WO2020044699A1 - Titanium copper plate, pressed product, and pressed-product manufacturing method - Google Patents

Titanium copper plate, pressed product, and pressed-product manufacturing method Download PDF

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Publication number
WO2020044699A1
WO2020044699A1 PCT/JP2019/021863 JP2019021863W WO2020044699A1 WO 2020044699 A1 WO2020044699 A1 WO 2020044699A1 JP 2019021863 W JP2019021863 W JP 2019021863W WO 2020044699 A1 WO2020044699 A1 WO 2020044699A1
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Prior art keywords
rolling
titanium copper
copper plate
heat treatment
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PCT/JP2019/021863
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French (fr)
Japanese (ja)
Inventor
明宏 柿谷
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Ｊｘ金属株式会社
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Priority to CN201980054988.0A priority Critical patent/CN112601828B/en
Priority to EP19854088.2A priority patent/EP3845676A4/en
Priority to KR1020217005796A priority patent/KR102455771B1/en
Publication of WO2020044699A1 publication Critical patent/WO2020044699A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Definitions

  • the present invention relates to a titanium copper plate, a pressed product, and a method for manufacturing a pressed product, particularly a non-milled hardened material that is subjected to a heat treatment after the pressing, and can be suitably used as a member for an electronic component such as a connector.
  • the present invention relates to a method for manufacturing a processed product and a pressed product.
  • Titanium copper is generally known to be an age hardening type copper alloy. Specifically, when a supersaturated solid solution of Ti, which is a solute atom, is formed by a solution treatment, and a heat treatment for a relatively long time is performed at a low temperature from that state, a periodic change in the Ti concentration in the parent phase due to spinodal decomposition occurs. Certain modulation structures develop and the strength increases. Various techniques have been studied based on such a strengthening mechanism with the aim of further improving the properties of titanium copper. In this case, what is problematic is that the strength and the bending workability are mutually contradictory characteristics. That is, when the strength is improved, the bending workability is impaired.
  • Patent Document 1 a third element such as Fe, Co, Ni, or Si is added (Patent Document 1), and the concentration of the impurity element group which forms a solid solution in the parent phase is regulated, and these are added to the second phase particles (Cu—Ti— (X-based particles) are deposited in a predetermined distribution form to increase the regularity of the modulation structure (Patent Document 2), and to define the density of the trace addition element and the second phase particles effective for refining the crystal grains. From the viewpoint of (Patent Document 3) and the like, research and development for achieving both strength and bending workability of titanium copper have been conventionally performed.
  • Patent Document 4 discloses an example in which a material is rapidly cooled at a cooling rate of 200 K (200 ° C.) / Sec or more after heat treatment of the material in order to suppress variation in characteristics. ing.
  • Patent Document 4 discloses an example in which a material is rapidly cooled at a cooling rate of 200 K (200 ° C.) / Sec or more after heat treatment of the material in order to suppress variation in characteristics. ing.
  • Patent Document 5 in order to increase the strength without impairing bending workability, a desired bending radius is obtained when a W bending test is performed in a direction perpendicular to the rolling direction. Titanium-copper alloys are disclosed as ratios.
  • Claim 16 of Patent Document 5 mentions titanium copper which is subjected to aging treatment (hereinafter, heat treatment) after press working, and has a hardness of 345 Hv or more after heat treatment. Poor stability.
  • heat treatment aging treatment
  • Table 10 of Patent Document 5 the amount of thermal expansion and contraction in the direction parallel to the rolling direction after the heat treatment was as large as 0.05% (500 ppm) or more.
  • the present invention aims to provide a titanium copper plate which is a non-mild hardened titanium copper material subjected to heat treatment after press working, and has excellent spring properties and dimensional stability after heat treatment.
  • the present inventors have conducted intensive studies on the spring property and dimensional stability after heat treatment and the properties of titanium copper, and found that titanium copper with adjusted tensile strength and electrical conductivity before heat treatment was heat-treated.
  • the present invention was later found out that it had excellent spring limit values and thermal expansion / contraction characteristics, and that the titanium copper was obtained by solution treatment conditions, warm rolling temperatures and rolling degrees, which will be described later.
  • the present invention contains 2.0 to 4.5% by mass of Ti, the balance is made of copper and unavoidable impurities, the tensile strength in the rolling parallel direction is 750 MPa or more, and the conductivity is 4%. 0.0-8.0% IACS, the spring limit value in the rolling parallel direction when heat-treated at 400 ° C. for 2 hours is 800 MPa or more, and the thermal expansion ratio in the rolling parallel direction when heat-treated at 400 ° C. for 2 hours. Is 100 ppm or less.
  • the conductivity is 4.0 to 6.0% IACS.
  • the spring limit value is 850 MPa or more.
  • the thermal expansion and contraction rate in the rolling parallel direction and the rolling direction in a direction parallel to the rolling surface and orthogonal to the rolling direction is 200 ppm or less.
  • the ratio of the minimum bending radius (MBR) to the plate thickness (t) is: MBR / t ⁇ 2.0.
  • the MBR / t ⁇ 1.8 In one embodiment of the titanium copper plate according to the present invention, the MBR / t ⁇ 1.8.
  • the third element is selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P.
  • One or more kinds are further contained in a total of 0.5% by mass or less.
  • a pressed product provided with any one of the above titanium copper plates.
  • the present invention is a method for manufacturing a pressed product, comprising performing pressing and aging treatments on any one of the above titanium copper plates in this order.
  • a titanium copper plate having excellent spring properties and dimensional stability after heat treatment can be obtained. Since the titanium copper plate according to the present invention is excellent in the spring limit value and the thermal expansion and contraction characteristics after heat treatment, it is an electronic component manufactured by bending and subsequent heat treatment, and is a small electronic device having good product dimensions and spring characteristics. It can be suitably used for manufacturing parts.
  • the titanium copper plate according to the present invention contains 2.0 to 4.5% by mass of Ti, the balance is made of copper and inevitable impurities, and the tensile strength in the rolling parallel direction is 750 MPa or more;
  • the conductivity is 4.0 to 8.0% IACS, the spring limit value in the rolling parallel direction is 800 MPa or more when heat-treated at 400 ° C. for 2 hours, and the rolling parallel direction when heat-treated at 400 ° C. for 2 hours.
  • Ti content One embodiment of the titanium copper plate according to the present invention has a desired Ti content so that Ti is solid-dissolved in a Cu matrix by a solution treatment, and fine precipitates are dispersed in an alloy by an aging treatment. This increases the strength. That is, the Ti content is 2.0% by mass or more and 2.5% by mass from the viewpoint that the tensile strength in the rolling parallel direction before the heat treatment is 750 MPa or more and a sufficient spring limit value is obtained after the heat treatment. Or more, more preferably 3.0% by mass or more. Further, from the viewpoint of suppressing the fracture of the material in hot rolling and further improving bending workability, the content is 4.5% by mass or less, preferably 3.5% by mass or less, and more preferably 3.3% by mass or less. Is more preferred.
  • the titanium copper plate according to the present invention can be used by containing a predetermined third element in addition to copper and titanium, if desired.
  • a predetermined third element in addition to copper and titanium, if desired.
  • at least one selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P as a third element is obtained by adding You may make it contain 0.5 mass% or less.
  • the total content of these elements is 0, that is, it is not necessary to include these elements.
  • it can be used in a range of 0.01 to 0.5% by mass, preferably 0.01 to 0.3% by mass, and more preferably 0.05 to 0.3% by mass.
  • the preferable addition amount of Fe is 0.5% by mass or less, and the more preferable addition amount is 0.25% by mass or less.
  • the preferable addition amount of Co is 0.5% by mass or less, and the more preferable addition amount is 0.1% by mass or less.
  • a preferable addition amount of Mg is 0.1% by mass or less, and a more preferable addition amount is 0.05% by mass or less.
  • the preferable addition amount of Si is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less.
  • the preferable addition amount of Ni is 0.5% by mass or less, and the more preferable addition amount is 0.1% by mass or less.
  • the preferable addition amount of Cr is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less.
  • a preferable addition amount of Zr is 0.1% by mass or less, and a more preferable addition amount is 0.05% by mass or less.
  • a preferable addition amount of Mo is 0.5% by mass or less, and a more preferable addition amount is 0.3% by mass or less.
  • the preferable addition amount of V is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less.
  • the preferable addition amount of Nb is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less.
  • a preferable addition amount of Mn is 0.1% by mass or less, and a more preferable addition amount is 0.05% by mass or less.
  • the preferable addition amount of B is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less.
  • the preferable addition amount of P is 0.5% by mass or less, and the more preferable addition amount is 0.1% by mass or less.
  • the amount is not limited to the above.
  • the thickness of the product that is, the plate thickness (t), is preferably from 0.02 to 1.5 mm.
  • the thickness is not particularly limited, but if the thickness is too large, bending becomes difficult.
  • tensile strength when the tensile strength of the titanium copper plate is 750 MPa or more in the rolling parallel direction and the following electrical conductivity is satisfied, a desired spring limit value is obtained when heat-treated at 400 ° C. for 2 hours. It is preferably at least 775 MPa, more preferably at least 800 MPa. However, although there is no particular upper limit, the tensile strength is preferably less than 900 MPa from the viewpoint of maintaining the dimensional stability of the product without excessive springback. On the other hand, when the tensile strength is lower than 750 MPa, the spring limit value after the heat treatment becomes low, and the spring property tends to decrease. The tensile strength is measured using a tensile tester according to JIS Z2241 (2011).
  • the titanium copper plate according to the present invention has an optimum balance of aging precipitation if the desired tensile strength is satisfied and the conductivity of the titanium copper plate is 4.0 to 8.0% IACS. For this reason, a desired thermal expansion and contraction ratio and a spring limit value can be obtained when heat treatment is performed at 400 ° C. for 2 hours. Preferably, it is 4.0 to 7.0% IACS, and more preferably, it is 4.0 to 6.0% IACS. If the conductivity is lower than 4.0% IACS, the tensile strength tends to be low, and the spring limit after the heat treatment may be low. On the other hand, if the conductivity exceeds 8.0% IACS, the spring limit value after the heat treatment tends to decrease. The electric conductivity is measured according to JIS H 0505.
  • the dimensional change due to the heat treatment is caused by the balance of the thermal expansion and contraction in the rolling parallel direction after the heat treatment, in the direction parallel to the rolling surface and in the direction perpendicular to the rolling direction and at right angles to the rolling direction, and in the thickness direction. It can be generally evaluated by a dimensional change in the direction parallel to the rolling when heat-treated for a long time.
  • the thermal expansion and contraction rate in the rolling parallel direction is preferably 100 ppm or less, more preferably 90 ppm or less, and still more preferably 60 ppm or less, from the viewpoint that the dimensional change of the product after the heat treatment is small and good.
  • the reason why the heating condition when measuring the thermal expansion and contraction rate is 400 ° C.
  • the lower limit of the thermal expansion and contraction rate is not limited in terms of the properties of the titanium copper plate, but the thermal expansion and contraction rate is usually less than 1 ppm.
  • the dimensional change in the direction perpendicular to the rolling direction perpendicular to the rolling direction is measured, and the sum of the thermal expansion ratio in the rolling parallel direction and the thermal expansion ratio in the rolling perpendicular direction is calculated.
