JP2012089359A - Glass yarn winding copper wire and production method of glass yarn winding copper wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass yarn winding copper wire having high productivity and excellent in conductivity, and softening temperature, and surface quality and a production method of glass yarn winding copper wire.SOLUTION: A glass yarn winding copper wire 1 comprises a conductor, a glass yarn winding layer formed with a glass yarn bundle winded around the conductor, and an insulating layer where insulating varnish is impregnated on the glass yarn winding layer. The conductor contains pure copper, oxygen of a concentration of 2 mass ppm or higher, an additional element selected from the group consisting of a Ti, Mg, Zr, Nb, Ca, V, Ni, Mn, and Cr, and the rest is an inevitable impurity.

Description

  The present invention relates to a glass wound copper wire and a method for producing a glass wound copper wire.

  As a conventional technique, a method for producing an oxygen-free copper material having a low softening temperature and high conductivity is known (see, for example, Patent Document 1). In this method of producing an oxygen-free copper material, in an upward pulling continuous casting apparatus, oxygen-free copper having an oxygen content of 0.0001% by mass or less and a metal such as titanium (Ti), zirconium (Zr), or vanadium (V) After producing a rough drawing material using a molten copper to which a small amount (0.0007 to 0.005 mass%) is added, and performing a cold drawing process on the rough drawing material, a cold drawing material is produced. The cold drawn wire is heat treated to produce an oxygen free copper material.

JP 2008-255417 A

  By the way, when producing a glass thread wound copper wire using the above oxygen-free copper material, in the conventional method for producing a glass thread wound copper wire, No. 3 rectangular copper wire (for soft electrical use as defined in JIS C3104-1994) No. 1 rectangular copper wire (hard rectangular copper wire specified in JIS C3104-1994) should be sufficiently softened and annealed using an electric resistance furnace or the like. Is required. However, the manufacturing process including this softening annealing process is a manufacturing cost of glass wound copper wire due to energy costs such as electric power consumed in the annealing process, equipment cost of the annealing process, equipment maintenance cost, time required for the annealing process and labor cost, etc. Is a problem.

  Accordingly, it is an object of the present invention to provide a glass wound copper wire and a method for producing a glass wound copper wire that have high productivity and excellent electrical conductivity, softening temperature, and surface quality.

  In order to achieve the above object, the present invention comprises a conductor, a glass wound layer formed by winding a glass yarn bundle around the conductor, and an insulating layer obtained by impregnating the glass wound layer with an insulating paint. Including pure copper, oxygen in an amount exceeding 2 mass ppm, and an additive element selected from the group consisting of Ti, Mg, Zr, Nb, Ca, V, Ni, Mn, and Cr, the balance being inevitable impurities Provide glass wound copper wire.

  The glass wound copper wire has an additive element of Ti, and the conductor is sulfur of 2 mass ppm or more and 12 mass ppm or less, oxygen of more than 2 mass ppm and 30 mass ppm or less, and Ti of 4 mass ppm or more and 55 mass ppm or less of Ti. It is preferable to contain.

In addition, the glass wound copper wire is a compound in which sulfur (S) and Ti have a TiO, TiO ₂ , TiS, or Ti—O—S bond, or a TiO, TiO ₂ , TiS, or Ti—O—S bond. It is preferable that the remaining Ti and S are contained as a solid solution.

In addition, the above-described glass wound copper wire has a compound or aggregate in the form of TiO, TiO ₂ , TiS, Ti—O—S distributed in crystal grains, and TiO has a size of 200 nm or less, TiO ₂ has a size of 1000 nm or less, TiS has a size of 200 nm or less, a compound or agglomerate in the form of Ti—O—S has a size of 300 nm or less, and particles of 500 nm or less. It is preferably 90% or more.

  In order to achieve the above object, the present invention includes oxygen in an amount exceeding 2 mass ppm and an additive element selected from the group consisting of Ti, Mg, Zr, Nb, Ca, V, Ni, Mn, and Cr. A conductor production process for producing a hard conductor obtained by processing a diluted copper alloy wire into a final wire diameter, a glass wound layer forming process for forming a glass wound layer by winding a glass yarn bundle around the outer circumference of the hard conductor, and a glass wound layer An insulating layer forming step of forming an insulating layer by applying an insulating material thereon, and a baking step of baking the insulating layer. The baking step burns the insulating layer and forms the hard conductor by the amount of heat generated in the baking step. Provided is a method for producing a glass wound copper wire that is transformed into a soft conductor.

  Further, in the above-described method for producing a glass wound copper wire, the additive element is Ti, the hard conductor is sulfur of 2 mass ppm to 12 mass ppm, oxygen of 2 mass ppm to 30 mass ppm, and 4 mass ppm to 55 mass ppm. It is preferable to contain Ti.

  Further, in the above-described method for producing a glass wound copper wire, the conductor producing step produces a dilute copper alloy material as a molten metal at a molten copper temperature of 1100 ° C. or higher and 1320 ° C. or lower by SCR continuous casting and rolling. It is preferable to include a step of producing a dilute copper alloy wire by hot rolling.

  Moreover, in the manufacturing method of said glass thread copper wire, it is preferable that the process of producing a dilute copper alloy wire is performed at the temperature of the rolling roll in hot rolling at 880 degreeC or less and 550 degreeC or more.

  According to the method for producing a glass wound copper wire and a glass wound copper wire according to the present invention, a glass thread wound copper wire and a method for producing a glass wound copper wire having high productivity and excellent electrical conductivity, softening temperature and surface quality are provided. can do.

FIG. 1 is a view showing an SEM image of TiS particles. FIG. 2 is a diagram showing the analysis result of FIG. FIG. 3 is a view showing an SEM image of TiO ₂ particles. FIG. 4 is a diagram showing the analysis result of FIG. FIG. 5 is a diagram showing an SEM image of Ti—O—S particles. FIG. 6 is a diagram showing the analysis result of FIG. Fig.7 (a) is sectional drawing of the glass wound copper wire which concerns on embodiment, (b) is a modification of a glass wound copper wire. FIG. 8 is a schematic view of the measuring apparatus at the time when the glass thread wound copper wire is bent at a predetermined angle. FIG. 9 is a schematic view of a measuring apparatus that is measuring the springback angle of the glass wound copper wire.

