JP2008192394A - Method of manufacturing electric wire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an efficient manufacturing method of a wire wherein not only a manufacturing speed can be increased, but also its surface can be directly printed, it can be decorated, and sealing performance in a wire harness can be improved. <P>SOLUTION: This manufacturing method of the wire includes a process to spray flame originated from fuel gas containing a modifier compound containing a silicon atom, a titanium atom, or an aluminum atom, air, and hydrocarbon gas, and the molar ratio of the mixture of air and hydrocarbon gas in the fuel gas is set to 23 or more. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing electric wires (including cables and the like), and more particularly to a method for manufacturing electric wires having a high manufacturing speed.

Conventionally, thermoplastic elastomers typified by EPDM resins have rubber properties at room temperature, and when they reach a temperature above a predetermined level, they are softened in the same way as thermoplastic resins, so they can be used for molding using an injection device or the like. is there.
In addition, olefin resins typified by polyethylene resins are widely used as wire covering materials because they are relatively inexpensive, environmentally friendly, and have a low dielectric constant.
However, such an electric wire coated with a thermoplastic elastomer or olefin resin has a hard-to-adhesive surface, and a coating film made of a thermosetting resin paint or an ultraviolet curable paint is formed thereon. In addition, there was a problem that when characters and symbols were printed, they were easily peeled off.

  Therefore, a flame treatment method for modifying the surface of the polymer substrate is disclosed. More specifically, a flame treatment method is disclosed in which a polymer substrate is exposed to a flame assisted by a fuel and an oxidant mixture containing hexamethyldisiloxane having a boiling point of 101 ° C. (for example, Patent Documents). 1).

On the other hand, the applicant has proposed a two-step surface treatment method for a solid substance, which can replace conventional corona treatment, primer treatment, flame treatment, and the like (see, for example, Patent Document 2).
That is, it mainly includes a step of modifying the surface of the solid substrate of metal or glass product by at least one oxidation flame treatment and a step of modifying the surface by at least one silicidation flame treatment. A method for modifying the surface of a solid substrate is proposed. According to such a method for modifying the surface of a solid substrate, the surface of the solid substrate can be surely modified, and an effect that a printing ink, an ultraviolet curable paint, or the like can be firmly bonded can be obtained.

The applicant has also proposed a one-step surface treatment method for a solid material, which is an improvement of the two-step surface treatment method (see, for example, Patent Document 3).
That is, a storage tank unit for storing a fuel gas containing a modifier compound having a boiling point of 10 ° C. to 100 ° C., a transfer unit for transferring the fuel gas to an injection unit, and a flame of the fuel gas A surface reforming apparatus including an injection unit for spraying, and subjecting the silicic acid flame obtained by burning the fuel gas to the surface of the solid substance to be completely or partially sprayed. This is a surface treatment method that greatly improves the wettability of the treatment part.

Furthermore, the applicant applies a silicic acid flame comprising a fuel gas containing a silicon-containing compound having a flash point in the range of 0 to 100 ° C. and a boiling point in the range of 105 to 250 ° C. to the surface of the solid substance. A surface treatment method has also been proposed in which the entire surface or part of the surface is sprayed to activate the processing section and improve wettability (see, for example, Patent Document 4).
Special Table 2001-500552 (Claims) JP 2002-53982 (Claims) JP 2003-238710 A (Claims) WO 2004-098792 (Claims)

  However, the polymer substrate surface modification method disclosed in Patent Document 1 does not use hexamethyldisiloxane having a high boiling point (boiling point: 101 ° C.) as the silane compound, and air / hydrocarbon gas. Therefore, when such a silane compound is mixed with a large amount of air or the like, the problem is that non-uniform combustion tends to occur and the reforming effect cannot be obtained stably. It was seen. Moreover, since no consideration was given to the mixed molar ratio of air / hydrocarbon gas, there was a problem that the effect of reforming by hexamethyldisiloxane decreased in a relatively short time.

  In addition, the surface modification method disclosed in Patent Document 2 uses an alkoxysilane compound such as tetramethoxysilane (boiling point: 122 ° C.) having a high boiling point as a silane compound, so that it can be used in environmental conditions such as winter. When such an alkoxysilane compound was mixed with a large amount of air or the like, a phenomenon of non-uniform combustion was observed. In addition, since a separate oxidation flame treatment step is included before the silicic acid flame treatment, a more excellent modification effect can be obtained on the surface of the solid substrate, but there is also a problem that it takes a long time for the surface treatment. .

Furthermore, the surface modification methods disclosed in Patent Documents 3 to 4 are basically surface modification methods for films and molded articles, and a predetermined surface treatment is performed on the electric wires for a short time. However, it has not been found that it can be accurately manufactured.
In addition, even in the surface treatment methods disclosed in Patent Documents 3 to 4, since no consideration is given to the mixed molar ratio of air / hydrocarbon gas, the difference in boiling point of silicon-containing compounds and the surrounding environment Depending on the conditions (temperature, humidity), etc., the improvement of wettability in the solid substance is insufficient, and it may be difficult to form a coating film having strong adhesion to the surface of the solid substance. It was.

Therefore, the inventor of the present invention has conducted further research on the surface modification of electric wires using a silicic acid flame or the like, and found that a fuel gas containing a predetermined modifier compound, air, and a hydrocarbon gas. In addition, by setting the mixed molar ratio of air / hydrocarbon gas to a value within a predetermined range, not only can the production speed of the electric wire be increased, but also printing or decorating directly on the resin-coated electric wire, Furthermore, it discovered that the sealing performance etc. in a wire harness could be improved, and came to complete this invention.
That is, an object of the present invention is to provide an efficient method for manufacturing an electric wire that is easy to manufacture and has high functionality (including handling properties).

According to the present invention, an electric wire including a step of blowing a flame composed of a fuel gas containing a modifier compound containing a silicon atom, a titanium atom or an aluminum atom, air, and a hydrocarbon gas against the surface of the electric wire. And a method of manufacturing an electric wire in which the mixed molar ratio of air / hydrocarbon gas in the fuel gas is 23 or more, and the above-described problems can be solved.
That is, by using such a specific fuel gas and subjecting an electric wire covered with a polyethylene resin having a low surface tension to surface treatment, predetermined silica particles having a large number of hydroxyl groups on the surface (silica particle layer, Including a titania particle layer and an alumina particle layer, the same applies hereinafter) can be laminated firmly and uniformly.
Therefore, the friction coefficient on the surface of the electric wire is reduced, and the production speed such as the winding speed can be remarkably increased without deteriorating the electric characteristics of the electric wire. Moreover, since the wettability of the surface is remarkably improved at an arbitrary position of the electric wire, it is possible to print directly on the electric wire, decorate it, and further improve the sealing performance in the wire harness. Furthermore, not only re-pelletization when recycling the coating resin of the electric wire is facilitated, but it can be integrally formed with high accuracy using a press device or the like.

Moreover, when implementing the manufacturing method of the electric wire of this invention, it is preferable that hydrocarbon gas is propane gas or LPG (liquefied petroleum gas other than propane gas alone).
Such kind of hydrocarbon gas is inexpensive, but can be burned at a predetermined temperature. Therefore, a predetermined surface treatment can be performed on any of the electric wires by stably thermally decomposing the silicon-containing compound or the like.

In carrying out the method for producing an electric wire of the present invention, the modifier compound is an alkylsilane compound, an alkoxysilane compound, a siloxane compound, a silazane compound, an alkyl titanium compound, an alkoxy titanium compound, an alkyl aluminum compound, and an alkoxy aluminum compound. It is preferably at least one silicon-containing compound, titanium-containing compound, or aluminum-containing compound selected from the group consisting of
With these types of silicon-containing compounds, etc., stable vaporization is achieved not only by controlling the concentration in the fuel gas, but also by stably evaporating using its own vapor pressure. Therefore, for any electric wire, predetermined silica particles having a large number of hydroxyl groups on the surface can be easily formed as the predetermined surface treatment.

Moreover, when implementing the manufacturing method of the electric wire of this invention, it is preferable to make the boiling point (760 mmHg) of a modifier compound into the value within the range of 20-250 degreeC.
If it is a silicon-containing compound or the like having such a boiling point, the concentration in the fuel gas can be easily controlled by evaporating stably using not only the heat of vaporization but also a vaporizer, etc. It is possible to effectively suppress the occurrence of a dew condensation phenomenon based on a temperature change or a concentration change.

