WO2011152124A1 - 電子材料用Cu-Co-Si系銅合金及びその製造方法 - Google Patents
電子材料用Cu-Co-Si系銅合金及びその製造方法 Download PDFInfo
- Publication number
- WO2011152124A1 WO2011152124A1 PCT/JP2011/058923 JP2011058923W WO2011152124A1 WO 2011152124 A1 WO2011152124 A1 WO 2011152124A1 JP 2011058923 W JP2011058923 W JP 2011058923W WO 2011152124 A1 WO2011152124 A1 WO 2011152124A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper alloy
- less
- phase particles
- aging
- mass
- Prior art date
Links
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- 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
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
-
- 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
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- 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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- 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
- C22C9/05—Alloys based on copper with manganese as the next major constituent
-
- 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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
- C22C9/10—Alloys based on copper with silicon as the next major constituent
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
Definitions
- the present invention relates to a precipitation hardening type copper alloy, and more particularly to a Cu—Co—Si based copper alloy suitable for use in various electronic parts.
- Copper alloys for electronic materials used in various electronic parts such as connectors, switches, relays, pins, terminals, and lead frames are required to have both high strength and high conductivity (or thermal conductivity) as basic characteristics. Is done. In recent years, high integration and miniaturization / thinning of electronic components have been rapidly progressing, and the level of demand for copper alloys used in electronic device components has been increased accordingly.
- the amount of precipitation hardening type copper alloys is increasing instead of conventional solid solution strengthened copper alloys such as phosphor bronze and brass as copper alloys for electronic materials.
- precipitation-hardened copper alloys by aging the supersaturated solid solution that has undergone solution treatment, fine precipitates are uniformly dispersed, increasing the strength of the alloy and reducing the amount of solid solution elements in the copper. Electrical conductivity is improved. For this reason, a material excellent in mechanical properties such as strength and spring property and having good electrical conductivity and thermal conductivity can be obtained.
- Cu-Ni-Si copper alloys commonly called Corson alloys
- Corson alloys are representative copper alloys that have relatively high electrical conductivity, strength, and bending workability, and are currently active in the industry. It is one of the alloys being developed. In this copper alloy, the strength and conductivity can be improved by precipitating fine Ni—Si intermetallic compound particles in the copper matrix.
- a Cu—Ni—Si alloy generally called a Corson copper alloy is conventionally known.
- the strength and conductivity can be improved by precipitating fine Ni—Si intermetallic compound particles in the copper matrix.
- a Cu—Co—Si alloy has attracted attention.
- the Cu—Co—Si based alloy has an advantage that it can be made higher in conductivity than the Cu—Ni—Si based copper alloy because the amount of cobalt silicide (Co 2 Si) solid solution is small.
- Processes that greatly affect the properties of Cu-Co-Si-based copper alloys include solution treatment, aging treatment, and final rolling work degree. Among these, aging conditions depend on the distribution and size of cobalt silicide precipitates. This is one of the processes that greatly affects.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2008-55977 describes a Cu—Co—Si based alloy focusing on the size and total amount of inclusions precipitated in the copper alloy as well as the composition of the copper alloy. It describes that after the solution treatment, an aging treatment is performed by heating at 400 ° C. to 600 ° C. for 2 hours to 8 hours. Accordingly, in this document, the size of inclusions precipitated in the copper alloy is 2 ⁇ m or less, and inclusions having a size of 0.05 ⁇ m or more and 2 ⁇ m or less in the copper alloy are controlled to 0.5% by volume or less. is doing.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2009-242814 discloses Cu—Co—Si as a precipitation-type copper alloy material that can stably realize a high conductivity of 50% IACS or more, which is difficult to achieve with a Cu—Ni—Si system.
- System alloys are exemplified. Here, it is described that the aging treatment is performed at 400 to 800 ° C. for 5 seconds to 20 hours.
- the second phase dispersion state is defined from the viewpoint of controlling the crystal grain size, and the second phase particles existing on the crystal grain boundary are present at a density of 10 4 to 10 8 particles / mm 2 , It is described that the value of r / f, which is the ratio of the particle diameter r (unit: ⁇ m) of all second phase particles including the inside of the crystal grains and the crystal grain boundary, to the volume fraction f of the particles is 1 to 100. Has been.
- Patent Document 3 (WO2009-096546) describes a Cu—Co—Si alloy characterized in that the size of a precipitate containing both Co and Si is 5 to 50 nm. It is described that the aging treatment after the solution recrystallization heat treatment is preferably performed at 450 to 600 ° C. for 1 to 4 hours.
- Patent Document 4 (WO2009-116649) describes a Cu—Co—Si alloy having excellent strength, electrical conductivity, and bending workability.
- the aging treatment is performed at 525 ° C. ⁇ 120 minutes
- the rate of temperature rise from room temperature to the maximum temperature is in the range of 3 to 25 ° C./min
- the temperature drop is up to 300 ° C. Describes that cooling was performed in the furnace at a rate of 1 to 2 ° C./min.
- the size of the precipitate is 5 to 50 nm
- the average size of the precipitates described in the invention examples is all 10 nm or more. That is, there is still room for improvement in the precipitation state of the second phase particles represented by cobalt silicide.
- the present inventor has made extensive studies to solve the above problems, and as a result of observing the structure of the Cu—Co—Si based alloy, the distribution state of extremely fine second phase particles having a particle size of about 50 nm or less. It has been found that it is important to appropriately control the temperature, and has an important influence on the improvement of strength, conductivity and sag resistance. Specifically, the second phase particles having a particle size in the range of 5 nm or more and less than 10 nm contribute to the improvement of strength and initial sag resistance, and the second phase particles having a particle size in the range of 10 nm to 50 nm. Has contributed to the improvement of sag resistance repeatedly, and it has been found that the strength and sag resistance can be improved in a balanced manner by controlling the number density and ratio thereof.
- the present invention completed on the basis of the above knowledge includes, in one aspect, Co: 0.5 to 3.0 mass%, Si: 0.1 to 1.0 mass%, with the balance being Cu and inevitable impurities.
- the number density of the second phase particles precipitated in the parent phase of the copper alloy for electronic materials having a particle size of 5 nm to 50 nm is 1 ⁇ 10 12 to 1 ⁇ 10 14 particles / mm 3
- the number density of those having a particle size of 5 nm or more and less than 10 nm is a copper alloy for electronic materials having a particle size of 3 to 6 as a ratio to the number density of those having a particle size of 10 nm or more and 50 nm or less.
- the number density of second phase particles having a particle size of 5 nm or more and less than 10 nm is 2 ⁇ 10 12 to 7 ⁇ 10 13 and the particle size is 10 nm or more and 50 nm or less.
- the number density of the two-phase particles is 3 ⁇ 10 11 to 2 ⁇ 10 13 .
- the copper alloy according to the present invention is a ratio of the minimum radius (MBR) to the plate thickness (t) at which cracks do not occur when performing a Badway W bending test according to JIS H 3130. / T value is 2.0 or less.
- the copper alloy according to the present invention further contains a maximum of 2.5% by mass of Ni.
- the copper alloy according to the present invention further contains up to 0.5% by mass of Cr.
- the copper alloy according to the present invention is further selected from the group consisting of Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn, and Ag. Contains a maximum of 2.0% by mass of seeds or two or more species.
- -Step 1 of melt casting an ingot having any of the above compositions A step 2 in which the material temperature is 950 ° C. or higher and 1050 ° C. or lower and hot rolling is performed after heating for 1 hour or more; -Optional cold rolling process 3; A step 4 of performing a solution treatment in which the material temperature is heated to 850 ° C. or higher and 1050 ° C. or lower; A first aging treatment step 5 in which the material temperature is heated to 400 ° C. or more and 600 ° C. or less for 1 to 12 hours, provided that the material temperature is 400 ° C.
- a cold rolling step 6 with a rolling reduction of 10% or more A second aging treatment step 7 in which the material temperature is heated at 300 ° C. to 400 ° C. for 3 to 36 hours, and the heating time is 3 to 10 times the heating time in the first aging treatment; Is a method for producing a copper alloy for electronic materials.
