JP6196435B2 - Titanium copper and method for producing the same - Google Patents

Description

  The present invention has excellent strength, fatigue characteristics, bending workability, suitable as a lead frame material for semiconductor devices such as conductive spring materials such as connectors, terminals, relays, switches, transistors, integrated circuits (ICs), etc. The present invention relates to titanium copper having stress relaxation resistance, conductivity, and the like, and a method for producing the same.

As a material that requires electrical conductivity and springiness for various terminals, connectors, relays, switches, etc. of electronic equipment, inexpensive brass is used when manufacturing costs are important, and phosphorous is used when springiness is important. Bronze is used, and when whiteness and corrosion resistance are important, Western white has been used. However, with the recent reduction in weight, thickness and size of electronic devices and their components, it is difficult to sufficiently improve the strength of these materials, so the demand for so-called high-grade springs such as titanium copper has increased. Yes.
Titanium copper prescribed | regulated to JIS alloy number C1990 is manufactured by performing an aging treatment after solution treatment. In the solution treatment, the coarse Cu—Ti compound generated during casting or hot rolling is dissolved in the Cu matrix and simultaneously the Cu matrix is recrystallized to adjust the crystal grain size of the recrystallized grains. In the aging treatment, Cu ₃ Ti or Cu ₄ Ti fine particles are precipitated, and these fine particles contribute to improvement of strength properties such as tensile strength, proof stress, and spring limit value.

For example, the connector is composed of a female terminal and a male terminal, and electrical connection can be obtained by fitting both terminals. In the electrical contact, the female terminal holds the male terminal by its spring force and obtains a desired contact force.
If the strength of the female terminal material is low, permanent deformation (sagging) occurs in the female terminal when the male terminal is inserted. When the sagging occurs, the contact force at the electrical contact portion decreases and the electrical resistance increases. Therefore, in order to suppress the occurrence of sagging, copper alloy materials having high proof stress and spring limit values have been developed (for example, Patent Document 1).

  Patent Document 2 proposes titanium copper in which the bending deflection coefficient in the rolling direction is adjusted to 80 to 110 GPa in order to facilitate the design of the connector. However, the sag characteristics of this material are not sufficient particularly when the spring is repeatedly bent, and there is also a problem in that the contact force of the spring is significantly reduced.

JP 2004-076091 A WO2012 / 029717

In order to improve the sag characteristics of the copper alloy material, it is effective to increase strength characteristics such as proof stress and spring limit values. However, there is a limit to the improvement in the sag due to the increase in the strength only because the bending workability deteriorates with the increase in the strength.
Accordingly, an object of the present invention is to provide titanium copper in which the occurrence of sag is remarkably suppressed by using means other than increasing the strength, and a method for producing the same.

The principle of the occurrence of sag will be described by simplifying the spring part of the connector as a cantilever. As shown in FIG. 1, when a deflection d is given to the position of length L from the fixed end of the leaf spring with one end fixed, a contact force P expressed by the following equation 1 is obtained, and the surface of the leaf spring is fixed to the fixed end surface. The maximum stress S shown by the following formula 2 is generated.
P = dEwt ³ / 4L ³ (Formula 1)
S = 3tEd / 2L ² (Formula 2)
Here, E is Young's modulus, w is the plate width, and t is the plate thickness.
When S exceeds the proof stress of the copper alloy that is the material of the leaf spring, the leaf spring is permanently deformed and the leaf spring is sag. From Formula 2, it is considered that the lower the Young's modulus of the material, the greater the deflection at which the occurrence of sag starts, that is, the sag does not easily occur.
Usually, a spring portion such as a connector is designed such that its longitudinal direction is perpendicular to the rolling direction in the rolling plane (90-degree direction in FIG. 2). Therefore, it can be said that it is important that the Young's modulus in the direction that forms an angle of 90 degrees with the rolling direction is low.
On the other hand, the deflection given to the spring portion of the connector or the like is not limited to one time, but is often given several thousand times or more by inserting and removing terminals. Especially in relays, the number of deflections is remarkably large.
The present inventor has not only the Young's modulus in the direction that forms an angle of 90 degrees with the rolling direction, but also the rolling direction for the sag in the case where repeated deflection is given in the direction that forms an angle of 90 degrees with the rolling direction. It has been found that the Young's modulus in the direction of an angle of 45 degrees has a great influence.

  The present invention completed on the basis of the above knowledge, in one aspect, contains 1.5 to 5.0% by mass of Ti, the balance is made of copper and inevitable impurities, and is in the direction of 90 degrees (degree is the rolling of copper foil) Titanium copper having a Young's modulus (bending deflection coefficient) of the angle formed with the rolling direction in the plane, the same applies hereinafter, of 100 to 120 GPa and a Young's modulus (bending deflection coefficient) in the 45 degree direction of 140 GPa or less.

