JPS58102405A - Snow deposition resistant wire - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a snow-resistant electric wire, and more particularly to a snow-resistant electric wire provided with a coating layer of a non-stick conductive fluororubber paint.

Typically, a strand of metal wire twisted together is used as an overhead electric wire, and various structures are known as described below. When snow accumulates on such a wire, eccentric rotational force is generated due to the eccentric load of the snow, and as a result, the snow may rotate around the wire, or the snow and the wire may rotate together, causing the snow to gradually accumulate. The amount may increase and develop into a large snow pipe, causing accidents such as wire breakage and collapse of supports.

Various proposals have been made to prevent snow from accumulating on electric wires. For example, by attaching rings at regular intervals along the length of the wire, or by winding the wire in a spiral in the direction opposite to the direction in which the wire is twisted, snow that has slipped along the wire can be removed using rings or rings. Stop with a winding,
One method is to increase the eccentric load of the snow itself to make it fall off.

However, since the electric wire itself is a metal body and the snow adheres to the metal, even if such measures are taken, it may not be possible to sufficiently prevent snow pipes depending on weather conditions such as temperature and snow density.

Therefore, we have developed anti-snow electric wires that have a conductive rubber/plastic coating layer formed on them (Utility Model Application Publication No. 55-96522) and anti-snow electric wires that have graphite, amorphous carbon and/or graphite fluoride coated on the surface of the electric wires. Snow electric wire (Utility Application No. 56-69761) and the like have been proposed. However, in the former,
The non-adhesive properties of the surfaces of the rubber and plastic used for this are not good, and on the other hand, there are difficulties in the processing method of the latter.

Based on this knowledge, the present inventors have conducted repeated research to develop electric wires with effective snow accretion resistance, and as a result, we have applied fluororubber paint of a specific composition containing conductive substances to the outside of conductive wires. They have discovered that an excellent snow-resistant electric wire can be obtained simply by coating the surface and curing it, and have completed the present invention.

That is, the gist of the present invention is to provide a non-adhesive conductive elastic coating formed by applying and curing a fluororubber paint containing fluororubber, fluororesin, a coupling agent, a conductive substance, and a liquid carrier to the outer surface of a conductive wire. The present invention relates to a snow-resistant electric wire characterized by having a layer.

The conductive wire used in the present invention is a bare wire that is used for power transmission lines, distribution lines, overhead ground wires, support wires, etc. by hanging in the air, and is, for example, aluminum, copper or alloy wires thereof, steel wires (plated It is a stranded metal wire made by tying together metal wires such as wires (including wires) or composite wires such as aluminum-covered wires or copper-covered wires.

In the present invention, the fluororubber coating film obtained by blending a specific amount of fluororesin imparts excellent non-adhesive properties to the surface of the conductive wire base material without substantially affecting its adhesion and mechanical properties. This is possible because the fluororesin, which itself is non-adhesive, surprisingly collects on the surface of the fluororubber coating, so the fluororesin can be coated without adversely affecting the adhesion to the substrate and the mechanical properties of the coating. q It is believed that the above performance is effectively exhibited on the surface of the fluororubber coating film.

According to our research, when we measure the fluorine content on the surface of a 50 μm thick coating film cured at 300°C for 130 minutes and on the adhesive surface with the substrate using fluorescent X-ray analysis, we find that It has been confirmed that the former shows about 1.5 times the amount, and the higher the curing temperature, the more the ratio of the former to post-folding tends to increase.

The fluororubber contained in the fluororubber paint used in the present invention is a highly fluorinated elastic copolymer, and particularly preferred fluororubbers are usually 40 to 85 mol% of vinylidene fluoride and copolymer thereof. Examples include elastomeric polymers with at least one other fluorine-containing ethylenically unsaturated monomer that can be copolymerized. Further, as the fluororubber, fluororubber containing iodine in the polymer chain is also preferably used.

This iodine-containing fluororubber has, for example, 0.001 to 10% by weight, preferably 0.01 to 5% by weight of iodine bonded to the end of the polymer chain, and is combined with the same 40 to 85 mol% of vinylidene fluoride as described above. Fluororubber whose main composition is an elastic copolymer consisting of at least one other fluorine-containing ethylenically unsaturated Vt substance that can be copolymerized (JP-A-52
-40543). Other fluorine-containing ethylenically unsaturated substances that degrade the elastic piece polymer by dust polymerization with vinylidene fluoride include hexafluoropropylene, pentafluoropropylene, trifluoroethylene, trifluorochloroethylene, and tetrafluoroethylene. Representative examples include fluoroethylene, vinyl fluoride, perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether). Particularly desirable fluororubbers include vinylidene fluoride/hexafluoropropylene dielastic copolymers and vinylidene fluoride/hexafluoropropylene dielastic copolymers.
It is a tetrafluoroethylene/hexafluoropropylene ternary elastic copolymer.