- the rolling reduction in the cold rolling step 6 is 10 to 50%.
- the present invention is a copper drawn product made of the copper alloy according to the present invention.
- the present invention is an electronic component including the copper alloy according to the present invention.
- a Cu—Co—Si based copper alloy having an improved balance of strength, electrical conductivity, and sag resistance can be obtained, and in a preferred embodiment, Cu—Co—Si is further excellent in bending workability.
- a copper alloy can be obtained.
- a Cu—Co—Si based alloy according to the present invention includes, in one embodiment, 0.5 to 3.0 mass% of Co and 0.1 to 1.0 mass% of Si. The remainder has a composition composed of Cu and inevitable impurities.
- Co and Si form an intermetallic compound by performing an appropriate heat treatment, and can increase the strength without deteriorating the electrical conductivity. If the added amounts of Co and Si are less than Co: 0.5% by mass and Si: less than 0.1% by mass, the desired strength cannot be obtained, and conversely, Co: more than 3.0% by mass, Si: 1. If it exceeds 0% by mass, the strength can be increased, but the electrical conductivity is remarkably lowered, and the hot workability is further deteriorated. Therefore, the addition amounts of Co and Si were set to Co: 0.5 to 3.0% by mass and Si: 0.1 to 1.0% by mass. The addition amounts of Co and Si are preferably Co: 0.5 to 2.0 mass% and Si: 0.1 to 0.5 mass%.
- Ni of Ni can form an intermetallic compound with Si as in the case of Co, and although not as high as Co, the strength can be increased without degrading the conductivity. Therefore, Ni may be added to the Cu—Co—Si alloy according to the present invention. However, when the amount is too large, the decrease in conductivity becomes remarkable as in the case of excessive addition of Co. Therefore, the addition amount of Ni should be 2.5% by mass or less, preferably 2.2% by mass or less, and more preferably 2.0% by mass or less.
- the composition of cobalt silicide which is the second phase particle that leads to improvement in strength, is Co 2 Si with respect to the mass ratio of Co and Si (Co / Si).
- the mass ratio is 4.2. The characteristics can be improved most efficiently. If the mass ratio of Co and Si is too far from this value, any element will be present in excess, but the excess element is not appropriate because it does not lead to an increase in strength or a decrease in conductivity. . Therefore, the mass% ratio of Co and Si is preferably 3.5 ⁇ Co / Si ⁇ 5.5, and more preferably 4 ⁇ Co / Si ⁇ 5.
- the mass% ratio of (Co + Ni) and Si is preferably 3.5 ⁇ [Ni + Co] /Si ⁇ 5.5, and 4 ⁇ [Ni + Co] / Si. It is preferable that ⁇ 5.
- the added amount Cr of Cr preferentially precipitates at the grain boundaries in the cooling process during melt casting, so that the grain boundaries can be strengthened, cracks during hot working are less likely to occur, and yield reduction can be suppressed. That is, Cr that has precipitated at the grain boundaries during melt casting is re-dissolved by solution treatment or the like, but during subsequent aging precipitation, precipitated particles having a bcc structure mainly composed of Cr or a compound with Si are generated. In a normal Cu—Ni—Si alloy, Si that did not contribute to aging precipitation of the added Si amount suppresses the increase in conductivity while being dissolved in the matrix, but the silicide-forming element Cr is reduced.
- the amount of dissolved Si can be reduced, and the conductivity can be increased without impairing the strength.
- Cr concentration exceeds 0.5% by mass, coarse second-phase particles are easily formed, so that product characteristics are impaired. Therefore, Cr can be added to the Cu—Co—Si alloy according to the present invention at a maximum of 0.5 mass%.
- the effect is small if it is less than 0.03% by mass, it is preferably added in an amount of 0.03 to 0.5% by mass, more preferably 0.09 to 0.3% by mass.
- Addition amounts of Mg, Mn, Ag and P Mg, Mn, Ag and P improve the product properties such as strength and stress relaxation characteristics without adding a small amount of addition by adding a small amount.
- the effect of addition is exhibited mainly by solid solution in the matrix phase, but further effects can be exhibited by inclusion in the second phase particles.
- the total concentration of Mg, Mn, Ag and P exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, it is preferable to add a total of 2.0% by mass or more of one or more selected from Mg, Mn, Ag and P to the Cu—Co—Si based alloy according to the present invention.
- the effect is small at less than 0.01% by mass, more preferably 0.01 to 2.0% by mass in total, still more preferably 0.02 to 0.5% by mass in total, typically Add 0.04 to 0.2 mass% in total.
- the addition of a small amount improves product properties such as strength, stress relaxation properties, and plating properties without impairing electrical conductivity.
- the effect of addition is exhibited mainly by solid solution in the matrix.
- the total amount of Sn and Zn exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, a maximum of 2.0% by mass in total of one or two selected from Sn and Zn can be added to the Cu—Co—Si based alloy according to the present invention.
- the amount is less than 0.05% by mass, the effect is small. Therefore, the total amount is preferably 0.05 to 2.0% by mass, and more preferably 0.5 to 1.0% by mass in total.
- Addition amounts of As, Sb, Be, B, Ti, Zr, Al, and Fe As, Sb, Be, B, Ti, Zr, Al, and Fe are also adjusted according to required product characteristics. This improves product properties such as conductivity, strength, stress relaxation properties, and plating properties.
- the effect of addition is exhibited mainly by solid solution in the parent phase, but it can also be exhibited by forming the second phase particles having a new composition or contained in the second phase particles. However, if the total amount of these elements exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired.
- the Cu—Co—Si based alloy according to the present invention one or more selected from As, Sb, Be, B, Ti, Zr, Al, and Fe are added up to 2.0 mass% in total. Can be added. However, if the amount is less than 0.001% by mass, the effect is small. Therefore, the total amount is preferably 0.001 to 2.0% by mass, and more preferably 0.05 to 1.0% by mass.
- the total amount of Mg, P, As, Sb, Be, B, Mn, Sn, Ti, Zr, Al, Fe, Zn, and Ag exceeds 2.0% by mass, manufacturability is likely to be impaired.
- the total of these is 2.0% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less.
- the second-phase particle mainly refers to silicide, but is not limited to this.
- Crystallized substances generated in the solidification process of melt casting and precipitation generated in the subsequent cooling process This refers to precipitates generated in the cooling process after hot rolling, precipitates generated in the cooling process after solution treatment, and precipitates generated in the aging process.
- fine second phase particles of nanometer order (generally less than 0.1 ⁇ m), mainly composed of intermetallic compounds, are deposited by applying an appropriate aging treatment, without deteriorating the conductivity. It is known that high strength can be achieved. However, among such fine second-phase particles, there are a particle size range that tends to contribute to strength and a particle size range that tends to contribute to sag resistance. It has not been known that the sag resistance can be improved in a well-balanced manner.
- the present inventor has found that the number density of very fine second-phase particles having a particle size of about 50 nm or less has an important influence on the improvement of strength, conductivity and sag resistance.
- the second phase particles having a particle size in the range of 5 nm or more and less than 10 nm contribute to the improvement of strength and initial sag resistance
- the second phase particles having a particle size in the range of 10 nm or more and 50 nm or less are Since it contributes to the improvement of repeated sag resistance, it has been found that the strength and sag resistance can be improved in a balanced manner by controlling the number density and ratio thereof.
- the number density of the second phase particles having a particle size of 5 nm to 50 nm is 1 ⁇ 10 12 to 1 ⁇ 10 14 particles / mm 3 , preferably 5 ⁇ 10 12 to 5 ⁇ 10 13 particles / mm 3 . It is important to control to mm 3 . If the number density of the second phase particles is less than 1 ⁇ 10 12 / mm 3 , the advantage of precipitation strengthening is hardly obtained, so that the desired strength and conductivity cannot be obtained, and sag resistance is obtained. Also gets worse. On the other hand, it is considered that the higher the number density of the second phase particles, the higher the feasible level, the better the characteristics. However, when the precipitation of the second phase particles is promoted to increase the number density, the second phase particles are improved. It becomes difficult to produce a number density exceeding 1 ⁇ 10 14 / mm 3 because the particles are easily coarsened.