  In one embodiment of titanium copper according to the present invention, it contains 1.5 to 5.0% by mass of Ti, the balance is made of copper and unavoidable impurities, and the Young's modulus (bending deflection coefficient) in the direction of 90 degrees. The Young's modulus (bending deflection coefficient) in the 45 degree direction is 111 to 140 GPa.

  In another embodiment of titanium copper according to the present invention, one or more of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Si, and Zr are 0.005 in total. 1.0% by mass is contained.

In another aspect of the present invention, an ingot containing 1.5 to 5.0% by mass of Ti and the balance being made of copper and unavoidable impurities is prepared. After hot rolling to 20 mm, cold rolling with a workability of 30 to 99% is performed, and an average temperature increase rate of 400 to 500 ° C. is set to 1 to 50 ° C./second in a temperature range of 500 to 650 ° C. for 5 to 80 seconds. Pre-annealing with a softening degree of 0.25 to 0.75 by holding, performing cold rolling with a working degree of 7 to 50%, then solution treatment at 700 to 900 ° C. for 5 to 300 seconds, and It is a method of performing an aging treatment for 2 to 20 hours at 350 to 550 ° C.,
A method for producing titanium copper, wherein the softening degree is represented by S in the following formula:
S = (σ ₀ −σ) / (σ ₀ −σ ₉₀₀ )
Here, σ ₀ is the tensile strength before pre-annealing, and σ and σ ₉₀₀ are the tensile strength after pre-annealing and after annealing at 900 ° C., respectively.

  In one embodiment of the method for producing titanium copper according to the present invention, the ingot is a total amount of at least one of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Si and Zr. It contains 0.005 to 1.0 mass%.

  In yet another aspect, the present invention is a copper-stretched product including the titanium copper of the present invention.

  In still another aspect, the present invention is an electronic device component including the titanium copper of the present invention.

  According to the present invention, when used as an electronic component such as a connector for designing a spring in a direction perpendicular to the rolling direction in the rolling plane, the occurrence of sag associated with the operation of the spring is significantly suppressed, and titanium copper and its A manufacturing method can be provided.

It is explanatory drawing of the principle which a sag occurs. It is a figure which shows the rolling direction in the rolling plane of the rolled copper foil of titanium copper, the direction which makes 45 degree | times with a rolling direction, and the direction which makes 90 degree | times with a rolling direction, respectively. It is a related figure of the annealing temperature when the alloy which concerns on this invention is annealed at various temperatures, and tensile strength. It is explanatory drawing of the bending test which concerns on an Example.

(Ti concentration)
Ti concentration shall be 1.5-5.0 mass%. Titanium copper improves strength and conductivity by dissolving Ti in a Cu matrix by solution treatment and dispersing fine precipitates in the alloy by aging treatment. If the Ti concentration is less than 1.5% by mass, precipitation of precipitates is insufficient and desired strength cannot be obtained. When the Ti concentration exceeds 5.0% by mass, the bendability is remarkably deteriorated. A more preferable Ti concentration is 2.9 to 3.4% by mass.

(Other additive elements)
Strength is further improved by adding 0.005 to 1.0 mass% of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Si, and Zr in a total amount of one or more. be able to. If the total content is less than 0.005% by mass, the above effect cannot be obtained, and if the total content exceeds 1.0% by mass, the bending workability deteriorates. More preferably, one or more of the above elements are contained in a total amount of 0.01 to 0.5% by mass.

(Young's modulus)
By controlling the Young's modulus in the 90-degree direction low, the settling of the spring designed in the direction perpendicular to the rolling is reduced. Normal titanium copper has a Young's modulus in the 90-degree direction of about 125 to 130 GPa. By adjusting this Young's modulus to 120 GPa or less, the sag is significantly smaller than that of ordinary titanium copper. On the other hand, when the Young's modulus decreases, as is apparent from the above formula 1, the contact force at the electrical contact decreases. When the Young's modulus in the 90-degree direction is less than 100 GPa, an increase in contact resistance accompanying a decrease in contact force cannot be ignored. Therefore, the Young's modulus in the 90-degree direction is adjusted to 100 to 120 GPa. From the point of contact force, the Young's modulus in the 90 degree direction is more preferably 111 GPa or more. A more preferable range of Young's modulus is 111 to 115 GPa.
On the other hand, with titanium copper whose Young's modulus in the 90 degree direction is adjusted to 100 to 120 GPa, the Young's modulus in the 45 degree direction exceeds 140 GPa and may reach 150 GPa or more. By suppressing the increase in Young's modulus in the 45 degree direction and adjusting the Young's modulus in the 45 degree direction to 140 GPa or less, more preferably 130 GPa or less, not only sag when a single deflection is applied, but also repeated deflection. The sagging when given is improved.
In addition, in the case of titanium copper whose 90 degree direction Young's modulus is adjusted to 100 to 120 GPa, the 45 degree direction Young's modulus is rarely less than 111 GPa and even less than 120 GPa no matter how the manufacturing method is adjusted. There are few. In other words, in the titanium copper of the present invention in which the Young's modulus in the 90 ° direction is adjusted to 100 to 120 GPa and the Young's modulus in the 45 ° direction is adjusted to 140 GPa or less, the Young's modulus in the 45 ° direction is typically 111 GPa or more. Is 120 GPa or more. The Young's modulus value of the present invention is a value measured as a bending deflection coefficient by a cantilever beam.