  • the sum of the thermal expansion ratio in the direction parallel to the rolling direction and the thermal expansion ratio in the direction perpendicular to the rolling direction after the heat treatment at 400 ° C. for 2 hours is 200 ppm or less, the dimensional stability after the heat treatment is further improved, and 150 ppm or less is preferable. , 100 ppm or less is more preferable. However, the smaller the sum of the thermal expansion and contraction rates, the better.
  • the thermal expansion and contraction rate is measured as follows.
  • the test piece of the titanium copper plate is collected so that the longitudinal direction of the test piece is parallel to the rolling direction. Further, another test piece of the titanium copper plate is sampled in a direction perpendicular to the rolling direction in which the longitudinal direction of the test piece is perpendicular to the plate thickness.
  • two predetermined dents are formed at predetermined intervals (L 0 ). Then, the test specimens in the direction parallel to the rolling direction and the direction perpendicular to the rolling direction are heated under predetermined conditions, and the dent intervals (L) after the heating are measured.
  • the evaluation of bending workability is performed by a W bending test (JIS H3130 (2012)) using a strip-shaped test piece having a width of 10 mm and a length of 30 mm.
  • the test piece sampling direction is a direction in which the bending axis is parallel to the rolling direction (BW direction), and evaluated by the ratio MBR / t between the minimum bending radius MBR (minimum bend radius) at which cracks do not occur and the plate thickness t. I do. It is preferable that the ratio (MBR / t) of the minimum bending radius (MBR) be 2.0 or less from the viewpoint of securing good bendability. A more preferred range of MBR / t is 1.8 or less.
  • the bending workability is measured according to JIS H 3130 (2012).
  • the spring limit value is measured for the titanium copper plate after heat treatment at 400 ° C. for 2 hours. If the spring limit value is 800 MPa or more, it is considered that the spring property used for the connector is sufficiently satisfied.
  • the upper limit is not particularly set, but is preferably 825 MPa or more, more preferably 850 MPa or more.
  • the spring limit value is measured by a moment type test specified in JIS H 3130 (2012).
  • the titanium copper plate according to the present invention can be manufactured by performing a solution treatment and a finish rolling (warm rolling) process immediately thereafter under appropriate conditions.
  • a solution treatment and a finish rolling (warm rolling) process immediately thereafter under appropriate conditions.
  • the addition amount of the third element is preferably 0.05% by mass or more.
  • the order of adding Ti and the third element to Cu is not particularly limited.
  • the homogenization annealing be carried out to form a solid solution in the mother phase as small as possible and to reduce as much as possible. This is because it is effective in preventing bending cracks.
  • the ingot manufacturing step it is preferable to perform hot rolling after heating to a material temperature of 900 to 970 ° C. and performing homogenizing annealing for 3 to 24 hours.
  • the material temperature is preferably set to 960 ° C. or lower before and during hot rolling.
  • the solution temperature is preferably 750 ° C or higher, more preferably 775 ° C or higher, and more preferably 790 ° C or higher, from the viewpoint of adjusting the conductivity to a suitable range and improving the spring limit after the heat treatment. More preferred.
  • the solution temperature is preferably 900 ° C or lower, more preferably 875 ° C or lower, and further preferably 850 ° C or lower. . It is preferable that the rate of temperature rise at this time be as high as possible.
  • the solution treatment time is preferably 5 seconds to 30 minutes, more preferably 10 seconds to 5 minutes.
  • the cooling after the solution treatment is preferably water cooling, and in a preferred embodiment, for example, the average cooling rate is preferably 150 ° C./sec or more, more preferably 155 ° C./sec or more. preferable. If the average cooling rate is less than 150 ° C./sec, the conductivity will increase due to precipitation during cooling, and the spring limit after heat treatment may be reduced. On the other hand, there is no upper limit for the cooling rate, but if it is water cooled, it has a necessary and sufficient cooling rate. However, from the viewpoint of sufficiently obtaining the effect of increasing the strength, the average cooling rate is preferably 1500 ° C./sec or less.
  • the conductivity after the solution can be adjusted in the range of 2.0 to 5.0% IACS.
  • the average cooling rate is the time required for cooling from 750 ° C. at the start of cooling to 100 ° C. (cooling time), and is calculated by (750-100) (° C.) / Cooling time (second). The value (° C./sec).
  • warm finish rolling (hereinafter, also referred to as "warm rolling") is performed.
  • the working ratio (reduction ratio) of warm rolling is 50% or less, preferably 40% or less, from the viewpoint of a suitable thermal expansion and contraction ratio, and from the viewpoint of further improving bendability. , 35% or less. However, it is 15% or more, preferably 20% or more, and more preferably 25% or more, from the viewpoint of setting the tensile strength in a suitable range and increasing the spring limit after the heat treatment.
  • the working ratio is defined by ⁇ ((thickness before rolling-thickness after rolling) / thickness before rolling) ⁇ 100% ⁇ .
  • the material temperature at the end of the warm rolling (hereinafter, the warm rolling temperature) is preferably adjusted within the range of 250 to 350 ° C., and Ti dissolved in the solution to form a nucleus necessary for precipitation by the warm rolling. Form. There is no problem if the starting temperature of warm rolling is lower than the solution temperature, and it is important to control the material temperature at the end of warm rolling.
  • the thermal expansion and contraction rate in the rolling parallel direction after heat treatment at 400 ° C. for 2 hours becomes 100 ppm or less, and the spring after heat treatment is further performed.
  • the above warm rolling temperature suppresses the spring limit after heat treatment without excessively generating nucleation of precipitation, preventing excessive precipitation of the Cu-Ti compound, increasing the electrical conductivity, and not increasing the conductivity.
  • the rolling parallel direction after the heat treatment at 400 ° C. for 2 hours and the direction perpendicular to the rolling direction in a direction parallel to the rolling surface and orthogonal to the rolling direction.
  • the sum of the thermal expansion and contraction is 200 ppm or more.
  • the conductivity after warm rolling is in the range of 4.0 to 8.0% IACS.
  • a Cu—Ti compound is precipitated by heat-treating the above-mentioned material after press working, and the change in lattice constant of titanium copper due to the precipitation affects the thermal expansion and contraction rate.
  • the amount of precipitation after press working can be suppressed by performing the above-mentioned warm rolling step, so that the amount of thermal expansion and contraction is reduced.
  • the desired properties and shape are obtained by pressing and aging the titanium copper plate manufactured by the above-described manufacturing method by a press maker. For example, press working and aging are performed in this order. Pressing and aging are performed under typical conditions.
  • the temperature of the aging treatment is preferably 300 to 440 ° C. so that the spring limit value and the dimensional stability of the material after the treatment are good. Further, the processing time of the aging treatment is preferably 0.5 to 10 hours.
  • the pressed product includes the above-described titanium copper plate.
  • electrolytic copper was melted in a vacuum melting furnace, and Ti was added so as to have a Ti concentration shown in Table 1 according to Invention Examples 1 to 15 and Comparative Examples 1 to 9, and in some cases, a concentration shown in Table 1 was added.
  • the third element is further added, and the ingot having the composition of the remaining copper and inevitable impurities is subjected to homogenization annealing at 950 ° C. for 3 hours, followed by hot rolling at 900 to 950 ° C. A hot-rolled sheet having a thickness of 10 mm was obtained.
  • surface shows a mass%.
  • a plate having a thickness of 0.25 mm was formed by cold rolling. Thereafter, a solution treatment was performed for 10 minutes under the conditions shown in Table 1, and then water cooling was performed. More specifically, the sample and the thermocouple were inserted into an electric furnace adjusted to 700 to 1000 ° C. in the solution treatment, and the material temperature was measured with the thermocouple. It was taken out, placed in a water bath (25 ° C.) or a furnace maintained at a predetermined temperature, and cooled. The cooling rate (° C./sec) other than water cooling was determined from the cooling time from the ultimate temperature of the material to the final temperature of 100 ° C. for the material temperature.
  • test pieces treated as described above were evaluated under the following conditions.
  • the test piece was sampled such that the longitudinal direction of the test piece was parallel to the rolling direction, and the conductivity at 20 ° C. was measured by a four-terminal method according to JIS H0505.
  • the absolute value of the value calculated by the equation (L ⁇ L 0 ) / L 0 ⁇ 10 6 was determined as the thermal expansion / contraction rate (ppm). Further, the sum of the thermal expansion and contraction in the direction parallel to the rolling and the thermal expansion and contraction in the direction perpendicular to the rolling was obtained.
  • test limit value After the material after the warm rolling is heated at 400 ° C. for 2 hours, a long strip-shaped test piece is subjected to a moment type test specified in JIS H 3130 (2012) so that the longitudinal direction of the test piece is parallel to the rolling direction.
  • the test piece (test piece width: 10 mm) was held in a cantilever manner, and the surface maximum stress was measured from a bending moment that caused a permanent deflection amount specified by the material plate thickness, and was set as a spring limit value in a direction perpendicular to the rolling direction.
  • titanium copper of each invention example and each comparative example was produced as a test piece under each condition shown in Table 1, and it was found that the test piece had the properties shown in Table 1.
  • the inventive examples 1 to 15 of the titanium copper plate had the above tensile strength and electrical conductivity, and had excellent spring properties and dimensional stability after heat treatment at 400 ° C. for 2 hours.
  • Invention Examples 1 to 15 of the titanium copper plate can be manufactured by performing hot rolling, intermediate rolling, solution treatment, and finish rolling by warming on the titanium copper having the above composition under the above-described conditions. .
  • a commercially available Cu-Be alloy (C1720- / H (manufactured by NGK)) is shown.
  • the aging temperature is 400 ° C (Reference Example 1)
  • the recommended aging temperature of the Cu-Be alloy is 315 ° C (Reference Example 2).
  • Invention Examples 1, 3 to 5, 9, and 10 of the titanium copper plate had a spring limit value equivalent to that of the Cu—Be alloy, and also had excellent thermal expansion and contraction characteristics.
  • Comparative Example 1 was extremely poor in hot workability due to high Ti concentration, so that the process could not proceed.
  • Comparative Example 2 the Ti concentration was less than 2.0%, so the tensile strength after warm rolling was low, and the spring limit after heat treatment was inferior.
  • Comparative Example 3 was low in tensile strength after finish rolling due to high solution heat temperature, and high in thermal expansion and contraction rate after heat treatment, resulting in inferior dimensional change and spring limit value.
  • Comparative Example 5 had a low cooling rate at the time of solution treatment, so the conductivity after warm rolling was high, and the spring limit value was inferior.
  • Comparative Example 6 had a high degree of warm rolling in the warm state, so the thermal expansion and contraction rate after heat treatment was high, and the dimensional stability was poor.
  • Comparative Example 7 had a low degree of warm rolling due to warmness, and therefore had a low tensile strength and an inferior spring limit after heat treatment.
  • Comparative Example 8 had a high warm rolling temperature, so the conductivity after warm rolling was high, and the spring limit after heat treatment was poor.

