CN102965539A - Rolled copper foil - Google Patents
Rolled copper foil Download PDFInfo
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- CN102965539A CN102965539A CN2012100408007A CN201210040800A CN102965539A CN 102965539 A CN102965539 A CN 102965539A CN 2012100408007 A CN2012100408007 A CN 2012100408007A CN 201210040800 A CN201210040800 A CN 201210040800A CN 102965539 A CN102965539 A CN 102965539A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000011889 copper foil Substances 0.000 title claims abstract description 93
- 239000010949 copper Substances 0.000 claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 claims abstract description 37
- 229910052796 boron Inorganic materials 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001301 oxygen Substances 0.000 claims abstract description 35
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 35
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 15
- 238000005096 rolling process Methods 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 abstract description 2
- 238000005452 bending Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 58
- 238000000034 method Methods 0.000 description 57
- 238000005097 cold rolling Methods 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 31
- 238000000137 annealing Methods 0.000 description 22
- 230000033228 biological regulation Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 238000001953 recrystallisation Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- 239000002184 metal Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 238000007669 thermal treatment Methods 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010875 treated wood Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- -1 JISH3100 Chemical compound 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- JJPWJEGNCRGGGA-UHFFFAOYSA-N 4-[[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]amino]benzoic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)NC1=CC=C(C(=O)O)C=C1 JJPWJEGNCRGGGA-UHFFFAOYSA-N 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
Abstract
The invention provides roller copper foil that exhibits both an excellent bending property and low rigidness. The rolled copper foil is formed by a foil body that is rolled and machined by a copper alloy and is above 1um and below 20um. The copper alloy contains 0.0002% to 0.003% by mass of silicon (Si), 0.0025% to 0.018% by mass of boron (B), the remainer being low-oxygen-concentration copper (Cu) containing below 0.002% by mass of oxygen-free copper or oxygen and being unavoidable impurities, wherein the silicon (Si) is below one-fifth of the boron (B) by mass.
Description
Technical field
The present invention relates to rolled copper foil.
Background technology
Flexible printed board (Flexible Printed Circuit, below also be called for short " FPC ") usually have a structure of stratification conductor foil on basement membrane (for example rolled copper foil), because the curved characteristic such as thin thickness, pliability is excellent, so high to the degree of freedom of the mounting means of electronics etc.Therefore, FPC is used to the distribution at the position that requires extra high curved characteristic of electronics etc., described position is for example: the kink of Collapsible mobile telephone, digital camera, the first-class movable part of printer, HDD (Hard Disc Drive, hard disk drive) or DVD (Digital Versatile Disc, digital versatile disc), CD (Compact Disk, compact disk) etc. are used for the movable part etc. of the disk set of recording medium.
As the FPC that is used for realizing such curved characteristic excellence, as rolled copper foil and the manufacture method thereof of its component parts, the following report is arranged.
Make the method for cubic texture prosperity (for example with reference to patent documentation 1 by the total degree of finish (for example more than 90%) that improves final cold rolling process.)。
Improve total degree of finish (for example more than 93%) of final cold rolling process, and the Copper Foil of having stipulated the development degree of the cubic texture after the recrystallization annealing, for example, the intensity of (200) face of trying to achieve with X-ray diffraction of rolling surface greater than 20 times Copper Foil of the intensity of (200) face of trying to achieve with powder x-ray diffraction (for example with reference to patent documentation 2.)。
Make during process annealing before final cold rolling process the flourishing and cubic texture after to make total degree of finish of final cold rolling process be to make recrystallize 93% or more of cubic texture further prosperity method and stipulated Copper Foil thickness of slab direction perforation crystal grain ratio Copper Foil (for example, in the section area rate, be the Copper Foil that connects crystal grain more than 40%) (for example with reference to patent documentation 3.)。
By adding trace additives semi-softening temperature is controlled at Copper Foil 120～150 ℃, the curved characteristic excellence (the total degree of finish that makes final cold rolling process is more than 90%) (for example with reference to patent documentation 4.)。
Behind final cold rolling process, implemented in the rolled copper foil of recrystallization annealing, rolled copper foil with grain orientation state as described below has been given play to excellent curved characteristic: according to measured the result who obtains by the X-ray diffraction utmost point figure take rolling surface as benchmark, the copper crystallization the 111} face with respect to orientation degree Δ β is below 10 ° in the face of 200} face, and the β scanning by α=35 ° measured of X-ray diffraction utmost point figure obtain aforementioned { the stdn average intensity [a] of 111} face diffraction peak is [a]/[b] 〉=3 with the ratio of the stdn average intensity [b] that β scanning by α=74 ° obtains.This rolled copper foil is more than 94% by the total degree of finish that makes the final cold rolling process before the recrystallize and the degree of finish of every a time (パ ス) is controlled to be 15～50% makes (for example with reference to patent documentation 5.)。
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-262296 communique
Patent documentation 2: No. 3009383 communique of Japanese Patent
Patent documentation 3: No. 3856616 communique of Japanese Patent
Patent documentation 4: No. 3856582 communique of Japanese Patent
Patent documentation 5: No. 4285526 communique of Japanese Patent
Summary of the invention
The problem that invention will solve
As mentioned above, up to now, in order to improve the desired curved characteristic of FPC, for the rolled copper foil that consists of it, also after recrystallization annealing, make the cubic texture of rolled copper foil flourishing by doing one's utmost to improve total degree of finish of final cold rolling process, thereby seek the raising of its curved characteristic.In addition, control softening temperature by adding trace additives.In other words, in order to obtain having the rolled copper foil of high curved characteristic, implement to improve total degree of finish of final cold rolling process.