Further, in carrying out the method for producing an electric wire of the present invention, the content of the modifier compound is within the range of 1 × 10 ⁻¹⁰ to 10 mol% when the total amount of fuel gas is 100 mol%. It is preferable to use a value.
With such a content of the modifier compound, not only the heat of vaporization but also a vaporizer or the like is used to stably evaporate or control the flow rate so that the temperature change and concentration in the pipe The occurrence of the dew condensation phenomenon based on the change can be effectively suppressed. Moreover, since it will thermally decompose stably if it is content of such a modifier compound, a predetermined | prescribed surface treatment can be effectively implemented with respect to the surface of an electric wire.

In carrying out the method for producing an electric wire of the present invention, the electric wire covering material is selected from olefin resin, polyvinyl chloride, polyester resin, urethane resin, silicone resin, fluororesin, natural rubber, synthetic rubber, and thermoplastic elastomer. It is preferably at least one selected from the group consisting of
An electric wire provided with a coating material made of such a coating material is not only highly versatile and inexpensive, but also easily surface-modified to form predetermined silica particles having many hydroxyl groups on the surface. be able to.

Further, in carrying out the method for producing an electric wire of the present invention, it includes a step of forming a coating film made of a thermosetting paint, an ultraviolet curable paint, a laser marking paint or a thermoplastic paint on the surface of the coating material of the electric wire. It is preferable.
If it is a coating film which consists of such a kind, while being able to improve the adhesiveness between with the coating | covering material of an electric wire, the outstanding discriminability and decorativeness can be exhibited. Moreover, if it is a coating film which consists of such a kind, it will reduce that repelletization at the time of recycling coating resin etc. is inhibited.

Moreover, when implementing the manufacturing method of the electric wire of this invention, it is preferable that an electric wire is an electric wire for wire harnesses, and bundles two or more.
By implementing in this way, the electric wire for wire harnesses which improved functionality and usability can be provided efficiently.

Embodiment of this invention includes the process of spraying the flame which consists of a modifier compound containing a silicon atom, a titanium atom, or an aluminum atom, air, and hydrocarbon gas with respect to the surface of an electric wire. A method for manufacturing an electric wire, wherein the mixed molar ratio of air / hydrocarbon gas in fuel gas is 23 or more.
That is, using a predetermined surface reformer, a flame composed of a predetermined modifier compound and a fuel gas containing air / hydrocarbon gas or the like is sprayed on the surface of the electric wire under predetermined surface treatment conditions. Predetermined silica particles having a large number of hydroxyl groups on the surface can be formed.
Therefore, it is possible to remarkably increase the winding speed, to improve the printing property, the decorative property, or the sealing property in the wire harness, and to improve the recyclability of the coating resin of the electric wire.

1. As shown in FIG. 1 (a), the type of the electric wire as an object to be manufactured is not particularly limited as long as the electric wire 10 includes the conductor 14 and the surrounding insulating covering material 12. For example, Examples thereof include a cable 10 ′ as shown in FIG. 1B, a coaxial cable 10 ″ as shown in FIG. 1C, or a flat cable, a wire harness (including grommets), etc., although not shown. Moreover, in the case of a wire harness, what is necessary is just to further provide the harness material which bundles a some electric wire. In the case of the coaxial cable 10 ″ as shown in FIG. 1C, a surface modification layer 13 is provided around the insulating coating material 12, and a coating film (decorative film) 15 is provided thereon. Is an example provided.

Here, examples of the material for the conductor include copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, silver, silver alloy, and gold.
The insulating coating material may be at least one selected from the group consisting of olefin resin, polyvinyl chloride, polyester resin, urethane resin, silicone resin, fluororesin, natural rubber, synthetic rubber, and thermoplastic elastomer. preferable.
The reason for this is that an electric wire having a covering material (sheath) made of such an insulating covering material is not only highly versatile and inexpensive, but also easily surface-modified and has many hydroxyl groups on the surface. This is because predetermined silica particles and the like can be formed.

Moreover, as shown in FIG.1 (c), the coating | coated film (decoration film | membrane) 15 which consists of a thermosetting coating, an ultraviolet curable coating, a laser marking coating, or a thermoplastic coating is included in the surface of the coating | covering material of an electric wire. Is preferred.
The reason for this is that a coating film made of such a type can enhance the adhesion between the coating material of the electric wire and can exhibit excellent discrimination and decorativeness. Moreover, if it is a coating film which consists of such kind, it is because it will reduce inhibiting repelletization at the time of recycling coating resin etc. Furthermore, since the method for producing an electric wire according to the present invention can partially perform a predetermined surface treatment and form a coating film only at a predetermined location, the coating film made of such a type may be used. In this case, obstruction of re-pelletization when the coating resin or the like is recycled is reduced.
On the other hand, in the case of an electric wire including such a coating film, conventionally, the processing cost for recycling is high, the processing time is long, and further, chemicals and release agents must be used, and the environment In particular, there was a problem that problems were likely to occur. On the other hand, if it is the manufacturing method of the electric wire of this invention, it is because the electric wire containing such various coating films can be surface-modified as it is, without removing previously, and can be newly shape | molded. . Therefore, the recycle process can be significantly shortened, and a composite electric wire with improved functionality and usefulness can be efficiently provided.

Moreover, it is preferable that an electric wire contains additives, such as various metal materials, ceramic materials (a filler and glass material are included), or a flame retardant (a halogen compound, a phosphorus compound, a silicon compound, etc.).
This is because an electric wire including such a metal material or ceramic material has a high electromagnetic shielding effect and is excellent in mechanical strength and durability.
Further, in the case of an electric wire containing a flame retardant, it is possible to effectively prevent the flame from spreading through the electric wire even if a fire occurs.
On the other hand, the electric wire obtained by the production method of the present invention can be easily recycled even if it contains such various metal materials, ceramic materials, or flame retardants. That is, the recycling process and time can be significantly shortened, and the molded product having a predetermined functionality (conductivity), mechanical characteristics, or flame retardancy can be regenerated.
In addition, when an electric wire contains additives, such as various metal materials, ceramic materials, or a flame retardant, although it is based also on the kind of the said additive, this addition amount is the total amount (100 weight%) of the coating | covering material of an electric wire. The value is preferably in the range of 0.1 to 50% by weight, more preferably in the range of 1 to 40% by weight, and the value in the range of 5 to 30% by weight. More preferably.

2. Surface Treatment Step (1) Surface Modification Device A surface modification device for carrying out the electric wire manufacturing method will be described with reference to the fluid flow shown in FIG.
First, the surface reforming apparatus 100 shown in the fluid flow basically includes a storage tank unit 102, a transfer path 105, a fuel gas storage tank 106, and a compressed air source 107. Are connected by piping.
That is, the storage tank portion 102 is a modifier compound containing silicon atoms, titanium atoms, and aluminum atoms, and includes an alkylsilane compound, an alkoxysilane compound, a siloxane compound, a silazane compound, an alkyl titanium compound, an alkoxy titanium compound, an alkyl A modifier compound 101 selected from the group consisting of an aluminum compound and an alkoxyaluminum compound is stored. Therefore, in the vaporizer (not shown) using vapor-liquid equilibrium, when the amount of the modifier compound decreases, it is added from the storage tank 102 for a while.
Note that a vaporizer (not shown) utilizing vapor-liquid equilibrium is provided inside or outside the storage tank unit 102 and vaporized by heating means 103 or natural evaporation. And the heating means 103 may mean including a vaporizer by natural evaporation.

Further, the transfer path 105 is a pipe for transferring the modifier compound 101 vaporized by the heating means 103 or natural evaporation in the vaporizer (not shown) toward the injection unit (burner) 104.
The surface reformer 100 is a storage tank 106 for hydrocarbon gas such as propane gas and LPG gas, which will be described later, combustion air for the hydrocarbon gas, and air (carrier) for transporting the modifier compound. Are further provided with a compressed air source 107.

A first mixer (sometimes referred to as a submixer) 108 and a second mixer (sometimes referred to as a main mixer) 109 are provided in the middle of the transfer path 105.
Here, the first mixer 108 includes a modifier compound vaporized in a vaporizer (not shown) (partially including air for transferring the vaporized modifier compound) and air from the compressed air source 107. Are uniformly mixed to obtain a primary fuel gas.
Further, the second mixer 109 may uniformly mix the primary fuel gas and the hydrocarbon gas transferred from the storage tank 106 to be called the final fuel gas (secondary fuel gas). ).
Furthermore, flow control valves 110, 111, 112 with flow meters for controlling the flow rate of the fluid are provided at the outlets of the storage tank unit 102, the compressed air source 107, and the storage tank 106, respectively. Yes.

