CN102575317A - Copper or copper-alloy foil and method of manufacturing double-sided copper-clad laminate using same - Google Patents

Copper or copper-alloy foil and method of manufacturing double-sided copper-clad laminate using same Download PDF

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CN102575317A
CN102575317A CN2010800495377A CN201080049537A CN102575317A CN 102575317 A CN102575317 A CN 102575317A CN 2010800495377 A CN2010800495377 A CN 2010800495377A CN 201080049537 A CN201080049537 A CN 201080049537A CN 102575317 A CN102575317 A CN 102575317A
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copper
alloy foil
copper alloy
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CN102575317B (en
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小野俊之
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JX Nippon Mining and Metals Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • 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
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1105—Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

Disclosed are a copper or copper-alloy foil which is capable of suppressing wrinkles and folding when the copper or copper-alloy foil is used for a double-sided copper-clad laminate and a method for manufacturing the double-sided copper-clad laminate using the same. In the copper or copper-alloy foil, which is used for the double-sided copper-clad laminate, assuming [sigma]A=(EA*[delta]LB)/2*1000, |10000*(EA*[delta]LB /2)|<=YSA is satisfied, and the number of times of bending is or above 400,000. In these formulas, EA is a horizontal Young's modulus (unit: GPa) of the copper or copper-alloy foil after being held at 350 DEG C for 30min and cooled down to a room temperature; [delta]LA is a rate of horizontal dimensional change (the unit is ppm, and contraction takes positive values) of the copper or copper-alloy foil when being warmed from the room temperature to 350 DEG C, held for 30min, and cooled down to the room temperature; YSA is 0.2% proof stress (unit: MPa) of the copper or copper-alloy foil in a tensile test; and the number of times of bending is set to be the number of times of bending at the end point when electric resistance is raised by 20% from the initial stage of the test using an IPC sliding and bending test apparatus.

Description

Copper or copper alloy foil and use the method for manufacture of the two sides copper-coated laminated board of this copper or copper alloy foil
Technical field
The present invention relates to a kind of method of manufacture that is applicable to the copper or the copper alloy foil of the two sides copper-coated laminated board that the lamination copper on the two sides of resin layer that for example is used for flexible wiring (FPC, Flexible Printed Circuit) or copper alloy foil form and has used the two sides copper-coated laminated board of this copper or copper alloy foil.
Background technology
As the copper-coated laminated board (CCL) that in flexible wiring (FPC), uses, can use single face copper-coated laminated board that the single face lamination Copper Foil at resin layer forms and the two sides copper-coated laminated board that forms at the two sides of resin layer lamination Copper Foil (below be called " two sides CCL ").The object that on the CCL of two sides, has formed circuit is the two sides flexible wiring, and it realizes the save spaceization of the becoming more meticulous of circuit, FPC easily, so the use of two sides CCL has the tendency of increase.
As the method for manufacture of this two sides CCL, the known varnish that has at the single face casting resin compsn of Copper Foil, and in the method (patent documentation 1) of back at other Copper Foils of resin face thermo-compressed that be heating and curing.In addition, just like inferior method: have the surface and the back side of the polyimide film of thermoplastic polyimide layer on the two sides, simultaneously the method for thermo-compressed Copper Foil; After the single face thermo-compressed Copper Foil of polyimide film with thermoplastic polyimide layer, with the polyimide face coating thermoplastic polyimide layer of Copper Foil opposition side, and in the method for these other Copper Foils of face thermo-compressed; At the precursor of the single face of Copper Foil casting polyimide, be varnish, after being cured, form thermoplastic polyimide layer, and in the method for these other Copper Foils of face thermo-compressed at resin surface with the Copper Foil opposition side.
Patent documentation 1: japanese kokai publication hei 05-212824 communique.