The fluororesin contained in the fluororubber paint used in the present invention includes polytetrafluoroethylene, tetrafluoroethylene, and at least one other ethylenically unsaturated monomer copolymerizable with it (e.g., ethylene, propylene, etc.). Copolymers with olefins, halogenated olefins such as hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, vinyl fluoride, perfluoroalkyl vinyl ethers, etc.),
Examples include polychlorotrifluoroethylene and polyvinylidene fluoride. Among them, tetrafluoroethylene, hexafluoropropylene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, hafluoropropyl vinyl ether,
! : is also a copolymer with one type (usually 40 mol% or less based on tetrafluoroethylene).

In the fluororubber paint used in the present invention, the coupling agent is a compound (1) that acts on the interface between an organic material and an inorganic material and forms a strong bridge between the image materials through chemical or physical bonding. It is a compound of silicon, titanium, zirconium, )1 hnium, thorium, tin, aluminum or magnesium, and has a group capable of bonding an organic material and an inorganic material. Among these coupling agents, preferred are silane coupling agents and orthoacid esters of Group I transition elements of the periodic table (such as titanium or zirconium) and derivatives thereof, and among these, aminosilane compounds are most preferred.

Examples of the silane coupling agent include the general formula: % formula % [wherein R1 is a chlorine atom, an amine group, an aminoalkyl group, a ureido group, a glycidoxy group, an epoxycyclohexyl group, an acryloyloxy group, a methacryloyloxy group, a mercapto group, and An alkyl group having 1 to 10 carbon atoms or a beer group having at least one functional atom or group selected from vinyl groups; R2 and R3 are each a chlorine atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and a 2-carbon group; -15 alkoxy-substituted alkoxy group, carbon number 2-4
an atom or group selected from a hydroxyalkyloxy group and an acyloxy group having 2 to 15 carbon atoms, 3 is 0.1
or 2. ] Examples include silane compounds represented by the following.

R1 is an alkyl group having a functional substituent, and preferable examples include β-aminoethyl group, γ-aminopropyl group, N-(β-aminoethyl)-r-aminopropyl group, r-ureidopropyl group, r-glycidoxypropyl group, β-(3,4-epoxycyclohexyl)ethyl group, γ-acryloyloxypropyl group, r-
methacryloyloxyglobil group, r-mercaptopropyl group, β-chloroethyl group, γ-chloropropyl group,
Examples include γ-vinylpropyl group.

Alternatively, 1 may be a vinyl group.

Specific examples of the above-mentioned silane compounds that are preferably used include γ-aminopropyltriethoxysilane, N-(β
-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-
Glycidoxyprobyltrimethoxysilane, β-(3,
4-epoxycyclohexyl)ethyltrimethylsilane, γ-methacryloxypropyltrimethoxysilane, r
-Mercaptopropyltrimethoxysilane, r-chloropropyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane,
Examples include N-(trimethoxysilylpropyl)ethylenediamine, N-β-aminoethyl-r-aminopropylmethyldimethoxysila/β-aminoethyl-β-aminoethyl-r-aminopropyltrimethoxysilane, and the like. Among these silane coupling agents, aminosilane compounds such as γ-aminopropyltriethoxysilane (hereinafter referred to as A-1100), N-β-aminoethyl-r-aminopropyltrimethoxysilane,
N-(trimethoxysilylpropyl)ethylenediamine, N-β-aminoethyl-r-aminopropylmethyldimethoxysilane, r-ureidopropyltriethoxysilane, β-aminoethyl-β-aminoethyl-r-aminopropyltrimethoxy Compounds such as silane are particularly preferred because they function as a vulcanizing agent for fluororubber, greatly contribute to improving the adhesion to the substrate, and are also safe for use with liquid carriers.