- the number density of second phase particles having a particle size of 5 nm or more and less than 10 nm which is likely to contribute to strength improvement, and particles that are likely to contribute to improvement of sag resistance. It is necessary to control the ratio of the number density of the second phase particles having a diameter of 10 nm to 50 nm. Specifically, the number density of second phase particles having a particle size of 5 nm or more and less than 10 nm is controlled to 3 to 6 in terms of the ratio to the number density of second phase particles having a particle size of 10 nm or more and 50 nm or less.
- the ratio of the second phase particles that contribute to the strength becomes too small, and the balance between strength and sag resistance deteriorates, so the strength decreases and the initial sag resistance also deteriorates. Become.
- the ratio is larger than 6, the ratio of the second phase particles that contribute to sag resistance becomes too small, and the balance between strength and sag resistance also deteriorates. Becomes worse.
- the number density of second phase particles having a particle size of 5 nm or more and less than 10 nm is 2 ⁇ 10 12 to 7 ⁇ 10 13 particles / mm 3 , and the second phase having a particle size of 10 nm or more and 50 nm or less.
- the number density of the particles is 3 ⁇ 10 11 to 2 ⁇ 10 13 particles / mm 3 .
- the strength depends on the number density of second phase particles having a particle size exceeding 50 nm, but by controlling the number density of second phase particles having a particle size of 5 nm or more and 50 nm or less as described above, The number density of the second phase particles having a diameter exceeding 50 nm naturally settles in an appropriate range.
- the copper alloy according to the present invention is a ratio of the minimum radius (MBR) to the plate thickness (t) where cracks do not occur when performing a Badway W bending test according to JIS H 3130.
- the t value is 2.0 or less.
- the MBR / t value can typically be in the range of 1.0 to 2.0.
- a Corson copper alloy In a general manufacturing process of a Corson copper alloy, first, an atmospheric melting furnace is used to melt raw materials such as electrolytic copper, Ni, Si, and Co to obtain a molten metal having a desired composition. Then, this molten metal is cast into an ingot. Thereafter, hot rolling is performed, and cold rolling and heat treatment are repeated to finish a strip or foil having a desired thickness and characteristics.
- Heat treatment includes solution treatment and aging treatment. In the solution treatment, heating is performed at a high temperature of about 700 to about 1000 ° C. to cause the second phase particles to be dissolved in the Cu matrix and simultaneously to recrystallize the Cu matrix. The solution treatment may be combined with hot rolling.
- the second phase particles that are heated in the temperature range of about 350 to about 550 ° C. for 1 hour or more and solid-dissolved by the solution treatment are precipitated as fine particles of nanometer order.
- This aging treatment increases strength and conductivity.
- cold rolling may be performed before and / or after aging.
- strain relief annealing low temperature annealing
- grinding, polishing, shot blast pickling and the like for removing oxide scale on the surface are appropriately performed.
- the copper alloy according to the present invention basically undergoes the above manufacturing process, but in the finally obtained copper alloy, in order to set the distribution form of the second phase particles within the range specified by the present invention. It is important to strictly control the hot rolling, solution treatment and aging treatment conditions. Unlike the conventional Cu—Ni—Si based Corson alloy, the Cu—Co—Si based alloy of the present invention is Co (which in some cases may further be Cr) as the secondary phase particles are likely to be coarsened as an essential component for age precipitation hardening. ) Is actively added. This is because the generation and growth rate of the second phase particles formed by the added Co together with Ni and Si are sensitive to the holding temperature and the cooling rate during the heat treatment.
- Hot rolling is performed after holding at 950 ° C. to 1050 ° C. for 1 hour or longer, and if the temperature at the end of hot rolling is 850 ° C. or higher, even if Co and further Cr are added, it is dissolved in the matrix. be able to.
- the temperature condition of 950 ° C. or higher is a higher temperature setting than other Corson alloys. If the holding temperature before hot rolling is less than 950 ° C., solid solution is insufficient, and if it exceeds 1050 ° C., the material may be dissolved.
- the purpose of the solution treatment is to increase the age-hardening ability after the solution treatment by solidifying the crystallized particles during melt casting and the precipitated particles after hot rolling.
- the holding temperature and time during the solution treatment are important.
- the holding time is constant, if the holding temperature is increased, the crystallized particles at the time of melting and casting and the precipitated particles after hot rolling can be dissolved, and the area ratio can be reduced.
- the solution treatment temperature is less than 850 ° C., the solid solution is insufficient and the desired strength cannot be obtained, while if the solution treatment temperature exceeds 1050 ° C., the material can be dissolved. There is sex.
- the material temperature is heated to 850 ° C. or higher and 1050 ° C. or lower, and it is more preferable to perform a solution treatment in which the material temperature is heated to 900 ° C. or higher and 1020 ° C. or lower.
- the solution treatment time is preferably 60 seconds to 1 hour.
- the cooling rate after the solution treatment is preferably quenched in order to prevent precipitation of the solid phase second phase particles.
- the Cu—Co—Si based alloy according to the present invention it is effective to perform a mild aging treatment in two stages after the solution treatment and to perform cold rolling between the two aging treatments. is there. Thereby, the coarsening of the precipitate is suppressed, and the distribution state of the second phase particles as defined in the present invention can be obtained.
- the solution treatment is performed while selecting a temperature slightly lower than that conventionally used as useful for the refinement of precipitates, and promoting the precipitation of fine second-phase particles.
- the first aging treatment is less than 400 ° C.
- the density of the second phase particles having a size of 10 nm to 50 nm, which repeatedly improves sag resistance tends to be low.
- the first aging treatment exceeds 500 ° C.
- the suitable temperature for the aging treatment varies depending on the Ni content in the alloy.
- the Cu—Co—Si alloy and the Cu—Co—Ni—Si alloy differ in the precipitation of the second phase particles, and the temperature at which Cu—Co—Si has the highest strength is Cu—Co—Ni—. This is because it shifts to a higher temperature side than Si.
- the material temperature is preferably 400 ° C. or more and 500 ° C. or less, and heating is preferably performed for 3 to 9 hours, and the Ni content is 1.0% by mass. When it is less than%, it is preferably heated at 450 to 550 ° C. for 3 to 9 hours.
- Cold rolling is performed after the first aging treatment.
- insufficient age hardening in the first aging treatment can be supplemented by work hardening.
- the rolling reduction at this time is less than 10%, the strain that becomes a precipitation site is small, and the second phase particles that precipitate in the second aging are difficult to precipitate uniformly.
- the rolling reduction of cold rolling exceeds 50%, the bending workability tends to deteriorate.
- the second phase particles precipitated by aging at the first time are dissolved again.
- the rolling reduction of the cold rolling after the first aging treatment is preferably 10 to 50%, more preferably 15 to 40%.
- the Ni content is 1.0 to 2.5% by mass, the ratio of the second phase particles having a particle size of 5 nm or more and less than 20 nm tends to be small if the rolling reduction is low. desirable.
- the second phase particles precipitated in the first aging treatment are newly grown as much as possible without growing the second phase particles precipitated in the first aging treatment as much as possible. It is the purpose. If the second aging temperature is set high, the second phase particles already precipitated grow too much, and the number density distribution of the second phase particles intended by the present invention cannot be obtained. Therefore, it should be noted that the second aging treatment is performed at a low temperature. However, new second phase particles do not precipitate even if the temperature of the second aging treatment is too low. Therefore, the second aging treatment is preferably performed in a temperature range of 300 ° C. to 400 ° C. for 3 to 36 hours, and more preferably in a temperature range of 300 ° C. to 350 ° C. for 9 to 30 hours.
- the second aging In order to control the number density of second phase particles having a particle size of 5 nm or more and less than 10 nm as a ratio to the number density of second phase particles having a particle size of 10 nm or more and 50 nm or less to 3 to 6, the second aging is used.
- the relationship between the processing time and the time of the first aging treatment is also important. Specifically, by setting the time of the second aging treatment to be three times or more of the time of the first aging treatment, a relatively large amount of the second phase particles having a particle size of 5 nm or more and less than 10 nm are precipitated.
- the density ratio can be 3 or more.