(Production method)
In a general manufacturing process of titanium copper, first, raw materials such as electrolytic copper and Ti are melted in a melting furnace to obtain a molten metal having a desired composition. Then, this molten metal is cast into an ingot. In order to prevent oxidation wear of titanium, melting and casting are preferably performed in a vacuum or in an inert gas atmosphere. Thereafter, the strips and foils having desired thickness and characteristics are finished in the order of hot rolling, cold rolling, solution treatment, and aging treatment. After the heat treatment, surface pickling or polishing may be performed in order to remove the surface oxide film generated during aging. In order to increase the strength, cold rolling may be performed between the solution treatment and aging or after aging.
In the present invention, in order to obtain the above Young's modulus, heat treatment (hereinafter also referred to as pre-annealing) and cold rolling (hereinafter also referred to as light rolling) with a relatively low degree of work are performed before the solution treatment.
In the pre-annealing, the material is held in a temperature zone of 500 to 650 ° C., preferably in a temperature zone of 500 to 600 ° C. for 5 to 80 seconds, thereby forming a rolled structure formed by cold rolling after hot rolling. , Partially generate recrystallized grains. There is an optimum value for the ratio of recrystallized grains in the rolled structure, and if it is too little or too much, the desired Young's modulus cannot be obtained. The optimum proportion of recrystallized grains can be obtained by adjusting the softening degree S defined below to 0.25 to 0.75.
FIG. 3 illustrates the relationship between the annealing temperature and the tensile strength when the pre-annealing material according to the present invention alloy is annealed at various temperatures. A sample with a thermocouple attached was inserted into a tube furnace at 950 ° C., and when the sample temperature measured by the thermocouple reached a predetermined temperature, the sample was removed from the furnace and cooled, and the tensile strength was measured. is there. Recrystallization proceeds between 500 and 700 ° C., and the tensile strength is rapidly reduced. The gradual decrease in tensile strength on the high temperature side is due to the growth of recrystallized grains.
The softening degree S in the pre-annealing is defined by the following equation.
S = (σ ₀ −σ) / (σ ₀ −σ ₉₀₀ )
Here, σ ₀ is the tensile strength before pre-annealing, and σ and σ ₉₀₀ are the tensile strength after pre-annealing and after annealing at 900 ° C., respectively. The temperature of 900 ° C. is adopted as a reference temperature for knowing the tensile strength after recrystallization because the alloy according to the present invention is stably completely recrystallized when annealed at 900 ° C.
When S is less than 0.25 or more than 0.75, the Young's modulus in the 90-degree direction exceeds 120 GPa.
In order to adjust S to 0.25 to 0.75, the maximum temperature of the material is adjusted to a range of 500 to 650 ° C., preferably 500 to 600 ° C., and the material temperature is 500 ° C. or higher. Hold material for 5 to 80 seconds. When the material temperature exceeds 650 ° C. or the holding time exceeds 80 seconds, it becomes difficult to adjust S to 0.75 or less. When the holding time is less than 5 seconds, it becomes difficult to adjust S to 0.25 or more. When the material arrival temperature is less than 500 ° C., the material holding time at 500 to 650 ° C. becomes zero, so that it is difficult to adjust S to 0.25 or more as in the case where the holding time is less than 5 seconds.
The adjustment of S to 0.25 to 0.75 can be performed by the following procedure.
(1) Measure the tensile test strength (σ ₀ ) of the material before pre-annealing.
(2) The material before preliminary annealing is annealed at 900 ° C. Specifically, the material to which the thermocouple is attached is inserted into a tubular furnace at 950 ° C., and when the sample temperature measured by the thermocouple reaches 900 ° C., the sample is taken out of the furnace and cooled with water.
(3) Obtain the tensile strength (σ ₉₀₀ ) of the material after annealing at 900 ° C.
(4) For example, when σ ₀ is 800 MPa and σ ₉₀₀ is 300 MPa, the tensile strengths corresponding to the softening degrees of 0.25 and 0.75 are 675 MPa and 425 MPa, respectively.
(5) The annealing conditions are determined so that the tensile strength after annealing is 425 to 675 MPa.
In addition to the control of S, the temperature rising rate of the material in the pre-annealing is controlled. In order to obtain a desired Young's modulus, the average rate of temperature increase from 400 ° C. to 500 ° C. is in the range of 1 to 50 ° C./second, more preferably in the range of 1.5 to 40 ° C./second, still more preferably 2 to 2. It is necessary to adjust to a range of 20 ° C./second.
Even if the average heating rate is less than 1 ° C./second or exceeds 50 ° C./second, the Young's modulus in the 45 degree direction exceeds 140 GPa. Further, when the average temperature rise rate is less than 1 ° C./second, the Young's modulus in the 90 ° direction may be less than 100 GPa, and when it exceeds 50 ° C./second, the Young's modulus in the 90 ° direction may exceed 120 GPa. .
As an annealing method that is industrially used in the manufacture of copper-drawn products, continuous annealing in which the strip is run and heated in the furnace, and a batch annealing furnace in which the coil wound with the strip is inserted and heated in the furnace There are two types. Generally, the rate of temperature increase from 400 to 500 ° C. for continuous strips in continuous annealing exceeds 50 ° C./second, and the rate of temperature increase from 400 to 500 ° C. for strips in batch annealing is less than 1 ° C./second. A temperature increase rate of 1 to 50 ° C./second can be achieved by measures such as inclining the temperature distribution in the furnace in continuous annealing, for example.
In the above step (2), “when the sample temperature measured by the thermocouple reaches 900 ° C., the sample is taken out of the furnace and water-cooled” is specifically, for example, the sample is wired in the furnace. When suspended, the wire is cut when it reaches 900 ° C. and dropped into a water tank provided below, or immediately after the sample temperature reaches 900 ° C. by hand from inside the furnace. Take it out quickly by immersing it in a water tank.