Further, as shown in FIG. 2, a heating means 103 such as a heater is provided below the storage tank portion 102 for storing the modifier compound, which is liquid reforming at normal temperature and normal pressure. The agent compound 101 is configured to evaporate or vaporize.
The heating means 103 preferably has not only a heating function but also a cooling function, and switching is controlled by a central processing unit (CPU) (not shown). In other words, the CPU is electrically connected to a liquid quantity sensor, liquid temperature sensor, etc. of the modifier compound, and the liquid quantity and liquid temperature of the modifier compound are held at values and positions within a specified range. As described above, the temperature of the heating unit 103 and the additional supply amount from the storage tank unit 102 are controlled.
In addition, as the liquid quantity sensor and liquid temperature sensor of the modifier compound, since the consumption amount of the modifier compound per unit time is extremely small, the liquid quantity sensor using a prism sensor or infrared rays as the liquid quantity sensor. Or as a liquid temperature sensor, precision sensors, such as a thermostat and a thermocouple, are mentioned.

In the first embodiment, an example is given in which a liquid modifier compound is used at normal temperature and normal pressure, but a gas or solid modifier compound is also used at normal temperature and normal pressure. can do.
For example, when a gaseous modifier compound is used, the storage tank unit 102 does not need to be provided with a heater, but instead may be provided with a flow rate adjusting means such as a pressure adjusting valve. Therefore, it becomes difficult to be affected by the temperature of the modifier compound added from the storage tank 102 to the vaporizer (not shown), and it becomes easy to maintain a certain vapor-liquid equilibrium state.
When a solid modifier compound is used, for example, the solid compound is dissolved in a solvent or melted with heat, and the piped liquid transportation from the storage tank of this example to the vicinity of the flame of the burner is performed. A predetermined surface modification treatment can be performed by passing the tube through and directly feeding it into the burner.

Further, as described above in part, as shown in FIG. 2, the transfer unit 105 usually has a “pipe” structure, and is supplied from the compressed air source 107 and delivered from the storage tank 102. A first mixer 108 is provided for mixing the vaporized modifier compound to be mixed.
Further, a second mixer 109 is provided for further uniformly mixing the mixed gas mixed by the first submixer 108 and the fuel gas sent from the fuel gas storage tank 106.

Moreover, the injection part (burner) 104 burns the combustion gas sent through the transfer part 105 as shown in FIG. 2, and the obtained flame 113 is applied to the surface to be reformed (not shown). This is for spraying.
The combustion state of the flame 113 includes the flow rate of the vaporized modifier compound 101, the amount of combustion air sent from the compressed air source 107, and the flow rate of hydrocarbon gas sent from the storage tank 106. By adjusting the opening degree of the flow rate adjusting valves 110, 111, 112 with a flow meter provided in this pipe, the optimum state is appropriately adjusted.
The type of the burner in the injection unit is not particularly limited, and may be any of a premix burner, a diffusion burner, a partial premix burner, a spray burner, an evaporation burner, and the like. . Further, the form of the burner is not particularly limited.

(2) Fuel gas (2) -1 Modifier compound The modifier compound is a compound containing a silicon atom, a titanium atom or an aluminum atom, and can burn in a flame of a general gas burner. If there is no restriction in particular.
In view of easy availability and handling, for example, a group consisting of an alkylsilane compound, an alkoxysilane compound, a siloxane compound, a silazane compound, an alkyl titanium compound, an alkoxy titanium compound, an alkyl aluminum compound, and an alkoxy aluminum compound. It is preferable that it is at least one compound selected from.

  Here, preferable examples of the alkylsilane compound include methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, tetraethylsilane, dimethyldichlorosilane, dimethyldiphenylsilane, diethyldichlorosilane, diethyldiphenylsilane, methyltrichlorosilane, and methyltriphenyl. Monosilane compounds that may have substituents such as silane and dimethyldiethylsilane, disilane compounds that may have substituents such as hexamethyldisilane, hexaethyldisilane, and chloroheptamethyldisilane, and octamethyltrisilane And a trisilane compound which may have a substituent.

  As preferable examples of the alkoxysilane compound, methoxysilane, dimethoxysilane, trimethoxysilane, tetramethoxysilane, ethoxysilane, diethoxysilane, triethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethyl Methoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trichloromethoxysilane, trichloro One kind or a combination of two or more kinds such as ethoxysilane, triphenylmethoxysilane, and triphenylethoxysilane are listed. It is.

  Moreover, as a suitable example of a siloxane compound, tetramethyldisiloxane, pentamethyldisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethyl Examples include cyclohexasiloxane.

Moreover, as a suitable example of a silazane compound, hexamethyldisilazane etc. are mentioned.
Moreover, as a suitable example of an alkyl titanium compound, tetramethyl titanium, tetraethyl titanium, tetrapropyl titanium, etc. are mentioned.
Moreover, as a suitable example of an alkoxy titanium compound, titanium methoxide, titanium ethoxide, etc. are mentioned.
Further, preferred examples of the alkylaluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum and the like.
Moreover, as a suitable example of an alkoxy aluminum compound, aluminum methoxide, aluminum ethoxide, etc. are mentioned. These compounds may be used alone or in combination.

Among the preferred examples of the modifier compound, silane compounds, alkoxysilane compounds, siloxane compounds, and silazane compounds are more preferable because they are easy to handle, easily vaporized, and easily available.
In particular, the silicon-containing compound is more preferably a compound having at least one of a nitrogen atom, a halogen atom, a vinyl group and an amino group in the molecule or at the molecular end.
More specifically, hexamethyldisilazane (boiling point: 126 ° C), vinyltrimethoxysilane (boiling point: 123 ° C), vinyltriethoxysilane (boiling point: 161 ° C), trifluoropropyltrimethoxysilane (boiling point: 144 ° C). ), Trifluoropropyltrichlorosilane (boiling point: 113 to 114 ° C), 3-aminopropyltrimethoxysilane (boiling point: 215 ° C), 3-aminopropyltriethoxysilane (boiling point: 217 ° C), hexamethyldisiloxane (boiling point) : About 101 ° C.) and at least one compound of 3-chloropropyltrimethoxysilane (boiling point: 196 ° C.).
The reason for this is that such a silicon-containing compound improves the miscibility with the carrier gas, and forms a granular material (predetermined silica particles having a large number of hydroxyl groups on the surface) on the surface of the electric wire for modification. As it becomes more uniform and part of the silane compound tends to remain on the surface of the wire due to the boiling point, etc., it can obtain better adhesion between the wire and various powder coatings. This is because it can.

Further, the addition amount of the silicon-containing compound or the like as the modifier compound is preferably set to a value in the range of 1 × 10 ⁻¹⁰ to 10 mol% when the total amount of the fuel gas is 100 mol%. .
The reason for this is that when the amount of the silicon-containing compound or the like is less than 1 × 10 ⁻¹⁰ mol%, the modification effect on the electric wire may not be exhibited.
On the other hand, when the added amount of the silicon-containing compound or the like exceeds 10 mol%, the mixability of the silicon-containing compound or the like with air or the like is lowered, and the silicon-containing compound or the like may be incompletely combusted accordingly. .
Therefore, the addition amount of the silicon-containing compound or the like is more preferably set to a value in the range of 1 × 10 ^{−9 to} 5 mol% when the total amount of the gaseous substance is 100 mol%. A value in the range of ⁻⁸ to 1 mol% is more preferable.

Moreover, it is preferable to add an alcohol compound with a modifier compound in fuel gas.
This is because the added alcohol compound is uniformly dissolved with the modifier compound, and the adjustment of the boiling point and flash point of the mixture containing the modifier compound becomes easy. In addition, by adding such an alcohol compound, it is easy to adjust the color of the flame, and it can be confirmed that the flame is reliably burned together with the modifier compound.
Here, as such an alcohol compound, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, benzyl alcohol, etc., may be used singly or in combination of two or more.
Moreover, it is preferable to make the addition amount of the alcohol compound added with a modifier compound into the value within the range of 0.01-30 mol%, when the whole amount of a modifier compound is 100 mol%.
The reason for this is that when the amount of the alcohol compound added is less than 0.01 mol%, it may be difficult to adjust the boiling point or flash point of the mixture. On the other hand, if the amount of the alcohol compound added exceeds 30 mol%, the surface modification effect on the electric wire may not be exhibited.

