TW202104404A - Flame-retardant anti-termite resin composition, cable and manufacturing method thereof having excellent flame retardancy, anti-termite properties, cold resistance, and extrusion processability, and capable of manufacturing cables at low cost - Google Patents

Abstract

The present invention provides a flame-retardant anti-termite resin composition, a cable and a cable manufacturing method. The flame-retardant anti-termite resin composition has an excellent flame retardancy, anti-termite properties, a cold resistance, and an extrusion processability, and can manufacture cables at a low cost. The flame-retardant anti-termite resin composition contains a polyvinyl chloride resin, a compound having an isocyanurate structure, and a boron-containing compound. With respect to 100 parts by mass of the aforementioned polyvinyl chloride resin, the content of the compound having an isocyanurate structure is in a range of 0.05 parts by mass to 10 parts by mass, and the content of the aforementioned boron-containing compound is in a range of 10 parts by mass to 55 parts by mass.

Description

Flame-retardant anti-termite resin composition, cable and manufacturing method thereof

The invention relates to a flame-retardant anti-termite resin composition, a cable and a manufacturing method thereof.

The outermost layer of cables and communication cables is provided with a protective outer coating (hereinafter referred to as sheath). Generally speaking, it is made by extruding general-purpose resins such as polyethylene and polyvinyl chloride (PVC). Press forming to form a coating. The sheath is required to have various functions depending on where the cable is laid. For example, when laying cables underground in areas where termite activities are frequent, a sheath is sought that has the characteristics of preventing erosion from termites, that is, anti-termite properties and flame retardancy. Therefore, the sheath is usually not composed of a single layer, but has the following structure: a two-layer structure, which is composed of PVC with excellent flame-retardant properties and nylon with excellent anti-termite properties in order; or, Three-layer structure, which is formed by layering PVC, nylon and PVC in sequence.

For example, there is a report in Patent Document 1 indicating an electric cable, which is a double structure formed by laminating an anti-ant layer on a flame-retardant layer to form a sheath, and has a sheath that is made of a flame-retardant vinyl layer. The laminated layer is used as a flame-retardant layer, and instead of nylon, the polypropylene (PP) laminated layer is used as an anti-termite layer to produce a double structure, which has flame-retardant and anti-termite properties. In addition, it has been proposed to use triallyl isocyanurate, tripropyl isocyanurate, or triethyl isocyanurate as an anti-termite agent (for example, refer to Patent Document 2). Among them, triallyl isocyanurate having three polymerizable allyl groups is also a crosslinking aid (see Patent Document 3). [Prior Technical Literature] (Patent Document)

Patent Document 1: Japanese Patent Application Publication No. 2015-096583 Patent Document 2: Japanese Patent Laid-Open No. 02-78110 Patent Document 2: Japanese Patent Laid-Open No. 2003-192865

[The problem to be solved by the invention] However, when the sheath is set to a two-layer structure or a three-layer structure, there are the following problems: the outer diameter of the cable will increase, and the problem of stacking different materials will increase the material cost and manufacturing cost. .

The conventional electric cable like the report in Patent Document 1 (for example, refer to Fig. 2), although the sheath has a two-layer structure, the manufacturing cost will increase as mentioned above, but there is still no high degree of satisfaction. It is a material with both flame-retardant and anti-termite properties, so the sheath cannot be made into a single layer.

In addition, the cable must meet the requirements for cold resistance in addition to flame retardancy and termite resistance.

In view of this situation, the problem to be solved by the present invention is to provide a flame-retardant anti-termite resin composition, a cable using the composition, and a method for manufacturing the cable. It has excellent ant resistance and cold resistance, excellent extrusion processability, and low-cost manufacturing of cables. [Technical means to solve the problem]

In order to use polyvinyl chloride resin (PVC) with excellent flame retardancy as the base resin of the flame retardant anti-termite resin composition, the present inventors have devoted themselves to research to satisfy the following performances: The suitability of extrusion processing by the compound of the compound of the cyanurate structure; and the basic performance of the cable for flame retardancy, termite resistance and cold resistance.

As a result, it was found that by using a composite containing polyvinyl chloride resin, a compound having an isocyanurate structure, and a boron-containing compound, a single layer can be formed with excellent flame retardancy, termite resistance, and cold resistance. jacket.

However, when a sheath with such a composition is formed in a single layer, when extrusion molding is performed at 190°C, if the compounding amount of the compound having an isocyanurate structure is excessively increased, white smoke and organic matter are likely to be generated. Because of the odor of the compound, it is necessary to install a local ventilating room, etc., which causes a new problem that the manufacturing cost is consequently increased.

Therefore, the inventors of the present invention conducted further studies and found the following facts and completed the present invention based on such technical ideas: by compounding a compound having an isocyanurate structure in a polyvinyl chloride resin, and a compound containing The boron compound is limited to an appropriate ratio, and white smoke and organic compound odor will not be generated during extrusion processing, thus satisfying the suitability of extrusion processing.

