CN101594737B - Printing wiring cardinal plate and method for producing the same - Google Patents
Printing wiring cardinal plate and method for producing the same Download PDFInfo
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- CN101594737B CN101594737B CN2009102028481A CN200910202848A CN101594737B CN 101594737 B CN101594737 B CN 101594737B CN 2009102028481 A CN2009102028481 A CN 2009102028481A CN 200910202848 A CN200910202848 A CN 200910202848A CN 101594737 B CN101594737 B CN 101594737B
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- 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
- H05K3/06—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 the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
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- 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
- H05K2203/03—Metal processing
- H05K2203/0369—Etching selective parts of a metal substrate through part of its thickness, e.g. using etch resist
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- 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
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
Abstract
The invention provides a printing wiring cardinal plate with high insulation reliability and corrosion resistance and method for producing the same, namely the conductor wiring is formed with high etching, when etching is performed by ferric chloride solution or hydrochloric acid solution of copper chloride, residual etching draff with ingredients of the base metal layer between the conductor wirings are few, when high voltage is exerted among the conductor wirings. On at least one surface of the insulating resin film A, a metallic layer B with nickel, or nickel-chromium alloy containing nickel above 70 quality percentage and chromium below 15 quality percentage is stacked in series without an adhesive agent; a metallic layer C made of alloy containing chromium over 15 weight percentage, unnecessary part of a metal membrane composed by copper tunica layer D with thickness 10 nm to 35 Mum, chemical etching processing is adopted for selective removal, and then the printing wiring cardinal plate of conductor wirings is formed.
Description
Technical field
The present invention relates to printed wiring board and manufacture method thereof, in more detail, relate between insulating resin film and copper are by rete, adopt the dry type galvanoplastic to form etching good metal layer and the high metal level of corrosion resistance successively, have the printed wiring board and the manufacture method thereof of high insulating reliability.
Background technology
The flexible printing wiring substrate, roughly be divided into: on insulating resin film, adopt bonding agent to be pasted with and on insulating resin film, do not adopt the dry type galvanoplastic of bonding agent or the wet type galvanoplastic directly form as the copper of conductor layer by 2 layers of resin molding metal film laminated base plate of rete as 3 layers of resin molding metal film laminated base plate (for example, with reference to patent documentation 1) of the Copper Foil of conductor layer.
But, be accompanied by the densification of electronic instrument in recent years, require the narrow wiring substrate of pitch, in the manufacturing of above-mentioned 3 layers of resin molding metal film laminated base plate, the copper that forms on insulating resin film according to desirable Wiring pattern, is formed conductor wirings portion by etching by rete, the side of this conductor wirings portion produces by the so-called lateral erosion of over etching and carves, and the section configuration that the result produces wiring part easily becomes bottom trapezoidal problem when roomy.
Therefore, in order to address this problem, now oneself becomes main flow to replace original stickup Copper Foil (3 layers of resin molding metal film laminated base plate) with 2 layers of resin molding metal film laminated base plate.
These 2 layers of resin molding metal film laminated base plates, the copper that forms uniform thickness on insulating resin film as its method, is adopted galvanoplastic by rete usually.And, in order to electroplate, generally be before electroplating formation, on insulating resin film, form thin metal level, give conductivity to whole surface, electroplate (for example, with reference to patent documentation 2) thereon.Also have, on insulating resin film, form thin metal level, can adopt dry type galvanoplastic such as vacuum vapour deposition, ion plating method to form.
Wherein, insulating resin film and copper are by the adaptation of rete, when forming CuO or Cu at its interface
2A little less than becoming very during layers such as O, so, for keep the printing distributing board requirement with copper by the dhering strength of rete, between insulating resin film and copper are by rete,, nickel-chromium alloy layer (with reference to patent documentation 3) is set as substrate metal layer.Below, the laminated body that substrate metal layer and copper are constituted by rete is as metal film.
The Wiring pattern of 2 layers of resin molding metal film laminated base plate can adopt subtraction (subtractiveprocess) to form.So-called this subtraction means the metal film of resin molding metal film laminated base plate is not wanted part, handles by chemical etching and is removed, and makes the manufacture method of printed wiring board.
This chemical etching is handled, by adopting chemical etching liquor that the metal film of not wanting is corroded and, when chemical etching is handled, generally being chemical etching liquor for the washing of removing chemical etching liquor constitutes, hydromining sprays with spray process etc., or dipping carries out in chemical etching liquor etc.
With copper by the corresponding chemical etching liquor of the etching of rete, for example, iron chloride (FeCl is arranged
32H
2O) aqueous solution, hydrochloric acid acidic copper chloride (CuCl
22H
2O) aqueous solution uses these chemical etching to handle, and can form conductor wirings.
Adopt the chemical method for etching of these chemical etching liquors, as substrate metal layer from corrosion proof viewpoint, when adopting the high nickel-chromium alloy of chromium content, chemical etching can not fully be carried out, between conductor wirings edge, conductor wirings, dissolve residual substrate metal layer, produce metallic residue, can not get sufficient etching achievement sometimes as etch residue.
In addition, as the problem points of insulating reliability aspect, in the index of insulating reliability, (the following HHBT that is called sometimes tests: HighTemperature High Humidity Bias Test) etc. can to implement constant temperature and humidity bias current test.Produce the substrate of above-mentioned etch residue and the flexible printing wiring substrate that adopts the low substrate metal layer of chromium content, in the HHBT test, show that clearly insulating reliability is insufficient.
Promptly, 2 layers of resin molding metal film laminated base plate with the high substrate metal layer of chrome content, when carrying out above-mentioned chemical etching and handling, substrate metal layers such as nickel-chromium alloy are owing to undercut dissolves when residual, when carrying out the HHBT test, adjacent conductor wirings, the metallic residue because of the residual base metal composition of layer of wiring closet dissolving constitutes produces problem of short-circuit.
On the other hand, adopt 2 layers of resin molding metal film laminated base plate with the low substrate metal layer of chrome content, no etch residue takes place, but owing to can not guarantee the corrosion resistance of substrate metal layer, can not guarantee the insulating reliability in the HHBT test.Therefore, substrate metal layer is required etching and corrosion proof opposite characteristic.
At this, as one of measure that realizes insulating reliability, must remove etch residue residual between above-mentioned conductor wirings, correction way as this related shortcoming, for example, propose in the patent documentation 4: adopt chemical etching liquor, after promptly ferric chloride solution or hydrochloric acid acid chlorization copper solution are carried out etch processes corresponding to the copper tunicle, and with the handling more than a kind or 2 kinds of alkaline etching liquids such as hydrochloric acidic etching liquid, liquor potassic permanganate, the etch residue of dissolving wiring closet.
In addition, propose in the patent documentation 5: the etch residue of wiring closet, carry out chemical etching with hydrochloric with solution sulfuric acid, in the mixed liquor of potassium permanganate and potassium hydroxide and NaOH, carry out impregnation process again.
Also have, propose in the patent documentation 6: the etch residue of wiring closet, with hydrochloric acidic chemical etching solution dissolving, handle with the alkaline etching liquid that contains the potassium ferricyanide or permanganate again.When use contains the alkaline etching liquid of the potassium ferricyanide or permanganate, adopt the lateral erosion of copper wiring to carve few method, it is possible that the residual nichrome of wiring closet dissolving or NI-CR-MO alloys are removed.