(2) -2 Air / hydrocarbon gas In addition to the temperature control of the flame and the exertion of the carrier effect, predetermined silica particles having a large number of hydroxyl groups on the surface can be uniformly formed in the fuel gas. Therefore, a predetermined amount of air is used.
That is, a predetermined amount of air is introduced into the fuel gas and used as a part of the fuel gas of the flame.
Here, the content of such air is preferably set to a value in the range of 80 to 99.9 mol% when the total amount of the fuel gas is 100 mol%.
This is because when the air content is less than 80 mol%, not only the combustion of the silicon-containing compound is incomplete, but also the generation of hydroxyl groups may be insufficient. On the other hand, when the air content exceeds 99.9 mol%, the surface modification effect may not be sufficiently exhibited.
Accordingly, the air content is more preferably set to a value in the range of 90 to 99.5 mol%, and more preferably in the range of 93 to 99 mol%, when the total amount of the fuel gas is 100 mol%. More preferably, it is a value.
Air may be used as a carrier gas or may be added at the final stage of the fuel gas as long as the value of air / hydrocarbon gas can be finally adjusted to a predetermined range.

(2) -3 Hydrocarbon Gas The hydrocarbon gas contained in the fuel gas is preferably propane gas or LPG (liquefied petroleum gas other than propane gas alone).
This is because such a type of hydrocarbon gas is inexpensive and can be burned at a predetermined temperature. Accordingly, it is possible to stably thermally decompose the silicon-containing compound and the like, and for any of the electric wires, predetermined silica particles having a large number of hydroxyl groups on the surface can be firmly and uniformly laminated.
Examples of LPG include butane (normal butane, isobutane), mixed gas of butane / propane, ethane, pentane (normal pentane, isopentane, cyclopentane) and the like.
On the other hand, the content of such hydrocarbon gas is preferably set to a value in the range of 0.1 to 10 mol%, when the total amount of fuel gas is 100 mol%.
The reason for this is that when the hydrocarbon gas content is less than 0.1 mol%, the flame temperature is lowered and the combustion of silicon-containing compounds and the like becomes incomplete, and the generation of hydroxyl groups becomes insufficient. This is because there are cases. On the other hand, if the content of such hydrocarbon gas exceeds 10 mol%, incomplete combustion may occur, and similarly, the surface modification effect may not be sufficiently exhibited.
Therefore, the hydrocarbon gas content is more preferably set to a value within the range of 0.5 to 8 mol%, when the total amount of fuel gas is 100 mol%, and 0.8 to 5 mol%. It is more preferable to set the value within the range.

(2) -4 Air / Hydrocarbon Gas Mixing Molar Ratio Next, the air / hydrocarbon gas mixing molar ratio in the fuel gas will be described in detail with reference to FIGS.
First, FIG. 3A is a conceptual diagram of a surface modification state of the electric wire 12 by predetermined silica particles 150 having a large number of hydroxyl groups on the surface.
Moreover, FIG.3 (b) is a conceptual diagram of the predetermined silica particle 150 which has many hydroxyl groups on the surface.
That is, by using a specific fuel gas, predetermined silica particles having a large number of such hydroxyl groups on the surface can be easily laminated firmly and uniformly. Regardless of the conditions, a predetermined surface modification effect can be obtained for any of the electric wires.
The average particle diameter of the predetermined silica particles having a large number of such hydroxyl groups on the surface is not particularly limited, but is preferably set to a value in the range of 0.001 to 10 μm, for example, 0.01 to 2 μm. More preferably, the value is within the range of 0.05 to 0.8 μm.

4A to 4D are conceptual diagrams showing how the surface modification status by the predetermined silica particles 150 having a large number of hydroxyl groups on the surface changes according to the degree of treatment.
FIG. 4A shows the surface state of an untreated polyethylene-coated electric wire, and FIG. 4B shows the surface modification when the surface treatment based on Example 1 is performed for 0.6 seconds. It shows the quality situation.
Therefore, by comparing the two, it is understood that predetermined silica particles having a large number of hydroxyl groups on the surface of the polyethylene-coated electric wire are sparsely attached.
That is, by using a specific fuel gas, predetermined silica particles having a large number of such hydroxyl groups on the surface can be easily and firmly laminated on the surface of the polyethylene-coated electric wire. Regardless of the difference and the surrounding environmental conditions, it can be said that a predetermined surface modification effect is obtained for any of the electric wires.

Here, FIG.4 (c) has shown the surface modification condition at the time of implementing the surface treatment based on Example 1 for 1 second with respect to the polyethylene-coated electric wire of Fig.4 (a). Therefore, by comparing the two, it is understood that the predetermined silica particles having a large number of hydroxyl groups on the surface of the polyethylene-coated electric wire are considerably uniformly and considerably attached.
Furthermore, FIG.4 (d) has shown the surface modification condition at the time of implementing the surface treatment based on Example 1 for 2 seconds with respect to the polyethylene covering electric wire of Fig.4 (a). Therefore, by comparing the two, it is understood that a part of the predetermined silica particles having a large number of hydroxyl groups on the surface of the polyethylene-coated electric wire are continuously attached in a large amount.
That is, when the predetermined silica particles having a large number of hydroxyl groups on the surface adhere, for example, in the state of FIGS. 4B to 4D, the value of the wetting index increases, and a predetermined surface modification effect is obtained. It can be said that.
However, in the case of the silica particles shown in FIG. 4 (d), the amount of hydroxyl groups on the surface tends to be less than that of the silica particles in FIGS. 4 (b) to 4 (d) depending on the elemental analysis method. Yes.
Therefore, what is important in the present invention is that the predetermined silica particles having a large number of hydroxyl groups on the surface are attached to the surface of the electric wire, and a large amount of silica particles not having a large number of hydroxyl groups are adhered to the surface. Even so, it can be said that an excellent surface modification effect cannot be obtained.

Moreover, the amount of hydroxyl groups on the surface of the silica particles can be estimated using, for example, FT-IR. That is, in the infrared absorption chart obtained by FT-IR, the peak height (P2) near 3400 cm ⁻¹ attributed to adsorbed water and the peak height (P1) near 3600 cm ⁻¹ attributed to a free hydroxyl group are expressed. In comparison, a value within a predetermined range is preferable in obtaining an excellent surface modification effect.
For example, the numerical value represented by P1 / P2 is preferably about 0.2 to 1.0, more preferably about 0.3 to 0.9, and further about 0.4 to 0.8. It can be said that it is preferable.
On the other hand, if a numerical value of P1 / P2 in such a range is obtained, it can be said that the silica particles have a predetermined number of hydroxyl groups on the surface.

The amount of hydroxyl groups on the surface of the silica particles can also be estimated by XPS (X-ray Photoelectron Spectroscopy). That is, in the elemental analysis data on the particle surface obtained by XPS, if the Si: O ratio is in the range of 1: 2.2 to 1: 3.2, the amount of hydroxyl groups on the surface of the silica particles is large, It can be said that it is preferable in obtaining an excellent surface modification effect.
Accordingly, the Si: O ratio is more preferably in the range of 1: 2.5 to 1: 3.0, and more preferably in the range of 1: 2.6 to 1: 2.9. I can say that.
On the contrary, if a Si: O ratio in such a range is obtained, it can be said that the silica particles have a predetermined number of hydroxyl groups on the surface.
In addition, in the elemental analysis data on the particle surface obtained by XPS, C (carbon) data is obtained at the same time, and if the Si: C ratio is in the range of 1: 0.0001 to 0.1, silica particles It can be further estimated that the amount of hydroxyl groups is large, not the amount of carboxyl groups on the surface.

Next, the reason why the air / hydrocarbon gas mixture molar ratio in the fuel gas is set to a value of 23 or more will be described in more detail with reference to FIG.
Here, FIG. 5 shows data based on Example 1 and the like, in which the horizontal axis represents the mixed molar ratio (−) of air / hydrocarbon gas, and the vertical axis represents the polyethylene-coated electric wire. The wetting index (dyn / cm) on the surface is taken.

