JP2013026171A - Composite for power transmission cable support - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite for a power transmission cable support, capable of being repaired by using a thermoplastic resin as a matrix resin.SOLUTION: In the composite for a power transmission cable support, a component (B) of a thermoplastic resin is impregnated in a component (A) of a continuous reinforced fiber so that 10-90 mass% of the component (A) of a continuous reinforced fiber and 90-10 mass% of the component (B) of a thermoplastic resin are contained when the total of the component (A) and the component (B) is taken as 100 mass%.

Description

  The present invention relates to a composite for supporting a power transmission cable. More specifically, the present invention relates to a composite for supporting a power transmission cable that can be repaired by using a thermoplastic resin as a matrix resin.

  Composites composed of reinforcing fibers and matrix resins are widely used for sports equipment applications, aerospace applications, and general industrial applications because they are lightweight and have excellent mechanical properties. Reinforcing fibers used in these composites reinforce molded products in various forms depending on the intended use. These reinforcing fibers include metal fibers such as aluminum fibers and stainless fibers, organic fibers such as aramid fibers and PBO fibers, inorganic fibers such as silicon carbide fibers, and carbon fibers. Carbon fibers are preferred from the viewpoint of the balance between rigidity and lightness, and among them, polyacrylonitrile-based carbon fibers are suitably used. The matrix resin includes a thermosetting resin and a thermoplastic resin. Epoxy resin, vinyl ester resin, etc. are used as the thermosetting resin, and polypropylene resin, polyamide resin, polyester resin, polyphenylene sulfide resin, etc. are used as the thermoplastic resin. Because of its excellent flame retardancy, polyphenylene sulfide resin (hereinafter sometimes abbreviated as PPS resin) has attracted attention as an electrical / electronic device member and an automotive device member.

  On the other hand, in order to improve the conductive efficiency, the power transmission cable has an increased conductor area such as aluminum. However, the increase in the conductor area, that is, the weight of the conductor increases the weight of the power transmission cable itself, and the power transmission cable between the towers. It contributes to the sagging of the water. Moreover, since the space between steel towers cannot be widened due to the slack of the power transmission cable, it also contributes to an increase in the cost for power transmission. Therefore, it is important to improve the load performance of the power transmission cable, and a member for supporting the power transmission cable has attracted attention.

  Patent Document 1 proposes to use a carbon fiber reinforced composite using an epoxy resin as a matrix resin for a cable core. Epoxy resins have an advantage that they can withstand the operating temperature when used as cable cores because of their high heat resistance.

  However, in general, epoxy resin has poor toughness and impact properties, and once it has been broken, such as cracks, it is difficult to repair, so there is a concern that physical properties may deteriorate when used for a long time. .

Japanese Patent No. 4589629

  An object of this invention is to provide the cable support composite which can be repaired by using a thermoplastic resin for a matrix resin in view of the background of a prior art.

As a result of intensive studies to achieve the above object, the present inventors have found the following composite for supporting a power transmission cable that can achieve the above-mentioned problems.
(1) Component (A) and component (B) as a total of 100% by mass, component (A) continuous reinforcing fiber 10 to 90% by mass and component (B) thermoplastic resin 90 to 10% by mass (A) A composite for supporting a power transmission cable in which a continuous reinforcing fiber is impregnated with a component (B) thermoplastic resin.

  The composite for supporting a power transmission cable according to the present invention can be repaired by using a thermoplastic resin as a matrix resin, can reduce the slack of the power transmission cable, and is extremely useful for long-term use of the power transmission cable. .

It is a figure which shows an example of the manufacturing apparatus used for manufacture of the composite for power transmission cable support which concerns on this invention. It is a figure which shows an example of the shape of the exit side of the drawing die used for manufacture of the composite for power transmission cable support which concerns on this invention. It is a figure which shows an example of the reinforced cable which integrated the composite for power transmission cable support which concerns on this invention with the conductor. It is a figure which shows an example of the cross section of the axial direction of the composite for power transmission cable support which concerns on this invention. It is a figure which shows an example of the cross section of the axial direction of the composite for power transmission cable support which concerns on this invention.

  The present invention relates to component (A) continuous reinforcing fiber (hereinafter, component (A) continuous reinforcing fiber may be referred to as component (A)), component (B) thermoplastic resin (hereinafter, component (B) thermoplastic resin. Is a composite for supporting a power transmission cable using the component (B). First, these components will be described.

  Although it does not specifically limit as a component (A) continuous reinforcement fiber used for this invention, For example, high intensity | strength and high elasticity, such as carbon fiber, glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber, etc. Rate fibers can be used, and these may be used alone or in combination of two or more. Among these, PAN-based, pitch-based, rayon-based carbon fibers and the like can be mentioned. From the viewpoint of the balance between the strength and elastic modulus of the obtained molded product, PAN-based carbon fibers are more preferable. For the purpose of imparting electrical conductivity, continuous reinforcing fibers coated with a metal such as nickel, copper, ytterbium, etc. can also be used.

  The term “continuous” as used herein means that the reinforcing fiber has substantially the same length as that of the composite for power transmission cable support in the composite for power transmission cable support. Since it becomes easy to express the intensity | strength of a reinforced fiber by making it continuous, it is preferable. In this case, the reinforcing fibers are preferably arranged in the axial direction of the composite for power transmission cable.

  Further, as the carbon fiber, the surface oxygen concentration ratio [O / C] which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy is 0.05-0. 0.5 is preferable, more preferably 0.08 to 0.4, and still more preferably 0.1 to 0.3. When the surface oxygen concentration ratio is 0.05 or more, the functional group amount on the surface of the carbon fiber can be secured, and a stronger adhesion to the thermoplastic resin can be obtained. Moreover, although there is no restriction | limiting in particular in the upper limit of surface oxygen concentration ratio, Generally it is preferable to set it as 0.5 or less from the balance of the handleability of carbon fiber, and productivity.

The surface oxygen concentration ratio of the carbon fiber is determined by X-ray photoelectron spectroscopy according to the following procedure. First, after cutting the carbon fiber bundle from which the sizing agent and the like adhering to the carbon fiber surface with a solvent was cut to 20 mm and spreading and arranging on a copper sample support base, using A1Kα1,2 as the X-ray source, The sample chamber is maintained at 1 × 10 ⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s is adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. Is obtained by drawing a straight base line in the range of 1191 to 1205 eV. O _1s peak area E. Is obtained by drawing a straight base line in the range of 947 to 959 eV.

Here, the surface oxygen concentration ratio is calculated as an atomic number ratio from the ratio of the O _1s peak area to the C _1s peak area using a sensitivity correction value unique to the apparatus. As an X-ray photoelectron spectroscopy apparatus, model ES-200 manufactured by Kokusai Electric Inc. is used, and the sensitivity correction value is set to 1.74.

  The means for controlling the surface oxygen concentration ratio [O / C] to 0.05 to 0.5 is not particularly limited. For example, techniques such as electrolytic oxidation, chemical oxidation, and vapor phase oxidation are used. Among these, electrolytic oxidation treatment is preferable.

  The average fiber diameter of the carbon fibers is not particularly limited, but is preferably in the range of 1 to 20 μm and preferably in the range of 3 to 15 μm from the viewpoint of the mechanical properties and surface appearance of the obtained molded product. More preferred. There is no restriction | limiting in particular in the number of single yarns at the time of setting it as a carbon fiber bundle, It can use within the range of 100-350,000, It can be used especially within the range of 1,000-250,000. preferable. Further, from the viewpoint of productivity of carbon fibers, those having a large number of single yarns are preferable, and it is preferable to use them within a range of 20,000 to 100,000.