[patent documentation 1] spy opens flat 6-132628 communique
[patent documentation 2] spy opens flat 8-139448 communique
[patent documentation 3] spy opens flat 6-120630 communique
[patent documentation 4] spy opens the 2005-23340 communique
No. the 3888587th, [patent documentation 5] special permission
[patent documentation 6] spy opens the 2008-28150 communique
Summary of the invention
The problem that invention will solve
But, nearest flexible printing wiring substrate, be accompanied by the densification more of Wiring pattern, carried out the narrow pitchization of distribution, also have, or be accompanied by the high performance requirement and use under high voltage, the result is that the insulating reliability of used printed wiring board becomes important, for high voltage withstanding, substrate metal layer is required higher corrosion resistance.
At this, consider that from corrosion proof viewpoint as seen the tendency of the high basalis of the chromium content of nickel-chromium alloy is set, and the result handles by chemical etching, between conductor wirings, the etch residue that the dissolving of base metal composition of layer is residual the tendency that increases arranged.
Also have, existing 2 layers of resin molding metal film laminated base plate, when adopting subtraction to form the conductor wirings pattern, owing to adopt a kind of chemical etching liquor of ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor to carry out etch processes, so increase new etch processes operation removing etch residue, essential brand-new introducing equipment then produces the problem of equipment cost and liquid management cost increase and the worry that causes the production efficiency reduction because of the operation increase.
The present invention proposes in order to address these problems, its objective is provides: in the manufacturing of the flexible printing wiring substrate that uses dry type galvanoplastic and galvanoplastic, on the single face at least of insulating resin film, form substrate metal layer, when on this substrate metal layer, forming copper by rete, when forming, conductor wirings has high etching, concrete is when adopting ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor to carry out etching, the etch residue of residual base metal composition of layer is few between conductor wirings, when applying high voltage between conductor wirings, with high insulating reliability and corrosion proof printed wiring board and manufacture method thereof.
Be used to solve the means of problem
In view of above-mentioned condition, what the inventor concentrated one's attention on to study found that, by bonding agent, lamination metal layer B, metal level C, copper can be realized guaranteeing insulating reliability and corrosion proof printed wiring board by rete D on the single face of insulating resin film or two sides.
The 1st invention of the present invention relates to printed wiring board, printed wiring board, its be by the chemical etching processing selecting remove not the part that do not need that metal film is stacked in the above-mentioned metal film on the resin molding metal film laminated base plate that forms at least one surface of insulating resin film A by binding agent and form conductor wirings, it is characterized in that, the metal film that constitutes above-mentioned conductor wirings comprises: at the metal level B of the surperficial superimposed layer of above-mentioned insulating resin film A, this metal level B is made of nickel or the nickel-chromium alloy that contains the nickel more than the 70 quality % and be lower than 15 quality % chromium; At the metal level C of the surperficial lamination of above-mentioned metal level B, that this metal level C comprises is nickeliferous, contain the above alloy of chromium 15 quality %; And, by rete D, only use the above-mentioned copper of etching not needed part at the copper of the thickness 10nm～35 μ m of the surperficial lamination of above-mentioned metal level C by what the chemical etching liquor of rete D came the described metal film of etching.
The 2nd invention of the present invention relates to the described printed wiring board of the 1st invention, it is characterized in that, lamination has above-mentioned metal level B, metal level C and copper by the conductor wirings of the above-mentioned metal film of rete D to comprising successively, adopt ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor to carry out the level of residue that back metal remained on above-mentioned insulating resin film A is handled in chemical etching, the per unit area of above-mentioned relatively insulating resin film A is 0.13 μ g/cm
2Below.
The 3rd invention relates to the 1st invention or the described printed wiring board of the 2nd invention, it is characterized in that, above-mentioned metal level B comprises and contains that vanadium 13 quality % are following, titanium 8 quality % following, below the molybdenum 20 quality %, surplus is made of nickel and the unavoidable impurities below the 1 quality %, perhaps by contain the nickel more than the 70 quality % and be lower than the nickel-chromium alloy of 15 quality % chromium and the unavoidable impurities below the 1 quality % to constitute thickness be 3～20nm.
The 4th invention relates to the 1st invention～the 3 any one described printed wiring board of invention, it is characterized in that, above-mentioned metal level C contains above, nickel 0.01～85 quality % of chromium 15 quality %, the alloy of the unavoidable impurities that 1 quality % is following, or contain that chromium 15 quality % are above, the alloy of unavoidable impurities that nickel 0.01～85 quality %, molybdenum 0.01～40 quality % and 1 quality % are following, thickness is 5～37nm, or is aggregated in below the 40nm more than the thickness 5nm and with metal level B.
The 5th invention relates to the 1st invention～the 3 any one described printed wiring board of invention, it is characterized in that above-mentioned chemical etching liquor does not contain manganese and cyanide.
The 6th invention relates to the 1st invention～the 3 any one described printed wiring board of invention, it is characterized in that above-mentioned chemical etching liquor is ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor.
The 7th invention relates to the 1st invention or the described printed wiring board of the 2nd invention, it is characterized in that above-mentioned insulating resin film A is the resin molding more than at least a kind that is selected from polyimide film, polyamide-based film, polyesters film, polytetrafluoroethylene class film, polyphenylene sulfide ethers film, PEN class film, liquid crystal polymer class film.
The 8th invention relates to the manufacture method of printed wiring board, its be at least 1 surface of insulating resin film A not by bonding agent and lamination the above-mentioned metal film of resin molding metal film laminated base plate of metal film, optionally remove the not part of above-mentioned metal film by chemical etching, form the manufacture method of the printed wiring board of conductor wirings, it is characterized in that, the above-mentioned resin molding metal film of following formation laminated base plate: on the surface of above-mentioned insulating resin film A, adopt the dry type galvanoplastic to form nickel or with the metal level B of nickel as principal component, then, surface at this metal level B, adopt the dry type galvanoplastic to form to contain the chromium more than the 15 quality % and the alloy of nickel, or contain the above chromium of 15 quality %, behind the metal level C that the alloy of nickel and molybdenum constitutes, form the metal film that the copper by thickness 10nm～35 μ m is become by rete D lamination on the surface of this metal level C, this metal film adopts a kind of etching solution optionally to remove, and forms conductor wirings.
The 9th invention relates to the manufacture method of the described printed wiring board of the 8th invention, it is characterized in that above-mentioned chemical etching liquor does not contain manganese and cyanide.
The 10th invention relates to the manufacture method of the described printed wiring board of the 8th invention, it is characterized in that above-mentioned chemical etching liquor is ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor.
The 11st invention relates to the manufacture method of the described printed wiring board of the 8th invention, it is characterized in that, above-mentioned copper is adopted galvanoplastic to form the copper layer on the copper laminar surface that adopts the dry type galvanoplastic to form by rete D and obtains.
The 12nd invention relates to the manufacture method of the 8th invention or the described printed wiring board of the 11st invention, it is characterized in that above-mentioned dry type galvanoplastic are any of vacuum vapour deposition, sputtering method or ion plating method.
