WO2016152648A1

WO2016152648A1 - Copper alloy sheet for heat dissipating component and heat dissipating component

Info

Publication number: WO2016152648A1
Application number: PCT/JP2016/058122
Authority: WO
Inventors: 大輔橋本; 昌泰西村
Original assignee: 株式会社神戸製鋼所
Priority date: 2015-03-23
Filing date: 2016-03-15
Publication date: 2016-09-29

Abstract

Provided is a copper alloy sheet, with which a heat dissipating component can be given sufficient strength and heat dissipation capacity after being manufactured, in cases where a process of heating to 650°C or more is included as part of a heat dissipating component manufacturing process. The copper alloy sheet for heat dissipating components comprises 0.07 to 0.7 mass% of Fe, 0.2 mass% or less of P, with the ratio of the Fe content [Fe] and the P content [P], or [Fe]/[P], being from 2 to 5, and a remainder of Cu and inevitable impurities. The 0.2% proof stress is no less than 100 Mpa and the conductivity is no less than 50% IACS, subsequent to heating for 30 minutes at 850°C followed by water cooling and then aging treatment. If the copper alloy includes Sn, the contents of Sn and Fe are set to be within the range surrounded by point A (0.1, 0.006), point B (0.5, 0.006), point C (0.05, 1.1), and point D (0.05, 0.05) shown in drawing.

Description

Copper alloy plate for heat dissipation parts and heat dissipation parts

The present invention relates to a copper alloy plate for a heat dissipation component and a heat dissipation component.

The speed of operation and the increase in density of CPUs mounted on desk-type PCs or notebook PCs are rapidly increasing, and the amount of heat generated from these CPUs is increasing further. When the temperature of the CPU rises to a certain level or more, it may cause malfunction or thermal runaway, so effective heat dissipation from a semiconductor device such as a CPU is a serious problem.
Heat sinks are used as heat dissipating parts that absorb the heat of semiconductor devices and dissipate them into the atmosphere. Since the heat sink is required to have high thermal conductivity, copper or aluminum having a high thermal conductivity is used as a material. However, the convective heat resistance limits the performance of the heat sink, and it has become difficult to satisfy the heat dissipation requirement of high-functional electronic components that increase the amount of heat generation.

For this reason, tubular heat pipes and flat heat pipes (vapor chambers) having high heat conductivity and heat transport capability have been proposed as heat dissipating parts having higher heat dissipating properties. The heat pipe exhibits higher heat dissipation characteristics than the heat sink by cyclically performing evaporation (heat absorption from the CPU) and condensation (release of absorbed heat) of the refrigerant sealed inside. In addition, it has been proposed to solve the heat generation problem of a semiconductor device by combining a heat pipe with a heat dissipation component such as a heat sink or a fan.

As a material for a heat radiating component used for a heat radiating plate, a heat sink or a heat pipe, a pure copper (oxygen-free copper: C1020) plate or tube having excellent conductivity and corrosion resistance is frequently used. In order to ensure molding processability, soft annealed material (O material) or 1 / 4H tempered material is used as a raw material. There are problems such as burrs being easily generated or punching dies being easily worn. On the other hand, Patent Documents 1 and 2 describe an Fe—P-based copper alloy plate as a material for a heat dissipation component.

For heatsinks and heatsinks, pure copper plates are processed into a predetermined shape by press molding, punching, cutting, drilling, etching, etc., and then subjected to Ni plating or Sn plating as necessary before soldering, brazing or adhesives, etc. To join with a semiconductor device such as a CPU.
A tubular heat pipe (see Patent Document 3) is formed by sintering copper powder in a tube to form a wick, heat-degassing treatment, brazing and sealing one end, and putting a refrigerant in the tube under vacuum or reduced pressure. And the other end is brazed and sealed.

The planar heat pipe (see Patent Documents 4 and 5) is a further improvement of the heat dissipation performance of the tubular heat pipe. As a flat heat pipe, in order to efficiently condense and evaporate the refrigerant, a pipe having a roughened surface or a groove formed on the inner surface has been proposed in the same manner as the tubular heat pipe. A method of brazing, etc. after joining two upper and lower pure copper plates that have undergone processing such as press molding, punching, cutting or etching, by brazing, diffusion bonding or welding, etc. Seal with. A degassing process may be performed in a joining process.

Further, as a planar heat pipe, one constituted by an outer member and an inner member accommodated in the outer member has been proposed. One or more internal members are arranged inside the outer surface member in order to promote the condensation, evaporation and transport of the refrigerant, and fins, protrusions, holes or slits of various shapes are processed. Also in this type of flat heat pipe, after the inner member is arranged inside the outer surface member, the outer surface member and the inner member are joined and integrated by a method such as brazing or diffusion joining, brazing, etc. It seals by the method of.

JP 2003-277853 A JP 2014-189816 A JP 2008-232563 A JP 2007-315754 A JP 2014-134347 A

In the manufacturing process of these heat radiating components, the heat radiating plate and the heat sink are heated to about 200 to 700 ° C. in the soldering or brazing process. Tubular heat pipes and planar heat pipes are heated to about 800 to 1000 ° C. by processes such as sintering, degassing, brazing using phosphor copper brazing (BCuP-2 or the like), diffusion bonding or welding.
For example, when a pure copper plate is used as the material for the heat pipe, the softening is severe when heated at a temperature of 650 ° C. or higher. In addition, a rapid coarsening of crystal grains occurs. For this reason, the manufactured heat pipe is easily deformed when attached to a heat sink or a semiconductor device, or incorporated into a PC housing, the structure inside the heat pipe changes, and the surface unevenness increases. There is a problem that the desired heat dissipation performance cannot be exhibited. Moreover, in order to avoid such a deformation | transformation, what is necessary is just to thicken the thickness of a pure copper plate, but if it does so, the mass and thickness of a heat pipe will increase. When the thickness increases, there is a problem that the gap inside the PC casing is reduced and the convective heat transfer performance is lowered.