[Summary of embodiment]
A glass wound copper wire according to an embodiment includes a conductor, a glass wound layer formed by winding a glass yarn bundle around the conductor, and an insulating layer obtained by impregnating the glass wound layer with an insulating paint, and the conductor is Including pure copper, oxygen in an amount exceeding 2 mass ppm, and an additive element selected from the group consisting of Ti, Mg, Zr, Nb, Ca, V, Ni, Mn, and Cr, the balance being inevitable impurities .

The reason why the elements selected from the group consisting of Mg, Zr, Nb, Ca, V, Ni, Mn, Ti, and Cr are selected as the additive elements is that these elements are active elements that are easily combined with other elements. This is because S can be trapped because it is easily combined with S, and the copper base material (matrix) can be highly purified. One or more additive elements may be included. Also, other elements and impurities that do not adversely affect the properties of the alloy can be included in the alloy.
Further, in the preferred embodiment described below, it is described that the oxygen content is more than 2 and not more than 30 mass ppm, but depending on the addition amount of the additive element and the S content, In the range having the property of, it is possible to include more than 2 and 400 mass ppm.

[Embodiment]
(Structure of glass wound copper wire)
The glass wound copper wire according to the present embodiment is, for example, more compact than aluminum (Al) from the viewpoint of downsizing a power module used in an automobile and / or increasing the current density of current supplied to the power module. It consists of copper (Cu) which is a material with high thermal conductivity.

For example, the glass wound copper wire according to the present embodiment has an electrical conductivity of 98% IACS (International Standard Copper Standard) or higher, and a resistivity of 1.7241 × 10 ⁻⁸ Ωm is 100%. ), Preferably 100% IACS or more, and more preferably, a soft dilute copper alloy material as a soft copper material satisfying 102% IACS or more.

  Moreover, the glass thread wound copper wire which concerns on this Embodiment uses an SCR (Southwire Continuous Rod) continuous casting installation, there are few surface damage | wounds, a manufacturing range is wide, and stable production is possible. The wire rod is made of a material having a softening temperature of 148 ° C. or less at a processing degree of 90% (for example, processing from φ8 mm to φ2.6 mm wire).

Moreover, the glass thread wound copper wire which concerns on this Embodiment WHEREIN: When using Ti as an additive element, 2 mass ppm or more and sulfur (S) of 12 mass ppm or less, oxygen exceeding 2 mass ppm and oxygen (O) of 30 mass ppm or less, and 4 mass and titanium (Ti) of not less than ppm and not more than 55 mass ppm. Furthermore, sulfur (S) and titanium (Ti) is, _TiO, agglomeration of TiO 2, TiS, or a compound having a TiO-S bond or _TiO, TiO 2, TiS, or a compound having a TiO-S bond It is contained in a glass wound copper wire as a product, and the remaining Ti and S are contained in a glass wound copper wire as a solid solution. In this embodiment, so-called low oxygen copper (LOC) is targeted because it contains oxygen exceeding 2 mass ppm and not more than 30 mass ppm.

Further, the compound or aggregate in the form of TiO, TiO ₂ , TiS, Ti—O—S is distributed inside the crystal grains constituting the glass wound copper wire, and TiO has a size of 200 nm or less, TiO ₂ has a size of 1000 nm or less, TiS has a size of 200 nm or less, and compounds or aggregates in the form of Ti—O—S have a size of 300 nm or less. Furthermore, the glass thread copper wire which concerns on this Embodiment contains 90% or more of particles of 500 nm or less. The crystal grain means a copper crystal structure.

(Method for producing glass wound copper wire)
The manufacturing method of the glass thread copper wire which concerns on this Embodiment is as follows. As an example, a case where Ti is selected as an additive element will be described. First, the manufacturing method of the conductor of a glass thread wound copper wire is demonstrated. For example, a soft dilute copper alloy material containing titanium (Ti) as a raw material for this conductor is prepared (raw material preparation step). Next, this soft dilute copper alloy material is made into a molten metal at a molten copper temperature of 1100 ° C. or higher and 1320 ° C. or lower (melt manufacturing process). Next, a wire rod is produced from the molten metal (wire rod production process). Subsequently, the wire rod is subjected to hot rolling using a rolling roll at a temperature of 880 ° C. or lower and 550 ° C. or higher (hot rolling step). Further, the wire rod that has undergone the hot rolling process is subjected to a drawing process (drawing process). Thereby, the conductor of the glass thread wound copper wire which concerns on this Embodiment is manufactured.

  In addition, for the production of a glass wound copper wire conductor, sulfur (S) of 2 mass ppm or more and 12 mass ppm or less, oxygen (O) exceeding 2 mass ppm and 30 mass ppm or less, and titanium (Ti) of 4 mass ppm or more and 55 mass ppm or less. And a soft dilute copper alloy material. Specifically, a soft dilute copper alloy material having a softening temperature of 130 ° C. or more and 148 ° C. or less with a size of φ2.6 mm is used.

  Hereinafter, the content which the inventor examined in the realization of the conductor of the glass thread wound copper wire according to the present embodiment will be described.

  First, high-purity copper having a purity of 6N (that is, 99.9999%) has a softening temperature of 130 ° C. at a workability of 90%. Therefore, the present inventor has a soft material having a softening temperature of 130 ° C. or higher and 148 ° C. or lower that enables stable production, and the conductivity of the soft material is 98% IACS or higher, preferably 100% IACS or higher, more preferably 102% IACS or higher. A soft dilute copper alloy material capable of stably producing soft copper and a method for producing the soft dilute copper alloy material were studied.