The invention effect
Printing distributing board of the present invention, configuration contains the metal level C more than the chromium 15 quality % and has good corrosion resistance between insulating resin film A and copper are by rete D, simultaneously, configuration comprises the metal level B that chromium content is lower than the alloy of 15 quality % between insulating resin film A and metal level C, metal film can adopt a kind of chemical etching liquor not remove with having residue, can guarantee the insulating reliability of printed wiring board greatly, its industrial value is high.
Description of drawings
Fig. 1 is the sectional drawing of the resin molding metal film laminated body used in the printing distributing board of the present invention.
Fig. 2 is the chromium amount of expression nickel-chromium alloy and the graph of a relation of etch residue amount.
Fig. 3 is the broach shape distribution skeleton diagram that uses during insulating reliability is estimated.
[explanation of symbol]
A insulating resin film A
B metal level B
C metal level C
D copper is by rete D
1a, 1b short bar (short bar)
2a, 2b broach shape conductor
10a, 10b comb type distribution
Embodiment
Printing distributing board of the present invention is on 2 layers of resin molding metal film laminated base plate (below be called resin molding metal film laminated base plate), implements to adopt the processing of subtraction or semi-additive process to make.
Resin molding metal film laminated base plate
The resin molding metal film laminated body of using in the printed wiring board of the present invention, at least 1 face of insulating resin film A, not forming successively by bonding agent, lamination has metal level B, metal level C and copper by the metal film of rete D.
The section of the resin molding metal film laminated body of in Fig. 1, using in the expression printed wiring board of the present invention.Metal level B and metal level C are equivalent to the substrate metal layer of 2 layers of resin molding metal film laminated base plate.Also have, this resin molding metal film laminated body is that insulating resin film A and each metal level lamination form, owing to do not have bond layer, so, be equivalent to 2 layers of resin molding metal film laminated base plate.
Below, each inscape of resin molding metal film laminated base plate of the present invention is described in detail.
(metal level B)
Metal level B is not situated between by the bonding agent lamination on the surface of insulating resin film A, comprises the alloy that nickeliferous or nickeliferous 70 quality % are above, chromium is lower than 15 quality %.Below the preferred 14.5 quality % of the chromium content of this metal level B, more preferably below the 14 quality %.When chromium content reaches 15 quality % when above, can not remove metal level B by the chemical etching of adopting ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor, can not keep insulating reliability.
Also have, metal level B can contain that vanadium 13 quality % are following, titanium 8 quality % are following, below the molybdenum 20 quality %.
Containing of these vanadium, titanium, molybdenum both can be added into metal level B with a kind of element of its selection, also can add multiple element.That is, metal level B comprises nickel and the alloy that is selected from a kind of element of vanadium, titanium, molybdenum, also can be to comprise nickel and the alloy of element more than 2 kinds that is selected from vanadium, titanium, molybdenum.In addition, both can be the alloy that comprises nickel and chromium and be selected from a kind of element of vanadium, titanium, molybdenum, also can be the alloy of element more than 2 kinds that comprises nickel, chromium and be selected from vanadium, titanium, molybdenum.
Each element of vanadium, titanium, molybdenum, can improve the corrosion resistance of metal level B, during content below containing vanadium 13 quality %, below the titanium 8 quality %, below the molybdenum 20 quality %, in the etching work procedure that adopts ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor, do not produce the residue of metal level B.Also have, when the interpolation element of metal level B only is made of titanium, in the etching work procedure that adopts ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor, produce the residue of metal level B.
Therefore, metal level B can as one man suitably add transition metal with the purpose characteristic in order to improve thermal endurance and corrosion resistance.Also have, except that these alloys, can also have the unavoidable impurities below the 1 quality % that enters when making target etc. and contain among the metal level B.
The formation method of metal level B can adopt known vapour deposition method, sputtering method, ion plating method, particularly sputtering method, and is because can not cause the alloy change of preferred constituent, therefore preferred.
When the thickness of metal level B during less than 3nm, conductor wirings adds in the chemical etching of adopting ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor man-hour, and metal level C is not dissolved and dissolving remains between conductor wirings with metal level B.Its reason, can think that because metal level B forms as complete film the part directly forms metal level C on insulating resin film A, or the phenomenon that metal level C dissolves with metal level B is difficult for taking place, when the corrosion resistance after the processing of consideration conductor wirings, metal level B is thin as far as possible to be advisable.When thickness during greater than 20nm, when conductor wirings was applied voltage, the stripping gradually of the composition of metal level B easily became the reason of poor short circuit.
Also have, the thickness of metal level B can be inferred from formation condition, and for example, during known employing sputtering method, according to formation conditions such as electric power that drops into to sputter cathode and sputtering times, thickness linearly changes, and can obtain the thickness of metal level B from condition.
(metal level C)
Metal level C is the surface of the metal level B on insulating resin film A, does not form by bonding agent.
Metal level C is with nickel and the chromium alloy as principal component, and when its chromium content was lower than 15 quality %, the corrosion resistance after the distribution processing can not fully keep, because the stripping of metal level C or copper and insulating reliability reduces.On the other hand, when chromium content during greater than 70 quality %, chromium might be separated out in the grain boundary, is not preferred, in addition, when metal level C only is made of Cr, because because of hydrochloric acid dissolves, so the acid resistance reduction, so when the time through etching work procedure and electroplating work procedure, relevant with insulating reliability, so preferred 15～70 quality %.
In addition, the nickel content of metal level C, after guaranteeing chromium content, 0.01～85 quality % is advisable.
Also have, in metal level C, can also contain molybdenum and reach 0.01～40 quality %.At this moment, much less should add up the content of nickel, chromium and unavoidable impurities and be adjusted to 100 quality %.
Molybdenum also has the corrosion proof effect of raising, and when molybdenum content surpassed 40 quality %, heat-resisting peel strength had the tendency of extreme reduction, is not preferred therefore.
When the thickness of metal level C is lower than 5nm, can not guarantee barrier to copper, insulating reliability reduces.Also have, when the total thickness of metal level B and metal level C during greater than 40nm, the stress of film uprises, generation hair check and warpage, and dhering strength might reduce, and the total thickness of preferred metal layers B and metal level C is below 40nm.
Also have, the thickness of metal level C can be obtained from formation condition, and for example, during known employing sputtering method, according to conditions such as the electric power that applies to sputter cathode, sputtering times, thickness linearly changes, and can obtain thickness from this condition.
(copper is by rete D)
Secondly, copper when forming thin copper by rete, is adopted the dry type galvanoplastic to form by rete D.On the other hand, also can adopt the dry type galvanoplastic form thin copper by rete after, adopt the thicker copper of wet type galvanoplastic lamination to be formed at this thin copper on by rete by rete.
This copper is by the thickness of the preferred 10nm of the thickness of rete～35 μ m, and when thickness was lower than 10nm, the conductivity of wiring part easily had problems, and the problem on the intensity maybe might occur.On the other hand, when thickness during greater than 35 μ m thickenings, produce hair check and warpage etc., dhering strength reduces sometimes, is not preferred.
