may not be obtained.

  Moreover, the production | generation of the above-mentioned mixture does not set it as a melt-kneading process, but a resin composition (A), an organic peroxide (B), a silane coupling agent (D), and an inorganic filler (C) together. A silane master batch can be prepared by mixing at a decomposition temperature of the organic peroxide (step a). In addition, since there exists a possibility that local bridge | crosslinking may arise and generate | occur | produce a flaw, it is preferable to produce | generate a mixture preferably in a melt-kneading process and a separate process.

  Thus, the silane masterbatch prepared in the step (a) includes at least a decomposition product of the organic peroxide (B) and a silane coupling agent (D) to the extent that it can be molded by the step (b) described later. Contains a silane graft polymer grafted onto a polyolefin resin (A-1) or the like.

In the method for producing a heat-resistant resin composition of the present invention, next, the step (b) of molding after melting and mixing the silane masterbatch and the silanol condensation catalyst (F) is carried out. This step (b) is a step in which the silane master batch and the silanol condensation catalyst (F) are melt-mixed, and the step (b) is preferably the following mode. That is, the silanol condensation catalyst (F) and the carrier resin (E) are mixed to produce a catalyst master batch (b-1), and the silanes prepared in the steps (a-2) and (b-1), respectively. The aspect which has the process (b-2) shape | molded after melt-mixing a masterbatch and a catalyst masterbatch, and prepared by the process (b-1), the process (a), and the process (b-1), respectively. And a step (b-3) of molding after melt-mixing the silane masterbatch and the catalyst masterbatch.
Thus, in a suitable process (b), the process (b-1) which mixes carrier resin (E) and a silanol condensation catalyst (F), and obtains a catalyst masterbatch is implemented.
Depending on the melting temperature of the carrier resin (E), the kneading temperature can be 80 to 250 ° C, more preferably 100 to 240 ° C. The kneading conditions such as kneading time can be set as appropriate.
The kneading method can be performed by the same method as the above kneading method.

  Here, as described above, the silanol condensation catalyst (F) is included in the catalyst master batch and is not included in the silane master batch. This is because when the silanol condensation catalyst (F) is contained in the silane masterbatch, the silane coupling agent (D) is condensed and melt mixing becomes difficult, and the desired shape cannot be obtained during extrusion molding. Because there is.

  Next, the silane masterbatch and the catalyst masterbatch are melt-kneaded in a coating apparatus while being heated, and, for example, covered with an extruded electric wire or fiber, and formed into a desired shape (step b-2). In addition, what is obtained by the (process a) can also be used for the silane masterbatch to be used (process (b-3)).

In some melt-kneading, there are resins whose melting point cannot be measured by DSC such as elastomer, but kneading is performed at a temperature at which at least one of the polyolefin-based resin (A-1) and the organic peroxide (B) is melted. The carrier resin (E) needs to be melted in order to disperse the silanol condensation catalyst (F). The kneading conditions such as kneading time can be set as appropriate.
The kneading method can be performed by the same method as the above kneading method.

  In this way, step (b) is performed. The molded product obtained in the step (b) is a mixture (uncrosslinked product) of a silane masterbatch and a silanol condensation catalyst (F), and contains at least the above-mentioned silane graft polymer.

In the method for producing a heat resistant resin composition of the present invention, next, a step (c) is performed in which the molded product is brought into contact with moisture to be crosslinked. The process itself of the step (c) of bringing the molded article into contact with moisture and crosslinking can be carried out by a usual method. By bringing moisture into contact with the molded product, the silane coupling agent (D) is hydrolyzed, and the silane coupling agent (D) is condensed with the silanol condensation catalyst (F) to form a crosslinked structure.
The condition of contacting with moisture proceeds only by storing at room temperature, but in order to further accelerate the crosslinking, it may be immersed in warm water, placed in a moist heat bath, or exposed to high temperature steam. Moreover, you may apply a pressure in order to permeate | transmit a water | moisture content inside in that case.