As can be understood from FIG. 5, when the air / hydrocarbon gas mixture molar ratio is about 10 to 20, the surface modification effect is hardly obtained. That is, although the surface treatment is performed, only a value of about 30 dyn / cm, which is a wetting index (corresponding to surface tension) with respect to an untreated polyethylene-coated electric wire, is obtained.
Next, when the air / hydrocarbon gas mixture molar ratio is in the range of more than 20 to about 22, the wetting index value tends to increase slightly, but after all it is about 30 dyn / cm, and the increase is It is understood that the surface modification effect is not yet obtained.

On the other hand, when the air / hydrocarbon gas mixture molar ratio is in the range of about 23 to 25, the wetting index increases remarkably and is about 45 to 58 dyn / cm. It is understood that it is obtained.
In addition, when the air / hydrocarbon gas mixture molar ratio is in the range of about 25 to 38, the wetting index increases remarkably and is about 70 to 72 dyn / cm. It is understood that
Therefore, as shown in FIG. 5, when the mixed molar ratio of air / hydrocarbon gas in the fuel gas is less than 23, the surface reforming effect is not stably exhibited, the flame becomes easy to extinguish, or incomplete combustion occurs. Therefore, it can be said that it is not preferable.

  However, when the mixed molar ratio of air / hydrocarbon gas exceeds 40, on the contrary, there is a tendency that the value of the obtained wetting index slightly varies. This is presumed to be because the flame is not stable if air is present in an excessive amount due to the air / hydrocarbon gas mixture molar ratio.

Therefore, by using a fuel gas having an air / hydrocarbon gas mixing molar ratio of 23 or more in this way, regardless of the difference in boiling point of silicon-containing compounds and the surrounding environmental conditions, In addition, predetermined silica particles having a large number of hydroxyl groups on the surface can be laminated firmly and uniformly. Therefore, even when a coating film made of a thermosetting resin paint or an ultraviolet curable paint is formed on the surface-treated electric wire, excellent adhesion can be obtained between the electric wire and the coating film. it can.
However, since there is little variation and the surface reforming effect is more stably exhibited, the air / hydrocarbon gas mixture molar ratio in the fuel gas is more preferably set to a value in the range of 24 to 45. 25 More preferably, the value is in the range of -38, and more preferably in the range of 28-35.

(3) Surface treatment conditions Moreover, regarding the surface treatment conditions, the flame temperature is preferably set to a value in the range of 500 to 1500C.
This is because it may be difficult to effectively prevent incomplete combustion of the silicon-containing compound when the flame temperature is less than 500 ° C.
On the other hand, when the flame temperature exceeds 1,500 ° C., the electric wire to be surface-modified may be thermally deformed or thermally deteriorated, and the types of electric wires that can be used are excessively limited. Because there is.
Therefore, the flame temperature is preferably set to a value within the range of 550 to 1 and 200 ° C, and more preferably set to a value within the range of 600 to less than 900 ° C.

Moreover, it is preferable to set the flame spraying time (injection time) to a value within the range of 0.1 to 100 seconds per unit area (100 cm ² ).
This is because when the injection time is less than 0.1 seconds, the modification effect by the silicon-containing compound or the like may not be expressed uniformly.
On the other hand, if the injection time exceeds 100 seconds, the electric wire to be surface-modified may be thermally deformed or thermally deteriorated, and the types of usable electric wires may be excessively limited. Because.
Therefore, the injection time is preferably set to a value in the range of 0.3 to 30 seconds per unit area (100 cm ² ), and more preferably set to a value in the range of 0.5 to 20 seconds.

3. Manufacturing method of electric wire As a manufacturing method of an electric wire, what makes the above-mentioned electric wire (cable) into a manufacturing object and includes the surface treatment process mentioned above should just be included. Therefore, typically, the method for manufacturing such an electric wire preferably includes each step as shown in FIG.
That is, the kneading process shown by S1 is a process which adds a predetermined additive and a coloring agent to vinyl chloride resin, polyethylene resin, etc. for covering an electric wire, and makes it a uniform resin composition.
Moreover, the wire drawing process shown by S2 is a process of manufacturing the conductor of an electric wire. Moreover, the insulation process shown by S3 is a process of coat | covering the resin composition obtained at the kneading | mixing process on a conductor. As needed, the process of heating and crosslinking a resin composition is also included.

Moreover, the twisting process shown by S4 is a process which winds a tape etc. in order to carry out collective twisting of the electric wire which carried out twisting and quad twisting, and to bundle it further.
Moreover, the braiding process shown by S5 is a process of coat | covering the electromagnetic wave shielding material.
Moreover, the sheath process shown by S6 is a process which uses the twisted electric wire as a core, and further coats the resin composition obtained in the kneading process around it to form a sheath.
Moreover, the surface treatment process shown by S7 is a process of performing silicic acid flame treatment, for example, on the whole or a part of the sheath.
Furthermore, the inspection process indicated by S8 is a process for confirming that the electrical characteristics and mechanical strength of the obtained electric wire are within a predetermined range.
And although not shown in figure, it is preferable to provide a coating process between a surface treatment process and an inspection process for the identification and decoration of the obtained electric wire.

Therefore, it can be set as the surface state of an electric wire as shown to FIG.7 (a)-(c), respectively. That is, as shown in FIG. 7 (a), silica particles 201 having a large number of hydroxyl groups obtained by silicic acid flame treatment on the surface are formed on an insulating coating material 200, on which a coating film 202 is formed. Thus, an electric wire (partial cross section) 210 in which is formed can be obtained.
Moreover, as shown in FIG.7 (b), the silica particle 201 which has many hydroxyl groups obtained by the silicic acid flame process on the surface is formed on the insulation coating material 200, and the metal layer 202a on it. In addition, an electric wire (partial cross section) 210 ′ on which the coating film 202 is formed can be obtained.
Further, as shown in FIG. 7C, silica particles 201b (first layer) having a large number of hydroxyl groups obtained by silicic acid flame treatment on the surface are formed on the insulating coating material 200. In addition, after the metal layer 202a is once formed, silica particles 201a (second layer) are formed, and an electric wire (partial cross section) 210 ″ having a coating film 202 formed thereon is obtained. Can do.

[Example 1]
1. Electric Wire Manufacturing Method (1) Preparation Step In Example 1, a coated electric wire (φ5 mm) made of a crosslinked polyethylene resin was prepared as an electric wire.
That is, the electric wire 10 as shown to Fig.1 (a) was prepared, and the surface was fully wash | cleaned using isopropyl alcohol (IPA).

(2) Surface treatment step Next, a surface modification layer having a thickness of the order of nm is obtained by subjecting the prepared electric wire to surface modification treatment using the surface modification apparatus 100 shown in FIG. 5 under the following modification conditions. Formed. In addition, it was confirmed that this surface modification layer is a discontinuous layer composed of silica particles having a large number of hydroxyl groups on the surface.

(Surface modification conditions)
Type of modifier compound: Tetramethylsilane (boiling point: 27 ° C)
Modifier compound containing air: 1.3 (liter / min)
Discharge amount of fuel gas: Propane gas air flow rate (Air): 84 (liter / min)
Gas flow rate (LPG): 3.0 (liter / min)
Air / hydrocarbon gas: 28
Mixing molar ratio treatment time: 5 seconds / 100 cm ²
Environmental conditions: 25 ° C, 50% Rh
When the total amount of the modifier compound containing air is 100 mol%, the content of the modifier compound is about 0.0002 mol%. Hereinafter, the content of the modifier compound is the same.

(3) Coating-film formation process Next, the surface of the surface-treated electric wire was coated with a polyurethane acrylate UV curable coating material: IMS-007 (manufactured by Ishimat Japan Co., Ltd.) using polyurethane acrylate as a prepolymer.
Thereafter, the UV curable coating material was cured with ultraviolet rays using an ultraviolet irradiation device (exposure amount: 800 mJ / cm ² , UV lamp) to form a coating film having a thickness of 15 μm.
By using the above-mentioned UV curable coating material, the coating film became a clear decorative layer of clear color.

2. Evaluation (1) Adhesion A cross-cut test (JIS standard) was carried out, and the adhesion between the electric wire and the coating film was evaluated based on the following criteria.
(Double-circle): There is no peeling at all in the 100 cross section test (JIS standard).
A: The number of peeling is 3 or less in a 100 cross section test (JIS standard).
(Triangle | delta): The number of peeling is 10 or less in a 100 cross section test (JIS standard).
X: The number of peeling is 10 or more in 100 cross-cut test (JIS standard).