After adopting dry type galvanoplastic formation copper by rete, when this copper adopts the thicker copper of wet type galvanoplastic lamination to be formed by rete on by rete, can adopt the dry type galvanoplastic form copper about thickness 10nm～1 μ m by rete after, adopt the wet type galvanoplastic carry out lamination up to the copper that reaches desired thickness by rete or conductor wirings.
(insulating resin film)
Insulating resin film, be the insulating resin film that is selected from polyesters film, polytetrafluoroethylene class film, polyphenylene sulfide ethers film, PEN class film or liquid crystal polymer class films such as polyimide film, polyamide-based film, PETG (PET) and PEN, can consider that the manufacturing process of thermal endurance, dielectric characteristic, electrical insulating property and printed wiring board and the resistance to chemical reagents of subsequent handling etc. suitably select according to purposes.
For example, the polyimide film has the Kapton (registered trade mark) of eastern beautiful Dupont (strain) preparation, ユ-ピ レ Star ケ ス (registered trade mark) that the emerging product of space portion (strain) is made, ア ピ カ Le (registered trade mark), Japan that clock deep pool chemical industry (strain) is made to spin XENO (registered trade mark) that (strain) make etc.In addition, as the aryl amide film of aromatic polyamide class film, the ミ Network ト ロ Application (registered trade mark) of east beautiful (strain) manufacturing, the ア ラ ミ カ (registered trade mark) that Supreme Being people ア De バ Application ス ト Off イ Le system (strain) is made etc. are arranged.
Also have, printed wiring board of the present invention is formed with on the single face of insulating resin film A the printed wiring board of conductor wirings, also can adopt the printed wiring board that is formed with conductor wirings on the two sides of insulating resin film A.In addition, but also a plurality of printed wiring boards of the present invention of lamination, as multilayer printed wiring board.
(level of residue of metal)
Secondly, insulating resin film A being gone up the metal remained level of residue describes.
As the residual layer that comprises metallic atom of wiring closet, in HHBT test, become be accompanied by wiring closet through the time short circuit, the reason that insulating reliability reduces greatly.Known also the existence stresses local residual part, and the metallic residue amount of all surfaces of insulating resin film during by 1 layer of metallic atom tunicle is equivalent to about 0.15 μ g/cm
2
At this, in order to understand the chromium content in the nickel-chromium alloy and the relation of the level of residue on the insulating resin film, obtain to go up and form nickel-chromium alloy (being equivalent to metal level B or metal level C) with sputter at the dry insulating resin film (polyimide film) of having removed moisture in advance, then, adopting sputter and plating to form copper by the substrate of rete, carry out etching with ferric chloride solution, the total of the composition of residual nickel-chromium alloy layer on chromium concn and the polyimide film in the nickel-chromium alloy of this moment is promptly with the relation of etch residue amount total.It the results are shown in Fig. 2.
In Fig. 2, when chromium content is 15 quality %, to the etch residue amount of insulating resin film for a long time, the every 1cm of insulating resin film
2Be 0.15 μ g/cm
2This value as mentioned above, be equivalent to the amount that the involved 1 layer metallic atom of all surfaces of insulating resin film covers, in fact, also exist and stress local residual part, as at the residual layer that comprises metallic atom of wiring closet, in HHBT test, be accompanied by wiring closet through the time short circuit, insulating reliability is reduced greatly.
Particularly in order to form the high meticulous distribution of tens of μ m pitches, require the metal film etching of not wanting part is removed, at the resin molding metal film laminated base plate that is formed with the metal film more than the high chromium content of the corrosion resistance 15 quality % on the surface with insulating resin film, carrying out chemical etching with ferric chloride in aqueous solution handles, when being processed into printed wiring board, remove metal film not, though perusal insulating resin film A exposes on the surface, but because the residual atomic layer of metal more than 1 layer of wiring closet, so can not get sufficient insulating reliability.
Otherwise, the metal level of chromium content less than 15 quality % is set on the surface of insulating resin film, when chromium content metal level how is set on this metal level, only be used as the ferric chloride in aqueous solution or the hydrochloric acid acid chlorization copper liquor of the chemical etching liquor of etch copper, also can handle and remove the not many metal levels of chromium content of part by chemical etching.On the contrary, at the metal level that is provided with on the insulating resin film more than the chromium content 15 quality %, when the poor metal level of chromium is set on this metal level, only with ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor, can not remove the chromium content of not wanting part is the above metal levels of 15 quality %, then removes difficulty when containing the chemical etching liquor of manganese or cyanogen without potassium permanganate or the potassium ferricyanide etc.
For this reason, in the printed wiring board of the present invention, comprise metal level B, metal level C and copper by the conductor wirings of the lamination of rete D, carry out after the etching metal remained level of residue on insulating resin film A with ferric chloride in aqueous solution, the per unit area of insulating resin film A is 0.13 μ g/cm relatively
2Below, more preferably 0.10 μ g/cm
2Below.
In addition, when removing lamination metal level B, metal level C and copper are arranged by the conductor wirings of rete D, expose on the surface of insulating resin film A, and the metallic residue due to the etching simultaneously also is presented on the surface of insulating resin film A.Mensuration goes the insulating resin film A that its surface exposes to go up the metal remained amount, can obtain the metallic residue amount after the etching, therefore, can infer insulating reliability.
Insulating resin film A goes up the metal remained level of residue, measures with following method.
The conductor wirings of printed wiring board is carried out chemical etching with ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor and is handled the part of not removing not, and the surface of insulating resin film A is exposed, and washs as required and even reprocessing.Secondly, in the top layer of the printed wiring board of having removed conductor wirings part, the metal remained composition dissolves on the top layer part of the insulating resin film A that has promptly exposed, obtains the lysate of kish composition.
In the dissolving of this kish composition, adopt acid, but when the metal ingredient quantitative analysis, can not use and contain the acid that hinders the composition that detects spectrum.For example, in order to dissolve kishs such as Ni, Cu, Mo, Ta, Ti, V, Cr, Fe, Co easily, hydrochloric acid is effectively, but the Cl of hydrochloric acid detects spectrum, might hinder the small detection spectrum of above-mentioned metal ingredient, is not preferred therefore.In addition, nitric acid does not hinder above-mentioned detection spectrum, but with behind the nitric acid dissolve, at side insulating film, the dissolving that metal ingredient easily takes place is residual, is unaccommodated as lysate.
At this, among the present invention,, use nitric acid 70～90% and the solution that hydrogen peroxide 10～30% constitutes for the dissolving of metal remained composition in the top layer part of the insulating resin film after the etching, adopt the microwave decomposition device to carry out dissolution process.Adopt this method, do not hinder detection spectrum during quantitative analysis, and can dissolve whole metal ingredients residual on the dielectric film fully.
In addition, different from when adopting hot plate etc. to carry out indirect adopting this microwave decomposition device, owing to directly heat acid in the closed container with microwave, thus few to the heat of external leaks, also have also less from the pollution of outside.Therefore, the kish composition can decompose with small amount of acid in the short time, and about about 5～6 hours of the decomposition of sample and minute can be estimated as quick as thought.