Yet, along with miniaturization, the slimming of in recent years electronics, for FPC, curved characteristic not only, low rigidity (low bounce (anti-development)) requirement also day by day improve.Therefore, rolled copper foil itself also requires low bounce gradually.But for rolled copper foil, the raising that focuses on curved characteristic of exploitation is considered to some extent about rigidity (bounce-back) for up to now flexible printed board.
In addition, about the control of such rigidity, from the viewpoint of Metallkunde, as one of its control method, consider trace additives.But the interpolation of trace additives up to now is to control softening temperature as purpose, and itself does not select the kind of this interpolation element from the viewpoint of rigidity yet.
Therefore, the object of the present invention is to provide a kind of excellent curved characteristic and rolled copper foil of low rigidity of having both.
Solve the method for problem
The discoveries such as the inventor by being formed on as the composition that contains the trace additives of regulation in the copper of mother metal with specified amount, can solve above-mentioned problem, thereby finish the present invention.That is, the present invention provides following rolled copper foil in order to reach above-mentioned purpose.
[1] a kind of rolled copper foil, it is by being that the paper tinsel shape body below the 20 μ m forms more than the 1 μ m with the rolling thickness that is processed into of copper alloy material, it is above and be that by quality ratio the sulphur below 1/5th (S) of described boron (B), remainder comprise oxygen free copper or the oxygen amount is copper (Cu) and the inevitable impurity of the low oxygen concentration below the 0.002 quality % that described copper alloy material contains the following boron (B) of the following silicon (Si) of the above 0.003 quality % of 0.0002 quality %, the above 0.018 quality % of 0.0025 quality % and 0.0002 quality %.
[2] such as aforementioned [1] described rolled copper foil, described copper alloy material further contains the 0.006 quality % following silver (Ag) of above 0.02 quality % and consists of.
[3] such as aforementioned [1] described rolled copper foil, described copper alloy material further contains the 0.0062 quality % following silver (Ag) of above 0.0197 quality % and consists of.
[4] such as aforementioned [1] described rolled copper foil, it is used for flexible printed board.
[5] such as aforementioned [1] or [4] described rolled copper foil, at least one face of described paper tinsel shape body coating layer by resin formation is set.
[6] such as aforementioned [1], [4] or [5] described rolled copper foil, it is used for the distribution of disk set or mobile telephone.
The invention effect
According to the present invention, can provide a kind of excellent curved characteristic and rolled copper foil of low rigidity of having both.
Description of drawings
Fig. 1 is the schema of an example of manufacturing process of the rolled copper foil of expression embodiments of the present invention.
Fig. 2 is the explanatory view of summary of the test method of the expression bounce of using the annular stiffness determinator.
Fig. 3 is the figure of the bounce (numerical value of table 2) of the rolled copper foil that obtains in expression embodiments of the invention and the comparative example, (a) and (b) represents respectively 150 ℃ * 60 minutes bounces, the bounce after the thermal treatment in 300 ℃ * 60 minutes after the thermal treatment.
Nomenclature
1 Copper Foil;
2 sample pressure head plates;
3 sample retaining plates.
Embodiment
[summary of embodiment]
The rolled copper foil of present embodiment contains trace additives in the copper as mother metal, for for the rolling Copper Foil that forms of mode of thickness with regulation, by being that the paper tinsel shape body below the 20 μ m forms more than the 1 μ m with the rolling thickness that is processed into of copper alloy material, described copper alloy material contains the following silicon (Si) of the above 0.003 quality % of 0.0002 quality %, 0.0025 the boron (B) that the above 0.018 quality % of quality % is following and 0.0002 quality % are above and be the sulphur below 1/5th (S) of described boron (B) by quality ratio, remainder comprises oxygen free copper or the oxygen amount is the copper (Cu) of the low oxygen concentration below the 0.002 quality %, and inevitable impurity.
Herein, inevitably impurity refers to be present in the raw material that consists of Copper Foil or the impurity of the trace of sneaking into inevitably in manufacturing process.About Si, B, S, Ag, the pass of additive and inevitable impurity ties up to rear detailed description.