Thus, the manufacturing method of the heat resistant resin composition of this invention is implemented, and the heat resistant resin composition of this invention is manufactured. In this heat resistant resin composition, the polyolefin resin (A-1) of the resin composition (A) is condensed after the organic groups Y ¹¹ , Y ¹² and Y ¹³ of the silane coupling agent (D) are hydrolyzed. The polyolefin resins (A-1) are cross-linked with each other through silanol bonds.
It can be confirmed that the polyolefin resin (A-1) is crosslinked with the polyolefin resins (A-1) via silanol bonds, for example, by heat deformation or hot set. It has been confirmed that the polyolefin resins (A-1) are cross-linked by the method.
On the other hand, the polyolefin-based resin (A-1) is bonded to the inorganic filler (C) through a silanol bond, and the mechanical strength and wear resistance are greatly improved.

In the present invention, the details of the reaction mechanism are not yet clear, but are considered as follows.
That is, the polyolefin resin (A-1) of the resin composition (A) is grafted in the presence of the organic peroxide (B) when heated and kneaded with the inorganic filler (C) and the silane coupling agent (D). It crosslinks with the inorganic filler (C) through the reacted silane coupling agent (D). Only when a specific amount of the silane coupling agent (D) is blended with the resin composition (A), it becomes possible to blend a large amount of the inorganic filler (C) without impairing the extrusion processability during molding. It has both heat resistance and mechanical properties while ensuring high flame retardancy.

Although the details of the mechanism by which the inorganic filler (C) mixed with the silane coupling agent (D) acts on the polyolefin resin (A-1) are not yet known, it is considered as follows. That is, by mixing the silane coupling agent (D) and the inorganic filler (C), the silane coupling agent (D) is bonded to the surface of the inorganic filler (C) with an alkoxy group, and vinyl existing at the other end. Without bonding to the uncrosslinked portion of the polyolefin resin (A-1) with an ethylenically unsaturated group such as a group, or to the hole or surface of the inorganic filler (C) without bonding to the inorganic filler (C). It is adsorbed and retained chemically and chemically. When kneading is performed by adding a peroxide in this state, the silane coupling agent (D) hardly volatilizes, and the ethylenically unsaturated group which is a reactive site of the silane coupling agent (D) is present. It reacts with the polyolefin resin (A-1) of the resin composition (A) and causes a graft reaction.
Furthermore, carrier resin (E) is added to this, and when it comes into contact with moisture, the silane coupling agent (D) bonded to an uncrosslinked portion such as polyolefin resin (A-1) is hydrolyzed and silanol condensed to form polyolefin. Resin (A-1) couple | bonds together through a silane coupling agent (D), and bridge | crosslinks. The heat resistance of the resin composition (also referred to as a crosslinked composition) and molded product obtained by this reaction is extremely high, and it becomes possible to obtain a resin composition and molded product that do not melt even at high temperatures.
On the other hand, the silane coupling agent (D) strongly bonded to the surface of the inorganic filler (C) in advance does not cause this hydrolysis reaction, and the bond with the inorganic filler (C) is maintained. Therefore, a bond between the polyolefin resin (A-1) and the inorganic filler (C) occurs, and crosslinking of the polyolefin resin (A-1) and the like through the inorganic filler (C) occurs. As a result, the adhesion between the polyolefin resin (A-1) and the like and the inorganic filler (C) is strengthened, and a heat resistant resin composition having good mechanical strength and wear resistance and less scratching is obtained.