Also, the copper alloy plates (Fe—P type) described in Patent Documents 1 and 2 are softened when heated at a temperature of 650 ° C. or higher, and the conductivity is greatly reduced as compared with pure copper. For this reason, when, for example, a planar heat pipe is manufactured through processes such as sintering, degassing, brazing, or diffusion bonding, the heat pipe is easily deformed by a process of transporting and handling or assembling the heat pipe. Moreover, the expected performance as a heat pipe cannot be obtained due to the decrease in conductivity.

The present invention has been made in view of the above problems when a process of heating to a temperature of 650 ° C. or higher is included in a part of the process of manufacturing a heat dissipation component from pure copper or a copper alloy plate. An object of the present invention is to provide a copper alloy plate capable of giving sufficient heat resistance and heat dissipation performance to a heat dissipation component manufactured through a heating process.

A precipitation hardening type copper alloy improves strength and conductivity by performing an aging treatment after the solution treatment. However, the precipitation hardening type copper alloy, after solution treatment, after applying plastic working in the cold and introducing the plastic strain that becomes the precipitation site into the alloy, if not aging treatment, strength and conductivity by aging treatment The rate improvement effect may be low.
In the case of a heat radiating component such as a vapor chamber manufactured through a heating process such as brazing, diffusion bonding, or welding, plastic processing is not applied after the heating process. Therefore, when the heat-radiating component is manufactured from a precipitation-strengthening-type copper alloy plate, the strength and conductivity may not be sufficiently improved even if an aging treatment is performed after the heating step corresponding to the solution treatment.
On the other hand, the present inventors apply plastic working after the heating step by limiting the composition range of Fe and P and the Fe / P ratio in the Cu—Fe—P alloy among precipitation hardening type copper alloys. The present inventors have found that the strength and conductivity of the heat dissipating parts are greatly improved even when the aging treatment is performed without any aging treatment, and the present invention has been achieved.

The copper alloy plate for heat dissipation component according to the present invention is used when a process of heating to 650 ° C. or more and an aging treatment are included as part of the process of manufacturing the heat dissipation component, and Fe: 0.07 to 0.7 % By mass, P: 0.2% by mass or less, Fe content (% by mass) is [Fe], and P content (% by mass) is [P]. ] / [P] is 2 to 5, the remainder is made of Cu and inevitable impurities, heated at 850 ° C. for 30 minutes, then water-cooled, then 0.2% proof stress after aging treatment is 100 MPa or more, conductivity is 50 % IACS or higher. The Fe content [Fe] and the P content [P] are both mass%.

The copper alloy plate for heat dissipation components according to the present invention can further contain Sn as an alloy element. In this case, the copper alloy plate has points A (0.1, 0.006), B (0.5, 0.006), C (0.05, 1.1), D shown in FIG. Fe and Sn within the range surrounded by (0.05, 0.05) (including on the boundary line). The P content and [Fe] / [P] are the same as above. This copper alloy is heated at 850 ° C. for 30 minutes, then water-cooled, and after aging treatment, the 0.2% proof stress is 100 MPa or more, and the conductivity is 45% IACS or more.
The copper alloy sheet further contains 1.5 mass% or less (not including 0 mass%) of Zn as an alloy element, if necessary, and / or Mn: 0.1 mass% or less (0 mass%) Mg: 0.2 mass% or less (not including 0 mass%), Si: 0.2 mass% or less (not including 0 mass%), Al: 0.2 mass% or less (0 mass) %), Cr: 0.2 mass% or less (not including 0 mass%), Ti: 0.1 mass% or less (not including 0 mass%) and Zr: 0.05 mass% or less (0 1 type or 2 types or more can be contained in a total of 0.5% or less (excluding 0 mass%).

The copper alloy plate according to the present invention is used when a process of heating to 650 ° C. or more and an aging treatment are included as part of the process of manufacturing a heat dissipation component. That is, the heat radiating component manufactured using the copper alloy plate according to the present invention is subjected to aging treatment after high-temperature heating to 650 ° C. or higher, and the strength is improved.
When the copper alloy sheet according to the present invention is heated to 850 ° C. for 30 minutes and then subjected to an aging treatment, the 0.2% proof stress is 100 MPa or more, and the conductivity is 50% IACS or more (when Sn is not included) or 45 % IACS or more (when Sn is included). Since the copper alloy plate according to the present invention has high strength after aging treatment, when a heat-radiating component such as a heat pipe manufactured using this copper alloy plate is attached to a heat sink or a semiconductor device, or incorporated into a PC housing or the like. In addition, the heat radiating component is not easily deformed. In addition, the copper alloy plate according to the present invention has a conductivity lower than that of a pure copper plate, but since the strength after the aging treatment is high, the copper alloy plate can be thinned and can compensate for a decrease in conductivity in terms of heat dissipation performance.

It is a figure which shows the range of Fe and Sn among the compositions of the copper alloy plate which concerns on this invention.

Hereinafter, the copper alloy plate for heat dissipation component according to the present invention will be described in more detail.
The copper alloy sheet according to the present invention is processed into a predetermined shape by press molding, punching, cutting or etching, and heated for high temperature heating (degassing, bonding (brazing, diffusion bonding or welding) or sintering). ) To finish heat dissipation parts. Although the heating conditions for the high-temperature heating differ depending on the type of heat-radiating component or the manufacturing method, the present invention assumes a case where the high-temperature heating is performed at about 650 ° C. to 1050 ° C. The copper alloy plate according to the present invention is made of an Fe—P based copper alloy having the composition described later, and when heated within the above temperature range, at least a part of the Fe—P compound or Fe, etc. precipitated before heating is dissolved. Then, crystal grains grow, and softening and conductivity decrease occur.