[embodiment]
The rolled copper foil of embodiments of the present invention is by being that the following paper tinsel shape body of the above 0.02mm of 0.001mm (1 μ m) (20 μ m) forms with the rolling thickness that is processed into of copper alloy material, described copper alloy material contains the following silicon (Si) of the above 0.003 quality % (30ppm) of 0.0002 quality % (2ppm), 0.0025 the boron (B) that the above 0.018 quality % (180ppm) of quality % (25ppm) is following and by quality ratio for boron (B) below 1/5th and be sulphur (S) more than the 0.0002 quality % (2ppm), remainder comprises oxygen free copper or the oxygen amount is the copper (Cu) of the following low oxygen concentration of 0.002 quality % (20ppm), and inevitable impurity, and be used to pliability distribution component such as flexible printed board (FPC) etc.
As an example, the rolled copper foil of present embodiment is the rolled copper foil that obtains after the final cold rolling process of the manufacturing process of rolled copper foil described later, before recrystallization annealing, for example, to be used for rolled copper foil that FPC uses as purpose, form in the mode with thickness below the 20 μ m more than the 1 μ m.Below, further describe for copper and inevitable impurity (following also be called for short " copper "), trace additives and thickness as mother metal.
(mother metal)
The mother metal of the rolled copper foil of present embodiment is made of copper (Cu) and inevitable impurity.
The rolled copper foil of the present embodiment for example copper material (Cu) take oxygen free copper or oxygen concn as the low oxygen concentration below the 20ppm forms as mother metal.Herein, present embodiment employed " oxygen free copper " for example is the oxygen free copper of stipulating among the JISC1020, is that purity is the copper more than 99.96%.In addition, oxygen level is not to be entirely zero, and the oxygen of not getting rid of about several ppm～tens ppm (more than 0.000 quality %～more than 0.001 quality %) is included in the used oxygen free copper of present embodiment.Therefore, oxygen concn is that the copper material of the following low oxygen concentration of 20ppm is also contained in " oxygen free copper " with extensive interpretation the time.
For the rolled copper foil of present embodiment, as mother metal, except above-mentioned copper (Cu), also contain inevitable impurity.Inevitably below the preferred 0.02 quality % (200ppm) of content of impurity, more preferably below the 0.01 quality % (100ppm).
(trace additives)
The rolled copper foil of present embodiment contains silicon (Si), boron (B) and the sulphur (S) as trace additives, and contains as required silver (Ag).
When used silicon (Si), boron (B) and the sulphur (S) of present embodiment satisfies respectively the afore mentioned rules amount simultaneously, has the effect that rigidity (bounce-back) reduces.These three kinds of elements must all contain simultaneously, even lack a kind of element, also can not bring into play low rigid nature.
The content of the boron (B) that present embodiment is used is below the above 0.018 quality % (180ppm) of 0.0025 quality % (25ppm), but because the nucleidic mass of boron (B) is little, the viewpoint of the control of boron (B) amount the casting process during therefore from volume production is preferably below the above 0.0165 quality % (165ppm) of 0.004 quality % (40ppm).The reason of in addition, lower value and higher limit respectively being dwindled respectively 15ppm is the concentration deviation (concentration tolerance) in the casting when considering volume production.
Used silver (Ag) is same with the effect that " silicon+boron+sulphur " brings as required in the present embodiment, has the effect of reduction rigidity (bounce-back).The content of silver (Ag) is below the above 0.02 quality % (200ppm) of 0.006 quality % (60ppm).Obtain effect of the present invention for stable, do not have special optimal conditions scope.But, as described later, when surpassing 200ppm, although can obtain effect of the present invention when implementing rational anneal, because the thermotolerance of rolled copper foil rises, therefore sometimes in the CCL of existing part operation, can't use.Therefore, from stable on heating viewpoint, more preferably below the above 0.0197 quality % (197ppm) of 0.0062 quality % (62ppm).In addition, although silver (Ag) reduces the effect of rigidity when using separately abundant, this effect larger (reference Fig. 2 described later and table 2) in the situation of " silicon+boron+sulphur ".In addition, as described later, silver (Ag) contains as inevitable impurity in mother metal sometimes.
(thickness)
The rolled copper foil of present embodiment for example is used for the rolled copper foil that FPC uses, and therefore preferably has the following thickness of the above 20 μ m of 1 μ m.
(manufacture method of rolled copper foil)
Fig. 1 is the schema of an example of manufacturing process of the rolled copper foil of expression embodiments of the present invention.Below, along operation shown in Figure 1, an example of the manufacture method of the rolled copper foil of embodiments of the present invention is described.