After the preliminary annealing, prior to the solution treatment, light rolling with a working degree of 7 to 50% is performed. The processing degree R (%) is defined by the following equation.
R = (t ₀ −t) / t ₀ × 100 (t ₀ : plate thickness before rolling, t: plate thickness after rolling)
If the degree of processing is out of this range, the Young's modulus in the 90 degree direction exceeds 120 GPa.

It is as follows when the manufacturing method of the alloy which concerns on this invention is listed in process order.
(1) Ingot casting (2) Hot rolling (temperature 800-1000 ° C, thickness 5-20mm)
(3) Cold rolling (working degree 30-99%)
(4) Pre-annealing (degree of softening: S = 0.25 to 0.75, average heating rate of 400 to 500 ° C .: 1 to 50 ° C./second)
(5) Light rolling (working degree 7-50%)
(6) Solution treatment (700 to 900 ° C. for 5 to 300 seconds)
(7) Cold rolling (working degree 1-60%)
(8) Aging treatment (2 to 20 hours at 350 to 550 ° C.)
(9) Cold rolling (working degree 1-50%)
(10) Strain relief annealing (at 300 to 700 ° C. for 5 seconds to 10 hours)
Here, the hot rolling (2) can be performed under the condition of general titanium copper, but the rolling to a predetermined thickness is finished in a state where the material temperature is maintained at 350 ° C. or higher, and then immediately cooled with water. It is preferable. Thereby, formation of coarse precipitates (not contributing to increase in strength of the product) during cooling after hot rolling is suppressed.
The degree of work in cold rolling (3) is preferably 30 to 99%. In order to generate recrystallized grains partially by pre-annealing (4), it is necessary to introduce strain by cold rolling (3), and effective strain can be obtained at a workability of 30% or more. On the other hand, if the degree of work exceeds 99%, cracks may occur at the edges of the rolled material and the material being rolled may break.
Cold rolling (7) and (9) is optionally performed to increase the strength, and the strength increases as the degree of rolling process increases, but the bendability decreases. The effect of the present invention that the sag is suppressed by controlling the Young's modulus can be obtained regardless of the presence or absence of cold rolling (7) and (9) and the degree of processing. Cold rolling (7) and (9) may or may not be performed. However, it is not preferable from the viewpoint of bendability that the respective working degrees in the cold rolling (7) and (9) exceed the above upper limit value, and the fact that each working degree is below the above lower limit effect of increasing the strength. From the point of view, it is not preferable.
The strain relief annealing (10) is optionally performed in order to recover the spring limit value and the like which are lowered by the cold rolling when the cold rolling (9) is performed. Regardless of the presence or absence of strain relief annealing (10), the effect of the present invention that the sag is suppressed by controlling the Young's modulus is obtained. The strain relief annealing (10) may or may not be performed.
In addition, what is necessary is just to select the general manufacturing conditions of titanium copper about process (6) and (8).

  The titanium copper of the present invention can be processed into various copper products, for example, plates, strips and foils. Furthermore, the titanium copper of the present invention is a lead frame, connector, pin, terminal, relay, switch, secondary battery. It can be used for electronic device parts such as foil materials.

  Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.