The copper alloy plate according to the present invention is heated at 850 ° C. for 30 minutes, then water-cooled, and then subjected to an aging treatment (strength (0.2% yield strength)) of 100 MPa or more, and conductivity of 50% IACS or more or 45% IACS or more. is there. Heating at 850 ° C. for 30 minutes is a heating condition that assumes the above-described high-temperature heating process in the manufacture of a heat dissipation component. When the copper alloy plate according to the present invention is heated at a high temperature under these conditions, the Fe—P compound or Fe or the like deposited before heating is dissolved, crystal grains grow, softening, and conductivity decrease. Next, when the copper alloy plate is subjected to an aging treatment, fine Fe—P compounds, Fe and the like are precipitated. Thereby, the intensity | strength and electrical conductivity which were reduced by the said high temperature heating improve notably.

The aging treatment is (a) maintained for a certain time in the precipitation temperature range during the cooling step after high-temperature heating, (b) cooled to room temperature after high-temperature heating, and then reheated to the precipitation temperature range and maintained for a certain time. (C) After the step (a), it can be carried out by a method such as reheating to the precipitation temperature range and holding for a certain period of time.
Specific aging treatment conditions include a condition of holding at a temperature range of 350 to 600 ° C. for 5 minutes to 10 hours. When priority is given to improving the strength, the temperature-time condition under which fine Fe-P precipitates are formed. When priority is given to improving the conductivity, the temperature-time condition is such that Fe and P that are dissolved in the solution are reduced. May be selected as appropriate.

The copper alloy plate after the aging treatment has a lower electrical conductivity than the pure copper plate after high-temperature heating, but the strength is significantly higher than that of the pure copper plate. In order to acquire this effect, heat dissipation parts, such as a heat pipe manufactured using the copper alloy board concerning the present invention, are subjected to aging treatment after high temperature heating. The aging treatment conditions are as described above. The heat-dissipating component (copper alloy plate) after the aging treatment has high strength and can prevent deformation of the heat-dissipating component when it is attached to a heat sink or a semiconductor device or incorporated in a PC housing or the like. In addition, the copper alloy plate according to the present invention (after aging treatment) has a higher strength than that of a pure copper plate, and therefore can be thinned (0.1 to 1.0 mm thick). The performance can be enhanced and the decrease in conductivity when compared with a pure copper plate can be compensated.
Note that the copper alloy plate according to the present invention has a 0.2% yield strength of 100 MPa or more after aging treatment even when the temperature of high-temperature heating is less than 850 ° C. (650 ° C. or more) or more than 850 ° C. (1050 ° C. or less). And conductivity of 50% IACS or higher or 45% IACS or higher.

The copper alloy plate according to the present invention is processed into a member of a heat dissipation component by press molding, punching, cutting, etching, or the like before being heated to a temperature of 650 ° C. or higher. It is preferable that the copper alloy plate has a strength that does not easily deform during conveyance and handling during the processing, and has mechanical characteristics that allow the processing to be performed without hindrance. More specifically, the copper alloy sheet according to the present invention has a 0.2% proof stress of 150 MPa or more, an elongation of 5% or more, an average crystal grain size of 20 μm or less, and excellent bending workability (see Examples described later). It is preferable. If the above characteristics are satisfied, the tempering of the copper alloy sheet is not a problem. For example, any of a solution treated material, an aging treated up material, a material obtained by cold rolling a solution treated material or a material obtained by cold rolling an aging treated up material can be used.
When the average crystal grain size exceeds 20 μm, roughing of the surface of the plate due to processing (press forming, bending processing, punching processing, cutting, etching, etc.) when processing into heat-radiating parts, generation of burrs or etching due to punching or cutting processing Problems such as a decrease in dimensional accuracy may occur. Further, the crystal grains are further coarsened by high-temperature heating to a temperature of 650 ° C. or higher thereafter, and flatness as a heat dissipation component is lowered. Therefore, the average crystal grain size measured on the surface of the plate before being heated at a high temperature to 650 ° C. or higher is preferably 20 μm or less, and more preferably 15 μm or less.

As described above, the heat dissipation component manufactured by processing the copper alloy plate according to the present invention softens when heated to a temperature of 650 ° C. or higher. It is preferable that the heat dissipating component after high-temperature heating has a strength that does not easily deform during conveyance and handling when performing an aging treatment. For that purpose, it is preferable to have a 0.2% yield strength of 40 MPa or more at the stage of heating at 850 ° C. for 30 minutes and then water cooling.

The heat-radiating component manufactured using the copper alloy plate according to the present invention is subjected to aging treatment, and if necessary, at least a part of the outer surface is coated with Sn for the purpose of improving corrosion resistance and solderability. A layer is formed. The Sn coating layer includes electroplating or electroless plating, or those formed by heating to a melting point of Sn or lower or higher than the melting point of Sn. The Sn coating layer includes Sn metal and an Sn alloy, and the Sn alloy includes one or more of Bi, Ag, Cu, Ni, In, and Zn as alloy elements in addition to Sn in a total amount of 5% by mass or less. Things.

A base plating such as Ni, Co or Fe can be formed under the Sn coating layer. These undercoats have a function as a barrier for preventing the diffusion of Cu or alloy elements from the base material and a function for preventing damage by increasing the surface hardness of the heat dissipation component. A Cu-Sn alloy layer is formed by plating Cu on the base plating, further plating Sn, and then performing a heat treatment to heat to a temperature lower than or higher than the melting point of Sn to form a Cu-Sn alloy layer and Sn A three-layer structure of the coating layer can also be used. The Cu—Sn alloy layer has a function as a barrier for preventing diffusion of Cu or an alloy element from the base material and a function for preventing damage by increasing the surface hardness of the heat dissipation component.

Further, after the heat dissipation component manufactured using the copper alloy plate according to the present invention is subjected to an aging treatment, a Ni coating layer is formed on at least a part of the outer surface as necessary. The Ni coating layer has a function as a barrier for preventing the diffusion of Cu or an alloy element from the base material, a function for preventing damage by increasing the surface hardness of the heat dissipation component, and a function for improving corrosion resistance.

