JP5337205B2 - Radiation-resistant wire / cable - Google Patents

Description

  The present invention relates to an electric wire / cable having high radiation resistance useful as an electric wire / cable used in a nuclear power plant or the like.

  Electric wires and cables used in and around the nuclear reactor containment containment are exposed to high radiation and heat during steady-state operation of the nuclear reactor. Exposed to radiation and heat. For this reason, it is required to have high radiation resistance and high heat resistance.

  Chlorinated rubbers such as chlorosulfonated polyethylene and chlorinated polyethylene are not only excellent in radiation resistance and heat resistance, but also in electrical characteristics, oil resistance, weather resistance, cold resistance, flame resistance, etc. A composition comprising rubber as a base polymer has been conventionally used as a coating material for electric wires and cables for the above-mentioned uses.

  However, in order to obtain good water resistance, the conventional chlorinated rubber composition based on chlorinated rubber is limited in terms of environmental protection as an acid acceptor that captures chlorine generated from chlorinated rubber during deterioration. Lead compounds such as Resurge (lead (II) oxide) and red lead (trilead tetroxide) are being formulated. Then, it replaced with resurge etc. and the electric wire and cable which coat | covered the radiation-resistant composition using the layered inorganic compound of a lead-free compound are proposed (for example, refer patent document 1). However, such a lead-free composition has poor workability, and the electric wires and cables coated therewith have a problem that heat resistance and mechanical properties are lowered as compared with the conventional one. For this reason, there is a demand for a lead-free radiation-resistant composition that has good processability and is excellent in heat resistance and mechanical properties.

  By the way, it is known that the crosslinking method has a considerable influence on the heat resistance of the rubber composition. That is, conventionally, for rubber crosslinking, sulfur crosslinking using a combination of sulfur and a vulcanization accelerator, resin crosslinking using a phenol resin, etc., peroxide crosslinking using radicals generated when dicumyl peroxide is decomposed, etc. Various crosslinking methods such as amine crosslinking using an amine compound and quinoid crosslinking using a quinonedioxime have been used. Of these crosslinking methods, a crosslinking method using a resin is known to be a method suitable for a case where high heat resistance is required. Therefore, in order to improve the heat resistance of the lead-free composition, it is conceivable to apply such a resin crosslinking system.

  However, the resin crosslinking method has a significantly slower crosslinking reaction than other crosslinking methods, and in order to develop sufficient physical properties (initial physical properties), a long-time crosslinking treatment is performed at a high temperature, or two It is necessary to carry out secondary crosslinking. For this reason, due to its low productivity, it is not suitable for use as a coating material for electric wires and cables, and the resin crosslinking method has not been used so far. However, if sufficient initial characteristics can be obtained with a relatively short time of crosslinking, it will be applicable to wire and cable coating materials, and will be an effective countermeasure against the problem of reduced heat resistance due to lead-free processing. .

JP 2010-27291 A

  The present invention has been made based on such a conventional situation, and by applying a resin crosslinking system that can be crosslinked in a short time, the processability is good, and the radiation resistance, heat resistance, and mechanical properties are improved. Another object of the present invention is to provide a radiation-resistant electric wire / cable coated with a lead-free polymer composition which is also excellent.

  The radiation-resistant electric wire / cable which is the first aspect of the present invention is (B) terpene-based hydrogenated resin 2.0-25.0 parts by mass with respect to 100 parts by mass of (A) chlorosulfonated polyolefin, ( C) Lead-free polymer composition containing 3.0 to 30.0 parts by mass of a bisphenol A type epoxy resin and (D) 0.4 to 5.0 parts by mass of γ-aminopropyltriethoxysilane, The outer periphery is covered.

  According to a second aspect of the present invention, in the radiation-resistant electric wire / cable according to the first aspect, the lead-free polymer composition contains (B) 100 parts by mass of the (A) chlorosulfonated polyolefin. ) Terpene-based hydrogenated resin 4.0 to 20.0 parts by mass, (C) Bisphenol A type epoxy resin 7.0 to 25.0 parts by mass, and (D) γ-aminopropyltriethoxysilane 0.7 to 3 0.0 part by mass is contained.

  According to a third aspect of the present invention, in the radiation-resistant electric wire / cable according to the first aspect, the lead-free polymer composition is (B) with respect to 100 parts by mass of the (A) chlorosulfonated polyolefin. ) Terpene-based hydrogenated resin 6.0-15.0 parts by mass, (C) bisphenol A type epoxy resin 10.0-20.0 parts by mass, and (D) γ-aminopropyltriethoxysilane 0.7-3 0.0 part by mass is contained.