  The production method of the present invention includes, for example, heat-resistant flame-retardant insulated wires / heat-resistant flame-retardant cable coating materials, other heat-resistant and flame-retardant electric wire parts, flame-resistant and heat-resistant sheets, flame-resistant and heat-resistant films, and other various molded products having heat resistance, In particular, power plugs, connectors, sleeves, boxes, tape bases, tubes, sheets, wiring materials used for internal and external wiring of electrical and electronic equipment, wire insulators, molded parts such as sheaths, especially It can be applied to the production of electric wires and optical cables. These shapes can be formed by coating while being melt kneaded in an extrusion coating apparatus. Such a molded article is a highly heat resistant high temperature non-melting cross-linking composition added with a large amount of inorganic filler, using a general-purpose extrusion coating apparatus without using a special machine such as an electron beam cross-linking machine, It can be produced by extrusion coating around the periphery, or around a conductor that is longitudinally or twisted with tensile strength fibers. For example, any conductor such as an annealed copper single wire or stranded wire can be used as the conductor. In addition to the bare wire, the conductor may be tin-plated or an enamel-covered insulating layer. The thickness of the insulating layer (the coating layer made of the heat resistant resin composition of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 mm to 5 mm.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these. In Tables 1 to 5, the numerical values in the examples and comparative examples represent parts by mass. In Tables 1 to 5, the conversion amount (first decimal place) with respect to 100 parts by mass of the inorganic filler (C) of the silane coupling agent (D) is described as “equivalent amount (C100 parts by mass)”.

  Examples 1 to 81 and Comparative Examples 1 to 17 were produced by changing the respective specifications using the components shown in Tables 1 to 5.

In addition, as each compound shown in Table 1-Table 5, the following were used.
<Components of resin composition (A)>
EV180 (trade name) is an ethylene / vinyl acetate copolymer VA content 33 mass% manufactured by Mitsui DuPont Chemical Co., Ltd.
V-9000 (trade name) is an ethylene-vinyl acetate copolymer manufactured by Mitsui DuPont Polychemical Co., Ltd. VA content 41 mass%
NUC6510 (trade name) is Dow ethylene ethyl acrylate resin EA content 22% by mass
KS240T (trade name) is a kernel (registered trademark) (low density polyethylene) manufactured by Nippon Polyethylene
UE320 (trade name) is Novatec PE (linear low-density polyethylene (PE)), Mitsubishi Oil Chemical Co., Ltd. PB222A (trade name) is Sun Allomer (trade name), random polypropylene, Sun Allomer Co., Ltd. Evolution SP0540 (Product) Name) is metallocene LLDPE, manufactured by Prime Polymer Co., Ltd. Septon 4077 (trade name) is a styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS, styrene elastomer), manufactured by Kuraray Co., Ltd., containing styrene components 30%
Mitsui 3092 EPM is ethylene-propylene-diene rubber (ethylene content 66%), Mitsui Chemicals, Inc. EP11 is ethylene-propylene-diene rubber (EPDM), JSR Dyna Process Oil PW90 (trade name) is paraffinic oil, Idemitsu Kosan Co., Ltd. Admer XE070 (trade name) is maleic acid-modified polyethylene, manufactured by Mitsui Chemicals, Inc.

<Inorganic filler (C)>
Tokuseal U (trade name) is a wet silica (precipitated silica) manufactured by Tokuyama Corporation
Crystallite 5X (trade name) is Tatsumori's crystalline silica Kisuma 5 (trade name) is Kyowa Chemical's untreated magnesium hydroxide Softon 1200 (trade name) is calcium carbonate made by Shiroishi Calcium GROMAX LL (trade name) is a calcined kaolin fire break 290 (trade name) manufactured by Takehara Chemical Co., Ltd. Zinc borate made by Borax Corporation Alkanex ZHS (trade name) is zinc hydroxystannate manufactured by Mizusawa Chemical Co., Ltd. Heidilite (registered trademark) H42M is an aluminum hydroxide MV talc (trade name) manufactured by Showa Denko Co., Ltd.

<Silane coupling agent (D)>
KBM1003 (trade name) is vinyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. KBE1003 (trade name) is vinyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. <Organic peroxide (B)>
DCP is dicumyl peroxide (decomposition temperature 151 ° C.) manufactured by Nippon Kayaku Co., Ltd.
Perhexa 25B (trade name) is 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (decomposition temperature 149 ° C.) manufactured by NOF Corporation.
<Silanol condensation catalyst (F)>
ADK STAB OT-1 (trade name) is dioctyltin laurate <carrier resin (E)> manufactured by Asahi Denka Kogyo Co., Ltd.
UE-320 and EV180

<Antioxidant (hindered phenolic antioxidant)>
Irganox 1076 (trade name) is octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate manufactured by Nagase & Co.