(1) ingot bar preparatory process
At first, as starting material, prepare the ingot bar (the ingot bar preparatory process: step 10 below is denoted as step " S ") of copper alloy material.Such as with oxygen level be oxygen free copper (such as JISH3100, JISC1020 etc.) below the 5ppm as mother metal, prepare to contain respectively the ingot casting (being ingot bar) of copper alloy material of silicon (Si), boron (B) and the sulphur (S) of specified amount.In addition, further contain the situation of silver (Ag) too, such as with oxygen level be oxygen free copper (such as JISH3100, JISC1020 etc.) below the 5ppm as mother metal, prepare to contain respectively specified amount silicon (Si), boron (B) and sulphur (S), and further contain the ingot casting of copper alloy material of the silver (Ag) of specified amount.
(2) hot-rolled process
Then ingot casting is implemented hot rolling and made sheet material (hot-rolled process: S20).
(3) the repeatedly operation of cold rolling process and process annealing operation
Behind hot-rolled process, will implement cold rolling operation (cold rolling process: S32) and implement operation (the process annealing operation: S34) repeatedly implement stipulated number (S30) of anneal to having carried out cold rolling sheet material to sheet material.In addition, process annealing operation (S34) is to relax the operation of the work hardening of having carried out cold rolling sheet material.Thus, make the copper bar be called as " blank " (below be also referred to as " copper bar before the final cold rolling process ").
(4) blank anneal operation
Then, this copper bar is implemented anneal (the blank anneal operation: S40) of regulation.The blank anneal operation preferably implements fully to relax the thermal treatment of the caused machining deformation of each operation before the experience blank anneal operation, anneal completely roughly for example.
(5) final cold rolling process
Then, " blank " of having implemented anneal (below be also referred to as " annealing blank ") implemented cold rolling (final cold rolling process (sometimes being also referred to as " finish rolling operation "): S50).Thus, make the rolled copper foil of the paper tinsel shape body with specific thickness of present embodiment.Herein, in order to have given play to the curved characteristic as the major premise of flexible printed board (FPC), prior art described above is such, and the total degree of finish that makes final cold rolling process is more than 93%.
(6) operation such as surface treatment
In addition, next, the rolled copper foil of present embodiment can be dropped in the manufacturing process of FPC.In this case, at first the rolled copper foil that has passed through final cold rolling process is implemented the (operation such as surface treatment: S60) such as surface treatment.
(7) FPC manufacturing process
Then, the rolled copper foil of having implemented surface treatment etc. is supplied to (FPC manufacturing process: S70) in the manufacturing process of FPC.Possesses the FPC that has implemented the rolled copper foil of surface treatment etc. at the rolled copper foil of present embodiment by going through FPC manufacturing process, can making.Below this FPC manufacturing process is roughly described.
FPC manufacturing process is such as comprising: the basement membrane (base material) that makes the Copper Foil that FPC uses and contain the resins such as polyimide fit and form CCL (copper-clad laminate, Copper Claded Laminate) operation (CCL operation), form the operation (distribution formation operation) of circuit layout and implement surface-treated operation (surface treatment procedure) in order to protect distribution at circuit layout at CCL by methods such as etchings.The CCL operation can be used following 2 kinds of methods: behind the stacked Copper Foil of caking agent and base material, make its driving fit by the heat treatment for solidification caking agent, thus the method for form layers lamination structural body (3 layers of CCL); And not by caking agent make implemented the surface-treated Copper Foil and directly sticked on the base material after, undertaken by heating, pressurization integrated, thereby the method for form layers lamination structural body (2 layers of CCL).
In FPC manufacturing process, from the viewpoint of the easiness made, sometimes use the Copper Foil (that is, the Copper Foil of the hard state after the work hardening) of having implemented cold rolling processing herein.This be because, softening Copper Foil is being cut out in the situation of this Copper Foil or is being made it to be layered in easily distortion in the situation on the base material (such as elongation, wrinkle, the distortion such as fracture) by annealing, it is bad that goods occur sometimes.On the other hand, compare with the state that keeps Copper Foil being implemented rolling processing, the curved characteristic of Copper Foil is significantly good in the situation of enforcement recrystallization annealing.Therefore, in the base material in making above-mentioned CCL operation and Copper Foil driving fit, the integrated thermal treatment, preferably adopt the manufacture method of double recrystallization annealing with Copper Foil.
In addition, although the heat-treat condition of recrystallization annealing can change according to the content of CCL operation, as an example, in the thermal treatment of implementing the time below 120 minutes more than 1 minute under the temperature below 300 ℃ more than 150 ℃.In addition, recrystallization annealing is the thermal treatment for implementing in the CCL operation not, also can implement in other operations.By the thermal treatment in the scope of such temperature condition, can make the Copper Foil with recrystallized structure.As mentioned above, from the viewpoint of curved characteristic, Copper Foil must carry out recrystallization annealing by FPC manufacturing process.Therefore, the low rigidity (low bounce) that becomes in the present invention problem also must be brought into play under the state after the recrystallization annealing.