Summary of the invention
Here, if remove on the two sides of resin layer (above-mentioned polyimide film etc.) situation of laminated copper foil simultaneously, the Copper Foil (the 1st Copper Foil) of then initial and resin layer lamination is heated to the temperature more than 300 ℃ when initial lamination, and temporarily cools off.Further, afterwards when other Copper Foils of opposing face lamination (the 2nd Copper Foil) of resin layer, too the 1st Copper Foil is carried out reheat and cool off.
Yet when cooling off after lamination the 2nd Copper Foil and the heating, the length direction with the 1st Copper Foil produces gauffer or folding line at the width middle position abreast and usually sometimes.Even the heating condition (thermo-compressed condition, tension force etc.) when adjusting the lamination conditioned disjunction lamination of the 2nd Copper Foil also is difficult to eliminate fully this gauffer or folding line.And; Think that above-mentioned gauffer or folding line produce under following situation: because the thermal process when being applied to the lamination on the 1st Copper Foil and the 2nd Copper Foil is different; Thereby the temperature variation when it being cooled off because of lamination the 2nd Copper Foil and after heating; And causing the clamping resin layer and the size changing rate of two Copper Foils that exist is different, Copper Foil can't bear consequent stress.
Promptly; The present invention is the invention of making in order to solve above-mentioned problem, and purpose is to provide a kind of method of manufacture that when being used for the two sides copper-coated laminated board, can suppress the copper or the copper alloy foil of gauffer or folding line and use the two sides copper-coated laminated board of this copper or copper alloy foil.
The inventor etc. have carried out various researchs; The result finds: when making two sides CCL; Even because of being applied to the different differences that make two paper tinsels produce dimensional change of the 1st Copper Foil with thermal process on the 2nd Copper Foil; Thereby on paper tinsel, produce stress, characteristic that also can be through adjusting two Copper Foils and suppresses gauffer or folding line so that Copper Foil is not buckled.
That is, copper of the present invention or copper alloy foil are being used for the two sides copper-coated laminated board, and σ A=(E A* Δ L A)/2 * 1000 o'clock, | 10 * σ A| ≦ YS A, number of bends is more than 400,000 times.
Wherein, E A: with above-mentioned copper or copper alloy foil 350 ℃ kept 30 minutes and be cooled to room temperature after width on yang type modulus (unit is GPa); Δ L A: be warming up to 350 ℃ from room temperature, kept 30 minutes and the width of above-mentioned copper when being cooled to room temperature or copper alloy foil on size changing rate (unit is ppm, with contraction be made as on the occasion of); YS A: above-mentioned copper in the tension test or 0.2% ys of copper alloy foil (unit is MPa);
Number of bends: use IPC slip flexing machine; It is that 12.5mm, length direction are the band shape of 200mm that paper tinsel is cut into width; And use after 0.5 hour 350 ℃ of heat treated; Bending radius is made as 1.5mm, when paper tinsel thickness is 12 μ m, is made as 1mm when paper tinsel thickness is 18 μ m, to the slip repeatedly of test film load PM 100 times, be the terminated number of times with resistance from the number of bends of initial rising 20%.
Preferred above-mentioned copper or copper alloy foil are rolling paper tinsel, and final cold rolling degree of finish R (%) is more than 93.0%, and the average crystallite particle diameter GS (μ m) behind the final annealing is GS ≦ 3.08 * R-260.
Δ L ABe preferably below the 145ppm.
The method of manufacture of two sides of the present invention copper-coated laminated board has: the single face at above-mentioned copper or copper alloy foil forms resin layer, and obtains the 1st step of single face copper-coated laminated board; With at above-mentioned other the above-mentioned copper of resin layer side lamination or the copper alloy foil of above-mentioned single face copper-coated laminated board and heat, and obtain the 2nd step of two sides copper-coated laminated board.
According to the present invention, when making the two sides copper-coated laminated board, can suppress gauffer or folding line.
The explanation of accompanying drawing
Fig. 1 is the figure of method of manufacture of the two sides copper-coated laminated board of expression embodiment of the present invention.