  Also, by applying a sizing agent to the carbon fiber, it is possible to improve the adhesive properties and the overall properties of the power cable supporting composite by adapting to the surface properties such as functional groups on the carbon fiber surface. In addition, it improves bundling, bending resistance, and abrasion resistance, and suppresses the occurrence of fluff and yarn breakage in the high-order processing step. It can also improve the high-order workability as a so-called paste and bundling agent. it can.

  The sizing agent adhesion amount is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, based on the mass of the carbon fiber alone, 0.1% More preferably, it is applied in an amount of from 2% by weight to 2% by weight. If it is 0.01% by mass or less, the effect of improving adhesiveness is hardly exhibited, and if it is 10% by mass or more, the physical properties of the matrix resin may be lowered.

  Examples of the sizing agent include a bisphenol type epoxy compound, a linear low molecular weight epoxy compound, polyethylene glycol, polyurethane, polyester, an emulsifier, or a surfactant. Moreover, these may use together 1 type, or 2 or more types.

  The means for applying the sizing agent is not particularly limited. For example, there are a method of immersing in a sizing liquid through a roller, a method of contacting a roller to which the sizing liquid is adhered, and a method of spraying the sizing liquid in a mist form. . Moreover, although either a batch type or a continuous type may be sufficient, the continuous type which has good productivity and small variations is preferable. At this time, it is preferable to control the sizing solution concentration, temperature, yarn tension, and the like so that the amount of the sizing agent active ingredient attached to the carbon fiber is uniformly attached within an appropriate range. Moreover, it is more preferable to vibrate the carbon fiber with ultrasonic waves when applying the sizing agent.

  The drying temperature and drying time should be adjusted according to the amount of the compound attached, but the time required for complete removal of the solvent used to apply the sizing agent and drying is shortened, while the thermal deterioration of the sizing agent is prevented and sizing is performed. From the viewpoint of preventing the carbon fiber bundle formed of the treated carbon fibers from becoming hard and deteriorating the spreadability of the bundle, the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower, preferably 180 ° C. More preferably, it is 250 degrees C or less.

  Examples of the solvent used for the sizing agent include water, methanol, ethanol, dimethylformamide, dimethylallylacetamide, and acetone. Water is preferable from the viewpoint of easy handling and disaster prevention. Accordingly, when a compound insoluble or hardly soluble in water is used as a sizing agent, it is preferable to add an emulsifier and a surfactant and disperse in water. Specifically, as an emulsifier and a surfactant, styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, formalin condensate of naphthalene sulfonate, anionic emulsifier such as sodium polyacrylate, Nonionic emulsifiers such as cationic emulsifiers such as polyethyleneimine and polyvinylimidazoline, nonylphenol ethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, sorbitan ester ethyl oxide adducts, etc. can be used. A nonionic emulsifier having a small size is preferable because it hardly inhibits the adhesive effect of the polyfunctional compound.

  Here, the composite for supporting a power transmission cable of the present invention is composed of 10 to 90% by mass of component (A). If it is less than 10% by mass, the mechanical properties of the resulting composite for cable support for power transmission may be insufficient. If it exceeds 90% by mass, impregnation of component (B) may occur during molding of the composite for cable support for power transmission. It may be difficult for voids to remain and physical properties to deteriorate. Preferably it is 20-80 mass%, More preferably, it is 30-70 mass%.

  The component (B) used in the present invention is preferably a thermoplastic resin because the composite for supporting a power transmission cable can be repaired. The thermoplastic resin here refers to a resin that can be remelted by heating and molded again. The thermoplastic resin is not particularly limited. Among them, polypropylene resin, polyamide resin, polyester resin, polycarbonate resin, polyphenylene sulfide resin, polyether ketone resin, polyether ether ketone resin, polyether ketone ketone resin, polyether sulfide resin, etc. Are preferably used. From the viewpoint of heat resistance and long-term durability, polyphenylene sulfide resin, polyether ether ketone resin, polyether ketone resin, polyether ether ketone resin, and polyether sulfide resin are more preferable.

  Although the preferable molecular weight of a component (B) is not specifically limited, The weight average molecular weight is 10,000 or more, Preferably it is 15,000 or more, More preferably, it is 17,000 or more. If the weight average molecular weight is less than 10,000, high impact characteristics and durability characteristics may not be obtained. When the weight average molecular weight is 10,000 or more, properties such as toughness and durability of the component (B) are enhanced. Although there is no restriction | limiting in particular in the upper limit of a weight average molecular weight, Less than 1,000,000 can be illustrated as a preferable range, More preferably, it is less than 500,000, More preferably, it is less than 200,000, Within this range, it is high durability. Can be obtained.

  The weight average molecular weight can be calculated in terms of polystyrene, for example, by gel permeation chromatography, which is a type of size exclusion chromatography.

  Moreover, since the composite for supporting a power transmission cable of the present invention is often used outdoors, it is preferable that the physical property value is not easily influenced by the temperature, and the glass transition temperature of the component (B) is preferably 50 to 250 ° C. . More preferably, it is 70-240 degreeC, More preferably, it is 90-230 degreeC. If the glass transition temperature is less than 50 ° C, the desired mechanical properties may not be obtained due to the outside air temperature. If the glass transition temperature exceeds 250 ° C, the resin becomes brittle and the power cable support composite is easily damaged. May be.

  Moreover, since the composite for supporting a power transmission cable of the present invention is used adjacent to a power transmission cable, it is preferable that the deterioration due to electricity is small. Specifically, the dielectric strength of the component (B) is 15 kV / mm or more. And preferred. More preferably, the dielectric strength is 17 kV / mm or more, and more preferably 20 kV / mm or more. When the dielectric strength is less than 15 kV / mm, a power transmission cable supporting composite may be energized due to a short circuit during power transmission, and may be damaged at the current-carrying portion. Although there is no restriction | limiting in particular in the upper limit of a dielectric strength, Less than 100 kV / mm can be illustrated.

  Furthermore, the alkali metal content contained in the component (B) is preferably 50 ppm or less. More preferably, it is 30 ppm or less, More preferably, it is 10 ppm or less. If the alkali metal content exceeds 50 ppm, electrical characteristics such as dielectric strength may be reduced. When the alkali metal content is 50 ppm or less, good electrical characteristics can be obtained.

  Furthermore, when a spark such as a short circuit or spark occurs during power transmission, it is preferably flame retardant, and is preferably V-0 in the UL-94 vertical test for component (B). When V-1 and V-2, the flame is difficult to disappear when ignited, and the shape of the power transmission cable support composite may not be maintained.

  Also, since thermoplastic resins generally have high viscosity and are difficult to impregnate, the component (A) is impregnated with a polymer precursor (B ′) such as a monomer or oligomer, then polymerized and converted to the component (B). By doing so, a composite for supporting a power transmission cable may be manufactured.

  Examples of the polymer precursor (B ′) used in the present invention include compounds represented by the following structural formula (1).

  The compound of the structural formula (1) has a repeating unit of-(Ar-X)-as a main structural unit, and preferably contains 80 mol% or more of the repeating unit. Component (B ′) contains at least 50% by weight of such a compound, preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more. Ar includes units represented by the following structural formulas (2) to (10), among which the following formula (2) is preferable. Examples of X include esters, carbonates, amides, ethers, ketones, sulfides, and sulfones, which can be selected according to the characteristics of the resulting composite cured product. For example, esters, carbonates and amides have excellent impact resistance, ethers and ketones have excellent durability and water resistance, and sulfides and sulfones tend to have excellent mechanical properties and flame retardancy.