Next, the composition of the copper alloy sheet according to the present invention will be described separately for the case where Sn is not included and the case where Sn is included.
(When the copper alloy does not contain Sn)
In this case, the composition of the copper alloy contains Fe: 0.07 to 0.7 mass%, P: 0.2 mass% or less, and the ratio of the Fe content [Fe] and the P content [P]. [Fe] / [P] is 2 to 5, with the balance being Cu and inevitable impurities. If necessary, Zn is contained in an amount of 1.5% by mass or less (not including 0% by mass), and / or Mn: 0.1% by mass or less (not including 0% by mass), Mg: 0.2 % By mass or less (not including 0% by mass), Si: 0.2% by mass or less (not including 0% by mass), Al: 0.2% by mass or less (not including 0% by mass), Cr: 0.00%. One of 2% by mass or less (not including 0% by mass), Ti: 0.1% by mass or less (not including 0% by mass) and Zr: 0.05% by mass or less (not including 0% by mass) Or 2 or more types can be contained 0.5% or less (excluding 0 mass%) in total. Hereinafter, the reason for adding each element will be described.

Fe forms a compound with P and has the effect of improving the strength and conductivity of the copper alloy sheet after aging treatment. However, if the Fe content is less than 0.07% by mass, the 0.2% yield strength after high-temperature heating and aging treatment is less than 100 MPa. On the other hand, if the Fe content exceeds 0.7% by mass, the conductivity after high-temperature heating and aging treatment is less than 50% IACS. Therefore, the Fe content is set to 0.07 to 0.7% by mass. The lower limit of the Fe content is preferably 0.15% by mass, and the upper limit is preferably 0.65% by mass. In the range of the Fe content of the copper alloy sheet according to the present invention, the Fe—P compound mainly precipitates when subjected to aging treatment without plastic working after solution treatment. In comparison, the precipitate of Fe alone is significantly reduced.

P has an action of reducing the amount of oxygen contained in the copper alloy by a deoxidation action and preventing hydrogen embrittlement when the heat dissipation component is heated in a reducing atmosphere containing hydrogen. The solid solution P is heated to the precipitation temperature to form an Fe—P compound to improve the strength, heat resistance, and conductivity of the copper alloy. However, if the P content exceeds 0.2% by mass, cracking occurs when the ingot is hot-rolled and subsequent processing becomes impossible, so the upper limit of the P content is 0.2% by mass. %.
Although the P content is required to some extent due to the above action, on the other hand, the P content that does not contribute to precipitation is preferably as small as possible within a range in which hydrogen embrittlement can be prevented. From this point, the ratio [Fe] / [P] when the Fe content (% by mass) is [Fe] and the P content (% by mass) is [P] is 2-5. Try to be within range. If [Fe] / [P] is less than 2, the amount of P that does not contribute to the formation of the Fe—P compound is increased, and if [Fe] / [P] exceeds 5, it is similarly dissolved. In any case, the conductivity of the copper alloy sheet after the aging treatment cannot be increased to 50% IACS or more. Further, when [Fe] / [P] is less than 2 or exceeds 5, Fe or P that does not contribute to the formation of the Fe—P compound increases, and the strength of the copper alloy sheet after the aging treatment is not sufficiently improved. The lower limit of [Fe] / [P] is preferably 2.5, more preferably 3.0, and the upper limit of [Fe] / [P] is preferably 4.5, more preferably 4.0. .

Zn has an effect of improving the heat-resistant peelability of the solder of the copper alloy plate and the heat-resistant peelability of Sn plating, and thus is added as necessary. When incorporating a heat dissipation component into a semiconductor device, soldering may be required, and Sn plating may be performed after manufacturing the heat dissipation component. A copper alloy plate containing Zn is suitably used for manufacturing such a heat dissipation component. However, if the Zn content exceeds 1.5% by mass, the solder wettability decreases and the electrical conductivity also decreases, so the Zn content is set to 1.5% by mass or less. The upper limit of the Zn content is preferably 0.7% by mass or less, and more preferably 0.5% by mass or less. On the other hand, if the Zn content is less than 0.01% by mass, it is insufficient for improving the heat-resistant peelability, and the Zn content is preferably 0.01% by mass or more. The lower limit of the Zn content is more preferably 0.05% by mass and even more preferably 0.1% by mass.

Since Mn, Mg, Si, Al, Cr, Ti, and Zr have the effect of improving the strength and heat resistance of the copper alloy, one or more of these are added as necessary. Even if a small amount of Mn, Mg, Si, and Al is contained, the electrical conductivity of the copper alloy is lowered, so that the upper limit values are Mn: 0.1% by mass, Mg: 0.2% by mass, Si: 0.0. 2% by mass and Al: 0.2% by mass. Cr, Ti, and Zr easily form inclusions such as oxides and sulfides of several μm to several tens of μm, and cold rolling creates a gap between the inclusions and the base material. When it is present on the surface, it reduces the corrosion resistance of the copper alloy. Therefore, the upper limit values of Cr, Ti, and Zr are Cr: 0.2 mass%, Ti: 0.1 mass%, and Zr: 0.05 mass%. Moreover, when multiple types of elements are contained in a copper alloy among Mn, Mg, Si, Al, Cr, Ti, and Zr and the total content exceeds 0.5 mass%, the electrical conductivity of the copper alloy decreases. . Therefore, the total content of these elements is 0.5% by mass or less (not including 0% by mass). On the other hand, the lower limit of the total content of one or more of these elements is preferably 0.01% by mass, more preferably 0.02% by mass, and even more preferably 0.03% by mass.