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Abstract

Provided is a titanium copper plate that is a titanium-copper-plate non-mill hardened material subjected to heat treatment after pressing, and that exhibits good spring properties and dimensional stability after the heat treatment. The present invention provides a titanium copper plate in which: 2.0-4.5 mass% of Ti is contained, and the remainder is copper and inevitable impurities; the tensile strength in a direction parallel to the rolling direction is equal to or greater than 750 MPa; the conductivity is 4.0-8.0% IACS; the spring deflection limit in the direction parallel to the rolling direction is equal to or greater than 800 MPa when heat treatment is performed for two hours at 400ºC; and the thermal expansion/contraction rate in the direction parallel to the rolling direction is equal to or less than 100 ppm when heat treatment is performed for two hours at 400ºC.

Description

チタン銅板、プレス加工品およびプレス加工品の製造方法Titanium copper plate, pressed product and method for manufacturing pressed product
　本発明はチタン銅板、プレス加工品およびプレス加工品の製造方法に関し、特にプレス加工後に熱処理を行うノンミルハードン材であり、コネクタ等の電子部品用部材として好適に用いることができるチタン銅板、プレス加工品およびプレス加工品の製造方法に関する。 The present invention relates to a titanium copper plate, a pressed product, and a method for manufacturing a pressed product, particularly a non-milled hardened material that is subjected to a heat treatment after the pressing, and can be suitably used as a member for an electronic component such as a connector. The present invention relates to a method for manufacturing a processed product and a pressed product.
　近年では携帯端末などに代表される電子機器の小型化が益々進み、該電子機器に使用されるコネクタは狭ピッチ化及び低背化の傾向が著しい。小型のコネクタとなればピン幅が狭く、小さく折り畳んだ加工形状となるため、使用する部材には、必要なばね性を得るための高い強度と、過酷な曲げ加工に耐えることのできる、優れた曲げ加工性が求められる。この点、チタンを含有する銅合金（以下、「チタン銅」と称する。）は、比較的強度が高く、応力緩和特性にあっては銅合金中最も優れているため、特に強度が要求される信号系端子用部材として、近年、需要が増大してきている。 In recent years, electronic devices typified by mobile terminals and the like have been increasingly miniaturized, and the connectors used in such electronic devices have been significantly reduced in pitch and height. If a small connector is used, the pin width will be narrow and it will be a small folded shape, so the members used will have high strength to obtain the required spring properties and an excellent strength that can withstand severe bending Bending workability is required. In this regard, a copper alloy containing titanium (hereinafter, referred to as “titanium copper”) has relatively high strength and is the most excellent in stress relaxation characteristics among copper alloys, so that particularly high strength is required. In recent years, demand for a signal terminal member has been increasing.
　チタン銅は、一般的に時効硬化型の銅合金であることが知られている。具体的には、溶体化処理によって溶質原子であるＴｉの過飽和固溶体を形成させ、その状態から低温で比較的長時間の熱処理を施すと、スピノーダル分解によって母相中にＴｉ濃度の周期的変動である変調構造が発達し、強度が向上する。かかる強化機構を基本としてチタン銅の更なる特性向上を目指して種々の手法が研究されている。この際、問題となるのは、強度と曲げ加工性が相反する特性である点である。すなわち、強度を向上させると曲げ加工性が損なわれ、その一方で、曲げ加工性を重視すると所望の強度が得られないということである。そこで、Ｆｅ、Ｃｏ、Ｎｉ、Ｓｉなどの第三元素を添加する（特許文献１）、母相中に固溶する不純物元素群の濃度を規制し、これらを第二相粒子（Ｃｕ－Ｔｉ－Ｘ系粒子）として所定の分布形態で析出させて変調構造の規則性を高くする（特許文献２）、結晶粒を微細化させるのに有効な微量添加元素と第二相粒子の密度を規定する（特許文献３）、などの観点から、チタン銅の強度と曲げ加工性の両立を図ろうとする研究開発が従来なされてきた。 Titanium copper is generally known to be an age hardening type copper alloy. Specifically, when a supersaturated solid solution of Ti, which is a solute atom, is formed by a solution treatment, and a heat treatment for a relatively long time is performed at a low temperature from that state, a periodic change in the Ti concentration in the parent phase due to spinodal decomposition occurs. Certain modulation structures develop and the strength increases. Various techniques have been studied based on such a strengthening mechanism with the aim of further improving the properties of titanium copper. In this case, what is problematic is that the strength and the bending workability are mutually contradictory characteristics. That is, when the strength is improved, the bending workability is impaired. On the other hand, when the bending workability is emphasized, a desired strength cannot be obtained. Therefore, a third element such as Fe, Co, Ni, or Si is added (Patent Document 1), and the concentration of the impurity element group which forms a solid solution in the parent phase is regulated, and these are added to the second phase particles (Cu—Ti— (X-based particles) are deposited in a predetermined distribution form to increase the regularity of the modulation structure (Patent Document 2), and to define the density of the trace addition element and the second phase particles effective for refining the crystal grains. From the viewpoint of (Patent Document 3) and the like, research and development for achieving both strength and bending workability of titanium copper have been conventionally performed.
　一般に、チタン銅の製造過程において第二相粒子が粗大化しすぎると、曲げ加工性が損なわれる傾向にあることが知られている。そのため、従来の最終溶体化処理においては、材料を所定の温度に加熱した後、水冷等によりできるだけ速い冷却速度で材料の冷却を行い、冷却過程での第二相粒子の析出を抑える手法が行われている。例えば特開２００１－３０３２２２号公報（特許文献４）では、特性のばらつきを抑制するために、材料の熱処理後に２００Ｋ（２００℃）／秒以上の冷却速度で材料を速やかに冷却する例が開示されている。また、特開２００２－３５６７２６号公報（特許文献５）では、曲げ加工性を損なわずに、高強度化を図るため、圧延方向に対し直角方向にＷ曲げ試験を行った際、所望の曲げ半径比となるチタン銅合金が開示されている。 Generally, it is known that if the second phase particles are excessively coarsened in the production process of titanium copper, bending workability tends to be impaired. Therefore, in the conventional final solution treatment, a method of heating the material to a predetermined temperature, cooling the material at a cooling rate as fast as possible by water cooling or the like, and suppressing precipitation of the second phase particles in the cooling process is performed. Have been done. For example, Japanese Patent Application Laid-Open No. 2001-303222 (Patent Document 4) discloses an example in which a material is rapidly cooled at a cooling rate of 200 K (200 ° C.) / Sec or more after heat treatment of the material in order to suppress variation in characteristics. ing. In Japanese Patent Application Laid-Open No. 2002-356726 (Patent Document 5), in order to increase the strength without impairing bending workability, a desired bending radius is obtained when a W bending test is performed in a direction perpendicular to the rolling direction. Titanium-copper alloys are disclosed as ratios.
特開２００４－２３１９８５号公報JP-A-2004-231985 特開２００４－１７６１６３号公報JP 2004-176163 A 特開２００５－９７６３８号公報JP 2005-97638 A 特開２００１－３０３２２２号公報JP 2001-303222A 特開２００２－３５６７２６号公報JP-A-2002-356726
　一方、プレス加工でコネクタ等の電子部品を製造する場合、強度が高い材料では曲げ加工後のスプリングバックが大きくプレス後の寸法が目標寸法に収まらない問題があった。また、プレスによる歪の導入でばね限界値が低下する問題があった。そのため、溶体化後に仕上冷間圧延を行った比較的強度が低い材料にプレス加工を行い所望の寸法を得たのち、熱処理を行い強度およびばね限界値を向上させるタイプの材料（ノンミルハードン材）を用いることも考えられる。プレス後に熱処理を行うことで高い強度と導電率を有する合金としてＣｕにＢｅを添加した材料が知られており、例えばＣ１７２００（１．８～２．０質量％Ｂｅ－０．２質量％以上のＮｉ＋Ｃｏ、残部Ｃｕ）が、ＣＤＡ（Ｃｏｐｐｅｒ　Ｄｅｖｅｌｏｐｍｅｎｔ　Ａｓｓｏｃｉａｔｉｏｎ）に登録されている。 On the other hand, when manufacturing electronic components such as connectors by press working, there is a problem that a material having high strength has a large springback after bending and the dimensions after press cannot be within the target dimensions. Further, there is a problem that the spring limit value is reduced by the introduction of strain by pressing. For this reason, a material having a relatively low strength, which has been subjected to finish cold rolling after solution treatment, is subjected to press working to obtain desired dimensions, and then subjected to heat treatment to improve strength and spring limit values (non-mild hardened material) ) May be used. A material obtained by adding Be to Cu as an alloy having high strength and electrical conductivity by performing heat treatment after pressing is known. For example, C17200 (1.8 to 2.0 mass% Be-0.2 mass% or more) Ni + Co and the balance Cu) are registered in CDA (Copper \ Development \ Association).
　特許文献５の請求項１６にはプレス加工後に時効処理（以下、熱処理）が行われ、熱処理後の硬さが３４５Ｈｖ以上となるチタン銅が挙げられているが、熱処理後の寸法変化が大きく寸法安定性が劣った。特に特許文献５の表１０の発明例（Ｎｏ．１～１０、１２、１４～１６）では熱処理後の圧延方向と平行方向の熱伸縮量は０．０５％（５００ｐｐｍ）以上と大きかった。 Claim 16 of Patent Document 5 mentions titanium copper which is subjected to aging treatment (hereinafter, heat treatment) after press working, and has a hardness of 345 Hv or more after heat treatment. Poor stability. In particular, in the invention examples (Nos. 1 to 10, 12, 14 to 16) in Table 10 of Patent Document 5, the amount of thermal expansion and contraction in the direction parallel to the rolling direction after the heat treatment was as large as 0.05% (500 ppm) or more.
　そこで、本発明は、一実施形態において、プレス加工後に熱処理を行うチタン銅のノンミルハードン材であり、熱処理後のばね性および寸法安定性が良好なチタン銅板を提供することを目的とする。 Therefore, in one embodiment, the present invention aims to provide a titanium copper plate which is a non-mild hardened titanium copper material subjected to heat treatment after press working, and has excellent spring properties and dimensional stability after heat treatment.
　本発明者は、上記課題を解決するために、熱処理後のばね性および寸法安定性とチタン銅の特性について鋭意検討したところ、熱処理前の引張強さおよび導電率を調整したチタン銅が、熱処理後に優れたばね限界値および熱伸縮特性を有していること、そのチタン銅が、後述する溶体化処理条件、温間圧延温度および圧延加工度によって得られることを見いだして、本発明に到達した。 In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the spring property and dimensional stability after heat treatment and the properties of titanium copper, and found that titanium copper with adjusted tensile strength and electrical conductivity before heat treatment was heat-treated. The present invention was later found out that it had excellent spring limit values and thermal expansion / contraction characteristics, and that the titanium copper was obtained by solution treatment conditions, warm rolling temperatures and rolling degrees, which will be described later.
　すなわち、本発明は一側面において、Ｔｉを２．０～４．５質量％含有し、残部が銅及び不可避的不純物からなり、圧延平行方向の引張強さが７５０ＭＰａ以上であり、導電率が４．０～８．０％ＩＡＣＳであり、４００℃で２時間熱処理したときに圧延平行方向のばね限界値が８００ＭＰａ以上であり、かつ４００℃で２時間熱処理したときに圧延平行方向の熱伸縮率が１００ｐｐｍ以下であるチタン銅板である。 That is, in one aspect, the present invention contains 2.0 to 4.5% by mass of Ti, the balance is made of copper and unavoidable impurities, the tensile strength in the rolling parallel direction is 750 MPa or more, and the conductivity is 4%. 0.0-8.0% IACS, the spring limit value in the rolling parallel direction when heat-treated at 400 ° C. for 2 hours is 800 MPa or more, and the thermal expansion ratio in the rolling parallel direction when heat-treated at 400 ° C. for 2 hours. Is 100 ppm or less.