- the time of the second aging treatment is less than 3 times the time of the first aging treatment, the second phase particles having a particle size of 5 nm or more and less than 10 nm are relatively reduced, and the number density ratio is less than 3.
- the time of the second aging treatment is very long compared to the time of the first aging treatment (eg, 10 times or more), the second phase particles having a particle size of 5 nm or more and less than 10 nm increase.
- Second phase particles having a particle size of 10 nm or more and 50 nm or less are also increased by growth of precipitates precipitated by the first aging treatment and growth of precipitates precipitated by the second aging treatment. It tends to be less than 3. Therefore, the time of the second aging treatment is preferably 3 to 10 times the time of the first aging treatment, and more preferably 3 to 5 times.
- the Cu—Ni—Si—Co alloy of the present invention can be processed into various copper products, such as plates, strips, tubes, bars and wires, and the Cu—Ni—Si—Co based copper according to the present invention.
- the alloy can be used for electronic parts such as lead frames, connectors, pins, terminals, relays, switches, and foil materials for secondary batteries, and is particularly suitable for use as a spring material.
- Example of the present invention (without addition of Ni) Copper alloys having respective component compositions shown in Table 1 were melted at 1300 ° C. in a high-frequency melting furnace and cast into an ingot having a thickness of 30 mm. Next, this ingot was heated at 1000 ° C. for 3 hours, then hot-rolled to a plate thickness of 10 mm at an ascending temperature (hot rolling end temperature) of 900 ° C., and rapidly cooled to room temperature after the hot rolling was completed. Next, the surface was chamfered to a thickness of 9 mm for removing the scale, and then a plate having a thickness of 0.15 mm was formed by cold rolling.
- solution treatment was performed at each temperature and time, and after the solution treatment was completed, the solution was quickly cooled to room temperature.
- a first aging treatment is performed at each temperature and time in an inert atmosphere, and cold rolling is performed at each reduction rate.
- a second aging treatment is performed at each temperature and time in an inert atmosphere. Each test piece was manufactured.
- the number density of the second phase particles and the alloy characteristics were measured for each test piece thus obtained as follows.
- the particle size of the second phase particles was (major axis + minor axis) / 2.
- the major axis is the length of the longest line segment that passes through the particle's center of gravity and has the intersections with the particle boundary line at both ends.
- the minor axis is the particle's boundary line through the particle's center of gravity. The length of the shortest line segment among the line segments that have the intersections with.
- the electrical conductivity (EC;% IACS) was determined by volume resistivity measurement using a double bridge.
- the sag resistance is sandwiched between each test piece processed 1mm wide x 100mm long x 0.08mm thick, using a knife edge with a bending distance of 5mm and a stroke of 1mm.
- the amount of permanent deformation (sagging) shown in Table 2 after 5 seconds of loading at room temperature was measured.
- the initial sag resistance was evaluated by setting the number of times of loading by the knife edge as 1, and the repeated sag resistance was evaluated by setting the number of times of load by the knife edge as 10.
- MBR minimum radius
- t thickness
- MBR / t can be generally evaluated as follows. MBR / t ⁇ 1.0 Excellent 1.0 ⁇ MBR / t ⁇ 2.0 Excellent 2.0 ⁇ MBR / t Insufficient
- Table 2 shows the measurement results for each test piece.
- Comparative example (without addition of Ni) Copper alloys having the respective component compositions shown in Table 3 were melted at 1300 ° C. in a high-frequency melting furnace and cast into an ingot having a thickness of 30 mm. Next, this ingot was heated at 1000 ° C. for 3 hours, then hot-rolled to a plate thickness of 10 mm at an ascending temperature (hot rolling end temperature) of 900 ° C., and rapidly cooled to room temperature after the hot rolling was completed. Next, the surface was chamfered to a thickness of 9 mm for removing the scale, and then a plate having a thickness of 0.15 mm was formed by cold rolling. Next, solution treatment was performed at each temperature and time, and after the solution treatment was completed, the solution was quickly cooled to room temperature. Next, a first aging treatment is performed at each temperature and time in an inert atmosphere, and cold rolling is performed at each reduction rate. Finally, a second aging treatment is performed at each temperature and time in an inert atmosphere. Each test piece was manufactured.
- the temperature in the first aging is high and the second phase particles having a particle size of 5 nm or more and 50 nm or less are generally small, or the second phase particles having a particle size of 10 nm or more and 50 nm or less and the second phase having a particle size of 5 nm or more and less than 10 nm. Particle balance is bad. ⁇ No. 1-53, 1-63, 1-70, 1-74> While the temperature at the first aging was low, the temperature at the second aging was high, and the balance between the second phase particles having a particle size of 10 nm to 50 nm and the second phase particles having a particle size of 5 nm to less than 10 nm was deteriorated.
- ⁇ No. 1-54, 1-64> The temperature in the second aging was high, and the ratio of the second phase particles having a particle size of 5 nm or more and less than 10 nm was reduced.
- ⁇ No. 1-55, 1-65, 1-71, 1-75> Since the temperature in the first aging and the second aging was high, and the second phase particles were excessively developed as a whole, the second phase particles having a particle size of 5 nm to 50 nm specified in the present invention were generally insufficient. .
- ⁇ No. 1-57, 1-67> The time in the first aging and the second aging was long, and the second phase particles having a particle size of 5 nm or more and less than 10 nm became insufficient. ⁇ No.
- Example of the present invention (with addition of Ni) Copper alloys having respective component compositions shown in Table 5 were melted at 1300 ° C. in a high frequency melting furnace and cast into an ingot having a thickness of 30 mm. Next, this ingot was heated at 1000 ° C. for 3 hours, then hot-rolled to a plate thickness of 10 mm at an ascending temperature (hot rolling end temperature) of 900 ° C., and rapidly cooled to room temperature after the hot rolling was completed. Next, the surface was chamfered to a thickness of 9 mm for removing the scale, and then a plate having a thickness of 0.15 mm was formed by cold rolling.
- solution treatment was performed at each temperature and time, and after the solution treatment was completed, the solution was quickly cooled to room temperature.
- a first aging treatment is performed at each temperature and time in an inert atmosphere, and cold rolling is performed at each reduction rate.
- a second aging treatment is performed at each temperature and time in an inert atmosphere. Each test piece was manufactured.
- Comparative example (with addition of Ni) Copper alloys having the respective component compositions shown in Table 7 were melted at 1300 ° C. in a high-frequency melting furnace and cast into an ingot having a thickness of 30 mm. Next, this ingot was heated at 1000 ° C. for 3 hours, then hot-rolled to a plate thickness of 10 mm at an ascending temperature (hot rolling end temperature) of 900 ° C., and rapidly cooled to room temperature after the hot rolling was completed. Next, the surface was chamfered to a thickness of 9 mm for removing the scale, and then a plate having a thickness of 0.15 mm was formed by cold rolling. Next, solution treatment was performed at each temperature and time, and after the solution treatment was completed, the solution was quickly cooled to room temperature. Next, a first aging treatment is performed at each temperature and time in an inert atmosphere, and cold rolling is performed at each reduction rate. Finally, a second aging treatment is performed at each temperature and time in an inert atmosphere. Each test piece was manufactured.
