JP2014009238A - Heat-resistant resin composition, and wiring material, cable and molded body including heat-resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant resin composition having excellent high temperature heat resistance as well as high flexibility and oil resistance, in addition to excellent external appearance of an extrusion-molded resin, applicable to a cabtire cable, and also to provide a wiring material, a cable and a molded body including the heat-resistant resin composition.SOLUTION: A heat-resistant resin composition includes: at least one of silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer of a predetermined amount and with a predetermined range of density before silane modification; polyolefin resin; at least one of styrenic elastomer and ethylene-α-olefin copolymer rubber; paraffinic oil; and a silanol condensation catalyst. Thus, there can be obtained a resin composition having excellent high temperature heat resistance as well as high flexibility and oil resistance, while maintaining mechanical characteristics required as a resin material, with excellent external appearance of an extrusion-molded resin. The heat-resistant resin composition can be manufactured into a resin composition applicable to a constituent material of a cabtire cable that requires heat resistance as well as oil resistance and flexibility.

Description

  The present invention relates to a heat resistant resin composition and a wiring material, a cable, and a molded article having the heat resistant resin composition. More specifically, the present invention relates to a heat-resistant resin composition applicable to a cabtyre cable or the like that requires oil resistance and flexibility in addition to heat resistance, and a wiring material, cable, and molded product having the heat-resistant resin composition.

  The cabtyre cable is a cable that can move while being energized, and is used, for example, for power feeding at a work site or the like. In addition to natural rubber with high mechanical strength, synthetic rubber, polyvinyl chloride, etc. were generally used as resin materials for such cabtyre cables. Of these, polyvinyl chloride is good. However, the heat resistance is inferior. On the other hand, synthetic rubber is widely used as a resin material for cabtyre cables because it has good flexibility and oil resistance and also has high heat resistance.

  However, in order to impart heat resistance to the synthetic rubber, a crosslinking process called a so-called peroxide vulcanization process is required. This cross-linking process requires a synthetic rubber to be cross-linked to pass through the vulcanizing tube for several minutes at high temperatures and pressures, and therefore has become a bottleneck in cable manufacturing. Cross-linked synthetic rubber cabtyre cables In the case of manufacturing, the linear velocity has to be about 10 m / min, and the productivity is poor. In addition, there is currently a shortage of rubber materials worldwide, and it is thought that supply will become unstable in the future. From such a background, it was necessary to examine a resin material for a cabtyre cable that replaces the synthetic rubber.

  As a resin material for a cabtyre cable that replaces a synthetic rubber, it is necessary to select a high heat-resistant resin material. As such a high heat-resistant resin material, for example, a fluororesin such as polytetrafluoroethylene (PTFE) However, PTFE is very expensive and is not preferred because it is not a general-purpose material. On the other hand, when a polyolefin resin, which is relatively inexpensive and known as a high heat resistance resin, is used as a resin material for a cabtyre cable, a polyolefin material having high flexibility and low crystallinity is in an amorphous part. Oil penetrates and swells, resulting in poor oil resistance. On the other hand, it has been difficult to maintain high flexibility with a highly crystalline polyolefin material. As described above, when a polyolefin material is applied alone to a resin material for a cabtyre cable, it has been considered difficult to achieve both oil resistance and flexibility.

  Therefore, in recent years, attempts have been made to add flexibility and oil resistance as a resin composition by adding other components to a polyolefin-based resin (see, for example, Patent Document 1), for example, a silane-modified polyolefin resin. A flame retardant resin composition comprising an ethylene resin, a polypropylene resin, a styrene elastomer, and a metal hydrate has been proposed (see, for example, Patent Document 2). The resin composition disclosed in Patent Document 2 achieves high flexibility with a small amount (20% by mass or less) of a styrene-based elastomer, while ensuring heat resistance with a highly crystalline propylene-based resin. Oil resistance is ensured by resin.

JP 2004-331842 A JP 2006-182875 A

  By the way, although the resin composition described in the above-mentioned patent document is intended to ensure heat resistance by containing a propylene-based resin, it melts at high temperatures, and synthetic rubber and The equivalent heat resistance could not be maintained. In addition, it is the actual situation that satisfactory flexibility is not obtained, and the resin composition described in the above patent document has sufficient heat resistance and flexibility as a resin material for a cabtyre cable. And it could not be said to have oil resistance.

  The present invention has been made in view of the above problems, and is excellent in high-temperature heat resistance, has high flexibility and oil resistance, and has no problem with the appearance of extruded resin. An object is to provide an applicable heat resistant resin composition and a wiring material, a cable, and a molded article having the heat resistant resin composition having the heat resistant resin composition.

In order to solve the above-described problems, the heat-resistant resin composition according to the present invention includes the following (A) to (E).
(A) At least one of silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer having a density before silane modification of 0.850 to 0.900 g / cm ³ (A) to (D) 10 to 80% by mass
(B) Polyolefin resin (A)-(D) 3-60 mass% with respect to the whole
(C) At least one of styrene-based elastomer and ethylene-α-olefin copolymer rubber (A) to (D) 10 to 50% by mass based on the whole
(D) Paraffinic oil (A)-(D) 5-60 mass% with respect to the whole
(E) Silanol condensation catalyst (A)-(D) 0.005-0.5 mass part with respect to a total of 100 mass parts

  The heat resistant resin composition according to the present invention is characterized in that, in the above-described present invention, the (B) polyolefin resin is at least one of polyethylene and an ethylene-α-olefin copolymer.

The heat-resistant resin composition according to the present invention has a density of 0.870 to 0.930 g / cm ³ selected from at least one of the polyethylene and the ethylene-α-olefin copolymer in the present invention. It is characterized by being.

The heat resistant resin composition according to the present invention is characterized in that, in the above-described present invention, the following (F-1) and (F-2) are further contained as a flame retardant (F).
(F-1) Bromine-based flame retardants 10 to 40 parts by mass with respect to a total of 100 parts by mass of (A) to (D) (F-2) To a total of 100 parts by mass of antimony trioxide (A) to (D) 0-35 parts by mass

The heat resistant resin composition according to the present invention is characterized in that, in the above-described present invention, the following (F-3) is further contained as a flame retardant (F).
(F-3) Metal hydrate (A) -40 mass parts with respect to a total of 100 mass parts of (D).

  The heat-resistant resin composition according to the present invention is the SEPS (styrene-ethylene-propylene-styrene block copolymer) in which the styrene-based elastomer (C) is 10 to 40% in the above-described present invention. ), SEEPS (styrene-ethylene-ethylene-propylene-styrene block copolymer) and SEBS (styrene-ethylene-butylene-styrene block copolymer).

  The wiring material which concerns on this invention has the above-mentioned heat resistant resin composition which concerns on this invention as a coating layer around a conductor or an optical fiber core wire.