(When the copper alloy contains Sn)
In this case, the composition of the copper alloy is as follows: point A (0.1, 0.006), point B (0.5, 0.006), point C (0.05, 1.1), point shown in FIG. Fe and Sn within a range surrounded by D (0.05, 0.05) (including on the boundary line), P is contained in an amount of 0.2% by mass or less, and the balance is made of Cu and inevitable impurities. The ratio [Fe] / [P] of the Fe content [Fe] and the P content [P] is 2 to 5. If necessary, Zn is contained in an amount of 1.5% by mass or less (not including 0% by mass), and / or Mn: 0.1% by mass or less (not including 0% by mass), Mg: 0.2 % By mass or less (not including 0% by mass), Si: 0.2% by mass or less (not including 0% by mass), Al: 0.2% by mass or less (not including 0% by mass), Cr: 0.00%. One of 2% by mass or less (not including 0% by mass), Ti: 0.1% by mass or less (not including 0% by mass) and Zr: 0.05% by mass or less (not including 0% by mass) Or 2 or more types are contained in total 0.5 mass% or less (0 mass% is not included).

Fe forms a compound with P, and has the effect | action which improves the intensity | strength and electrical conductivity of the copper alloy plate after an aging treatment. If the content of Fe and Sn is within the range surrounded by points A, B, C and D shown in FIG. 1, the strength after aging treatment (0.2% proof stress) is 100 MPa or more and the conductivity is 45. % IACS or higher.
The lower limit of the Fe content is preferably 0.07% by mass, more preferably 0.15% by mass. On the other hand, from FIG. 1, the upper limit value of Fe is determined depending on the Sn content, and is a value equal to or smaller than the line segment BC of FIG. When the Fe content (% by mass) is [Fe] and the Sn content (% by mass) is [Sn], the relational expression between [Fe] and [Sn] by the line segment BC is as follows: It can be expressed by the following formula.
[Fe] = − 0.411 × [Sn] +0.502
For example, when the Sn content is 0.4 mass%, the upper limit of the Fe content is 0.338 mass%, and when the Sn content is 0.2 mass%, the upper limit of the Fe content is 0.420% by mass.
The lower limit of the Sn content is preferably 0.01% by mass, more preferably 0.02% by mass, and the upper limit is preferably 0.5% by mass, more preferably 0.4% by mass.
About the effect | action and content of P and Zn and Mn, Mg, Si, Al, Cr, Ti, and Zr, it is the same as the case where a copper alloy does not contain Sn, and description is abbreviate | omitted.

The copper alloy plate according to the present invention is manufactured, for example, by hot rolling an ingot and then repeating cold rolling and heat treatment (aging treatment) once or twice or more. A copper alloy sheet produced using the copper alloy having the above composition under the following conditions has a 0.2% proof stress of 150 MPa or more, an elongation of 5% or more, and excellent bending workability. In addition, after heating at 850 ° C. for 30 minutes, it has a 0.2% yield strength of 40 MPa or more, and then an aging treatment, and then a 0.2% yield strength of 100 MPa or more and a conductivity of 50% IACS or more or 45% IACS or more. Have.

Melting or casting can be performed by a normal method such as continuous casting or semi-continuous casting. In addition, it is preferable to use what has little content of S, Pb, Bi, Se, and As as a copper melt | dissolution raw material. In addition, it is preferable to reduce O and H by paying attention to the red heat (moisture removal) of charcoal to be coated on the molten copper alloy, bare metal, scrap raw material, firewood, mold drying, deoxidation of the molten metal, and the like.

The ingot is preferably subjected to a homogenization treatment, and the homogenization treatment is preferably held for 30 minutes or more after the temperature inside the ingot reaches 800 ° C. The holding time of the homogenization treatment is more preferably 1 hour or more, and further preferably 2 hours or more.
After the homogenization treatment, hot rolling is started at a temperature of 800 ° C. or higher. In order to prevent coarse Fe or Fe—P precipitates from being formed on the hot rolled material, the hot rolling is preferably finished at a temperature of 600 ° C. or higher and then rapidly cooled by a method such as water cooling. When the rapid cooling start temperature after hot rolling is lower than 600 ° C., coarse Fe—P precipitates are formed, the structure tends to be uneven, and the strength of the copper alloy plate (product plate) is lowered.

After hot rolling, (a) hot-rolled material is cold-rolled to product thickness and subjected to aging treatment, (b) hot-rolled material is subjected to cold-rolling and aging treatment, and further cold-rolled to product thickness. Or (c) Low temperature annealing (recovery of ductility) is performed after (b).
The aging treatment (precipitation treatment) is performed under the condition of holding at a heating temperature of about 300 to 600 ° C. for 0.5 to 10 hours. When the heating temperature is less than 300 ° C., the amount of precipitation is small, and when it exceeds 600 ° C., the precipitate tends to be coarsened. The lower limit of the heating temperature is preferably 350 ° C, and the upper limit is preferably 580 ° C. The holding time for the aging treatment is appropriately selected depending on the heating temperature, and is carried out within the range of 0.5 to 10 hours. When the holding time is 0.5 hours or less, the precipitation is insufficient, and even if the holding time exceeds 10 hours, the amount of precipitation is saturated and the productivity is lowered. The lower limit of the holding time is preferably 1 hour, more preferably 2 hours.

A copper alloy having a composition shown in Tables 1 to 4 (pure copper only in Comparative Example 13) was cast to produce ingots each having a thickness of 45 mm. Each ingot was subjected to a soaking treatment at 965 ° C. for 3 hours, followed by hot rolling to obtain a hot-rolled material having a plate thickness of 15 mm, and quenching (water cooling) from a temperature of 700 ° C. or higher. After polishing both sides of the hot-rolled material after quenching by 1 mm each, cold rough rolling to a target plate thickness of 0.6 mm, aging treatment held at 500 ° C. for 2 hours, then 50% finish cold rolling And a copper alloy plate having a thickness of 0.3 mm was produced.

Using the obtained copper alloy plate as a test material, each measurement test of conductivity, mechanical properties, bending workability, and solder wettability was performed in the following manner.
In addition, the obtained copper alloy plate was evacuated at room temperature, heated with Ar gas substitution, heated for 30 minutes after the plate temperature reached 850 ° C., and further cooled with water at 500 ° C. Each test for electrical conductivity and mechanical properties was performed using samples heated for 2 hours (aging treatment) as test materials.
The test results are shown in Tables 1 to 4.

