CN109790597A

CN109790597A - The manufacturing method of heat dissipation element copper alloy plate, heat dissipation element and heat dissipation element

Info

Publication number: CN109790597A
Application number: CN201780060263.3A
Authority: CN
Inventors: 桥本大辅; 西村昌泰
Original assignee: Kobe Steel Ltd
Current assignee: Kobe Steel Ltd
Priority date: 2016-10-05
Filing date: 2017-09-26
Publication date: 2019-05-21
Also published as: JP6850233B2; TWI683012B; TW201827614A; KR102226988B1; KR20190043583A; WO2018066414A1; JP2018059198A

Abstract

A kind of heat dissipation element copper alloy plate, it is characterized in that, there is the phosphide containing one or more of Fe, Ni, Co to be precipitated, 0.2% yield strength and excellent bendability with 100MPa or more, 0.2% yield strength measured at 850 DEG C is 10MPa or more, water cooling after being heated 30 minutes with 850 DEG C, then with 0.2% yield strength after the ageing treatment of 500 DEG C of progress 2 hours for 100MPa or more, conductivity is 50%IACS or more, includes the process and ageing treatment for being heated to 650 DEG C or more in a part of the process of manufacture heat dissipation element.

Description

The manufacturing method of heat dissipation element copper alloy plate, heat dissipation element and heat dissipation element

Technical field

It is used when the heat dissipation element for manufacturing vapor chamber (tabular heat pipe) etc. the present invention relates to engagement multiple element Heat dissipation element copper alloy plate.More particularly to including diffusion bonding and solder brazing etc., be heated to 650 DEG C or more of temperature Heat dissipation element copper alloy plate used when process.

Background technique

The CPU mounted such as Desktop PC, notebook type PC, tablet computer terminal, mobile phone representated by smart phone Operating rate high speed and high-density integrated be rapidly in progress, the calorific value of the unit area from these CPU is further Increase.If the temperature of CPU rises to more than a certain amount of temperature, become maloperation, the reason of thermal runaway etc., therefore, from CPU etc. Semiconductor device effectively radiate become practical problem.

It as the heat of absorption semiconductor device, and is allowed to diffuse the heat dissipation element in atmosphere, can be used heat sink.Due to heat Heavy requirement has high-termal conductivity, so using the big copper of thermal conductivity, aluminium etc. as former material.Using by CPU in Desktop PC Heat pass to and be set to heat sink cooling fin etc., the method that the intracorporal small-sized fans of Desktop PC frame carry out heat extraction is arranged in.

But among the notebook type PC of the installation space of not fan, tablet computer terminal etc., as limited The heat dissipation element for possessing higher heat transfer potential under area is able to use vapor chamber (tabular heat pipe).Heat pipe passes through Circulation carries out for the evaporation (absorbing heat from CPU) and condensation (releasing the heat absorbed) for being sealing into internal refrigerant, and plays specific heat Sink higher heat dissipation performance.In addition, it is also proposed that be combined heat pipe and heat dissipation element as heat sink or fan, to solve The certainly heat dissipation problem of semiconductor device.

Vapor chamber further increases the heat dissipation performance of tubulose heat pipe (referring to patent document 1~4).As vapor chamber, It is proposed has in order to which the condensation of refrigerant and evaporation is effectively performed, same as tubulose heat pipe, proposes that inner surface carries out surface It is roughening processing, fluting processing, powder sintered and form micropore etc..

In addition, proposing to be fixed on the inside of the inside of external component by external component (framework), and receiving as vapor chamber Component is constituted.In order to promote the condensation, evaporation, conveying of refrigerant, in the inside of external component, configured with one or more internal Component, and be processed fin of various shapes, protrusion, hole, slit etc..The vapor chamber of this form, in the following way Manufacture, that is, internal component is configured to after the inside of external component, by the method for diffusion bonding, solder brazing etc., makes external structure Between part and external component it is integrated with internal component engagement.Vapor chamber is after internal embedding with refrigerant, by solder brazing etc. Method is sealed.

The fever of electronic component is further enlarged, when heat removal capacity beyond vapor chamber, can be used have with vapor chamber it is same The internal structure of sample, from such heat dissipation element (not needing to make internal in low pressure) of external continuous supply refrigerant. The manufacturing method of component used in the framework of the heat dissipation element of this type and framework is identical as vapor chamber (referring to patent document 5)。

As the former material of vapor chamber, by thermal conductivity, corrosion resistance, processability and excellent oxygen-free copper (OFC) structure of etching At, such as soft material (state code O)~hard material (state code H) plate of multi-purpose 0.3~1.0mm of plate thickness or so (contains Item).It is as follows if illustrating an example of the production process of the vapor chamber using OFC plate.

Firstly, the single side face of the board member of the rectangle in the case where intercepting from OFC plate, by etching and processing or has used mould The punch process of tool forms the pattern of multiple grooves, bumps etc..Secondly, this face for being formed with the pattern is made to be in inside, it will Two panels board member is overlapped up and down, is diffused engagement (B referring to Fig.1) with this state.Diffusion bonding proceeds as follows, in height In 10^{- 2}Under the vacuum atmosphere of air pressure, applies the stress (plus-pressure) of 2~6MPa or so to junction, be warming up to this state 800~900 DEG C of high temperature, after reaching assigned temperature, synthermal lower holding 10~120 minutes or so.In addition, in upper and lower plate It is embedded with jet pipe (thin diameter tube) between component, also engages the jet pipe.

After diffusion bonding, under vacuum or reduced atmosphere, working fluid is injected in the inside of vapor chamber by the jet pipe (water etc.), then seals the jet pipe.

When making vapor chamber by solder brazing, between the board member being overlapped up and down, the silver-bearing copper every the shape at joint portion is pressed from both sides The thin plate or foil of solder, P-Cu Brazing Materials etc. are continuously inserted into heating furnace in this state and are heated, and carry out solder brazing engagement.Firmly The atmosphere of soldering is 10^{- 1}Vacuum atmosphere, reducing atmosphere or the inactive gas atmosphere of air pressure or so, heating temperature be 650~ 900℃.In addition, in solder brazing heating process, in a manner of it joint portion will not be made to shift because of vibration etc., to junction Apply the stress (plus-pressure) of 2~5MPa or so, heating and solder brazing are carried out with this state.

[advanced technical literature]

[patent document]

[patent document 1] Japanese Unexamined Patent Publication 2004-238672 bulletin

[patent document 2] Japanese Unexamined Patent Publication 2007-315745 bulletin

[patent document 3] Japanese Unexamined Patent Publication 2014-134347 bulletin

[patent document 4] Japanese Unexamined Patent Publication 2015-121355 bulletin

[patent document 5] International Publication No. 2014/171276

Diffusion bonding or the plus-pressure of solder brazing, in general, at a temperature of the holding that diffusion bonding or solder brazing may be selected No more than the range of 0.2% yield strength (tensile strength when permanent extension rate reaches 0.2% in tension test) of material Inside value big as far as possible.The plus-pressure is bigger, can more shorten the retention time for keeping temperature, connect in addition, more can be improved The reliability (generation not being leaked, without non-joint etc.) in conjunction portion.In addition, in diffusion bonding or solder brazing, it is additional to be more than When the plus-pressure of 0.2% yield strength, the reliability at joint portion can be further increased, further shortens the retention time, but is added Splenium can be plastically deformed, and cannot maintain expected shape (design shape).

In the diffusion bonding or solder brazing of vapor chamber, even if former material is OFC plate, plus-pressure is also at a temperature of holding 0.2% yield strength no more than OFC plate in the range of determine, if 0.2% yield strength be σ_0.2When, plus-pressure is usual For (0.5~0.8) × σ_0.2Range.

After being kept for 30 minutes with 700~900 DEG C, 0.2% yield strength of the OFC plate measured at this temperature is small, and 700 DEG C Down it is 8MPa, is 6MPa at 800 DEG C, is 5MPa at 900 DEG C.

For the single side face for the OFC plate that plate thickness is 0.45mm, flat shape is 60mm × 60mm, retain the frame section of surrounding And it is etched to certain depth, the board member 1 (A referring to Fig.1) of the framework of production simulation vapor chamber.In the board member 1, frame section 2 width is 7mm, and the wall thickness of etched thinner wall section 3 is 0.2mm.Then, make two board members 1,1, as shown in Figure 1B this Being overlapped facing towards inside for etching is heated to 850 DEG C by sample, and applying the plus-pressure of 3MPa to frame section, (0.2% surrender is strong 50% or more of degree) and kept for 30 minutes, it is diffused engagement.