Fig. 2 is the sectional view of the formation example of expression two sides copper-coated laminated board.
Fig. 3 is expression because the heat that when manufacturing two sides copper-coated laminated board, is applied causes on the 1st bronze medal or copper alloy foil, producing the figure of the state of gauffer (folding line).
Embodiment
Below, describe for the method for manufacture of the two sides copper-coated laminated board of copper that has used embodiment of the present invention or copper alloy foil.And in the present invention, so-called % as long as do not specify, then representes quality % (quality %).Fig. 1 representes that the two sides covers the method for manufacture of metal laminate 8.
Among Fig. 1, lead the 1st bronze medal or the copper alloy foil 4 of uncoiling shape at first continuously, use application roller 10,11 etc., be coated with varnish shape resin combination 2a continuously with specific thickness at the single face of the 1st bronze medal of leading out or copper alloy foil 4.Resin combination 2a becomes resin layer 2 after curing.Then, the 1st bronze medal that is coated with resin combination 2a or copper alloy foil 4 are imported in the drying installation 15, make resin combination 2a solidify (or semicure).So, at the single face formation resin layer of the 1st bronze medal or copper alloy foil 4, and obtain single face copper-coated laminated board (the 1st step).Here, also after the 1st step finishes, this single face copper-coated laminated board is wound into web-like sometimes, proceeds to the 2nd step again.And;, heats the single face of the 1st bronze medal or copper alloy foil 4 when forming resin layer; But except that after the above-mentioned resin combination of coating, heating, for example also can be on the single face of the 1st bronze medal or copper alloy foil 4 with the material thermo-compressed that becomes resin layer as resin molding.In addition, the Heating temperature in common the 1st step forms the above temperature of Heating temperature in the 2nd step.Then, lead the 2nd bronze medal or the copper alloy foil 6 of uncoiling shape continuously, for example be heated to 350～400 ℃ lamination roller 20, between 21 continuously through the 1st bronze medal or copper alloy foil 4 and the 2nd bronze medal or copper alloy foil 6.At this moment, at resin layer 2 side laminations the 2nd bronze medal or the copper alloy foil 6 of the 1st bronze medal or copper alloy foil 4 and heat, and obtain two sides copper-coated laminated board 8 (the 2nd step).Two sides copper-coated laminated board 8 suitably is wound into coiled material.
And as shown in Figure 2, two sides copper-coated laminated board 8 is at resin layer 2 side laminations the 2nd bronze medal of the 1st bronze medal or copper alloy foil 4 or copper alloy foil 6 and constitute.
As the 1st bronze medal or copper alloy foil 4 and the 2nd bronze medal or copper alloy foil 6, for example can enumerate: fine copper, tough pitch copper (JIS-1100), oxygen free copper (JIS-1020) or in these fine copper, tough pitch copper, oxygen free copper, added the Sn that adds up to 40～400 quality ppm and/or material that Ag forms.Can the thickness of the 1st bronze medal or copper alloy foil 4 and the 2nd bronze medal or copper alloy foil 6 be made as for example about 6～18 μ m.The 1st bronze medal or copper alloy foil 4 use identical material with the 2nd bronze medal or copper alloy foil 6.The 1st bronze medal or copper alloy foil 4 and the 2nd bronze medal or copper alloy foil 6 can be rolling paper tinsel, also can be the electrolysis paper tinsel.
Resin layer 2 can use thermosetting resins such as polyimide, PET (polyethylene terephthalate), epoxy resin, phenol resins; Thermoplastic resins such as saturated polyester resin, but be not limited to these resins.In addition; The varnish (the for example polyamic acid solution of the precursor of polyimide) that also can the composition of these resin layers of dissolving in solvent be formed is coated the single face of the 1st bronze medal or copper alloy foil 4 and is heated; Remove solvent thus, reaction (for example imidization reaction) is carried out and made its curing.The thickness of resin layer 2 can be made as for example about 1～15 μ m.