  The cable according to the present invention is characterized by having the above-described heat-resistant resin composition according to the present invention as a coating layer around the cable core.

  The molded product according to the present invention is characterized by having the above-described heat-resistant resin composition according to the present invention.

  The heat resistant resin composition according to the present invention has high heat resistance while maintaining the mechanical properties required as a resin material, and also has high flexibility and oil resistance, and the appearance of the extruded resin is also a problem. It becomes a resin composition without. Therefore, the heat-resistant resin composition of the present invention is a resin composition that can be applied as a constituent material of a cabtire cable or the like that requires flexibility and oil resistance in addition to heat resistance. Since the heat resistant resin composition according to the present invention is particularly excellent in flexibility, it can be applied without problems to uses requiring high flexibility.

  Moreover, since the wiring material, cable and molded product according to the present invention have the heat-resistant resin composition according to the present invention as a constituent material, the above-mentioned effects are enjoyed, and both high heat resistance, flexibility and oil resistance are obtained. It becomes a wiring material, a cable, and a molded product with a good appearance.

Hereinafter, one embodiment of the present invention will be described. The heat-resistant resin composition according to the present invention has at least one of a silane-modified polyethylene and a silane-modified ethylene-α-olefin copolymer having a density before silane modification of 0.850 to 0.900 g / cm ³ . In addition to (B) a polyolefin resin, (C) at least one of a styrene-based elastomer and an ethylene-α-olefin copolymer rubber, (D) a paraffinic oil, (E) a silanol condensation catalyst is included as a basic configuration.

(A) At least one of silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer:
The silane-modified polyethylene and the silane-modified ethylene-α-olefin copolymer (hereinafter sometimes simply referred to as “silane-modified polyethylene etc.”) constituting the heat-resistant resin composition according to the present invention are polyethylene or ethylene-α. -This refers to a polyolefin in which a hydrolyzable silanol compound is copolymerized with an olefin copolymer and is silane-modified. Such a silane-modified polyethylene or the like is used as a component and has a cross-linked structure so that oil can enter. Therefore, oil resistance is improved and heat resistance is also excellent. One kind of silane-modified polyethylene or silane-modified ethylene-α-olefin copolymer may be used alone, or two kinds may be used in combination.

  As a copolymerization method, a conventionally known method such as production of polyolefin such as silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer can be used. For example, polyethylene or ethylene-α-olefin copolymer can be used. A target product is obtained by melt-mixing a polymer (hereinafter, sometimes simply referred to as “polyethylene”), a hydrolyzable silanol compound, an organic peroxide, and the like at a temperature equal to or higher than the decomposition temperature of the organic peroxide. It is possible to obtain a silane-modified polyethylene and a silane-modified ethylene-α-olefin copolymer.

(A-1) Polyethylene, ethylene-α-olefin copolymer:
Examples of polyethylene include ethylene homopolymers such as LLDPE (linear low density polyethylene), LDPE (low density polyethylene), and VLDPE (very low density polyethylene).

  Examples of the ethylene-α-olefin copolymer include an ethylene-α-olefin copolymer synthesized in the presence of a single site catalyst, EPR (ethylene-propylene copolymer rubber), EPDM (ethylene -Ethylene copolymer rubber containing 30 to 95% of ethylene component as a constituent component such as -propylene terpolymer rubber) and EBR (ethylene-1-butene copolymer rubber). The ethylene-α-olefin copolymer may be modified with, for example, an unsaturated carboxylic acid such as maleic anhydride.

  As the polyethylene constituting the silane-modified polyethylene, it is particularly preferable to use LLDPE, VLDPE or the like. As the ethylene-α-olefin copolymer constituting the silane-modified ethylene-α-olefin copolymer, a single site catalyst exists. It is particularly preferable to use the ethylene-α-olefin copolymer synthesized below.

In the heat resistant resin composition according to the present invention, the polyethylene constituting the silane-modified polyethylene and the ethylene-α-olefin copolymer constituting the silane-modified ethylene-α-olefin copolymer have a density before the silane modification. Is 0.850-0.900 g / cm ³ . By setting the density within such a range, it is possible to provide a heat resistant resin composition having a high balance between high flexibility and oil resistance in addition to high heat resistance. On the other hand, when the density is less than 0.850 g / cm ³ , the oil resistance is lowered, and when it exceeds 0.900 g / cm ³ , the flexibility is deteriorated. Density before silane-modified polyethylene and ethylene -α- olefin copolymer is preferably in a 0.855~0.890g / cm ^3, it is particularly preferable that the 0.857~0.885g / cm ³ .

(A-2) Hydrolyzable silanol compound:
The hydrolyzable silanol compound used in combination with the polyolefin resin is not particularly limited, and conventionally known silanol compounds used for silane crosslinking can be used. For example, the following general formula (1) The hydrolyzable silanol compound represented by these can be used.

Here, in formula (1), R _a11 is a group containing an ethylenically unsaturated group, Y ¹¹ and Y ¹² are each an organic group to be hydrolyzed, R _b11 is a hydrogen atom, an aliphatic hydrocarbon group, or a hydrolysis An organic group (for convenience, Y ¹³ ). Y ¹¹ , Y ¹² and Y ¹³ may be the same or different from each other.

R _a11 of the organic unsaturated silane compound represented by the general formula (1) is a group containing an ethylenically unsaturated group, such as a vinyl group, a (meth) acryloyloxyalkylene group, or a p-styryl group. Of these, vinyl groups are preferred.

Y ¹¹ , Y ¹² and Y ¹³ are organic groups that are hydrolyzed, and examples thereof include an alkoxy group, an aryloxy group, and an acyloxy group. Among these, an alkoxy group is preferable. Examples of the alkoxy group to be hydrolyzed include a methoxy group, an ethoxy group, a butoxy group, and an acyloxy group. Among these, a methoxy group or an ethoxy group is preferable from the viewpoint of reactivity.

R _b11 is a hydrogen atom, an aliphatic hydrocarbon group, or an organic group to be hydrolyzed (referred to as Y ¹³ as described above). Examples of the aliphatic hydrocarbon group include a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms excluding the aliphatic unsaturated hydrocarbon group. R _b11 is preferably an organic group (Y ¹³ ) that is hydrolyzed as described above.

The hydrolyzable silanol compound is preferably an organic unsaturated silane compound having a high hydrolysis rate, more preferably an organic group (Y ¹³ ) that hydrolyzes R _b11 , and hydrolysis. It is particularly preferable to use an organic unsaturated silane compound in which Y ¹¹ , Y ¹² and Y ¹³ which are organic groups are common.

  Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltriethoxysilane, vinyltriacetoxysilane Examples include organosilanes such as methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, and silane coupling agents having an ethylenic double bond at the end, such as methacryloxypropylmethyldimethoxysilane. One of these silane coupling agents may be used alone, or two or more thereof may be used in combination. Among such crosslinkable silane coupling agents, a silane coupling agent having a vinyl group and an alkoxy group at a terminal is more preferable, and vinyltrimethoxysilane, vinyltriethoxysilane, and the like are particularly preferable.

(A-3) Organic peroxide:
As the organic peroxide, a conventionally known organic peroxide used for silane crosslinking can be used. For example, R—OO—R ′, R—OO—C (═O) R ″ and R ″ C It is preferable to use a compound represented by (═O) —OO (C═O) R ″ ′. In the above-mentioned compounds, R and R ′, R ″, R ″ ′ are each independently an alkyl group. In the present invention, R and R ′, R and R ″, R ″ and R ″ ′ are both alkyl groups, or one is an alkyl group and the other is an acyl group. It is preferable that

  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, can be used tert- butyl cumyl peroxide and the like. Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- in terms of odor, colorability, and scorch stability. It is preferable to use (tert-butylperoxy) hexyne-3 or the like.

  In addition, when polyethylene or ethylene-α-olefin copolymer is silane-modified with a hydrolyzable silanol compound and an organic peroxide to obtain silane-modified polyethylene or the like, the amount used is polyethylene or ethylene-α- For example, 0.5 to 7.0 parts by mass of a hydrolyzable silanol compound and 0.01 to 0.5 parts by mass of an organic peroxide are preferably used with respect to 100 parts by mass of the olefin copolymer. It is particularly preferable to use 1.0 to 6.0 parts by mass of the functional silanol compound and 0.03 to 0.3 parts by mass of the organic peroxide.

Examples of commercially available silane-modified polyethylene that can be used in the heat-resistant resin composition according to the present invention include Wrinklon (trade name: manufactured by Mitsubishi Chemical Corporation). The density of silane-modified polyethylene or the like (silane-modified polyethylene or the like) or polyethylene before silane modification in a commercially available silane-modified polyethylene or the like depends on the type of resin to be constructed and the amount of silane modification. And about 0.01 to 0.1 g / cm ³ .

  In the heat resistant resin composition according to the present invention, the content of at least one of (A) the silane-modified polyethylene and the silane-modified ethylene-α-olefin copolymer is a resin component ((A), ( B), (C) and (D), the same shall apply hereinafter)) 10 to 80% by mass with respect to the whole (100% by mass, the same shall apply hereinafter) When the content is less than 10% by mass, the heat resistance is lowered, and it may be difficult to pass the hot set test described in JIS C3660-2-1 which is a test for evaluating high heat resistance. On the other hand, when the content exceeds 80% by mass, flexibility may be lowered. The content of the silane-modified polyolefin resin is preferably 11 to 70% by mass, and particularly preferably 13 to 60% by mass.

(B) Polyolefin resin:
As polyolefin resin which comprises the heat resistant resin composition which concerns on this invention, conventionally well-known polyolefin resin can be used, for example, polypropylene resin, polyethylene resin, ethylene-alpha-olefin copolymer, ethylene-alpha. -Ethylene resins, such as ethylene copolymers other than an olefin copolymer, are mentioned. One of these resins may be used alone, or two or more thereof may be used in combination.

  Examples of the polypropylene resin include propylene homopolymer (homopolypropylene), ethylene-propylene random copolymer, ethylene-propylene block copolymer, propylene and α-olefin (for example, 1-butene, 1-hexene, 4 -Methyl-1-pentene, etc.), polypropylene containing atactic propylene as a constituent, block copolymer of propylene and ethylene copolymer rubber, and the like. In the present invention, as a polypropylene resin, in addition to a propylene homopolymer, a propylene component of a copolymer having at least one of an ethylene component and an α-olefin component and a propylene component as a constituent component Means 85% by mass or more.

  Examples of the polyethylene resin include ethylene homopolymers such as HDPE (high density polyethylene), LLDPE (linear low density polyethylene), LDPE (low density polyethylene), and VLDPE (very low density polyethylene). Examples of the ethylene-α-olefin copolymer include an ethylene-α-olefin copolymer synthesized in the presence of a single site catalyst, EPR (ethylene-propylene copolymer rubber), EPDM (ethylene -Ethylene copolymer rubber containing 30 to 95% of ethylene component as a constituent component such as -propylene terpolymer rubber) and EBR (ethylene-1-butene copolymer rubber). The ethylene-α-olefin copolymer may be modified with, for example, an unsaturated carboxylic acid such as maleic anhydride.

  Examples of the ethylene-based copolymer other than the ethylene-α-olefin copolymer include EVA (ethylene-vinyl acetate copolymer), ethylene- (meth) acrylic acid copolymer, and ethylene- (meth) acrylate alkyl copolymer. Etc.

  In addition, it is preferable to use a polyethylene resin and an ethylene-α-olefin copolymer as the polyolefin resin. By using the polyolefin resin as polyethylene, etc., the compatibility between (A) silane-modified polyethylene and (B) polyolefin resin is improved at the time of molding by using in common with polyethylene used in (A) silane-modified polyethylene. , Heat resistance and elongation characteristics are improved. As the polyolefin resin, it is particularly preferable to use LLDPE, LDPE, HDPE, VLDPE, an ethylene-α-olefin copolymer synthesized in the presence of a single site catalyst, or the like.

In addition, when using polyethylene and an ethylene-alpha-olefin copolymer as polyolefin resin, it is preferable that a density shall be 0.855-0.955 g / cm < ³ >. By setting the density to such a range, the heat-resistant resin composition having a good balance between oil resistance and flexibility in addition to high heat resistance in the same manner as the density of the polyethylene constituting (A) is set to the above-described range. Things can be provided. On the other hand, when the density is less than 0.855 g / cm ³ , the oil resistance may be lowered, and when it exceeds 0.955 g / cm ³ , the flexibility is deteriorated. The density of the polyethylene or ethylene-α-olefin copolymer is more preferably 0.870 to 0.930 g / cm ^3, and in this range, in addition to high heat resistance, oil resistance and flexibility It is possible to efficiently provide a heat resistant resin composition having a good balance. The density of polyethylene or ethylene-α-olefin copolymer is particularly preferably 0.880 to 0.925 g / cm ³ .

  In the heat resistant resin composition according to the present invention, the content of the (B) polyolefin resin is at least one of (A) the silane-modified polyethylene and the silane-modified ethylene-α-olefin copolymer. Except for this, the content is 3 to 60% by mass based on the entire resin component. When the content is less than 3% by mass, a load is not applied at the time of kneading, and there are cases where compounding cannot be performed. On the other hand, when the content exceeds 60% by mass, flexibility may be deteriorated. The content of the polyolefin resin is preferably 5 to 50% by mass, particularly preferably 7 to 40% by mass.