  According to a fourth aspect of the present invention, in the radiation-resistant electric wire / cable according to any one of the first to third aspects, the lead-free polymer composition is the (A) chlorosulfonated It further contains 3.0 to 10.0 parts by mass of (E) hydrotalcite compound with respect to 100 parts by mass of polyolefin.

  According to the present invention, radiation resistance coated with a lead-free polymer composition that can be crosslinked in a short time, has good workability, and is excellent in radiation resistance, heat resistance, and mechanical properties. Electric wires and cables can be obtained.

It is a cross-sectional view which shows one Embodiment of the radiation resistant electric wire and cable of this invention.

  Embodiments of the present invention will be described below.

  First, the lead-free polymer composition used for the radiation-resistant electric wire / cable of the present invention will be described.

  The lead-free polymer composition used in the present invention is a composition that is crosslinked by a so-called resin crosslinking method, and includes (A) chlorosulfonated polyolefin, (B) terpene-based hydrogenated resin, and (C) bisphenol A. Type epoxy resin and (D) γ-aminopropyltriethoxysilane.

  The chlorosulfonated polyolefin as the component (A) is not particularly limited in terms of production method, physical properties and the like, but from the viewpoint of weather resistance and processability, a chlorine content of 30 to 45% by mass is preferable. In general, chlorosulfonated polyolefins are polyethylene or ethylene / α-olefin copolymers such as ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, ethylene / 1- Rubber elasticity is developed by removing crystals of octene copolymer or the like by adding chlorine.

As the component (A), chlorosulfonated polyethylene obtained by chlorinating and chlorosulfonated polyethylene is particularly preferable. Examples of preferred commercially available chlorosulfonated polyethylene include TOSO-CSM TS-530 (trade name; chlorine content 35 mass%, sulfur content 1.0 mass%, Mooney viscosity ML _{1 + 4} manufactured by Tosoh Corporation. (100 ° C.) = 56), the same TOSO-CSM TS-430 (trade name; chlorine content = 35 mass%, sulfur content = 1.0 mass%, Mooney viscosity ML _{1 + 4} (100 ° C.) = 46), etc. Can be mentioned.

  The (B) component terpene-based hydrogenated resin is a component blended mainly for imparting good mechanical properties (such as tensile strength) to the lead-free polymer composition. Moreover, a flame retardance can be improved by using together with a flame retardant. Examples of terpene-based hydrogenated resins include hydrogenated terpene resins obtained by polymerizing or copolymerizing terpene monomers such as α-pinene, β-pinene, limonene, and dipentene, and α-pinene, β-pinene, and limonene. And hydrogenated products of aromatic modified terpene resins obtained by copolymerizing aromatic monomers such as styrene with terpene monomers such as dipentene. Examples of preferable commercially available terpene-based hydrogenated resins include Clearon M-115, Clearon M-105, Clearon P-150, Clearon P-135, Clearon P-125, Clearon P-115, Clearon P-105, Clearon K-100 (above, product name manufactured by Yasuhara Chemical Co., Ltd.).

  The blending amount of the (B) component terpene-based hydrogenated resin is 2.0 to 25.0 parts by mass, preferably 4.0 to 20.0 parts per 100 parts by mass of the (A) component chlorosulfonated polyolefin. It is 6.0 mass parts, More preferably, it is 6.0-15.0 mass parts. When the blending amount is less than 2.0 parts by mass, good mechanical properties cannot be imparted and flame retardancy cannot be improved. Moreover, when a compounding quantity exceeds 25.0 mass parts, there exists a possibility that an effect may not only change, but an external appearance may become bad.

  The component (C) bisphenol A type epoxy resin is a component that acts as a resin crosslinking agent, and is obtained by condensing bisphenol A with epihalohydrin such as epichlorohydrin or epibromohydrin. The bisphenol A type epoxy resin preferably has an epoxy equivalent of 160 to 220 g / eq, and more preferably 180 to 200 g / eq. When the epoxy equivalent of the bisphenol A type epoxy resin is less than 160 g / eq, there is a possibility that good thermal characteristics and mechanical characteristics cannot be imparted. On the other hand, when the epoxy equivalent exceeds 220 g / eq, poor appearance or the like may occur. Specific examples of commercially available products suitable as the component (C) include EPICLON 840 and EPICLON 850 (both are trade names manufactured by Dainippon Ink and Chemicals, Inc.).