(2) Environmental characteristics The surface conditions are the same as described above except that the environmental conditions for the surface modification treatment are 40 ° C. and 95% Rh. The adhesion was evaluated.
(Double-circle): There is no peeling at all in the 100 cross section test (JIS standard).
A: The number of peeling is 3 or less in a 100 cross section test (JIS standard).
(Triangle | delta): The number of peeling is 10 or less in a 100 cross section test (JIS standard).
X: The number of peeling is 10 or more in 100 cross-cut test (JIS standard).

[Examples 2 to 5, Comparative Example 1]
In Examples 2 to 5 and Comparative Example 1, adhesion and environmental characteristics were evaluated in the same manner as in Example 1 by changing the mixed molar ratio (20 to 40) of air / hydrocarbon gas (LPG) in the fuel gas. . The obtained results are shown in Table 1.

[Examples 6 to 10, Comparative Example 2]
In Examples 6 to 10 and Comparative Example 2, a hexamethyldisiloxane / ethyl alcohol mixture (weight ratio 99: 1) was used as the modifier compound instead of the tetramethylsilane compound, and the boiling point (measured under atmospheric pressure). The adhesiveness and environmental characteristics were evaluated in the same manner as in Example 1 except that the temperature was 90 ° C. or lower. The obtained results are shown in Table 2.

According to the present invention, a flame comprising a fuel gas containing a predetermined modifier compound and having a controlled molar ratio of air / hydrocarbon gas is blown against the surface of the electric wire, thereby Regardless of the difference in boiling point or the surrounding environmental conditions, predetermined silica particles having a large number of hydroxyl groups on the surface can be laminated firmly and uniformly on any electric wire.
That is, by using such a specific fuel gas and surface-treating an electric wire coated with a polyethylene resin having a low surface tension, predetermined silica particles having a large number of hydroxyl groups on the surface can be made strong and uniform. Can be laminated. Therefore, the friction coefficient on the surface of the electric wire is reduced, and the production speed (winding speed, unwinding speed, etc.) can be remarkably increased without deteriorating the electric characteristics of the electric wire.

Moreover, since the wettability of the surface is remarkably improved at an arbitrary position of the electric wire, it is possible to print directly on the electric wire, decorate it, and further improve the sealing performance in the wire harness.
Furthermore, if the electric wire is obtained through such a surface treatment, not only re-pelletization when recycling the coating resin or the like is facilitated, but it can be integrally formed with high accuracy using a press device or the like. .
In addition, on the surface of the electric wire thus manufactured, predetermined silica particles having a large number of hydroxyl groups on the surface are protruded and laminated, so that the frictional resistance is reduced and wound in a roll shape. In addition, excessive tightening of the electric wire can be prevented, and rewinding or the like can be easily performed.
Therefore, the manufacturing method of the electric wire of the present invention not only simplifies the manufacturing process and the manufacturing time, but also improves the handleability of the electric wire or the processing time when recycling, compared with the conventional electric wire manufacturing method. It can be said that this is a very advantageous new technology from the viewpoints of economy and environment.

(A)-(c) is a figure provided in order to demonstrate the one aspect | mode of an electric wire, respectively. It is a figure which shows the fluid flow based on a surface modification apparatus. (A)-(b) is a figure provided in order to demonstrate the predetermined | prescribed silica particle which has many surface modification conditions and the hydroxyl group on the surface of a recycled material. (A)-(d) is a figure provided in order to demonstrate a surface modification condition. It is a figure provided in order to demonstrate the relationship between the mixing molar ratio of air / hydrocarbon gas, and a wetting index. It is a figure provided in order to demonstrate the manufacturing process of an electric wire. (A)-(c) is a figure provided in order to demonstrate the partial surface state of an electric wire, respectively.

Explanation of symbols

10, 10 ′, 10 ″: Electric wire 12: Insulation coating material 13: Surface modified layer (predetermined silica particles having a large number of hydroxyl groups on the surface)
14: Conductor 15: Coating film 20: Band 22: Cable 100: Surface modification device 101: Modifier compound 102: Storage tank unit 103: Heating means 104: Injection unit (burner)
105: transfer section 106: storage tank 107: compressed air source 108: first mixer 109: second mixer 110-112: flow control valve 113: flame 150: silica particles having many hydroxyl groups on the surface (modifier particles) )
152: Base material 200: Insulation coating material 201, 201a, 201b: Surface modified layer (silica particles having many hydroxyl groups on the surface)
202: Coating film 202a: Metal layer

According to the present invention, the coating material includes a step of blowing a flame derived from a fuel gas containing a silicon-containing compound as a modifier compound containing silicon atoms , air, and propane gas or LPG as a hydrocarbon gas. a wire-producing method of having a boiling point of the silicon-containing compound as a modifying agent compound (760 mmHg) to a value within the range of 20 to 250 [° C., the content of the modifying compound, the total fuel gas When the amount is 100 mol% , the value is within the range of 1 × 10 ⁻¹⁰ to 10 mol%, and when the hydrocarbon gas content is 100 mol%, the total amount of the fuel gas is 0.1%. Provided is a method of manufacturing an electric wire having a value in the range of 1 to 5 mol% and an air / hydrocarbon gas mixture molar ratio in the fuel gas in a range of 25 to 40, and solves the above-described problems can do.
That is, using such a specific fuel gas, surface treatment is performed on an electric wire coated with a polyethylene resin or the like having a low surface tension, whereby predetermined silica particles having a large number of hydroxyl groups on the surface can be made strong and uniform. Can be stacked.
Therefore, the friction coefficient on the surface of the electric wire is reduced, and the production speed such as the winding speed can be remarkably increased without deteriorating the electric characteristics of the electric wire. Moreover, since the wettability of the surface is remarkably improved at an arbitrary position of the electric wire, it is possible to print directly on the electric wire, decorate it, and further improve the sealing performance in the wire harness. Furthermore, not only re-pelletization when recycling the coating resin of the electric wire is facilitated, but it can be integrally formed with high accuracy using a press device or the like.
Moreover, if it is such kind of hydrocarbon gas and content, while it is cheap, it can combust at predetermined temperature. Accordingly, it is possible to stably thermally decompose silicon-containing compounds and the like and to firmly and uniformly laminate predetermined silica particles having a large number of hydroxyl groups on the surface of any solid substance.
Also, if it is a silicon-containing compound having such a boiling point, the concentration in the fuel gas can be easily controlled by evaporating stably using not only the heat of vaporization but also a vaporizer, etc. It is possible to effectively suppress the occurrence of the dew condensation phenomenon based on the temperature change and concentration change in the inside.
Furthermore, with such a modifier compound content, not only the heat of vaporization but also a vaporizer or the like can be used to stably evaporate or control the flow rate to change the temperature in the pipe. It is possible to effectively suppress the occurrence of the dew condensation phenomenon based on the concentration change. Moreover, since it will thermally decompose stably if it is content of such a modifier compound, a predetermined | prescribed surface treatment can be effectively implemented with respect to the surface of an electric wire.

Moreover, when implementing the manufacturing method of the electric wire of this invention, it is preferable that a modifier compound is at least 1 compound selected from the group which consists of an alkylsilane compound , an alkoxysilane compound, a siloxane compound, and a silazane compound .
With these types of silicon-containing compounds, etc., stable vaporization is achieved not only by controlling the concentration in the fuel gas, but also by stably evaporating using its own vapor pressure. Therefore, for any electric wire, predetermined silica particles having a large number of hydroxyl groups on the surface can be easily formed as the predetermined surface treatment.

An embodiment of the present invention is a coating comprising a step of blowing a flame derived from a fuel gas comprising a silicon-containing compound as a modifier compound containing silicon atoms, air, and propane gas or LPG as a hydrocarbon gas. A method of manufacturing an electric wire provided with a material, wherein a boiling point (760 mmHg) of a silicon-containing compound as a modifier compound is set to a value within a range of 20 to 250 ° C., and the content of the modifier compound When the total amount is 100 mol% , the value is in the range of 1 × 10 ⁻¹⁰ to 10 mol%, and the hydrocarbon gas content is 0 when the total amount of fuel gas is 100 mol%. This is a method of manufacturing an electric wire having a value in the range of 1 to 5 mol% and an air / hydrocarbon gas mixture molar ratio in the fuel gas in a range of 25 to 40.
That is, using a predetermined surface reformer, a flame composed of a predetermined modifier compound and a fuel gas containing air / hydrocarbon gas or the like is sprayed on the surface of the electric wire under predetermined surface treatment conditions. Predetermined silica particles having a large number of hydroxyl groups on the surface can be formed.
Therefore, it is possible to remarkably increase the winding speed, to improve the printing property, the decorative property, or the sealing property in the wire harness, and to improve the recyclability of the coating resin of the electric wire.