Secondly, to characteristic of the present invention, promptly the characteristic of the 1st bronze medal or copper alloy foil 4 and the 2nd bronze medal or copper alloy foil 6 describes.
Below, expression is when after the single face of the 1st bronze medal or copper alloy foil 4 forms resin layer, when lamination the 2nd bronze medal or copper alloy foil 6 and manufacturing two sides CCL, and the stress that produces by the difference of the dimensional change of two copper of clamping resin or copper alloy foil 4,6.
At first, when in temperature T 1(T 1Heating temperature during for lamination the 2nd bronze medal or copper alloy foil 6) lamination is two sides CCL and is cooled to T down 2Till the time, be applied to the stress σ on the 1st bronze medal or the copper alloy foil 4 ARepresent with following formula 1:
σ A＝E A×E B／（E A＋E B）×（α B×（T 1－T 2）＋ΔL B－（α A×（T 1－T 2）＋ΔL A））×1000?（1）。And the dimensional change Δ is that contraction just is made as, and is the variation of width (the web width direction when making CCL continuously by the coiled material of copper or copper alloy foil).
Here, the copper or the copper alloy foil that are used for CCL are similar to fine copper, even therefore contain added ingredients a little, also can thermalexpansioncoefficient (subscript A, B represent the 1st bronze medal or copper alloy foil the 4, the 2nd bronze medal or copper alloy foil 6 respectively) be regarded as identical (α A≒ α B).Therefore, formula 1 usefulness following formula 2 is represented:
σ A＝E A×E B／（E A＋E B）×（ΔL A－ΔL B）×1000（2）。
Wherein, E A: with above-mentioned the 1st bronze medal or copper alloy foil after 350 ℃ kept 30 minutes and are cooled to room temperature; Kept 30 minutes and be cooled in the 1st thermal process of room temperature the yang type modulus on the width of above-mentioned the 1st bronze medal or copper alloy foil (unit is GPa) at 350 ℃ once more; E B: by with above-mentioned the 2nd bronze medal or the copper alloy foil yang type modulus (unit is GPa) on the width of above-mentioned the 2nd bronze medal that 350 ℃ of the 2nd thermal processs that kept 30 minutes and be cooled to room temperature are produced or copper alloy foil; Δ L A: be of a size of benchmark when being warming up to 350 ℃ from room temperature, keeping 30 minutes and being cooled to room temperature; Once more 350 ℃ kept 30 minutes and be cooled to room temperature after the width of above-mentioned the 1st bronze medal or copper alloy foil on size changing rate (unit is ppm, with contraction be made as on the occasion of); Δ L B: be warming up to 350 ℃ from room temperature, kept 30 minutes and be cooled to room temperature after the width of above-mentioned the 2nd bronze medal or copper alloy foil on size changing rate (unit is ppm, with contraction be made as on the occasion of).
And room temperature is meant 25～35 ℃ (being generally 25 ℃).
That is,, and make poor (the Δ L of the size changing rate of copper or copper alloy foil 4,6 if the two yang type modulus of copper or copper alloy foil 4,6 is diminished A-Δ L B) diminish stress σ then ADiminish, be difficult for producing gauffer or the folding line when making two sides CCL.
Here, though copper or copper alloy foil 4,6 the two use identical material, also produce poor (the Δ L of size changing rate A-Δ L B), therefore obviously this difference is not to be caused by thermal expansion.And, if to METAL HEATING PROCESS, then produce tissues such as recrystallize or recovery and change, therefore if cool off after the heating of metal, then shorten (thermal contraction) or elongated (heat is extended) with original size compared.In addition, the refrigerative metal will be heated to below the uniform temp once more and will cool off even will temporarily heat also, also can not produce thermal contraction or heat extension.And these phenomenons all can produce in rolling paper tinsel and electrolysis paper tinsel, but rolling paper tinsel by rolling caused should change big; In addition; According to the difference of the composition of paper tinsel, be changed to recrystallized structure by the heat that when making CCL, is applied from rolling structure, so thermal contraction or heat are extended and are become big.