  Into the 10 L Henschel mixer made by Toyo Seiki, the inorganic filler (C), the silane coupling agent (D), the organic peroxide, etc. (B), etc., in the mass part ratio described in the column “II” in Tables 1 to 5 Then, the mixer was mixed at room temperature for 1 hour to obtain a powder mixture (step (a-1)).

Next, each component of the powder mixture and the resin composition (A) is put in a 2 L Banbury mixer manufactured by Nippon Roll at a mass part ratio described in “I” column and “II” column of Tables 1 to 5. The mixture is kneaded for about 12 minutes at a temperature higher than the decomposition temperature of the organic peroxide (B), specifically 180 to 190 ° C, and discharged at a material discharge temperature of 180 to 190 ° C. Thus, a silane master batch was obtained (step (a-2)).
In addition, about Example 9, each component described in the "I" column and the "II" column of Table 1 was mixed at once with a Banbury mixer, without previously mixing with a Henschel mixer (process (a)). .

  Carrier resin (E), silanol condensation catalyst (F), etc. are separately mixed in a Banbury mixer at a temperature of 180 to 190 ° C. at a mass part ratio described in the column “III” in Tables 1 to 5, and the material is discharged. The mixture was melt-kneaded at a temperature of 180 to 190 ° C. to obtain a catalyst master batch (step (b-1)).

  Next, the silane masterbatch and the catalyst masterbatch were melt-mixed at a ratio of 100: 5 (mass ratio) at 180 ° C. by a Banbury mixer, and a 40 mm extruder with L / D = 24 (compressor screw temperature 190 ° C., head The temperature was 200 ° C.), and an uncrosslinked heat-resistant resin composition having a thickness of 1 mm was coated on the outside of the 1 / 0.8 mm TA conductor to obtain an electric wire having an outer diameter of 2.8 mm (step (b-2)). ). Thereafter, the wire was left in an atmosphere of 80 ° C. and 95% humidity for 24 hours to contact with moisture to obtain a wire having a heat-resistant resin composition coating obtained by crosslinking an uncrosslinked heat-resistant resin composition ( Step (c)).

  For Example 21 and Comparative Example 17, a silane masterbatch and a catalyst masterbatch were melt-mixed at a ratio of 100: 5 (mass ratio) at 180 ° C. by a Banbury mixer for the vertical flame retardant test, and the L / D = 24 mm 40 mm extruder (compressor screw temperature 190 ° C., head temperature 200 ° C.), the outside of the 1 / 1.6 mm TA conductor is coated with a 1.5 mm thick uncrosslinked heat resistant resin composition, An electric wire having an outer diameter of 4.6 mm was obtained (step (b-2)). Thereafter, the electric wire was left in an atmosphere of 80 ° C. and 95% humidity for 24 hours to contact with moisture to obtain an electric wire having a heat-resistant resin composition coating obtained by crosslinking an uncrosslinked heat-resistant resin composition. (Step (c)).

About each obtained electric wire, the following heat deformation, a hot set, and an extrusion external appearance were measured, and the result is shown in Tables 1-5.
In Comparative Example 9, the mixture of the silane masterbatch and the catalyst masterbatch was so rough that extrusion molding was not possible.

  Heat deformation 1 was performed at a measurement temperature of 150 ° C. and a load of 3 N based on the conditions of JIS C 3005. In addition, 50% or less was set as the pass.

  Heat deformation 2 was performed at a measurement temperature of 180 ° C. and a load of 3 N based on the conditions of UL1581. In addition, although 50% or less is preferable, this test was shown for reference.

  In Hot Set 1, after creating a tubular piece of electric wire and marking it with a length of 50 mm, attach a weight of 117 g in a constant temperature bath at 170 ° C., leave it for 15 minutes, and measure the length after leaving it. The elongation was determined. An elongation of 120% or less was accepted.

  In Hot Set 2, after creating a tubular piece of electric wire and marking it with a length of 50 mm, attach a 180 g weight in a constant temperature bath at 180 ° C., leave it for 15 minutes, and measure the length after leaving it. The elongation was determined. The elongation is preferably 120% or less, but this test is shown for reference.