In board member 1,1 after diffusion bonding, slight recess is observed near the central portion of thinner wall section 3 and is heaved. The reason of such deformation occurs, thus it is speculated that be since in diffusion bonding, board member 1 is heated above the height of recrystallization temperature Temperature, the Young's modulus and yield strength (yield stress) of material significantly reduce together, therefore, because acting in thinner wall section 3 Gravity near the portion of centre leads to that the deformation of creep occurs in the thinner wall section 3.It is additionally contemplated that plus-pressure when due to diffusion bonding, Cause frame section 2 to transversely deforming, inside stress occurs in the inside of frame section 2 (upper and lower thinner wall section 3) as a result, but should Stress is also only speculated as one of the reason of deformation (be recessed and heave) occurs.

In the vapor chamber that this deformation occurs, the shape and volume of the inner space of chamber change, and evaporate and cold The flow direction (flow path) and flow of solidifying refrigerant change, it is impossible to play expected hot property.In addition, vapor chamber and fever Gap is formed between portion (CPU etc.), heat transfer property reduces.

In addition, due to being heated to 600 DEG C or more of temperature secondary recrystallization occurs for OFC plate, coarse grains.If such as 800 DEG C are heated to, even if then heating time is short, average crystal grain diameter also can be coarse to 100 μm~several 100 μm or so.Thick The crystal boundary for the crystal grain changed greatly, gas, impurity element, field trash density get higher, therefore, crystal boundary becomes fragile than transgranular.

In the vapor chamber that the OFC plate using 0.3~0.5mm of plate thickness makes, the plate for the part that etching and punch process are crossed Thickness is thinned to 0.1~0.3mm or so.When average crystal grain diameter is coarse to 100 μm~several 100 μm or so, in such thin-walled Portion, crystal grain only exist 1~3 or so in wall thickness direction.In vapor chamber, because refrigerant evaporates and cold repeatedly in use It is solidifying, so pressure change at this moment will lead to stretching and compression stress is iteratively operating on thinner wall section.If average crystal grain diameter is coarse, Then readily occur in crystal boundary propagation crackle, have perforation thinner wall section crackle there is a situation where.If like that, then chamber interior Refrigerant is leaked by crystal boundary, cannot function as vapor chamber use.In addition, copper alloy plate (steams if average crystal grain diameter coarsening Vapour chamber) surface roughness become larger, become larger with the gap of heating part (CPU etc.), from heating part to the heat transfer property of vapor chamber drop It is low.

The problem of diffusion bonding described above (deformation, coarsening of crystal grain of thinner wall section etc.), by solder brazing system Can also it occur when making vapor chamber.

As the former material of vapor chamber, if the material big using the intensity under high temperature, then it is assumed that be capable of increasing diffusion bonding Or plus-pressure when solder brazing and shorten the retention time, improve the reliability at joint portion, can additionally prevent diffusion bonding Or the deformation of the board member 1 when solder brazing.In addition, if using the material that can inhibit the coarse grains under high temperature, then it is assumed that Even if also crystal grain can be made largely to exist in wall thickness direction in the thinner wall section of board member 1, letting out for the refrigerant of vapor chamber is prevented Leakage, can prevent the reduction of heat transfer property.In addition, when using such material, even if including in a part of manufacturing process In other heat dissipation elements of the process of high-temperature heating, it is believed that can also obtain same effect.

Summary of the invention

Therefore, embodiments of the present invention, its main purpose is, the former material of the heat dissipation element as vapor chamber etc., mentions For a kind of big material (copper alloy plate) of the intensity (0.2% yield strength value) under high temperature.In addition, embodiments of the present invention, Its another object is that the former material of the heat dissipation element as vapor chamber etc. provides a kind of coarse grains that can inhibit under high temperature Material (copper alloy plate).

The heat dissipation element copper alloy plate of embodiments of the present invention, which is characterized in that be used for following situation, i.e. conduct Manufacture a part of the process of heat dissipation element, the case where including the process and ageing treatment for being heated to 650 DEG C or more, containing Fe, The phosphide of one or more of Ni, Co are precipitated, with 0.2% yield strength of 100MPa or more and excellent Bendability, 0.2% yield strength measured at 850 DEG C be 10MPa or more, and with 850 DEG C heat 30 minutes after water cooling, Then with 0.2% yield strength after the ageing treatment of 500 DEG C of progress 2 hours for 100MPa or more, conductivity 50% IACS or more.In the copper alloy plate, the average crystal grain diameter after preferably being heated 30 minutes with 850 DEG C is 100 μm or less.In addition, Plate described in embodiments of the present invention includes item.

In the copper alloy plate, for example, containing one or more of Fe, Co, Ni and the mass % of P:0.01~0.2, Total content [Fe+Co+Ni] of Fe, Co, Ni are 0.2~2.3 mass %, and surplus is made of Cu and inevitable impurity.It should In copper alloy, as needed, also containing one or more of Mg, Al, Si, Cr, Ti, Zr, Zn, Sn, Mn, add up to 0.01~0.3 mass %.

In addition, another heat dissipation element copper alloy plate of embodiments of the present invention, which is characterized in that containing in Ni, Co One or two kinds of silicides be precipitated, have 200MPa or more 0.2% yield strength and excellent bendability, 0.2% yield strength measured at 850 DEG C be 10MPa or more, and with 850 DEG C heat 30 minutes after water cooling, then with 500 DEG C 0.2% yield strength after ageing treatment when carrying out small 2 is 300MPa or more, and conductivity is 50%IACS or more.It is preferred that Average crystal grain diameter after the copper alloy plate is heated 30 minutes with 850 DEG C is 100 μm or less.

In the copper alloy plate, for example, containing one or both of Ni and Co and Si, total content [Ni+Co] of Ni and Co For total content [Ni+Co] of 1.6~3.5 mass %, Ni and Co and ratio [Ni+Co]/[Si] of Si content [Si] be 3.5~ 5.5, surplus is made of Cu and inevitable impurity.In the copper alloy, as needed also containing Mg, Al, Cr, Ti, Zr, Zn, One or more of Sn, Mn add up to 0.01~0.3 mass %.

The heat dissipation element copper alloy plate of embodiments of the present invention, by the precipitation hardening type copper containing phosphide or silicide Alloy is constituted, and compared with existing OFC, the intensity under high temperature is high.Therefore, plus-pressure when being capable of increasing diffusion bonding and shorten Retention time improves the reliability at joint portion, and board member (such as the framework member of vapor chamber when can prevent diffusion bonding Part) deformation.

In addition, when inhibiting the coarsening of the crystal grain under high temperature, even if in the thin-walled of board member (such as framework of vapor chamber) Portion also can be such that crystal grain largely exists in wall thickness direction, prevent refrigerant from internal leakage.

In addition, the heat dissipation element of embodiments of the present invention is age-hardening type with copper alloy plate, after high-temperature heating Ageing treatment, intensity and conductivity improve.Therefore, 650 DEG C or more of process (diffusion bonding, solder brazing, Laser Welding are being heated to Connect) after, ageing treatment is carried out, high-intensitive, heat dissipation performance excellent heat dissipation element can be obtained.

Detailed description of the invention

Figure 1A is perspective view that illustrate the diffusion bonding of vapor chamber, the figuratum board member of formation.

Figure 1B illustrates the diffusion bonding of vapor chamber, in order to engage makes two board members (the framework element of vapor chamber) The sectional view of state after overlapping.

Fig. 2 is indicated with the figure of the shape and size of test film used in the tension test of 850 DEG C of progress.

Specific embodiment

Hereinafter, being illustrated in more detail for the heat dissipation element copper alloy plate of embodiments of the present invention.

[composition of alloy]

The precipitation hardening type copper alloy of heat dissipation element as the framework for being suitable for vapor chamber etc., can enumerate commonly known per se Cu- (Fe, Co, Ni)-P system's alloy and Cu- (Ni, Co)-Si system alloy.

(Cu- (Fe, Co, Ni)-P system alloy)

The copper alloy for being, one or more and P containing Fe, Ni, Co, and Fe, Ni, Co and p-shaped are at chemical combination Object (phosphide).