(R1, R2, R3, and R4 are substituents selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, and a halogen group. , R1, R2, R3, and R4 may be the same or different, and R5 is an alkyl chain having 1 to 12 carbon atoms, A is selected from ester, carbonate, amide, ether, ketone, sulfide, and sulfone. 1 type.

  In the structural formula (1), different — (Ar—X) — repeating units may be included randomly or in blocks, or they may be mixed. Moreover, the repeating units such as the structural formulas (2) to (10) may be included randomly, may be included in blocks, or may be mixed.

  Representative compounds of the structural formula (1) include cyclic polyphenylene sulfide, cyclic polyphenylene sulfide sulfone, cyclic polyphenylene sulfide ketone, cyclic polyphenylene ether ketone, cyclic polyphenylene ether ether ketone, cyclic polyphenylene ether sulfone, cyclic aromatic polycarbonate, Examples include cyclic polyethylene terephthalate, cyclic polybutylene terephthalate, cyclic random copolymers and cyclic block copolymers containing these. Particularly preferred compounds of the structural formula (1) include cyclic compounds containing 80 mol% or more, particularly 90 mol% or more of the p-phenylene sulfide unit of the following structural formula (11) as the main structural unit.

  Although there is no restriction | limiting in particular in the repeating number m in the said Structural formula (1), 2-50 are preferable, 2-25 are more preferable, and 2-15 can be illustrated as a still more preferable range. As will be described later, the conversion of the component (B ′) to the component (B) by heating is preferably performed at a temperature equal to or higher than the temperature at which the component (B ′) melts, but when m increases, the melt solution of the component (B ′) increases. Since the temperature tends to increase, it is advantageous to set m in the above range from the viewpoint that the conversion of the component (B ′) to the component (B) can be performed at a lower temperature.

  In addition, the component (B ′) may include a single compound having a single repeating number or a mixture of cyclic compounds having different repeating numbers as the compound of the structural formula (1), but different repeating numbers. The mixture of cyclic compounds having a tendency to have a lower melt solution temperature than a single compound having a single number of repetitions, and the use of a mixture of cyclic compounds having different numbers of repetitions is converted to component (B) Since the temperature at the time of performing can be made lower, it is preferable.

  In addition to the compound of the structural formula (1), the component (B ′) may contain an oligomer having a repeating unit of — (Ar—X) — as a main structural unit. A linear homo-oligomer or co-oligomer containing 80 mol% or more of the repeating unit is preferable. Ar includes units represented by the structural formulas (2) to (10) described above. As long as the repeating unit of-(Ar-X)-is used as a main structural unit, it can contain a small amount of branching units or crosslinking units represented by the following structural formula (12).

  The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-X)-units. Further, the oligomer may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.

  Typical examples of these include polyphenylene sulfide oligomer, polyphenylene sulfide sulfone oligomer, polyphenylene sulfide ketone oligomer, polyphenylene ether ketone oligomer, polyphenylene ether ether ketone oligomer, polyphenylene ether sulfone oligomer, aromatic polycarbonate oligomer, polyethylene terephthalate oligomer, polybutylene terephthalate. Examples include oligomers, random copolymers thereof, block copolymers, and mixtures thereof. Particularly preferred oligomers include polyphenylene sulfide oligomers containing 80 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units as the main structural unit of the polymer.

  The molecular weight of the oligomer is preferably less than 10,000 in terms of weight average molecular weight. More preferably, it is less than 8,000, and more preferably less than 5,000. On the other hand, the lower limit is preferably 300 or more, preferably 400 or more, and more preferably 500 or more in terms of weight average molecular weight.

  When the component (B ′) contains the oligomer, the amount of the oligomer is particularly preferably smaller than that of the compound of the structural formula (1). That is, the weight ratio of the compound of the structural formula (1) to the oligomer (the structural formula (1) / the oligomer) in the component (B ′) preferably exceeds 1, more preferably 2.3 or more. The above is more preferable, and 9 or more is even more preferable. By using such a component (B ′), it is possible to easily obtain a component (B) having a weight average molecular weight of 10,000 or more.

  The component (B) obtained by using the component (B ′) is a homopolymer containing a repeating unit of — (Ar—X) — as a main constituent unit, preferably containing 80 mol% or more of the repeating unit. A copolymer. Ar includes units represented by the above structural formulas (2) to (10), among which the structural formula (2) is particularly preferable. Examples of X include esters, carbonates, amides, ethers, ketones, sulfides, and sulfones, which can be selected according to the characteristics of the resulting composite cured product. For example, esters, carbonates and amides have excellent impact resistance, ethers and ketones have excellent durability and water resistance, and sulfides and sulfones tend to have excellent mechanical properties and flame retardancy.

  As long as this repeating unit is a main structural unit, it can contain a small amount of branching units or crosslinking units represented by the structural formula (12). The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-X)-units.

  In addition, the component (B) in the present invention may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.

  Typical examples of these include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene ether ketone, polyphenylene ether ether ketone, polyphenylene ether sulfone, aromatic polycarbonate, polyethylene terephthalate, polybutylene terephthalate, random copolymers of these, and blocks Examples thereof include copolymers and mixtures thereof. Particularly preferably, as the main structural unit of the polymer, polyphenylene sulfide containing 80 mol% or more, particularly 90 mol% or more of the p-phenylene sulfide unit of the structural formula (11) may be mentioned.

  In the case of converting the component (B ′) to the component (B), the conversion rate is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.

  In addition, the component (B ′) is polymerized by heating to obtain the component (B). However, the reaction may be promoted by using a compound having a radical generating ability as a polymerization catalyst. As such a polymerization catalyst, a zero-valent transition metal compound or the like is preferable, and the component (B) can be easily obtained by heating the component (B ′) in the presence of a zero-valent transition metal compound.

  As the zero-valent transition metal, metals of Group 8 to Group 11 and Period 4 to Period 6 of the periodic table are preferably used. For example, nickel, palladium, platinum, iron, ruthenium, rhodium, copper, silver, and gold can be exemplified as the metal species. Various complexes are suitable as the zero-valent transition metal compound. For example, triphenylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, 1,2-bis (diphenylphosphino) ethane, 1 , 1'-bis (diphenylphosphino) ferrocene, dibenzylideneacetone, dimethoxydibenzylideneacetone, cyclooctadiene, and carbonyl complexes. Specifically, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (tri-t-butylphosphine) palladium, bis [1,2-bis (diphenylphosphine) Fino) ethane] palladium, bis (tricyclohexylphosphine) palladium, [P, P′-1,3-bis (di-i-propylphosphino) propane] [P-1,3-bis (di-i-propyl) Phosphino) propane] palladium, 1,3-bis (2,6-di-i-propylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, 1,3-bis (2,4 , 6-Trimethylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, bi (3,5,3 ′, 5′-dimethoxydibenzylideneacetone) palladium, bis (tri-t-butylphosphine) platinum, tetrakis (triphenylphosphine) platinum, tetrakis (trifluorophosphine) platinum, ethylenebis (tri Phenylphosphine) platinum, platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, Examples thereof include bis (1,5-cyclooctadiene) nickel, dodecacarbonyl triiron, pentacarbonyl iron, dodecacarbonyl tetrarhodium, hexadecacarbonyl hexarhodium, dodecacarbonyl triruthenium and the like. These polymerization catalysts may be used alone or in combination of two or more.