(C) At least one of styrene-based elastomer and ethylene-α-olefin copolymer rubber:
By adding a styrene-based elastomer or an ethylene-α-olefin copolymer rubber to the heat resistant resin composition according to the present invention, it is possible to improve elongation characteristics and flexibility. Such styrene elastomers and ethylene-α-olefin copolymer rubbers may be used alone or in combination of two.

(C-1) Styrene elastomer:
Examples of the styrenic elastomer include a block mainly composed of a block of a conjugated diene compound and an aromatic vinyl compound and a random structure, 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, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, Examples include vinyl toluene and p-tert-butylstyrene.

  Specific examples of the styrene elastomer 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) Etc. 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.

(C-2) Ethylene-α-olefin copolymer rubber:
Examples of the ethylene-α-olefin copolymer rubber include EPR (ethylene-propylene rubber), EBR (ethylene-1 butene rubber), EPDM (ethylene-propylene-diene rubber), and the like. As the ethylene-α-olefin copolymer rubber, it is preferable to avoid the use of an ethylene-propylene block copolymer having an ethylene content of about 5 to 15% or an ethylene-propylene random copolymer.

  As the styrene-based elastomer, it is preferable to use SEPS, SEEPS, SEBS, or ethylene-α-olefin copolymer rubber having a styrene content of 10 to 40% alone or in combination of two or more thereof. . By using these, the tensile strength characteristics and flexibility of the heat-resistant resin composition can be further improved.

  In the heat resistant resin composition according to the present invention, the (C) styrene elastomer and ethylene-α-olefin copolymer rubber (the (A) silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer The content of at least one of at least one of the above and (B) the polyolefin resin is excluded) is 10 to 50% by mass with respect to the entire resin component. When the content is less than 10% by mass, flexibility may be deteriorated. On the other hand, if the content exceeds 50% by mass, melt-kneading may become difficult or cost may increase. The content of at least one of the styrene-based elastomer and the ethylene-α-olefin copolymer rubber is preferably 12 to 45% by mass, and particularly preferably 15 to 40% by mass.

(D) Paraffinic oil:
By adding paraffinic oil to the heat-resistant resin composition of the present invention, the resin component becomes fluid, elongation characteristics and flexibility are improved, and oil resistance is improved. In addition, by preliminarily dispersing the paraffinic oil in the resin component, it is possible to prevent the resin from swelling due to the oil during the oil resistance test and deteriorating the remaining tensile strength.

  As the paraffinic oil constituting the heat resistant resin composition, for example, non-aromatic mineral oil or liquid or low molecular weight synthetic softening agent 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. They are called paraffinic, and those having a naphthene ring carbon number of 30-40% are called naphthenes, and those having 30% or more aromatic carbons are called aromatics. Of these, paraffinic oil can be used in the present invention.

  Examples of commercially available paraffinic oil that can be used in the heat-resistant resin composition according to the present invention include Dyna Process Oil (trade name, manufactured by Idemitsu Kosan Co., Ltd.).

  In the heat resistant resin composition according to the present invention, the content of the (D) paraffinic oil is 5 to 60% by mass with respect to the entire resin component. When the content is less than 5% by mass, flexibility and oil resistance may be deteriorated. On the other hand, if the content exceeds 60% by mass, the oil may bleed out and the appearance of the electric wire may be deteriorated. The content of the paraffinic oil is preferably 5 to 50% by mass, particularly preferably 10 to 40% by mass.

(E) Silanol condensation catalyst:
The silanol condensation catalyst constituting the heat resistant resin composition according to the present invention serves to bind the whole (A) (grafted organic unsaturated silane compound) in the presence of moisture by a condensation reaction. Based on the function of the silanol condensation catalyst, the polymers are cross-linked through the organic unsaturated silane compound. As a result, the heat resistant resin composition according to the present invention is a resin composition having excellent heat resistance.

  As the silanol condensation catalyst, for example, an organic tin compound, a metal soap, a platinum compound, or the like can be used. Common silanol condensation catalysts include, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, zinc stearate, lead stearate, barium stearate, calcium stearate, sodium stearate, Lead naphthenate, lead sulfate, zinc sulfate, organic platinum compounds and the like are used.

  Content of the silanol catalyst in the heat resistant resin composition which concerns on this invention shall be 0.005-0.5 mass part with respect to a total of 100 mass parts of an above described resin component of (A)-(D). When the content is less than 0.005 parts by mass, the crosslinking may not proceed. On the other hand, when the content exceeds 0.5 parts by mass, the appearance may be deteriorated when manufacturing a cabtire cable or the like. The content of the silanol condensation catalyst is preferably 0.01 to 0.2 parts by mass.

(F) Flame retardant:
Flame retardance can be improved by adding a flame retardant to the heat resistant resin composition according to the present invention. When the heat-resistant resin composition according to the present invention is used as an insulating material or a sheath material for a flame-retardant cabtyre cable, it has flame retardancy that passes the 60 ° inclined flame-retardant test defined in JIS C3005. Necessary. As the flame retardant, (F-1) bromine-based flame retardant, (F-2) antimony trioxide, and (F-3) metal hydrate can be used.

(F-1) Brominated flame retardant:
The brominated flame retardant is not particularly limited as long as it excludes polybromophenyl ether and polybromophenyl. For example, organic bromine-containing flame retardants such as brominated ethylene bisphthalimide derivatives, bisbrominated phenylterephthalamide derivatives, brominated bisphenol derivatives, and 1,2-bis (bromophenyl) ethane can be used. Among these, 1,2-bis (bromophenyl) ethane is preferable, and for example, Firemaster (trade name, manufactured by Chemtura Japan Co., Ltd.) and the like can be used.

  The content of the (F-1) brominated flame retardant in the heat-resistant resin composition according to the present invention is 10 to 40 parts by mass with respect to 100 parts by mass in total of the resin components (A) to (D). It is preferable. If the content is less than 10 parts by mass, the flame retardancy may not be improved. On the other hand, if the content exceeds 40 parts by mass, not only the flame retardant effect corresponding to the added amount is not obtained but also the flexibility is lowered. There is a case. The brominated flame retardant content is more preferably 15 to 40 parts by mass, and particularly preferably 15 to 35 parts by mass.

(F-2) Antimony trioxide:
In addition to brominated flame retardants, antimony trioxide can also be used. The content of (F-2) antimony trioxide in the heat resistant resin composition according to the present invention is 0 to 35 parts by mass with respect to 100 parts by mass in total of the resin components (A) to (D). preferable. If the content exceeds 35 parts by mass, not only the flame retardant effect commensurate with the amount added may be obtained, but the flexibility may be lowered. The content of antimony trioxide is preferably 3 to 30 parts by mass, particularly preferably 5 to 25 parts by mass. Antimony trioxide is used in combination as a flame retardant aid for the brominated flame retardant described above.