In the copper alloy, preferably total content [Fe+Co+Ni] of Fe, Co, Ni are 0.2~2.3 mass %, and P content is 0.01~0.2 mass %, surplus are made of Cu and inevitable impurity.

In the copper alloy, as needed also containing one or both of Mg, Al, Si, Cr, Ti, Zr, Zn, Sn, Mn with On, add up to 0.01~0.3 mass %.

At compound (phosphide), the intensity and conductivity of the copper alloy plate after making ageing treatment are mentioned for Fe, Co and Ni and p-shaped Height, and have the function of coarse grains when inhibiting high-temperature heating.Fe, the Co for not forming phosphide are precipitated with monomer, With with the similarly effect of above-mentioned phosphide, on the other hand, the Ni for not forming phosphide is dissolved in Cu, makes copper alloy plate Intensity improves.But [Fe+Co+Ni], when being lower than 0.2 mass %, 0.2% yield strength at 850 DEG C is lower than 10MPa.It is another Aspect, if [Fe+Co+Ni] is higher than 2.3 mass %, conductivity is reduced, in addition, coarse in the melting casting process of alloy Compound crystallization, bendability, forging process and corrosion resistance reduce.Therefore, [Fe+Co+Ni] is preferably 0.2~2.3 In the range of quality %.In addition, when the content of Ni is lower than 0.1 mass %, said effect is insufficient, another in this copper alloy Aspect, if being higher than 1 mass %, said effect saturation.Therefore, when containing Ni, in the range of Ni content is 0.1~1.0 mass %. The preferred lower limit value of [Fe+Co+Ni] is 0.25%, and preferred upper limit value is 2.1%, and in addition the preferred lower limit value of Ni is 0.15%, preferred upper limit value is 0.9%.

In above-mentioned copper alloy, the one or two containing Fe and Co among Fe, Co, Ni, total content [Fe+ of Fe and Co Co] it is preferably 0.2~2.3 mass %.It in this case, being capable of Ni as needed containing 0.1~1.0 mass %.According to this One composition can inhibit the average crystal grain diameter after 850 DEG C × heating 30 minutes at 100 μm or less.

The effect that P has is that oxygen amount contained in copper alloy is reduced by deoxidation, is prevented in hydrogeneous also Primordial Qi Hydrogen brittleness when heat dissipation element is heated in atmosphere.To P content required for hydrogen embrittlement is 0.01 mass % or more in order to prevent.Separately Outside, the P of solid solution reduces the conductivity of copper alloy, but forms phosphide with Fe, Co, Ni and being heated to Precipitation Temperature, by This, intensity, heat resistance and the conductivity of copper alloy improve.But if the content of P is higher than 0.2 mass %, the amount for the P being dissolved Increase, conductivity reduces.Therefore, the content of P is 0.01~0.2 mass %.Mainly pursued by the precipitation of above-mentioned phosphide When the raising of intensity, heat resistance and conductivity, ratio [Fe+Co+Ni]/[P] of [Fe+Co+Ni] and P content [P] is preferably 2~5 Left and right.The preferred lower limit value of P be 0.013%, preferred upper limit value be 0.17%, [Fe+Co+Ni]/[P] it is preferred under Limit value is 2.3, and preferred upper limit value is 4.5.

Mg, Al, Si, Cr, Ti, Zr, Zn, Sn, Mn have the function of that the intensity for making copper alloy and heat resistance improve, therefore Its one or more can be added as needed.But total content of one or more of these elements is lower than When 0.005 mass %, effect is small, and on the other hand, if being higher than 0.3 mass %, conductivity is reduced.Therefore, in these elements One or more kinds of total contents be 0.005~0.3 mass % in the range of.The one or more of these elements Total content, preferred lower limit value 0.01, more preferable lower limit value be 0.02 mass %, preferred upper limit value be 0.25 mass %.

Even if wherein Si, Al, Mn, Ti are allowed on a small quantity containing the conductivity of copper alloy can also reducing, therefore preferred each member Element makes 0.1 mass % of upper limit value.Cr, Zr are few for the solid solution capacity of copper, can be precipitated even if relatively high temperature region, Therefore, the big element of coarse grains inhibitory effect when being heated to high temperature.Therefore, it is desirable to keep the crystal grain of copper alloy plate fine When change, containing one or both of Cr and Zr, add up to 0.03 mass % or more, be preferably allowed to containing 0.06 mass % with On.When making Cr and Zr contain one or two to add up to 0.03 mass % or more, even if [Fe+Co] is lower than 0.2 mass % (its In, [Fe+Co+Ni] is 0.2 mass % or more), the average crystal grain diameter after 850 DEG C × heating 30 minutes can also be inhibited 100 μm or less.On the other hand, Cr and Zr reduce conductivity, therefore total content of one or both of these elements is excellent It is selected as 0.2 mass % or less.

Other than the effect that intensity and resistance to stress relaxation behavior improve, Sn, Mg, which also have, mentions resistance to stress relaxation behavior High effect.If the temperature or use environment of heat dissipation element be 80 DEG C or herein more than, the deformation of creep occurs, with CPU's etc. The contact area of heat source becomes smaller, and thermal diffusivity reduces, but improves resistance to stress relaxation behavior, is able to suppress this phenomenon.It is terrible To the effect, preferably Sn content is 0.01 mass % or more, and Mg content is 0.005 mass % or more.On the other hand, from preventing copper From the perspective of the conductivity of alloy sheets reduces, preferably Sn content is 0.2 mass % hereinafter, it is preferred that Mg content is 0.2 mass % Below.

Zn improves the resistance to thermally strippable of solder and the resistance to thermally strippable of plating Sn.Vapor chamber solder is in the electricity as heating part In subcomponent, in addition, having the case where carrying out plating Sn for vapor chamber to improve corrosion resistance.In this case, as steam The former material of the framework of chamber is suitable for using the copper alloy plate containing Zn.Even if Zn a small amount of addition, it may have improve above-mentioned resistance to hot soarfing Effect from property, but it is higher than 0.3 mass % containing Zn, effect is also saturation, therefore the content of preferably Zn is 0.3% or less. The lower limit value of Zn content is more preferably 0.005 mass %, further preferably 0.01 mass %.

(Cu- (Ni, Co)-Si system alloy)

The copper alloy for being, containing one or both of Ni, Co and Si, and Ni, Co and Si form compound (silication Object).

In the copper alloy, total content [Ni+Co] of preferably Ni and Co are total the containing of 1.6~3.5 mass %, Ni and Co Ratio [Ni+Co]/[Si] for measuring [Ni+Co] and Si content [Si] is 3.5~5.5, and surplus is made of Cu and inevitable impurity.

In the copper alloy, also closed as needed containing one or more of Mg, Al, Cr, Ti, Zr, Zn, Sn, Mn It is calculated as 0.01~0.3 mass %.

Ni and Co and Si forms compound (silicide), and the intensity and conductivity of the copper alloy after making ageing treatment improve, And there is the coarsening effect of crystal grain when inhibiting high-temperature heating.But [Ni+Co] when being lower than 1.6 mass %, at 850 DEG C 0.2% yield strength be lower than 10MPa, in addition, inhibit coarse grains effect it is small.On the other hand, if [Ni+Co] is higher than 3.5 mass %, then conductivity reduces, and coarse compound crystallization or precipitation, hot-workability reduce.Therefore, [Ni+Co] is 1.6 In the range of~3.5 mass %.

In addition, when [Ni+Co]/[Si] is lower than 3.5, superfluous Si solid solution, if being higher than 5.5, superfluous Ni or Co solid solution, Conductivity reduces.Therefore, in the range of [Ni+Co]/[Si] is 3.5~5.5.

In order to inhibit the average crystal grain diameter after 850 DEG C × heating 30 minutes at 100 μm hereinafter, it is preferred that making [Ni+Co] For 2.4 mass % or more.

Mg, Al, Cr, Ti, Zr, Zn, Sn, Mn can be as needed because having the function of improving the intensity of copper alloy Add its one or more.But total content of one or more of these elements is lower than 0.005 matter % is measured, effect is small, and on the other hand, if being higher than 0.3 mass %, conductivity is reduced.Therefore, one of these elements or two Kind or more total content be 0.005~0.3 mass % in the range of.The total of one or more of these elements contains Amount, preferred lower limit value are 0.01 mass %, and preferred lower limit value is 0.02 mass %, and preferred upper limit value is 0.25 matter Measure %.