(Measurement of conductivity)
The conductivity was measured by a four-terminal method using a double bridge in accordance with the nonferrous metal material conductivity measurement method defined in JIS-H0505. The dimensions of the test piece are 15 mm wide and 300 mm long.
(Mechanical properties)
A JIS No. 5 tensile test piece was cut out from the test material so that the longitudinal direction was parallel to the rolling direction, and a tensile test was performed in accordance with JIS-Z2241 to measure the yield strength and elongation. The yield strength is a tensile strength corresponding to a permanent elongation of 0.2%.
(Average crystal grain size)
A square test piece having a length of 30 mm and a width of 30 mm was cut out from the test material, and its surface (rolled surface) was mirror-polished, followed by water 120 × 10 ⁻⁶ m ³ , hydrochloric acid 30 × 10 ⁻⁶ m ³ , chloride chloride It etched with the corrosive liquid which consists of 10 g of ferrous iron. The etched plate surface was observed with an optical microscope (observation magnification: 100 to 400 times) and determined by the cutting method of JISH0501-1986. The cutting direction was a direction perpendicular to the rolling direction. The average crystal grain size was obtained at three locations for the same sample, and the average value at three locations (rounded to the nearest 0.1 μm) was taken as the average crystal grain size for that sample.

(Bending workability)
The measurement of the bending workability was carried out according to the W bending test method specified in JBMA-T307 standard of the copper elongation association. A test piece having a width of 10 mm and a length of 30 mm was cut out from each specimen, and a jig with R / t = 0.2 was used to W. (Good Way (bending axis is perpendicular to rolling direction)) and B.I. W. (Bad Way (bending axis is parallel to the rolling direction)) was performed. Next, the presence or absence of cracks in the bent portion was visually observed with a 100 × optical microscope. W. Or B. W. No cracks on both sides (circle) (pass), G. W. Or B. W. Those in which cracking occurred in either one or both were evaluated as x (failed).

(Solder wettability)
A strip-shaped test piece was collected from each test material, and the inactive flux was dip coated for 1 second, and then the solder wetting time was measured by the menisograph method. The solder used was Sn-3 mass% Ag-0.5 mass% Cu maintained at 260 ± 5 ° C., and the test was performed under the test conditions of an immersion speed of 25 mm / sec, an immersion depth of 5 mm, and an immersion time of 5 sec. A solder wetting time of 2 seconds or less was evaluated as having excellent solder wettability. Except for Comparative Examples 10 and 24, the solder wetting time was 2 seconds or less.

The copper alloy sheets of Examples 1 to 17 shown in Table 1 have an alloy composition that satisfies the provisions of the present invention, and are heated at 850 ° C. for 30 minutes and then subjected to aging treatment (0.2% yield strength) of 100 MPa or more. And the electrical conductivity is 50% IACS or more.

On the other hand, the copper alloy plates of Comparative Examples 1 to 12 and the pure copper plate of Comparative Example 13 shown in Table 2 are inferior in some characteristics as shown below.
Since the comparative example 1 has little Fe content, the intensity | strength after an aging treatment is low.
In Comparative Examples 2 to 4, [Fe] / [P] is high, the Fe—P compound is not sufficiently precipitated even after the aging treatment, and the electrical conductivity after the aging treatment is low. Comparative Examples 2 and 3 also have low strength after aging treatment.
In Comparative Example 5, since the Fe content is excessive, the electrical conductivity after the aging treatment is low.
In Comparative Example 6, the P content was excessive and cracked during hot rolling, and the process could not proceed to the process after hot rolling.
In Comparative Example 12, since the Fe content exceeds 1.0%, the Fe content is excessive, and [Fe] / [P] exceeds 7, the conductivity after the aging treatment is lower than that of Comparative Example 5.

In Comparative Examples 7 and 8, since [Fe] / [P] is low, P that does not contribute to the precipitation of the Fe—P compound even after the aging treatment is dissolved, and the electrical conductivity after the aging treatment is low.
In Comparative Example 9, since [Fe] / [P] is low, the Fe—P compound is hardly precipitated even after the aging treatment, and the strength is low.
In Comparative Example 10, the Zn content is excessive, the electrical conductivity after the aging treatment is low, and the solder wettability is inferior.
In Comparative Example 11, the content of other elements is excessive, and the electrical conductivity after aging treatment is low.
Comparative Example 13 is a conventional pure copper plate, which has high electrical conductivity but has low strength even after aging treatment.

The copper alloy plates of Examples 18 to 38 shown in Table 3 have an alloy composition that satisfies the provisions of the present invention, and are heated at 850 ° C. for 30 minutes and then subjected to aging treatment (0.2% yield strength) of 100 MPa or more. And the electrical conductivity is 45% IACS or higher.

On the other hand, the copper alloy sheets of Comparative Examples 14 to 24 shown in Table 4 are inferior in some characteristics as shown below.
In Comparative Example 14, the content of Fe and Sn is out of the range of ABCD in FIG. 1 (the Fe content is small), so the strength after aging treatment is low.
In Comparative Examples 15 to 17, the Fe and Sn contents are out of the range of ABCD in FIG. 1 (the Sn content is excessive), so the conductivity after the aging treatment is low.
In Comparative Examples 18 to 20, the strength after aging treatment is low because the Fe and Sn contents are out of the range of ABCD in FIG. 1 (the Fe content is small).
In Comparative Example 21, since [Fe] / [P] is low, P which does not contribute to the precipitation of the Fe—P compound after the aging treatment is dissolved, and the electrical conductivity after the aging treatment is low.
In Comparative Example 22, the P content was excessive and cracked during hot rolling, and the process after hot rolling could not proceed.
In Comparative Example 23, since [Fe] / [P] is high, Fe that does not contribute to the precipitation of the Fe—P compound is dissolved, and the electrical conductivity after the aging treatment is low.
In Comparative Example 24, the Zn content is excessive and the solder wettability is poor.