(F-3) Metal hydrate:
The metal hydrate may be used in combination with a brominated flame retardant or antimony trioxide, or may be used alone. The type of metal hydrate is not particularly limited. For example, hydroxyl groups or crystals such as aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, aluminum orthosilicate, hydrotalcite, etc. Examples thereof include metal compounds having water. These metal hydrates may be used alone or in combination of two or more. Of these metal hydrates, aluminum hydroxide and magnesium hydroxide are preferably used.

  Such metal hydrate may be surface-treated. Examples of surface treatment agents for metal hydrates include fatty acids such as stearic acid and oleic acid, phosphate esters, silane coupling agents having vinyl groups or epoxy groups at the end, and commercially available products such as Kisuma (trade name). And Kyowa Chemical Industry Co., Ltd.) can be used.

  The content of (F-3) metal hydrate in the heat resistant resin composition according to the present invention is 40 to 120 parts by mass with respect to 100 parts by mass in total of the resin components (A) to (D). Is preferred. If the content is less than 40 parts by mass, the flame retardancy may not be improved. On the other hand, if the content exceeds 120 parts by mass, the flexibility may be adversely affected. The content of the metal hydrate is preferably 45 to 115 parts by mass, particularly preferably 50 to 110 parts by mass.

(G) Additive:
In addition, various resin components other than those described above and various additives can be appropriately added to the heat-resistant resin composition of the present invention as necessary within the range not hindering the object and effect of the present invention. As additives, conventionally known additives can be used, and various commonly used additives such as antioxidants, metal deactivators, weathering agents, lubricants, flame retardant aids, filling An agent and the like can be appropriately blended within a range not impairing the object of the present invention.

  Examples of the antioxidant include amines such as 4,4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, and a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline. Antioxidant, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate, phenolic antioxidants such as 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (2-methyl-4) -(3-n-alkylthiopropionyloxy) -5-t-butylphenyl) sulfide, 2-mercaptobenzimidazole and its zinc salt, penta Risuritoru - tetrakis (3-lauryl - thiopropionate) sulfur-based antioxidants such as and the like. Among these, a phenolic antioxidant is preferable, and specifically, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) is preferable.

  Examples of the metal deactivator include N, N′-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2 , 4-triazole, 2,2′-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.

  Examples of the weathering agent include general weathering agents such as a light stabilizer (for example, a hindered amine light stabilizer) and an ultraviolet absorber (for example, a benzotriazole-based ultraviolet absorber, carbon black).

  Examples of the flame retardant aid and filler include carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide silicone compound, quartz, talc, calcium carbonate, magnesium carbonate, and white carbon.

  Examples of the lubricant include hydrocarbon-based, fatty acid-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based, and silicone-based materials. Among these, hydrocarbon-based and silicone-based materials are preferable.

  The heat-resistant resin composition according to the present invention is not particularly limited. For example, at least one of (I) silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer (silane-modified polyethylene, etc.) ), And (II) a resin composition (masterbatch) of components other than silane-modified polyethylene and the like, and the obtained (I) and (II) can be mixed by melt mixing or the like.

  In addition, even if (I) and (II) are performed by a separate process, both processes may be implemented at once with a tandem extruder, a twin screw extruder, etc., and you may make it melt-mix together. However, when melt-mixing at once, (A) silane-modified polyethylene or the like undergoes a condensation reaction with the (E) silanol condensation catalyst during the melt-mixing, and crosslinks before the molding step, and the appearance of the molded product deteriorates. After the compound, the silane-modified polyethylene is hydrolyzed by the moisture of the flame retardant component, and during the molding process, (A) the silane-modified polyethylene or the like causes the condensation reaction by the (E) silanol condensation catalyst, and the inside of the extruder during the molding process. It is preferable to carry out (I) and (II) in separate steps. When (I) and (II) are performed in separate steps, the obtained (I) and (II) are dry-blended and mixed at a desired ratio at room temperature, and melt mixing and molding are performed in a molding machine. It is preferable to make it. The method of dry blending is not particularly limited, and a conventionally known method such as a Henschel mixer or a tumbler mixer can be used.

  In general, ethylene resin and polypropylene resin are poorly compatible, so when they are mixed only by dry blending before coating extrusion, mixing is insufficient, which may cause problems in mechanical strength and heat resistance. there were. Therefore, when (A) silane-modified polyethylene, which is an ethylene resin, is selected as a (B) polyolefin resin and (I) and (II) are carried out in separate steps, mixing becomes insufficient. Problems with mechanical strength and heat resistance may occur. However, as described above, when (I) and (II) are performed simultaneously, the appearance of the molded product may be deteriorated. Accordingly, also from the viewpoint of flexibility, it is preferable to use (A) silane-modified polyethylene or the like in combination with (B) an ethylene resin such as polyethylene or an ethylene-α-olefin copolymer as the polyolefin resin.

(I) Silane-modified polyethylene, etc .:
(A) A conventionally well-known general method can be used for manufacture of a silane modified polyethylene etc. For example, (A-1-1) polyethylene resin or (A-1-2) ethylene-α-olefin copolymer with a predetermined amount of (A-2) hydrolyzable silanol compound, (A-3) organic peroxidation It is possible to use a method in which products are mixed and further melt mixed at a temperature of 150 to 250 ° C. For such melt mixing, for example, a conventionally known single-screw extruder or twin-screw extruder can be used.

(II) Resin composition of a component other than silane-modified polyethylene (masterbatch):
Component (B) which is a component other than silane-modified polyethylene, (C) at least one of styrene elastomer and ethylene-α-olefin copolymer rubber, (D) paraffinic oil, (E) silanol condensation catalyst The essential components and, if necessary, (F) a flame retardant and, further, (G) additives as necessary, are added and kneaded by heating. Kneading conditions such as kneading temperature and kneading time can be appropriately determined depending on the type of resin component to be used, etc., but it is generally preferable to set the temperature at 160 to 240 ° C. for 1 to 20 minutes.

  The kneading method may be any method that is usually used as a kneading method for rubber, plastic, etc. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, or various devices such as various kneaders. The conventional kneading method may be used. Then, as described above, (I) and (II) are carried out in separate steps, and the obtained product is dry blended and mixed at a desired ratio at room temperature, and melt-mixed in a molding machine to obtain a desired shape. Mold together. In addition, the method of dry blend mixing is not particularly limited, and a conventionally known method can be used.

  The heat-resistant resin composition according to the present invention described above is a silane-modified polyethylene and a silane-modified ethylene-α-olefin copolymer having a specific amount and density in a specific range before silane modification, polyolefin resin, styrene At least one of an ethylene-based elastomer and an ethylene-α-olefin copolymer rubber, containing a silanol condensation catalyst in addition to paraffinic oil, maintaining high mechanical properties required as a resin material, and having high heat resistance and high flexibility It becomes a resin composition having both properties and oil resistance and having no problem in the appearance of the extruded resin. Therefore, the heat-resistant resin composition of the present invention is a resin composition that can be applied as a constituent material of a cabtire cable or the like that requires flexibility and oil resistance in addition to heat resistance. Since the heat resistant resin composition according to the present invention is particularly excellent in flexibility, it can be applied without problems to uses requiring high flexibility.