The heat that Fig. 3 is applied when representing owing to manufacturing CCL produces above-mentioned heat extends or thermal contraction, on the 1st bronze medal or copper alloy foil 4, produces the state of gauffer (folding line) 100.
At first, if when in above-mentioned the 1st step, making the single face copper-coated laminated board, with the 1st bronze medal or copper alloy foil 4 heating and cool off, then thermal contraction and littler than original length.Then, if when in above-mentioned the 2nd step, making the two sides copper-coated laminated board, with the 2nd bronze medal or copper alloy foil 6 heating and cool off, then desire thermal contraction and than original length little (arrow of Fig. 3).On the other hand, in the 1st step the 1st bronze medal of thermal contraction or copper alloy foil 4 in the 2nd step, carry out thermal contraction (arrow of Fig. 3) hardly.
Therefore, during cooling after the heating in the 2nd step, the power of shrinking through the 2nd bronze medal or copper alloy foil 6 desires and on the 1st bronze medal or copper alloy foil 4, apply stress under compression.Then, the 1st bronze medal or copper alloy foil 4 can't bear this stress under compression and buckle (producing gauffer or folding line).
Yet, when the 1st bronze medal or copper alloy foil 4 sides apply stress under compression, if the ys of this Copper Foil is greater than the stress under compression (σ of formula 2 A), then can not cause and buckle, and be difficult to produce gauffer or folding line.Usually can't obtain the ys for compression of Copper Foil, can be but whether produce the cut off value of buckling by replacing for tensile ys (YS).That is, think if be σ with YS AAbove mode is selected the 1st bronze medal or copper alloy foil 4, then can not produce gauffer or folding line.
And the inventor etc. obtain the condition that when making the two sides copper-coated laminated board, does not produce gauffer or folding line through experiment, and if the result can know with the σ for formula 2 AAnd form
|10×σ A|≦YS A?（3）
Mode select the 1st bronze medal or copper alloy foil 4, then be difficult to produce gauffer or folding line.
On the other hand, can know when on the 2nd bronze medal or copper alloy foil 6, applying stress under compression, if with σ for formula 2 BAnd form
|10×σ B|≦YS B?（4）
Mode select the 2nd bronze medal or copper alloy foil 6, then be difficult to produce gauffer or folding line.Yet, generally on the 1st bronze medal or copper alloy foil 4, apply stress under compression.
For satisfying formula 3 (or formula 4), σ A(σ B), be poor (the Δ L of size changing rate A-Δ L B) more little good more, therefore the difference of the suffered heat of the suffered heat of the 1st bronze medal or copper alloy foil 4 and the 2nd bronze medal in the 2nd step or copper alloy foil 6 is more little good more in the 1st step.In addition, in the 1st step the suffered strain of the 1st bronze medal or copper alloy foil 4 more little, poor (the Δ L of size changing rate A-Δ L B) also become more little.
According to the above, satisfy the concrete grammar of formula 3,4 and can enumerate: 1) heat the 1st bronze medal or copper alloy foil 4 and the 2nd bronze medal or copper alloy foil 6 in advance; 2) when the 1st bronze medal or copper alloy foil 4 and the 2nd bronze medal or copper alloy foil 6 are rolling paper tinsel, be rolled with low degree of finish; 3) make according to the thickness of paper tinsel and mechanical properties set rolling the time tension force be no more than limit; 4) the 1st bronze medal or copper alloy foil 4 and the 2nd bronze medal or copper alloy foil 6 use the electrolysis paper tinsel.Yet, if consider it generally is to apply stress under compression, also can only implement 1 to the 2nd bronze medal or copper alloy foil 6 at the 1st bronze medal or copper alloy foil 4 sides) to 4) method.