- the temperature in the first aging is high and the second phase particles having a particle size of 5 nm or more and 50 nm or less are generally small, or the second phase particles having a particle size of 10 nm or more and 50 nm or less and the second phase having a particle size of 5 nm or more and less than 10 nm. Particle balance is bad. ⁇ No. 2-60, 2-70, 2-77, 2-81> While the temperature at the first aging was low, the temperature at the second aging was high, and the balance between the second phase particles having a particle size of 10 nm to 50 nm and the second phase particles having a particle size of 5 nm to less than 10 nm was deteriorated.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
Description
-上記何れかの組成をもつインゴットを溶解鋳造する工程1と、
-材料温度を950℃以上1050℃以下として1時間以上加熱後に熱間圧延を行う工程2と、
-随意的な冷間圧延工程3と、
-材料温度を850℃以上1050℃以下に加熱する溶体化処理を行う工程4と、
-材料温度を400℃以上600℃以下で1~12時間加熱する第一の時効処理工程5と、ただし、インゴットがNiを1.0~2.5質量%含有するときは材料温度400℃以上500℃以下とし、
-圧下率が10%以上である冷間圧延工程6と、
-材料温度を300℃以上400℃以下で3~36時間加熱し、当該加熱時間を第1の時効処理における加熱時間の3~10倍とする第二の時効処理工程7と、
を順に行なうことを含む電子材料用銅合金の製造方法である。
本発明に係るCu-Co-Si系合金は一実施形態において、Coを0.5~3.0質量%、及び、Siを0.1~1.0質量%含有し、残部がCu及び不可避的不純物からなる組成を有する。
Co及びSiは、適当な熱処理を施すことにより金属間化合物を形成し、導電率を劣化させずに高強度化が図れる。
Co及びSiの添加量がそれぞれCo:0.5質量%未満、Si:0.1質量%未満では所望の強度が得られず、逆に、Co:3.0質量%超、Si:1.0質量%超では高強度化は図れるが導電率が著しく低下し、更には熱間加工性が劣化する。よってCo及びSiの添加量はCo:0.5~3.0質量%、Si:0.1~1.0質量%とした。Co及びSiの添加量は好ましくは、Co:0.5~2.0質量%、Si:0.1~0.5質量%である。
NiはCoと同様にSiと金属間化合物を形成することができ、Coほどではないが導電率を劣化させずに高強度化が図れる。従って、本発明に係るCu-Co-Si系合金には、Niを添加してもよい。ただし、その量が多すぎるとCoの過剰添加と同様に導電率の低下が著しくなる。従って、Niの添加量は2.5質量%以下とするべきであり、好ましくは2.2質量%以下であり、より好ましくは2.0質量%以下である。
Crは溶解鋳造時の冷却過程において結晶粒界に優先析出するため粒界を強化でき、熱間加工時の割れが発生しにくくなり、歩留低下を抑制できる。すなわち、溶解鋳造時に粒界析出したCrは溶体化処理などで再固溶するが、続く時効析出時にCrを主成分としたbcc構造の析出粒子またはSiとの化合物を生成する。通常のCu-Ni-Si系合金では添加したSi量のうち、時効析出に寄与しなかったSiは母相に固溶したまま導電率の上昇を抑制するが、珪化物形成元素であるCrを添加して、珪化物をさらに析出させることにより、固溶Si量を低減でき、強度を損なわずに導電率を上昇できる。しかしながら、Cr濃度が0.5質量%を超えると粗大な第二相粒子を形成しやすくなるため、製品特性を損なう。従って、本発明に係るCu-Co-Si系合金には、Crを最大で0.5質量%添加することができる。但し、0.03質量%未満ではその効果が小さいので、好ましくは0.03~0.5質量%、より好ましくは0.09~0.3質量%添加するのがよい。
Mg、Mn、Ag及びPは、微量の添加で、導電率を損なわずに強度、応力緩和特性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮されるが、第二相粒子に含有されることで一層の効果を発揮させることもできる。しかしながら、Mg、Mn、Ag及びPの濃度の総計が2.0質量%を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るCu-Co-Si系合金には、Mg、Mn、Ag及びPから選択される1種又は2種以上を総計で最大2.0質量%添加するのが好ましい。但し、0.01質量%未満ではその効果が小さいので、より好ましくは総計で0.01~2.0質量%、更により好ましくは総計で0.02~0.5質量%、典型的には総計で0.04~0.2質量%添加する。
Sn及びZnにおいても、微量の添加で、導電率を損なわずに強度、応力緩和特性、めっき性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮される。しかしながら、Sn及びZnの総計が2.0質量%を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るCu-Co-Si系合金には、Sn及びZnから選択される1種又は2種を総計で最大2.0質量%添加することができる。但し、0.05質量%未満ではその効果が小さいので、好ましくは総計で0.05~2.0質量%、より好ましくは総計で0.5~1.0質量%添加するのがよい。
As、Sb、Be、B、Ti、Zr、Al及びFeにおいても、要求される製品特性に応じて、添加量を調整することで、導電率、強度、応力緩和特性、めっき性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮されるが、第二相粒子に含有され、若しくは新たな組成の第二相粒子を形成することで一層の効果を発揮させることもできる。しかしながら、これらの元素の総計が2.0質量%を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るCu-Co-Si系合金には、As、Sb、Be、B、Ti、Zr、Al及びFeから選択される1種又は2種以上を総計で最大2.0質量%添加することができる。但し、0.001質量%未満ではその効果が小さいので、好ましくは総計で0.001~2.0質量%、より好ましくは総計で0.05~1.0質量%添加する。
本発明において、第二相粒子とは主にシリサイドを指すが、これに限られるものではなく、溶解鋳造の凝固過程に生ずる晶出物及びその後の冷却過程で生ずる析出物、熱間圧延後の冷却過程で生ずる析出物、溶体化処理後の冷却過程で生ずる析出物、及び時効処理過程で生ずる析出物のことを言う。
コルソン系銅合金の一般的な製造プロセスでは、まず大気溶解炉を用い、電気銅、Ni、Si、Co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。その後、熱間圧延を行い、冷間圧延と熱処理を繰り返して、所望の厚み及び特性を有する条や箔に仕上げる。熱処理には溶体化処理と時効処理がある。溶体化処理では、約700~約1000℃の高温で加熱して、第二相粒子をCu母地中に固溶させ、同時にCu母地を再結晶させる。溶体化処理を、熱間圧延で兼ねることもある。時効処理では、約350~約550℃の温度範囲で1時間以上加熱し、溶体化処理で固溶させた第二相粒子をナノメートルオーダーの微細粒子として析出させる。この時効処理で強度と導電率が上昇する。より高い強度を得るために、時効前及び/又は時効後に冷間圧延を行なうことがある。また、時効後に冷間圧延を行なう場合には、冷間圧延後に歪取焼鈍(低温焼鈍)を行なうことがある。
上記各工程の合間には適宜、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等が適宜行なわれる。
まず、第1の時効処理では析出物の微細化に有用であるとして慣用的に行われている条件よりも若干低い温度を選択し、微細な第二相粒子の析出を促しながら、溶体化処理で析出した可能性のある析出物の粗大化を防止する。第1の時効処理を400℃未満にすると、繰り返し耐へたり性を向上する10nm~50nmの大きさの第二相粒子の密度が低くなりやすい一方で、1回目の時効を500℃超にすると、過時効条件になり、強度及び初期耐へたり性に寄与する5nm~10nmの大きさの第二相粒子の密度が低くなりやすい。よって、第1の時効処理は400℃以上600℃以下の温度範囲で1~12時間とするのが好ましい。ただし、合金中のNiの含有量によって時効処理の好適な温度は変化してくる。Cu-Co-Si系合金とCu-Co-Ni-Si系合金では、第2相粒子の析出のしかたが異なり、Cu-Co-Siの最も強度が高くなる温度は、Cu-Co-Ni-Siよりも高温側にシフトするからである。具体的には、Niの含有量が1.0~2.5質量%の場合は材料温度400℃以上500℃以下として3~9時間加熱するのが好ましく、Niの含有量が1.0質量%未満のときは450℃以上550℃以下として3~9時間加熱するのが好ましい。
しかし、第2の時効処理の時間が第1の時効処理の時間に比べて非常に長い場合(例:10倍以上)には、粒径が5nm以上10nm未満の第二相粒子は増加するものの、1回目の時効処理で析出した析出物の成長及び2回目の時効処理で析出した析出物の成長により粒径が10nm以上50nm以下の第二相粒子も増加するため、上記個数密度比はやはり3未満となりやすい。
よって、第2の時効処理の時間を第1の時効処理の時間の3~10倍とするのが好ましく、3~5倍とするのがより好ましい。