  The heat-resistant resin composition according to the present invention can be used as an insulating material or a sheath material of a cabtire cable as described above, but applicable applications are not limited to these, and for example, a heat-resistant insulated wire It can also be used as a coating material such as a heat-resistant cable, a wiring material such as a general insulated wire, and a cable coating material. Moreover, it can be applied as a constituent material for other heat-resistant electric wire parts, heat-resistant sheets, heat-resistant films, and other various heat-resistant molded products. Specifically, for example, it can be used as a power plug, a connector, a sleeve, a box, a tape substrate, a tube, a sheet, a wiring material used for internal and external wiring of an electric / electronic device, a molded product, etc. .

  Such a wiring material (insulated electric wire), cable, molded product, and the like can be manufactured by extrusion molding using a molding apparatus of a conventionally known extrusion coating apparatus, for example. In this case, the temperature of the extrusion molding machine depends on conditions such as the types of components constituting the heat-resistant resin composition, the take-up speed of conductors, etc., but is 150 to 220 ° C. in the cylinder part and 170 to 220 in the head part. It is preferable to make it 230 degreeC. When other molding methods are used, molding conditions and the like of the molding apparatus may be appropriately determined depending on the types of components constituting the heat resistant resin composition, the contents of each component, usage, and the like.

In addition, when manufacturing a wiring material, the heat-resistant resin composition is made around a conductor made of a single wire,
A wiring material can be manufactured by forming a coating layer (an insulating layer in the case of a conductor) by extrusion coating around an optical fiber core wire or a conductor in which tensile strength fibers are vertically attached or twisted together. For example, any conductor such as a single wire or stranded wire of annealed copper can be used as the conductor. In addition to a bare wire, a conventionally known conductor such as a tin-plated one or an enamel-coated insulating layer can be used. Can be used. The thickness of the insulating layer (the coating layer made of the heat resistant resin composition according to the present invention) formed around the conductor is not particularly limited, but can be, for example, about 0.15 to 7 mm. Similarly, when manufacturing a cable having the heat resistant resin composition as a coating layer around the cable core, the thickness of the coating layer (sheath) is, for example, about 0.15 to 10 mm. be able to.

  In addition, the heat resistant resin composition according to the present invention may be subjected to a crosslinking treatment. For example, when manufacturing a wiring material such as an insulated wire, a coating layer is formed by extrusion coating on a conductor or the like. Then, the wiring material on which the heat-resistant silane cross-linking coating layer is formed can be obtained by leaving it at room temperature or leaving it under hot water, water, or wet heat conditions. Moreover, in order to permeate | transmit a water | moisture content inside in that case, you may make it apply a pressure. As described above, since the crosslinking treatment can be carried out by a simple operation without requiring a special crosslinking facility, the cost is low and the productivity is excellent.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to these.

[Production Example A-1 to Production Example A-5]
(I) Production of silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer (such as silane-modified polyethylene):
By melt-mixing polyethylene, ethylene-α-olefin copolymer, hydrolyzable organic unsaturated silane, and organic peroxide in the composition shown in Table 1 with a single screw extruder, Production Example A-1 (I) Silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer of Production Example A-5 were obtained. The single screw extruder is a 70 mm single screw extruder, L / D = 25, 180 ° C. single screw extruder is melt-mixed so that the residence time of the resin in the extruder is 2 minutes, and silane modified A polyethylene and silane-modified ethylene-α-olefin copolymer was produced. In addition, in Table 1, content has shown the mass part of the hydrolysable organic unsaturated silane and organic peroxide when polyethylene and an ethylene-alpha-olefin copolymer are 100 mass parts.

(Composition of silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer)

  Hereinafter, the polyolefin resins constituting (A-1) to (A-5) listed in Table 1 are shown.

(A) polyethylene, ethylene-α-olefin copolymer;
(Polyethylene constituting A-1)
Linear low density polyethylene (LLDPE) (trade name: NUCG-5130, manufactured by Dow Chemical Company, density: 0.923 g / cm ³ )

(Polyethylene constituting A-2)
Metallocene-catalyzed linear low-density polyethylene (metallocene LLDPE) (trade name: Engage 8845, manufactured by Dow Chemical Company, density: 0.910 g / cm ³ )

(Polyethylene constituting A-3)
Metallocene-catalyzed linear low-density polyethylene (metallocene LLDPE) (trade name: Evolue SP0540, manufactured by Prime Polymer Co., Ltd., density: 0.903 g / cm ³ )

(Ethylene-α-olefin copolymer constituting A-4)
Ethylene-butene copolymer (trade name: Engage 7256, manufactured by Dow Chemical Company, density: 0.885 g / cm ³ )

(Ethylene-α-olefin copolymer constituting A-5)
Ethylene-octene copolymer (trade name: Engage 8842, manufactured by Dow Chemical Company, density: 0.857 g / cm ³ )

(Hydrolyzable organounsaturated silane)
Vinyltrimethoxysilane (trade name: KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Organic peroxide)
Dicumyl peroxide (trade name: Perkadox BC-FF, manufactured by Kayaku Akzo Co., Ltd.)

(II) Resin composition of a component other than silane-modified polyethylene (masterbatch):
The components (B), (C), (D), (E), (F) and (G) shown below were dry blended at room temperature with the compositions shown in Tables 2 to 5 and mixed, Melting and mixing was performed using a Banbury mixer to obtain a resin composition (masterbatch) of components other than (II) silane-modified polyethylene and the like.

  In Tables 2 to 5, the contents of (A), (B), (C) and (D) are the same as (A), (B), (C) and (D). (E), (F), and (G) are when the total of (A), (B), (C), and (D) is 100 parts by mass. Part by mass.

[Examples 1 to 28, Comparative Examples 1 to 8]
(Manufacture of insulated wires)
Next, (I) (silane-modified polyethylene, silane-modified ethylene-α-olefin copolymer) and (II) (resin composition of components other than the silane-modified polyolefin resin (masterbatch) obtained as described above. ) At a room temperature with the compositions shown in Table 2 to Table 5, and then using an extrusion coating device for manufacturing insulated wires, on the conductor (1 / 0.8 A), the wall thickness: 1.0 mm The outer diameter was 2.8 mm, and the resin composition was extrusion coated. Here, a 50 mm extruder (L / D = 25) was used as the extruder, the extrusion temperature was a cylinder temperature of 210 ° C., the head temperature was 220 ° C., and the linear velocity was 50 m / min.