  These polymerization catalysts may be added with a zero-valent transition metal compound as described above, or may form a zero-valent transition metal compound in the system. Here, in order to form a zero-valent transition metal compound in the system as in the latter case, a transition metal compound such as a transition metal salt and a ligand compound are added to form a transition metal complex in the system. And a method of adding a complex formed of a transition metal compound such as a transition metal salt and a compound serving as a ligand. Since transition metal salts other than zero valence do not promote the conversion of component (A), it is necessary to add a compound serving as a ligand. Examples of transition metal compounds and ligands used in the present invention and complexes formed of transition metal compounds and ligands are given below. Examples of the transition metal compound for forming a zero-valent transition metal compound in the system include acetates and halides of various transition metals. Examples of the transition metal species include nickel, palladium, platinum, iron, ruthenium, rhodium, copper, silver, gold acetate, halide and the like. Specifically, nickel acetate, nickel chloride, nickel bromide. , Nickel iodide, nickel sulfide, palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium sulfide, platinum chloride, platinum bromide, iron acetate, iron chloride, iron bromide, iron iodide, ruthenium acetate, chloride Examples include ruthenium, ruthenium bromide, rhodium acetate, rhodium chloride, rhodium bromide, copper acetate, copper chloride, copper bromide, silver acetate, silver chloride, silver bromide, gold acetate, gold chloride, and gold bromide. Moreover, as a ligand added simultaneously in order to form a zerovalent transition metal compound in a system, if a component (A) and a transition metal compound are heated and a zerovalent transition metal is produced | generated, Although there is no particular limitation, basic compounds are preferable, for example, triphenylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,1′-bis (diphenylphosphino). ) Ferrocene, dibenzylideneacetone, sodium carbonate, ethylenediamine and the like. Moreover, as a complex formed with the compound used as a transition metal compound and a ligand, the complex which consists of the above various transition metal salts and a ligand is mentioned. Specifically, bis (triphenylphosphine) palladium diacetate, bis (triphenylphosphine) palladium dichloride, [1,2-bis (diphenylphosphino) ethane] palladium dichloride, [1,1′-bis (diphenylphosphine) Fino) ferrocene] palladium dichloride, dichloro (1,5′-cyclooctadiene) palladium, bis (ethylenediamine) palladium dichloride, bis (triphenylphosphine) nickel dichloride, [1,2-bis (diphenylphosphino) ethane] nickel Examples include dichloride, [1,1′-bis (diphenylphosphino) ferrocene] nickel dichloride, dichloro (1,5′-cyclooctadiene) platinum and the like. These polymerization catalysts and ligands may be used alone or in combination of two or more.

  The valence state of the transition metal compound can be grasped by X-ray absorption fine structure (XAFS) analysis. The peak of the absorption coefficient when the transition metal compound used as a catalyst or the mixture of the transition metal compound and the component (B ′) or the mixture of the transition metal compound and the component (B) is irradiated with X-rays and the absorption spectrum is normalized. This can be grasped by comparing the maximum values.

  For example, when evaluating the valence of a palladium compound, it is effective to compare the absorption spectrum of the L3 end X-ray absorption near edge structure (XANES), and the X-ray energy is 3173 eV as a reference, 3163 to 3168 eV. This can be determined by comparing the peak maximum value of the absorption coefficient when the average absorption coefficient in the range of 0 and 3191 to 3200 eV is normalized to 1. In the example of palladium, the peak value of the absorption coefficient when normalized with the zero-valent palladium compound tends to be small compared to the divalent palladium compound, and further promotes the conversion of the cyclic polyarylene sulfide. A transition metal compound having a larger effect tends to have a smaller peak maximum value. The reason for this is presumed that the absorption spectrum for XANES corresponds to the transition of core electrons to empty orbitals, and the absorption peak intensity is affected by the electron density of d orbitals.

  In order for the palladium compound to promote the conversion of the component (B ′) to the component (B), the peak maximum value of the absorption coefficient when normalized is preferably 6 or less, more preferably 4 or less, Preferably it is 3 or less, and conversion of a component (B ') can be accelerated | stimulated within this range.

  Specifically, the peak maximum value is 6.32 for divalent palladium chloride that does not promote the conversion of component (B ′), and zero-valent tris (dibenzylideneacetone) divalent that promotes the conversion of component (B ′). For palladium and tetrakis (triphenylphosphine) palladium and bis [1,2-bis (diphenylphosphino) ethane] palladium it is 3.43 and 2.99 and 2.07, respectively.

  The concentration of the polymerization catalyst used varies depending on the molecular weight of the target polymer (B ′) and the type of the polymerization catalyst, but is usually 0.001 to 20 mol% with respect to X in the component (B ′), preferably Is 0.005 to 15 mol%, more preferably 0.01 to 10 mol%. If it is 0.001 mol% or more, the component (B ′) is sufficiently converted to the component (B), and if it is 20 mol% or less, the component (B) having the above-mentioned characteristics can be obtained.

  The polymerization catalyst may be added as it is, but it is preferable to add the polymerization catalyst to the component (B ′) and then disperse it uniformly. Examples of the uniform dispersion method include a mechanical dispersion method and a dispersion method using a solvent. Specific examples of the mechanical dispersion method include a pulverizer, a stirrer, a mixer, a shaker, and a method using a mortar. Specific examples of the method of dispersing using a solvent include a method of dissolving or dispersing the component (B ′) in an appropriate solvent, adding a predetermined amount of a polymerization catalyst thereto, and then removing the solvent. In addition, when the polymerization catalyst is dispersed, when the polymerization catalyst is a solid, it is preferable that the average particle size of the polymerization catalyst is 1 mm or less because more uniform dispersion is possible.

  Here, the power transmission cable supporting composite of the present invention is composed of 90 to 10% by mass of component (B). If it exceeds 90% by mass, the resulting molded article may have insufficient mechanical properties, and if it is less than 10% by mass, it may be difficult to impregnate during production of a power cable supporting composite, and voids may remain. Preferably it is 80-20 mass%, More preferably, it is 70-30 mass%.

  Next, the manufacturing method of the power transmission cable supporting composite of the present invention will be described. Although it does not specifically limit about a manufacturing method, Manufacturing by pultrusion molding is mentioned, and pultrusion molding draws a component (A) continuously, supplies a component (B), and is made with the component (B) fuse | melted. By passing component (A) through a filled mold, component (A) is impregnated with component (B), and then continuously drawn out from the mold and wound up, so that a composite for supporting a power transmission cable is obtained. Can be manufactured.

  In the step of supplying the component (B) to the mold and impregnating the component (A) with the component (B) by passing the component (A) through the mold filled with the molten component (B), As a method for supplying the component (B), a known device such as an extruder, a plunger, or a melting bath can be used, but a device having a function of transferring the molten component (B) such as a screw or a gear pump. Is preferred.

  For example, by melting the component (B) using an extruder and supplying it into the mold, and passing the component (A) while squeezing it in the mold filled with the melted component (B). The method of impregnation can be illustrated.