Example 1
3.2 Alloys containing 2% by mass of Ti and the balance being copper and inevitable impurities are used as experimental materials, the relationship between pre-annealing and light rolling conditions and Young's modulus, and the effect of Young's modulus on the sag characteristics of products It was investigated.
In a high frequency melting furnace, 2.5 kg of electrolytic copper was melted using a graphite crucible having an inner diameter of 60 mm and a depth of 200 mm in an argon atmosphere. Alloy elements were added to obtain the above alloy composition, the melt temperature was adjusted to 1300 ° C., and then cast into a cast iron mold to produce an ingot having a thickness of 30 mm, a width of 60 mm, and a length of 120 mm. This ingot was hot-rolled, heated at 950 ° C. for 3 hours, rolled to a thickness of 10 mm while maintaining the material temperature at 350 ° C. or higher, and then immediately cooled with water. The oxidized scale on the surface of the hot rolled plate was removed by grinding with a grinder. The thickness after grinding was 9 mm. Thereafter, rolling and heat treatment were performed in the following order of steps to produce a product sample having a thickness of 0.15 mm.
(1) Cold rolling: Cold rolling was performed to a predetermined thickness according to the rolling degree of light rolling.
(2) Pre-annealing: The sample was inserted into an electric furnace adjusted to a predetermined temperature and held for a predetermined time, and then the sample was left in the air and cooled. Meanwhile, the sample temperature was measured using a thermocouple welded to the sample, and the ultimate temperature, the average temperature rise rate of 400 to 500 ° C, and the holding time of 500 to 650 ° C were determined.
(3) Light rolling: Cold rolling to various thicknesses of 0.18 mm was performed.
(4) Solution treatment: The sample was inserted into an electric furnace adjusted to 800 ° C. and held for 10 seconds, and then the sample was placed in a water bath and cooled.
(5) Aging treatment: Heated in an Ar atmosphere at 450 ° C. for 5 hours using an electric furnace.
(6) Cold rolling: Cold rolled from 0.18 mm to 0.15 mm at a workability of 17%.
(7) Strain relief annealing: The sample was inserted into an electric furnace adjusted to 400 ° C. and held for 10 seconds, and then the sample was left in the air and cooled.

The following evaluation was performed on the sample after the preliminary annealing and the product sample (in this case, the strain relief annealing was completed).
(Evaluation of softening degree in preliminary annealing)
With respect to the sample before pre-annealing and after pre-annealing, the tensile strength was measured in parallel with the rolling direction using a tensile tester in accordance with JIS Z 2241, and the respective values were taken as σ ₀ and σ. In addition, an annealed sample at 900 ° C. was prepared by the above procedure (inserted into a 950 ° C. furnace and cooled when the sample reached 900 ° C.), and the tensile strength was measured in parallel with the rolling direction to obtain σ ₉₀₀ . It was. The degree of softening S was determined from σ ₀ , σ, and σ ₉₀₀ by the following formula.
S = (σ ₀ −σ) / (σ ₀ −σ ₉₀₀ )

(Product tensile test)
A 0.2% proof stress was measured in parallel with the rolling direction in accordance with JIS Z2241 using a tensile tester.

(Young's modulus measurement)
The Young's modulus was measured according to the Japan Copper and Brass Association (JACBA) technical standard “Method of measuring bending deflection coefficient of cantilevered copper and copper alloy strips”.
A strip-shaped sample having a plate thickness t, a width w (= 10 mm), and a length of 100 mm, in a direction in which the longitudinal direction of the sample shown in FIG. 2 forms an angle of 90 degrees with the rolling direction and an angle of 45 degrees, Each was collected. One end of this sample was fixed, a load of P (= 0.15 N) was applied to a position L (= 100 t) from the fixed end, and the Young's modulus E was determined from the deflection d at this time using the following equation.
E = 4 · P · (L / t) ³ / (w · d)

(Bending test)
A strip-shaped sample having a width of 5 mm was taken in a direction in which the longitudinal direction of the sample shown in FIG. 2 forms an angle of 90 degrees with the rolling direction.
Next, as shown in FIG. 4, one end of the sample is fixed, and a punch whose tip is processed into a knife edge is pressed to a position at a distance L from the fixed end to give a deflection d to the sample. Returned to position and unloaded. The moving speed of the punch was 1 mm / min.
First, a single deflection was applied and the contact force P (load acting on the punch) was measured to determine the sag δ after unloading. In addition, the sagging δ after unloading was determined by giving 5000 times of deflection.
Table 1 shows the evaluation results. Here, the deflection test was performed under the conditions of t (plate thickness) = 0.15 mm, w (plate width) = 5 mm, L (spring length) = 9.3 mm, and d (deflection) = 3 mm. Further, the sag δ is measured with a resolution of 0.01 mm, and when the sag δ is not detected, it is expressed as <0.01 mm.