2. Surface Treatment Step (1) Surface Modification Device A surface modification device for carrying out the electric wire manufacturing method will be described with reference to the fluid flow shown in FIG.
First, the surface reforming apparatus 100 shown in the fluid flow basically includes a storage tank unit 102, a transfer path 105, a fuel gas storage tank 106, and a compressed air source 107. Are connected by piping.
That is, the storage tank unit 102 stores a modifier compound 101 containing a silicon atom and selected from the group consisting of an alkylsilane compound , an alkoxysilane compound, a siloxane compound, and a silazane compound. is there. Therefore, in the vaporizer (not shown) using vapor-liquid equilibrium, when the amount of the modifier compound decreases, it is added from the storage tank 102 for a while.
Note that a vaporizer (not shown) utilizing vapor-liquid equilibrium is provided inside or outside the storage tank unit 102 and vaporized by heating means 103 or natural evaporation. And the heating means 103 may mean including a vaporizer by natural evaporation.

(2) Fuel gas (2) -1 Modifier compound The modifier compound is a compound containing a silicon atom and can be burned in the flame of a general gas burner. Absent.
In view of easy availability and handling, for example, it is preferably at least one compound selected from the group consisting of an alkylsilane compound , an alkoxysilane compound, a siloxane compound, and a silazane compound .

  Moreover, as a suitable example of a silazane compound, hexamethyldisilazane etc. are mentioned.

(2) -3 Hydrocarbon gas
The hydrocarbon gas contained in the fuel gas is propane gas or LPG (liquefied petroleum gas other than propane gas alone).
This is because such a type of hydrocarbon gas is inexpensive and can be burned at a predetermined temperature. Accordingly, it is possible to stably thermally decompose the silicon-containing compound and the like, and for any of the electric wires, predetermined silica particles having a large number of hydroxyl groups on the surface can be firmly and uniformly laminated.
Examples of LPG include butane (normal butane, isobutane), mixed gas of butane / propane, ethane, pentane (normal pentane, isopentane, cyclopentane) and the like.
On the other hand, the content of such hydrocarbon gas is preferably set to a value in the range of 0.1 to 5 mol% when the total amount of fuel gas is 100 mol%.
The reason for this is that when the hydrocarbon gas content is less than 0.1 mol%, the flame temperature is lowered and the combustion of silicon-containing compounds and the like becomes incomplete, and the generation of hydroxyl groups becomes insufficient. This is because there are cases. On the other hand, when the content of the hydrocarbon gas exceeds 5 mol%, incomplete combustion occurs, and similarly, the surface modification effect may not be sufficiently exhibited.
Therefore, the hydrocarbon gas content is more preferably set to a value within the range of 0.5 to 5 mol% , when the total amount of fuel gas is 100 mol%, and 0.8 to 5 mol%. It is more preferable to set the value within the range.

Therefore, by using the fuel gas having an air / hydrocarbon gas mixture molar ratio of 25 or more and 40 or less in this way, any wire can be used regardless of the difference in boiling point of silicon-containing compounds and the surrounding environmental conditions. On the other hand, predetermined silica particles having a large number of hydroxyl groups on the surface can be laminated firmly and uniformly. Therefore, even when a coating film made of a thermosetting resin paint or an ultraviolet curable paint is formed on the surface-treated electric wire, excellent adhesion can be obtained between the electric wire and the coating film. it can.
However, since the variation is small and the surface reforming effect is more stably exhibited, the air / hydrocarbon gas mixture molar ratio in the fuel gas is more preferably set to a value in the range of 25 to 38. More preferably, the value is in the range of -35.

According to the present invention, the coating material includes a step of blowing a flame derived from a fuel gas containing a silicon-containing compound as a modifier compound containing silicon atoms, air, and propane gas or LPG as a hydrocarbon gas. The boiling point (760 mmHg) of the silicon-containing compound as the modifier compound is set to a value in the range of 20 to 250 ° C., and the content of the modifier compound is adjusted to the entire fuel gas. When the amount is 100 mol%, the value is within the range of 1 × 10 ⁻¹⁰ to 10 mol%, and when the hydrocarbon gas content is 100 mol%, the total amount of the fuel gas is 0.1%. Provided is a method of manufacturing an electric wire having a value within a range of 1 to 5 mol% and an air / hydrocarbon gas mixture molar ratio in a fuel gas within a range of 30 to 40, and solves the above-described problems can do.
That is, using such a specific fuel gas, surface treatment is performed on an electric wire coated with a polyethylene resin or the like having a low surface tension, whereby predetermined silica particles having a large number of hydroxyl groups on the surface can be made strong and uniform. Can be stacked.
Therefore, the friction coefficient on the surface of the electric wire is reduced, and the production speed such as the winding speed can be remarkably increased without deteriorating the electric characteristics of the electric wire. Moreover, since the wettability of the surface is remarkably improved at an arbitrary position of the electric wire, it is possible to print directly on the electric wire, decorate it, and further improve the sealing performance in the wire harness. Furthermore, not only re-pelletization when recycling the coating resin of the electric wire is facilitated, but it can be integrally formed with high accuracy using a press device or the like.
Moreover, if it is such kind of hydrocarbon gas and content, while it is cheap, it can combust at predetermined temperature. Accordingly, it is possible to stably thermally decompose silicon-containing compounds and the like and to firmly and uniformly laminate predetermined silica particles having a large number of hydroxyl groups on the surface of any solid substance.
Also, if it is a silicon-containing compound having such a boiling point, the concentration in the fuel gas can be easily controlled by evaporating stably using not only the heat of vaporization but also a vaporizer, etc. It is possible to effectively suppress the occurrence of the dew condensation phenomenon based on the temperature change and concentration change in the inside.
Furthermore, with such a modifier compound content, not only the heat of vaporization but also a vaporizer or the like can be used to stably evaporate or control the flow rate to change the temperature in the pipe. It is possible to effectively suppress the occurrence of the dew condensation phenomenon based on the concentration change. Moreover, since it will thermally decompose stably if it is content of such a modifier compound, a predetermined | prescribed surface treatment can be effectively implemented with respect to the surface of an electric wire.

An embodiment of the present invention is a coating comprising a step of blowing a flame derived from a fuel gas comprising a silicon-containing compound as a modifier compound containing silicon atoms, air, and propane gas or LPG as a hydrocarbon gas. A method of manufacturing an electric wire provided with a material, wherein a boiling point (760 mmHg) of a silicon-containing compound as a modifier compound is set to a value within a range of 20 to 250 ° C., and the content of the modifier compound When the total amount is 100 mol%, the value is in the range of 1 × 10 ⁻¹⁰ to 10 mol%, and the hydrocarbon gas content is 0 when the total amount of fuel gas is 100 mol%. This is a method of manufacturing an electric wire having a value in the range of 1 to 5 mol% and an air / hydrocarbon gas mixture molar ratio in the fuel gas in the range of 30 to 40 .
That is, using a predetermined surface reformer, a flame composed of a predetermined modifier compound and a fuel gas containing air / hydrocarbon gas or the like is sprayed on the surface of the electric wire under predetermined surface treatment conditions. Predetermined silica particles having a large number of hydroxyl groups on the surface can be formed.
Therefore, it is possible to remarkably increase the winding speed, to improve the printing property, the decorative property, or the sealing property in the wire harness, and to improve the recyclability of the coating resin of the electric wire.

Therefore, by using the fuel gas having an air / hydrocarbon gas mixture molar ratio of 30 or more and 40 or less in this way, any wire can be used regardless of the difference in boiling point of silicon-containing compounds and the surrounding environmental conditions. On the other hand, predetermined silica particles having a large number of hydroxyl groups on the surface can be laminated firmly and uniformly. Therefore, even when a coating film made of a thermosetting resin paint or an ultraviolet curable paint is formed on the surface-treated electric wire, excellent adhesion can be obtained between the electric wire and the coating film. it can.
However, since there is little variation and the surface reforming effect is more stably exhibited, the air / hydrocarbon gas mixture molar ratio in the fuel gas is more preferably set to a value in the range of 30 to 38. More preferably, the value is in the range of -35 .