Representative copper alloy plates shown in Tables 1 to 4 (Examples 1, 3, 19, and 24 and Comparative Examples 1, 5, 14, and 15) were evacuated at room temperature and then replaced with Ar gas and heated. Then, after the temperature of the plate material reaches 1000 ° C., it is heated for 30 minutes and then water-cooled, and the water-cooled material is further heated at 500 ° C. for 2 hours (aging treatment). Each measurement test of mechanical properties was performed by the method described in Example 1. The results are shown in Table 5.

As shown in Table 5, in Examples 1, 3, 19 and 24, the strength (0.2% proof stress) after heating at 1000 ° C. for 30 minutes and then aging treatment was 100 MPa or more and the conductivity was 50. % IACS or more (when Sn is not included) or 45% IACS or more (when Sn is included). When the individual numerical values are compared with the measurement results after heating at 850 ° C. for 30 minutes and then aging treatment (see Tables 1 and 3), there is no significant difference in the numerical values.
On the other hand, Comparative Examples 1, 5, 14 and 15 are inferior in one or both of strength and conductivity after heating at 1000 ° C. for 30 minutes and then aging treatment.

The disclosure of the present specification includes the following aspects.
Aspect 1:
Fe: 0.07 to 0.7% by mass, P: 0.2% by mass or less, and the ratio [Fe] / [P] of Fe content [Fe] to P content [P] is 2 The balance consists of Cu and inevitable impurities, and after heating at 850 ° C. for 30 minutes and then water cooling, 0.2% proof stress after aging treatment is 100 MPa or more, conductivity is 50% IACS or more, and heat dissipation A copper alloy sheet for a heat-radiating component, characterized in that a part of the process for producing the component includes a process of heating to 650 ° C. or more and an aging treatment.

Aspect 2:
Point A (0.1, 0.006), point B (0.5, 0.006), point C (0.05, 1.1), point D (0.05, 0.05) shown in FIG. ) Fe and Sn in the range enclosed (including the boundary line), and P: 0.2 mass% or less, the ratio [Fe] / [P] of the Fe content [Fe] and P content [P] P] is 2 to 5, the balance is made of Cu and inevitable impurities, and after heating at 850 ° C. for 30 minutes, water cooling, and then aging treatment, 0.2% proof stress is 100 MPa or more, and conductivity is 45% IACS. A copper alloy plate for a heat radiating component, characterized in that a part of the process for manufacturing the heat radiating component includes a process of heating to 650 ° C. or more and an aging treatment.

Aspect 3:
Furthermore, Zn is 1.5 mass% or less (excluding 0 mass%), Zn is contained, The copper alloy plate for heat radiating components described in the aspect 1 characterized by the above-mentioned.

Aspect 4:
Furthermore, Mn: 0.1% by mass or less (not including 0% by mass), Mg: 0.2% by mass or less (not including 0% by mass), Si: 0.2% by mass or less (including 0% by mass) ), Al: 0.2% by mass or less (not including 0% by mass), Cr: 0.2% by mass or less (not including 0% by mass), Ti: 0.1% by mass or less (0% by mass) Not including) and Zr: 0.05% by mass or less (not including 0% by mass), including one or more in total of 0.5% by mass or less (not including 0% by mass) The copper alloy for heat radiating components described in the aspect 1 or 3.

Aspect 5:
Furthermore, it contains 1.5 mass% or less (excluding 0 mass%) of Zn, The copper alloy plate for heat radiating components described in the aspect 2 characterized by the above-mentioned.

Aspect 6:
Furthermore, Mn: 0.1% by mass or less (not including 0% by mass), Mg: 0.2% by mass or less (not including 0% by mass), Si: 0.2% by mass or less (including 0% by mass) ), Al: 0.2% by mass or less (not including 0% by mass), Cr: 0.2% by mass or less (not including 0% by mass), Ti: 0.1% by mass or less (0% by mass) Not including) and Zr: 0.05% by mass or less (not including 0% by mass), including one or more in total of 0.5% by mass or less (not including 0% by mass) The copper alloy for heat radiating components described in the aspect 2 or 5.

Aspect 7:
The copper alloy for a heat-radiating component according to any one of aspects 1, 3 and 4, wherein the average crystal grain size of the plate surface measured in the plate material before heating at 850 ° C. for 30 minutes is 20 μm or less.

Aspect 8:
The copper alloy for heat-radiating components according to any one of aspects 2, 5 and 6, wherein the average crystal grain size of the plate surface measured in the plate material before heating at 850 ° C. for 30 minutes is 20 μm or less.

Aspect 9:
A copper alloy plate for a heat-dissipating part described in any one of aspects 1, 3, 4, or 7, wherein an Fe—P compound is deposited, and has a 0.2% proof stress of 100 MPa or more and an electric conductivity of 50% IACS or more. A heat dissipating component characterized by comprising:

Aspect 10:
A copper alloy plate for a heat-dissipating component described in any one of aspects 2, 5, 6 or 8, on which an Fe—P compound is deposited, 0.2% proof stress of 100 MPa or more, and conductivity of 45% IACS or more A heat dissipating component characterized by comprising:

Aspect 11:
The heat radiating component according to the aspect 9 or 10, wherein an Sn coating layer is formed on at least a part of the outer surface.

Aspect 12:
The heat dissipating component according to aspect 9 or 10, wherein a Ni coating layer is formed on at least a part of the outer surface.

The present application includes a Japanese patent application filed on March 23, 2015, Japanese Patent Application No. 2015-058957, and a Japanese patent application filed on October 12, 2015, Japanese Patent Application No. 2015-2015. Accompanied by priority claim with 2016655 as the basic application. Japanese Patent Application No. 2015-058957 and Japanese Patent Application No. 2015-201665 are incorporated herein by reference.