表1に記載の各成分組成の銅合金を、高周波溶解炉で1300℃で溶製し、厚さ30mmのインゴットに鋳造した。次いで、このインゴットを1000℃で3時間加熱後、上り温度(熱間圧延終了温度)を900℃として板厚10mmまで熱間圧延し、熱間圧延終了後は速やかに室温まで水冷した。次いで、表面のスケール除去のため厚さ9mmまで面削を施した後、冷間圧延により厚さ0.15mmの板とした。次に各温度及び時間で溶体化処理を行い、溶体化処理終了後は速やかに室温まで水冷した。次いで、不活性雰囲気中、各温度及び時間で第一の時効処理を施し、各圧下率で冷間圧延し、最後に、不活性雰囲気中、各温度及び時間で第二の時効処理をして、各試験片を製造した。
MBR/t≦1.0 大変優れている
1.0<MBR/t≦2.0 優れている
2.0<MBR/t 不充分である
表3に記載の各成分組成の銅合金を、高周波溶解炉で1300℃で溶製し、厚さ30mmのインゴットに鋳造した。次いで、このインゴットを1000℃で3時間加熱後、上り温度(熱間圧延終了温度)を900℃として板厚10mmまで熱間圧延し、熱間圧延終了後は速やかに室温まで水冷した。次いで、表面のスケール除去のため厚さ9mmまで面削を施した後、冷間圧延により厚さ0.15mmの板とした。次に各温度及び時間で溶体化処理を行い、溶体化処理終了後は速やかに室温まで水冷した。次いで、不活性雰囲気中、各温度及び時間で第一の時効処理を施し、各圧下率で冷間圧延し、最後に、不活性雰囲気中、各温度及び時間で第二の時効処理をして、各試験片を製造した。
<No.1-1~1-47>
第二相粒子の個数密度が適切であったため、強度、導電率、耐へたり性及び曲げ加工性が共に優れていた。
<No.1-48、1-58、1-68、1-72>
第1時効及び第2時効における温度が低く、粒径5nm以上50nm以下の第二相粒子が全体的に不十分となった。
<No.1-49、1-59>
第2時効における温度が低く、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.1-50、1-60、1-69、1-73>
第1時効における温度が高い一方で、第2時効における温度が低く、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.1-51、1-61>
第1時効における温度が低く、粒径5nm以上50nm以下の第二相粒子が全体的に不十分となった。
<No.1-52、1-56、1-62、1-66>
第1時効における温度が高く、粒径5nm以上50nm以下の第二相粒子が全体的に少ないか、又は、粒径10nm以上50nm以下の第二相粒子と粒径5nm以上10nm未満の第二相粒子のバランスが悪い。
<No.1-53、1-63、1-70、1-74>
第1時効における温度が低い一方で、第2時効における温度が高く、粒径10nm以上50nm以下の第二相粒子と粒径5nm以上10nm未満の第二相粒子のバランスが悪くなった。
<No.1-54、1-64>
第2時効における温度が高く、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.1-55、1-65、1-71、1-75>
第1時効及び第2時効における温度が高く、第二相粒子が全体的に発達しすぎたため、本発明で規定する粒径5nm以上50nm以下の第二相粒子は全体的に不十分となった。
<No.1-57、1-67>
第1時効及び第2時効における時間が長く、粒径5nm以上10nm未満の第二相粒子が不十分となった。
<No.1-76、1-77>
第1時効と第2時効の間の冷間圧延の圧下率が低く、第2時効の効果が薄れ、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.1-78、1-79>
No.1-78及び1-79は発明例ではあるが、第1時効と第2時効の間の冷間圧延の圧下率が高く、第2時効の効果が高くなり、曲げ加工性が低下した。
<No.1-80、1-81>
第2時効を省略したため、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.1-82>
第1時効に比べて第2時効の時効時間が短かったため、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.1-83>
第1時効に比べて第2時効の時効時間が長すぎたため、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
表5に記載の各成分組成の銅合金を、高周波溶解炉で1300℃で溶製し、厚さ30mmのインゴットに鋳造した。次いで、このインゴットを1000℃で3時間加熱後、上り温度(熱間圧延終了温度)を900℃として板厚10mmまで熱間圧延し、熱間圧延終了後は速やかに室温まで水冷した。次いで、表面のスケール除去のため厚さ9mmまで面削を施した後、冷間圧延により厚さ0.15mmの板とした。次に各温度及び時間で溶体化処理を行い、溶体化処理終了後は速やかに室温まで水冷した。次いで、不活性雰囲気中、各温度及び時間で第一の時効処理を施し、各圧下率で冷間圧延し、最後に、不活性雰囲気中、各温度及び時間で第二の時効処理をして、各試験片を製造した。
表7に記載の各成分組成の銅合金を、高周波溶解炉で1300℃で溶製し、厚さ30mmのインゴットに鋳造した。次いで、このインゴットを1000℃で3時間加熱後、上り温度(熱間圧延終了温度)を900℃として板厚10mmまで熱間圧延し、熱間圧延終了後は速やかに室温まで水冷した。次いで、表面のスケール除去のため厚さ9mmまで面削を施した後、冷間圧延により厚さ0.15mmの板とした。次に各温度及び時間で溶体化処理を行い、溶体化処理終了後は速やかに室温まで水冷した。次いで、不活性雰囲気中、各温度及び時間で第一の時効処理を施し、各圧下率で冷間圧延し、最後に、不活性雰囲気中、各温度及び時間で第二の時効処理をして、各試験片を製造した。
<No.2-1~2-54>
第二相粒子の個数密度が適切であったため、強度、導電率、耐へたり性及び曲げ加工性が共に優れていた。
<No.2-55、2-65、2-75、2-79>
第1時効及び第2時効における温度が低く、粒径5nm以上50nm以下の第二相粒子が全体的に不十分となった。
<No.2-56、2-66>
第2時効における温度が低く、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.2-57、2-67、2-76、2-80>
第1時効における温度が高い一方で、第2時効における温度が低く、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.2-58、2-68>
第1時効における温度が低く、粒径5nm以上50nm以下の第二相粒子が全体的に不十分となった。
<No.2-59、2-63、2-69、2-73>
第1時効における温度が高く、粒径5nm以上50nm以下の第二相粒子が全体的に少ないか、又は、粒径10nm以上50nm以下の第二相粒子と粒径5nm以上10nm未満の第二相粒子のバランスが悪い。
<No.2-60、2-70、2-77、2-81>
第1時効における温度が低い一方で、第2時効における温度が高く、粒径10nm以上50nm以下の第二相粒子と粒径5nm以上10nm未満の第二相粒子のバランスが悪くなった。
<No.2-61、2-71>
第2時効における温度が高く、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.2-62、2-72、2-78、2-82>
第1時効及び第2時効における温度が高く、第二相粒子が全体的に発達しすぎたため、本発明で規定する粒径5nm以上50nm以下の第二相粒子は全体的に不十分となった。
<No.2-64、2-74>
第1時効及び第2時効における時間が長く、粒径5nm以上10nm未満の第二相粒子が不十分となった。
<No.2-83、2-84>
第1時効と第2時効の間の冷間圧延の圧下率が低く、第2時効の効果が薄れ、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.2-85、2-86>
No.2-85及び2-86は発明例ではあるが、第1時効と第2時効の間の冷間圧延の圧下率が高く、第2時効の効果が高くなり、曲げ加工性が低下した。
<No.2-87、2-88>
第1時効における温度が高く、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.2-89、2-90>
第2時効を省略したため、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.2-91>
第1時効に比べて第2時効の時効時間が短かったため、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
<No.2-92>
第1時効に比べて第2時効の時効時間が長すぎたため、粒径5nm以上10nm未満の第二相粒子の比率が小さくなった。
12 ナイフエッジ
13 標点距離
14 バイス
15 ストローク
16 へたり
Claims (10)
- Co:0.5~3.0質量%、Si:0.1~1.0質量%を含有し、残部がCu及び不可避不純物からなる電子材料用銅合金であって、母相中に析出した第二相粒子のうち、粒径が5nm以上50nm以下のものの個数密度が1×1012~1×1014個/mm3であり、粒径が5nm以上10nm未満のものの個数密度は、粒径が10nm以上50nm以下のものの個数密度に対する比で表して3~6である電子材料用銅合金。
- 粒径が5nm以上10nm未満の第二相粒子の個数密度が2×1012~7×1013であり、粒径が10nm以上50nm以下の第二相粒子の個数密度が3×1011~2×1013である請求項1記載の電子材料用銅合金。
- JIS H 3130に従って、BadwayのW曲げ試験を行ったときの、割れの発生しない最小半径(MBR)の板厚(t)に対する比であるMBR/t値が2.0以下である請求項1又は2記載の電子材料用銅合金。
- 更にNiを最大2.5質量%含有する請求項1~3何れか一項記載の電子材料用銅合金。
- 更にCrを最大0.5質量%含有する請求項1~4何れか一項記載の電子材料用銅合金。
- 更にMg、P、As、Sb、Be、B、Mn、Sn、Ti、Zr、Al、Fe、Zn及びAgよりなる群から選ばれる1種又は2種以上を総計で最大2.0質量%含有する請求項1~5何れか一項記載の電子材料用銅合金。