In other words, the essential structure of the present invention is as follows. (1) A flame-retardant anti-termite resin composition comprising a polyvinyl chloride resin, a compound having an isocyanurate structure, and a boron-containing compound, and relative to 100 parts by mass of the aforementioned polyvinyl chloride resin, The content of the cyanurate structure compound is in the range of 0.05 parts by mass to 10 parts by mass, and the content of the boron-containing compound is in the range of 10 parts by mass to 55 parts by mass relative to 100 parts by mass of the polyvinyl chloride resin. (2) The flame-retardant anti-termite resin composition according to (1), wherein the content of the compound having an isocyanurate structure is 0.05 to 0.6 parts by mass relative to 100 parts by mass of the polyvinyl chloride resin Within the range of servings. (3) The flame-retardant anti-termite resin composition according to (1) or (2), wherein the content of the boron-containing compound is 10 to 20 parts by mass relative to 100 parts by mass of the polyvinyl chloride resin Within range. (4) The flame-retardant anti-termite resin composition according to any one of (1) to (3), which is a raw material for a sheath, which is used to form the outermost layer of a cable. (5) A cable having a structure in which at least an inner semiconducting layer, an insulator layer, an outer semiconducting layer, a shielding layer, and a sheath are laminated on the outer circumference of a conductor in sequence, and the aforementioned sheath is ( The flame-retardant anti-termite resin composition described in any one of 1) to (4) is formed as a raw material. (6) The cable according to (5), wherein the sheath is composed of a single layer. (7) A method for manufacturing a cable, the cable having a structure in which at least an inner semiconducting layer, an insulator layer, an outer semiconducting layer, a shielding layer, and a sheath are laminated on the outer circumference of the conductor, and the manufacturing The method is to extrude the flame-retardant anti-termite resin composition described in any one of (1) to (4) to coat the outer periphery of the shielding layer to form a sheath. [effect]

According to the present invention, it is possible to provide a flame-retardant anti-termite resin composition, a cable and a cable manufacturing method using the resin composition, the flame-retardant anti-termite resin composition is highly superior in flame retardancy, termite resistance, and cold resistance, and The extrusion processability is excellent and the cable can be manufactured inexpensively.

Hereinafter, the flame-retardant anti-termite resin composition of the present invention, which can be suitably used as a raw material for the sheath of a cable, will be described in detail in order.

>>Flame retardant anti-termite resin composition>> The flame-retardant anti-termite resin composition of the present invention contains polyvinyl chloride resin (PVC), a compound having an isocyanurate structure, and a boron-containing compound. In the present invention, the content of the flame-retardant anti-termite resin composition of these components is: relative to 100 parts by mass of the polyvinyl chloride resin, the content of the compound having an isocyanurate structure is 0.05 parts by mass to 10 parts by mass, The content of the boron-containing compound is 10 parts by mass to 55 parts by mass.

>Base resin> The flame-retardant anti-termite resin composition of the present invention contains polyvinyl chloride as a base resin. Among general-purpose plastics, vinyl chloride resin is excellent in flame retardancy, and it is possible to suppress the blending amount of flame retardant materials such as flame retardants. Polyvinyl chloride may contain an average degree of polymerization, a unit structure obtained from other monomer components, and a repeating unit structure. In the present invention, the average degree of polymerization of the polyvinyl chloride resin is preferably 900 to 5,000. In addition, a homopolymer of vinyl chloride is preferred. As the base resin, other resins may be added. With respect to 100 parts by mass of the base resin, it is preferable to contain polyvinyl chloride resin at least 80 parts by mass, more preferably contain polyvinyl chloride resin at least 90 parts by mass, and it is particularly preferable to contain polyvinyl chloride resin substantially. 100 parts by mass of vinyl chloride resin.

>Compounds with isocyanurate structure> The compound having an isocyanurate structure is not particularly limited as long as it has an isocyanurate skeleton. In the present invention, it is preferable to use a compound represented by the following general formula (I).

此處，R¹ ～R³ 分別獨立地表示氫原子、脂肪族烴基、芳基或雜環基。

Here, R ¹ to R ³ each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group.

^{The aliphatic hydrocarbon group for constituting R 1} to R ³ of the above general formula (I) may be a saturated hydrocarbon group, an unsaturated hydrocarbon group, or a cyclic hydrocarbon group. As an aliphatic hydrocarbon group, more specifically, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a cycloalkenyl group are mentioned, for example. In addition, the carbon number of the aliphatic hydrocarbon group is preferably 1-20, preferably 1-12, more preferably 1-8, and particularly preferably 1-6. In addition, the aliphatic hydrocarbon group is preferably an alkyl group and an alkenyl group, and preferably an alkyl group having 1-20 carbon atoms and an alkenyl group having 2-20 carbon atoms. Specific examples of aliphatic hydrocarbon groups include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, 2-ethylhexyl, decyl, vinyl, Allyl, isopropenyl, ethynyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl.

^{The carbon number of the aryl group used to form R 1} to R ³ of the general formula (I) is preferably 6-20, preferably 6-16, and more preferably 6-10. As a specific example of an aryl group, a phenyl group and a naphthyl group are mentioned, for example.