　本発明に係るチタン銅板の一実施形態においては、前記導電率は４．０～６．０％ＩＡＣＳである。 に お い て In one embodiment of the titanium copper plate according to the present invention, the conductivity is 4.0 to 6.0% IACS.
　本発明に係るチタン銅板の一実施形態においては、前記ばね限界値は８５０ＭＰａ以上である。 に お い て In one embodiment of the titanium copper plate according to the present invention, the spring limit value is 850 MPa or more.
　本発明に係るチタン銅板の一実施形態においては、４００℃で２時間熱処理後において、圧延平行方向の熱伸縮率と、圧延面に平行な方向であって圧延平向方向に対して直交する圧延直角方向の熱伸縮率の和が２００ｐｐｍ以下である。 In one embodiment of the titanium copper plate according to the present invention, after the heat treatment at 400 ° C. for 2 hours, the thermal expansion and contraction rate in the rolling parallel direction and the rolling direction in a direction parallel to the rolling surface and orthogonal to the rolling direction. The sum of thermal expansion and contraction in the perpendicular direction is 200 ppm or less.
　本発明に係るチタン銅板の一実施形態においては、圧延方向に対して曲げ軸が平行（ＢＷ方向）となるＷ曲げ試験において、最小曲げ半径（ＭＢＲ）の、板厚（ｔ）に対する割合が、ＭＢＲ／ｔ≦２．０である。 In one embodiment of the titanium copper plate according to the present invention, in a W bending test in which the bending axis is parallel to the rolling direction (BW direction), the ratio of the minimum bending radius (MBR) to the plate thickness (t) is: MBR / t ≦ 2.0.
　本発明に係るチタン銅板の一実施形態においては、前記ＭＢＲ／ｔ≦１．８である。 に お い て In one embodiment of the titanium copper plate according to the present invention, the MBR / t ≦ 1.8.
　本発明に係るチタン銅板の一実施形態においては、第３元素としてＦｅ、Ｃｏ、Ｍｇ、Ｓｉ、Ｎｉ、Ｃｒ、Ｚｒ、Ｍｏ、Ｖ、Ｎｂ、Ｍｎ、Ｂ、及びＰからなる群から選択された１種以上を合計０．５質量％以下で更に含有する。 In one embodiment of the titanium copper plate according to the present invention, the third element is selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P. One or more kinds are further contained in a total of 0.5% by mass or less.
　また、本発明は別の一側面において、上記何れかのチタン銅板を備えたプレス加工品である。 According to another aspect of the present invention, there is provided a pressed product provided with any one of the above titanium copper plates.
　また、本発明は別の一側面において、上記何れかのチタン銅板を、プレス加工及び時効処理をこの順に行うことを含むプレス加工品の製造方法である。 {Circle over (1)} In another aspect, the present invention is a method for manufacturing a pressed product, comprising performing pressing and aging treatments on any one of the above titanium copper plates in this order.
　本発明によれば、熱処理後のばね性および寸法安定性に優れたチタン銅板を得ることができる。本発明に係るチタン銅板は、熱処理後のばね限界値および熱伸縮特性に優れているため、曲げ加工およびその後の熱処理によって製造される電子部品で、良好な製品寸法およびばね特性を有した小型電子部品の製造に好適に使用することができる。 According to the present invention, a titanium copper plate having excellent spring properties and dimensional stability after heat treatment can be obtained. Since the titanium copper plate according to the present invention is excellent in the spring limit value and the thermal expansion and contraction characteristics after heat treatment, it is an electronic component manufactured by bending and subsequent heat treatment, and is a small electronic device having good product dimensions and spring characteristics. It can be suitably used for manufacturing parts.
熱収縮率測定用の試験片を説明する図である。It is a figure explaining a test piece for heat shrinkage measurement.
　以下に、好適な実施の態様をあげて、本発明を詳細に説明する。なお、本発明は以下の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲で種々の変更が可能である。 本 Hereinafter, the present invention will be described in detail with reference to preferred embodiments. Note that the present invention is not limited to the following embodiments, and various changes can be made without changing the gist of the present invention.
　［１．チタン銅板］
　本発明に係るチタン銅板は、一実施形態において、Ｔｉを２．０～４．５質量％含有し、残部が銅及び不可避的不純物からなり、圧延平行方向の引張強さが７５０ＭＰａ以上であり、導電率が４．０～８．０％ＩＡＣＳであり、４００℃で２時間熱処理したときに圧延平行方向のばね限界値が８００ＭＰａ以上であり、および４００℃で２時間熱処理したときに圧延平行方向の熱伸縮率が１００ｐｐｍ以下である。以下、各構成について好適な態様を説明する。 [1. Titanium copper plate]
In one embodiment, the titanium copper plate according to the present invention contains 2.0 to 4.5% by mass of Ti, the balance is made of copper and inevitable impurities, and the tensile strength in the rolling parallel direction is 750 MPa or more; The conductivity is 4.0 to 8.0% IACS, the spring limit value in the rolling parallel direction is 800 MPa or more when heat-treated at 400 ° C. for 2 hours, and the rolling parallel direction when heat-treated at 400 ° C. for 2 hours. Has a thermal expansion and contraction rate of 100 ppm or less. Hereinafter, preferred embodiments of each configuration will be described.
　（Ｔｉ含有量）
　本発明に係るチタン銅板の一実施形態は、所望とするＴｉ含有量にすることで、溶体化処理によりＣｕマトリックス中へＴｉを固溶させ、時効処理により微細な析出物を合金中に分散させることにより、強度を上昇させる。すなわち、Ｔｉ含有量は、熱処理前の圧延平行方向の引張強さが７５０ＭＰａ以上であり、熱処理後に十分なばね限界値を得るという観点から、２．０質量％以上であり、２．５質量％以上が好ましく、３．０質量％以上がより好ましい。また、熱間圧延において材料の破断を抑制、更に曲げ加工性が優れたものとするという観点から、４．５質量％以下であり、３．５質量％以下が好ましく、３．３質量％以下がより好ましい。 (Ti content)
One embodiment of the titanium copper plate according to the present invention has a desired Ti content so that Ti is solid-dissolved in a Cu matrix by a solution treatment, and fine precipitates are dispersed in an alloy by an aging treatment. This increases the strength. That is, the Ti content is 2.0% by mass or more and 2.5% by mass from the viewpoint that the tensile strength in the rolling parallel direction before the heat treatment is 750 MPa or more and a sufficient spring limit value is obtained after the heat treatment. Or more, more preferably 3.0% by mass or more. Further, from the viewpoint of suppressing the fracture of the material in hot rolling and further improving bending workability, the content is 4.5% by mass or less, preferably 3.5% by mass or less, and more preferably 3.3% by mass or less. Is more preferred.
　（第３元素）
　本発明に係るチタン銅板は、所望によって、銅及びチタン以外に、所定の第３元素を含有させて、使用することができる。好適な実施の態様において、第３元素としてＦｅ、Ｃｏ、Ｍｇ、Ｓｉ、Ｎｉ、Ｃｒ、Ｚｒ、Ｍｏ、Ｖ、Ｎｂ、Ｍｎ、Ｂ、及びＰからなる群から選択された１種以上を、合計０．５質量％以下含有させてもよい。但し、これらの元素の合計含有量は０、つまり、これら元素を含まなくてもよい。例えば、０．０１～０．５質量％、好ましくは０．０１～０．３質量％、さらに好ましくは０．０５～０．３質量％の範囲で含有させて、使用することができる。このような第３元素の添加によって、チタン銅の時効硬化を改善することができるが、第３元素を添加しないチタン銅もまた、本発明の優れた効果を奏するものとなっている。 (Third element)
The titanium copper plate according to the present invention can be used by containing a predetermined third element in addition to copper and titanium, if desired. In a preferred embodiment, at least one selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P as a third element is obtained by adding You may make it contain 0.5 mass% or less. However, the total content of these elements is 0, that is, it is not necessary to include these elements. For example, it can be used in a range of 0.01 to 0.5% by mass, preferably 0.01 to 0.3% by mass, and more preferably 0.05 to 0.3% by mass. Although the age hardening of titanium copper can be improved by the addition of such a third element, titanium copper without the addition of the third element also exhibits the excellent effects of the present invention.
　また、Ｆｅの好ましい添加量は０．５質量％以下であり、より好ましい添加量は０．２５質量％以下である。Ｃｏの好ましい添加量は０．５質量％以下であり、より好ましい添加量は０．１質量％以下である。Ｍｇの好ましい添加量は０．１質量％以下であり、より好ましい添加量は０．０５質量％以下である。Ｓｉの好ましい添加量は０．１質量％以下であり、より好ましい添加量は０．０５質量％以下である。Ｎｉの好ましい添加量は０．５質量％以下であり、より好ましい添加量は０．１質量％以下である。Ｃｒの好ましい添加量は０．１質量％以下であり、より好ましい添加量は０．０５質量％以下である。Ｚｒの好ましい添加量は０．１質量％以下であり、より好ましい添加量は０．０５質量％以下である。Ｍｏの好ましい添加量は０．５質量％以下であり、より好ましい添加量は０．３質量％以下である。Ｖの好ましい添加量は０．１質量％以下であり、より好ましい添加量は０．０５質量％以下である。Ｎｂの好ましい添加量は０．１質量％以下であり、より好ましい添加量は０．０５質量％以下である。Ｍｎの好ましい添加量は０．１質量％以下であり、より好ましい添加量は０．０５質量％以下である。Ｂの好ましい添加量は０．１質量％以下であり、より好ましい添加量は０．０５質量％以下である。Ｐの好ましい添加量は０．５質量％以下であり、より好ましい添加量は０．１質量％以下である。ただし、上記の添加量に限定されない。 好 ま し い Also, the preferable addition amount of Fe is 0.5% by mass or less, and the more preferable addition amount is 0.25% by mass or less. The preferable addition amount of Co is 0.5% by mass or less, and the more preferable addition amount is 0.1% by mass or less. A preferable addition amount of Mg is 0.1% by mass or less, and a more preferable addition amount is 0.05% by mass or less. The preferable addition amount of Si is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less. The preferable addition amount of Ni is 0.5% by mass or less, and the more preferable addition amount is 0.1% by mass or less. The preferable addition amount of Cr is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less. A preferable addition amount of Zr is 0.1% by mass or less, and a more preferable addition amount is 0.05% by mass or less. A preferable addition amount of Mo is 0.5% by mass or less, and a more preferable addition amount is 0.3% by mass or less. The preferable addition amount of V is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less. The preferable addition amount of Nb is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less. A preferable addition amount of Mn is 0.1% by mass or less, and a more preferable addition amount is 0.05% by mass or less. The preferable addition amount of B is 0.1% by mass or less, and the more preferable addition amount is 0.05% by mass or less. The preferable addition amount of P is 0.5% by mass or less, and the more preferable addition amount is 0.1% by mass or less. However, the amount is not limited to the above.
