WO2010087268A1 - 電子回路用の圧延銅箔又は電解銅箔及びこれらを用いた電子回路の形成方法 - Google Patents
電子回路用の圧延銅箔又は電解銅箔及びこれらを用いた電子回路の形成方法 Download PDFInfo
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- WO2010087268A1 WO2010087268A1 PCT/JP2010/050707 JP2010050707W WO2010087268A1 WO 2010087268 A1 WO2010087268 A1 WO 2010087268A1 JP 2010050707 W JP2010050707 W JP 2010050707W WO 2010087268 A1 WO2010087268 A1 WO 2010087268A1
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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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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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
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
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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
- 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
- H05K2201/0338—Layered conductor, e.g. layered metal substrate, layered finish layer, layered thin film adhesion layer
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
- Y10T428/12438—Composite
Definitions
- the present invention relates to a rolled copper foil or electrolytic copper foil for an electronic circuit that forms a circuit by etching, and a method for forming an electronic circuit using these.
- Copper foil for printed circuits is widely used in electronic and electrical equipment, but this copper foil for printed circuits is generally used with a base material such as a synthetic resin board or film with or without an adhesive.
- a copper-clad laminate is produced by bonding under high temperature and high pressure, and then a circuit is printed by a resist coating and exposure process to form the desired circuit, followed by an etching process that removes unnecessary portions of the copper foil. Further, various elements are soldered to form a printed circuit for an electro device.
- Copper foils used in such printed circuits are broadly divided into electrolytic copper foils and rolled copper foils depending on the type of manufacturing method, both of which are used according to the types of printed circuit boards and quality requirements. Yes. These copper foils have a surface to be bonded to the resin base material and a non-bonded surface, and are each subjected to a special surface treatment (treating treatment). In some cases, the copper foil used for the inner layer of the multilayer printed wiring board has a function of adhering to the resin on both sides (double treatment).
- electrolytic copper foil is produced by electrodepositing copper onto a rotating drum and continuously peeling it to produce a copper foil.
- the surface that contacts the rotating drum is a glossy surface and the opposite surface. Has many irregularities (rough surface).
- a thin plating layer may be formed in order to prevent such copper particles from falling off while enhancing such unevenness.
- a series of these steps is called roughening treatment.
- Such a roughening treatment is required not only for the electrolytic copper foil but also for the rolled copper foil, and the same roughening treatment is also carried out for the rolled copper foil.
- Copper-clad laminates are manufactured by hot pressing and continuous processes using the above copper foil.
- this laminated plate is produced by synthesize epoxy resin, impregnate paper substrate with phenol resin, and dry it to produce a prepreg, and further combine this prepreg and copper foil with a combination press. It is manufactured through processes such as hot pressing.
- the copper-clad laminate produced in this way is printed with a resist coating and exposure process to form the desired circuit, and further undergoes an etching process to remove unnecessary portions of the copper foil.
- the circuit is formed, there is a problem that the circuit does not have the intended width. That is, the copper portion of the etched copper foil circuit is etched away from the surface of the copper foil, that is, toward the resin layer (sagging). Normally, the angle of the side of the circuit is “sag” around 50 °, and when a particularly large “sag” occurs, the copper circuit may be short-circuited near the resin substrate, resulting in a defective product. 2).
- the present inventors have proposed a copper foil in which a metal or alloy layer having a slower etching rate than copper is formed on the copper foil on the etching surface side (see Patent Document 1).
- the metal or alloy includes nickel, cobalt, and alloys thereof.
- the etching solution penetrates from the resist coating side, that is, from the surface of the copper foil, so if there is a metal or alloy layer with a slow etching rate directly under the resist, the etching of the copper foil portion in the vicinity is suppressed.
- the “sag” is reduced, and an effect that a circuit with a more uniform width can be formed, and the angle of the circuit side surface is 63 ° to 75 °, compared with the conventional technology. It is possible to form a steep circuit, and it can be said that a great progress has been made.