Inventive Examples 1 to 16 were pre-annealed and light-rolled under the conditions specified by the present invention. The Young's modulus in the 90 ° direction and 45 ° direction satisfied the specification of the present invention, and after one deflection. And after 5000 times, no sag was detected. Inventive Examples 3, 6, 9, 12, and 13 in which the Young's modulus in the 90-degree direction tends to decrease and the Young's modulus in the 90-degree direction is less than 111 GPa are other inventions. Although it was slightly lower than the contact force of the examples, the contact force exceeding 1.7 N could be maintained in all the inventive examples.
The contact force (P) obtained by the deflection test is not limited to the alloy properties such as Young's modulus (E) and proof stress, but also as shown by the above formula 1 [P = dEwt ³ / 4L ³ ]. , W) and deflection conditions (L, d). It can be said that the contact force obtained in the invention example was a sufficient level with respect to the contact force expected from the sample shape and the deflection condition.
Comparative Example 1 does not undergo pre-annealing and light rolling, and corresponds to general titanium copper. Since the Young's modulus in the 90-degree direction exceeded 120 GPa, a sag occurred with one deflection, and this sag increased slightly with a 5,000 deflection.
Although the comparative example 2 performed preliminary annealing and light rolling, the ultimate temperature in the case of preliminary annealing exceeded 650 degreeC and the softening degree exceeded 0.75. Since the degree of softening was excessive, the Young's modulus in the 90-degree direction exceeded 120 GPa. As a result, a sag occurred after a single deflection, and this sag increased slightly after 5000 deflections.
In Comparative Example 3, although pre-annealing and light rolling were performed, the holding time during pre-annealing was less than 5 seconds, and the softening degree was less than 0.25. Since the degree of softening was too small, the Young's modulus in the 90-degree direction exceeded 120 GPa. As a result, a sag occurred after a single deflection, and this sag increased slightly after 5000 deflections.
In Comparative Examples 4 and 5, although pre-annealing and light rolling were performed, the degree of processing during light rolling was too small and too large, so the Young's modulus in the 90 degree direction exceeded 120 GPa. As a result, a sag occurred after a single deflection, and this sag increased slightly after 5000 deflections.
In Comparative Example 6, since the softening degree of pre-annealing and the workability of light rolling were appropriate conditions, the Young's modulus in the 90 degree direction entered 100 to 120 GPa. However, since the temperature increase rate at 400 to 500 ° C. in the pre-annealing was less than 1 ° C./second, the Young's modulus in the 45 ° direction exceeded 140 GPa. As a result, no sag was detected in one deflection, but sag occurred in 5000 deflections.
In Comparative Example 7, as in Comparative Example 6, the rate of temperature increase during the pre-annealing was too low, but because the rate of temperature increase was particularly slow, the Young's modulus in the 45 degree direction exceeded 140 GPa and the deflection was 5000 times. In addition, the Young's modulus in the 90-degree direction was less than 100 GPa, and the contact force was reduced to about 2/3 of the inventive example. When the contact force decreases to this level, problems such as abnormal increase in contact electrical resistance of contacts occur when the connector is processed and used.
In Comparative Example 8, since the softening degree of pre-annealing and the workability of light rolling were appropriate conditions, the Young's modulus in the 90 degree direction entered 100 to 120 GPa. However, since the temperature increase rate at 400 to 500 ° C. in the pre-annealing exceeded 50 ° C./second, the Young's modulus in the 45 ° direction exceeded 140 GPa. As a result, no sag was detected in one deflection, but sag occurred in 5000 deflections.
In Comparative Example 9, as in Comparative Example 8, the rate of temperature increase during pre-annealing was excessive, but because the rate of temperature increase was particularly large, not only the Young's modulus in the 45 degree direction exceeded 140 GPa. The Young's modulus in the 90 degree direction exceeded 120 GPa. As a result, a sag has already occurred after one deflection, and this sag increased significantly after 5,000 deflections.
In Comparative Example 10, although pre-annealing and light rolling were performed, the holding time at the time of pre-annealing exceeded 80 seconds, the softening degree was excessive, and the heating rate was excessive. The Young's modulus in the 90-degree direction exceeded 120 GPa, and a sag occurred with one deflection, and this sag increased slightly with a 5,000 deflection.

(Example 2)
It was verified that the effect of improving the sag shown in Example 1 was obtained with titanium copper having different components and production conditions.
Casting, hot rolling and surface grinding were performed in the same manner as in Example 1 to obtain a 9 mm thick plate having the components shown in Table 2. This plate was subjected to rolling and heat treatment in the following process order to obtain a product sample having a plate thickness shown in Table 2.
(1) Cold rolling (2) Pre-annealing: Performed in the same manner as in Example 1.
(3) Light rolling (4) Solution treatment: The sample was inserted into an electric furnace adjusted to a predetermined temperature and held for 10 seconds, and then the sample was placed in a water bath and cooled. The temperature was selected so that the average diameter of the recrystallized grains was in the range of 5 to 25 μm.
(5) Cold rolling (Rolling 1)
(6) Aging treatment: Heating was performed in an Ar atmosphere using an electric furnace at a predetermined temperature for 5 hours. The temperature was selected to maximize the tensile strength after aging.
(7) Cold rolling (Rolling 2)
(8) Strain relief annealing: The sample was inserted into an electric furnace adjusted to a predetermined temperature and held for 10 seconds, and then the sample was left in the air and cooled.
Evaluation similar to Example 1 was performed about the sample after pre-annealing, and a product sample. In the deflection test, w = 5 mm, and L and d were set for each alloy group described later so that the effects of the present invention are easily exhibited.
Tables 2 and 3 show the evaluation results. When any one of rolling 1, rolling 2, and strain relief annealing is not performed, “none” is written in the column of the degree of processing or temperature.