  Here, high-purity copper (4N) having an oxygen concentration of 1 to 2 mass ppm was prepared, and a small continuous casting machine (small continuous casting machine) installed in a laboratory was used. ). And several mass ppm of titanium (Ti) was added to this molten metal. Subsequently, a φ8 mm wire rod was manufactured from the molten metal to which titanium (Ti) was added. Next, a φ8 mm wire rod was processed to φ2.6 mm (that is, the processing degree was 90%). The softening temperature of the φ2.6 mm wire rod was 160 ° C. to 168 ° C., and the softening temperature was not lower than this temperature. The conductivity of the φ2.6 mm wire rod was about 101.7% IACS. That is, even if the oxygen concentration contained in the wire rod is lowered and titanium (Ti) is added to the molten metal, the softening temperature of the wire rod cannot be lowered, and the conductivity of high purity copper (6N) is 102.8%. The inventor has found that the conductivity is lower than that of IACS.

  The reason why the softening temperature could not be lowered and the conductivity was lower than that of 6N high-purity copper was that sulfur (S) of several mass ppm or more as an inevitable impurity was contained during the production of the molten metal. I guessed that. That is, it was speculated that the softening temperature of the wire rod does not decrease due to insufficient formation of sulfides such as TiS between sulfur (S) and titanium (Ti) contained in the molten metal. .

  Therefore, the present inventor has examined the following two measures in order to realize a decrease in the softening temperature of the conductor of the glass wound copper wire and an improvement in the electrical conductivity of the conductor of the glass wound copper wire. And the glass thread wound copper wire which concerns on this Embodiment was obtained by using together the following two measures for manufacture of the conductor of a glass thread wound copper wire.

FIG. 1 is an SEM (Scanning Electron Microscope) image of TiS particles, and FIG. 2 shows the analysis result of FIG. FIG. 3 is an SEM image of TiO ₂ particles, and FIG. 4 shows the analysis result of FIG. 5 is an SEM image of Ti—O—S particles, and FIG. 6 shows the analysis result of FIG. In the SEM image, each particle is shown near the center of the figure. 1 to 6 are SEM observation and EDX analysis of a cross section of a φ8 mm copper wire (wire rod) having oxygen concentration, sulfur concentration, and Ti concentration shown in the third row from the top in Example 1 of Table 1. It has been evaluated. The observation conditions were an acceleration voltage of 15 KeV and an emission current of 10 μA.

First, the first policy is to prepare a molten copper (Cu) in a state where titanium (Ti) is added to copper having an oxygen concentration exceeding 2 mass ppm. In this molten metal, it is considered that oxides of TiS and titanium (Ti) (for example, TiO ₂ ) and Ti—O—S particles are formed. This is a consideration from the SEM image of FIG. 1 and the analysis result of FIG. 2, and the SEM image of FIG. 3 and the analysis result of FIG. 2, 4, and 6, platinum (Pt) and palladium (Pd) are metal elements that are vapor-deposited on an observation object when SEM observation is performed.

Next, the second strategy is to introduce a dislocation into copper (Cu) to facilitate the precipitation of sulfur (S), and to set the temperature in the hot rolling step under the normal copper production conditions. It is to set temperature (880 degreeC-550 degreeC) lower than temperature (namely, 950 degreeC-600 degreeC). With such a temperature setting, sulfur (S) can be deposited on dislocations, or sulfur (S) can be deposited using titanium (Ti) oxide (for example, TiO ₂ ) as a nucleus. As an example, as shown in FIGS. 5 and 6, Ti—O—S particles and the like are formed together with molten copper.

  By the above first and second measures, sulfur (S) contained in copper (Cu) crystallizes and precipitates, so that a copper wire rod having a desired softening temperature and a desired conductivity is cooled. It can be obtained after wire drawing.

  Moreover, the conductor of the glass thread wound copper wire which concerns on this Embodiment is manufactured using SCR continuous casting rolling equipment. Here, the following three conditions were provided as restrictions on the manufacturing conditions when using the SCR continuous casting and rolling equipment.

(1) About composition When obtaining a soft copper material having an electrical conductivity of 98% IACS or more, as pure copper (base material) containing inevitable impurities, 3-12 mass ppm of sulfur (S), and more than 2 and less than 30 mass ppm A soft dilute copper alloy material containing oxygen (O) and 4-55 mass ppm titanium (Ti) is used, and a wire rod (rough drawn wire) is produced from the soft dilute copper alloy material.

  Here, when obtaining a soft copper material having an electrical conductivity of 100% IACS or more, as pure copper (base material) containing inevitable impurities, 2-12 mass ppm of sulfur (S) and 2-30 mass ppm of oxygen ( O) and a soft dilute copper alloy material containing 4 to 37 mass ppm of titanium (Ti) is used. Further, when obtaining a soft copper material having an electrical conductivity of 102% IACS or more, as pure copper (base material) containing inevitable impurities, 3-12 mass ppm of sulfur (S) and oxygen of more than 2 and less than 30 mass ppm. A soft dilute copper alloy material containing (O) and 4 to 25 mass ppm of titanium (Ti) is used.

  Usually, in the industrial production of pure copper, since sulfur (S) is taken into copper (Cu) when producing electrolytic copper, it is difficult to reduce sulfur (S) to 3 mass ppm or less. The upper limit of the sulfur concentration of general-purpose electrolytic copper is 12 mass ppm.

  When the oxygen concentration is low, the softening temperature of the conductor of the glass thread wound copper wire is difficult to decrease, so the oxygen concentration is controlled to an amount exceeding 2 mass ppm. Further, when the oxygen concentration is high, the surface of the glass wound copper wire conductor is likely to be damaged in the hot rolling step, so the amount is controlled to 30 mass ppm or less.

(2) About dispersed substances It is preferable that the size of the dispersed particles dispersed in the conductor of the glass wound copper wire is small, and that many dispersed particles are dispersed in the conductor of the glass wound copper wire. Is preferred. This is because the dispersed particles have a function as a precipitation site of sulfur (S), and the precipitation site is required to have a small size and a large number.