(effect of embodiment)
The rolled copper foil of present embodiment since have oxygen free copper or oxygen amount be the copper (Cu) of the low oxygen concentration 0.002 quality % (20ppm) below and inevitably contain silicon (Si), boron (B) in the impurity and by quality ratio for boron (B) below 1/5th and be the composition of the sulphur (S) more than the 0.0002 quality % (2ppm), so can bring into play the miniaturization of following electronics, slimming and the low rigidity (hanging down bounce) that requires again to improve gradually.In addition, excellent curved characteristic is major premise, and the rolled copper foil of embodiments of the present invention is made according to the manufacture method of the patent documentation 5 of having given play to excellent curved characteristic basically, so curved characteristic is also excellent.In addition and since the rolled copper foil of present embodiment can give play to simultaneously as mentioned above low rigidity (low bounce) and excellent curved characteristic the two, so can expect purposes in every field.
Below further describe the present invention based on embodiment, but the present invention is not subjected to any restriction of these embodiment.
Embodiment
(embodiment 1)
Make as shown below the rolled copper foil of embodiment 1.That is, at first melt the B of Si, 26ppm of main raw material take oxygen free copper as mother metal, 2ppm and the S of 5ppm, thus the ingot bar of cast thickness 150mm, width 500mm (ingot bar preparatory process).
In addition, in the additive, particularly about Si, S, in the starting material of oxygen free copper and B, as inevitable impurity, sometimes exist 0ppm above and to about the 20ppm.In this case, as long as the amount of Si contained among oxygen free copper and the B and S of considering decides the amount of Si and the S of interpolation.In addition, about B, think that the B that contains more than the 0.0025 quality % is rare in starting material, will not exist as the reason that the existence of the B of inevitable impurity is got rid of from present embodiment and present embodiment.In other words, about Si, B, S (and Ag described later), when existing as inevitable impurity, as long as considering to form final desirable amount under its state, be inevitable impurity or the material of interpolation or the two all has.
In addition, do not add Ag (being made as 0ppm) in the present embodiment, but Ag contains above 0ppm and to about the 20ppm (surpass 0 quality % and to about the 0.002 quality %) as inevitable impurity in the oxygen free copper of main raw material sometimes.The Ag that contains as inevitable impurity in main raw material is in most cases inevitable.But as described later, Ag is by containing more than the 60ppm, can obtain the descend effect of (bounce decline) of rigidity, but this effect that does not only have Ag to bring during not enough 60ppm does not have detrimentally affect.Namely to note, the situation that contains the Ag of 0～60ppm, the 20 above ppm that namely estimate below the above 20ppm of 0ppm of the amount of estimating as inevitable impurity and to the Ag as additive and arbitrary situation of not enough 60ppm all are included in present embodiment and the present embodiment.
Then, according to the manufacture method of the rolled copper foil of embodiment, ingot bar is implemented hot rolling, making thickness is the sheet material (hot-rolled process) of 10mm.Then, sheet material is carried out cold rolling (cold rolling process) and anneal (process annealing operation) repeatedly thus make " blank ".Then, " blank " implemented anneal (blank anneal operation).Here, the anneal in the blank anneal operation was implemented by maintenance under about 750 ℃ temperature in about 1 minute.
Then, implement cold rolling to the annealing blank that has passed through the blank anneal operation.Herein, the method that final cold rolling process is put down in writing based on the patent documentation 5 that can obtain excellent curved characteristic is studied, and implements rolling processing by degree of finish condition and the total degree of finish of adjusting the every a time in the rolling manufacturing procedure.In the present embodiment, total degree of finish of final cold rolling process is made as 96%.In addition, what the manufacture method that is used for obtaining excellent curved characteristic was not limited to that embodiment puts down in writing creates conditions, and also can realize by other method.Namely be noted that when having the composition that the application puts down in writing, in order to obtain low rigidity, other effect, can be suitable for aptly other method such as the raising of curved characteristic etc.
Thus, making thickness is the rolled copper foil of 0.012mm.
(embodiment 2～17)
Except the quantitative change with the silicon among the embodiment 1 (Si), boron (B), sulphur (S) and silver (Ag) becomes the value shown in the table 1, similarly to Example 1 operation, the rolled copper foil of manufacturing embodiment 2～17.In addition, Si, the B of the embodiment 1～17 of table 1 and the rolled copper foil of comparative example described later 1～13, the amount of S, Ag are to analyze the analytical value of gained by ICP (inductively coupled plasma, Inductively Coupled Plasma).
(comparative example 1～13)
Except the quantitative change with the silicon among the embodiment 1 (Si), boron (B), sulphur (S) and silver (Ag) becomes the value shown in the table 1, similarly to Example 1 operation, the rolled copper foil of manufacturing comparative example 1～13.