  The blending amount of the bisphenol A type epoxy resin as the component (C) is 3.0 to 30.0 parts by mass, preferably 7.0 to 25 parts per 100 parts by mass of the chlorosulfonated polyolefin as the component (A). 0.0 part by mass, more preferably 10.0 to 20.0 parts by mass. When the amount is less than 3.0 parts by mass, good heat resistance and mechanical properties cannot be imparted. Moreover, when a compounding quantity exceeds 30.0 mass parts, there exists a possibility that not only the effect may not change but an external appearance defect etc. may arise.

  In addition, epoxy resins other than bisphenol A type epoxy resins such as bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, phenol novolak resin, and cresol novolak resin are also blended within the range that does not impair the effects of the present invention. can do.

  Component (D), γ-aminopropyltriethoxysilane, is known as a silane coupling agent, and is a component formulated mainly to impart good processability and mechanical properties to a lead-free polymer composition. It is. In addition, by blending this γ-aminopropyltriethoxysilane, the crosslinking time can be shortened, and the stickiness of the surface can be improved. Specific examples of commercially available products suitable as component (D) include KBE903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

  The blending amount of γ-aminopropyltriethoxysilane as the component (D) is 0.4 to 5.0 parts by mass, preferably 0.7 with respect to 100 parts by mass of the chlorosulfonated polyolefin as the component (A). -3.5 mass parts, More preferably, it is 0.7-3.0 mass parts. If the amount is less than 0.4 parts by mass, good processability and mechanical properties cannot be imparted. Moreover, when a compounding quantity exceeds 5.0 mass parts, there exists a possibility that the effect may not change but it may bloom on the surface.

  In addition, the silane coupling agent other than the said (D) component can also be mix | blended in the range which does not inhibit the effect of this invention.

In the lead-free polymer composition used in the present invention, an acid acceptor, that is, a scavenger for chlorine released from the chlorosulfonated polyolefin as the component (A) can be blended. As the acid acceptor, it is preferable to use hydrotalcite. Hydrotalcite is a general formula ^{_{[M 2+ 1-x M 3+}} x (OH) 2] layered inorganic compound represented by _{[A n- x / n · zH} 2 O]. ^{Here, M 2+} is a divalent metal ^{ion, M 3+} is a trivalent metal ^{ion, A n-anions} (anions). The hydrotalcite may be a natural product or a synthetic product. Hydrotalcite produced ^{naturally, M 2+} is is ^{Mg 2+, M 3+} is the ^{Al 3+, A n-} is _CO ³ is ^2. The range of x is 0 <x <1, and preferably 0.3 ≦ x ≦ 0.33. Furthermore, the range of z is preferably 0 <z.

  The blending amount of hydrotalcite is preferably 3.0 to 10.0 parts by mass, more preferably 4.0 to 8.0 parts by mass with respect to 100 parts by mass of the chlorosulfonated polyolefin. If the blending amount is less than 3.0 parts by mass, the effect of the addition may not be sufficiently obtained, and if it exceeds 10.0 parts by mass, the mechanical properties may be deteriorated.

  Note that magnesia (MgO) is also a compound that can function as an acid acceptor. However, it is preferable not to use magnesium chloride because it is soluble in magnesium chloride produced by reaction with chlorine and lowers water resistance.

  In order to further improve heat resistance, the lead-free polymer composition used in the present invention can be blended with inorganic fillers such as silica and reinforcing carbon black. As an inorganic filler, from the viewpoint of improving heat resistance, silica is preferable, wet silica is more preferable, and a sieve residue of 7.0% by mass (150 μm) (JIS K 5101) is particularly preferable. Specific examples of commercially available silica suitable as an inorganic filler include Nipsil VN3 (trade name, manufactured by Tosoh Silica Co., Ltd.). In addition, specific examples of commercially available reinforcing carbon black include HTC # 80 (trade name, manufactured by Chubu Carbon Co., Ltd.).

  The blending amount of the inorganic filler in the lead-free polymer composition is preferably 10 to 40 parts by mass, more preferably 15 to 35 parts by mass, and even more preferably 20 to 100 parts by mass of the chlorosulfonated polyolefin. 30 parts by mass. If the blending amount is less than 10 parts by mass, the effect due to the addition may not be sufficiently obtained, and if it exceeds 40 parts by mass, the processability may be deteriorated or the appearance may be deteriorated.