Sulfur (S) and titanium (Ti) contained in the conductor of the glass wound copper wire are TiO, TiO ₂ , TiS, or a compound having a Ti—O—S bond, or TiO, TiO ₂ , TiS, or Ti—O—. It is contained as an aggregate of compounds having S bonds, and the remaining Ti and S are contained as a solid solution. As a soft dilute copper alloy material that is a raw material for a glass wound copper wire conductor, TiO has a size of 200 nm or less, TiO ₂ has a size of 1000 nm or less, TiS has a size of 200 nm or less, Ti A soft dilute copper alloy material in which a compound in the form of —O—S has a size of 300 nm or less and these are distributed in crystal grains is used.

  In addition, since the particle size formed in a crystal grain changes according to the holding | maintenance time of molten copper at the time of casting, and cooling conditions, it is necessary to set casting conditions appropriately.

(3) Casting conditions By SCR continuous casting and rolling, wire rods are produced with an ingot rod working degree of 90% (30 mm) to 99.8% (5 mm). As an example, a condition for manufacturing a wire rod of φ8 mm with a processing degree of 99.3% is adopted. Hereinafter, casting conditions (a) to (c) will be described.

[Casting conditions (a)]
The molten copper temperature in the melting furnace is controlled to 1100 ° C. or higher and 1320 ° C. or lower. When the temperature of the molten copper is high, blowholes increase, and scratches are generated and the particle size tends to increase, so the temperature is controlled to 1320 ° C. or lower. The reason why the temperature is controlled to 1100 ° C. or higher is that copper (Cu) tends to harden and the production is not stable, but the molten copper temperature is preferably as low as possible.

[Casting conditions (b)]
As for the temperature of the hot rolling process, the temperature in the first rolling roll is controlled to 880 ° C. or lower, and the temperature in the final rolling roll is controlled to 550 ° C. or higher.

  Unlike normal pure copper production conditions, for the purpose of further reducing the solid solubility limit, which is the driving force for crystallization of sulfur (S) in molten copper and precipitation of sulfur (S) during hot rolling, It is preferable to set the molten copper temperature and the hot rolling temperature to the conditions described in “Casting Condition (a)” and “Casting Condition (b)”.

  Further, the temperature in the normal hot rolling process is 950 ° C. or less in the first rolling roll and 600 ° C. or more in the final rolling roll, but for the purpose of reducing the solid solution limit, The first rolling roll is set to 880 ° C. or lower, and the final rolling roll is set to 550 ° C. or higher.

  In addition, the reason for setting the temperature in the final rolling roll to 550 ° C. or more is that the wire rod wound obtained at a temperature lower than 550 ° C. increases, and the produced glass thread wound copper wire cannot be handled as a product. . The temperature in the hot rolling process is preferably as low as possible while controlling the temperature to 880 ° C. or lower in the first rolling roll and 550 ° C. or higher in the final rolling roll. By setting such a temperature, the softening temperature of the conductor of the glass thread wound copper wire (softening temperature after being processed into φ8 to φ2.6 mm) is changed to the softening temperature of 6N high-purity copper (that is, 130 ° C.). You can get closer.

[Casting conditions (c)]
The conductivity of oxygen-free copper is about 101.7% IACS, and the conductivity of 6N high-purity copper is 102.8% IACS. In the present embodiment, the conductivity of a wire rod having a diameter of φ8 mm is 98% IACS or more, preferably 100% IACS or more, more preferably 102% IACS or more. In the present embodiment, a soft dilute copper alloy in which the softening temperature of the wire rod of the wire rod (for example, φ2.6 mm) after cold drawing is 130 ° C. or higher and 148 ° C. is manufactured, and this soft dilute copper is manufactured. The alloy is used for the production of glass wound copper wire conductors.

  In order to use industrially, the electrical conductivity of 98% IACS or more is requested | required as electrical conductivity of the soft copper wire of the purity utilized industrially manufactured from electrolytic copper. Further, the softening temperature is 148 ° C. or less judging from industrial value. Since the softening temperature of 6N high-purity copper is 127 ° C to 130 ° C, the upper limit value of the softening temperature is set to 130 ° C from the obtained data. This slight difference is due to the presence of unavoidable impurities not contained in 6N high purity copper.

  After the base material copper (Cu) is melted in the shaft furnace, it is preferably flowed in a reduced state in a trough. That is, in a reducing gas (for example, CO) atmosphere, the wire rod is stably manufactured by casting while controlling the sulfur concentration, titanium concentration, and oxygen concentration of the dilute alloy and rolling the material. It is preferable. In addition, that copper oxide mixes and / or that a particle size is larger than predetermined size will reduce the quality of the glass wound copper wire manufactured.

  Here, the reason for adding titanium (Ti) as an additive element to the conductor of the glass wound copper wire is as follows. That is, (a) titanium (Ti) is likely to be a compound by combining with sulfur (S) in molten copper, and (b) easy to process and handle compared to other additive metals such as zirconium (Zr). This is because (c) it is cheaper than niobium (Nb) and the like, and (d) it is easy to deposit with oxide as a nucleus.

  From the above, a practical soft dilute copper alloy material having high productivity and excellent electrical conductivity, softening temperature, and surface quality can be obtained as a raw material for the conductor of the glass wound copper wire according to the present embodiment. A plating layer can also be formed on the surface of the soft dilute copper alloy material. For the plating layer, for example, a material mainly containing tin (Sn), nickel (Ni), silver (Ag), or Pb-free plating can be used. Further, the shape of the soft dilute copper alloy material is not particularly limited, and can be a round cross-section, a rod shape, or a flat conductor.

  In the present embodiment, the wire rod is manufactured by the SCR continuous casting and rolling method, and the soft material is manufactured by hot rolling, but the twin roll type continuous casting rolling method or the Properti type continuous casting and rolling method is adopted. You can also. Below, the Example and comparative example of the conductor of the glass thread wound copper wire produced by said manufacturing method are demonstrated.