For above-mentioned 1) method, known fine copper is the metal with face-centred cubic structure, if carry out recrystallize through heating, then cubes orientation expansion, toughness improves.The yang type modulus of the Copper Foil of cubes orientation expansion is lower, and 0.2% ys in the tension test is also lower.That is, we can say that the Copper Foil of expanding in this cubes orientation (when carrying out the 2nd step) when making two sides CCL is easy to generate folding line or gauffer most.Experiment according to the inventor etc. can be known, for example pure copper foil is kept 30 minutes and cools off at 350 ℃, and yang type modulus is about 70GPa as a result, and 0.2% ys is about 50MPa.So, though think copper that ys is little or copper alloy foil be heated to about 350 ℃ once more till and cool off, dimensional change also is almost 0.
Therefore, the 1st bronze medal or copper alloy foil 4 use identical material (E with the 2nd bronze medal or copper alloy foil 6 A≒ E B, | σ A| ≒ | σ B|), with Δ L AWhen ≒ 0 was similar to, formula 2 usefulness following formulas 5 were represented:
σ A＝（E A×ΔL B）／2×1000（5）。
And, according to formula 3 and formula 5, and form following formula 6:
|10000×（E A×ΔL B／2）|≦YS A（6），
As long as use is satisfied formula 6 such copper or copper alloy foils and is made two sides CCL.
In addition, according to above-mentioned experimental result, if with E A=70GPa, YS AIn=50MPa substitution the formula 5, then can obtain Δ L B=143 (ppm).That is,, use Δ L as if heating before use to major general's the 2nd bronze medal or copper alloy foil 6 BThe material of ≦ 143 (ppm) then has toughness concurrently and is difficult to produce folding line or gauffer.As long as the heating condition of the 2nd bronze medal or copper alloy foil 6 is made as 50 ℃～200 ℃ heating about 1 second～10 hours, but is not limited thereto.For example heating condition can be enumerated at 60 ℃ and keep 3 hours or kept 3 seconds at 130 ℃.That is,, be used further to make two sides CCL and get final product as long as in advance copper or copper alloy foil are applied above-mentioned thermal treatment.
Secondly, for above-mentioned 2) method, rolling degree of finish, a time draught, tension force and the processing temperatures etc. of the strain of rolling paper tinsel after according to final annealing change.Yet, draught or tension force can depend on processing object paper tinsel thickness or rolls performance and be difficult to likewise stipulate.In addition, the high more then strain of processing temperature is more little, but rollingly in rolling waves the effect of refrigerant with fry dried food ingredients, and is difficult to the regulation processing temperature of moment.
Therefore, come regulation paper tinsel conditions needed according to rolling degree of finish.Here, if reduce rolling degree of finish, then the strain of paper tinsel diminishes, but the cubes orientation is difficult to expansion and toughness descends during recrystallize, thereby not preferred.With respect to this, if reduce rolling preceding crystallization particle diameter, even then be rolled with identical degree of finish, the cubes orientation is also expanded.According to above opinion; After experimentizing, the inventor etc. can know: if final cold rolling degree of finish R (%) is more than 93.0%; And the average crystallite particle diameter GS (μ m) behind the final annealing is GS ≦ 3.08 * R-260, then can not damage toughness, and can suppress the generation of folding line or gauffer.Yet if R is too high, therefore the tendency that exists toughness to descend does not heat the method for copper or copper alloy foil (not carrying out above-mentioned 1) before use in advance) time, preferred R is below 98%.
As stated, for copper of the present invention or copper alloy foil, need toughness excellent, and the number of bends of copper or copper alloy foil need be for more than 400,000 times.
Here, number of bends is to use IPC (U.S.'s printed wiring industry meeting) slip flexing machine, will make paper tinsel be cut into the width (direction rectangular with rolling direction.For the situation of electrolysis paper tinsel for and the rectangular direction of MD (machine direction)) use after 0.5 hour 350 ℃ of heat treated for 12.5mm, length direction are the test film that gets of the band shape of 200mm.Bending radius is made as 1.5mm, when paper tinsel thickness is 12 μ m, is made as 1mm when paper tinsel thickness is 18 μ m, to the slip repeatedly of test film load PM 100 times, be the terminated number of times with the resistance of test film from the number of bends of initial rising 20%.The number of bends of known copper or copper alloy foil is that the number of times more than 400,000 times is equivalent to be made as qualified number of bends among the actual two sides CCL.