  After coating, the obtained insulated wire was placed in a 60 ° C. × 95% wet heat bath for 24 hours to crosslink the coating layer, and the insulated wires of Examples 1 to 28 and Comparative Examples 1 to 8 were obtained. Obtained.

(Composition 1: Examples 1 to 3, Comparative Examples 1 to 6)

(Composition 2: Example 4 to Example 11, Comparative Example 7)

(Composition 3: Example 12 to Example 19, Comparative Example 8)

(Composition 4: Example 20 to Example 28)

(II) Resin composition of a component other than silane-modified polyethylene (masterbatch):
(B) Polyolefin resin:
(Polyolefin resin of B-1)
Random polypropylene (trade name: PB222A, manufactured by Sun Allomer Co., Ltd., density 0.900 g / cm ³ )

(B-2 polyolefin resin)
High density polyethylene (HDPE) (trade name: Hi-Zex 5305E, manufactured by Prime Polymer Co., Ltd., density: 0.951 g / cm ³ )

(B-3 polyolefin resin)
Linear low density polyethylene (LLDPE) (trade name: NUCG-5130, manufactured by Nippon Unicar Co., Ltd., density: 0.923 g / cm ³ )

(B-4 polyolefin resin)
Metallocene linear low density polyethylene (trade name: Evolue SP0540, manufactured by Prime Polymer Co., Ltd., density: 0.903 g / cm ³ )

(B-5 polyolefin resin)
Ethylene-butene copolymer (trade name: Engage 7256, manufactured by Dow Chemical Company, density: 0.885 g / cm ³ )

(B-6 polyolefin resin)
Ethylene-octene copolymer (trade name: Engage 8842, manufactured by Dow Chemical Company, density: 0.857 g / cm ³ )

(B-7 polyolefin resin)
Ethylene-vinyl acetate copolymer (EVA) (trade name: EV180, manufactured by Mitsui & DuPont Polychemical Co., Ltd.)

(B-8 polyolefin resin)
Acid-modified polyethylene (trade name: Admer QE800, manufactured by Mitsui Chemicals, Inc.)

(C) At least one of styrene-based elastomer and ethylene-α-olefin copolymer rubber:
(C-1-1 styrene elastomer)
Styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS) (trade name: Septon 4077, manufactured by Kuraray Co., Ltd., styrene content 30%)

(C-1-2 styrene elastomer)
Styrene-ethylene-propylene-styrene copolymer (SEPS) (trade name: Septon 2003, manufactured by Kuraray Co., Ltd., styrene content 18%)

(C-2-1 ethylene-α-olefin copolymer rubber)
Ethylene-α-olefin copolymer rubber (trade name: EPT3092PM, manufactured by Mitsui Chemicals, Inc.)

(D) Paraffinic oil:
(D-1 paraffinic oil)
Paraffin oil (trade name: Dyna Process Oil PW90, manufactured by Idemitsu Kosan Co., Ltd.)

(E) Silanol condensation catalyst:
(Eanol silanol condensation catalyst)
Dibutyltin dilaurate (trade name: KS-120, manufactured by Sakai Chemical Industry Co., Ltd.)

(E-2-silanol condensation catalyst)
Dioctyltin dilaurate (trade name: TN-12, manufactured by Sakai Chemical Industry Co., Ltd.)

(F) Flame retardant:
(F-1-1 brominated flame retardant)
Brominated flame retardant (trade name: Firemaster 2100, manufactured by Chemtura Japan)

(F-2-1 antimony trioxide)
Antimony trioxide (trade name: PATOX-C, manufactured by Nippon Seiko Co., Ltd.)

(Metal hydrate of F-3-1)
Magnesium hydroxide (trade name: Kisuma 5L, manufactured by Kyowa Chemical Industry Co., Ltd., with silane coupling agent surface treatment)

(Metal hydrate of F-3-2)
Aluminum hydroxide (trade name: Heidilite 42M, manufactured by Showa Denko KK, untreated surface)

(G) Additive:
(G-1 additive)
Findert phenolic antioxidant (trade name: Irganox 1010, manufactured by Ciba-Gaiky Japan Limited)

(G-2 additive)
Polyethylene wax (lubricant) (trade name: AC polyethylene No. 6, manufactured by Honeywell Japan Co., Ltd.)

(Additive of G-3)
Silicone gum (lubricant) (trade name: X-21-3043, manufactured by Shin-Etsu Polymer Co., Ltd.)

(G-4 additive)
Carbon black (colorant and weathering agent) (trade name: Asahi # 70, manufactured by Asahi Carbon Co., Ltd.)

[Test Example 1]
The insulated wires of Examples 1 to 28 and Comparative Examples 1 to 8 obtained by the above methods were compared and evaluated by the evaluation items and evaluation methods shown in the following (1) to (7).

  In the evaluation items, “(1) mechanical properties”, “(2) heat resistance test A”, “(3) oil resistance test A”, “(4) appearance (bleed) test” and “(5) difficulty”. Those that passed all of the "flammability tests" (no x was attached) were regarded as the overall pass. On the other hand, “(6) Heat resistance test B” and “(7) Heat resistance test C” were conducted as reference tests. The results are shown in Tables 2 to 5.

(1) Mechanical properties:
Mechanical properties were subjected to a tensile test based on JIS C3005. A tubular piece was cut out from the above-mentioned cross-linked insulated wire, and the tensile strength, elongation, and 100% Mo were measured with a distance between front lines of 20 mm and a tensile speed of 200 mm / min. Here, “100% Mo” is the tensile stress when the elongation of the test piece reaches 100%, and the lower the value of 100% Mo, the lower the stress at the time of bending, and the more excellent the flexibility. . In the evaluation, the tensile strength was evaluated as ◯ when 8 MPa or more, the elongation as 200% or more as ◯, the other as x, and ◯ as acceptable. 100Mo was an index indicating flexibility, and less than 4 MPa was evaluated as ◯, 4 MPa or more and less than 5 MPa as Δ, 5 MPa or more as x, and Δ and ○ as acceptable.

(2) Heat resistance test A:
The heat resistance test A was a hot set test based on JIS C3660. The test temperature was 200 ° C., the load time was 15 minutes, and the load was 20 N / mm ² . Evaluation was acceptable when the elongation under load was 100% or less and the permanent elongation after cooling was 25% or less.

(3) Oil resistance test A:
The oil resistance test A was performed based on JIS C3005-4.18. The oil used for the immersion is a test lubricant No. stipulated in JIS K6258. Two oils were used. The oil immersion temperature was 85 ° C. and the oil immersion time was 4 hours. In the evaluation, the tensile strength and the residual ratio of elongation were measured, and x was less than 60%, Δ was 60% or more and less than 80%, and ○ was 80% or more, and Δ and ○ were acceptable.