^{It is preferable that the heterocyclic ring in the heterocyclic group of R 1} to R ³ for constituting the above-mentioned general formula (I) has at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. In addition, the heterocyclic ring contained in the heterocyclic group may be a saturated ring, an unsaturated ring, or an aromatic ring. The number of carbon atoms of such a heterocyclic group is preferably 0-20, more preferably 1-12. Specific examples of the heterocyclic ring contained in the heterocyclic group include, for example, a tetrahydrofuran ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a thiazole ring, and a pyridine ring. .

In the compound represented by the general formula (I), it is preferable that R ¹ to R ³ are each independently a hydrogen atom or an aliphatic hydrocarbon group, more preferably ^{any one of R 1} to R ³ is an aliphatic hydrocarbon group, and still more It is ^{preferable that any one of R 1} to R ³ is a group selected from an alkyl group and an alkenyl group, and among them, it is preferable that R ¹ to R ³ are the same group.

As the compound represented by the general formula (I), trimethyl isocyanurate, triethyl isocyanurate, tripropyl isocyanurate, and triallyl isocyanurate are preferred , With triallyl isocyanurate (ie 1,3,5-gin (2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)- Triketone) is the best.

Relative to 100 parts by mass of the polyvinyl chloride resin, the content of the compound having an isocyanurate structure must be 0.05 parts by mass to 10 parts by mass, preferably 0.05 parts by mass to 5 parts by mass, and 0.05 parts by mass to 1 part by mass Preferably, it is more preferably 0.05 to 0.6 parts by mass.

>Boron-containing compounds> The boron-containing compound is a compound having a boron atom in the molecule, for example, borate compounds, boron oxides, boron sulfides, boron nitrides, etc., borate compounds are preferred, and zinc borate is particularly preferred.

Relative to 100 parts by mass of the polyvinyl chloride resin, the content of the boron-containing compound must be 10 parts by mass to 55 parts by mass, preferably 10 parts by mass to 35 parts by mass, and more preferably 10 parts by mass to 20 parts by mass.

In order to improve the termite resistance of the cable sheath, the more compounds with an isocyanurate structure are added, the more odors of organic compounds will be generated when the flame retardant termite resin composition is extruded to obtain the sheath. And smoke, so the manufacturability suitability will deteriorate. According to the research of the present inventors, although boron-containing compounds such as zinc borate may act as flame retardants or flame retardant additives, they exhibit anti-termite properties. Moreover, compounds with an isocyanurate structure will also improve cold resistance. Furthermore, the boron-containing compound tends to decrease the cold resistance as the compounding amount increases.

As described above, with respect to 100 parts by mass of the polyvinyl chloride resin, the content of the boron-containing compound is set to 10 parts by mass to 55 parts by mass, and the content of the compound having an isocyanurate structure is set to 0.05 parts by mass to 10 parts by mass In this way, any of flame retardancy, termite resistance, and cold resistance can be maintained at a high level, and the manufacturing suitability in extrusion processing is also excellent.

>Other ingredients> The flame-retardant anti-termite resin composition of the present invention may contain other components as needed. For example, the flame-retardant anti-termite resin composition of this embodiment may contain a flame-retardant agent or a flame-retardant auxiliary agent other than the boron-containing compound. The flame retardant or flame retardant auxiliary is not particularly limited, and examples include antimony trioxide, polytetrafluoroethylene, silicon dioxide, hydrotalcite, magnesium bicarbonate, magnesium hydroxide or calcium hydroxide. Metal hydroxide, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, vanadium oxide, molybdenum oxide, phosphorus compounds and their surface treatments, melamine, melamine cyanurate, pentaerythritol, dipentaerythritol, tripentaerythritol, monopentaerythritol , PTFE, etc. Among these, antimony trioxide and metal hydroxide are preferable from the viewpoint of further improving flame retardancy. The content of the flame retardant or flame retardant auxiliary agent other than the boron-containing compound is not particularly limited as long as it is within a range that does not impair the characteristics of the flame retardant anti-termite resin composition of the present invention.

In addition, it can be formulated according to needs: ultraviolet absorbers, light stabilizers, antioxidants, lubricants, crystallization nucleating agents, softeners, antistatic agents, metal deactivators, antibacterial/antifungal agents, pigments and other additives. The content of such additives is not particularly limited as long as it is within a range that does not impair the characteristics of the flame-retardant anti-termite resin composition of the present invention.

>Use of flame-retardant anti-termite resin composition> The flame-retardant anti-termite resin composition of the present invention is particularly preferably used as a raw material for a sheath, which is used to form the outermost layer of a cable. In particular, the flame-retardant anti-termite resin composition of the present invention is excellent in any of flame retardancy, anti-termite property, and cold resistance, and the sheath can be made into a single layer, so that the manufacturing cost of the cable can be reduced.