Even if wherein Al, Mn, Ti contain on a small quantity, the conductivity of copper alloy can also reduced, therefore preferably make the upper limit respectively Value is 0.1 mass %.The big element of coarse grains inhibitory effect when Cr, Zr are heated to high temperature, wants to miniaturize crystal grain When, total 0.03% or more containing one or both of Cr and Zr, preferably 0.06 mass % or more.Containing Cr and When one or both of Zr adds up to 0.03% or more, even if [Ni+Co] is lower than 2.4 mass % (1.6 mass % or more), Average crystal grain diameter after 850 DEG C × heating 30 minutes can be inhibited at 100 μm or less.But conductivity drops in Cr and Zr It is low, therefore total content of one or both of these elements is preferably 0.2 mass % or less.

[manufacturing method of copper alloy plate]

The copper alloy plate of embodiments of the present invention, can be after carrying out homogeneous heat treatment for ingot bar, with such as inferior process Manufacture: (1) hot rolling-cold rolling-annealing；(2) hot rolling-cold rolling-annealing-cold rolling；(3) hot rolling-cold rolling-annealing-is cold Roll-low-temperature annealing.In above-mentioned (1)~(3), cold rolling-annealing process can also be carried out repeatedly.

In the annealing, including soft annealing, recrystallization annealing or precipitation annealing (ageing treatment).Soft annealing is tied again In the case where crystalline substance annealing, heating temperature is selected from 600~950 DEG C of ranges, selectes heating time from 5 seconds~1 hour range ?.When solution treatment is held a concurrent post in soft annealing or recrystallization annealing, carry out heating 5 seconds~3 minutes continuous with 650~950 DEG C Annealing.In the case where precipitation annealing, carried out with the condition that 350~600 DEG C or so of temperature range is kept for 0.5~10 hour ?.When solution treatment is held a concurrent post in soft annealing or recrystallization annealing, precipitation annealing can be carried out in subsequent handling.

Final cold rolling meets 0.2% yield strength and bendability as target, from the range of working modulus 5~80% It is selected.

In low-temperature annealing, because of the recovery of the ductility of copper alloy plate, copper alloy plate will not be made to recrystallize and be allowed to Softening, in the case where continuous annealing, setting means is kept for 1 second~5 minutes or so in 300~650 DEG C of atmosphere.Separately Outside, in the case where box annealing, copper alloy plate is determined in a manner of being kept for 5 minutes~1 hour or so at 250 DEG C~400 DEG C Entity temperature.

In the case where Cu- (Fe, Co, Ni)-P system alloy, by above manufacturing method, 0.2% surrender can be manufactured Intensity is 100MPa or more, the copper alloy plate with excellent bendability.The copper alloy plate measured at 850 DEG C ( 850 DEG C keep 30 minutes after measure) 0.2% yield strength be 10MPa or more, with 850 DEG C heat 30 minutes after water cooling, then into Row heats 2 hours ageing treatments with 500 DEG C, 0.2% yield strength with 100MPa or more, the conduction of 50%IACS or more Rate.

In the case where Cu- (Ni, Co)-Si system alloy, by above manufacturing method, it is strong that 0.2% surrender can be manufactured Degree is 200MPa or more, the copper alloy plate with excellent bendability.The copper alloy plate measures at 850 DEG C (at 850 DEG C Keep 30 minutes after measure) 0.2% yield strength be 10MPa or more, with 850 DEG C heat 30 minutes after water cooling, then carry out When heating 2 hours ageing treatments with 500 DEG C, 0.2% yield strength with 300MPa or more, the conduction of 50%IACS or more Rate.

In the bending machining, it is desirable that crackle does not occur in bending section.In addition, bending line and its neighborhood, preferably do not send out Raw rough surface.Even the copper alloy plate of identical material, crackle caused by bending and shaggy easy occurrence degree also can Depend on ratio R/t of radius of curvature R Yu plate thickness t.When manufacturing the heat dissipation element of vapor chamber etc. using copper alloy plate, closed as copper The bendability of golden plate, usually requiring that will not occur when rolling parallel direction, right angle orientation carrying out the bending of R/t≤2 Crackle.As the bendability of copper alloy plate, crackle does not preferably occur in the bending of R/t≤1.5, more preferably R/t≤ Crackle will not occur in 1.0 bending.The bendability of copper alloy plate is generally tested with the test film of the wide 10mm of plate (bendability referring to aftermentioned embodiment is tested).When carrying out bending machining for copper alloy plate, bending width is bigger, Crackle is more easy to happen, therefore, if bending width is especially big, when being tested with the test film of the wide 10mm of plate, preferably in R/t Crackle does not occur in=1.0 bending, it is then preferred that crackle does not occur in the bending of R/t=0.5.In addition, in order to be bent Rough surface does not occur for line and its neighborhood, preferably (cuts on the surface of copper alloy plate along the average crystal grain diameter that plate width direction measures Disconnected method) it is 20 μm hereinafter, more preferably 15 μm or less.

When manufacturing the heat dissipation element of vapor chamber etc., copper alloy plate is heated at high temperature to before 650 DEG C or more of temperature, is passed through Stamping, punching processing, cutting, etching, bending machining etc. are processed to designated shape, by high-temperature heating (degassing, engagement (solder brazing, diffusion bonding, welding (TIG, MIG, laser etc.), the heating for being sintered etc.), is processed to heat dissipation element.This hair The copper alloy plate of bright embodiment, due to being less likely to occur in the conveying and processing in the processing with above-mentioned characteristic Deformation, and will not break down on implementing the processing.In addition, 0.2% yield strength measured under high temperature (850 DEG C) is 10MPa or more, plus-pressure when being capable of increasing diffusion bonding or when solder brazing and shorten the retention time, make the reliability at joint portion It improves, when being furthermore possible to prevent diffusion bonding or the deformation of copper alloy plate when solder brazing.In addition, being heated to 650 DEG C or more Process after, by carry out ageing treatment, the heat dissipation element with high 0.2% yield strength and conductivity can be obtained.

The heat dissipation element manufactured using the copper alloy plate of embodiments of the present invention is being heated to 650 DEG C or more above-mentioned After process, as needed, to improve corrosion resistance and solderability as the main purpose, a part at least in outer surface is formed Sn coating.Include electroplated, electroless plating formation in Sn coating, or after these platings, is again heated to Sn's It is formed below fusing point or more than fusing point.Include Sn metal and Sn alloy in Sn coating, as Sn alloy, in addition to Sn with Outside, as alloying element, more than one can be enumerated among Bi, Ag, Cu, Ni, In, Zn, adds up to and contains 5 mass % or less.

Under Sn coating, it is capable of forming the substrate coating of Ni, Co, Fe etc..These substrate coating have prevent from coming from The function as barrier of the diffusion of the Cu and alloying element of base material, and prevent from causing because of the surface hardness of increase heat dissipation element The function of scratch.Cu can be also plated on the substrate coating, then after plating Sn, carry out being heated to the fusing point of Sn or less or molten Or more heat treatment and form Cu-Sn alloy-layer, thus become substrate coating, Cu-Sn alloy-layer and Sn coating this three Layer structure.Cu-Sn alloy-layer, have the function of preventing the diffusion of Cu and alloying element from base material as barrier, and it is anti- The function of only being scratched caused by the surface hardness because increasing heat dissipation element.

In addition, the heat dissipation element manufactured using the copper alloy plate of embodiments of the present invention, is being heated to 650 DEG C or more After the above process, as needed, Ni coating is at least formed in a part of outer surface.Ni coating have prevent from coming from The Cu of base material and the function as barrier of diffusion of alloy elements prevent from scratching caused by the surface hardness because of increase heat dissipation element, With the function of improving corrosion resistance.

The copper alloy plate of embodiments of the present invention carries out homogeneous heat treatment preferably for ingot bar, after hot rolling, with cold rolling, companion It is manufactured with the process of the recrystallization processing of solid solution, cold rolling, ageing treatment.It, can not also be into after the recrystallization processing of solid solution Row cold rolling and carry out ageing treatment, then carry out cold rolling again.

Melting, casting can be carried out by the usual way of continuously casting, semi-continuous casting etc..In addition, molten as copper Raw material is refined, it is preferable to use S, Pb, Bi, Se, As are poor.It is further noted that being coated on the red heat of the charcoal of molten alloyed copper Change (removing moisture), parent metal, waste material, casting chute, the drying of mold and deoxidation of melt etc., preferably reduction O and H.