- -請求項1、4~6何れか一項に記載の組成をもつインゴットを溶解鋳造する工程1と、
-材料温度を950℃以上1050℃以下として1時間以上加熱後に熱間圧延を行う工程2と、
-随意的な冷間圧延工程3と、
-材料温度を850℃以上1050℃以下に加熱する溶体化処理を行う工程4と、
-材料温度を400℃以上600℃以下で1~12時間加熱する第一の時効処理工程5と、ただし、インゴットがNiを1.0~2.5質量%含有するときは材料温度400℃以上500℃以下とし、
-圧下率が10%以上である冷間圧延工程6と、
-材料温度を300℃以上400℃以下で3~36時間加熱し、当該加熱時間を第1の時効処理における加熱時間の3~10倍とする第二の時効処理工程7と、
を順に行なうことを含む電子材料用銅合金の製造方法。 - 冷間圧延工程6における圧下率が10~50%である請求項7に記載の電子材料用銅合金の製造方法。
- 請求項1~6何れか一項記載の電子材料用銅合金からなる伸銅品。
- 請求項1~6何れか一項記載の電子材料用銅合金を備えた電子部品。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180004186.2A CN102575320B (zh) | 2010-05-31 | 2011-04-08 | 电子材料用Cu-Co-Si系铜合金及其制造方法 |
US13/701,267 US9460825B2 (en) | 2010-05-31 | 2011-04-08 | Cu-Co-Si-based copper alloy for electronic materials, and method of manufacturing same |
KR1020127009703A KR101377316B1 (ko) | 2010-05-31 | 2011-04-08 | 전자 재료용 Cu-Co-Si계 구리 합금 및 그 제조 방법 |
EP11789534.2A EP2578709B1 (en) | 2010-05-31 | 2011-04-08 | Cu-co-si-based copper alloy for electronic material, and process for production thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010125338A JP4672804B1 (ja) | 2010-05-31 | 2010-05-31 | 電子材料用Cu−Co−Si系銅合金及びその製造方法 |
JP2010-125338 | 2010-05-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011152124A1 true WO2011152124A1 (ja) | 2011-12-08 |
Family
ID=44080001
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/058923 WO2011152124A1 (ja) | 2010-05-31 | 2011-04-08 | 電子材料用Cu-Co-Si系銅合金及びその製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9460825B2 (ja) |
EP (1) | EP2578709B1 (ja) |
JP (1) | JP4672804B1 (ja) |
KR (1) | KR101377316B1 (ja) |
CN (1) | CN102575320B (ja) |
TW (1) | TWI437108B (ja) |
WO (1) | WO2011152124A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104342582A (zh) * | 2013-07-31 | 2015-02-11 | Jx日矿日石金属株式会社 | Cu-Co-Si系铜合金条及其制造方法 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4677505B1 (ja) * | 2010-03-31 | 2011-04-27 | Jx日鉱日石金属株式会社 | 電子材料用Cu−Ni−Si−Co系銅合金及びその製造方法 |
JP4672804B1 (ja) | 2010-05-31 | 2011-04-20 | Jx日鉱日石金属株式会社 | 電子材料用Cu−Co−Si系銅合金及びその製造方法 |
JP4834781B1 (ja) * | 2010-08-24 | 2011-12-14 | Jx日鉱日石金属株式会社 | 電子材料用Cu−Co−Si系合金 |
JP5451674B2 (ja) | 2011-03-28 | 2014-03-26 | Jx日鉱日石金属株式会社 | 電子材料用Cu−Si−Co系銅合金及びその製造方法 |
JP4799701B1 (ja) | 2011-03-29 | 2011-10-26 | Jx日鉱日石金属株式会社 | 電子材料用Cu−Co−Si系銅合金条及びその製造方法 |
JP6222885B2 (ja) * | 2011-11-10 | 2017-11-01 | Jx金属株式会社 | 電子材料用Cu−Ni−Si−Co系銅合金 |
JP5802150B2 (ja) * | 2012-02-24 | 2015-10-28 | 株式会社神戸製鋼所 | 銅合金 |
JP6039999B2 (ja) | 2012-10-31 | 2016-12-07 | Dowaメタルテック株式会社 | Cu−Ni−Co−Si系銅合金板材およびその製造法 |
KR20150103049A (ko) * | 2013-01-09 | 2015-09-09 | 미쓰비시 마테리알 가부시키가이샤 | 전자·전기 기기용 구리 합금, 전자·전기 기기용 구리 합금 박판, 전자·전기 기기용 구리 합금의 제조 방법, 전자·전기 기기용 도전 부품 및 단자 |
JP5647703B2 (ja) | 2013-02-14 | 2015-01-07 | Dowaメタルテック株式会社 | 高強度Cu−Ni−Co−Si系銅合金板材およびその製造法並びに通電部品 |
JP6140032B2 (ja) * | 2013-08-30 | 2017-05-31 | Dowaメタルテック株式会社 | 銅合金板材およびその製造方法並びに通電部品 |
CN105018782B (zh) * | 2015-07-23 | 2017-09-26 | 宁波博威合金板带有限公司 | 一种含钴硅的铜合金 |
KR102021442B1 (ko) | 2019-07-26 | 2019-09-16 | 주식회사 풍산 | 강도와 도전율이 우수한 동합금 판재의 제조 방법 및 이로부터 제조된 동합금 판재 |
WO2022092139A1 (ja) * | 2020-10-29 | 2022-05-05 | 古河電気工業株式会社 | 銅合金板材、銅合金板材の製造方法及び接点部品 |
JP7051029B1 (ja) * | 2020-10-29 | 2022-04-08 | 古河電気工業株式会社 | 銅合金板材、銅合金板材の製造方法及び接点部品 |
CN115354251B (zh) * | 2022-08-29 | 2023-02-10 | 西安交通大学 | 一种提高析出程度且抑制析出相粗化的热处理方法 |
CN117107110B (zh) * | 2023-07-20 | 2024-05-10 | 宁波博威合金板带有限公司 | 一种电子材料用铜合金带材及其制备方法与应用 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007169765A (ja) * | 2005-12-26 | 2007-07-05 | Furukawa Electric Co Ltd:The | 銅合金とその製造方法 |
JP2008056977A (ja) | 2006-08-30 | 2008-03-13 | Mitsubishi Electric Corp | 銅合金及びその製造方法 |
WO2009096546A1 (ja) | 2008-01-31 | 2009-08-06 | The Furukawa Electric Co., Ltd. | 電気電子部品用銅合金材およびその製造方法 |
WO2009116649A1 (ja) | 2008-03-21 | 2009-09-24 | 古河電気工業株式会社 | 電気電子部品用銅合金材 |
JP2009242890A (ja) * | 2008-03-31 | 2009-10-22 | Nippon Mining & Metals Co Ltd | 電子材料用Cu−Ni−Si−Co系銅合金及びその製造方法 |
JP2009242926A (ja) * | 2008-03-31 | 2009-10-22 | Nippon Mining & Metals Co Ltd | 電子材料用Cu−Ni−Si系合金 |
JP2009242814A (ja) | 2008-03-28 | 2009-10-22 | Furukawa Electric Co Ltd:The | 銅合金材およびその製造方法 |
WO2010013790A1 (ja) * | 2008-07-31 | 2010-02-04 | 古河電気工業株式会社 | 電気電子部品用銅合金材料とその製造方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3408021B2 (ja) | 1995-06-30 | 2003-05-19 | 古河電気工業株式会社 | 電子電気部品用銅合金およびその製造方法 |
JP3797736B2 (ja) | 1997-02-10 | 2006-07-19 | 株式会社神戸製鋼所 | 剪断加工性に優れる高強度銅合金 |
US7182823B2 (en) | 2002-07-05 | 2007-02-27 | Olin Corporation | Copper alloy containing cobalt, nickel and silicon |
EP1537249B1 (en) * | 2002-09-13 | 2014-12-24 | GBC Metals, LLC | Age-hardening copper-base alloy |