[Reference Example 1]
1. Electric Wire Manufacturing Method (1) Preparation Step In Example 1, a coated electric wire (φ5 mm) made of a crosslinked polyethylene resin was prepared as an electric wire.
That is, the electric wire 10 as shown to Fig.1 (a) was prepared, and the surface was fully wash | cleaned using isopropyl alcohol (IPA).

[ Reference Examples 6-7, Examples 8-10 , Comparative Example 2]
In Reference Examples 6-7, Examples 8-10 , and Comparative Example 2, a hexamethyldisiloxane / ethyl alcohol mixture (weight ratio 99: 1) was used as the modifier compound instead of the tetramethylsilane compound, and the boiling point Adhesion and environmental characteristics were evaluated in the same manner as in Example 1 except that (measurement under atmospheric pressure) was 90 ° C. or lower. The obtained results are shown in Table 2.

According to the present invention, the coating material includes a step of blowing a flame derived from a fuel gas containing a silicon-containing compound as a modifier compound containing silicon atoms, air, and propane gas or LPG as a hydrocarbon gas. The boiling point (760 mmHg) of the silicon-containing compound as the modifier compound is set to a value in the range of 20 to 250 ° C., and the content of the modifier compound is adjusted to the entire fuel gas. When the amount is 100 mol%, the value is within the range of 1 × 10 ⁻¹⁰ to 10 mol%, and when the hydrocarbon gas content is 100 mol%, the total amount of the fuel gas is 0.1%. Provided is a method of manufacturing an electric wire having a value in the range of 1 to 5 mol% and a mixed molar ratio of air / hydrocarbon gas in the fuel gas in a range of 30 to 38, and solves the above-mentioned problems can do.
That is, using such a specific fuel gas, surface treatment is performed on an electric wire coated with a polyethylene resin or the like having a low surface tension, whereby predetermined silica particles having a large number of hydroxyl groups on the surface can be made strong and uniform. Can be stacked.
Therefore, the friction coefficient on the surface of the electric wire is reduced, and the production speed such as the winding speed can be remarkably increased without deteriorating the electric characteristics of the electric wire. Moreover, since the wettability of the surface is remarkably improved at an arbitrary position of the electric wire, it is possible to print directly on the electric wire, decorate it, and further improve the sealing performance in the wire harness. Furthermore, not only re-pelletization when recycling the coating resin of the electric wire is facilitated, but it can be integrally formed with high accuracy using a press device or the like.
Moreover, if it is such kind of hydrocarbon gas and content, while it is cheap, it can combust at predetermined temperature. Accordingly, it is possible to stably thermally decompose silicon-containing compounds and the like and to firmly and uniformly laminate predetermined silica particles having a large number of hydroxyl groups on the surface of any solid substance.
Also, if it is a silicon-containing compound having such a boiling point, the concentration in the fuel gas can be easily controlled by evaporating stably using not only the heat of vaporization but also a vaporizer, etc. It is possible to effectively suppress the occurrence of the dew condensation phenomenon based on the temperature change and concentration change in the inside.
Furthermore, with such a modifier compound content, not only the heat of vaporization but also a vaporizer or the like can be used to stably evaporate or control the flow rate to change the temperature in the pipe. It is possible to effectively suppress the occurrence of the dew condensation phenomenon based on the concentration change. Moreover, since it will thermally decompose stably if it is content of such a modifier compound, a predetermined | prescribed surface treatment can be effectively implemented with respect to the surface of an electric wire.

An embodiment of the present invention is a coating comprising a step of blowing a flame derived from a fuel gas comprising a silicon-containing compound as a modifier compound containing silicon atoms, air, and propane gas or LPG as a hydrocarbon gas. A method of manufacturing an electric wire provided with a material, wherein a boiling point (760 mmHg) of a silicon-containing compound as a modifier compound is set to a value within a range of 20 to 250 ° C., and the content of the modifier compound When the total amount is 100 mol%, the value is in the range of 1 × 10 ⁻¹⁰ to 10 mol%, and the hydrocarbon gas content is 0 when the total amount of fuel gas is 100 mol%. A method for producing an electric wire having a value in the range of 1 to 5 mol% and a mixed molar ratio of air / hydrocarbon gas in the fuel gas in a range of 30 to 38.
That is, using a predetermined surface reformer, a flame composed of a predetermined modifier compound and a fuel gas containing air / hydrocarbon gas or the like is sprayed on the surface of the electric wire under predetermined surface treatment conditions. Predetermined silica particles having a large number of hydroxyl groups on the surface can be formed.
Therefore, it is possible to remarkably increase the winding speed, to improve the printing property, the decorative property, or the sealing property in the wire harness, and to improve the recyclability of the coating resin of the electric wire.

Therefore, by using the fuel gas having an air / hydrocarbon gas mixture molar ratio of 30 or more and 38 or less in this way, regardless of the difference in boiling point of the silicon-containing compound or the like and the surrounding environmental conditions, On the other hand, predetermined silica particles having a large number of hydroxyl groups on the surface can be laminated firmly and uniformly. Therefore, even when a coating film made of a thermosetting resin paint or an ultraviolet curable paint is formed on the surface-treated electric wire, excellent adhesion can be obtained between the electric wire and the coating film. it can.
However, it is more preferable to set the air / hydrocarbon gas mixture molar ratio in the fuel gas to a value within the range of 30 to 35 because there is little variation and the surface reforming effect is more stably exhibited .

[Examples 2-3, Reference Examples 4-5, and Comparative Example 1]
In Examples 2 to 3, Reference Examples 4 to 5, and Comparative Example 1 , adhesion was performed in the same manner as in Example 1 by changing the air / hydrocarbon gas (LPG) mixture molar ratio (20 to 40) in the fuel gas. Sexuality and environmental characteristics were evaluated. The obtained results are shown in Table 1.

[Reference Examples 6-7, Examples 8-9, Reference Example 10, and Comparative Example 2]
In Reference Examples 6 to 7, Examples 8 to 9, Reference Example 10, and Comparative Example 2, as a modifier compound, a hexamethyldisiloxane / ethyl alcohol mixture (weight ratio 99: 1) was used instead of the tetramethylsilane compound. ) And the boiling point (measured under atmospheric pressure) was set to 90 ° C. or lower, and the adhesion and environmental characteristics were evaluated in the same manner as in Example 1 and the like. The obtained results are shown in Table 2.

Claims (8)

A method for producing an electric wire comprising a step of blowing a flame derived from a fuel gas containing a modifier compound containing a silicon atom, a titanium atom or an aluminum atom, air, and a hydrocarbon gas,
A method for producing an electric wire, wherein a mixing molar ratio of air / hydrocarbon gas in the fuel gas is set to a value of 23 or more.   The method for producing an electric wire according to claim 1, wherein the hydrocarbon gas is propane gas or LPG.   The modifier compound is at least one compound selected from the group consisting of alkylsilane compounds, alkoxysilane compounds, siloxane compounds, silazane compounds, alkyltitanium compounds, alkoxytitanium compounds, alkylaluminum compounds, and alkoxyaluminum compounds. The manufacturing method of the electric wire according to claim 1 or 2 characterized by things.   The method for producing an electric wire according to any one of claims 1 to 3, wherein a boiling point (760 mmHg) of the modifier compound is set to a value within a range of 20 to 250 ° C. 5. The content of the modifier compound is set to a value within a range of 1 × 10 ⁻¹⁰ to 10 mol% when the total amount of fuel gas is 100 mol%. The manufacturing method of the electric wire as described in any one of these.   The wire covering material is at least one selected from the group consisting of olefin resin, polyvinyl chloride, polyester resin, urethane resin, silicone resin, fluororesin, natural rubber, synthetic rubber, and thermoplastic elastomer. The manufacturing method of the electric wire as described in any one of Claims 1-5 characterized by the above-mentioned.   7. The method according to claim 1, further comprising a step of forming a coating film made of a thermosetting paint, an ultraviolet curable paint, a laser marking paint, or a thermoplastic paint on the surface of the wire covering material. The method for producing an electric wire according to one item.   The said electric wire is an electric wire for wire harnesses, Comprising: Plural pieces are bundled, The manufacturing method of the electric wire as described in any one of Claims 1-7 characterized by the above-mentioned.