  In addition, the mold temperature for impregnating the component (A) with the component (B) is only required to melt the component (B), but is preferably 100 to 350 ° C. More preferably, it includes a step of heating to 150 to 300 ° C, more preferably 170 to 280 ° C. Above 350 ° C., component (B) decomposes and volatilizes, so voids may remain inside the pultruded product. Moreover, since it polymerizes and becomes high molecular weight, impregnation becomes difficult and impregnation may become inadequate. Below 100 ° C., component (B) does not melt, or even when melted, the viscosity is high and impregnation may be insufficient. By impregnating at 100 to 350 ° C., a pultruded product free from voids can be obtained.

  Moreover, it is more preferable to open the component (A) in advance in the previous stage. Opening is an operation of separating the converged component (A), and an effect of further enhancing the impregnation property of the component (B) can be expected. With the opening, the thickness of the component (A) is reduced, the width of the component (A) before opening is b1 (mm), the thickness is a1 (μm), and the width of the component (A) after opening is b2 ( mm) and a thickness of a2 (μm), the spread ratio = (b2 / a2) / (b1 / a1) is preferably 2.0 or more, and more preferably 2.5 or more.

  The method for opening component (A) is not particularly limited. For example, a method in which concavo-convex rolls are alternately passed, a method in which drum rolls are used, a method in which tension variation is applied to axial vibration, and a reciprocating motion in the vertical direction 2 A method of changing the tension of the component (A) by the individual friction bodies and a method of blowing air to the component (A) can be used.

  In addition, it is important to supply the component (A) continuously to the production line for the purpose of producing with good economic efficiency and productivity. The term “continuous” means that the raw material component (A) is supplied without being completely cut, and the supply speed may be constant or supply and stop may be repeated intermittently.

  Also included is the purpose of extracting the component (A) and arranging it in a predetermined arrangement. That is, the continuous component (A) to be supplied may be in the form of a yarn, in the form of a sheet aligned in one direction, or in the form of a preform that has been pre-shaped. Specifically, the component (A) is creeled, the fiber bundle is drawn out, passed through a roller and supplied to the production line, and similarly, a plurality of fiber bundles are arranged in a row and leveled into a sheet, Examples thereof include a method of supplying a production line through a roll bar, and a method of supplying a production line by passing a plurality of roll bars arranged to have a predetermined shape. Furthermore, when the component (A) is processed into a base material, it may be directly supplied to the production line from a folded state or the like. In addition, if a drive device is provided in various rollers and a roll bar, adjustment of a supply speed etc. can be performed and it is more preferable on production.

  Furthermore, you may include the process heated to 50-500 degreeC in the step before supplying a component (A) to a metal mold | die. By heating component (A), the impregnation property of component (B) into component (A) can be improved in step (I). Moreover, the sizing agent etc. which have adhered to the component (A) can also be removed. The heating method is not particularly limited, and examples thereof include known methods such as non-contact heating using hot air or an infrared heater, contact heating using a pipe heater or electromagnetic induction, and the like.

  Further, different components (A) can be arranged at arbitrary positions in the cross-section of the pultruded product. For example, glass fibers are arranged in the outermost layer of the composite cross section for supporting a power transmission cable, and carbon fibers are arranged in the central layer. It can also be arranged. When supplying to the pultrusion mold, the reinforcing fibers may be guided in the order of arrangement in the yarn path guide. Moreover, even if it guides so that arrangement | positioning of a reinforced fiber may not change in a metal mold | die, it can be set as the cross section which arrange | positioned the reinforced fiber arbitrarily.

  Further, in the above step, when the component (B ′) is impregnated instead of the component (B), the component (B ′) impregnated in the component (A) is subsequently polymerized by heating. , Converted to component (B). It is important that the component (B ′) is subjected to ring-opening polymerization to be the component (B) by the heating. The mold temperature at this time is 200-450 degreeC, Preferably it is 230-420 degreeC, More preferably, it is 250 degreeC-400 degreeC, More preferably, it is 280-380 degreeC. When the temperature is less than 200 ° C., ring-opening polymerization does not proceed sufficiently, and a low molecular weight component (B ′) is excessively contained, resulting in a pultruded product having inferior mechanical strength. Moreover, when it exceeds 450 degreeC, unfavorable side reactions, such as a component (B ') and a component (B) causing a decomposition reaction, may arise.

  Here, it is important that the step of converting into the component (B) is performed with the same pultrusion mold. By performing two steps with one pultrusion mold, not only is it excellent in productivity and economy, but it can be heated and melted only once, so coloring, crosslinking reaction, and decomposition reaction due to oxidation can be suppressed. Therefore, it is preferable.

  In addition, the shorter the reaction time until ring-opening polymerization is completed, the better the productivity and economy, such as shortening the process length or increasing the take-up speed. The reaction time is preferably 30 minutes or less, more preferably 10 minutes or less, and even more preferably 3 minutes or less. There is no restriction | limiting in particular about the minimum of reaction time, 0.5 minutes or more can be illustrated.

  Moreover, in the said process, it is preferable to heat in non-oxidizing atmosphere from a viewpoint of suppressing generation | occurrence | production of an unfavorable side reaction, such as a crosslinking reaction and a decomposition reaction. Here, the non-oxidizing atmosphere is an atmosphere having an oxygen concentration of 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, an inert gas atmosphere such as nitrogen, helium or argon. Of these, a nitrogen atmosphere is particularly preferred from the standpoints of economy and ease of handling.

  Similarly, it is preferable to heat under a reduced pressure of 0.1 to 50 kPa. Here, it is more preferable that the atmosphere in the reaction system is once changed to a non-oxidizing atmosphere and then adjusted to a reduced pressure condition. Here, “under reduced pressure” means that the inside of the reaction system is lower than atmospheric pressure, more preferably 0.1 to 20 kPa, and further preferably 0.1 to 10 kPa.

  Specifically, the component (A) is drawn into the pultrusion mold while nitrogen is blown into the system substituted with nitrogen, and the pressure is reduced using a vacuum pump from the vent portion installed in the pultrusion mold. A method of molding can be exemplified.

  Furthermore, as a subsequent step, a step of shaping the component (A) impregnated with the component (B) into a specific cross-sectional shape can be mentioned. The cross-sectional shape is not particularly limited, but any cross-section such as a circular cross-section, a Δ cross-section, a Y-shaped cross-section, a □ cross-section, a cross-section, a hollow cross-section, a C-shaped cross-section, a rice-shaped cross-section, or a star-shaped cross-section Can be adopted. In particular, a circular cross section or a square cross section is preferable for maintaining strength during winding. As a method for shaping, the exit portion of the pultrusion mold may be formed into the shape, and more preferably, the shape is tapered so that the space in the mold is expanded toward the exit direction of the pultrusion mold. It is preferable to form by forming. The taper angle is preferably as small as possible, preferably 60 degrees or less, more preferably 45 degrees or less, and even more preferably 30 degrees or less. When it is larger than 60 degrees, the component (A) is easily rubbed and fluff may be generated.

  Moreover, what is necessary is just to set the thickness of the composite for cable support for power transmission obtained to arbitrary thickness, Preferably, it is 0.4-50 mm, More preferably, it is 1-25 mm, More preferably, it is 2 ~ 15 mm. If it is 0.4 mm or less, the strength may be insufficient when used alone, and if it exceeds 50 mm, voids may remain inside the power transmission cable support composite.

  Furthermore, in the subsequent step, a step of cooling the obtained pultruded product can be mentioned. The cooling method is not particularly limited, but a method of contacting a roller equipped with a cooling device, a method of cooling by jetting air, a method of spraying cooling water, a method of passing through a cooling bath, A known method such as a method of passing over a plate can be used. Among them, a method of contacting a roller equipped with a cooling device and a method of passing a cooling bath are preferable, and a method of cooling a power transmission cable supporting composite by a roller equipped with a cooling device is particularly preferable. Then, since it can pressurize at the time of cooling, since the cross-sectional shape of the composite for power transmission cable support can be manufactured stably, it is preferable.