The metal ingredient of the lysate that quantitative analysis obtains like this.As analytical method, be not particularly limited, the employing quantitatively plasma ion source quality analysis apparatus of inducing combination of trace meter composition (the following ICP-MS that is called sometimes) is preferred.
(chemical etching liquor)
The chemical etching liquor that uses among the present invention is that copper is carried out etched chemical etching liquor by rete, any chemical etching liquor of preferred ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor.Ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor are carrying out the etched while with the copper oxidation, remove metal level B and metal level C in the laminated construction of metal film of the present invention.
Generally from corrosion proof viewpoint, the surface of insulating resin film is provided with the resin molding metal film laminated body of the substrate metal layer (the metal level C among the present invention) of the high nickel-chromium alloy of chromium content, carry out chemical etching and handle with copper is carried out etched ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor by rete, when making printed wiring board, since the not part of substrate metal layer fully etching remove and residual, become the metallic residue due to the etching sometimes.
Particularly when substrate metal layer chromium content when 15 quality % are above, can significantly see the generation of the metallic residue due to the etching, from the insulating resin film surface with 0.1～the residual base metal composition of layer of number nm thickness, in order to be removed, must employing can dissolve the dissolution process of the potassium ferricyanide aqueous solution of this metallic residue or alkaline permanganate aqueous solution etc.Also have, substrate metal layer also can adopt ferric chloride in aqueous solution to make its passivation, and the passivation of this substrate metal layer becomes the metallic residue in the etching, also becomes the reason that insulating reliability reduces.
On the other hand, printed wiring board of the present invention, the surface that is insulating resin film A is disposed with metal level B, metal level C, copper is by the laminated construction of rete D, contain the above metal level C of chromium 15 quality % and be arranged on insulating resin film A and copper by between the rete D, between metal level C and insulating resin film A, owing to be situated between by adopting etch copper to be contained the metal level B that chromium is lower than 15 quality % by the chemical etching liquor of rete D is etched, by the chemical etching liquor of rete D (for example only adopt corresponding to copper, ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor) carry out the chemical etching processing, also can remove the not part of the metal film of metal-containing layer C.
The metal film that is provided with on the surface of this insulating resin film A, owing to be by metal level B, metal level C, the laminated construction that copper is provided with by the order of rete D, even do not handle so do not adopt the potassium ferricyanide aqueous solution or the alkaline permanganate aqueous solution to carry out chemical etching, still can remove metal level B, metal level C, though copper is not clear by the reason of rete D, but order at the surperficial lamination of insulating resin film A, when changing over as metal level C, metal level B, copper is by rete D when such, when adopting ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor to carry out the chemical etching processing, produce the metallic residue of metal level C composition.
(2) manufacture method of printed wiring board
Secondly, the manufacture method to printed wiring board of the present invention is elaborated.
Resin molding metal film laminated base plate is made printed wiring board by the processing of adopting subtraction or semi-additive process.That is, the comprising by copper of this resin molding metal film laminated base plate surface by the metal film of rete D, metal level C and metal level B, its not part do not adopt chemical etching etc. to be removed, form conductor wirings.
Below, adopt the situation of subtraction manufacturing to describe to printed wiring board of the present invention.So-called subtraction, the metal film that means resin molding metal film laminated base plate not part are removed by chemical etching processing etc., make the manufacture method of printed wiring board thus.
Printed wiring board of the present invention, the surface as the residual place of conductor wirings in the metal film of resin molding metal film laminated base plate is provided with resist.That is, resist forms the shape of Wiring pattern.Then, handled by the chemical etching of the corresponding chemical etching liquor of rete through adopting with copper, washing, the not part of optionally removing metal film forms conductor wirings.
This is optionally removed, can adopt etch copper by only a kind of chemical etching liquor of the chemical etching liquor of rete, metal film be carried out chemical etching handle, so need not increase the etch processes operation newly, again introducing equipment does not have the increase of equipment cost, solution management cost and operating time.
In addition, resist can adopt known resist, and chemical etching liquor is had tolerance, behind the formation distribution, can remove just passable.Resist is if formed with silk screen printing by the surface of rete D at copper, or the photonasty resist that solidifies with irradiation ultraviolet radiation etc. gets final product, and is solidified into regulation shape etc. and disposed.
In the present invention, adopt copper is carried out etched ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor by rete any chemical etching liquor only a kind of to carry out the metal film etching, remove part not.Ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor carry out etching with the copper oxidation, in the laminated construction of metal film of the present invention, also have the effect of removing metal level B and metal level C simultaneously.
So, chemical etching liquor does not adopt cyanides such as the permanganate aqueous solution such as potassium permanganate solution or potassium ferricyanide aqueous solution, so behind etching work procedure, also needn't remove demanganize, owing to do not contain manganese and cyanide in the chemical etching liquor, so the printed wiring board before implementing golden electroplating work procedure does not contain manganese and cyanide, even the printed wiring board of implementing to the gold plating does not contain manganese yet.
Also have, do not contain manganese and cyanide is meant, be left out as the manganese and the cyanide of inevitable impurity.
Also have, printed wiring board of the present invention does not adopt the chemical etching liquor corresponding with the etching of metal level C to carry out chemical etching and handles.The chemical etching liquor neutral and alkali permanganate water solution corresponding with the etching of metal level C, the top layer that can remove insulating resin film A, but owing to do not adopt the alkaline permanganate aqueous solution, even metal level C is removed, the surface of insulating resin film is not removed.That is, known packets metal-containing layer B, metal level C and copper is by the conductor wirings of rete D, adopt ferric chloride in aqueous solution to remove, and the surface of the insulating resin film A that has exposed concavo-convex adopts the optical profile processing machine to measure, and is level and smooth measuring below the boundary.This surface that means the insulating resin film A that has exposed can not dissolved by chemical etching liquor.
Removing of the oxidation film that generates on the conductor wirings surface after the formation conductor wirings, also can adopt known microetch method, also have, after the conductor wirings of printed wiring board forms, adopt the chemical etching liquor chemical etching liquor in addition of copper tunicle correspondence, can suitably select by following operation.
Secondly, to printed wiring board of the present invention, adopt the situation of the manufacturing of semi-additive process to be illustrated.
So-called semi-additive process, mean metallic film surface, in the place of wanting to form distribution metal film is adhered to, behind the thickness of guaranteeing as distribution at resin molding metal film laminated base plate, remove the metal film that does not want on the surface of insulating resin film, make the method for printed wiring board.
In detail, metallic film surface at resin molding metal film laminated base plate, do not wishing that the place that forms distribution forms resist film, on the metallic film surface of having exposed, adopt to electroplate to wait and form copper wiring, remove resist after forming copper wiring, the above-mentioned metal film that has exposed is handled by chemical etching and to be removed, form distribution, make printed wiring board.
Here used resist is as long as anti-copper electroplating liquid can adopt any known resist.In addition, removing of metal film not since surface be copper by rete, adopt the chemical etching liquor corresponding to be removed with copper, the same method of employing and subtraction is carried out.
Also have, for the flexible printing wiring substrate that adopts flexible insulating resin film, the present invention has been described before this, certainly, adopt the rigidity printed wiring board of epoxy resin or phenolic resins, Teflon materials such as (registered trade marks), also can implement the present invention.