　（厚み）
　製品の厚み、つまり板厚（ｔ）は０．０２～１．５ｍｍであることが好ましい。特に板厚に制限はないが、板厚が大きすぎると、曲げ加工が困難になる。 (Thickness)
The thickness of the product, that is, the plate thickness (t), is preferably from 0.02 to 1.5 mm. The thickness is not particularly limited, but if the thickness is too large, bending becomes difficult.
　（引張強さ）
　本発明では、チタン銅板の引張強さが圧延平行方向において７５０ＭＰａ以上であり、下記に示す導電率を満たす場合、４００℃で２時間熱処理したときに所望のばね限界値が得られる。好ましくは７７５ＭＰａ以上、さらに好ましくは８００ＭＰａ以上とする。但し、特に上限は設けないものの、スプリングバックが過度とならずに、製品の寸法安定性を維持するという観点から、引張強さが９００ＭＰａ未満であることが好ましい。一方、引張強さが７５０ＭＰａより低いと、熱処理後のばね限界値が低くなり、ばね性が低下しやすい。
　なお、引張強さは、引張試験機を用いてＪＩＳ　Ｚ２２４１（２０１１）に準拠して測定する。 (Tensile strength)
In the present invention, when the tensile strength of the titanium copper plate is 750 MPa or more in the rolling parallel direction and the following electrical conductivity is satisfied, a desired spring limit value is obtained when heat-treated at 400 ° C. for 2 hours. It is preferably at least 775 MPa, more preferably at least 800 MPa. However, although there is no particular upper limit, the tensile strength is preferably less than 900 MPa from the viewpoint of maintaining the dimensional stability of the product without excessive springback. On the other hand, when the tensile strength is lower than 750 MPa, the spring limit value after the heat treatment becomes low, and the spring property tends to decrease.
The tensile strength is measured using a tensile tester according to JIS Z2241 (2011).
　（導電率）
　本発明に係るチタン銅板は、一実施形態では、上記所望とする引張強さを満たし、かつ当該チタン銅板の導電率が４．０～８．０％ＩＡＣＳであれば、時効析出のバランスが最適化されるという理由により、４００℃で２時間熱処理したときに所望の熱伸縮率およびばね限界値が得られる。好ましくは４．０～７．０％ＩＡＣＳ、さらに好ましくは４．０～６．０％ＩＡＣＳである。導電率が４．０％ＩＡＣＳより低くなると、引張強さが低くなりやすく、当該熱処理後のばね限界値が低くなるおそれがある。一方、導電率が８．０％ＩＡＣＳ超だと当該熱処理後のばね限界値が低くなる傾向にある。
　なお、導電率は、ＪＩＳ　Ｈ　０５０５に準拠して測定する。 (conductivity)
In one embodiment, the titanium copper plate according to the present invention has an optimum balance of aging precipitation if the desired tensile strength is satisfied and the conductivity of the titanium copper plate is 4.0 to 8.0% IACS. For this reason, a desired thermal expansion and contraction ratio and a spring limit value can be obtained when heat treatment is performed at 400 ° C. for 2 hours. Preferably, it is 4.0 to 7.0% IACS, and more preferably, it is 4.0 to 6.0% IACS. If the conductivity is lower than 4.0% IACS, the tensile strength tends to be low, and the spring limit after the heat treatment may be low. On the other hand, if the conductivity exceeds 8.0% IACS, the spring limit value after the heat treatment tends to decrease.
The electric conductivity is measured according to JIS H 0505.
　（熱伸縮率）
　熱処理による寸法変化は熱処理後の圧延平行方向、圧延面に平行な方向であって圧延方向に対して直交する圧延直角方向、および板厚方向の熱伸縮変化のバランスによって生じるが、４００℃で２時間熱処理したときに圧延平行方向の寸法変化で概ね評価できる。この圧延平行方向の熱伸縮率は、当該熱処理後の製品の寸法変化が小さく良好であるという観点から、１００ｐｐｍ以下が好ましく、９０ｐｐｍ以下がより好ましく、６０ｐｐｍ以下が更に好ましい。ここで、熱伸縮率を測定する際の加熱条件を４００℃で２時間とした理由は、この条件で測定したときに、チタン銅板の強度が最も高くなりやすいためである。なお、熱伸縮率の下限値については、当該チタン銅板の特性の点からは制限されないが、熱伸縮率が１ｐｐｍ以下になることは通常少ない。 (Thermal expansion and contraction rate)
The dimensional change due to the heat treatment is caused by the balance of the thermal expansion and contraction in the rolling parallel direction after the heat treatment, in the direction parallel to the rolling surface and in the direction perpendicular to the rolling direction and at right angles to the rolling direction, and in the thickness direction. It can be generally evaluated by a dimensional change in the direction parallel to the rolling when heat-treated for a long time. The thermal expansion and contraction rate in the rolling parallel direction is preferably 100 ppm or less, more preferably 90 ppm or less, and still more preferably 60 ppm or less, from the viewpoint that the dimensional change of the product after the heat treatment is small and good. Here, the reason why the heating condition when measuring the thermal expansion and contraction rate is 400 ° C. for 2 hours is that the strength of the titanium copper plate tends to be the highest when measured under this condition. The lower limit of the thermal expansion and contraction rate is not limited in terms of the properties of the titanium copper plate, but the thermal expansion and contraction rate is usually less than 1 ppm.
　さらに、４００℃で２時間熱処理したときに圧延方向に直交する圧延直角方向の寸法変化を測定して、上記圧延平行方向の熱伸縮率と圧延直角方向の熱伸縮率との和を算出する。このとき、４００℃で２時間の熱処理後の圧延平行方向の熱伸縮率と圧延直角方向の熱伸縮率の和が２００ｐｐｍ以下であれば熱処理後の寸法安定性はさらに良好となり、１５０ｐｐｍ以下が好ましく、１００ｐｐｍ以下がより好ましい。ただし、上記熱伸縮率の和は、小さければ小さいほど好ましい。 Furthermore, when heat-treated at 400 ° C. for 2 hours, the dimensional change in the direction perpendicular to the rolling direction perpendicular to the rolling direction is measured, and the sum of the thermal expansion ratio in the rolling parallel direction and the thermal expansion ratio in the rolling perpendicular direction is calculated. At this time, if the sum of the thermal expansion ratio in the direction parallel to the rolling direction and the thermal expansion ratio in the direction perpendicular to the rolling direction after the heat treatment at 400 ° C. for 2 hours is 200 ppm or less, the dimensional stability after the heat treatment is further improved, and 150 ppm or less is preferable. , 100 ppm or less is more preferable. However, the smaller the sum of the thermal expansion and contraction rates, the better.
　なお、熱伸縮率は以下のように測定する。
　当該チタン銅板の試験片を、試験片の長手方向が圧延方向と平行となるように採取する。また、当該チタン銅板の別の試験片を、試験片の長手方向が板厚と直交する圧延直角方向に採取する。次いで、図１に示すように、所定の間隔（Ｌ0）を空け二点の打痕を刻印する。そして、圧延平行方向および圧延直角方向の試験片を所定の条件で加熱し、加熱後の打痕間隔（Ｌ）をそれぞれ測定する。 The thermal expansion and contraction rate is measured as follows.
The test piece of the titanium copper plate is collected so that the longitudinal direction of the test piece is parallel to the rolling direction. Further, another test piece of the titanium copper plate is sampled in a direction perpendicular to the rolling direction in which the longitudinal direction of the test piece is perpendicular to the plate thickness. Next, as shown in FIG. 1, two predetermined dents are formed at predetermined intervals (L 0 ). Then, the test specimens in the direction parallel to the rolling direction and the direction perpendicular to the rolling direction are heated under predetermined conditions, and the dent intervals (L) after the heating are measured.
　（曲げ加工性）
　曲げ加工性の評価は幅１０ｍｍ×長さ３０ｍｍの短冊状の試験片を用いて、Ｗ曲げ試験（ＪＩＳ　Ｈ３１３０（２０１２））により行う。試験片採取方向は、圧延方向に対して曲げ軸が平行になる方向（ＢＷ方向）とし、割れの発生しない最小曲げ半径ＭＢＲ（Ｍｉｎｉｍｕｍ　Ｂｅｎｄ　Ｒａｄｉｕｓ）と板厚ｔとの比ＭＢＲ／ｔにて評価する。この最小曲げ半径（ＭＢＲ）の割合（ＭＢＲ／ｔ）は、２．０以下とすることが、良好な曲げ性を確保するとの観点から好ましい。ＭＢＲ／ｔのさらに好適な範囲は、１．８以下である。
　なお、曲げ加工性は、ＪＩＳ　Ｈ　３１３０（２０１２）に準拠して測定する。 (Bendability)
The evaluation of bending workability is performed by a W bending test (JIS H3130 (2012)) using a strip-shaped test piece having a width of 10 mm and a length of 30 mm. The test piece sampling direction is a direction in which the bending axis is parallel to the rolling direction (BW direction), and evaluated by the ratio MBR / t between the minimum bending radius MBR (minimum bend radius) at which cracks do not occur and the plate thickness t. I do. It is preferable that the ratio (MBR / t) of the minimum bending radius (MBR) be 2.0 or less from the viewpoint of securing good bendability. A more preferred range of MBR / t is 1.8 or less.
The bending workability is measured according to JIS H 3130 (2012).
　（ばね限界値）
　４００℃で２時間熱処理した後のチタン銅板についてばね限界値を測定する。ばね限界値が８００ＭＰａ以上であれば、コネクタに使用するばね性を十分に満たしていると考えられる。上限は特に設けないものの好ましくは８２５ＭＰａ以上、さらに好ましくは８５０ＭＰａ以上が好適である。
　なお、ばね限界値の測定方法は、ＪＩＳ　Ｈ　３１３０（２０１２）に規定されているモーメント式試験を実施する。 (Spring limit value)
The spring limit value is measured for the titanium copper plate after heat treatment at 400 ° C. for 2 hours. If the spring limit value is 800 MPa or more, it is considered that the spring property used for the connector is sufficiently satisfied. The upper limit is not particularly set, but is preferably 825 MPa or more, more preferably 850 MPa or more.
The spring limit value is measured by a moment type test specified in JIS H 3130 (2012).
　［２．チタン銅板の製造方法］
　チタン銅板の一般的な製造プロセスでは、まず溶解炉で電気銅、Ｔｉ等の原料を溶解し、所望の組成の溶湯を得る。そして、この溶湯をインゴットに鋳造する。チタンの酸化損耗を防止するため、溶解及び鋳造は真空中又は不活性ガス雰囲気中で行うことが好ましい。その後、熱間圧延、冷間圧延、溶体化処理の順で所望の厚みおよび特性を有する板に仕上げる。溶体化処理後には、熱処理時に生成した表面酸化膜を除去するために、表面の酸洗や研磨等を行ってもよい。また、高強度化のために、溶体化処理後に冷間圧延を行ってもよい。 [2. Manufacturing method of titanium copper plate]
In a general production process of a titanium copper plate, 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, the molten metal is cast into an ingot. In order to prevent oxidation wear of titanium, melting and casting are preferably performed in vacuum or in an inert gas atmosphere. Thereafter, a plate having desired thickness and properties is finished in the order of hot rolling, cold rolling and solution treatment. After the solution treatment, pickling or polishing of the surface may be performed in order to remove the surface oxide film generated during the heat treatment. Further, in order to increase the strength, cold rolling may be performed after the solution treatment.