>>Cable>> The cable of the present invention has a structure in which at least an inner semiconducting layer, an insulator layer, an outer semiconducting layer, a shielding layer, and a sheath are laminated on the outer circumference of the conductor, and the sheath is the flame retardant of the present invention. The anti-termite resin composition is formed as a raw material. Specifically, for example, as shown in the cable 10 in Fig. 1, the outer circumference of the conductor is sequentially covered with an inner semiconductive layer 2, an insulator layer 3, an outer semiconductive layer 4, a shielding layer 5, and a sheath 6. Among them, the sheath 6 is composed of a single layer. In the present invention, since the sheath 6 can be constituted by a single layer, it is not necessary to set the sheath into a two-layer structure and a three-layer structure like the conventional cable. Furthermore, FIG. 2 shows the structure of the conventional cable 100, the sheath 106 has a two-layer structure, and an anti-termite sheath 108 is formed on the outer periphery of the flame-retardant sheath 107.

In the present invention, the number of cores of the cable can be single core (1 core) or multiple cores (for example, 3 cores). Here, when a 3-core cable is formed, it can be made into a structure in which 3 single-core bundles are bundled and the bundled surface is covered with a sheath via an interposer as needed. The single core has an inner semiconducting layer, an insulator layer, an outer semiconducting layer, and a shielding layer sequentially laminated on the outer circumference of the conductor, but it is not limited to this. The following descriptions are made in order from the conductors.

>Conductor> The conductor is preferably made of copper or copper alloy, aluminum or aluminum alloy, and its cross-sectional shape can be either circular or rectangular. In the present invention, a circular conductor made of copper alloy is preferred. In addition, the surface of the metal wire made of the above-mentioned material may be plated with tin, silver, or the like. The conductor may be any one of single wire and twisted wire.

The cross-sectional area and shape of the conductor will vary depending on the voltage level and laying conditions of the cable and are not limited. The cross-sectional area of the conductor is preferably 2 mm ² to 4000 mm ^2, preferably 150 mm ² to 2000 mm ² . In addition, the surface of such a metal wire may be plated with tin, silver, etc., and the conductor may be any of a single wire and a stranded wire. As the structure or shape of the conductor, for example: the structure or shape used in a normal cable, for example, when it is a twisted wire, for example: a round twisted wire [7/0.6 (branch/mm), 7/ 0.8 (branch/mm), 7/1.0 (branch/mm), 7/1.2 (branch/mm)], split compression stranded wire or round compression stranded wire, among them, it is preferable to use a round compression stranded wire. Furthermore, the split compression strand is also called a split conductor, which is a split conductor for a cable formed by interposing an interposer between each section.

>Internal semiconducting layer> As the internal semiconducting layer, an internal semiconducting layer generally used in cables can be used. As the internal semi-conductive layer, for example, a layer formed by applying a conductive material of a fibrous (cloth) tape, a layer formed by mixing carbon with polyethylene and extrusion molding, a layer formed by combining these, etc. . In addition, the internal semiconducting layer is preferably formed by using a resin composition for the internal semiconducting layer and crosslinking it. The resin composition for the internal semiconducting layer usually contains: the resin for the internal semiconducting layer, a conductive substance, a crosslinking agent, and an anti-aging agent.

The resin for the internal semiconductive layer is not particularly limited, but an ethylene-based polymer is generally used. Here, the ethylene-based polymer is not particularly limited as long as it contains ethylene as a repeating unit, and examples include polyethylene (low-density polyethylene, high-density polyethylene), and ethylene-vinyl acetate copolymer. (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-1-butene copolymer, ethylene-α-olefin copolymer , Ethylene-propylene diene rubber (EPDM). These can be used individually or in combination of 2 or more types. Among these, polyethylene and ethylene-vinyl acetate copolymer (EVA) are preferred, polyethylene is preferred, and cross-linked polyethylene is more preferred. Here, the cross-linked polyethylene can be cross-linked by including polyethylene and a cross-linking agent in the resin composition for the internal semiconductive layer.

The conductive material is not particularly limited, but conductive carbon is usually used. Examples of conductive carbon include carbon black, acetylene black, furnace black, Ketjen black, thermal black, graphite, and the like. These can be used individually or in combination of 2 or more types. Among them, because the content of impurities is small, the electrical characteristics of the resin for the internal semiconducting layer are not deteriorated, and large aggregates are not formed at the interface with the resin for the internal semiconducting layer. Do not produce electrical defects, that is, conductive bumps, and acetylene black is preferred.

For the internal semiconducting layer, commercially available semiconducting compounds NUCV-9563, 9585, 9589 [manufactured by NUC Co., Ltd.], etc. can be used.

The thickness of the internal semi-conductive layer varies with the voltage level of the cable and is not limited. The thickness of the internal semi-conductive layer is preferably 2 mm or less, preferably 1 mm to 2 mm.

>Insulator layer> The insulator layer is an insulating layer for covering the internal semiconducting layer, and is generally formed by using a resin composition for the insulator layer and crosslinking it. The resin composition for an insulator layer usually contains a resin for an insulator layer, a crosslinking agent, and an anti-aging agent.