Below, with embodiment the present invention is described.
Insulating resin film A adopts the polyimide film (" Kapton 150EN " that eastern beautiful Dupont (strain) makes) of thickness 38 μ m, and lamination metal layer B, metal level C, copper are made resin molding metal film laminated base plate by rete D successively.To metallic residue amount, the insulating reliability after resulting resin molding metal film laminated base plate evaluation initial stage peel strength, heat-resisting peel strength, etching, the etching.The sample that is made for each characteristic is not particularly limited, adopts following (a) and (b), (c) described sample.
(a) peel strength is measured
The initial stage buckling strength carries out according to its assay method in IPC-TM-650, NUMBER 2.4.9.Its condition determination is that the angle of peeling off is 90 °.Sample forms with following subtraction: conductor width is that (Tokyo should be changed (strain) and make by coating photonasty resist on the surface of rete D for the copper of 1mm, resin molding metal film laminated base plate, PMER P-RH30PM), expose and make the pattern that forms wide 1mm, aqueous sodium carbonate with concentration 0.3 quality % develops, in the ferric chloride solution (40 ° of Baumes of proportion, 43 ℃ of temperature) dipping wash after 2 minutes, drying.Peeling off of resist, the sodium hydrate aqueous solution of employing concentration 4 quality %.
Also have, heat-resisting peel strength, with the sample of the same shape of initial stage peel strength in 150 ℃ keep 168 hours after taking-up, be cooled to room temperature after, same with the initial stage peel strength, be 90 ° with the angle of peeling off and measure this peel strength.
As the initial stage peel strength be peel strength (heat-resisting peel strength) more than the 600N/m, after the heat resistant test for more than the 400N/m, then be judged as good.
(b) etching and metallic residue amount
The evaluation of etching is that resin molding metal film laminated base plate is cut into 3cm * 3cm, and dipping was washed drying after 2 minutes in chemical etching liquor.It is residual that range estimation confirms on the insulating resin film whether metal level dissolves, and when residual, judges then that can not only carry out distribution with above-mentioned chemical etching liquor processes as obvious.On the other hand, when range estimation is confirmed difficult judgment and can't be confirmed to dissolve when residual, in order to measure the metallic residue amount after the etching, remove metal level, the insulating resin film A that the surface has been exposed adopts the microwave decomposition device, dissolves with the solution of nitric acid 5ml and hydrogen peroxide 1ml formation, resulting solution metal composition carries out quantitative analysis with ICP-MS (beam split/quality analysis of high-frequency induction luminescence of plasma), measures metallic residue amount (the total amount of metal level B and metal level C).
(c) insulating reliability
The evaluation of insulating reliability is to be undertaken by the JPCA-ET04 standard.
Measure sample,,, form with subtraction equally with peel strength mensuration the comb type distribution of 40 μ m pitches shown in Figure 3 (live width 20 μ m, interval width 20 μ m) to resin molding metal film laminated base plate.Comb type distribution is, the overlap length (10) of broach shape conductor is 20mm, and the gap (11a, 11b) of broach shape conductor front end and short bar (short bar) is 5mm.Wiring closet is applied potential difference DC60V, placed 1000 hours in 85 ℃ of temperature, relative humidity 85%, insulating resistance value adopts the migration test machine, and (IMV society makes, trade name: MIG-87) measure.Resistance value is reached 10
6The following time point of Ω is judged as poor short circuit, just reaches 10 after 1000 hours
6More than the Ω, it is qualified then to be judged as.
The polyimide film of thick 38 μ m (" Kapton150EN " that eastern beautiful Dupont (strain) makes), be arranged on the sputter equipment vacuum exhaust to 1 * 10
-1Behind the Pa, heat polyimide film with infrared heater, after the moisture in the film is removed, vacuum exhaust to 1 * 10
-4Pa.Then, import Ar gas, the handle assembly internal pressure remains on 0.3Pa, after the copper that forms the Ni-18 quality %Cr-10 quality %Mo layer of the Ni-7 quality %Cr layer of thickness 10nm, thickness 10nm, thickness 0.1 μ m on the single face of polyimide film with sputtering method successively is by rete, takes out from sputter equipment.Then, form the copper layer of thickness 8 μ m with galvanoplastic on by rete, obtain dielectric film metal film laminated body 1 at copper.
Make peel strength by resultant resin molding metal film laminated base plate 1 and measure sample and insulating reliability mensuration sample, supply with each test.
Because initial bonding strength is that 654N/m, heat-resisting peel strength are 576N/m, for well.Also have, the insulating reliability test is tested 3 samples, and any one sample still kept 10 after 1000 hours
6The resistance that Ω is above is for well.
The evaluation of etching, resin molding metal film laminated base plate 1 is cut into 3cm * 3cm,, adopts ferric chloride in aqueous solution (40 ° of Baumes of proportion as chemical etching liquor, 43 ℃ of temperature) carry out 2 minutes etching results in, all dissolve with the metal level on the visual observations insulating resin film.In addition, metal remained composition slightly on the top layer part of insulating resin film is used the microwave decomposition device, and the solution that constitutes with nitric acid 5ml and hydrogen peroxide 1ml dissolves, resulting solution metal composition carries out quantitative analysis with I CP-MS, and the result is 0.034 μ g/cm
2Few like this, for well.
It the results are summarized in table 1.
Remove the Ni-20 quality %Cr that the Ni-7 quality %Cr, the metal level C that use metal level B to adopt thickness 3nm adopt thickness 10nm, beyond the resin molding metal film laminated base plate 2 that forms metal film and obtain, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Embodiment 3
The resin molding metal film laminated base plate 3 that obtains except that using metal level B to adopt Ni, the metal level C of thickness 5nm to adopt the Ni-20 quality %Cr of thickness 20nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Embodiment 4
The resin molding metal film laminated base plate 4 that obtains except that using metal level B to adopt Cr, the metal level C of the Ni-7 quality % of thickness 20nm to adopt the Mo of the Ni-18 quality %Cr-10 quality % of thickness 10nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
The resin molding metal film laminated base plate 5 that obtains except that using metal level B to adopt Cr, the metal level C of the Ni-7 quality % of thickness 15nm to adopt the Ni-18 quality %Cr-10 quality %Mo of thickness 5nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Embodiment 6
The resin molding metal film laminated base plate 6 that obtains except that using metal level B to adopt Ni-14 quality %Cr, the metal level C of thickness 5nm to adopt the Ni-20 quality %Cr of thickness 20nm to form metal film, make sample similarly to Example 1, carry out various tests, it the results are shown in table 1.