  Examples of inorganic fillers other than silica and reinforcing carbon black that can be blended in the lead-free polymer composition include, for example, clay, talc, alumina, zirconia, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride. , Silicon nitride, aluminum nitride, and the like.

  In order to improve flame retardancy, the lead-free polymer composition used in the present invention can be blended with a flame retardant and a flame retardant aid that are generally blended in this type of composition. Flame retardants include metal hydroxides such as aluminum hydroxide, zirconium hydroxide, calcium hydroxide, and barium hydroxide, nitrogen flame retardants such as guanidine and melamine, and phosphorus-based flame retardants such as ammonium phosphate and red phosphorus. Flame retardant, phosphorus-nitrogen flame retardant, calcium carbonate, barium sulfate, tetrabromobisphenol A (TBA), hexabromobenzene, decabromodiphenyl ether, tetrabromoethane (TBE), tetrabromobutane (TBB), hexabromocyclodecane ( Examples thereof include brominated flame retardants such as HBCD). Examples of the flame retardant aid include antimony trioxide and zirconium oxide.

  The total amount of these flame retardants and flame retardant assistants is preferably 30 to 80 parts by mass, more preferably 45 to 70 parts by mass with respect to 100 parts by mass of the chlorosulfonated polyolefin. If the blending amount is less than 30 parts by mass, the effect of addition may not be sufficiently obtained, and if it exceeds 80 parts by mass, the flame retardant and the flame retardant aid may bloom.

  In the lead-free polymer composition used in the present invention, if necessary, a softener, a plasticizer, a processing aid, a vulcanization accelerator, a lubricant, as long as the effects of the present invention are not impaired. Various additives such as a colorant, an antioxidant, an ultraviolet absorber, and a heat aging inhibitor can be blended.

  Softeners include petroleum-based softeners such as petroleum jelly, process oil, lubricating oil, paraffin, liquid paraffin, and petroleum asphalt, and fatty oil-based softeners such as soybean oil, palm oil, castor oil, linseed oil, rapeseed oil and coconut oil. Agents, waxes such as tall oil, sub, beeswax, carnauba wax and lanolin, and fatty acids such as linoleic acid, palmitic acid, stearic acid and lauric acid.

  Examples of the processing aid include polymer polyhydric alcohols such as polyethylene glycol, polymer fatty acid esters, and the like.

  Examples of the vulcanization accelerator include thiurams such as dipentamethylene thiuram tetrasulfide, thiazoles such as 2-benzothiazolyl disulfide, and guanidine vulcanization accelerators such as di-o-tolylguanidine.

  Antioxidants and heat aging inhibitors include morpholine-N-oxydiethylenedithiocarbamate and dibenzothiazyl disulfide reaction product, nickel diethyldithiocarbamate, nickel diisobutyldithiocarbamate, dilauryl-3,3'-thiodipropionate 4,4'-thiobis- (6-tert-butyl-3-methylphenol), dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, 2-mercaptobenzo Sulfur antioxidants such as imidazole, 2-mercaptomethylbenzimidazole, 1,3-bis (dimethylaminopropyl) -2-thiourea, tributylthiourea; 1,1,3-tris- (2-methyl-4 -Hydroxy-5-t-butylphenyl) butane, 4 ', 4 Butylidenebis- (3-methyl-6-tert-butylphenol), tetrakis- [methylene-3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, triethyleneglycol-bis [3- ( 3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 2, 4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, tris- (3,5-di-t-butyl-4- Hydroxybenzyl) isocyanurate, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, , N'-hexamethylene bis (3,5-di-t-butyl-4-hydroxyhydrocinnamamide), bis (3,5-di-t-butyl-4-hydroxybenzyl sulfonate) calcium, 3 , 5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid ester, 1,3,5-tris Hindered phenolic antioxidants such as (3,5-di-t-butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione; distearyl-pentaerythritol -Diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphite, bis (2,4-di-t-butylphenyl) Le) pentaerythritol - diphosphite and the like phosphorus-based antioxidants such as. Note that nickel dibutyldithiocarbamate is known as a dithiocarbamate antioxidant among sulfur-based antioxidants.

  Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 -Dihydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-acryloyloxyethoxybenzophenone, 4- (2-acryloyloxyethoxy) -2-hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2'-hydroxy -5'-me Ruphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) ) Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6 ″ -Tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetrahydrophthalimidomethyl)- -(2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,4-di-t -Butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, phenyl salicylate, pt-butylphenyl salicylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl -2-cyano-3,3-diphenyl acrylate and the like.