Homogenize process, after the temperature preferably inside ingot bar reaches 800 DEG C or more of temperature, kept for 30 minutes or more.? The retention time of matterization processing is more preferably 1 hour or more, further preferably 2 hours or more.

After homogenize process, start hot rolling in 800 DEG C or more of temperature.It is preferred that hot rolling terminates in 650 DEG C or more of temperature, By the method chilling of water cooling etc. from the temperature, so as to not will form coarse (Fe, Ni, Co)-P precipitate in hot rolling material, Or (Ni, Co)-Si precipitate.If the chilling start temperature after hot rolling is lower than 650 DEG C, coarse (Fe, Ni, Co)-P is precipitated Object, or (Ni, Co)-Si precipitate are formed, and tissue is easy to become uneven, the strength reduction of copper alloy plate (sheet).Hot rolling End temperature (chilling start temperature) be preferably 700 DEG C or more of temperature, more preferably 750 DEG C or more of temperature.In addition, hot The tissue for rolling the hot rolling material of rear chilling is recrystallized structure.It can be by carrying out hot rolling with the recrystallization processing of aftermentioned solid solution Chilling afterwards is taken into account.

By the cold rolling after hot rolling, apply certain strain to copper alloy plate, then after recrystallization processing, can obtain Copper alloy plate with desired recrystallized structure (fine recrystallized structure).

With the recrystallization processing of solid solution to keep 3 minutes conditions below to carry out at 650~950 DEG C, preferably with 670 ~900 DEG C are kept for 3 minutes or less.When the content of alloying element in copper alloy is few, preferred within the said temperature range lower Temperature area carries out recrystallization processing, and when the content of the element is more, higher temperatures region preferably within the said temperature range is carried out Recrystallization processing.It is handled by the recrystallization, alloying element can be made to be dissolved in copper alloy base material, and be capable of forming bending The good recrystallized structure of processability (crystal grain diameter is 1~20 μm).If the recrystallization processing temperature be lower than 650 DEG C, Ni, Fe, Co, P or Ni, the solid solution capacity of Co, Si are few, strength reduction.On the other hand, if the temperature of recrystallization processing is higher than 950 DEG C or place Managing the time is more than 3 minutes, then recrystal grain coarsening.

After the recrystallization processing of solid solution, following any process: (a) cold rolling-ageing treatment can be selected；(b) cold Roll-ageing treatment-cold rolling；(c) cold rolling-ageing treatment-cold rolling-low-temperature annealing；(d) ageing treatment-cold rolling；(e) when Effect processing-cold rolling-low-temperature annealing.

With 300~600 DEG C of heating temperature or so, the condition kept for 0.5~10 hour carries out ageing treatment (precipitation annealing). When the heating temperature is lower than 300 DEG C, amount of precipitation is few, if being higher than 600 DEG C, precipitate is easy coarsening.The lower limit of heating temperature Preferably 350 DEG C, the upper limit is preferably 580 DEG C, and more preferably 560 DEG C.The retention time of ageing treatment is suitable according to heating temperature Selection, carries out in the range of 0.5~10 hour.If the retention time be lower than 0.5 hour, be precipitated it is insufficient, more than 10 Hour, amount of precipitation is also saturation, and productivity reduces.The lower limit of retention time is preferably 1 hour, and more preferably 2 hours.

In the case where Cu- (Fe, Co, Ni)-P system alloy, by the copper alloy plate of above preferred process and condition manufacture In, 0.2% yield strength is 300MPa or more, and has excellent bendability.

In the case where Cu- (Ni, Co)-Si system alloy, by the above preferred process and the copper alloy plate of condition manufacture, 0.2% yield strength is also in 300MPa or more, it may have excellent bendability.

In addition, can be carried out by the method for diffusion bonding, solder brazing etc. good in order to 650 DEG C or more of temperature It engages (bad, the bond strength height etc. of no engagement), the surface roughness of copper alloy plate (product), in terms of arithmetic average roughness Ra For 0.3 μm hereinafter, maximum height roughness Rz is calculated as 1.5 μm hereinafter, internal oxidation depth is 0.5 μm hereinafter, preferably 0.3 μm Below.

In order to make Ra:0.3 μm of surface roughness of copper alloy plate (product), Rz:1.5 μm hereinafter, make final cold rolling institute The surface roughness of the roll axial direction of roll is, for example, Ra:0.15 μm, Rz:1.0 μm hereinafter, or for final cold rolling after Copper alloy plate polished, the grinding of electrolytic polishing etc..In addition, the internal oxidation depth in order to make copper alloy plate (product) For 0.5 μm hereinafter, by making annealing atmosphere reproducibility, and make -5 DEG C of dew point hereinafter, or for the copper alloy after annealing Plate carries out mechanical lapping (polishing, scratch brushing etc.) or electrolytic polishing, to remove the inner oxide layer of generation, or is allowed to be thinned i.e. It can.

[manufacturing method of heat dissipation element]

The copper alloy plate of embodiments of the present invention, such as used by the former material of the framework as vapor chamber.Vapor chamber Production process, it is identical as the process of OFC plate of existing material is used, form two plate structures of fluted and concave-convex etc. pattern Part is engaged via diffusion bonding or solder brazing, becomes the framework of vapor chamber.Copper alloy plate is added in this bonding process by high temperature Heat is to 650 DEG C or more.

The copper alloy plate of embodiments of the present invention, even if still 0.2% surrender with 10MPa or more is strong at 850 DEG C Degree, therefore, when the OFC plate of existing material compared with the case where former material, can be increased to diffusion bonding or when solder brazing Plus-pressure.Therefore, the reliability in diffusion bonding portion or solder brazing portion can be made to improve, and shorten the guarantor of diffusion bonding or solder brazing Hold the time.In addition, 0.2% yield strength when passing through high temperature increases, such as heated in diffusion bonding or when solder brazing Cheng Zhong can prevent board member from the deformation for being recessed and heaving etc. occurs.0.2% yield strength at 850 DEG C be preferably 12MPa with On, which can reach in the copper alloy plate of embodiments of the present invention.

In the copper alloy plate of embodiments of the present invention, the average crystal grain after high-temperature heating (850 DEG C × 30 minutes) is straight When diameter is suppressed in 100 μm or less, the generation and system of the crackle of the perforation thinner wall section of the heat dissipation element of vapor chamber etc. can be prevented The leakage of cryogen.In addition, can prevent the surface roughness of heat dissipation element from becoming larger, can prevent between heating part (CPU etc.) Gap increase, and the reduction of the following heat transfer property.

Be heated at high temperature (650 DEG C or more of heating) although after heat dissipation element softening, because of embodiments of the present invention Copper alloy be precipitation hardening type, so, then by the condition (300~600 DEG C × 0.5~10 hour) with previously illustrated into Row ageing treatment can be such that intensity improves.In addition, the conductivity reduced by high-temperature heating is restored by the ageing treatment.Also Have, for the copper alloy plate of embodiments of the present invention, carries out heating (being equivalent to diffusion bonding condition) in 850 DEG C × 30 minutes Afterwards, when carrying out ageing treatment with the condition, show 100MPa's or more in Cu- (Fe, Co, Ni)-P system alloy 0.2% yield strength shows 0.2% yield strength of 300MPa or more in Cu- (Ni, Co)-Si system alloy.In addition, By the ageing treatment, the conductivity of the copper alloy plate of embodiments of the present invention, no matter which kind of alloy system is 50%IACS More than.The copper alloy plate of embodiments of the present invention, although the conductivity after ageing treatment is lower than OFC, because intensity is high, institute With can be than OFC thinner walls, thus, it is possible to make up lower conductivity.

After high-temperature heating (after bonding process), that is, it is heated to 650 DEG C or more, the ageing treatment after engagement, such as can be with As under type carries out.

(1) after the heat dissipation element after high-temperature heating being cooled to 300 DEG C of temperature below, it is again heated to the temperature model It encloses, certain time is kept in co-extensive, be allowed to be hardened by precipitation.In this case, the heat dissipation element after being preferably heated at high temperature is still Just with chillings such as water coolings during high temperature, or the heat dissipation element after high-temperature heating is again heated to chilling after solid solubility temperature, in advance It is dissolved copper alloy.

(2) keep certain by the heat dissipation element after high-temperature heating in the way from High-temperature cooling, in Yu Suoshu temperature range Time is allowed to be hardened by precipitation.Heat dissipation element can be kept under the certain temperature within the scope of the Precipitation Temperature, can also be in institute It states within the scope of Precipitation Temperature and persistently cools down.