  Table 1 shows the experimental conditions and results.

  First, as an experimental material, a φ8 mm copper wire (wire rod, workability 99.3%) having the oxygen concentration, sulfur concentration, and titanium concentration shown in Table 1 was prepared. The φ8 mm copper wire is hot-rolled by SCR continuous casting and rolling. Ti flows the molten copper melted in the shaft furnace into the reed in the reducing gas atmosphere, guides the molten copper flowing in the reed to the casting pot of the same reducing gas atmosphere, and after adding Ti in this casting pot, An ingot rod was made with a mold formed between the cast ring and the endless belt through the nozzle. This ingot rod is hot-rolled to produce a φ8 mm copper wire. Next, cold drawing was applied to each experimental material. Thus, a copper wire having a size of φ2.6 mm was produced. And while measuring the semi-softening temperature and electrical conductivity of a copper wire of φ 2.6 mm size, the dispersed particle size in the copper wire of φ 8 mm was evaluated.

  The oxygen concentration was measured with an oxygen analyzer (Leco (registered trademark) oxygen analyzer), and the concentrations of sulfur and titanium were analyzed by ICP emission spectroscopic analysis.

  The measurement of the semi-softening temperature in the φ2.6 mm size was obtained from the result of quenching in water after holding each temperature at 400 ° C. or lower for 1 hour and conducting a tensile test. The value obtained by using the result of the tensile test at room temperature and the result of the tensile test of the soft copper wire heat-treated at 400 ° C. for 1 hour, and adding the tensile strengths of the two tensile tests and dividing by two. The temperature corresponding to the strength was determined as the semi-softening temperature.

As described above, the size of the dispersed particles dispersed in the conductor of the glass wound copper wire is preferably small, and it is preferable that many dispersed particles are dispersed in the conductor of the glass wound copper wire. Therefore, the case where the number of dispersed particles having a diameter of 500 nm or less is 90% or more was regarded as acceptable. Here, the “size” is the size of the compound and means the size of the major axis of the diameter and minor axis of the shape of the compound. The “particles” refer to the TiO, TiO ₂ , TiS, and Ti—O—S. “90%” indicates the ratio of the number of corresponding particles to the total number of particles.

  In Table 1, Comparative Example 1 is the result of trial production of a copper wire having a diameter of φ8 mm in an argon (Ar) atmosphere in a laboratory, and 0 to 18 mass ppm of titanium (Ti) was added to the molten copper. While the semi-softening temperature of the copper wire not added with titanium (Ti) was 215 ° C., the softening temperature of the copper wire added with 13 mass ppm of titanium (Ti) decreased to 160 ° C. Is the minimum temperature.) As shown in Table 1, as the Ti concentration increased to 15 mass ppm and 18 mass ppm, the semi-softening temperature also increased, and the required softening temperature of 148 ° C. or lower could not be realized. Moreover, although the electrical conductivity requested | required industrially was 98% IACS or more, comprehensive evaluation was disqualified (henceforth, a disqualification is represented as "x").

  Therefore, as Comparative Example 2, a Φ8 mm copper wire (wire rod) having an oxygen concentration adjusted to 7 to 8 mass ppm was prototyped using the SCR continuous casting and rolling method.

  In Comparative Example 2, it was a copper wire having a minimum Ti concentration (that is, 0 mass ppm, 2 mass ppm) among the prototype manufactured by the SCR continuous casting and rolling method, and the conductivity was 102% IACS or more, but the semi-softening temperature. Was 164 ° C. and 157 ° C., and was not less than the required 148 ° C., so the overall evaluation was “x”.

  In Example 1, the oxygen concentration and the sulfur concentration substantially coincide (that is, the oxygen concentration: 7 to 8 mass ppm, the sulfur concentration: 5 mass ppm), and different copper wires are used within the range of the Ti concentration of 4 to 55 mass ppm. Prototype.

  When the Ti concentration is in the range of 4 to 55 mass ppm, the softening temperature is 148 ° C. or lower, the conductivity is 98% IACS or higher and 102% IACS or higher, and the dispersed particle size is 90% or higher for particles of 500 nm or less. there were. Moreover, since the surface of the wire rod was also clean (that is, the surface was smooth) and all satisfied the product performance, the comprehensive evaluation was a pass (hereinafter, the pass was expressed as “◯”).

  Here, the copper wire satisfying an electrical conductivity of 100% IACS or more was a case where the Ti concentration was 4 to 37 mass ppm, and the copper wire satisfying the 102% IACS or more was a case where the Ti concentration was 4 to 25 mass ppm. When the Ti concentration was 13 mass ppm, the conductivity showed a maximum value of 102.4% IACS, and the conductivity was slightly lower around this concentration. This is because, when the Ti concentration is 13 mass ppm, by capturing the sulfur content in copper (Cu) as a compound, the conductivity is close to that of high-purity copper (6N).

  Therefore, both the semi-softening temperature and the conductivity can be satisfied by increasing the oxygen concentration and adding titanium (Ti).

  In Comparative Example 3, a copper wire having a Ti concentration of 60 mass ppm was prototyped. Although the copper wire which concerns on the comparative example 3 satisfy | fills a request | requirement, semi-softening temperature is 148 degreeC or more, and did not satisfy | fill product performance. Furthermore, there are many scratches on the surface of the wire rod, making it difficult to adopt as a product. Therefore, it was shown that the addition amount of titanium (Ti) is preferably less than 60 mass ppm.

  In the copper wire which concerns on Example 2, while setting sulfur concentration to 5 mass ppm and controlling Ti concentration in the range of 13-10 mass ppm, the influence of oxygen concentration was examined by changing oxygen concentration.