  Each of the above additives may be used alone or in combination of two or more.

  The lead-free polymer composition used in the present invention includes (A) chlorosulfonated polyolefin, (B) terpene hydrogenated resin, (C) bisphenol A type epoxy resin, (D) γ- By uniformly mixing aminopropyltriethoxysilane and the above-mentioned various components blended as necessary using a conventional kneader such as a Banbury mixer, tumbler, pressure kneader, kneading extruder, mixing roller, etc. It can be manufactured easily.

  The lead-free polymer composition thus prepared is extrusion-coated directly on the conductor or through another coating and crosslinked to obtain the radiation-resistant electric wire / cable of the present invention. In addition, the material of the conductor, the outer diameter, the presence or absence of twisting, and the like are not particularly limited, and are appropriately selected depending on the application. In addition, any method such as hot pressing, steam, hot air, etc. can be applied to the crosslinking, and a sufficiently crosslinked coating is formed at a temperature of 140 to 180 ° C. and a time of about 15 to 40 minutes. be able to.

  FIG. 1 is a cross-sectional view showing a radiation-resistant electric wire / cable according to an embodiment of the present invention.

  As shown in FIG. 1, the flame-retardant electric wire / cable 10 of the present embodiment shows a conductor 11 made of one or more tin-plated annealed copper wires or the like. On this conductor 11, an insulator 12 made of cross-linked polyethylene is provided by a conventional method. A sheath 13 is formed on the insulator 12 by extrusion-coating and crosslinking the lead-free polymer composition described above.

  In the radiation resistant electric wire / cable 10 of this embodiment, (A) chlorosulfonated polyolefin, (B) terpene-based hydrogenated resin, (C) bisphenol A type epoxy resin, (D) γ-aminopropyltriethoxysilane The coating is formed by extrusion-coating and crosslinking a lead-free polymer composition formulated with a specific ratio. The uncrosslinked lead-free polymer composition has good processability, and the radiation-resistant wire / cable 10 can be provided with a coating excellent in radiation resistance, heat resistance, and mechanical properties.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all. In addition, the component used by the Example and the comparative example is as follows.

Chlorosulfonated polyolefin:
Tosoh Corporation product name TOSO-CSM TS-530;
Chlorine content = 35 mass%, sulfur content 1.0 mass%,
Mooney viscosity ML _{1 + 4} (100 ° C.) = 56
Hydrotalcite:
Product name DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.
Terpene-based hydrogenated resin:
Product name Clearon M-115 manufactured by Yasuhara Chemical Co., Ltd.
Bisphenol A type epoxy resin:
Product name EPICRON 850 manufactured by Dainippon Ink & Chemicals, Inc.
Epoxy equivalent = 188 g / eq
γ-aminopropyltriethoxysilane:
Product name KBE903 manufactured by Shin-Etsu Chemical Co., Ltd.
Bis (3-ethoxysilylpropyltetrasulfide):
Product name KBC1003 manufactured by Shin-Etsu Chemical Co., Ltd.
Polymer fatty acid ester:
Product name STRUCTOR HT254
Product name HTC # 80 made by Chubu Carbon Co., Ltd.
Wet silica:
Product name Nipsil VN3 manufactured by Tosoh Silica Corporation

Example 1
100 parts by mass of chlorosulfonated polyolefin, 4.0 parts by mass of hydrotalcite, 2.5 parts by mass of terpene-based hydrogenated resin, 0.6 parts by mass of γ-aminopropyltriethoxysilane, 3.6 parts by mass of bisphenol A type epoxy resin Parts, 1.5 parts by mass of dipentamethylene thiuram sulfide, 0.5 parts by mass of 2-benzothiazolidisulfide, 0.3 parts by mass of 1,3-di-o-tolylguanidine, 20.0 parts by mass of carbon black, sulfuric acid 50.0 parts by mass of barium, 15.0 parts by mass of antimony trioxide, 2.0 parts by mass of polymeric fatty acid ester, 20.0 parts by mass of wet silica, and 4.0 parts by mass of petroleum jelly are uniformly kneaded with a mixing roll. A compound of a non-containing polymer composition was obtained.

Next, a 1.2 mm thick insulator made of cross-linked polyethylene was coated on a copper stranded wire conductor having a cross-sectional area of 38 mm ^{2 by} a conventional method, and then the above compound was extrusion coated to a thickness of 1.5 mm on the conductor at 160 ° C. Radiation-resistant electric wires and cables having an outer diameter of about 12.5 mm were produced by resin crosslinking under conditions of 35 minutes.