　本発明に係るチタン銅板は、特に溶体化処理、その直後の仕上圧延（温間圧延）の工程を適切な条件で実施することにより製造可能である。以下に、好適な製造例を工程毎に順次説明する。 チ タ ン The titanium copper plate according to the present invention can be manufactured by performing a solution treatment and a finish rolling (warm rolling) process immediately thereafter under appropriate conditions. Hereinafter, preferred production examples will be sequentially described for each process.
　１）インゴット製造
　溶解及び鋳造によるインゴットの製造は、基本的に真空中又は不活性ガス雰囲気中で行う。溶解において添加元素の溶け残りがあると、強度の向上に対して有効に作用しない。よって、溶け残りをなくすため、ＦｅやＣｒ等の高融点の第３元素は、添加してから十分に攪拌したうえで、一定時間保持する必要がある。一方、ＴｉはＣｕ中に比較的溶け易いので第３元素の溶解後に添加すればよい。従って、Ｃｕに、第３元素としてＦｅ、Ｃｏ、Ｍｇ、Ｓｉ、Ｎｉ、Ｃｒ、Ｚｒ、Ｍｏ、Ｖ、Ｎｂ、Ｍｎ、Ｂ、及びＰよりなる群から選択される１種以上を合計で０．５質量％以下含有するように添加し、次いで第２元素としてＴｉを２．０～４．５質量％含有するように添加してインゴットを製造することが望ましい。但し、第３元素の添加量は、０．０５質量％以上が好ましい。なお、ＣｕにＴｉと第３元素とを添加する順序は、特に限定されるものではない。 1) Production of Ingot The production of an ingot by melting and casting is basically performed in a vacuum or in an inert gas atmosphere. If there is any remaining undissolved element in the dissolution, it does not effectively work to improve the strength. Therefore, in order to eliminate the undissolved portion, the third element having a high melting point, such as Fe or Cr, needs to be maintained for a certain period of time after being sufficiently stirred after being added. On the other hand, since Ti is relatively easily dissolved in Cu, it may be added after the third element is dissolved. Accordingly, one or more elements selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P as Cu as a third element are added in a total amount of 0.3. It is desirable to add in such a manner that it contains 5% by mass or less, and then add Ti so as to contain 2.0 to 4.5% by mass as a second element to produce an ingot. However, the addition amount of the third element is preferably 0.05% by mass or more. The order of adding Ti and the third element to Cu is not particularly limited.
　２）均質化焼鈍及び熱間圧延
　インゴット製造時に生じた凝固偏析や晶出物は粗大なので均質化焼鈍を行うことにより、できるだけ母相に固溶させて小さくし、可能な限り無くすことが望ましい。これは曲げ割れの防止に効果があるからである。具体的には、インゴット製造工程後には、材料温度９００～９７０℃に加熱して３～２４時間均質化焼鈍を行った後に、熱間圧延を実施するのが好ましい。液体金属脆性を防止するために、熱間圧延前及び熱間圧延中は材料温度９６０℃以下とするのが好ましい。 2) Homogenization annealing and hot rolling Since solidification segregation and crystallization generated during the production of the ingot are coarse, it is desirable that the homogenization annealing be carried out to form a solid solution in the mother phase as small as possible and to reduce as much as possible. This is because it is effective in preventing bending cracks. Specifically, after the ingot manufacturing step, it is preferable to perform hot rolling after heating to a material temperature of 900 to 970 ° C. and performing homogenizing annealing for 3 to 24 hours. In order to prevent liquid metal embrittlement, the material temperature is preferably set to 960 ° C. or lower before and during hot rolling.
　３）溶体化処理
　その後、冷間圧延と焼鈍を適宜繰り返してから、溶体化処理を行うのが好ましい。本発明においては、導電率を好適な範囲に調整して、熱処理後のばね限界値を向上させるという観点から、溶体化温度は７５０℃以上が好ましく、７７５℃以上がより好ましく、７９０℃以上がさらに好ましい。一方、金属組織が緻密なものとなり、引張強さが高く、曲げ加工性が良好であるという観点から、溶体化温度は９００℃以下が好ましく、８７５℃以下がより好ましく、８５０℃以下がさらに好ましい。なお、このときの昇温速度は、極力速くすることが好ましい。
　また、一実施形態においては、溶体化処理を十分に行うため、溶体化時間を５秒～３０分とするのが好ましく、１０秒～５分とするのがより好ましい。 3) Solution treatment After that, it is preferable to perform the solution treatment after cold rolling and annealing are appropriately repeated. In the present invention, the solution temperature is preferably 750 ° C or higher, more preferably 775 ° C or higher, and more preferably 790 ° C or higher, from the viewpoint of adjusting the conductivity to a suitable range and improving the spring limit after the heat treatment. More preferred. On the other hand, from the viewpoint that the metal structure becomes dense, the tensile strength is high, and the bending workability is good, the solution temperature is preferably 900 ° C or lower, more preferably 875 ° C or lower, and further preferably 850 ° C or lower. . It is preferable that the rate of temperature rise at this time be as high as possible.
In one embodiment, in order to sufficiently perform the solution treatment, the solution treatment time is preferably 5 seconds to 30 minutes, more preferably 10 seconds to 5 minutes.
　一方で、この溶体化処理後の冷却は水冷が好ましく、好適な実施の態様において、例えば、平均冷却速度としては１５０℃／ｓｅｃ以上であることが好ましく、１５５℃／ｓｅｃ以上であることがより好ましい。平均冷却速度が１５０℃／ｓｅｃ未満であると、冷却時に析出が生じるため導電率が高くなり、熱処理後のばね限界値が低くなるおそれがある。一方、冷却速度の上限は設けないが水冷であれば必要十分な冷却速度を有する。ただし、強度上昇の効果を十分に得るという観点から、平均冷却速度が１５００℃／ｓｅｃ以下であることが好ましい。溶体化後の導電率は２．０～５．０％ＩＡＣＳの範囲に調整することができる。ここで、平均冷却速度とは、冷却開始時の７５０℃から１００℃まで冷却するのに要した時間（冷却時間）を計測し、（７５０－１００）（℃）／冷却時間（秒）によって算出した値（℃／ｓｅｃ）をいう。 On the other hand, the cooling after the solution treatment is preferably water cooling, and in a preferred embodiment, for example, the average cooling rate is preferably 150 ° C./sec or more, more preferably 155 ° C./sec or more. preferable. If the average cooling rate is less than 150 ° C./sec, the conductivity will increase due to precipitation during cooling, and the spring limit after heat treatment may be reduced. On the other hand, there is no upper limit for the cooling rate, but if it is water cooled, it has a necessary and sufficient cooling rate. However, from the viewpoint of sufficiently obtaining the effect of increasing the strength, the average cooling rate is preferably 1500 ° C./sec or less. The conductivity after the solution can be adjusted in the range of 2.0 to 5.0% IACS. Here, the average cooling rate is the time required for cooling from 750 ° C. at the start of cooling to 100 ° C. (cooling time), and is calculated by (750-100) (° C.) / Cooling time (second). The value (° C./sec).
　４）仕上圧延
　溶体化処理後に温間による仕上圧延（以下、「温間圧延」ともいう。）を行う。好適な実施の態様において、温間圧延の加工度（圧下率）は、好適な熱伸縮率とする観点から、５０％以下であり、４０％以下が好ましく、曲げ性がさらに向上するという観点から、３５％以下がより好ましい。だたし、引張強さが好適な範囲とし、熱処理後のばね限界値を上げるという観点から、１５％以上であり、２０％以上が好ましく、２５％以上がより好ましい。なお、加工度は｛（（圧延前の厚み－圧延後の厚み）／圧延前の厚み）×１００％｝で定義される。 4) Finish rolling After the solution treatment, warm finish rolling (hereinafter, also referred to as "warm rolling") is performed. In a preferred embodiment, the working ratio (reduction ratio) of warm rolling is 50% or less, preferably 40% or less, from the viewpoint of a suitable thermal expansion and contraction ratio, and from the viewpoint of further improving bendability. , 35% or less. However, it is 15% or more, preferably 20% or more, and more preferably 25% or more, from the viewpoint of setting the tensile strength in a suitable range and increasing the spring limit after the heat treatment. The working ratio is defined by {((thickness before rolling-thickness after rolling) / thickness before rolling) × 100%}.
　また、温間圧延終了時の材料温度（以下、温間圧延温度）は２５０～３５０℃の範囲に調整することが好ましく、溶体化によって固溶したＴｉが温間圧延によって析出に必要な核を形成する。温間圧延の開始温度は溶体化温度より低くければ問題なく、温間圧延終了時の材料温度を制御することが重要である。 Further, the material temperature at the end of the warm rolling (hereinafter, the warm rolling temperature) is preferably adjusted within the range of 250 to 350 ° C., and Ti dissolved in the solution to form a nucleus necessary for precipitation by the warm rolling. Form. There is no problem if the starting temperature of warm rolling is lower than the solution temperature, and it is important to control the material temperature at the end of warm rolling.
　上記温間圧延温度は、圧延後の導電率が４．０％ＩＡＣＳ以上となるので、４００℃で２時間の熱処理後の圧延平行方向の熱伸縮率が１００ｐｐｍ以下となり、さらに、熱処理後のばね限界値が高くなるという観点から、２５０℃以上が好ましく、２８０℃以上がより好ましく、３００℃以上がさらに好ましい。ただし、上記温間圧延温度は、析出の核生成が多く発生しすぎずに、Ｃｕ-Ｔｉ化合物の析出が過度に生じず、導電率が高くならずに、熱処理後のばね限界値を抑制するという観点から、３５０℃以下が好ましく、３３０℃以下がより好ましく、３２０℃以下がさらに好ましい。このような温間圧延温度を好適な範囲とすることで、４００℃で２時間の熱処理後の圧延平行方向と、圧延面に平行な方向であって圧延方向に対して直交する圧延直角方向の熱伸縮率の和が２００ｐｐｍ以上となる。 As for the above-mentioned warm rolling temperature, since the conductivity after rolling is 4.0% IACS or more, the thermal expansion and contraction rate in the rolling parallel direction after heat treatment at 400 ° C. for 2 hours becomes 100 ppm or less, and the spring after heat treatment is further performed. From the viewpoint of increasing the limit value, 250 ° C. or higher is preferable, 280 ° C. or higher is more preferable, and 300 ° C. or higher is further preferable. However, the above warm rolling temperature suppresses the spring limit after heat treatment without excessively generating nucleation of precipitation, preventing excessive precipitation of the Cu-Ti compound, increasing the electrical conductivity, and not increasing the conductivity. In light of this, 350 ° C or lower is preferable, 330 ° C or lower is more preferable, and 320 ° C or lower is further preferable. By setting such a warm rolling temperature in a suitable range, the rolling parallel direction after the heat treatment at 400 ° C. for 2 hours and the direction perpendicular to the rolling direction in a direction parallel to the rolling surface and orthogonal to the rolling direction. The sum of the thermal expansion and contraction is 200 ppm or more.