- the thickness of the metal or alloy layer having a slow etching rate as much as possible in order to shorten the etching removal time as much as possible and to remove it cleanly.
- the underlying copper layer is oxidized (discolored so it is commonly referred to as “burning”), resulting in poor resist coating properties (uniformity, adhesion) and interfacial oxides during etching. Since there is a problem that defects such as etching property in pattern etching, short circuit, and controllability of circuit width occur due to excessive etching or the like, further improvement or replacement with another material is required.
- Patent Document 1 Japanese Patent Laid-Open No. 2002-176242
- Patent Document 2 Japanese Patent Laid-Open No. 2006-261270
- an object of the present invention is to obtain a rolled copper foil or an electrolytic copper foil for an electronic circuit and a method for forming an electronic circuit using these, which can shorten the circuit formation time by etching as much as possible and prevent the occurrence of a short circuit or a defective circuit width. To do.
- the inventors of the present invention have formed a metal layer composed of at least one of platinum group, gold, and silver or an alloy layer mainly composed of these on the etching surface of the rolled copper foil or the electrolytic copper foil, By adjusting the etching rate in the thickness direction of the copper foil, a steep copper circuit with less sagging than nickel and cobalt, which has been known so far, is formed, and a uniform circuit with no sagging is formed. I got the knowledge that I can do it.
- the present invention is based on this finding. 1.
- rolled copper foil or electrolytic copper foil for electronic circuits that perform circuit formation by etching, any of platinum group, gold, and silver having a lower etching rate than copper formed on the etched surface side of the rolled copper foil or electrolytic copper foil 1.
- a rolled copper foil or an electrolytic copper foil for an electronic circuit comprising a metal layer comprising one or more metals or an alloy layer mainly composed of these metal layers.
- the layer (A) having a lower etching rate than copper is a platinum alloy, and the alloy component contained in the platinum alloy is at least one or more selected from zinc, phosphorus, boron, molybdenum, tungsten, nickel, iron or cobalt. 3.
- the present invention also provides: 5). 5.
- the heat-resistant layer (B) is a layer made of either zinc or a zinc alloy, and the zinc alloy is an alloy element selected from the group consisting of platinum group elements, gold, palladium group elements and silver.
- the present invention also provides: 7).
- the present invention provides 8).
- the etching surface side of the copper foil is made of a platinum group, gold, or silver having a lower etching rate than copper.
- Form any one metal layer or alloy layer containing them as a main component and etch the copper foil with an aqueous ferric chloride solution or an aqueous cupric chloride solution to remove unnecessary portions of copper 8.
- the etching rate is obtained by using the rolled copper foil or the electrolytic copper foil for electronic circuits described in 1 to 12 above.
- a copper-clad laminate is prepared using the lower layer (A) as an etching surface, the copper foil is etched using a ferric chloride aqueous solution or a cupric chloride aqueous solution, and unnecessary portions of copper are removed.
- a method for forming an electronic circuit is provided.
- the present invention realizes and provides a more uniform circuit with a desired circuit width by forming a circuit with a small “sag” by etching when forming a circuit by etching the copper foil of the copper-clad laminate. It has the effect that it can be done. As a result, it is possible to provide a rolled copper foil or an electrolytic copper foil for an electronic circuit that can prevent occurrence of a short circuit or a defective circuit width, and it is possible to provide an excellent method for forming an electronic circuit.
- the rolled copper foil or electrolytic copper foil for electronic circuit that forms a circuit by etching according to the present invention is a platinum group, gold, silver having a lower etching rate than copper formed on the etched surface side of the rolled copper foil or electrolytic copper foil.
- a copper-clad laminate is formed using the copper foil thus produced.
- This copper foil can be applied to both electrolytic copper foil and rolled copper foil.
- electrolytic copper foil although it can apply similarly to a rough surface (M surface) or a glossy surface (S surface), the surface to be etched usually uses the glossy surface side.
- the rolled copper foils there are high-purity copper foils or alloy copper foils with improved strength, but the present invention encompasses all these copper foils.