Table 1
| Silicon (Si) [ppm] | Boron (B) [ppm] | Sulphur (S) [ppm] | Silver (Ag) [ppm] | |
| |
2 | 26 | 5 | 0 |
| |
30 | 152 | 10 | 0 |
| |
21 | 25 | 5 | 0 |
| Embodiment 4 | 28 | 179 | 19 | 0 |
| Embodiment 5 | 3 | 32 | 2 | 0 |
| Embodiment 6 | 12 | 90 | 8 | 62 |
| Embodiment 7 | 16 | 104 | 9 | 87 |
| Embodiment 8 | 12 | 80 | 7 | 99 |
| Embodiment 9 | 23 | 120 | 8 | 116 |
| Embodiment 10 | 9 | 93 | 11 | 130 |
| Embodiment 11 | 14 | 164 | 12 | 197 |
| Embodiment 12 | 14 | 96 | 7 | 22 |
| Embodiment 13 | 19 | 110 | 9 | 31 |
| Embodiment 14 | 5 | 75 | 6 | 45 |
| Embodiment 15 | 23 | 120 | 9 | 52 |
| Embodiment 16 | 18 | 134 | 14 | 32 |
| Embodiment 17 | 8 | 169 | 10 | 15 |
| Comparative example 1 | 0 | 115 | 9 | 0 |
| Comparative example 2 | 36 | 97 | 12 | 0 |
| Comparative example 3 | 24 | 22 | 4 | 0 |
| Comparative example 4 | 3 | 196 | 11 | 0 |
| Comparative example 5 | 19 | 34 | 9 | 0 |
| Comparative example 6 | 17 | 35 | 1 | 0 |
| Comparative example 7 | 1 | 112 | 12 | 23 |
| Comparative example 8 | 34 | 86 | 8 | 39 |
| Comparative example 9 | 24 | 19 | 4 | 54 |
| Comparative example 10 | 3 | 204 | 13 | 16 |
| Comparative example 11 | 19 | 48 | 12 | 31 |
| Comparative example 12 | 17 | 35 | 0 | 56 |
| Comparative example 13 | 14 | 122 | 10 | 204 |
Rolled copper foil to gained carries out curved characteristic shown below and the evaluation of rigidity.
(evaluation of curved characteristic)
The slip bend test device that Engineering Co., Ltd. of SHIN-ETSU HANTOTAI makes (model: SEK-31B2S), and implement (flexible life test) according to the IPC standard is used in the evaluation of curved characteristic.Present embodiment and comparative example all in, the method that total degree of finish of final cold rolling process etc. are put down in writing based on patent documentation 5 is implemented, therefore (under 150 ℃, kept 60 minutes in final cold rolling rear enforcement recrystallization annealing, 300 ℃ of lower maintenances 60 minutes) curved characteristic indifference in embodiment 1～17 and comparative example 1～13 of rolled copper foil, all can obtain the curved characteristic of excellence in the past.
(evaluation of rigidity)
Rigidity uses the smart mechanism of Japan to make the annular stiffness determinator (Loop stiffness tester) of Co., Ltd. of institute manufacturing, estimate by the test film bounce of making ring-type.Although the method does not become the JIS standard, it is the method that the FPC technical field is commonly used recently.Fig. 2 is the explanatory view of summary of the test method of the expression bounce of utilizing the annular stiffness determinator.In addition, be the left side of Fig. 2 represent load additional before, the right side of Fig. 2 represents the sectional view of load additivity.At first, the both ends of the test film of Copper Foil 1 are formed altogether the shape of ring-type.Then, press certain stroke degree (ス ト ロ one Network divides) towards the summit of the annular of 3 pairs of these test films of sample retaining plate with sample pressure head plate 2.Measure the power (bounce) of compression this moment.
Below represent concrete condition determination.At first, behind the rolled copper foil before the recrystallization annealing behind the final cold rolling process (thickness 0.012mm (12 μ m)) cut-out length 100mm, width 10mm, be implemented in respectively 150 ℃ and keep down 60 minutes, 60 minutes thermal treatments (recrystallization annealing) of maintenance under 300 ℃.Use the smart mechanism of above-mentioned Japan to make the annular stiffness determinator that Co., Ltd. of institute makes, long in the annular of Copper Foil 1: the stroke of 70mm, sample pressure head plate 2: the bounce of the rolled copper foil under the condition of 5mm after the mensuration thermal treatment.Measurement result is shown in table 2.