(3) after the process of above-mentioned (2), then the reheating of above-mentioned (1) is carried out, precipitation hardening type copper alloy is precipitated Hardening.

In embodiments of the present invention, after bonding process, do not apply plastic processing and carry out ageing treatment.If for height Engagement material (after bonding process) after temperature heating, applies plastic processing before ageing treatment, then the internal structure of heat dissipation element and Size changes, therefore the shape and size of refrigerant flow path can not be as design value, as a result, as heat dissipation element Target heat transfer property cannot be played.

In general, in precipitation type alloy, the aspect raising intensity that plastic processing carries out ageing treatment again later is carried out It is big with the degree of conductivity, but in the CuFeP system of embodiments of the present invention and CuNiSi system alloy, even if not implementing to mould Property processing and when carrying out ageing treatment, can also reach and the case where plastic processing with the raising of the intensity and conductivity of degree.

[embodiment 1]

By the copper alloy of composition shown in table 1,2, atmosphere (No.1~16,18~29) or vacuum atmosphere are coated in charcoal (No.17) fusing, is cast in the book mold of graphite in 1200 DEG C of melt temperature, makes thickness 50mm, width The ingot bar of 200mm, long 70mm.Each ingot bar is heated to 950 DEG C (No.1~16,18~29) or 800 DEG C (No.17), holding 1 is small Shi Hou is hot-rolled down to thickness 16mm, and water cooling immediately after hot rolling obtains the hot rolling material of thick 16mm, width 200mm, long 215mm.It is right In No.1~16,18~29 hot rolling material, 850 DEG C are heated to, is kept for 30 minutes after reaching 850 DEG C, then carries out water quenching. In addition, also identical as the value of table 1,2 to the composition of each hot rolling material analysis of plate thickness 16mm.In addition, its rough surface of each hot rolling material Degree is Ra:0.08~0.15 μm, and plate thickness section is ground in Rz:0.8~1.2 μm, by scanning electron microscope (observation multiplying power 15000 times) measurement internal oxidation depth at 0.1 μm or less.

No.1~16 of table 1 are Cu- (Fe, Co, Ni)-P systems, and No.17 is OFC, and No.18~29 of table 2 are Cu- The copper alloy of (Ni, Co)-Si system.

[table 1]

[table 2]

No.1~16,18~29 hot rolling material, facing 1mm is respectively carried out to two sides, it is (wide to be cold-rolled to thickness 1.25mm 200mm, long 2400mm), it is divided into the B material of the A material and length 500mm for length 1900mm.

For above-mentioned A material, it is cold-rolled to thickness 0.75mm, implements to heat 2 hours ageing treatments with 500 DEG C, then be cold-rolled to (working modulus: 60%), heat in niter oven 30 seconds stress relief annealings with 350 DEG C after thickness 0.3mm.With what is obtained Copper alloy plate is used as 0.2% yield strength and elongation percentage and bendability for test material, under measurement room temperature (20 DEG C).Separately Outside, using each for test material, by following main points, average crystal grain diameter after 850 DEG C of measurement × heating 30 minutes and it is further when Effect treated 0.2% yield strength and conductivity.It is as the result is shown in table 3,4.

For above-mentioned B material, after implementing to heat 2 hours ageing treatments with 500 DEG C, be cold-rolled to thickness 0.5mm (working modulus: 60%), carry out heating 30 seconds stress relief annealings in niter oven with 350 DEG C.Using obtained copper alloy plate as test material, 0.2% yield strength at 850 DEG C is measured by following main points.It is as the result is shown in table 3,4.

The hot rolling material of No.17, facing 1mm each to two sides are cold-rolled to thickness 0.71mm (wide 200mm, long 4200mm), By the D material of the C material of its cutting growth 3700mm and long 500mm.

For above-mentioned C, it is cold-rolled to thickness 0.43mm, heat with 350 DEG C annealing in 2 hours, then is cold-rolled to thickness (working modulus: 30%), heat in niter oven 30 seconds stress relief annealings with 350 DEG C after 0.3mm.The copper sheet that will be obtained As 0.2% yield strength and elongation percentage and bendability for test material, measured under room temperature (20 DEG C).In addition, using each For test material, average crystal grain diameter after being measured 850 DEG C × heating 30 minutes by following main points, and after carrying out ageing treatment again 0.2% yield strength and conductivity.It is as the result is shown in table 3.

For above-mentioned D material, after heat with 350 DEG C annealing in 2 hours, be cold-rolled to thickness 0.5mm (working modulus: 30%), carry out heating 30 seconds stress relief annealings in niter oven with 350 DEG C.Using obtained copper sheet as test material, press State 0.2% yield strength at 850 DEG C of main points measurement.It is as the result is shown in table 3.

(0.2% yield strength and elongation percentage (room temperature))

From each for intercepting No. JIS5 stretching examination in such a way that longitudinally is rolling parallel direction on test material (A material and C material) Piece is tested, implements tension test according to JIS-Z2241, measures yield strength and elongation percentage.Yield strength is comparable to permanent extension The tensile strength of rate 0.2%.

(bendability (room temperature))

The measurement of bendability, it then follows the W bend test method for stretching copper association criterion JBMA-T307 defined is implemented. From each for intercepting width 10mm on test material (A material and C material), the test film of long 30mm carries out G.W. using the fixture of R/t=0.5 (Good Way (bending axis is vertical with the rolling direction)) and B.W. (bending of Bad Way (bending axis is parallel with rolling direction).It connects , using 100 times of optical microscopy, visually observing bending section, whether there are cracks, and the both sides of G.W. or B.W. do not have crackle Be evaluated as P (P:Pass, qualified), what the either or both of G.W. or B.W. had that crackle occurs be evaluated as F (F:Fail, It is unqualified).

(average crystal grain diameter (after 850 DEG C × heating 30 minutes))

From each in such a way that longitudinally is rolling parallel direction, intercepting each 3 test films on test material (A material and C material) (wide 10mm, long 250mm).Each test film is put into vacuum drying oven, makes about 90 DEG C/min of the average heating speed from room temperature and adds Heat is to 850 DEG C, after reaching 850 DEG C, in synthermal lower holding 30 minutes.Then, in the state of maintaining vacuum atmosphere from furnace It takes out test film to take out from vacuum atmosphere after being cooled to 250 DEG C with 240 seconds, carries out water cooling.3 are respectively extracted from each test film The sample of a long 20mm measures average crystal grain diameter by the process of chopping and (surveys in the section of rolling direction for being parallel to each sample Measuring direction is rolling parallel direction).Each average value for the data of 9 (3 × 3) samples in test material is straight as average crystal grain Diameter.

(0.2% yield strength and conductivity (after heating in 850 DEG C × 30 minutes and ageing treatment))

From each for intercepting No. JIS5 stretching examination in such a way that longitudinally is rolling parallel direction on test material (A material and C material) Test piece and conductivity test film (wide 10mm, long 250mm).Each test film is put into vacuum drying oven, makes the average heating from room temperature About 90 DEG C/min of speed and be heated to 850 DEG C, reach 850 DEG C after, it is synthermal it is lower keep 30 minutes.Then, vacuum is being maintained Test film is taken out in the state of atmosphere from furnace, after being cooled to 250 DEG C with 240 seconds, is taken out from vacuum atmosphere, water cooling is carried out. Then each test film is heated to 500 DEG C, after synthermal lower holding 2 hours, is cooled to room temperature with 90 clocks.

Using tension test sheet, implements tension test according to JIS-Z2241, measure 0.2% yield strength and elongation percentage.

Using conductivity test film, according to the nonferrous materials conductivity measurement method of JIS-H0505 defined, so that Conductivity is measured with the four-terminal method of double bridge.

(0.2% yield strength (850 DEG C))

By each for test material (B material and D material), the tension test sheet each 3 of shape and size shown in Fig. 2 (unit: mm) is made It is a.Tension test sheet is using the 13B test film of JISZ2241 (2011) defined as basic configuration, in the both ends position for being equivalent to gauge length Set the protrusion (height 1.2mm) to form extensometer assembly.It is twin shaft symmetric shape that tension test sheet, which is overlooked lower, is processed into gauge length (distance between the vertex of protrusion) is 50mm, and the length of parallel portion is 70mm, and the width between the protrusion of parallel portion is 12.5mm, in parallel The width of the two sides of the protrusion in portion is 12.8mm, and the vertex of protrusion is radius 0.1mm.The longitudinally and rolling direction of test film In parallel.