Embodiment 7
The resin molding metal film laminated base plate 7 that obtains except that using metal level B to adopt Ni-7 quality %Cr, the metal level C of thickness 15nm to adopt the Ni-40 quality %Cr of thickness 25nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Embodiment 8
The resin molding metal film laminated base plate 8 that obtains except that using metal level B to adopt Ni-7 quality %Cr, the metal level C of thickness 10nm to adopt the Ni-70 quality %Cr of thickness 5nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Embodiment 9
The resin molding metal film laminated base plate 9 that obtains except that using metal level B to adopt Ni-5.6 quality %Cr-20 quality %Mo, the metal level C of thickness 10nm to adopt the Ni-20 quality %Cr of thickness 10nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
The resin molding metal film laminated base plate 10 that obtains except that using metal level B to adopt Ni-13 quality %V, the metal level C of thickness 10nm to adopt the Ni-20 quality %Cr of thickness 10nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Embodiment 11
The resin molding metal film laminated base plate 11 that obtains except that using metal level B to adopt Ni-7.5 quality %Ti, the metal level C of thickness 10nm to adopt the Ni-20 quality %Cr of thickness 10nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Embodiment 12
Remove the chemical etching liquor that the etching of resin molding metal film laminated base plate 1 is estimated, adopt hydrochloric acid acid chlorization copper liquor (HCl concentration: 1mol/l, CuCl
2: proportion 1.3, ORP:580mV, temperature: 40 ℃) in addition, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Comparative example 1
The resin molding metal film laminated base plate 13 that obtains except that using metal level B to adopt Ni-18 quality %Cr-10 quality %Mo, the metal level C of thickness 10nm to adopt the Ni-7 quality %Cr of thickness 10nm to form, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Comparative example 2
Remove to use metal level B adopt thickness 20nm Ni-18 quality %Cr-10 quality %Mo, metal level C is not set, beyond the resin molding metal film laminated base plate 14 that formation copper is obtained by rete D, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Comparative example 3
Remove Ni-20 quality %Cr that metal level B adopts thickness 20nm, metal level C is not set, form beyond the resin molding metal film laminated base plate 15 that copper obtained by rete D, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Comparative example 4
Remove to use metal level B adopt thickness 10nm Ni-7 quality %Cr, metal level C is not set, form beyond the resin molding metal film laminated base plate 16 that copper obtained by rete D, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Comparative example 5
The resin molding metal film laminated base plate 17 that obtains except that using metal level B to adopt Ni-7 quality %Cr, the metal level C of thickness 2nm to adopt the Ni-20 quality %Cr of thickness 15nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Comparative example 6
The resin molding metal film laminated base plate 18 that obtains except that using metal level B to adopt the Ni-7 quality %Cr alloy of thickness 10nm, Ni-18 quality %Cr-10 quality %Mo that metal level C adopts thickness 3nm to form metal film, make sample similarly to Example 1, carry out each test, it the results are shown in table 1.
Reference example
The resin molding metal film laminated base plate 19 that obtains except that using metal level B to adopt the Ni-7 quality %Cr alloy of thickness 5nm, Ni-20 quality %Cr that metal level C adopts thickness 100nm to form metal film, make sample similarly to Example 1, carry out the etching test, it the results are shown in table 1.
As table 1 as can be known, the example of the present invention 1～12 that embodiment 1～12 makes, the surface of insulating resin film A, lamination chromium content is lower than the metal level B of 15 quality %, on the surface of metal level B, the metal level C that lamination chromium content 15 quality % are above, on the surface of metal level C, lamination copper is had good peel strength by the printed wiring board of rete, metallic residue after the etching is also few, obtains high insulating reliability.
On the other hand, comparative example 1, the chromium content that the chromium content of metal level B surpasses 15 quality %, metal level C is lower than 15 quality %.Because the chromium content of metal level B surpasses 15 quality %, range estimation can be observed metallic residue after the etching, can not guarantee insulating reliability as can be known.
Comparative example 2, because only the chromium content metal level B that surpasses 15 quality % is a substrate metal layer, same with comparative example 1, range estimation can be observed metallic residue after the etching, can not guarantee insulating reliability as can be known.And comparative example 3 is same with comparative example 2, and only metal level B forms substrate metal layer, and the visual observations etching can be observed the surface of polyimide film and expose, and surpasses 0.15 μ g/cm when measuring the metallic residue amount
2, can not guarantee insulating reliability as can be known.
Comparative example 4, the chromium content of metal level B are 7 quality %, and etching and metallic residue amount are good, but because substrate metal layer only is made of metal level B, can not guarantee insulating reliability as can be known.
Comparative example 5, the chromium content of metal level B and metal level C is in the claim of the present invention, but because the thickness of metal level B is 2nm, even can satisfy the etching of range estimation, but the metallic residue amount is 0.15 μ g/cm
2, can not guarantee insulating reliability as can be known, comparative example 6, the chromium content of metal level B and metal level C is in the claim of the present invention, but the thickness of metal level C is 3nm, can not guarantee insulating reliability as can be known.
In the reference example, the chromium content of metal level B and metal level C is in the claim of the present invention, and only the thickness of metal level C reaches 100nm, and is thick more a lot of than general, but the etching of range estimation is good, and the metallic residue amount also is 0.035 μ g/cm
2Few like this, be good.
Claims (13)
1. printed wiring board, its be by the chemical etching processing selecting remove not the part that do not need that metal film is stacked in the above-mentioned metal film on the resin molding metal film laminated base plate that forms at least one surface of insulating resin film A by binding agent and form conductor wirings, it is characterized in that
The metal film that constitutes above-mentioned conductor wirings comprises: at the metal level B of the surperficial superimposed layer of above-mentioned insulating resin film A, this metal level B is made of nickel or is made of the nickel-chromium alloy that contains the nickel more than the 70 quality % and be lower than the chromium of 15 quality %;
At the metal level C of the surperficial lamination of above-mentioned metal level B, this metal level C comprises the alloy nickeliferous and chromium that 15 quality % are above;
And, at the copper of the thickness 10nm～35 μ m of the surperficial lamination of above-mentioned metal level C by rete D,
Only use the above-mentioned copper of etching not needed part by what the chemical etching liquor of rete D came that optionally etching removes described metal film.
2. according to the printed wiring board described in the claim 1, it is characterized in that, lamination has above-mentioned metal level B, metal level C and copper by the conductor wirings of the above-mentioned metal film of rete D to comprising successively, adopt ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor to carry out the level of residue that back metal remained on above-mentioned insulating resin film A is handled in chemical etching, the per unit area of above-mentioned relatively insulating resin film A is 0.13 μ g/cm
2Below.
3. printed wiring board, its be by the chemical etching processing selecting remove not the part that do not need that metal film is stacked in the above-mentioned metal film on the resin molding metal film laminated base plate that forms at least one surface of insulating resin film A by binding agent and form conductor wirings, it is characterized in that
The metal film that constitutes above-mentioned conductor wirings comprises: at the metal level B of the surperficial superimposed layer of above-mentioned insulating resin film A, above-mentioned metal level B comprises and contains that vanadium 13 quality % are following, titanium 8 quality % following, below the molybdenum 20 quality %, surplus is made of nickel and the unavoidable impurities below the 1 quality %, perhaps be made of with the nickel-chromium alloy and the unavoidable impurities below the 1 quality % that are lower than 15 quality % chromium the nickel that contains more than the 70 quality %, thickness is 3～20nm;
At the metal level C of the surperficial lamination of above-mentioned metal level B, this metal level C comprises the alloy nickeliferous and chromium that 15 quality % are above;
And, at the copper of the thickness 10nm～35 μ m of the surperficial lamination of above-mentioned metal level C by rete D,
Only use the above-mentioned copper of etching not needed part by what the chemical etching liquor of rete D came that optionally etching removes described metal film.