Claims

Fe: 0.07 to 0.7% by mass, P: 0.2% by mass or less, and the ratio [Fe] / [P] of Fe content [Fe] to P content [P] is 2 The balance consists of Cu and inevitable impurities, and after heating at 850 ° C. for 30 minutes and then water cooling, 0.2% proof stress after aging treatment is 100 MPa or more, conductivity is 50% IACS or more, and heat dissipation A copper alloy sheet for a heat-radiating component, characterized in that a part of the process for producing the component includes a process of heating to 650 ° C. or more and an aging treatment.
Point A (0.1, 0.006), point B (0.5, 0.006), point C (0.05, 1.1), point D (0.05, 0.05) shown in FIG. ) Fe and Sn in the range enclosed (including the boundary line), and P: 0.2 mass% or less, the ratio [Fe] / [P] of the Fe content [Fe] and P content [P] P] is 2 to 5, the balance is made of Cu and inevitable impurities, and after heating at 850 ° C. for 30 minutes, water cooling, and then aging treatment, 0.2% proof stress is 100 MPa or more, and conductivity is 45% IACS. A copper alloy plate for a heat radiating component, characterized in that a part of the process for manufacturing the heat radiating component includes a process of heating to 650 ° C. or more and an aging treatment.
Furthermore, the copper alloy plate for heat-radiating components according to claim 1, further comprising Zn in an amount of 1.5% by mass or less (not including 0% by mass).
Furthermore, Mn: 0.1% by mass or less (not including 0% by mass), Mg: 0.2% by mass or less (not including 0% by mass), Si: 0.2% by mass or less (including 0% by mass) ), Al: 0.2% by mass or less (not including 0% by mass), Cr: 0.2% by mass or less (not including 0% by mass), Ti: 0.1% by mass or less (0% by mass) Not including) and Zr: 0.05% by mass or less (not including 0% by mass), including one or more in total of 0.5% by mass or less (not including 0% by mass) The copper alloy for heat dissipation components according to claim 1.
Furthermore, Mn: 0.1% by mass or less (not including 0% by mass), Mg: 0.2% by mass or less (not including 0% by mass), Si: 0.2% by mass or less (including 0% by mass) ), Al: 0.2% by mass or less (not including 0% by mass), Cr: 0.2% by mass or less (not including 0% by mass), Ti: 0.1% by mass or less (0% by mass) Not including) and Zr: 0.05% by mass or less (not including 0% by mass), including one or more in total of 0.5% by mass or less (not including 0% by mass) The copper alloy for heat radiating components according to claim 3.
Furthermore, the copper alloy plate for heat-radiating components according to claim 2, further comprising Zn in an amount of 1.5% by mass or less (not including 0% by mass).
Furthermore, Mn: 0.1% by mass or less (not including 0% by mass), Mg: 0.2% by mass or less (not including 0% by mass), Si: 0.2% by mass or less (including 0% by mass) ), Al: 0.2% by mass or less (not including 0% by mass), Cr: 0.2% by mass or less (not including 0% by mass), Ti: 0.1% by mass or less (0% by mass) Not including) and Zr: 0.05% by mass or less (not including 0% by mass), including one or more in total of 0.5% by mass or less (not including 0% by mass) The copper alloy for heat radiating components according to claim 2.
Furthermore, Mn: 0.1% by mass or less (not including 0% by mass), Mg: 0.2% by mass or less (not including 0% by mass), Si: 0.2% by mass or less (including 0% by mass) ), Al: 0.2% by mass or less (not including 0% by mass), Cr: 0.2% by mass or less (not including 0% by mass), Ti: 0.1% by mass or less (0% by mass) Not including) and Zr: 0.05% by mass or less (not including 0% by mass), including one or more in total of 0.5% by mass or less (not including 0% by mass) The copper alloy for heat radiating components according to claim 6.
6. The copper alloy for heat dissipation components according to claim 1, wherein the average crystal grain size of the plate surface measured in the plate material before heating at 850 ° C. for 30 minutes is 20 μm or less. .
9. The copper alloy for heat-radiating components according to claim 2, wherein the average crystal grain size of the plate surface measured in the plate material before heating at 850 ° C. for 30 minutes is 20 μm or less. .
It consists of the copper alloy plate for heat radiating components as described in any one of Claims 1, 3, 4, or 5, and the Fe-P compound has precipitated, 0.2% yield strength of 100 MPa or more, and conductivity of 50% IACS or more. A heat dissipation component characterized by having a rate.
A heat dissipation component comprising the copper alloy plate for heat dissipation component according to claim 9, wherein an Fe-P compound is deposited, and has a 0.2% proof stress of 100 MPa or more and a conductivity of 50% IACS or more. parts.
A copper alloy plate for a heat dissipation component according to any one of claims 2, 6, 7, or 8, wherein an Fe-P compound is deposited, and has a 0.2% proof stress of 100 MPa or more and a conductivity of 45% IACS or more. A heat dissipation component characterized by having a rate.
A heat dissipation comprising the copper alloy plate for a heat dissipation component according to claim 10, wherein an Fe-P compound is precipitated, and has a 0.2% proof stress of 100 MPa or more and a conductivity of 45% IACS or more. parts.
The heat-radiating component according to claim 11, wherein an Sn coating layer is formed on at least a part of the outer surface.
The heat dissipating component according to claim 12, wherein an Sn coating layer is formed on at least a part of the outer surface.
The heat-radiating component according to claim 11, wherein a Ni coating layer is formed on at least a part of the outer surface.
13. The heat dissipating component according to claim 12, wherein a Ni coating layer is formed on at least a part of the outer surface.
14. The heat dissipating component according to claim 13, wherein an Sn coating layer is formed on at least a part of the outer surface.
The heat-radiating component according to claim 14, wherein a Sn coating layer is formed on at least a part of the outer surface.
The heat dissipating component according to claim 13, wherein a Ni coating layer is formed on at least a part of the outer surface.
The heat dissipating component according to claim 14, wherein a Ni coating layer is formed on at least a part of the outer surface.