Table 2
Herein, in the comparative example 13, keeping the bounce of 60 minutes heat-treated wood under 300 ℃ is 0.0055N (0.56g), be low bounce, well, be 0.0319N (3.25g) but under 150 ℃, keep the bounce of 60 minutes heat-treated wood, very high.This is because the concentration of Ag surpasses 200ppm, so thermotolerance raises, thereby insufficient at 150 ℃ of lower recrystallize that keep in 60 minutes the thermal treatment.Even the concentration of Ag surpasses 200ppm conversely speaking,, as long as under the temperature condition that fully carries out recrystallize, heat-treat, also can obtain the performance of good low bounce.But as previously mentioned, because the low temperature condition of CCL operation is 150 ℃, thereby need to fully finish recrystallize under 150 ℃, so the upper limit of Ag concentration is made as 200ppm.Therefore, the such higher limit of the 200ppm of Ag is not the value of considering from the viewpoint of low rigidity (low bounce), but the value of considering from the viewpoint of the temperature condition of existing CCL operation.
Next, with the bounce drafting pattern of the rolled copper foil of the embodiment 1～17 of table 2 and comparative example 1～13 and be shown in Fig. 3.Under 150 ℃, 60 minutes heat-treated wood with 300 ℃ under, the bounce of 60 minutes heat-treated wood is identical (wherein, the value of bounce is smaller in the situation of 300 ℃ of materials) at embodiment 1～17 with tendency in the comparative example 1～13.Therefore, the following presentation of results to each embodiment and comparative example omits mentioning temperature.
At first, bounce weak (rigidity is low) is good result among the embodiment 1～5.Then, owing to also contain silver (Ag), therefore compare with the embodiment 1～5 of argentiferous (Ag) not among the embodiment 6～11, bounce further weakens about 1/10th (rigidity reductions).
Next, embodiment 12～17 is following formation: although the quality % of the amount of Si, B and S and B/S ratio all within the limits prescribed, the amount of Ag contains (only Ag lacks than specified amount) in the mode of the extraneous not enough 60ppm of regulation.Among the embodiment 12～17, although the amount of Ag lack than regulation, the amount of Si, B and S and the quality % of B/S be than all within the limits prescribed, is the weak bounce (hanging down rigidity) with the situation same degree of the embodiment 1～5 that does not contain Ag.From above result as can be known, even the amount of Ag is lower than the 60ppm as the lower value of regulation, on rigidity (bounce) also not impact.That is, Ag has the effect of reduction rigidity (weakening bounce) when 60ppm is above, but only is this effect not during not enough 60ppm, does not make the detrimentally affects such as other performance degradations.
Then, in comparative example 1 and the comparative example 2, because the amount of silicon (Si) departs from the scope of regulation, so bounce strengthens (rigidity increases).Next, in comparative example 3 and the comparative example 4, because the amount of boron (B) departs from the scope of regulation, so bounce strengthens (rigidity increases).
Then, in the comparative example 5, difference within the limits prescribed when the amount of silicon (Si), boron (B) and sulphur (S) was independent, but " the quality % of the quality % of boron (B)/sulphur (S) "=3.8, be below 5, thereby the ratio of B and the quality % of S is outside specialized range, so bounce strengthens (rigidity increases).
Next, in the comparative example 6, the ratio of the quality % of the amount of Si, the amount of B and B and S is all in specialized range, but the S amount is outside specialized range, so bounce strengthens (rigidity increases).
Then, comparative example 7 and comparative example 8 is following formation: contain respectively silver (Ag) 23ppm (comparative example 7), 39ppm (comparative example 8) in the Si amount in for the extraneous comparative example 1 of regulation and comparative example 2.With regard to comparative example 7 and comparative example 8, although Ag amount also outside the scope of regulation (60ppm that is less than specified amount), bounce and comparative example 1 and comparative example 2 are about equally.
Then, comparative example 9 and comparative example 10 is following formation: contain respectively silver (Ag) 54ppm (comparative example 9), 16ppm (comparative example 10) in the B amount in for the extraneous comparative example 3 of regulation and comparative example 4.With regard to comparative example 9 and comparative example 10, although Ag amount also outside the scope of regulation (60ppm that is less than specified amount), bounce and comparative example 3 and comparative example 4 are about equally.
Then, comparative example 11 is following formation: contain silver (Ag) 31ppm (comparative example 11) in the extraneous comparative example 5 of ratio for regulation of the quality % of B and S.With regard to comparative example 11, although Ag amount also outside the scope of regulation (60ppm that is less than specified amount), bounce and comparative example 5 are about equally.In addition, comparative example 12 is following formation: contain silver (Ag) 56ppm (comparative example 12) in the extraneous comparative example 6 of S amount for regulation.
Then, the Ag of comparative example 13 amount is also outside the scope of regulation (more than the 200ppm of specified amount).At first, because Ag amount is many, so softening temperature, be that the temperature of recrystallized structure prosperity raises.Therefore, Ag measures when many, and according to the temperature of the FPC manufacturing process that carries out recrystallization annealing, characteristic is slightly different.