4. according to the printed wiring board described in the claim 3, it is characterized in that, lamination has above-mentioned metal level B, metal level C and copper by the conductor wirings of the above-mentioned metal film of rete D to comprising successively, adopt ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor to carry out the level of residue that back metal remained on above-mentioned insulating resin film A is handled in chemical etching, the per unit area of above-mentioned relatively insulating resin film A is 0.13 μ g/cm
2Below.
5. according to any one described printed wiring board in the claim 1～4, it is characterized in that, above-mentioned metal level C contains above, nickel 0.01～85 quality % of chromium 15 quality %, the alloy of the unavoidable impurities that 1 quality % is following, or contain that chromium 15 quality % are above, the alloy of unavoidable impurities that nickel 0.01～85 quality %, molybdenum 0.01～40 quality % and 1 quality % are following, thickness 5～37nm, or be aggregated in below the 40nm more than the thickness 5nm and with metal level B.
6. according to any one described printed wiring board in the claim 1～4, it is characterized in that above-mentioned chemical etching liquor does not contain manganese and cyanide.
7. according to any one described printed wiring board in the claim 1～4, it is characterized in that above-mentioned chemical etching liquor is ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor.
8. according to the printed wiring board described in claim 1 or 2, it is characterized in that above-mentioned insulating resin film A is the resin molding more than a kind that is selected from polyimide film, polyamide-based film, polyesters film, polytetrafluoroethylene class film, polyphenylene sulfide ethers film, PEN class film, liquid crystal polymer class film.
9. the manufacture method of printed wiring board, its be by the chemical etching processing selecting remove not the part that do not need that metal film is stacked in the above-mentioned metal film on the resin molding metal film laminated base plate that forms at least one surface of insulating resin film A by binding agent and form conductor wirings, it is characterized in that
The above-mentioned resin molding metal film of following formation laminated base plate: on the surface of above-mentioned insulating resin film A, adopt the dry type galvanoplastic to form nickel or with the metal level B of nickel as principal component, then, surface at above-mentioned metal level B, adopt the dry type galvanoplastic to form alloy with nickeliferous and chromium more than the 15 quality %, or it is nickeliferous, behind the metal level C that the alloy of the chromium that molybdenum and 15 quality % are above constitutes, form the metal film that the copper by thickness 10nm～35 μ m is formed by rete D lamination on the surface of above-mentioned metal level C, above-mentioned metal film adopts a kind of etching solution optionally to remove, and forms conductor wirings.
10. according to the manufacture method of the printed wiring board described in the claim 9, it is characterized in that above-mentioned chemical etching liquor does not contain manganese and cyanide.
11. the manufacture method according to the printed wiring board described in the claim 9 is characterized in that, above-mentioned chemical etching liquor is ferric chloride in aqueous solution or hydrochloric acid acid chlorization copper liquor.
12. the manufacture method according to the printed wiring board described in the claim 9 is characterized in that, above-mentioned copper is adopted galvanoplastic to form the copper layer on the copper laminar surface that adopts the dry type galvanoplastic to form by rete D and obtains.
13. the manufacture method according to the printed wiring board described in claim 9 or 12 is characterized in that, above-mentioned dry type galvanoplastic are any of vacuum vapour deposition, sputtering method or ion plating method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008137169 | 2008-05-26 | ||
| JP2008137169A JP5517019B2 (en) | 2008-05-26 | 2008-05-26 | Printed wiring board and method for manufacturing printed wiring board |
| JP2008-137169 | 2008-05-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101594737A CN101594737A (en) | 2009-12-02 |
| CN101594737B true CN101594737B (en) | 2011-09-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102028481A Active CN101594737B (en) | 2008-05-26 | 2009-05-26 | Printing wiring cardinal plate and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP5517019B2 (en) |
| KR (1) | KR101086141B1 (en) |
| CN (1) | CN101594737B (en) |
| TW (1) | TW201006337A (en) |
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|---|---|---|---|---|
| KR101886297B1 (en) * | 2011-11-09 | 2018-08-09 | 엘지이노텍 주식회사 | Thin Multi Layer Printed Circuit Board using PI Core and Manufaturing mathod therefor |
| KR20150008703A (en) * | 2013-07-15 | 2015-01-23 | (주)이엔에이치 | Electrostatic capacity type touch screen panel and method for fabricating the same |
| CN104427755A (en) * | 2013-08-23 | 2015-03-18 | 富葵精密组件(深圳)有限公司 | Flexible circuit board and manufacturing method thereof |
| CN107107554B (en) * | 2015-01-10 | 2020-04-03 | 三菱化学株式会社 | Double-sided metal laminated film |
| WO2017183489A1 (en) * | 2016-04-18 | 2017-10-26 | 住友金属鉱山株式会社 | Conductive substrate and method for producing conductive substrate |
| JP7049759B2 (en) * | 2016-07-12 | 2022-04-07 | 住友金属鉱山株式会社 | Laminated board, conductive board, method of manufacturing laminated board, method of manufacturing conductive board |
| CN111472000B (en) * | 2020-04-15 | 2021-07-27 | 苏州华星光电技术有限公司 | Etching method of copper-molybdenum film layer and array substrate |
| US11756797B2 (en) | 2020-04-15 | 2023-09-12 | Tcl China Star Optoelectronics Technology Co., Ltd. | Etching method of copper-molybdenum film and array substrate |
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| CN1899002A (en) * | 2003-12-26 | 2007-01-17 | 三井金属矿业株式会社 | Printed-circuit board, its manufacturing method and circuit device |
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| JP2002252257A (en) * | 2000-12-18 | 2002-09-06 | Mitsui Mining & Smelting Co Ltd | Semiconductor carrier film and its manufacturing method |
| JP2003318532A (en) * | 2002-04-24 | 2003-11-07 | Toyo Metallizing Co Ltd | Flexible printed wiring board |
| JP4008388B2 (en) * | 2003-06-30 | 2007-11-14 | シャープ株式会社 | Film for semiconductor carrier, semiconductor device using the same, and liquid crystal module |
| JP2007069561A (en) * | 2005-09-09 | 2007-03-22 | Sumitomo Metal Mining Co Ltd | Two-layered flexible substrate and manufacturing method therefor |
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| CN1899002A (en) * | 2003-12-26 | 2007-01-17 | 三井金属矿业株式会社 | Printed-circuit board, its manufacturing method and circuit device |
Non-Patent Citations (3)
| Title |
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| JP特开2005-23240A 2005.01.27 |
| JP特开平6-120630A 1994.04.28 |
| JP特开平8-139448A 1996.05.31 |
Also Published As
| Publication number | Publication date |
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| JP5517019B2 (en) | 2014-06-11 |
| JP2009283872A (en) | 2009-12-03 |
| TW201006337A (en) | 2010-02-01 |
| KR20090122881A (en) | 2009-12-01 |
| CN101594737A (en) | 2009-12-02 |
| KR101086141B1 (en) | 2011-11-25 |
| TWI362911B (en) | 2012-04-21 |
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