　温間圧延後の導電率は４．０～８．０％ＩＡＣＳの範囲になるように上記条件を調整することが好ましい。特に本発明を制限することはないが、プレス加工後に上記材料を熱処理することでＣｕ－Ｔｉ化合物が析出するが、析出することによってチタン銅の格子定数が変化することが熱伸縮率に影響している可能性がある。上記温間圧延工程を行うことでプレス加工後の析出量を抑えられるため、熱伸縮量が小さくなると考えられる。 上 記 It is preferable to adjust the above conditions so that the conductivity after warm rolling is in the range of 4.0 to 8.0% IACS. Although the present invention is not particularly limited, a Cu—Ti compound is precipitated by heat-treating the above-mentioned material after press working, and the change in lattice constant of titanium copper due to the precipitation affects the thermal expansion and contraction rate. Could be. It is considered that the amount of precipitation after press working can be suppressed by performing the above-mentioned warm rolling step, so that the amount of thermal expansion and contraction is reduced.
　なお、当業者であれば、上記各工程の合間および仕上圧延後に適宜、表面の酸化スケール除去のための研削、研磨、ショットブラスト酸洗および脱脂等を行なうことができることは理解できるであろう。 It should be noted that those skilled in the art can understand that grinding, polishing, shot blast pickling, degreasing, etc. can be appropriately performed between the above-described steps and after the finish rolling to remove oxide scale on the surface.
　［３．プレス加工品の製造方法］
　上述の製造方法で製造されたチタン銅板を、プレスメーカーにてプレス加工および時効処理によって所望の特性および形状を得る。例えばプレス加工および時効処理をこの順で実施する。プレス加工および時効処理は、典型的な条件で実施される。時効処理の温度は、当該処理後の材料のばね限界値や寸法安定性が良好となるように、３００～４４０℃とするのが好ましい。また、時効処理の処理時間は、０．５～１０ｈとするのが好ましい。なお、プレス加工品は、上述のチタン銅板を備える。 [3. Manufacturing method of pressed product]
The desired properties and shape are obtained by pressing and aging the titanium copper plate manufactured by the above-described manufacturing method by a press maker. For example, press working and aging are performed in this order. Pressing and aging are performed under typical conditions. The temperature of the aging treatment is preferably 300 to 440 ° C. so that the spring limit value and the dimensional stability of the material after the treatment are good. Further, the processing time of the aging treatment is preferably 0.5 to 10 hours. The pressed product includes the above-described titanium copper plate.
　以下に本発明の実施例を比較例と共に示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。 実 施 Examples of the present invention are shown 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.
［チタン銅板の製造］
　発明例１～１５及び比較例１～９のチタン銅板を製造するに際しては、活性金属であるＴｉが第２元素として添加されるから、溶製には真空溶解炉を用いた。また、本発明で規定した元素以外の不純物元素の混入による予想外の副作用が生じることを未然に防ぐため、原料は比較的純度の高いものを厳選して使用した。 [Manufacture of titanium copper plate]
In manufacturing the titanium copper plates of Inventive Examples 1 to 15 and Comparative Examples 1 to 9, Ti as an active metal was added as a second element, so that a vacuum melting furnace was used for melting. In addition, in order to prevent unexpected side effects due to mixing of impurity elements other than the elements specified in the present invention, materials having relatively high purity were carefully selected and used.
　まず、真空溶解炉にて電気銅を溶解し、発明例１～１５及び比較例１～９に応じて表１に記載のＴｉ濃度となるようＴｉを添加し、場合により表１に記載の濃度で第３元素を更に添加して、残部銅及び不可避的不純物の組成を有するインゴットに対して９５０℃で３時間加熱する均質化焼鈍を行った後、９００～９５０℃で熱間圧延を行い、板厚１０ｍｍの熱延板を得た。なお、表中に示される各成分の数字は質量％を示す。 First, electrolytic copper was melted in a vacuum melting furnace, and Ti was added so as to have a Ti concentration shown in Table 1 according to Invention Examples 1 to 15 and Comparative Examples 1 to 9, and in some cases, a concentration shown in Table 1 was added. In addition, the third element is further added, and the ingot having the composition of the remaining copper and inevitable impurities is subjected to homogenization annealing at 950 ° C. for 3 hours, followed by hot rolling at 900 to 950 ° C. A hot-rolled sheet having a thickness of 10 mm was obtained. In addition, the number of each component shown in a table | surface shows a mass%.
　次いで、面削による脱スケール後、冷間圧延により厚さ０．２５ｍｍの板とした。その後、表１に記載の条件で溶体化処理を１０分で行った後、水冷を行った。より具体的には、溶体化処理において７００～１０００℃に調整した電気炉に試料と熱電対を挿入し、熱電対で材料温度を測定し材料温度が７００～１０００℃に到達した時点で炉から取り出し、水槽（２５℃）または所定の温度に保持した炉内に入れ冷却した。水冷以外の冷却速度（℃／ｓｅｃ）は材料温度について材料の到達温度から最終温度１００℃となるまでの冷却時間から求めた。その後、酸洗による脱スケールを行った後、最終圧延として、表１に記載の加工度および終了時の材料温度になるように調整して温間圧延（板厚０．１５ｍｍ）を行い、発明例１～１５及び比較例１～９の各試験片を得た。 Next, after descaling by facing, a plate having a thickness of 0.25 mm was formed by cold rolling. Thereafter, a solution treatment was performed for 10 minutes under the conditions shown in Table 1, and then water cooling was performed. More specifically, the sample and the thermocouple were inserted into an electric furnace adjusted to 700 to 1000 ° C. in the solution treatment, and the material temperature was measured with the thermocouple. It was taken out, placed in a water bath (25 ° C.) or a furnace maintained at a predetermined temperature, and cooled. The cooling rate (° C./sec) other than water cooling was determined from the cooling time from the ultimate temperature of the material to the final temperature of 100 ° C. for the material temperature. Then, after descaling by pickling, warm rolling (sheet thickness 0.15 mm) was performed as final rolling by adjusting the working degree and the material temperature at the end of the process as shown in Table 1. Test pieces of Examples 1 to 15 and Comparative Examples 1 to 9 were obtained.
　上記のように処理を行った各試験片について、以下の条件で特性評価を行った。 (4) The characteristics of the test pieces treated as described above were evaluated under the following conditions.
　［成分組成］
　歪取焼鈍後の材料の合金元素濃度をＩＣＰ－質量分析法で分析した。その結果、添加した元素の組成比と実質的に同じであった。 [Component composition]
The alloy element concentration of the material after the strain relief annealing was analyzed by ICP-mass spectrometry. As a result, the composition ratio of the added element was substantially the same.
　［引張強さ］
　試験片の長手方向が圧延方向と平行となるように、ＪＩＳ　Ｚ２２４１（２０１１）に従い、引張試験機を用いて引張強さをそれぞれ測定した。 [Tensile strength]
According to JIS Z2241 (2011), the tensile strength was measured using a tensile tester such that the longitudinal direction of the test piece was parallel to the rolling direction.
　［導電率］
　試験片の長手方向が圧延方向と平行になるように試験片を採取し、ＪＩＳ　Ｈ０５０５に準拠し四端子法により２０℃での導電率を測定した。 [conductivity]
The test piece was sampled such that the longitudinal direction of the test piece was parallel to the rolling direction, and the conductivity at 20 ° C. was measured by a four-terminal method according to JIS H0505.
　［曲げ加工性］
　最終的に得られた各試験片の曲げ加工性を、ＪＩＳ　Ｈ　３１３０（２０１２）に従った、Ｂａｄｗａｙ（曲げ軸が圧延方向と同一方向）のＷ曲げ試験によって、割れが発生しない最小半径（ＭＢＲ）と板厚（ｔ）と比であるＭＢＲ／ｔ値を測定して、評価した。 [Bendability]
The bending property of each finally obtained test piece was measured by a minimum radius (MBR) at which cracking did not occur in a Badway (bending axis is the same direction as the rolling direction) W bending test according to JIS H 3130 (2012). ) And the plate thickness (t) were evaluated by measuring the MBR / t value.
　［熱伸縮率］
　温間圧延後の材料から、幅２０ｍｍ、長さ２１０ｍｍの短冊形状の試験片を、試験片の長手方向が圧延方向と平行となるように採取した。また、別の試験片を、試験片の長手方向が板厚に直交する圧延直角方向に採取した。次いで、図１に示すようにＬ0（＝２００ｍｍ）の間隔を空け二点の打痕を刻印した。その後、圧延平行方向および圧延直角方向の試験片を４００℃で２時間加熱し、加熱後の打痕間隔（Ｌ）をそれぞれ測定した。そして、熱伸縮率（ｐｐｍ）として、（Ｌ－Ｌ0）／Ｌ0×１０6の式で算出される値の絶対値を求めた。さらに、圧延平行方向の熱伸縮率と圧延直角方向の熱伸縮率の和を求めた。 [Thermal expansion and contraction rate]
From the material after the warm rolling, a strip-shaped test piece having a width of 20 mm and a length of 210 mm was sampled such that the longitudinal direction of the test piece was parallel to the rolling direction. Further, another test piece was sampled in a direction perpendicular to the rolling direction in which the longitudinal direction of the test piece was perpendicular to the plate thickness. Next, as shown in FIG. 1, two dents were formed at intervals of L 0 (= 200 mm). Thereafter, the test specimens in the direction parallel to the rolling direction and the direction perpendicular to the rolling direction were heated at 400 ° C. for 2 hours, and the dent intervals (L) after the heating were measured. Then, the absolute value of the value calculated by the equation (L−L 0 ) / L 0 × 10 6 was determined as the thermal expansion / contraction rate (ppm). Further, the sum of the thermal expansion and contraction in the direction parallel to the rolling and the thermal expansion and contraction in the direction perpendicular to the rolling was obtained.
　［ばね限界値］
　温間圧延後の材料を４００℃で２時間加熱した後、ＪＩＳ　Ｈ　３１３０（２０１２）に規定されているモーメント式試験により、試験片の長手方向が圧延方向と平行になるように長い短冊状の試験片（試験片幅１０ｍｍ）を片持ち式に保持し、材料板厚により規定した永久たわみ量を生じさせる曲げモーメントから表面最大応力を測定し、圧延直角方向のばね限界値とした。
　試験条件は材料板厚ｔ（ｍｍ）、材料の固定端から負荷点までの距離ｌ（ｍｍ）、永久たわみ量δ（ｍｍ）について、ｌ2＝４０００ｔ、δ＝０．１とし、試験を行った。 [Spring limit value]
After the material after the warm rolling is heated at 400 ° C. for 2 hours, a long strip-shaped test piece is subjected to a moment type test specified in JIS H 3130 (2012) so that the longitudinal direction of the test piece is parallel to the rolling direction. The test piece (test piece width: 10 mm) was held in a cantilever manner, and the surface maximum stress was measured from a bending moment that caused a permanent deflection amount specified by the material plate thickness, and was set as a spring limit value in a direction perpendicular to the rolling direction.
The test conditions were as follows: material thickness t (mm), distance l (mm) from the fixed end of the material to the load point, and permanent deflection δ (mm): l 2 = 4000 t, δ = 0.1. Was.