It, under an ar atmosphere will be each using accurate universal testing machine (Shimadzu Scisakusho Ltd's system, AG100kNG/XR type) Test film is heated to 850 DEG C, is kept for 30 minutes after reaching 850 DEG C, carries out tension test later.The heating rate of test film is with reality Thermometer body is 30 DEG C/min, and it is after this 5.0mm/ that tensile speed, which is measured as 1.0mm/ points by 0.2% yield strength, Minute.Respectively for minimum value among the measured value of 0.2% yield strength of 3 test films each in test material, as each for test material 0.2% yield strength.

In 850 DEG C of tension test, triable minimum plate thickness is 0.5mm or so.(C before A material and B material its ageing treatment Before material and D material are annealing) cold rolling working modulus it is slightly different, but the item of ageing treatment (C material and D material be anneal) thereafter Part, due to identical as the condition of the working modulus of cold rolling and stress relief annealing, it is believed that the characteristic of A material and B material (C material and D material) It is substantially the same.Moreover, the influence of process so far is generally eliminated by being heated 30 minutes with 850 DEG C.Cause This, 0.2% yield strength of 850 DEG C of A material and B material (C material and D material) is considered roughly the same, therefore in this embodiment, uses The B material and D material of thickness 0.5mm carries out the measurement of 0.2% yield strength at 850 DEG C.

[table 3]

[table 4]

If observing table 1~4, the No.17 of the OFC as conventional example is equivalent to the heating temperature of the bonding process of vapor chamber 0.2% yield strength at 850 DEG C of degree only has 5.4MPa.In addition, the average crystal grain diameter after being heated 30 minutes with 850 DEG C is 125 μm, coarse grains, can deduce perforation plate thickness crystal boundary a possibility that.In addition, 850 DEG C × 30 minutes heating and Yield strength after heating in 350 DEG C × 2 hours is down to 40MPa.

In contrast, No.1~12,18~26,0.2% yield strength at room temperature is 300MPa or more, bendability Excellent, 0.2% yield strength at 850 DEG C is 10MPa or more.

Yield strength after heating in 850 DEG C × 30 minutes and 500 DEG C × 2 hours ageing treatments, No.1~12 are 100MPa More than, No.18~26 are 300MPa or more, and conductivity is 50%IACS or more.

Among No.1~12, total content [Fe+Co] of Fe and Co are No.1,3~9,11,12 of 0.2~2.3 mass % And the No.10 of 0.09 mass % is added up to containing Cr and Zr, the average crystal grain diameter after being heated 30 minutes with 850 DEG C is 100 μ M or less.In addition, among No.18~26, total content [Ni+Co] of Ni and Co be No.19~22 of 2.4~3.5 mass %, 24, the No.23 of 0.04 mass %, and the No.26 for being 0.07 mass % containing Ti are added up to containing Cr and Zr, are added with 850 DEG C Average crystal grain diameter of the heat after 30 minutes is 100 μm or less.

On the other hand, No.13, in 14, [Fe+Co+Ni] is insufficient；In No.27, [Ni+Co] is insufficient, therefore at 850 DEG C 0.2% yield strength is lower than 10MPa.In addition, [Fe+Co+Ni] is superfluous in No.15；In No.28, [Ni+Co] is superfluous；No.16, In 29, other elements are superfluous, therefore the yield strength conductivity after 850 DEG C × 30 points heating and 500 DEG C × 2 hours ageing treatments Lower than 50%IACS.

The disclosure of the specification includes following manner.

Mode 1:

A kind of heat dissipation element copper alloy plate, which is characterized in that have the phosphorus containing one or more of Fe, Ni, Co Compound is precipitated, 0.2% yield strength and excellent bendability with 100MPa or more, 0.2% measured at 850 DEG C Yield strength is 10MPa or more, water cooling after being heated 30 minutes with 850 DEG C, after 2 hours ageing treatments are then carried out with 500 DEG C 0.2% yield strength be 100MPa or more, conductivity be 50%IACS or more, manufacture heat dissipation element process a part Process and ageing treatment including being heated to 650 DEG C or more.

Mode 2:

A kind of heat dissipation element copper alloy plate, which is characterized in that have the silicide analysis containing one or both of Ni, Co Out, 0.2% yield strength with 200MPa or more and excellent bendability, 0.2% surrender measured at 850 DEG C are strong Degree is 10MPa or more, and water cooling after being heated 30 minutes with 850 DEG C then carries out after 500 DEG C of progress, 2 hours ageing treatments 0.2% yield strength is 300MPa or more, and conductivity is 50%IACS or more, in a part packet of the process of manufacture heat dissipation element Include 650 DEG C or more of the process and ageing treatment of being heated to.

Mode 3:

According to heat dissipation element copper alloy plate described in mode 1, which is characterized in that contain one or both of Fe and Co Total content [Fe+Co] with the mass of P:0.01~0.2 %, Fe and Co is 0.2~2.3 mass %, and surplus is by Cu and can not keep away The impurity exempted from is constituted.

Mode 4:

According to heat dissipation element copper alloy plate described in mode 3, which is characterized in that also contain the mass % of Ni:0.1~1.0, The content [Fe+Co+Ni] of Fe and Co and Ni is 0.2~2.3 mass %.

Mode 5:

The heat dissipation element copper alloy plate according to mode 3 or 4, which is characterized in that containing Mg, Al, Si, Cr, Ti, One or more of Zr, Zn, Sn, Mn add up to 0.01~0.3 mass %.

Mode 6:

According to heat dissipation element copper alloy plate described in mode 2, which is characterized in that contain one or both of Ni and Co The total content [Ni+Co] and Si content that total content [Ni+Co] with Si, Ni and Co is 1.6~3.5 mass %, Ni and Co Ratio [Ni+Co]/[Si] of [Si] is 3.5~5.5, and surplus is made of Cu and inevitable impurity.

Mode 7:

According to heat dissipation element copper alloy plate described in mode 6, which is characterized in that containing Mg, Al, Cr, Ti, Zr, Zn, One or more of Sn, Mn add up to 0.01~0.3 mass %.

Mode 8:

The heat dissipation element copper alloy plate according to any one of mode 1 and 3~5, which is characterized in that added with 850 DEG C Average crystal grain diameter of the heat after 30 minutes is 100 μm or less

Mode 9:

The heat dissipation element copper alloy plate according to any one of mode 2,6 and 7, which is characterized in that heated with 850 DEG C Average crystal grain diameter after 30 minutes is 100 μm or less.

Mode 10:

A kind of heat dissipation element, which is characterized in that mode 1,3 as made of being interconnected by diffusion bonding or solder brazing Multiple heat dissipation elements described in any one of~5 and 8 are constituted with copper alloy plate.

Mode 11:

A kind of heat dissipation element, which is characterized in that the mode 2 as made of being interconnected by diffusion bonding or solder brazing, 6, multiple heat dissipation elements described in any one of 7 and 9 are constituted with copper alloy plate.

Mode 12:

The heat dissipation element according to mode 10 or 11, which is characterized in that be formed at least part of outer surface Sn coating.

Mode 13:

The heat dissipation element according to mode 10 or 11, which is characterized in that be formed at least part of outer surface Ni coating.

Mode 14:

A kind of manufacturing method of heat dissipation element, which is characterized in that by the member of heat dissipation described in any one of mode 1,3~5 and 8 After part is processed into designated shape with copper alloy plate, implements the process for being heated to 650 DEG C or more and being engaged, do not apply then Add plastic processing and carry out ageing treatment, obtains that there is 0.2% yield strength of 100MPa or more and leading for 50%IACS or more The heat dissipation element of electric rate.

Mode 15:

A kind of manufacturing method of heat dissipation element, which is characterized in that by the member of heat dissipation described in any one of mode 2,6,7 and 9 After part is processed into designated shape with copper alloy plate, implements the process for being heated to 650 DEG C or more and being engaged, do not apply then Add plastic processing and carry out ageing treatment, obtains that there is 0.2% yield strength of 300MPa or more and leading for 50%IACS or more The heat dissipation element of electric rate.

Mode 16:

The manufacturing method of the heat dissipation element according to mode 14 or 15, which is characterized in that be heated to 650 DEG C or more of mistake After journey, Sn coating is formed at least part of the outer surface of heat dissipation element.