Here, as the resin for constituting the resin composition for the insulator layer, a polyolefin resin is preferred, and a polyolefin resin modified with an unsaturated organic acid or a derivative thereof is preferred. Polyolefin resins are preferably polyethylene, polypropylene, and copolymers with ethylene or propylene. Polyethylene and polypropylene are more preferable, polyethylene is more preferable, and low-density polyethylene is particularly preferable. In addition, the resin used to form the insulator layer is preferably a cross-linked resin. As the insulator layer, commercially available insulating composite HFDA-9253NT SC, insulating composite NUCV-9253 [manufactured by NUC Co., Ltd.], and the like can be used.

The thickness and shape of the insulator layer will vary depending on the voltage level and laying conditions of the cable, and is not limited. The thickness of the insulator layer is preferably 10 mm to 23 mm, preferably 10 mm to 17 mm.

>External semiconducting layer> The outer semiconducting layer generally has the same belt method and extrusion method as the inner semiconducting layer. The outer semiconducting layer is a semiconducting layer for covering the insulator layer, and is generally formed by using a resin composition for the outer semiconducting layer and making it crosslink. The resin composition for the outer semiconducting layer used to form the outer semiconducting layer generally includes: the resin for the outer semiconducting layer, a conductive substance, a crosslinking agent, and an anti-aging agent.

The resin for the outer semiconducting layer is not particularly limited, but an ethylene-based polymer is usually used. As a specific example of an ethylene-based polymer, for example, the same ethylene-based polymer as the resin for the internal semiconductive layer described above, and the like can be given. Among the ethylene-based polymers, the resin for the external semiconductive layer is preferably polyethylene or ethylene-vinyl acetate copolymer (EVA), preferably polyethylene, and preferably cross-linked polyethylene. Here, the cross-linked polyethylene can be cross-linked by including polyethylene and a cross-linking agent in the resin composition for the outer semiconductive layer.

The conductive material is not particularly limited, but conductive carbon is usually used. As a specific example of conductive carbon, the same conductive carbon as the resin for internal semiconductive layers mentioned above, etc. are mentioned, for example.

The thickness and shape of the external semi-conductive layer will vary depending on the voltage level and laying conditions of the cable, and is not limited. The thickness of the external semi-conductive layer is preferably 1.5 mm or less, preferably 0.1 mm to 1.5 mm.

>Shading layer> As the shielding layer (metal shielding layer), for example, a band-shaped metal and a metal formed by extrusion molding can be mentioned. Examples of strip-shaped metals include copper strips and aluminum laces. In addition, as the metal to be formed by extrusion molding, for example, aluminum, lead, stainless steel (SUS), etc., are exemplified, and aluminum is preferred.

The thickness and shape of the shielding layer will vary depending on the voltage level of the cable and the laying conditions, and there is no limitation. The thickness of the shielding layer is for example: if it is a strip, it is better to be 0.3 mm or less, and 0.1 mm to 0.3 mm is better. good.

>Sheath> The sheath will exert anti-termite, flame-retardant and cold resistance, and protect the cable from external influences, mainly as the outermost layer of the cable. The sheath can improve the mechanical strength of the cable or prevent the penetration of moisture from the outside. In the cable of the present invention, the sheath is formed using the above-mentioned flame-retardant anti-termite resin composition as a raw material. The thickness and shape of the sheath will vary depending on the voltage level and laying conditions of the cable, and are not limited. For example, the thickness of the sheath is preferably 4.0 mm to 6.0 mm, preferably 4.0 mm to 5.5 mm.

>>The manufacturing method of the cable>> The method for manufacturing a cable of the present invention has a structure in which at least an inner semiconducting layer, an insulator layer, an outer semiconducting layer, a shielding layer, and a sheath are laminated on the outer circumference of the conductor in this order, and the manufacturing method It includes the step of covering and forming a sheath on the outer periphery of the conductor, more specifically, the outer periphery of the shielding layer by extrusion molding the flame-retardant anti-termite resin composition. Thereby, it is possible to obtain a cable in which a sheath is formed on the outer peripheral side of the conductor as the outermost layer.

The method of using the flame-retardant anti-termite resin composition to provide a sheath on the outer periphery of the shielding layer is not particularly limited. In the present invention, it is preferable to coat the flame-retardant anti-termite resin composition to form the sheath by extrusion molding. In this case, from the viewpoint of ease of handling and simplicity, it is preferable to pelletize the flame-retardant anti-termite resin composition and use the pellets for extrusion coating. In the present invention, it is also preferable when the inner semiconducting layer, the insulator layer, the outer semiconducting layer, and the shielding layer are sequentially arranged on the outer circumference of the conductor, for example, for the inner semiconducting layer, the insulator layer, and the outer semiconducting layer. The layers are simultaneously extruded. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples.

[Example 1] (Preparation and performance evaluation of flame-retardant anti-termite resin composition) The flame-retardant anti-termite resin composition was prepared in the following manner, and the flame-retardant anti-termite resin composition was used to obtain each sheet and perform each evaluation.