Compounds of titanium, zirconium, hafnium and hytrium include, for example, the general formula: % formula %) [In the formula, T is titanium, zirconium, ), hunium or thorium, and k represents an alkyl group, cycloalkyl group or aryl group. . ] and at least 1 orthoacid ester represented by
The derivatives obtained by reacting one or more compounds having a functional group with H can be mentioned. At least one of the above
Examples of compounds having functional groups include glycerin,
Ethylene glycol, 1,3-butanediol, 2,3
- Polyhydric alcohols such as butanediol, hexylene glycol and octylene glycol, oxyaldehydes such as salicylaldehyde and glucose, oxyketones such as diacetone alcohol and fructose, glycolic acid, lactic acid, dioxymaleic acid , oxyamines such as citric acid, diketones such as diacetylacetone, ketone acids such as acetoacetic acid, esters of ketonic acids such as ethyl acetoacetate, νs, triethanolamine,
Oxyamines such as jetanolamine and oxyphenol compounds such as catechol and pyrogallol can be used.

Examples of specific compounds when T is titanium include tetraalkyl titanate (e.g., tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate),
Tetraethylene glycol titanate, triethanolamine titanate, titanium acetylacetonate, isopropyltrioctanoyl titanate, isopropyl trimethacryl titanate, isopropyl triacryl titanate, inprovir tri(butyl, methylpyrophosphate) titanate, tetraisoprovir di(di) Examples include lauryl phosphite) titanate, dimethacryloxyacetate titanate, diacryloxyacetate titanate, di(dioctyl phosphate) ethylene titanate, and the like.

As the zirconium compound, a compound similar to the above titanium compound can be used. As a specific example, Nato 2
Tetraalkyl zirconates such as ethyl zirconate and tetrabutyl zirconate, n-propyl zirconate, isopropyl zirconate, n-butyl zirconate, imbutyl zirconate, zirconium acetylacetonate, and the like.

As the hafnium and thorium compounds, compounds similar to titanium and zirconium can be used.

As the tin compound, an organic or inorganic compound such as 5nCj 4 can be used.

Examples of aluminum compounds include aluminum isopropylate, mono-5ec-butoxyaluminum diisopropylate, aluminum 5ec-butyrate, ethyl acetoacetate aluminum diisopropylate, and aluminum tris [ethylacetoacetate].

Examples of the magnesium compound include magnesium alcoholades such as magnesium methylate and magnesium dithylate.

As the conductive substance, conventionally used substances such as carbon, graphite, metals and antistatic agents can be used. For example, carbon includes conductive carbons such as channel black, furnace black, thermal black, etc. Metals include gold, silver, copper, aluminum, titanium, etc., and antistatic agents include anionic, nonionic, cationic, and amphoteric antistatic agents. These may be used alone or in combination of two or more.

The liquid carrier contained in the fluororubber paint used in the present invention is selected from organic solvents such as lower ketones, lower esters, and cyclic ethers, water, and mixtures of water and water-soluble organic liquids. Alcohols can be exemplified. Among these liquid carriers, water is most preferred since it does not impair coating workability.

Inorganic fibrous substances as other substances contained in the fluororubber coating of the present invention are used to improve the compression recovery properties of the fluororubber coating, and typical examples include glass fiber, carbon fiber, asbestos fiber, Examples include potassium titanate fiber. It is desirable that the inorganic fibrous material has an average length of at least 1μ, preferably 1 to 100μ.

The amine compound optionally added to the fluororubber paint used in the present invention primarily functions as a vulcanizing agent for the fluororubber, and together with the coupling agent, improves mechanical properties. Examples of such compounds include monoamines such as ethylamine, propylamine, butylamine, benzylamine, toryamine, n-amylamine, and ethanolamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, and 3,9-bis. (3-Aminopropyl)-2,4,8,10-tetraoxaspiro[: 5
, 5 ] undecane (hereinafter referred to as v-11), polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. An amine compound having the following is preferred.

To prepare the fluororubber paint used in the present invention, a conductive substance, a pigment, an acid acceptor, a filler, etc. are usually added to a mixture of fluororubber, fluororesin, and a liquid carrier, and if necessary, a surfactant is added. Agents may also be used. ], Add a coupling agent and, if necessary, an amine compound to the resulting dispersion (additives such as the pigment, acid acceptor, filler, etc. may be added as necessary), and mix thoroughly using a conventional method. By doing so, a uniform fluororubber paint is obtained.

The ratio of fluororubber and fluororesin is 95 = 5 to 35 by weight.
: 65 is desirable; if the proportion of fluororesin is less than the above lower limit, the desired improvement in non-adhesiveness and lubricity will not be sufficient; on the other hand, if it is greater than the above upper limit, the coating film will not have the desired thickness. is not obtained, and cracks and pinholes are likely to occur in the coating film.