  In Hot Set 3, after creating a tubular piece of electric wire and marking it with a length of 50 mm, attach a weight of 117 g in a constant temperature bath at 220 ° C., leave it for 15 minutes, and measure the length after leaving it. The elongation was determined. The elongation is preferably 120% or less, but this test is shown for reference.

  Extrusion appearance 1 observed the extrusion appearance when manufacturing an electric wire. In addition, when the appearance was good with a 25 mm extruder at a linear speed of 10 m, the appearance was good as “A”, the appearance was slightly bad as “B”, the appearance as remarkably bad as “C”, “ B ”or higher was regarded as acceptable at the product level.

  The extrusion appearance 2 observed the extrusion appearance when manufacturing the electric wire. When the 65 mm extruder was used to produce a line speed of 80 m, the appearance was good as “A”, the appearance was slightly bad as “B”, and the appearance was acceptable but bad as “C”. . This test is shown for reference.

Extrusion appearance 3 observed the extrusion appearance in Examples 10-14 and 51-81, when manufacturing an electric wire. In addition, after flowing the molten mixture of the silane masterbatch and the catalyst masterbatch with a 65 mm extruder, the extruder was stopped for 15 minutes, and the extruder was operated again to melt the silane masterbatch and the catalyst masterbatch in the extruder. After sufficiently flowing the mixture, an electric wire was prototyped at a line speed of 40 m / min. Observe the produced wire for 10 m, and “A” indicates that no external appearance is confirmed, and “C” indicates that there are 1 or more external appearances per wire (10 or more in total). The following (10 or less in total) was designated as “B”.
“B” or higher was accepted as a product level, but this test does not necessarily pass.

Extrusion appearance 4 observed the extrusion appearance in Examples 10-14 and 51-81, when manufacturing an electric wire. In addition, after flowing the molten mixture of a silane masterbatch and a catalyst masterbatch with a 65 mm extruder, the extruder was stopped for 15 minutes, the extruder was operated again, and an electric wire was prototyped at a line speed of 40 m / min. Observe the produced wire for 5 m, and “A” indicates no flaws on the appearance, “C” indicates that there are one or more appearances on the 50 cm electric wire (10 or more in total), one on the 50 cm The following (10 or less in total) was designated as “B”.
Although “B” or higher was accepted as a product level, this test does not necessarily pass.

  The vertical flame retardant test was performed based on the test method of IEC603332-1, using an electric wire with an outer diameter of 4.6 mm, which was prepared for the vertical flame retardant test in Example 21 and Comparative Example 17. The number of tests is n = 3. The vertical flame retardant test need not necessarily pass.

  For the elongation and tensile strength of the insulator, a tubular piece of electric wire was prepared in the same manner as in Example 21 and Comparative Example 17, and the test was performed based on JIS C3005. The tensile strength is 10 MPa or more and the elongation is 100% or more, but it is not always necessary to pass.

  As is apparent from the results of Tables 1 to 5, Comparative Examples 1 to 17 cannot achieve both heat deformation, hot set and extrusion appearance, whereas Examples 1 to 81 have heat deformation, hot set and extrusion. Appearance was compatible.

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

This application claims the priority based on Japanese Patent Application No. 2012-081354 for which it applied for a patent in Japan on March 30, 2012, and this is referred to as a part of description of this specification. take in.

Claims (17)