(4) Appearance (bleed) test:
In the appearance (bleed) test, the insulated wires obtained in the above-mentioned Examples and Comparative Examples were wound around a φ4.0 mandrel for 20 turns and left in a constant temperature bath at 10 ° C. and 70 ° C. for 240 hours to The presence or absence of bleeding was confirmed. In the evaluation, the case where bleed was confirmed with the naked eye was evaluated as x, and the case where bleed was not confirmed with the naked eye was evaluated as ◯.

(5) Flame retardancy test A:
In the flame retardancy test, 60 ° inclined flame retardancy was performed. The 60 ° inclined flame retardant was carried out based on JIS C3005, and the combustion time was 30 seconds. In the evaluation, a self-extinguishing time of 60 seconds or less and a combustion length of 250 mm or less were marked with ◯, and those not satisfying it were marked with x.
In addition, this test was implemented only about what added (F) which is a flame retardant.

(6) Heat resistance test B:
The heat resistance test B was a hot set test based on JIS C3660. The test temperature was 200 ° C., the load time was 15 minutes, and the load was 25 N / mm ² . Evaluation was acceptable when the elongation under load was 100% or less and the permanent elongation after cooling was 25% or less.
In addition, as above-mentioned, this test was implemented as a reference test.

(7) Heat resistance test C:
The heat resistance test C was a hot set test based on JIS C3660. The test temperature was 200 ° C., the load time was 15 minutes, and the load was 30 N / mm ² . Evaluation was acceptable when the elongation under load was 100% or less and the permanent elongation after cooling was 25% or less.
In addition, as above-mentioned, this test was implemented as a reference test.

(8) Oil resistance test B:
The oil resistance test B was performed based on JIS C3005-4.18. The oil used for the immersion is a test lubricant No. stipulated in JIS K6258. Two oils were used. The oil immersion temperature was 75 ° C. and the oil immersion time was 4 hours. In the evaluation, the tensile strength and the residual ratio of elongation were measured, and x was less than 60%, Δ was 60% or more and less than 80%, and ○ was 80% or more, and Δ and ○ were acceptable.

  As shown in Tables 2 to 5, the insulated wires of Examples 1 to 31 or the heat-resistant resin composition coated on the insulated wires are “(1) mechanical properties” and “(2) heat resistance test”. It passed all of "A", "(3) Oil resistance test A", "(4) Appearance (bleed) test" and "(5) Flame resistance test", and was a comprehensive pass. In particular, all of the examples passed “(1) mechanical characteristics: 100-Mo” which is relatively strict as a condition for the flexibility test, and the insulated wire excellent in flexibility or the heat resistance coated on the insulated wire was used. It was confirmed that it was a resin composition.

  In addition, when Example 1 and Example 2 are compared, since Example 1 uses polyethylene for (B), it also passed the heat resistance test B that was rejected (x) in Example 1, and was carried out. The heat resistance was higher than in Example 1. In Example 7, since the density of the polyolefin resin (HDPE) used in (B) was larger than that in Example 8 or the like, the test passed, but the flexibility was slightly lower than that in Example 7 or the like. In Example 11, since the density of the polyolefin resin (ethylene-octene copolymer) used in (B) is small compared to Example 10 and the like, the test passed, but the oil resistance compared to Example 10 and the like. Was slightly lower.

  On the other hand, Comparative Examples 1 to 3 with a small amount of silane-modified polyethylene had poor heat resistance, and Comparative Examples 1 and 2 with high density of silane-modified polyethylene had poor oil resistance. Moreover, the comparative example 4 in which the density before silane modification | denaturation of polyethylene etc. (HDPE) used in (A) is larger than Example 1 and Example 2 was inferior to heat resistance and a softness | flexibility. On the other hand, Comparative Example 5 and Comparative Example 6 in which the density before silane modification of polyethylene or the like (ethylene-butene copolymer) used in (A) is smaller than Example 3 were inferior in oil resistance. (B) The comparative example 7 which does not contain polyolefin resin was not able to make a masterbatch. (E) The comparative example 8 which does not contain a silanol condensation catalyst was inferior to heat resistance compared with the example 18 containing a (E) silanol condensation catalyst. Thus, the insulated wire of the comparative example or the heat resistant resin composition coated on the insulated wire could not pass the overall test.

  INDUSTRIAL APPLICABILITY The present invention can be used as a constituent material for cabtyre cables and the like that require heat resistance, oil resistance, flexibility, and the like, and has high industrial applicability.

Claims (9)

A heat resistant resin composition comprising the following (A) to (E):
(A) At least one of silane-modified polyethylene and silane-modified ethylene-α-olefin copolymer having a density before silane modification of 0.850 to 0.900 g / cm ³ (A) to (D) 10 to 80% by mass
(B) Polyolefin resin (A)-(D) 3-60 mass% with respect to the whole
(C) At least one of styrene-based elastomer and ethylene-α-olefin copolymer rubber (A) to (D) 10 to 50% by mass based on the whole
(D) Paraffinic oil (A)-(D) 5-60 mass% with respect to the whole
(E) Silanol condensation catalyst (A)-(D) 0.005-0.5 mass part with respect to a total of 100 mass parts   The heat-resistant resin composition according to claim 1, wherein the (B) polyolefin resin is at least one of polyethylene and an ethylene-α-olefin copolymer. ^3. The heat-resistant resin composition according to claim 2, wherein a density of at least one selected from the polyethylene and the ethylene-α-olefin copolymer is 0.870 to 0.930 g / cm ^3. object. The heat resistant resin composition according to any one of claims 1 to 3, further comprising (F-1) and (F-2) as (F) a flame retardant.
(F-1) Bromine-based flame retardants 10 to 40 parts by mass with respect to a total of 100 parts by mass of (A) to (D) (F-2) To a total of 100 parts by mass of antimony trioxide (A) to (D) 0-35 parts by mass Furthermore, the following (F-3) is contained as a flame retardant (F), The heat resistant resin composition in any one of the Claims 1 thru | or 4 characterized by the above-mentioned.
(F-3) Metal hydrate (A) -40 mass parts with respect to a total of 100 mass parts of (D).   SEPS (styrene-ethylene-propylene-styrene block copolymer), SEEPS (styrene-ethylene-ethylene-propylene-styrene block copolymer) having a styrene content of 10 to 40% as the styrene-based elastomer (C). ) And SEBS (styrene-ethylene-butylene-styrene block copolymer). 6. The heat-resistant resin composition according to claim 1, wherein the heat-resistant resin composition is any one of the following.   A wiring material comprising the heat-resistant resin composition according to any one of claims 1 to 6 as a coating layer around a conductor or an optical fiber core wire.   A cable comprising the heat-resistant resin composition according to any one of claims 1 to 6 as a coating layer around a cable core.   A molded article comprising the heat resistant resin composition according to any one of claims 1 to 6.