For example, in Copper Foil in the past, also having R (%) is that average crystallite particle diameter GS (μ m) more than 93.0% and behind the final annealing is the Copper Foil of GS ≦ 3.08 * R-260 (oxygen free copper that for example contains 1200ppmSn), but its number of bends is less than 400,000 times.In addition; Even use the Copper Foil that utilizes known method to make with known composition and in order to have high toughness (being 99.2% to carry out final rolling paper tinsel for example) with degree of finish; 50 ℃～200 ℃ carry out preheating about 1 second～10 hours after; Also satisfy above-mentioned formula 6, so toughness is excellent, is applicable to the two sides copper-coated laminated board.
Embodiment
Use the Copper Foil of forming shown in the table 1 (copper alloy foil), make two sides CCL with mode shown in Figure 1.Here, though the 1st Copper Foil 4 is identical with the 2nd Copper Foil 6,, distinguish the 1st Copper Foil 4 and the 2nd Copper Foil 6 describes according to employed order in making CCL.
And,, or implement thermal pretreatment to a part of Copper Foil crystallization particle diameter GS and degree of finish adjusted as shown in table 1.And thermal pretreatment is carried out after following chemical treatment (plating), also can before will making CCL, carry out.
At first, the single face of the 1st Copper Foil 4 is carried out chemical treatment (plating), be coated with the precursor varnish (the emerging U-Varnish A that makes that produces of space portion) of polyimide resin so that thickness is the mode of 25 μ m at this face.Then, in being set at 130 ℃ heated air circulation type high temperature groove dry 30 minutes, interimly with being warming up to 350 ℃ and be cured (imidization), formation resin layer 2, thereby making single face CCL in 2000 seconds.Then, at the resin side of single face CCL coating thermoplastic polyimide (adhesion layer) and after carrying out drying, overlapping the 2nd Copper Foil 6, the hot pressing that utilizes the pressing machine be heated to 350 ℃ to carry out 10 minutes fetches makes two sides CCL.Then, CCL is cooled to room temperature with the two sides, and the production of folding line or gauffer is judged in range estimation.
Δ L ABe that Copper Foil is cut into width is that 150mm, length direction are the band shape of 12.5mm, utilize Vickers hardness tester to get the indenture that punctuate is spaced apart 80mm, measure the coordinate of two indentures, obtain the distance L before the heating thus.And,, after this thermal treatment, obtain distance equally for the situation of having carried out heat treated Copper Foil sample before the lamination in advance.Then, sample is kept taking out after 30 minutes in 350 ℃ baking oven, is cooled to room temperature, measure the coordinate of two indentures then, obtain distance L '.Δ L ACan calculate with (L-L')/L respectively, during contraction be on the occasion of.
In addition, the yang type modulus E of Copper Foil ACan be according to JIS-Z2280-1993, utilize vibratory drilling method and obtain 0.2% ys YS ABe to use tensile testing machine, obtain according to JIS-Z2241-1998.
Toughness is estimated as follows.At first, it is that 12.5mm, length direction are that the band shape of 200mm is processed test film that Copper Foil is cut into width, and it is used after 0.5 hour 350 ℃ of heat treated.Pliability test is used IPC (U.S.'s printed wiring industry meeting) slip flexing machine, and bending radius is made as 1.5mm, when copper thickness is 12 μ m, is made as 1mm when copper thickness is 18 μ m.Copper thickness is thin more, and then toughness is good more, therefore in order to estimate with same datum, as long as change bending radius according to copper thickness.Then, to the slip repeatedly of test film load PM 100 times, be the terminated number of times from the number of bends of initial rising 20% with the resistance of test film.The number of bends of known copper or copper alloy foil is that the number of times more than 400,000 times is equivalent to be made as qualified number of bends among the actual two sides CCL.