The amount of the conductive substance added can vary depending on the type of conductive substance, but it is preferable that the volume resistivity value, which is the limit that does not cause partial discharge in a semiconductive layer applied on a conductor, be 106 g-a or less. may be added so that it becomes 10312-C11 or less.

The amount of the coupling agent added is usually 1 to 50 parts by weight, preferably 1 to 20 parts by weight per 100 parts by weight of fluororubber. When an amine compound is added as desired, it is blended so that the total sum of the coupling agent and the amine compound takes the above value. In this case, the molar ratio of the coupling agent to the amine compound is selected from the range of 1=99 to 99:1.

As the acid acceptor, those commonly used in the vulcanization of fluororubber can be similarly used, such as one or more divalent metal oxides or hydroxides. Specific examples include oxides or hydroxides of magnesium, calcium, zinc, lead, and the like. Further, as the filler, silica, clay, diatomaceous earth, talc, carbon, etc. are used.

The fluororubber paint used in the present invention is applied or impregnated onto a conductive wire base material by a normal coating method, and is heated at room temperature to 400°C.
The desired fluororubber coating can be obtained by curing for an appropriate time preferably at a temperature of 100 to 400°C.

In the present invention, the thickness of the fluororubber coating film is preferably 5 μm or more. If the film thickness is less than 5 μm, there is a risk that unevenness will occur over the entire surface of the substrate and that some parts will not be coated. The fluororubber coating film of the present invention thus obtained is
The inherent properties of fluororubber include heat resistance, weather resistance, abrasion resistance, oil resistance, solvent resistance, and chemical resistance, as well as electrical conductivity, adhesion to base materials, and its own mechanical properties. It also provides non-stick and lubricious properties to the surface.

The invention will now be described in detail with reference to embodiments shown in the accompanying drawings.

FIG. 1 shows a steel-core aluminum stranded wire for power transmission and distribution in which hard aluminum wires 2 are twisted around a steel core in which steel wires 1 are twisted together [hereinafter referred to as AC5R]. ] and Al. (7) ACS
A fluororubber coating layer 4 is formed on the aluminum wire 2', which is the outermost layer of It, before being twisted together.

Figure 2 shows a twisted wire similar to AC8R in Figure 1, but the fluororubber coating layer 4 is formed by twisting two outermost aluminum wires together, then applying and curing fluororubber paint. There is.

Fig. 3 shows a method in which deformed aluminum wires 3 formed into a ladder-shaped cross section are twisted around a steel core in which steel wires 1 are twisted together.
Alternatively, the compression type AC8 is made by compression molding the outer layer of aluminum wire to smooth the stranded wire surface and improve the cross-sectional space factor.
It is R. The aluminum wire 3' in this outermost layer has
As with AC5R in FIG. 1, a fluororubber coating layer is formed before twisting.

FIG. 4 shows a twisted wire similar to the compression type AC5R shown in FIG. 3, but the fluororubber coating layer 4 is the outermost aluminum wire 3.
It is formed by twisting the strands together, applying fluororubber paint, and curing it.

In each of the above embodiments, the fluororubber coating layer is provided only on the surface of the metal wire, which is the outer surface of the stranded wire, but in addition to this, a coating layer may be provided on other surface portions.

As shown in Examples below, the fluororubber coating film of the present invention has a much larger contact angle with water, which is an indicator of the adhesion of snow to a substance, than that of metal, so it can effectively prevent snow from accreting. Furthermore, as mentioned above, since the fluororesin is present in a relatively large proportion on the surface of the coating film, the surface has particularly excellent non-stick properties.

Furthermore, the fluororubber coating film of the present invention has excellent weather resistance and abrasion resistance, and is resistant to salt damage and aging. In addition, because the coating is electrically conductive, it does not impair the electrical performance of conventional power transmission lines.

The non-adhesive conductive elastic coating layer of the present invention exhibits a sufficient snow accretion prevention effect by itself, but it cannot be combined with conventional snow accretion prevention measures applied to conductive wires, such as the above-mentioned frinzo or spiral winding. If so, a synergistic effect can be obtained.
- Next, the present invention will be explained by showing examples and comparative examples. Note that parts indicate parts by weight.

Examples 1 to 4 and Comparative Examples The following liquid A and the following B containing each component in the proportions shown in Table 1
The liquids were uniformly mixed in a ratio of 100 parts of liquid A and 5 parts of liquid B, and then purified door-to-door using a 200-mesh wire mesh to prepare a fluororubber water-based paint.