  Specific examples of the drawing method include a drawing method using a nip roller or a belt conveyor, a winding method using a drum winder, and a method of holding the substrate with a fixing jig and drawing the jig together. Moreover, when pulling out, it may be processed into a predetermined length with a guillotine cutter or the like, or it may be a continuous composite for supporting a power transmission cable.

  Further, the longer the continuous molding time is, the better the productivity and the economical efficiency are. As continuous molding time, it is 30 minutes or more, Preferably, it is 1 hour or more, More preferably, it is 3 hours or more, More preferably, it is 6 hours or more.

  In addition, another process can be combined within the range which does not impair an effect. For example, an electron beam irradiation process, a plasma treatment process, a strong magnetic field application process, a skin material laminating process, a protective film attaching process, an after-cure process, and the like can be given. For example, it is also possible to further cover the obtained power transmission cable supporting composite with a thermoplastic resin using an electric wire coating apparatus and dispose an insulating layer.

  The wire coating device is a device that covers the periphery of the power transmission cable support composite with a thermoplastic resin by discharging the thermoplastic resin melted by the extruder from the base and passing the power transmission cable support composite through the base portion. is there. Although it does not specifically limit as a thermoplastic resin to be used, Polypropylene resin, polyamide resin, polyester resin, polycarbonate resin, polyphenylene sulfide resin, polyether ketone resin, polyether ether ketone resin, polyether ketone ketone resin, polyether sulfide resin, etc. Are preferably used. Moreover, you may use the thing similar to the thermoplastic resin used for the component (B). Further, from the viewpoint of heat resistance and long-term durability, polyphenylene sulfide resin, polyether ether ketone resin, polyether ketone resin, polyether ether ketone resin, and polyether sulfide resin are more preferable.

  Although it does not specifically limit as thickness of resin to coat | cover, 0.01-10 mm can be illustrated. More preferably, it is 0.1-5 mm, More preferably, it is 0.5-3 mm. When the thickness is less than 0.01 mm, sufficient insulation characteristics may not be obtained. When the thickness is 10 mm or more, the weight as a composite for supporting a power transmission cable may be increased, and required load characteristics may not be obtained.

  In the composite for supporting a power transmission cable obtained by the production method of the present invention, the weight ratio of the component (A) and the component (B) is preferably 10 to 90:90 to 10% by weight, more preferably 20 from the mechanical properties. It is -80: 80-20 weight%, More preferably, it is 30-70: 70-30 weight%. These weight ratios can be implemented by controlling the supply amount of the component (A) and the dimensions of the pultrusion mold outlet.

Moreover, the void ratio of the composite for supporting a power transmission cable of the present invention is preferably as low as possible, and is preferably less than 30% because mechanical characteristics are easily exhibited. A more preferable void ratio range is less than 20%, and even more preferably less than 10%. Void fraction is measured by ASTM D2734 (1997) test method for the portion of the composite, or by observing voids present in the cross section of the transmission cable support composite, and the total area of the transmission cable support composite and the total void area. It can be calculated from the area using the following formula.
Void ratio (%) = total area of void part / (total area of composite part + total area of void part) × 100

  As a method for controlling the void ratio, the temperature and pressure when impregnating the component (B) or component (B ′) and the temperature and pressure when converting the component (B ′) to the component (B) are used. Can be adjusted. Usually, the higher the temperature and the applied pressure, the lower the void ratio.

  Moreover, it is preferable that the heat deformation temperature of the power cable supporting composite is 150 ° C. or higher. More preferably, it is 180 degreeC or more, More preferably, it is 210 degreeC or more, More preferably, it is 240 degreeC or more. When the cable generates heat during power transmission, the cable may not be supported if the thermal deformation temperature is less than 150 ° C.

  Further, as the long-term heat resistance characteristics of the composite for supporting a power transmission cable, the tensile strength after heating at 150 ° C. for 8 hours is preferably less than 20% from the tensile strength before heating. More preferably, it is less than 15%, and more preferably less than 10%. When the power is transmitted, heat generation of the cable may continue for a long time, and when the strength reduction rate is 20% or more, the cable design may be difficult.

  Moreover, since the composite for supporting a power transmission cable may be transported in a state of being wound by a winder or the like, it is preferable that a decrease in physical properties at the time of winding is small. Specifically, it is left for 8 hours in a state where it is wound around a drum having a diameter 200 times the thickness of the composite for supporting a power transmission cable, and the tensile strength after being left is 20% lower than the tensile strength before winding. It is preferable that it is less than%. More preferably, it is less than 15%, and more preferably less than 10%. If the rate of strength reduction due to winding is 20% or more, cable design may be difficult.

  Further, the method of supporting the power transmission cable of the power transmission cable supporting composite is not particularly limited, but it is preferably exemplified that it is arranged at the center of a conductor such as aluminum or copper, and FIG. 3 shows an example. FIG. 3 shows a power transmission cable support composite covered with an insulating thermoplastic coating resin 17 in an aluminum conductor 16. In addition, aluminum is preferable when a plurality of strands are used together because they are not easily broken even when a cable such as torsion is deformed.

  Further, when the power transmission cable support composite is used in contact with the power transmission cable conductor, insulation of the power transmission cable support composite may be required. Specifically, the dielectric strength of the composite for supporting a power transmission cable is preferably 15 kV / mm or more. More preferably, the dielectric strength is 17 kV / mm or more, and more preferably 20 kV / mm or more. If the dielectric strength is less than 15 kV / mm, the power transmission cable support composite may be energized during power transmission and may be damaged at the energization portion. Although there is no restriction | limiting in particular in the upper limit of a dielectric strength, Less than 100 kV / mm can be illustrated.

  The composite for supporting a power transmission cable of the present invention can be repaired by using a thermoplastic composition resin, and is further useful as a composite for supporting a power cable because it is excellent in durability, mechanical properties, and flame retardancy. .

  EXAMPLES The present invention will be described more specifically with reference to examples below, but the present invention is not limited to the description of these examples.

(1) Measuring method of glass transition temperature (Tg) Using a molded product of a single matrix resin, the temperature is raised at a frequency of 1 Hz, a temperature of 25 to 300 ° C., and 5 ° C./min using a tester ARES made by Rheometric Scientific. Was measured. The glass transition temperature is the intersection of the base line on the lower temperature side of the step change portion due to the glass transition of G ′ and the tangent drawn at the point where the gradient of the step change portion is maximum, that is, the extrapolated glass transition start temperature The transition temperature (Tg) was used.

(2) Determination of alkali metal content A sample of the matrix resin alone was weighed in a quartz crucible and incinerated using an electric furnace, and the incinerated product was dissolved in concentrated nitric acid, and then dissolved in dilute nitric acid. The obtained constant solution was subjected to ICP gravimetric analysis (apparatus: 4500 manufactured by Agilent) and ICP emission spectroscopic analysis (apparatus: Optima 4300DV manufactured by PerkinElmer) to determine the alkali metal content.