When the temperature of FPC manufacturing process is hanged down, for example, implementing under 150 ℃ in 60 minutes the heat treated situation, the rolling machining deformation of the rolling manufacturing procedure before this operation (final cold rolling process) accumulation can't be fully flourishing and remaining to recrystallized structure.Therefore, material hardens, rigidity raises.
On the other hand, when in FPC manufacturing process, implementing 300 ℃ * 60 minutes thermal treatment, finish owing to recrystallize, therefore can obtain the low rigidity equal with embodiment.In the situation that the temperature of FPC manufacturing process is high, the time also can fully obtain, although can increase the Ag amount, it is noted that the common cost of such operation is high.
In addition, the present invention is not limited to above-mentioned embodiment and above-described embodiment, can carry out various distortion and implement in the scope that does not break away from main idea of the present invention.The flexible printed board of the rolled copper foil that has for example used above-mentioned embodiment can be provided and use disk set or the mobile telephone of this flexible printed board.
Claims (6)
1. rolled copper foil, it is by being that the paper tinsel shape body below the 20 μ m forms more than the 1 μ m with the rolling thickness that is processed into of copper alloy material,
It is above and be that by quality ratio the sulphur below 1/5th (S) of described boron (B), remainder comprise oxygen free copper or the oxygen amount is copper (Cu) and the inevitable impurity of the low oxygen concentration below the 0.002 quality % that described copper alloy material contains the following boron (B) of the following silicon (Si) of the above 0.003 quality % of 0.0002 quality %, the above 0.018 quality % of 0.0025 quality % and 0.0002 quality %.
2. rolled copper foil as claimed in claim 1, described copper alloy material further contain the 0.006 quality % following silver (Ag) of above 0.02 quality % and consist of.
3. rolled copper foil as claimed in claim 1, described copper alloy material further contain the 0.0062 quality % following silver (Ag) of above 0.0197 quality % and consist of.
4. rolled copper foil as claimed in claim 1 or 2, it is used for flexible printed board.
5. such as claim 1 or 4 described rolled copper foils, at least one face of described paper tinsel shape body coating layer by resin formation is set.
6. such as claim 1,4 or 5 described rolled copper foils, it is used for the distribution of disk set or mobile telephone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011190592A JP5177268B2 (en) | 2011-09-01 | 2011-09-01 | Rolled copper foil |
| JP2011-190592 | 2011-09-01 |
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| Publication Number | Publication Date |
|---|---|
| CN102965539A true CN102965539A (en) | 2013-03-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100408007A Pending CN102965539A (en) | 2011-09-01 | 2012-02-21 | Rolled copper foil |
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| JP (1) | JP5177268B2 (en) |
| KR (1) | KR20130025317A (en) |
| CN (1) | CN102965539A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110392485A (en) * | 2019-06-18 | 2019-10-29 | 昆山维嘉益材料科技有限公司 | A kind of LP316L STA high-order camera module FPC base plate processing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10190225B2 (en) | 2017-04-18 | 2019-01-29 | Chang Chun Petrochemical Co., Ltd. | Electrodeposited copper foil with low repulsive force |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001011550A (en) * | 1999-06-30 | 2001-01-16 | Kobe Steel Ltd | Copper alloy rolled foil |
| JP2001152267A (en) * | 1999-11-18 | 2001-06-05 | Kobe Steel Ltd | Copper alloy rolled foil |
| JP2008088492A (en) * | 2006-09-29 | 2008-04-17 | Nikko Kinzoku Kk | Copper alloy foil and copper-resin organic matter flexible laminate |
| JP5235080B2 (en) * | 2007-09-28 | 2013-07-10 | Ｊｘ日鉱日石金属株式会社 | Copper alloy foil and flexible printed circuit board using the same |
-
2011
- 2011-09-01 JP JP2011190592A patent/JP5177268B2/en not_active Expired - Fee Related
- 2011-12-21 KR KR1020110138759A patent/KR20130025317A/en not_active Application Discontinuation
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110392485A (en) * | 2019-06-18 | 2019-10-29 | 昆山维嘉益材料科技有限公司 | A kind of LP316L STA high-order camera module FPC base plate processing method |
| CN110392485B (en) * | 2019-06-18 | 2022-04-12 | 淮安维嘉益集成科技有限公司 | LP316L STA high-order camera module FPC substrate processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130025317A (en) | 2013-03-11 |
| JP2013053323A (en) | 2013-03-21 |
| JP5177268B2 (en) | 2013-04-03 |
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| ASS | Succession or assignment of patent right |
Owner name: SH COPPER INDUSTRY CO., LTD. Free format text: FORMER OWNER: HITACHI CABLE CO., LTD. Effective date: 20130808 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20130808 Address after: Ibaraki Applicant after: Sh Copper Products Co Ltd Address before: Tokyo, Japan, Japan Applicant before: Hitachi Cable Co., Ltd. |
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Application publication date: 20130313 |