Solution A (1) Fluorine gonophobic dispersion (fluorine resin content 60% by weight, containing Nonion H8-208) (2) Fluorine resin ml vermilion dispersion (fluorine resin content 50% by weight, Nonion H8) -2,,08 included.

] (3) Magnesium oxide (4) Conductive substance 0 (5) Nonion H5-210 (6) Water B liquid A-110040 parts V-1120 parts Water 40
Notes 1) Vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene elastomeric copolymer.

Note 9 Tetrafluoroethylene/hexafluoropropylene copolymer.

Note J In Examples 1 to 3, conductive carbon Conductex 950 (Columbia Carbon Co., Ltd.) was used, and in Example 4
Here, we used a blend of Conductex 950 and 1) C13250 (Nippon Graphite Co., Ltd.) in a ratio of 4=6 (weight ratio).

An aluminum plate with a length of 100 mm, a width of 50 m, and a thickness of Im was degreased by washing with acetone. The above-mentioned paint was spray-painted on the degreased aluminum plate surface, and then dried at 50 to 70'C for 10 minutes to form a coating film with a thickness of 30μ, and the coating film was cured at 3006C for 10 minutes.

The volume resistivity of the coating film of the obtained test piece was measured by the potential drop method, and the contact angle of the coating film with water was measured by dropping one drop of pure water at 24°C and measuring the contact angle with a goniometer (Elma). (manufactured by Kogaku Co., Ltd.). The results are shown in Table 2 along with the contact angles of aluminum, copper and zinc to water.

Table 2 Examples 5 and 6 In Examples 1 to 4, di-n-butoxybis[triethanolamine] titanate was used as a coupling agent in place of A-1100 in Solution B in Example 5 and zirconium tetra in Example 6. A fluororubber water-based paint was prepared using the same procedure except that a zirconium chelate prepared by reacting 327 parts of isopropoxide and 180 parts of lactic acid at 25 to 509 C and then distilling it under reduced pressure to remove impropatol was used. did. Note that the composition of liquid A is as shown in Table 3.

The volume resistivity and water contact angle of the coating films obtained from these fluororubber paints were measured in the same manner as in Examples 1 to 4. The results are shown in Table 3.

Table 3

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are cross-sectional views of an electric wire in which a fluororubber coating layer of the present invention is provided on a normal AC8R. Figure 3 and Figure 4 are cross-sectional views of an electric wire in which a compression type AC8R is provided with the fluororubber coating layer of the present invention. 1... Steel wire, 2, 2', 2#-... Hard aluminum wire, 3.3I, 31. ,, deformed aluminum wire, 4.
...Fluororubber coating layer. Patent applicant: Daikin Industries, Ltd. (and 1 other person) on behalf of
Person Patent Attorney-mae Yamaboshi (and 2 others) 1-2-1 Sendai Koriyama

Claims (1)

[Claims] 1. A non-adhesive conductive elastic coating made by applying and curing a fluororubber paint containing fluororubber, fluororesin, a coupling agent, a conductive substance, and a liquid carrier to the outer surface of a conductive wire. A snow-resistant electric wire characterized by a layered structure. 2.7 The snow-resistant electric wire according to claim 1, wherein the weight ratio of fluororubber and fluororesin contained in the fluorine comb paint is 95=5 to 35:65. 3. The ratio of the coupling agent contained in the fluororubber paint to the fluororubber is 1 to 50 parts by weight of the former per 100 parts by weight of the latter.
The snow-resistant electric wire according to claim 1, which is in parts by weight. 4. The snow-resistant electric wire according to any one of claims 1 to 3, wherein the fluororubber coating further contains an amine compound having at least one terminal amino group directly connected to an aliphatic hydrocarbon group. . 5. The snow-resistant electric wire according to claim 4, wherein the amine compound has at least two terminal amino groups. 6. The molar ratio of coupling agent and amine compound is 1:99
The snow-resistant electric wire according to claim 4 or 5, which has a ratio of 99:1 to 99:1. 7. The conductive substance contained in fluororubber paint is carbon,
The snow-resistant electric wire according to any one of claims 1 to 6, which is selected from the group consisting of graphite, metal powder, and antistatic agent. 8. The snow-resistant electric wire according to any one of claims 1 to 7, wherein the fluororubber coating further contains an inorganic fibrous substance.