  Regarding the oxygen concentration, copper wires having greatly different concentrations from 2 mass ppm to 30 mass ppm or less were prepared. However, since copper wires with an oxygen concentration of less than 2 mass ppm are difficult to produce and cannot be stably manufactured, the overall evaluation is “△” (“△” is an intermediate evaluation between “○” and “×”) .) Further, even when the oxygen concentration was 30 mass ppm, both the semi-softening temperature and the conductivity met the requirements.

  In Comparative Example 4, when the oxygen concentration was 40 mass ppm, there were many scratches on the surface of the wire rod, and the product could not be used as a product.

  Therefore, by setting the oxygen concentration in the range of more than 2 and 30 mass ppm or less, all the characteristics of the semi-softening temperature, the electrical conductivity of 102% IACS or more, and the dispersed particle size can be satisfied. It was shown to be clean and satisfy product performance.

  Example 3 is a copper wire in which the oxygen concentration and the Ti concentration are set close to each other and the sulfur concentration is changed within a range of 4 to 20 mass ppm. In Example 3, a copper wire having a sulfur concentration of less than 2 mass ppm could not be realized due to restrictions on raw materials. However, by controlling the Ti concentration and the sulfur concentration, the requirements for both the semi-softening temperature and the conductivity could be satisfied.

  In Comparative Example 5, when the sulfur concentration was 18 mass ppm and the Ti concentration was 13 mass ppm, the semi-softening temperature was as high as 162 ° C., and the required characteristics were not satisfied. In particular, the surface quality of the wire rod was poor and it was difficult to produce a product.

  From the above, when the sulfur concentration is in the range of 2 to 12 mass ppm, the semi-softening temperature, the conductivity of 102% IACS or more, and the dispersed particle size can be satisfied, and the surface of the wire rod is also clean. It was shown that the product performance can be satisfied.

  Comparative Example 6 is a copper wire using 6N high-purity copper. In the copper wire according to Comparative Example 6, the semi-softening temperature was 127 ° C. to 130 ° C., the conductivity was 102.8% IACS, and no particles having a dispersed particle size of 500 nm or less were observed.

  Table 2 shows the temperature of molten copper and the rolling temperature as production conditions.

  In Comparative Example 7, a wire rod having a molten copper temperature of 1330 ° C. to 1350 ° C. and a rolling temperature of 950 to 600 ° C. and a diameter of 8 mm was produced. Although the wire rod according to Comparative Example 7 satisfies the requirements for the semi-softening temperature and the electrical conductivity, there are about 1000 nm of particles with respect to the dispersed particle size, and more than 10% of the particles are over 500 nm. . Therefore, the wire rod according to Example 7 was determined to be inappropriate.

  In Example 4, the molten copper temperature was controlled in the temperature range of 1200 ° C. to 1320 ° C., and the rolling temperature was controlled in the temperature range of 880 ° C. to 550 ° C. to produce a φ8 mm wire rod. The wire rod according to Example 4 had good wire rod surface quality and dispersed particle size, and the overall evaluation was “◯”.

  In Comparative Example 8, the molten copper temperature was controlled to 1100 ° C., and the rolling temperature was controlled to a temperature range of 880 ° C. to 550 ° C. to produce a φ8 mm wire rod. The wire rod according to Comparative Example 8 was not suitable as a product because there were many scratches on the surface of the wire rod because the molten copper temperature was low. This is because, since the molten copper temperature is low, scratches are likely to occur during rolling.

  In Comparative Example 9, the molten copper temperature was controlled to 1300 ° C. and the rolling temperature was controlled to a temperature range of 950 ° C. to 600 ° C. to produce a φ8 mm wire rod. The wire rod according to Comparative Example 9 has a high quality in the surface of the wire rod because the temperature in the hot rolling process is high, but the dispersed particle size includes a large size, and the overall evaluation is “x”. It was.

  In Comparative Example 10, the molten copper temperature was controlled to 1350 ° C., and the rolling temperature was controlled to a temperature range of 880 ° C. to 550 ° C. to produce a φ8 mm wire rod. The wire rod according to Comparative Example 10 had a large dispersed particle size due to the high molten copper temperature, and the overall evaluation was “x”. Below, the glass thread wound copper wire produced using the conductor shown above is demonstrated.

(About glass wound copper wire)
Fig.7 (a) is sectional drawing of the glass wound copper wire which concerns on embodiment, (b) is a modification of a glass wound copper wire.

  As shown in FIG. 7A, the glass wound copper wire 1 includes a conductor 2, a lower glass wound layer 3 that covers the conductor 2, an upper glass wound layer 4 that covers the lower glass wound layer 3, and an upper layer. And an insulating film 5 that covers the glass bobbin layer 4. 7 (b) is a modification of the glass wound copper wire 1 shown in FIG. 7 (a), and includes a conductor 2, a glass wound layer 3a covering the conductor 2, and a glass And an insulating film 5 that covers the pincushion layer 3a. Below, the glass thread copper wire 1 is mainly demonstrated.

  In the following, the characteristics of the glass thread wound copper wire 1 will be described specifically by taking a double glass wound rectangular copper wire having a rectangular cross section as an example, but the single glass wound copper wire having a circular cross section is used. And it is applicable also to a double glass winding copper wire.

  The conductor 2 is a copper wire rod manufactured according to the method described in each of the above embodiments. The cross-sectional shape of the conductor 2 is a flat shape (rectangular shape).

  The conductor 2 is formed into a rectangular conductor through a hot rolling process, for example. This hot rolling process is not limited to a roll rolling process that is sandwiched between twin rolls, and may be a conform extrusion process in which a round wire is extruded by a conform extruder to form a rectangular conductor.

  The glass yarn bundle used for forming the lower glass wound layer 3 and the upper glass wound layer 4 is, for example, a non-alkali glass yarn defined in JIS R3413 (glass yarn). The glass yarn bundle is not limited to the alkali-free glass yarn defined in JIS R3413 (glass yarn), and a glass yarn having a quality higher than that of the glass yarn may be used.