[Examples of the present invention (sheet No. 1 to No. 5) and comparative examples (sheet No. c1 to No. c5)] Polyvinyl chloride resin (PVC) [ZEST1400Z manufactured by Shin Dai-ichi Vinyl Co., Ltd., average degree of polymerization 1,400] and triallyl isocyanurate [ TAIC (registered trademark) manufactured by Nippon Kasei Co., Ltd. and zinc borate (FIREBREAK290 manufactured by BORAX, USA) are obtained, and the resin composition is kneaded in a roller set at a kneading temperature of 150°C to produce resin After that, two sheet-like samples with different thicknesses were produced. This sample was press-molded at 170°C and 11 MPa for 15 minutes to obtain smooth sheets No.1 to No.5 and No.c1 to No.c5 with thicknesses of 2 mm and 3 mm, respectively. Here, sheet No. 1 to No. 5 are examples of the invention, and sheet No. c1 to No. c5 are comparative examples.

[Table 1] Sheet No. No.1 No.2 No.3 No.4 No.5 PVC 100 100 100 100 100 Zinc borate 15 10 10 55 20 Triallyl isocyanurate 0.6 0.6 0.05 10 0.6 Sheet No. No.c1 No.c2 No.c3 No.c4 No.c5 PVC 100 100 100 100 100 Zinc borate 0 0 5 60 10 Triallyl isocyanurate 0 0.3 0.01 0.05 15

2) Manufacturing of sheet No.c6 The granular nylon [UBEC nylon 3024LU manufactured by Ube Industries Co., Ltd.] was subjected to uniaxial extrusion at 210°C, and then subjected to compression molding at 220°C for 10 minutes to obtain thicknesses of 2 mm and 3, respectively. mm flat sheet of comparative example No.c6.

3) Performance evaluation of each sheet With respect to each sheet obtained in the above-mentioned manner, the evaluation of anti-termite property, flame retardancy, and cold resistance was performed in the following manner.

(Evaluation of termite resistance) The 2 mm-thick sheets obtained in the examples of the present invention and the comparative examples were cut to produce 3 small pieces of 20 mm in length and 20 mm in width. The samples were in accordance with JIS K 1571 (2010) "Wood Preservative-Performance Benchmark Test Method" to implement mandatory feeding test. Use an acrylic cylindrical container with an inner diameter of 80 mm and a height of 60 mm with the bottom cured with anhydrite, and set a plastic net in the cylindrical container. For each container, put a small sample, 150 workers of C. termites, and 15 soldier ants on this network, close the lid of the container and keep it at room temperature 28±2℃ and relative humidity in the dark Let stand for 3 weeks in more than 80% environment. Here, the lid of the container is a lid with a small hole that has been opened for ventilation. Then, after 3 weeks, the following mathematical formula 1 is used to compare the mass of the small sample before and after the test, and the average mass reduction rate X caused by termites is obtained, thereby quantifying the anti-termite property. X=(W ₀ －W ₁ )/W ₀ ×100[%] ・・・(Math 1) Here, W ₀ is the mass of the small sample at the beginning of the test, and W ₁ is the mass of the small sample at the end of the test quality.

The average value of the numerical value [%] of the average mass reduction rate X caused by termites and the average value of the death rate [%] of worker ants calculated by the above-mentioned formula 1 are as shown in Table 2. Among them, the "average mass reduction rate" preferably has a smaller value, and more specifically, it is more preferably 0.03% or less.

(Evaluation of flame retardancy) The 3 mm thick slices obtained in the examples of the present invention and the comparative examples were cut to prepare small pieces of samples with a length of 130 mm and a width of 6.5 mm, according to JIS K 7201-2 "Plastic-Oxygen Index Flammability Test Method" To implement the test. The oxygen index [%] obtained by this test is shown in Table 2. It is preferable that the flame retardancy has a larger value of the oxygen index.

(Evaluation of cold resistance) The 2 mm-thick sheets obtained in the examples of the present invention and the comparative examples were cut to prepare small pieces of samples with a length of 38 mm and a width of 6 mm, and the cold resistance temperature was measured in accordance with JIS C 3005 "Testing Methods for Rubber and Plastic Insulated Wires". The cold resistance temperature [°C] obtained by this test is shown in Table 2. For the cold resistance, it is preferable that the cold resistance temperature is a low temperature.

(Evaluation of manufacturing suitability) After melting and mixing each flame-retardant anti-termite resin composition at 190°C using a Banbury mixer, the mixture was discharged and processed into granulated particles by an extruder at 190°C. Repeat this procedure 3 times. Observing the state at this time, when the extrusion process can be carried out without producing white smoke and organic compound odor in 3 times, it is evaluated as grade "A". When it is confirmed that white smoke or organic compound is produced once in 3 times The compound odor is evaluated as grade "B", and when white smoke or organic compound odor can be confirmed two or more times, it is evaluated as grade "C". The evaluation results are shown in Table 2.