(Alloy A)
The alloy A contains only Ti as an alloy component, and the balance is composed of copper and inevitable impurities. Moreover, all of rolling 1, rolling 2, and strain relief annealing are performed. In Invention Example A-1, since the Young's modulus satisfied the regulation, no sag was detected after one deflection and after 5,000 deflections.
In Comparative Example A-1, since the degree of softening in the pre-annealing exceeded 0.75 and the Young's modulus in the 90-degree direction exceeded 120 GPa, sag occurred due to a single deflection.
In Comparative Example A-2, the temperature increase rate of the pre-annealing was less than 1 ° C./second, and the Young's modulus in the 45 ° direction exceeded 140 GPa, so that sag occurred after 5000 deflections.
In Comparative Example A-3, since the Ti concentration was too low, the yield strength of the product was reduced, and sag occurred due to a single deflection.
As for the contact force, in Invention Example A-1, Comparative Example A-1 and Comparative Example A-2, the Young's modulus in the 90-degree direction was 100 GPa or more, and therefore the contact level expected from the sample shape and deflection conditions. Power was obtained. On the other hand, in Comparative Example A-3 in which the Young's modulus in the 90-degree direction exceeded 100 GPa but the proof stress was remarkably low, 2/3 of Invention Example A-1, Comparative Example A-1 and Comparative Example A-2 Only a moderate contact force was obtained.

(Alloy B)
Alloy B contains 3.5% Ti and 0.2% Fe (% is mass%, the same applies hereinafter) as alloy components, and the balance is composed of copper and inevitable impurities. Moreover, rolling 1 is performed.
In Invention Example B-1, because the Young's modulus satisfied the regulation, no sag was detected after one deflection and after 5,000 deflections.
In Comparative Example B-1, pre-annealing and light rolling were not performed, and the Young's modulus in the 90-degree direction exceeded 120 GPa, so that sag occurred due to a single deflection.
In Comparative Example B-2, since the temperature increase rate of the pre-annealing exceeded 50 ° C./second and the Young's modulus in the 45 degree direction exceeded 140 GPa, sag occurred at 5000 times of deflection.
In each of Invention Example B-1, Comparative Example B-1, and Comparative Example B-2, the Young's modulus in the 90-degree direction was 100 GPa or more, so that the contact force at the level expected from the sample shape and the deflection condition was obtained. It was.

(Alloy C)
Alloy C contains 2.0% Ti, 0.1% Ag, 0.1% Co and 0.1% Ni as alloy components, and the balance is composed of copper and inevitable impurities. Further, rolling 2 and strain relief annealing are performed.
In Invention Example C-1, because the Young's modulus satisfied the regulation, no sag was detected after one deflection and after 5,000 deflections.
In Comparative Example C-1, since the degree of softening during pre-annealing exceeded 0.75 and the Young's modulus in the 90-degree direction exceeded 120 GPa, sag occurred due to a single deflection.
In Comparative Example C-2, the degree of softening in the pre-annealing was less than 0.25, and the Young's modulus in the 90-degree direction exceeded 120 GPa, so that sag occurred with a single deflection.
In Comparative Example C-3, the temperature increase rate of the pre-annealing was less than 1 ° C./second, and the Young's modulus in the 45 ° direction exceeded 140 GPa, so that sag occurred after 5000 times of deflection.
In addition, since the Young's modulus in the 90-degree direction was 100 GPa or more in all of Invention Example C-1, Comparative Example C-1, Comparative Example C-2, and Comparative Example C-3, the level expected from the sample shape and deflection conditions The contact force was obtained.

(Alloy D)
Alloy D contains 4.5% Ti, 0.05% Si, 0.1% Ni, 0.1% Zr and 0.1% Cr as the alloy components, with the balance being composed of copper and inevitable impurities Is done. Moreover, rolling 1 is performed.
In Invention Example D-1, since the Young's modulus satisfied the regulation, no sag was detected after one deflection and after 5,000 deflections.
In Comparative Example D-1, since the workability of light rolling exceeded 50% and the Young's modulus in the 90-degree direction exceeded 120 GPa, sag occurred with a single deflection.
In Comparative Example D-2, since the temperature increase rate of the pre-annealing exceeded 50 ° C./second and the Young's modulus in the 45 degree direction exceeded 140 GPa, sag occurred after 5000 times of deflection.
In each of Invention Example D-1, Comparative Example D-1 and Comparative Example D-2, the Young's modulus in the 90-degree direction was 100 GPa or more, so that the contact force at the level expected from the sample shape and the deflection condition was obtained. It was.