(Examples 2-8, Comparative Examples 1-7)
Except for changing the composition of the compound as shown in Table 1, a compound of a lead-free polymer composition was obtained in the same manner as in Example 1, and a radiation-resistant electric wire / cable was obtained using these compounds. Manufactured.

Various characteristics of the lead-free polymer compositions and radiation-resistant wires / cables obtained in the above Examples and Comparative Examples were evaluated by the methods described below.
[Mooney viscosity]
The Mooney viscosity was measured based on JIS K6300-1 using a Mooney viscometer (manufactured by Ueshima Seisakusho Co., Ltd.) under the conditions of a preheating time of 1 minute and a test temperature of 125 ° C.
[Tensile strength / elongation]
A test sheet prepared by cross-linking a lead-free polymer composition using a press at a temperature of 160 ° C. for 35 minutes was measured under a tensile speed of 200 mm / min based on JIS K 6251.
[Heat aging characteristics]
For the test sheet prepared in the same manner as in the case of tensile strength / elongation, the tensile strength and tensile elongation after heat aging (120 ° C. × 120 hours) were determined based on JIS K 6251 under the conditions of a tensile speed of 200 mm / min. The tensile strength residual ratio and the tensile elongation residual ratio with respect to the tensile strength and tensile elongation measured in the same manner before heat aging were calculated.
[Oxygen index]
The test sheet produced in the same manner as in the case of tensile strength / elongation was measured according to JIS K7201-2.

  These results are shown in Table 1.

As is clear from Table 1, in Examples 1 to 8, good results were obtained in Mooney viscosity, tensile strength / elongation (initial characteristics, thermal aging characteristics), and oxygen index.
In addition, 4.0 to 20.0 parts by mass of a terpene-based hydrogenated resin, 7.0 to 25.0 parts by mass of a bisphenol A type epoxy resin, and γ-aminopropyltriethoxy with respect to 100 parts by mass of chlorosulfonated polyolefin. By setting the silane to 0.7 to 3.5 parts by mass, better results were obtained in tensile strength and elongation (initial characteristics) (Examples 3 to 7).
Furthermore, with respect to 100 parts by mass of chlorosulfonated polyolefin, 6.0 to 15.0 parts by mass of terpene-based hydrogenated resin, 10.0 to 20.0 parts by mass of bisphenol A type epoxy resin, and γ-aminopropyltriethoxy By setting the silane to 0.7 to 3.0 parts by mass, better results were obtained in tensile strength / elongation (thermal aging characteristics) (Example 5).

  DESCRIPTION OF SYMBOLS 10 ... Radiation-resistant electric wire and cable, 11 ... Conductor, 12 ... Insulator, 13 ... Sheath.

Claims (4)

  (A) To 100 parts by mass of chlorosulfonated polyolefin, (B) 2.0-25.0 parts by mass of terpene-based hydrogenated resin, (C) 3.0-30.0 parts by mass of bisphenol A type epoxy resin, And (D) a radiation-resistant electric wire / cable, wherein the conductor outer periphery is coated with a lead-free polymer composition containing 0.4 to 5.0 parts by mass of γ-aminopropyltriethoxysilane.   The lead-free polymer composition comprises (B) terpene-based hydrogenated resin in an amount of 4.0 to 20.0 parts by mass and (C) bisphenol A-type epoxy with respect to 100 parts by mass of (A) chlorosulfonated polyolefin. The radiation-resistant electric wire / cable according to claim 1, comprising 7.0 to 25.0 parts by mass of resin and 0.7 to 3.5 parts by mass of (D) γ-aminopropyltriethoxysilane. .   The lead-free polymer composition comprises (B) terpene-based hydrogenated resin 6.0 to 15.0 parts by mass and (C) bisphenol A type epoxy with respect to 100 parts by mass of (A) chlorosulfonated polyolefin. The radiation-resistant electric wire / cable according to claim 1, comprising 10.0 to 20.0 parts by mass of resin and 0.7 to 3.0 parts by mass of (D) γ-aminopropyltriethoxysilane. .   The lead-free polymer composition further comprises 3.0 to 10.0 parts by mass of (E) a hydrotalcite compound with respect to 100 parts by mass of the (A) chlorosulfonated polyolefin. The radiation-resistant electric wire / cable according to any one of claims 1 to 3.

Images