Furthermore, in Table 2, "-" means that no evaluation has been performed.

[Table 2] Sheet No. No.1 No.2 No.3 No.4 No.5 Anti-termite Average quality reduction rate (%) 0.00 0.00 0.00 0.00 0.00 Worker ants mortality rate (%) 29.8 33.8 31.5 37.1 34.2 Flammability Oxygen Index(%) 35 33 32 42 37 cold resistance Cold resistance temperature (℃) -14 -17 -14 -4 -10 Manufacturing suitability Extrusion process at 190℃ A A A B A Sheet No. No.c1 No.c2 No.c3 No.c4 No.c5 No.c6 Anti-termite Average quality reduction rate (%) 0.13 0.03 0.07 0.00 0.00 0.03 Worker ants mortality rate (%) 32.2 37.3 32.8 35.3 32.4 38.4 Flammability Oxygen Index(%) 33 33 34 45 34 - cold resistance Cold resistance temperature (℃) -twenty one -twenty four -20 0 －47 - Manufacturing suitability Extrusion process at 190℃ A A A A C A

From Table 2 above, it can be seen that the examples of the present invention composed of the flame-retardant anti-termite resin composition of the present invention, that is, any one of sheets No. 1 to No. 5, are among the anti-termite, flame-retardant, and cold resistance properties. All of them are excellent, and when extrusion processing is performed at 190°C, No. 1 to No. 5 are also grades A or B, and any of them are excellent in manufacturing suitability. Furthermore, from the results of the average mass reduction rate, it can be seen that the sheet No. 1 to No. 5, which is the example of the present invention, is superior to No. c6, which is the comparative example, which is a conventional anti-termite material. In contrast, like the comparative example No. c2, when only triallyl isocyanurate is contained in the boric acid compound and triallyl isocyanurate, it is compared with the comparative example. The comparison of sheet No. c1 shows that although it shows anti-termite properties, the average mass reduction rate is 0.03%, which is not necessarily sufficient compared to 0.00% of the sheets of No. 1 to No. 5, which are examples of the present invention. In addition, even if triallyl isocyanurate and zinc borate are used in combination, when the content of the compound having an isocyanurate structure and the boron-containing compound does not meet the amount specified in the present invention relative to 100 parts by mass of PVC , At least any one of termite resistance, cold resistance and manufacturing suitability does not meet a satisfactory level. For example, a comparative example in which any of triallyl isocyanurate and zinc borate is less than the prescribed amount of the present invention, namely flake No. c3, and a comparative example in which the content of zinc borate is higher, namely No In .c4, termite resistance and cold resistance cannot coexist, and either of termite resistance and cold resistance is inferior. In addition, in No. c5, which is a comparative example of 15 parts by mass of triallyl isocyanurate, since a large amount of smoke can be confirmed, we think that the manufacturability is poor.

Here, from the comparison of the comparative examples, that is, the sheet Nos. c1, c2, and c4, it can be seen that zinc borate also exhibits an anti-termite effect. In addition, if zinc borate is as much as 60 parts by mass as the comparative example, which is the sheet No. c4, it will be compared with the comparative example, which is No. c1 and c2, and compared with the invention example, which is the sheet No. 4 Comparing 55 parts by mass of the product, it can be seen that the cold resistance will decrease, that is, the cold resistance temperature will increase to 0°C, and there is a concern that it cannot withstand use in cold regions. Furthermore, comparing the sheet No. c1 and No. c2 which is a comparative example, and comparing sheet No. 2 and 3 which is an example of the present invention, it can be seen that triallyl isocyanurate exhibits a cold resistance improvement effect.

[Example 2] (Cable manufacturing and performance evaluation) A cable 10 as shown in Figure 1 is manufactured in the following manner. The cable 10 is sequentially formed with an inner semiconducting layer 2, an insulator layer 3, an outer semiconducting layer 4, a shielding layer 5, and an outer circumference of the conductor 1 Sheath 6.

1) The production of the cable of the example of the present invention uses ^{a circular compressed conductor made of copper with a cross-sectional area of 800 mm 2} as the conductor, and is arranged in order: a thickness of 1 mm made of cross-linked polyethylene with carbon added Internal semi-conductive layer, 11 mm thick insulator layer made of cross-linked polyethylene [Insulation compound NUCV-9253 manufactured by NUC Co., Ltd.], 0.5 mm thick made of cross-linked polyethylene with carbon added External semi-conductive layer. Then, on the outer periphery of the outer semiconducting layer, a shielding layer of aluminum metal, a compound of the same formula as the sheet No. 2 of the present invention prepared in Example 1, was added with a thickness of 5 mm. There is a water-shielding shell structure (sheath), and the cable is made. The sheath obtained here is a sheath 6 of a single layer structure as shown in FIG. 1.