(A) A resin composition containing a polyolefin-based resin, 0.01 to 0.6 parts by mass of an organic peroxide and 10 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of the resin composition, and the inorganic filler A step of melt-kneading 0.5 to 15.0 parts by mass of a silane coupling agent with respect to 100 parts by mass above the decomposition temperature of the organic peroxide and preparing a silane masterbatch without mixing a silanol condensation catalyst When,
(B) a step of molding after melt-kneading the silane masterbatch and the silanol condensation catalyst;
(C) The manufacturing method of the heat resistant resin composition characterized by including the process of making the molded article of the said (b) process contact with a water | moisture content, and bridge | crosslinking. (A-1) To 100 parts by mass of a resin composition containing a polyolefin-based resin, 0.01 to 0.6 parts by mass of an organic peroxide and 10 to 400 parts by mass of an inorganic filler, and 100 parts by mass of an inorganic filler On the other hand, a step of preparing a mixture by mixing 0.5 to 15.0 parts by mass of a silane coupling agent,
(A-2) melting and kneading the mixture and the resin composition at or above the decomposition temperature of the organic peroxide, and preparing a silane masterbatch without mixing the silanol condensation catalyst;
(B-1) a step of producing a catalyst master batch by mixing a silanol condensation catalyst and a carrier resin;
(B-2) a step of melt-kneading the silane masterbatch and the catalyst masterbatch prepared in the steps (a-2) and (b-1), respectively, and then molding,
(C) The manufacturing method of the heat resistant resin composition of Claim 1 including the process of making the molded article of the said (b-2) process contact with a water | moisture content, and bridge | crosslinking. (A) A resin composition containing a polyolefin-based resin, 0.01 to 0.6 parts by mass of an organic peroxide and 10 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of the resin composition, and an inorganic filler 100 Melting and kneading 0.5 to 15.0 parts by mass of the silane coupling agent with respect to parts by mass above the decomposition temperature of the organic peroxide, and preparing a silane masterbatch without mixing the silanol condensation catalyst,
(B-1) a step of producing a catalyst master batch by mixing a silanol condensation catalyst and a carrier resin;
(B-3) a step of melt-kneading and molding the silane masterbatch and the catalyst masterbatch prepared in the steps (a) and (b-1), respectively,
(C) The manufacturing method of the heat resistant resin composition of Claim 1 including the process of making the molded article of the said (b-3) process contact with a water | moisture content, and bridge | crosslinking.   The heat resistance according to any one of claims 1 to 3, wherein 0.5 to 18.0 parts by mass of the silane coupling agent is contained with respect to 100 parts by mass of the resin composition. A method for producing a resin composition.   The method for producing a flame retardant crosslinking composition according to claim 4, wherein the silane coupling agent is contained in an amount of more than 4 parts by mass and not more than 15 parts by mass.   The method for producing a flame retardant crosslinking composition according to claim 4, wherein the silane coupling agent is contained in an amount of 5 to 12 parts by mass.   The method for producing a flame retardant crosslinking composition according to claim 4, wherein the silane coupling agent is contained in an amount of 6 to 10 parts by mass.   The resin composition contains at least one of an ethylene-α-olefin copolymer and a styrene elastomer and paraffinic oil in a mass ratio of 4 to 70% by mass. The manufacturing method of the flame-retardant crosslinked composition of any one of -7.   The said mass ratio is 8-70 mass%, The manufacturing method of the flame-retardant crosslinked composition of Claim 8 characterized by the above-mentioned.   The method for producing a flame retardant crosslinking composition according to claim 8 or 9, wherein at least one of the ethylene-α-olefin copolymer and the styrene elastomer is the styrene elastomer.   The method for producing a flame retardant crosslinked composition according to any one of claims 8 to 10, wherein the ethylene-α-olefin copolymer is ethylene-propylene-diene rubber.   The method for producing a heat-resistant resin composition according to any one of claims 1 to 11, wherein the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.   The inorganic filler is at least one selected from the group consisting of silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, zinc borate, zinc hydroxystannate and talc. 12. A method for producing a heat-resistant resin composition according to any one of 12 above.   The method for producing a heat-resistant resin composition according to any one of claims 1 to 13, wherein the melt-kneading in the production of the silane masterbatch is performed with a closed mixer.   A molded product comprising a molded product of the heat resistant resin composition produced by the method for producing a heat resistant resin composition according to any one of claims 1 to 14.   The molded article according to claim 15, wherein the molded article is an electric wire or optical fiber cable coating.   It is a heat resistant resin composition manufactured by the manufacturing method of the heat resistant resin composition of any one of Claims 1-14, Comprising: The said polyolefin resin bridge | crosslinks with an inorganic filler through a silanol bond. The heat resistant resin composition characterized by the above-mentioned.