  Moreover, although the glass wound copper wire 1 and the glass wound copper wire 1a did not coat | cover plating on the conductor 2, it is not limited to this, The plating process may be performed.

  The insulating film 5 is formed using, for example, an insulating film material corresponding to the heat class of class E (130 ° C.), class F (155 ° C.), or class H (180 ° C.) according to the use of the glass wound copper wire to be manufactured. Is done. As an example, the insulating film 5 according to the present embodiment is formed using an F-type (heat resistance class 155 ° C.) insulating paint (for example, Hitachi Chemical WF651).

(About Example 7 to Example 9)
The manufacturing method of the glass thread wound copper wire 1 of Example 7- Example 9 is as follows. First, a wire rod φ2.6 mm, which is the fifth material from the top in Example 1 in Table 1, is drawn to produce a round wire of φ12 mm.

  Next, without passing through the annealing process, a hot rolling process using a roll is performed to produce a rectangular wire (conductor thickness: 2.0 mm, conductor width: 5.0 mm) from the round wire.

  Next, the non-alkali glass yarn specified by JIS R3413 (glass yarn) is tightly wound around a flat wire to form the lower glass yarn wound layer 3.

  Next, the same glass yarn is wound on the lower glass wound layer 3 in the direction opposite to the winding direction of the lower glass wound layer 3 to form the upper glass wound layer 4 to provide a glass having a double glass layer A wound copper wire is produced. The non-alkali glass yarn defined in JIS R3413 (glass yarn) is a yarn having a two-layer structure in which 200 twisted glass yarns having a diameter of 7 μm are bundled, and 14 in the lower layer and 12 in the upper layer. It is a bunch.

  Next, an F type (heat resistance class 155 ° C.) insulating paint (for example, Hitachi Chemical WF651) is uniformly applied, and the insulating paint is baked.

  Specifically, the insulating paint is applied by using, for example, an insulating paint coating device that impregnates the insulating paint by passing a glass-wrapped copper wire wound with glass yarn through a tank containing the insulating paint. The insulating paint is baked by an insulating baking apparatus. The insulating paint was baked by passing the glass wound copper wire through the electric furnace of the insulating paint coating apparatus having a furnace length of 4 m at a temperature of 480 ° C. at a speed of 5.0 m / min after applying the insulating paint. .

  Next, the glass wound copper wire on which the insulating paint was baked was allowed to come to room temperature.

  Next, application of the above-mentioned insulating paint and baking of the insulating paint were repeated three times to form an insulating film 5 to produce a glass wound copper wire 1.

  Next, the produced glass wound copper wire 1 was wound around a bobbin, and three samples having a length of about 400 mm were taken from the same bobbin, which were designated as Example 7, Example 8, and Example 9, respectively.

(Comparative Example 13 to Comparative Example 15)
The glass thread wound copper wires of Comparative Examples 13 to 15 are hot to form a round wire into the above-mentioned round wire, in which tough pitch copper (TPC) is used to produce a conductor. Same as Example 7, Example 8 and Example 9, except that the rectangular wire passed through the rolling process was subjected to an annealing process by batch annealing at a temperature of 300 ° C. for 30 minutes. A glass wound copper wire was produced under the conditions.

  Moreover, the produced glass thread copper wire was wound around the bobbin, and three samples having a length of about 400 mm were taken from the same bobbin, which were designated as Comparative Example 13, Comparative Example 14 and Comparative Example 15, respectively.

(About the softening characteristic of the glass wound copper wire of Examples 7-Example 9 and Comparative Examples 13-15)
FIG. 8 is a schematic view of the measuring apparatus at the time when the glass thread wound copper wire is bent at a predetermined angle. FIG. 9 is a schematic view of a measuring apparatus that is measuring the springback angle of the glass wound copper wire.

  In order to measure the softening characteristics of the glass wound copper wires of Examples 7 to 9 and Comparative Examples 13 to 15 produced by the above manufacturing method, the softness test defined by JIS C3006-199 10.2. Was carried out using the measuring apparatus 6 shown in FIGS.

  The measuring device 6 shown in FIGS. 8 and 9 is schematically configured to include a clamp 60, a lever arm 61, and a protractor 62.

  The clamp 60 fixes the sample 7 of the glass thread wound copper wire.

  The lever arm 61 has a plate shape and is configured to be rotatable around a fulcrum. Further, the lever arm 61 has a blade 610 at a point 40 times the thickness of the conductor of the sample 7 from the fulcrum, for example. Here, the thickness of the conductor 2 is the thickness in the vertical direction of the paper surface of FIG. When the lever arm 61 rotates around the fulcrum, the sample 7 is bent from the base of the clamp 60.

  The protractor 62 measures a springback angle of the sample 7 described later.

  The softness test is performed as follows. First, after straightening the sample 7 of Example 7 to Example 9 and Comparative Example 13 to Comparative Example 15, a part was fixed to the clamp 60, and the sample 7 was taken for 2 to 5 seconds as shown in FIG. Bend 30 degrees. Next, after the sample 7 reaches the 30 ° position, the lever arm 61 is returned to the original position within 2 seconds. Next, after the blade 610 moves away from the sample, as shown in FIG. 9, the lever arm 61 is moved until the blade 610 contacts the sample 7 without bending, and the spring back angle of the contacted sample 7 is determined by the protractor 62. taking measurement.

  Moreover, the method prescribed | regulated by JISC3006-19999 was employ | adopted for the measuring method of "elongation%". Furthermore, the method defined in 5.1.2.1.2 and 5.1.5 defined in JIS C3006-19999 was adopted for “conductor dimensions” and “insulation thickness on both sides”.

  Table 3 shows the results of measuring the samples 7 of Examples 7 to 9 and Comparative Examples 13 to 15 in the above softness test.