(Alloy E)
Alloy E contains 3.0% Ti, 0.05% Mg, 0.1% Mn, and 0.1% Mo as alloy components, and the balance is composed of copper and inevitable impurities. Further, rolling 2 and strain relief annealing are performed.
In Invention Example E-1, since the Young's modulus satisfied the regulation, no sag was detected after one deflection and after 5,000 deflections.
In Comparative Example E-1, the degree of work in light rolling was less than 7%, and the Young's modulus in the 90-degree direction exceeded 120 GPa, so that sag occurred with a single deflection.
In both Invention Example E-1 and Comparative Example E-1, the Young's modulus in the 90-degree direction was 100 GPa or more, so that the contact force at the level expected from the sample shape and deflection conditions was obtained.
In Comparative Example E-2, the temperature increase rate of the preliminary annealing was very small. For this reason, the Young's modulus in the 45 degree direction exceeded 140 GPa, and sag occurred after 5000 times of deflection. Furthermore, the Young's modulus in the 90-degree direction was less than 100 GPa, and the contact force decreased to less than half that of Invention Example E-1 and Comparative Example E-1.

(Alloy F)
Alloy F contains 2.2% Ti, 0.05% P and 0.05% B as alloy components, and the balance is composed of copper and inevitable impurities. Further, rolling 2 is performed.
In Invention Example F-1, because the Young's modulus satisfied the regulation, no sag was detected after one deflection and after 5,000 deflections.
In Comparative Example F-1, since the temperature increase rate of the pre-annealing was very large, the Young's modulus in the 45 degree direction exceeded 140 GPa, and at the same time, the Young's modulus in the 90 degree direction exceeded 120 GPa. As a result, sag occurred with one deflection, and this sag increased with 5000 deflections.
In addition, since the Young's modulus in the 90-degree direction was 100 GPa or more in both Invention Example F-1 and Comparative Example F-1, a contact force at a level expected from the sample shape and deflection conditions was obtained.

Claims (7)

  It contains 1.5 to 5.0 mass% of Ti, the balance is made of copper and unavoidable impurities, and the Young's modulus in the direction of 90 degrees (degree is the angle formed with the rolling direction in the rolling plane of the copper foil, the same applies hereinafter) Titanium copper having a bending deflection coefficient) of 100 to 120 GPa and a Young's modulus (bending deflection coefficient) in the 45 degree direction of 140 GPa or less.   It contains 1.5 to 5.0% by mass of Ti, the balance is made of copper and inevitable impurities, the Young's modulus in the 90 degree direction (bending deflection coefficient) is 111 to 120 GPa, and the Young's modulus in the 45 degree direction ( Titanium copper according to claim 1, wherein the bending deflection coefficient is 111 to 140 GPa.   The content of 0.005 to 1.0 mass% in total of one or more of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Si, and Zr, according to claim 1 or 2. Titanium copper. An ingot containing 1.5 to 5.0% by mass of Ti and the balance being made of copper and inevitable impurities was manufactured, and the ingot was hot rolled to a thickness of 5 to 20 mm at 800 to 1000 ° C., and then processed. The degree of softening is 0.25 by performing cold rolling at a temperature of 30 to 99% and holding the temperature in the temperature range of 500 to 650 ° C. for 5 to 80 seconds with an average temperature increase rate of 400 to 500 ° C. being 1 to 50 ° C./second. ˜0.75 pre-annealing, cold rolling with a working degree of 7 to 50%, then solution treatment at 700 to 900 ° C. for 5 to 300 seconds, cold rolling with a working degree of 1 to 60%, It is a method of performing aging treatment for 2 to 20 hours at 350 to 550 ° C., cold rolling at a working degree of 1 to 50%, and strain relief annealing arbitrarily performed at 300 to 700 ° C. for 5 seconds to 10 hours in this order,
The method for producing titanium copper according to claim 1, wherein the degree of softening is represented by S of the following formula:
S = (σ ₀ −σ) / (σ ₀ −σ ₉₀₀ )
Here, σ ₀ is the tensile strength before pre-annealing, and σ and σ ₉₀₀ are the tensile strength after pre-annealing and after annealing at 900 ° C., respectively.   5. The ingot according to claim 4, wherein the ingot contains 0.005 to 1.0 mass% in total of one or more of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Si, and Zr. Manufacturing method of titanium copper.   The copper-stretched article provided with the titanium copper in any one of Claims 1-3.   The electronic device component provided with the titanium copper in any one of Claims 1-3.