2) Fabrication of the cable of the comparative example When making the above-mentioned cable, the sheath 6 in Figure 1 is replaced with the sheath 106 shown in Figure 2, that is, a two-layered sheath 106 consisting of a flame-retardant sheath 107 and an anti-termite sheath 108. , Manufacturing cable 100. Here, a compound with the same prescription as the comparative example, sheet No. c1, with a thickness of 4 mm was used as the flame-retardant sheath 107, and a polypropylene compound with a thickness of 1.5 mm [CALP manufactured by LION IDEMITSU COMPOSITES Co., Ltd. ] Is used as an anti-termite sheath 108, which is sequentially extruded to form a coating. Except for this, the same procedure as the cable of the example of the present invention was carried out, and the cable of the comparative example was manufactured.

For each cable prepared in the above manner, the following combustion test was performed.

(Evaluation of the flammability of cables) For each cable, a burning test is carried out in accordance with IEEE std. 383-1974. This test is used to determine whether it meets the three types of vinyl sheaths described in JEC3403-2001. The cable made this time was subjected to three burning tests, and the average value of the burning length and residual burning (emerging) time calculated from the burner port to be measured was calculated. The results obtained are shown in Table 3 below. In addition, for any cable whose combustion length is less than 1200 mm from the burner port and the residual combustion time is less than about 1 hour, the three types of ethylene-based sheaths described in JEC3403-2001 are set as shown in the table. The judgment column of 3 is described as "○". Furthermore, in Table 3 below, the estimated relative manufacturing costs are also described.

[table 3] Cable of Example of the Invention Cable of Comparative Example Burning length 1000 mm 800 mm Afterburn time 3 minutes 20 minutes determination ○ ○ Sheath thickness 5.0 mm 5.5 mm (2 layers total) Relative cost 0.87 1

From Table 3 above, it can be confirmed that although the total thickness of the sheath of the cable of the present invention is 5.0 mm, which is 10% thinner than the cable of the comparative example using the conventional laminated two-layer sheath, it is still 10% thinner. All comply with the three types of vinyl sheaths described in JEC3403-2001. This fact means that the single-layer sheath, which has been considered difficult so far, can maintain at least the same level of excellent performance as a cable with two-layer sheaths. Moreover, when the manufacturing cost of the cable of the example of the present invention is compared with that of the comparative example, it can be seen that the cable of the example of the present invention is a single layer, etc., because the total thickness of the sheath is 10% thinner, so the manufacturing cost is relatively estimated. When the manufacturing cost of the cable of the comparative example is 1, it is 0.87, and the manufacturing cost can be reduced by about 13%.

10, 100: cable 1.101: Conductor 2.102: Internal semi-conductive layer 3.103: Insulator layer 4.104: External semi-conductive layer 5.105: shielding layer (metal shielding layer) 6, 106: Sheath 107: Flame Retardant Jacket 108: Anti-ant sheath

Fig. 1 is a schematic cross-sectional view showing an example of the structure of the cable of the present invention. Fig. 2 is a schematic cross-sectional view showing an example of the structure of a conventional cable.

Domestic deposit information (please note in order of deposit institution, date and number) no

Foreign hosting information (please note in the order of hosting country, institution, date, and number) no

10: Cable

1: Conductor

2: Internal semiconducting layer

3: Insulator layer

4: External semi-conductive layer

5: Masking layer (metallic masking layer)

6: Sheath

Claims (7)

A flame-retardant anti-termite resin composition, which contains polyvinyl chloride resin, a compound with an isocyanurate structure, and a boron-containing compound, In addition, the content of the compound having an isocyanurate structure is in the range of 0.05 parts by mass to 10 parts by mass relative to 100 parts by mass of the aforementioned polyvinyl chloride resin, The content of the boron-containing compound is in the range of 10 parts by mass to 55 parts by mass relative to 100 parts by mass of the polyvinyl chloride resin. The flame-retardant anti-termite resin composition according to claim 1, wherein the content of the compound having an isocyanurate structure is in the range of 0.05 parts by mass to 0.6 parts by mass relative to 100 parts by mass of the polyvinyl chloride resin Inside. The flame-retardant anti-termite resin composition according to claim 1 or 2, wherein the content of the boron-containing compound is in the range of 10 parts by mass to 20 parts by mass relative to 100 parts by mass of the polyvinyl chloride resin. The flame-retardant anti-termite resin composition according to any one of claims 1 to 3, which is a raw material for a sheath used to form the outermost layer of a cable. A cable having a structure in which at least an inner semiconducting layer, an insulator layer, an outer semiconducting layer, a shielding layer, and a sheath are sequentially laminated on the outer circumference of a conductor, In addition, the aforementioned sheath is formed using the flame-retardant anti-termite resin composition according to any one of claims 1 to 4 as a raw material. The cable according to claim 5, wherein the sheath is composed of a single layer. A method for manufacturing a cable. The cable has a structure at least sequentially laminated with an inner semiconducting layer, an insulator layer, an outer semiconducting layer, a shielding layer, and a sheath on the outer circumference of a conductor, In addition, in this manufacturing method, the flame-retardant anti-termite resin composition according to any one of claims 1 to 4 is extruded to form a sheath on the outer periphery of the shielding layer.

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