(3) Dielectric strength As described in JIS C2110 (2010) using a molded product of a matrix resin alone or a composite for supporting a power transmission cable using a 100 kV dielectric breakdown test apparatus YST-243-100RHO manufactured by Yamayo Tester Co., Ltd. According to the method, the dielectric strength (strength of dielectric breakdown voltage) was measured at a specimen thickness of 3 mm. When measuring the composite for supporting a power transmission cable, a molded product having the same shape as the structure on the diagonal of the cross section was formed by press molding and used for measurement.

(4) Flame-retardant evaluation Flame-retardant evaluation was performed with a test piece thickness of 0.3 mm in accordance with a UL94 vertical test using a molded product of a matrix resin alone. Only V-0 was accepted.

(5) Measurement of tensile strength The tensile strength of the composite for supporting a power transmission cable was measured according to the method described in JIS K7165 (1991). The measurement was conducted by a tensile test along the axial direction of the composite.

(6) Measurement of tensile strength after heating In a hot air oven set at 150 ° C ± 5 ° C, the power cable supporting composite after heating for 8 hours was subjected to the tensile test shown in (5) above, and the power cable before heating The strength reduction rate was calculated by comparison with the tensile strength of the supporting composite.

(7) Tensile strength measurement after winding Wrap around a drum having a diameter 200 times the thickness of the composite for supporting the power transmission cable, and conduct the tensile test shown in (5) above for the composite for power transmission cable after standing for 8 hours. The strength reduction rate was calculated by comparison with the tensile strength of the composite for supporting the transmission cable.

(8) Measurement of deflection temperature under load The deflection temperature under load of the composite for supporting a power transmission cable was measured according to the method described in Method A of JIS K7191 (1999). The measurement was performed along the axial direction of the composite for supporting the transmission cable.

(9) Evaluation of repairability Transmission cable supporting composite cut to 50 mm in the axial direction was pressed at a surface pressure of 2 MPa for 300 seconds with a 70 t press machine heated at 350 ° C., the matrix resin melted, and the transmission cable The repair composite was deformed when the support composite deformed, and the power cable support composite that could not be deformed or cracked was rated as x. Only ○ was accepted. The surface pressure refers to the surface pressure with respect to the horizontal maximum cross-sectional area of the power cable supporting composite.

Reference Example 1 (Preparation of cyclic polyphenylene sulfide)
A stainless steel autoclave equipped with a stirrer was charged with 14.03 g (0.120 mol) of a 48 wt% aqueous solution of sodium hydrosulfide and 12.50 g (0.144 mol) of a 48 wt% aqueous solution prepared using 96% sodium hydroxide. ), 615.0 g (6.20 mol) of N-methyl-2-pyrrolidone (NMP), and 18.08 g (0.123 mol) of p-dichlorobenzene (p-DCB). The reaction vessel was sufficiently purged with nitrogen, and then sealed under nitrogen gas.

  While stirring at 400 rpm, the temperature was raised from room temperature to 200 ° C. over about 1 hour. At this stage, the pressure in the reaction vessel was 0.35 MPa as a gauge pressure. Next, the temperature was raised from 200 ° C. to 270 ° C. over about 30 minutes. The pressure in the reaction vessel at this stage was 1.05 MPa as a gauge pressure. After maintaining at 270 ° C. for 1 hour, the contents were recovered after quenching to near room temperature.

  The content obtained was analyzed by gas chromatography and high performance liquid chromatography. As a result, the consumption rate of monomer p-DCB was 93%, and the sulfur content in the reaction mixture was assumed to be all converted to cyclic PPS. The formula PPS production rate was found to be 18.5%.

  500 g of the obtained contents were diluted with about 1500 g of ion-exchanged water, and then filtered through a glass filter having an average opening of 10 to 16 μm. The filter-on component was dispersed in about 300 g of ion-exchanged water, stirred at 70 ° C. for 30 minutes, and filtered again in the same manner three times to obtain a white solid. This was vacuum dried at 80 ° C. overnight to obtain a dry solid.

  The obtained solid was charged into a cylindrical filter paper, and Soxhlet extraction was performed for about 5 hours using chloroform as a solvent to separate low molecular weight components contained in the solid.

  The solid component remaining in the cylindrical filter paper after the extraction operation was dried under reduced pressure at 70 ° C. overnight to obtain about 6.98 g of an off-white solid. As a result of analysis, this was a compound having a phenylene sulfide structure, and the weight average molecular weight was 6,300, from the absorption spectrum in infrared spectroscopic analysis.

  After removing the solvent from the extract obtained by the chloroform extraction operation, about 5 g of chloroform was added to prepare a slurry, which was added dropwise to about 300 g of methanol with stirring. The precipitate thus obtained was collected by filtration and vacuum dried at 70 ° C. for 5 hours to obtain 1.19 g of a white powder. This white powder was confirmed to be a compound composed of phenylene sulfide units from an absorption spectrum in infrared spectroscopic analysis. Moreover, this white powder has p-phenylene sulfide unit as the main constituent unit based on the mass spectrum analysis of the component divided by high performance liquid chromatography (apparatus; M-1200H manufactured by Hitachi) and molecular weight information by MALDI-TOF-MS. It was found that the compound contains about 99% by weight of a cyclic compound having 4 to 13 repeating units and is preferably used in the present invention. As a result of GPC measurement, the cyclic polyphenylene sulfide was completely dissolved in 1-chloronaphthalene at room temperature, and the weight average molecular weight was 900.

Reference Example 2 (Method for producing composite for supporting transmission cable using polyphenylene sulfide)
Using the apparatus shown in FIG. 1, a method for producing a composite for supporting a power transmission cable was performed. The pultrusion mold 3 was supplied with the cyclic polyphenylene sulfide obtained in Reference Example 1 from the resin supply port 6 and filled with the molten cyclic polyphenylene sulfide. Moreover, the set temperature of the thermocouple installed in the intermediate part from the pultrusion mold inlet 14 to the center of the pultrusion mold 3 was set to 250 ° C. (Hereafter, the part from the pultrusion mold inlet 14 to the center of the pultrusion mold 3 is referred to as zone 1.) Setting of the thermocouple installed in the intermediate part from the center of the pultrusion mold 3 to the pultrusion mold outlet 15 The temperature was 370 ° C. (Hereinafter, the portion from the pultrusion mold inlet 15 to the center of the pultrusion mold 3 is referred to as zone 2).

  First, a plurality of carbon fiber trading cards (registered trademark) T700S-12K (manufactured by Toray Industries, Inc.) (A) -1 are aligned from the reinforcing fiber bobbin 1 so that the distance between the fiber bundles is 1 to 5 mm. Then, the fiber bundle was applied to the roll bar 2 for leveling and supplied from the pultrusion mold inlet 3 of the pultrusion mold 3. At this time, in the zone 1, the reinforcing fiber was impregnated with cyclic polyphenylene sulfide without voids by being immersed in cyclic polyphenylene sulfide melted at 250 ° C. while touching the impregnation roll 5. The obtained reinforcing fiber impregnated with cyclic polyphenylene sulfide was drawn into zone 2 heated to 370 ° C. to convert the impregnated cyclic polyphenylene sulfide into polyphenylene sulfide (B) -1. Next, as shown in FIG. 2, the composite for power transmission cable support was shaped into a circle by passing through a pultrusion die outlet 15 designed in a circle. Subsequently, the composite for supporting the power transmission cable drawn from the pultrusion mold outlet 15 is solidified on the cooling roller 7 having a temperature of 150 ° C., and the component (B) -1 is solidified and drawn by the belt conveyor 10 for drawing. While taking up with the roller 11, the continuous pultruded product 13 was taken up with the take-up winder 12 to obtain a composite. The drawing speed was 1 m / min. The impregnation rate was 95%.