Mode 17:

The manufacturing method of the heat dissipation element according to mode 14 or 15, which is characterized in that be heated to 650 DEG C or more of mistake After journey, Ni coating is formed at least part of the outer surface of heat dissipation element.

The application is with the Japanese Patent Application for taking the applying date as on October 5th, 2016, Patent 2016-196884 The claim of priority applied based on number.Patent the 2016-196884th by referring to and be incorporated into this specification.

[explanation of symbol]

1 board member

Claims

1. a kind of heat dissipation element copper alloy plate, which is characterized in that the phosphatization containing one or more of Fe, Ni, Co Object is precipitated, and 0.2% yield strength and excellent bendability with 100MPa or more, 0.2% measured at 850 DEG C Yield strength be 10MPa or more, with 850 DEG C heat 30 minutes after water cooling, then with 500 DEG C carry out 2 hours ageing treatment it 0.2% yield strength afterwards is 100MPa or more, and conductivity is 50%IACS or more, at one of the process of manufacture heat dissipation element It include the process and ageing treatment for being heated to 650 DEG C or more in point.

2. a kind of heat dissipation element copper alloy plate, which is characterized in that the Precipitation of Silicide containing one or both of Ni, Co, And 0.2% yield strength and excellent bendability with 200MPa or more, 0.2% surrender measured at 850 DEG C are strong Degree is 10MPa or more, water cooling after being heated 30 minutes with 850 DEG C, after then carrying out 2 hours ageing treatments with 500 DEG C 0.2% yield strength is 300MPa or more, and conductivity is 50%IACS or more, in a part of the process of manufacture heat dissipation element Process and ageing treatment including being heated to 650 DEG C or more.

3. heat dissipation element copper alloy plate according to claim 1, which is characterized in that contain one of Fe and Co or two It kind is 0.2~2.3 mass % with total content [Fe+Co] of the mass of P:0.01~0.2 %, Fe and Co, surplus is by Cu and can not The impurity avoided is constituted.

4. heat dissipation element copper alloy plate according to claim 3, which is characterized in that also contain the matter of Ni:0.1~1.0 The content [Fe+Co+Ni] for measuring %, Fe and Co and Ni is 0.2~2.3 mass %.

5. heat dissipation element copper alloy plate according to claim 3, which is characterized in that containing Mg, Al, Si, Cr, Ti, Zr, One or more of Zn, Sn, Mn add up to 0.01~0.3 mass %.

6. heat dissipation element copper alloy plate according to claim 4, which is characterized in that containing Mg, Al, Si, Cr, Ti, Zr, One or more of Zn, Sn, Mn add up to 0.01~0.3 mass %.

7. heat dissipation element copper alloy plate according to claim 2, which is characterized in that contain one of Ni and Co or two Total content [Ni+Co] that kind and total content [Ni+Co] of Si, Ni and Co are 1.6~3.5 mass %, Ni and Co contains with Si Ratio [Ni+Co]/[Si] for measuring [Si] is 3.5~5.5, and surplus is made of Cu and inevitable impurity.

8. heat dissipation element copper alloy plate according to claim 7, which is characterized in that containing Mg, Al, Cr, Ti, Zr, Zn, One or more of Sn, Mn add up to 0.01~0.3 mass %.

9. according to claim 1 with heat dissipation element copper alloy plate described in any one of 3~6, which is characterized in that with 850 DEG C Average crystal grain diameter after heating 30 minutes is 100 μm or less.

10. the heat dissipation element copper alloy plate according to any one of claim 2,7 and 8, which is characterized in that with 850 DEG C Average crystal grain diameter after heating 30 minutes is 100 μm or less.

11. a kind of heat dissipation element, which is characterized in that the claim as made of being interconnected by diffusion bonding or solder brazing Multiple heat dissipation elements described in any one of 1 and 3~6 are constituted with copper alloy plate.

12. a kind of heat dissipation element, which is characterized in that the claim 9 as made of being interconnected by diffusion bonding or solder brazing Multiple heat dissipation elements are constituted with copper alloy plate.

13. a kind of heat dissipation element, which is characterized in that the claim 2 as made of being interconnected by diffusion bonding or solder brazing, Multiple heat dissipation elements described in any one of 7 and 8 are constituted with copper alloy plate.

14. a kind of heat dissipation element, which is characterized in that the claim 10 as made of being interconnected by diffusion bonding or solder brazing Multiple heat dissipation elements are constituted with copper alloy plate.

15. heat dissipation element according to claim 11, which is characterized in that be formed with Sn at least part of outer surface Coating.

16. heat dissipation element according to claim 12, which is characterized in that be formed with Sn at least part of outer surface Coating.

17. heat dissipation element according to claim 13, which is characterized in that be formed with Sn at least part of outer surface Coating.

18. heat dissipation element according to claim 14, which is characterized in that be formed with Sn at least part of outer surface Coating.

19. heat dissipation element according to claim 11, which is characterized in that be formed with Ni at least part of outer surface Coating.

20. heat dissipation element according to claim 12, which is characterized in that be formed with Ni at least part of outer surface Coating.

21. heat dissipation element according to claim 13, which is characterized in that be formed with Ni at least part of outer surface Coating.

22. heat dissipation element according to claim 14, which is characterized in that be formed with Ni at least part of outer surface Coating.

23. a kind of manufacturing method of heat dissipation element, which is characterized in that by heat dissipation described in any one of claim 1 and 3~6 After element is processed into designated shape with copper alloy plate, implements the process for being heated to 650 DEG C or more and being engaged, do not apply then Add plastic processing and carry out ageing treatment, obtains that there is 0.2% yield strength of 100MPa or more and leading for 50%IACS or more The heat dissipation element of electric rate.

24. a kind of manufacturing method of heat dissipation element, which is characterized in that by heat dissipation element copper alloy plate as claimed in claim 9 After being processed into designated shape, implement the process that is heated to 650 DEG C or more and is engaged, do not apply plastic processing then and into Row ageing treatment obtains the heat dissipation element of 0.2% yield strength with 100MPa or more and the conductivity of 50%IACS or more.

25. a kind of manufacturing method of heat dissipation element, which is characterized in that by the member of heat dissipation described in any one of claim 2,7 and 8 After part is processed into designated shape with copper alloy plate, implements the process for being heated to 650 DEG C or more and being engaged, do not apply then Plastic processing and carry out ageing treatment, obtain that there is 0.2% yield strength of 300MPa or more and the conduction of 50%IACS or more The heat dissipation element of rate.

26. a kind of manufacturing method of heat dissipation element, which is characterized in that by heat dissipation element copper alloy plate described in any one of claim 10 After being processed into designated shape, implement the process that is heated to 650 DEG C or more and is engaged, do not apply plastic processing then and into Row ageing treatment obtains the heat dissipation element of 0.2% yield strength with 300MPa or more and the conductivity of 50%IACS or more.

27. the manufacturing method of heat dissipation element according to claim 23, which is characterized in that be heated to 650 DEG C or more After process, Sn coating is formed at least part of the outer surface of heat dissipation element.

28. the manufacturing method of heat dissipation element according to claim 24, which is characterized in that be heated to 650 DEG C or more After process, Sn coating is formed at least part of the outer surface of heat dissipation element.

29. the manufacturing method of heat dissipation element according to claim 25, which is characterized in that be heated to 650 DEG C or more After process, Sn coating is formed at least part of the outer surface of heat dissipation element.

30. the manufacturing method of heat dissipation element according to claim 26, which is characterized in that be heated to 650 DEG C or more After process, Sn coating is formed at least part of the outer surface of heat dissipation element.

31. the manufacturing method of heat dissipation element according to claim 23, which is characterized in that be heated to 650 DEG C or more After process, Ni coating is formed at least part of the outer surface of heat dissipation element.

32. the manufacturing method of heat dissipation element according to claim 24, which is characterized in that be heated to 650 DEG C or more After process, Ni coating is formed at least part of the outer surface of heat dissipation element.

33. the manufacturing method of heat dissipation element according to claim 25, which is characterized in that be heated to 650 DEG C or more After process, Ni coating is formed at least part of the outer surface of heat dissipation element.

34. the manufacturing method of heat dissipation element according to claim 26, which is characterized in that be heated to 650 DEG C or more After process, Ni coating is formed at least part of the outer surface of heat dissipation element.