　［寸法安定性］
　熱処理前の曲げ角度としては、曲げ割れが生じない範囲で温間圧延後の材料にＷ曲げ加工を行った後、曲げ加工部の実際の曲げ変形角度θを求めた。曲げ方向はＧｏｏｄｗａｙ（曲げ軸が圧延方向と直交する方向）で板厚（ｔ）０．１５ｍｍの場合は曲げ条件をＲ／ｔ＝３．３としたが、曲げ割れが生じない範囲であれば任意の曲げＲをとることができる。さらに、熱処理後の曲げ角度としては、その試験片を４００℃で２時間加熱した後、上記と同様に行い、曲げ変形角度θ’を求めた。
　以上より、熱処理前後の曲げ角度変化「θ’－θ」の絶対値を算出した。表１では、この値が０．５°未満を「◎」とし、０．５°以上１．０°未満を「○」とし、１．０°以上を「×」とした。なお、「◎」は熱処理後の寸法安定性が優れ、「○」は熱処理後の寸法安定性が良好で、「×」は熱処理後の寸法安定性が悪いと判断できる。 [Dimensional stability]
As the bending angle before the heat treatment, the material after the warm rolling was subjected to W bending to the extent that bending cracks did not occur, and then the actual bending deformation angle θ of the bent portion was obtained. The bending direction is Goodway (the direction in which the bending axis is perpendicular to the rolling direction) and the thickness (t) is 0.15 mm. The bending condition is R / t = 3.3. Any bend R can be taken. Further, as the bending angle after the heat treatment, the test piece was heated at 400 ° C. for 2 hours, and then the same as above, and the bending deformation angle θ ′ was obtained.
From the above, the absolute value of the bending angle change “θ′−θ” before and after the heat treatment was calculated. In Table 1, "こ の" indicates that the value is less than 0.5 °, "O" indicates that the value is 0.5 ° or more and less than 1.0 °, and "X" indicates that the value is 1.0 ° or more. In addition, “◎” indicates that the dimensional stability after the heat treatment was excellent, “○” indicates that the dimensional stability after the heat treatment was good, and “×” indicates that the dimensional stability after the heat treatment was poor.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　［結果］
　上述のように、試験片として、各発明例及び各比較例のチタン銅を、表１に示す各条件下で製造したところ、表１に示す特性を有することがわかった。このように、チタン銅板の発明例１～１５は、上記引張強さおよび導電率を有し、４００℃で２時間熱処理後に優れたばね性および寸法安定性を有した。また、チタン銅板の発明例１～１５は、上記組成のチタン銅に対して、熱間圧延、中間圧延、溶体化処理、温間による仕上圧延を上記各条件で行うことにより製造できることが分かった。 [result]
As described above, titanium copper of each invention example and each comparative example was produced as a test piece under each condition shown in Table 1, and it was found that the test piece had the properties shown in Table 1. As described above, the inventive examples 1 to 15 of the titanium copper plate had the above tensile strength and electrical conductivity, and had excellent spring properties and dimensional stability after heat treatment at 400 ° C. for 2 hours. In addition, it was found that Invention Examples 1 to 15 of the titanium copper plate can be manufactured by performing hot rolling, intermediate rolling, solution treatment, and finish rolling by warming on the titanium copper having the above composition under the above-described conditions. .
　また、発明例１、３～７、１０～１４では温間圧延後の仕上加工度を３５％以下とすることで、ばね限界値および熱伸縮率に加えて曲げ加工性も優れていた。 発 明 In addition, in Invention Examples 1, 3 to 7, and 10 to 14, the bending workability was excellent in addition to the spring limit value and the thermal expansion and contraction rate by setting the finish working degree after warm rolling to 35% or less.
　さらに参考例として市販のＣｕ－Ｂｅ合金（Ｃ１７２０－１／４Ｈ（日本ガイシ製））を示すが、時効温度４００℃（参考例１）およびＣｕ－Ｂｅ合金の推奨時効温度３１５℃（参考例２）に対して、チタン銅板の発明例１、３～５、９、１０はＣｕ－Ｂｅ合金と同等のばね限界値を有した上、熱伸縮特性が大きく優れていた。 Further, as a reference example, a commercially available Cu-Be alloy (C1720- ／ H (manufactured by NGK)) is shown. The aging temperature is 400 ° C (Reference Example 1), and the recommended aging temperature of the Cu-Be alloy is 315 ° C (Reference Example 2). On the other hand, Invention Examples 1, 3 to 5, 9, and 10 of the titanium copper plate had a spring limit value equivalent to that of the Cu—Be alloy, and also had excellent thermal expansion and contraction characteristics.
　比較例１はＴｉ濃度が高いため熱間加工性が著しく悪く工程を進められなかった。 Comparative Example 1 was extremely poor in hot workability due to high Ti concentration, so that the process could not proceed.
　比較例２はＴｉ濃度が２．０％を下回ったため、温間圧延後の引張強さが低く、熱処理後のばね限界値が劣った。 In Comparative Example 2, the Ti concentration was less than 2.0%, so the tensile strength after warm rolling was low, and the spring limit after heat treatment was inferior.
　比較例３は溶体化温度が高いため、仕上圧延後の引張強さが低く、また、熱処理後の熱伸縮率が高いため、寸法変化およびばね限界値が劣った。 Comparative Example 3 was low in tensile strength after finish rolling due to high solution heat temperature, and high in thermal expansion and contraction rate after heat treatment, resulting in inferior dimensional change and spring limit value.
　比較例４は溶体化温度が低いため、温間圧延後の導電率が高く、ばね限界値が劣った。 In Comparative Example 4, since the solution heat temperature was low, the conductivity after warm rolling was high, and the spring limit value was inferior.
　比較例５は溶体化時の冷却速度が遅いため、温間圧延後の導電率が高く、ばね限界値が劣った。 Comparative Example 5 had a low cooling rate at the time of solution treatment, so the conductivity after warm rolling was high, and the spring limit value was inferior.
　比較例６は温間による温間圧延加工度が高いため、熱処理後の熱伸縮率が高くなり、寸法安定性が悪化した。 Comparative Example 6 had a high degree of warm rolling in the warm state, so the thermal expansion and contraction rate after heat treatment was high, and the dimensional stability was poor.
　比較例７は温間による温間圧延加工度が低いため、引張強さが低く、熱処理後のばね限界値が劣った。 Comparative Example 7 had a low degree of warm rolling due to warmness, and therefore had a low tensile strength and an inferior spring limit after heat treatment.
　比較例８は温間圧延温度が高いため、温間圧延後の導電率が高く、熱処理後のばね限界値が劣った。 Comparative Example 8 had a high warm rolling temperature, so the conductivity after warm rolling was high, and the spring limit after heat treatment was poor.
　比較例９は温間圧延温度が低く、温間圧延後の導電率が低かったため、熱処理後の熱伸縮率が高いことから寸法安定性が悪化し、また、熱処理時の析出の核が少ないため、ばね限界値が劣った。 In Comparative Example 9, the warm rolling temperature was low, the conductivity after warm rolling was low, and the dimensional stability was deteriorated because the thermal expansion and contraction rate after heat treatment was high, and the number of precipitation nuclei during heat treatment was small. , The spring limit was inferior.

Claims (9)

  1. 　Ｔｉを２．０～４．５質量％含有し、残部が銅及び不可避的不純物からなり、圧延平行方向の引張強さが７５０ＭＰａ以上であり、導電率が４．０～８．０％ＩＡＣＳであり、４００℃で２時間熱処理したときに圧延平行方向のばね限界値が８００ＭＰａ以上であり、かつ４００℃で２時間熱処理したときに圧延平行方向の熱伸縮率が１００ｐｐｍ以下であるチタン銅板。 It contains 2.0 to 4.5% by mass of Ti, the balance consists of copper and inevitable impurities, the tensile strength in the rolling parallel direction is 750 MPa or more, and the electric conductivity is 4.0 to 8.0% IACS. Yes, a titanium copper plate having a spring limit in the parallel direction of rolling of 800 MPa or more when heat-treated at 400 ° C. for 2 hours, and a thermal expansion rate in the parallel direction of rolling of 100 ppm or less when heat-treated at 400 ° C. for 2 hours.
  2. 　前記導電率は４．０～６．０％ＩＡＣＳである請求項１に記載のチタン銅板。 チ タ ン The titanium copper plate according to claim 1, wherein the electrical conductivity is 4.0 to 6.0% IACS.
  3. 　前記ばね限界値は８５０ＭＰａ以上である請求項１または２に記載のチタン銅板。 チ タ ン The titanium copper plate according to claim 1 or 2, wherein the spring limit value is 850 MPa or more.
  4. 　４００℃で２時間熱処理後において、圧延平行方向の熱伸縮率と、圧延面に平行な方向であって圧延方向に対して直交する圧延直角方向の熱伸縮率の和が２００ｐｐｍ以下である請求項１～３の何れか一項に記載のチタン銅板。 After heat treatment at 400 ° C. for 2 hours, the sum of the thermal expansion and contraction in the direction parallel to the rolling direction and the thermal expansion and contraction in the direction perpendicular to the rolling direction that is parallel to the rolling surface and perpendicular to the rolling direction is 200 ppm or less. 4. The titanium copper plate according to any one of items 1 to 3.
  5. 　圧延方向に対して曲げ軸が平行（ＢＷ方向）となるＷ曲げ試験において、最小曲げ半径(ＭＢＲ)の、板厚（ｔ)に対する割合が、ＭＢＲ／ｔ≦２．０である請求項１～４の何れか一項に記載のチタン銅板。 The ratio of the minimum bending radius (MBR) to the plate thickness (t) in a W bending test in which the bending axis is parallel to the rolling direction (BW direction) is MBR / t ≦ 2.0. 5. The titanium copper plate according to any one of 4.
  6. 　前記ＭＢＲ／ｔ≦１．８である請求項５に記載のチタン銅板。 チ タ ン The titanium copper plate according to claim 5, wherein MBR / t ≤ 1.8.
  7. 　第３元素としてＦｅ、Ｃｏ、Ｍｇ、Ｓｉ、Ｎｉ、Ｃｒ、Ｚｒ、Ｍｏ、Ｖ、Ｎｂ、Ｍｎ、Ｂ、及びＰからなる群から選択された１種以上を合計０．５質量％以下で更に含有する請求項１～６の何れか一項に記載のチタン銅板。 One or more selected from the group consisting of Fe, Co, Mg, Si, Ni, Cr, Zr, Mo, V, Nb, Mn, B, and P as a third element in a total of 0.5% by mass or less. The titanium copper plate according to any one of claims 1 to 6, further comprising:
  8. 　請求項１～７の何れか一項に記載のチタン銅板を備えたプレス加工品。 プ レ ス A pressed product provided with the titanium copper plate according to any one of claims 1 to 7.
  9. 　請求項１～７の何れか一項に記載のチタン銅板を、プレス加工及び時効処理をこの順に行うことを含むプレス加工品の製造方法。 (8) A method for producing a pressed product, comprising: performing a pressing and an aging treatment on the titanium copper plate according to any one of (1) to (7) in this order.
PCT/JP2019/021863 2018-08-30 2019-05-31 Titanium copper plate, pressed product, and pressed-product manufacturing method WO2020044699A1 (en)

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