Reference example 3 (molded product of matrix resin alone)
The cyclic polyphenylene sulfide obtained in Reference Example 1 was charged into a 1 L autoclave equipped with a stirrer and replaced with nitrogen. The autoclave was heated to 300 ° C. in 1 hour. When the cyclic PPS compound was melted in the course of temperature increase, the rotation of the stirrer was started, and the mixture was melted and heated for 60 minutes with stirring at a rotational speed of 10 rpm. Then, the gut was taken out from the discharge port by nitrogen pressure, and the gut was pelletized. The polymerization average molecular weight measured by GPC was 61700, the molecular weight distribution was 1.9, the Na content was 10 ppm, and no other alkali metals were detected. Using the obtained pellets, a test piece for characteristic evaluation was molded at a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. using a J350EIII type injection molding machine manufactured by Nippon Steel Works.

Example 1
When the composite for power transmission cable support was manufactured according to Reference Example 2 and the matrix resin was extracted from the composite for power transmission cable support, the weight average molecular weight of component (B) -1 was 42,000. Moreover, content of component (A) -1 was 50 mass%, and the thickness of the composite for power transmission cable support was 10 mm. The characteristic evaluation results are collectively shown in Table 1.

Example 2
In addition to the component (A) -1, glass fibers (Nittobo glass fibers RS460A-782) (A) -2 were used, and glass fibers were arranged in the outermost layer. Other than that was carried out similarly to Example 1, and produced the composite for power transmission cable support. Moreover, FIG. 4 shows a sectional view in the axial direction of the obtained composite for supporting a power transmission cable. Content of component (A) -1 at this time was 40 mass%, and content of component (A) -2 was 10 mass%. The characteristic evaluation results are collectively shown in Table 1.

Example 3
The composite for supporting a power transmission cable described in Example 1 was further coated with a polyphenylene sulfide resin (Torelina (registered trademark) A670X01 manufactured by Toray Industries, Inc.) at a thickness of 2.0 mm using a wire coating apparatus. Moreover, sectional drawing of the axial direction of the obtained composite for power transmission cable support is shown in FIG. The characteristic evaluation results are collectively shown in Table 1.

Example 4
A composite was prepared in the same manner as in Example 1 except that polyphenylene sulfide (B) -2 having a weight average molecular weight of 59,700 and an alkali metal content of 1000 ppm was prepared in place of the component (B) -1. In both zones 1 and 2, the temperature was set to 320 ° C., and a composite was prepared. The physical property evaluation results are collectively shown in Table 1.

Comparative Example 1
“JER (registered trademark)” 828 (bisphenol A type epoxy resin, viscosity: 13000 mPa · s, manufactured by Japan Epoxy Resins Co., Ltd.) / “Ricacid (registered trademark)” MH700 (methylhexahydrophthalic anhydride / hexahydrophthalic anhydride , 70/30, viscosity: 60 mPa · s, manufactured by Nihon Rika Co., Ltd.) / “JER Cure (registered trademark)” EMI24 (2-ethyl-4-methylimidazole, solid, manufactured by Japan Epoxy Resin Co., Ltd.) = A mixing ratio of 100/90/2 was mixed at 25 ° C to obtain a thermosetting resin composition. The above component (A) -1 is passed through the raw material tank containing the resin composition, impregnated with the resin, then inserted into a mold, and cured by heating at 170 ° C. for 2 minutes, and at 150 ° C. for 15 minutes. After curing, a 10 mm thick composite was obtained. In addition, the physical property evaluation of the matrix resin was performed with the molded article cured at 150 ° C. for 15 minutes using the thermosetting resin composition alone.

  The physical property evaluation results are collectively shown in Table 1.

  As described above, in Examples 1 to 4, the composite for supporting a power transmission cable in the present invention is a composite that can be repaired by using a thermoplastic resin, and is excellent in durability and electrical characteristics.

  On the other hand, in the comparative example, since the thermosetting resin was used, repair was difficult, and the composite was not excellent in durability and flame retardancy.

  By using the composite for supporting a transmission cable of the present invention, it is possible to reduce the deflection of the transmission cable, improving the transmission efficiency by shortening the transmission cable, extending the distance between transmission towers, and reducing the height of the transmission tower. This is useful for reducing equipment costs for power transmission. Furthermore, by using a thermoplastic resin as the matrix resin, it can be repaired, has excellent long-term durability, and can be said to be extremely useful.

DESCRIPTION OF SYMBOLS 1 Reinforcing fiber bobbin 2 Roll bar 3 Drawing mold 4 Molten resin 5 Impregnation roller 6 Resin supply port 7 Cooling roller 8 Supply port 9 Chamber 10 Pulling belt conveyor 11 Nip roller 12 Winding winder 13 Continuous drawing product 14 Drawing Mold entrance 15 Draw-out mold exit 16 Aluminum conductor 17 Coating resin 18 Fiber reinforced composite 19 Carbon fiber reinforced composite 20 Glass fiber reinforced composite 21 Coating resin

Claims (14)

Component (A) is such that the total of component (A) and component (B) is 100% by mass, and that component (A) continuous reinforcing fiber is 10 to 90% by mass and component (B) thermoplastic resin is 90 to 10% by mass. A composite for supporting a power transmission cable, in which a continuous reinforcing fiber is impregnated with a component (B) thermoplastic resin. The composite for supporting a power transmission cable according to claim 1, wherein the glass transition temperature of the component (B) thermoplastic resin is 50 to 250 ° C. The component (B) thermoplastic resin is at least one selected from polyphenylene sulfide resin (PPS), polyphenylene ether ether ketone resin (PEEK), polyphenylene ether ketone resin (PEK), and polyether ketone ketone resin (PEKK). The composite for supporting a power transmission cable according to claim 1 or 2. The dielectric strength of the said component (B) is 15 kV / mm or more, The composite for power transmission cable support in any one of Claims 1-3. The composite for supporting a power transmission cable according to any one of claims 1 to 4, wherein the alkali metal content of the component (B) thermoplastic resin is 50 ppm or less. The said component (B) is V-0, The composite for power transmission cable support in any one of Claims 1-5. The composite for supporting a power transmission cable according to any one of claims 1 to 6, wherein a rate of decrease in tensile strength after heating at 150 ° C for 8 hours is less than 20%. The composite for power transmission cable support according to any one of claims 1 to 7, wherein the composite for power transmission cable is wound around a circular drum 200 times the thickness of the composite for power transmission cable, and the strength reduction rate after 8 hours is less than 20%. The composite for power transmission cable support according to any one of claims 1 to 8, wherein the thickness of the composite for power transmission cable support is 0.4 to 50 mm. The composite for supporting a power transmission cable according to any one of claims 1 to 9, wherein a cross section of the composite for supporting a power transmission cable is any one of a circle, an ellipse, and a star. The power cable supporting composite according to any one of claims 1 to 10, wherein the component (A) is arranged in the axial direction in the power cable supporting composite. The composite for power transmission cable support according to any one of claims 1 to 11, wherein glass fiber is used as the component (A) on the outermost periphery of the composite for power transmission cable support. The composite for power transmission cable support in any one of Claims 1-12 which coat | covered the outermost periphery of the composite for power transmission cable support with the thermoplastic resin (C). The composite for supporting a power transmission cable according to claim 13 or 14, wherein the dielectric strength is 15 kV / mm or more.

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