  As shown in Table 3, the springback angle of Example 7 is 3.5 °, the springback angle of Example 8 is 3.5 °, and the springback angle of Example 9 is 4.0 °. Met. Further, the spring back angle of Comparative Example 13 was 3.5 °, the spring back angle of Comparative Example 14 was 4.0 °, and the spring back angle of Comparative Example 15 was 4.0 °. From this measurement result, after the glass thread wound copper wire which is the sample 7 of Example 7 to Example 9 reaches the final wire diameter, the glass wire wound copper wire reaches the final wire diameter even though the annealing process is not performed. The spring back angles of the same level as those of the glass wound copper wires of Comparative Examples 13 to 15 using oxygen-free copper (OFC: Oxygen Free Copper) subjected to the annealing process were shown.

  In Examples 7 to 9, “conductor dimensions” and “insulation thickness on both sides” are the same as those in Comparative Examples 13 to 15, and “elongation%” is substantially the same as in Comparative Examples 13 to 15. Met.

  From the above results, by using a raw material in which a small amount of titanium (Ti) is added to a copper material having a predetermined oxygen content and a predetermined sulfur content for a rectangular copper wire, the processing strain of a rectangular copper wire that has been conventionally performed can be reduced. Even if the annealing step to be removed is not performed, the hard copper wire can be sufficiently annealed and transformed into a soft copper wire by the amount of heat in the insulating paint baking step after the formation of the lower glass wound layer 3 and the upper glass wound layer 4. I understand that I can do it.

(Effect of embodiment)
The glass wound copper wire according to the present embodiment does not require copper purification (99.9999% by mass or more), and can achieve high conductivity by an inexpensive continuous casting and rolling method. Cost can be reduced. Since the glass wound copper wire is formed of a material having high conductivity, the temperature rise of the semiconductor element can be suppressed by improving the heat dissipation, and the reliability is improved. Since the added titanium (Ti) traps sulfur (S), which is an impurity, the copper matrix (matrix) is highly purified, and the soft properties of the material are improved.

  Moreover, since the glass thread wound copper wire which concerns on this Embodiment can skip the annealing process of a flat copper wire, the manufacturing method which winds a glass thread bundle around a hard copper wire can be employ | adopted, and an annealing process Energy costs such as power consumption, equipment costs for the annealing process, equipment maintenance costs, time required for the annealing process, and labor costs can be reduced.

  As mentioned above, although embodiment of this invention and its modification were demonstrated, embodiment and modification which were described above do not limit the invention which concerns on a claim. In addition, it should be noted that not all combinations of features described in the embodiments and the modifications are necessarily essential to the means for solving the problems of the invention.

DESCRIPTION OF SYMBOLS 1 ... Glass wound copper wire 1a ... Glass wound copper wire 2 ... Conductor 3 ... Lower glass wound layer 3a ... Glass wound layer 4 ... Upper glass wound layer 5 ... Insulating film 6 ... Measuring apparatus 7 ... Sample 60 ... Clamp 61 ... Lever arm 62 ... Protractor 610 ... Blade

Claims (8)

Conductors,
A glass yarn wound layer formed by winding a glass yarn bundle around the conductor;
An insulating layer obtained by impregnating the glass spool layer with an insulating paint;
With
The conductor includes pure copper, oxygen in an amount exceeding 2 mass ppm, and an additive element selected from the group consisting of Ti, Mg, Zr, Nb, Ca, V, Ni, Mn, and Cr, and the remainder is inevitable. Glass wound copper wire, which is a typical impurity.   The said additive element is Ti, The said conductor contains 2 mass ppm or more and 12 mass ppm or less of sulfur, 2 mass ppm or more and 30 mass ppm or less of oxygen, and 4 mass ppm or more and 55 mass ppm or less of Ti. Glass wound copper wire. The sulfur (S) and the Ti are a compound having a TiO, TiO ₂ , TiS, or Ti—O—S bond, or the compound having the TiO, the TiO ₂ , the TiS, or the Ti—O—S bond. The glass thread wound copper wire according to claim 1, which is contained as an agglomerate and the remaining Ti and S are contained as a solid solution. The TiO, the TiO ₂ , the TiS, the compound of Ti—O—S or the aggregates are distributed in the crystal grains,
The TiO has a size of 200 nm or less;
The TiO ₂ has a size of 1000 nm or less;
The TiS has a size of 200 nm or less;
The compound or aggregate in the form of Ti-O-S has a size of 300 nm or less,
The glass wound copper wire according to claim 3, wherein the particle size of 500 nm or less is 90% or more. A dilute copper alloy wire containing oxygen in an amount exceeding 2 mass ppm and an additive element selected from the group consisting of Ti, Mg, Zr, Nb, Ca, V, Ni, Mn, and Cr is processed into a final wire diameter. Conductor production process for producing an implemented hard conductor;
A glass wound layer forming step of forming a glass wound layer by winding a glass yarn bundle around the outer periphery of the hard conductor;
An insulating layer forming step of forming an insulating layer by applying an insulating material on the glass spool layer;
A baking step of baking the insulating layer;
Including
The said baking process bakes the said insulating layer, The manufacturing method of the glass wound copper wire which changes the said hard conductor into a soft conductor with the calorie | heat amount which generate | occur | produces at the said baking process. The additive element is Ti;
6. The method for producing a glass wound copper wire according to claim 5, wherein the hard conductor contains 2 mass ppm to 12 mass ppm of sulfur, 2 mass ppm to 30 mass ppm of oxygen, and 4 mass ppm to 55 mass ppm of Ti. .   In the conductor production step, the diluted copper alloy material is produced as a molten metal at a molten copper temperature of 1100 ° C. or higher and 1320 ° C. or lower by SCR continuous casting and rolling, and the diluted copper alloy material is hot-rolled to obtain a diluted copper alloy wire. The manufacturing method of the glass thread wound copper wire of Claim 6 including the process to produce.   The manufacturing method of the glass wound copper wire of Claim 7 with which the process of producing the said dilute copper alloy wire is performed at the temperature of the rolling roll in a hot rolling process at 880 degrees C or less and 550 degrees C or more.