Resulting result is shown in table 1.
Figure 808590DEST_PATH_IMAGE001
Can clearly learn by table 1,, form for the situation of Copper Foil having been carried out the embodiment 1～13 of thermal pretreatment | 10 * σ A| ≦ YS A, non-wrinkled or folding line among the resulting two sides CCL, and toughness is also excellent.
In addition, making R for the rolling condition of adjusting Copper Foil is more than 93.0% and below 98.0%, and the situation of the embodiment 12,13 of while GS ≦ 3.08 * R-260 even do not carry out thermal pretreatment, also forms | 10 * σ A| ≦ YS A, non-wrinkled or folding line among the resulting two sides CCL, and toughness is also excellent.
On the other hand, for R being made as less than 93.0% and not carrying out the situation of the comparative example 1～3 of thermal pretreatment, toughness descends.For using electrolytic copper foil and not carrying out the situation of the comparative example 4 of thermal pretreatment, toughness also descends.
Mode for the GS that obtains GS＞3.08 * R-260 anneals, rolling comparative example 5 and R is made as the situation less than 93.0% comparative example 6, and toughness also descends.
For surpassing the situation that is rolled and does not carry out the comparative example 7～10 of thermal pretreatment under 98.0% the condition, form at R | 10 * σ A|＞YS A, produce gauffer or folding line among the resulting two sides CCL.
Surpass the situation of the comparative example 11,12 of 400ppm for the amount of the element that in copper, adds (Sn or Ag), toughness descends.
The explanation of symbol
2 resin layers
The 2a resin combination
4 the 1st bronze medal or copper alloy foils
6 the 2nd bronze medal or copper alloy foils
8 two sides copper-coated laminated boards

Claims (4)

1. copper or copper alloy foil, it is used for the two sides copper-coated laminated board, and works as σ A=(E A* Δ L A)/2 * 1000 o'clock, | 10 * σ A| ≦ YS A, number of bends is more than 400,000 times,
Wherein, E A: with above-mentioned copper or copper alloy foil 350 ℃ kept 30 minutes and be cooled to room temperature after width on yang type modulus (unit is GPa); Δ L A: the size changing rate on the above-mentioned copper when room temperature is warming up to 350 ℃, kept 30 minutes and is cooled to room temperature or the width of copper alloy foil (unit is ppm, with contraction be made as on the occasion of); YS A: 0.2% ys of above-mentioned copper or copper alloy foil in the tension test (unit is MPa);
Number of bends: use IPC slip flexing machine; It is that 12.5mm, length direction are the banded of 200mm and use after 0.5 hour 350 ℃ of heat treated that paper tinsel is cut into width; Bending radius is made as 1.5mm, when paper tinsel thickness is 12 μ m, is made as 1mm when paper tinsel thickness is 18 μ m; To the slip repeatedly of test film load PM 100 times, be the terminated number of times from the number of bends of initial rising 20% with resistance.
2. copper as claimed in claim 1 or copper alloy foil, wherein, above-mentioned copper or copper alloy foil are rolling paper tinsel, and final cold rolling degree of finish R (%) is more than 93.0%, and the average crystallite particle diameter GS (μ m) behind the final annealing is GS ≦ 3.08 * R-260.
3. according to claim 1 or claim 2 copper or copper alloy foil, wherein, Δ L ABelow 145ppm.
4. the method for manufacture of two sides copper-coated laminated board, it has:
The 1st step: the single face of each described copper or copper alloy foil forms resin layer in claim 1～3, and obtains the single face copper-coated laminated board; With
The 2nd step: the above-mentioned resin layer side lamination of above-mentioned single face copper-coated laminated board other above-mentioned copper or copper alloy foil and heat, and obtain the two sides copper-coated laminated board.
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