JP4441467B2 (ja) | 2004-12-24 | 2010-03-31 | 株式会社神戸製鋼所 | 曲げ加工性及び耐応力緩和特性を備えた銅合金 |
EP1873266B1 (en) | 2005-02-28 | 2012-04-25 | The Furukawa Electric Co., Ltd. | Copper alloy |
JP2006265731A (ja) | 2005-02-28 | 2006-10-05 | Furukawa Electric Co Ltd:The | 銅合金 |
WO2006101172A1 (ja) | 2005-03-24 | 2006-09-28 | Nippon Mining & Metals Co., Ltd. | 電子材料用銅合金 |
JP5247021B2 (ja) | 2005-11-28 | 2013-07-24 | Jx日鉱日石金属株式会社 | 曲げ部のしわを低減させたCu−Ni−Si系合金板・条及びその製造方法 |
JP2007169764A (ja) | 2005-12-26 | 2007-07-05 | Furukawa Electric Co Ltd:The | 銅合金 |
JP4247922B2 (ja) | 2006-09-12 | 2009-04-02 | 古河電気工業株式会社 | 電気・電子機器用銅合金板材およびその製造方法 |
JP5170881B2 (ja) | 2007-03-26 | 2013-03-27 | 古河電気工業株式会社 | 電気・電子機器用銅合金材およびその製造方法 |
JP4937815B2 (ja) | 2007-03-30 | 2012-05-23 | Jx日鉱日石金属株式会社 | 電子材料用Cu−Ni−Si−Co系銅合金及びその製造方法 |
KR20110039372A (ko) | 2008-08-05 | 2011-04-15 | 후루카와 덴키 고교 가부시키가이샤 | 전기·전자부품용 동합금재 |
WO2010016429A1 (ja) * | 2008-08-05 | 2010-02-11 | 古河電気工業株式会社 | 電気・電子部品用銅合金材料 |
KR101113356B1 (ko) * | 2008-10-22 | 2012-03-13 | 후루카와 덴키 고교 가부시키가이샤 | 동합금 재료, 전기전자 부품 및 동합금 재료의 제조방법 |
WO2010064547A1 (ja) | 2008-12-01 | 2010-06-10 | 日鉱金属株式会社 | 電子材料用Cu-Ni-Si-Co系銅合金及びその製造方法 |
JP4672804B1 (ja) | 2010-05-31 | 2011-04-20 | Jx日鉱日石金属株式会社 | 電子材料用Cu−Co−Si系銅合金及びその製造方法 |
-
2010
- 2010-05-31 JP JP2010125338A patent/JP4672804B1/ja active Active
-
2011
- 2011-04-08 WO PCT/JP2011/058923 patent/WO2011152124A1/ja active Application Filing
- 2011-04-08 KR KR1020127009703A patent/KR101377316B1/ko active IP Right Grant
- 2011-04-08 EP EP11789534.2A patent/EP2578709B1/en active Active
- 2011-04-08 CN CN201180004186.2A patent/CN102575320B/zh active Active
- 2011-04-08 US US13/701,267 patent/US9460825B2/en active Active
- 2011-04-27 TW TW100114571A patent/TWI437108B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007169765A (ja) * | 2005-12-26 | 2007-07-05 | Furukawa Electric Co Ltd:The | 銅合金とその製造方法 |
JP2008056977A (ja) | 2006-08-30 | 2008-03-13 | Mitsubishi Electric Corp | 銅合金及びその製造方法 |
WO2009096546A1 (ja) | 2008-01-31 | 2009-08-06 | The Furukawa Electric Co., Ltd. | 電気電子部品用銅合金材およびその製造方法 |
WO2009116649A1 (ja) | 2008-03-21 | 2009-09-24 | 古河電気工業株式会社 | 電気電子部品用銅合金材 |
JP2009242814A (ja) | 2008-03-28 | 2009-10-22 | Furukawa Electric Co Ltd:The | 銅合金材およびその製造方法 |
JP2009242890A (ja) * | 2008-03-31 | 2009-10-22 | Nippon Mining & Metals Co Ltd | 電子材料用Cu−Ni−Si−Co系銅合金及びその製造方法 |
JP2009242926A (ja) * | 2008-03-31 | 2009-10-22 | Nippon Mining & Metals Co Ltd | 電子材料用Cu−Ni−Si系合金 |
WO2010013790A1 (ja) * | 2008-07-31 | 2010-02-04 | 古河電気工業株式会社 | 電気電子部品用銅合金材料とその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2578709A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104342582A (zh) * | 2013-07-31 | 2015-02-11 | Jx日矿日石金属株式会社 | Cu-Co-Si系铜合金条及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2578709A1 (en) | 2013-04-10 |
EP2578709A4 (en) | 2014-04-09 |
EP2578709B1 (en) | 2015-09-09 |
TWI437108B (zh) | 2014-05-11 |
US20130087255A1 (en) | 2013-04-11 |
US9460825B2 (en) | 2016-10-04 |
JP4672804B1 (ja) | 2011-04-20 |
KR101377316B1 (ko) | 2014-03-25 |
CN102575320A (zh) | 2012-07-11 |
KR20120053085A (ko) | 2012-05-24 |
TW201142051A (en) | 2011-12-01 |
JP2011252188A (ja) | 2011-12-15 |
CN102575320B (zh) | 2014-01-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4672804B1 (ja) | 電子材料用Cu−Co−Si系銅合金及びその製造方法 | |
JP5319700B2 (ja) | 電子材料用Cu−Ni−Si−Co系銅合金及びその製造方法 | |
JP5367999B2 (ja) | 電子材料用Cu−Ni−Si系合金 | |
JP4937815B2 (ja) | 電子材料用Cu−Ni−Si−Co系銅合金及びその製造方法 | |
JP4799701B1 (ja) | 電子材料用Cu−Co−Si系銅合金条及びその製造方法 | |
WO2011068124A1 (ja) | 銅合金板材 | |
JP2008081762A (ja) | 電子材料用Cu−Cr系銅合金 | |
TWI429764B (zh) | Cu-Co-Si alloy for electronic materials | |
WO2012132765A1 (ja) | 電子材料用Cu-Si-Co系銅合金及びその製造方法 | |
WO2012043170A1 (ja) | 電子材料用Cu-Co-Si系銅合金及びその製造方法 | |
JP4620173B1 (ja) | Cu−Co−Si合金材 | |
WO2012133651A1 (ja) | 銅合金および銅合金の製造方法 | |
JP2013104068A (ja) | 電子材料用Cu−Ni−Si−Co系銅合金 | |
JP5232794B2 (ja) | 熱間加工性に優れた高強度高導電性銅合金 | |
JP2012229467A (ja) | 電子材料用Cu−Ni−Si系銅合金 | |
JP4175920B2 (ja) | 高力銅合金 | |
JP5101149B2 (ja) | 熱間加工性に優れた高強度高導電性銅合金 | |
WO2012096351A1 (ja) | Cu-Co-Si-Zr合金材及びその製造方法 | |
JP4349631B2 (ja) | 電機、電子機器部品用コルソン合金細線の製造方法 | |
JP4679040B2 (ja) | 電子材料用銅合金 | |
JP5623960B2 (ja) | 電子材料用Cu−Ni−Si系銅合金条及びその製造方法 | |
JP5595961B2 (ja) | 電子材料用Cu−Ni−Si系銅合金及びその製造方法 | |
JP2013117060A (ja) | 電子材料用Cu−Co−Si系合金 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180004186.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11789534 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20127009703 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13701267 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011789534 Country of ref document: EP |