- a resist is applied to the surface of the copper-clad laminate, the pattern is exposed with a mask, and developed to form a resist pattern soaked in an etching solution.
- Etching of the copper foil on the resist side is a metal layer composed of one or more of platinum group, gold, and silver, or an alloy containing these as a main component, which is near the resist portion on the copper foil. Is a portion of the copper layer away from this layer at a speed higher than the rate at which the vicinity of the metal layer composed of one or more of the platinum group, gold and silver or the alloy layer containing these as a main component is etched. As the etching of the layers progresses, the copper circuit progresses almost vertically, and a rectangular copper foil circuit is formed.
- the metal layer composed of at least one of platinum group, gold, and silver is preferably 50 ⁇ g / dm 2 or more and 1000 ⁇ g / dm 2 or less. If it is less than 50 ⁇ g / dm 2 , the copper circuit is etched almost vertically, and the effect of the layer on which the rectangular copper foil circuit is formed is small, and if it exceeds 1000 ⁇ g / dm 2 , the effect that the rectangular copper foil circuit is formed. On the other hand, when the thickness of the noble metal becomes thicker, the noble metal is basically not dissolved in the aqueous ferric chloride solution (etching solution), and therefore cannot be etched. Further, when this layer is removed after the circuit is formed, it is desirable that the thinner layer is easier to remove.
- etching solution such as an aqueous solution of cupric chloride or an aqueous solution of ferric chloride
- a metal composed of at least one of a platinum group, gold, and silver
- the etching rate of this layer or the alloy layer (A) containing these as a main component is sufficiently smaller than that of copper, and therefore has an effect of improving the etching factor.
- platinum or a platinum alloy is particularly effective. Any alloy component contained in the platinum alloy can be used as long as it is a generally known alloy. For example, it can be confirmed that an alloy with at least one element selected from zinc, phosphorus, boron, molybdenum, tungsten, nickel, iron or cobalt has an etching rate slower than copper and has an effect of improving an etching factor.
- a heat-resistant layer (B) can be further formed on or below a metal layer composed of at least one of platinum group, gold, and silver or an alloy layer (A) containing these as a main component.
- the heat-resistant layer is preferably zinc or a zinc alloy, and the zinc alloy preferably contains one or two kinds of metals composed of one or more of platinum group, gold, and silver as an alloy element.
- a chromium layer or a chromate layer and / or a silane-treated layer is further formed on the metal layer composed of at least one of the platinum group, gold, and silver or the alloy layer (A) containing these as a main component. Can do.
- the total zinc content contained in the heat-resistant layer (B) and the layer (A) is 30 ⁇ g / dm 2 to 1000 ⁇ g / in metal zinc conversion.
- dm 2 is desirable. If it is less than 30 ⁇ g / dm 2 , there is no effect on the oxidation resistance (improving burn resistance). If it exceeds 1000 [mu] g / dm 2, an effect is saturated, so would not offset the effect of the layer (A), a metal zinc terms, it is preferable to 30 ⁇ g / dm 2 ⁇ 1000 ⁇ g / dm 2.
- chromium amount when providing the said chromium layer or chromate layer, chromium amount shall be 100 microgram / dm ⁇ 2 > or less in conversion of metal chromium. Moreover, when forming the said silane treatment layer, it is desirable that it is 20 microgram / dm ⁇ 2 > or less in conversion of silicon simple substance. This is to suppress the difference in etching rate with respect to the pattern etching solution.
- the present invention relates to a method for forming an electronic circuit by etching a copper clad laminate made of rolled copper foil or electrolytic copper foil, and having a lower etching rate than copper on the etched surface side of the copper foil.
- the copper foil is etched using a ferric chloride aqueous solution or a cupric chloride aqueous solution.
- Any etching solution can be used, but an aqueous ferric chloride solution is particularly effective. This is because the fine circuit takes time to etch, but the ferric chloride aqueous solution has a higher etching rate than the cupric chloride aqueous solution.
- the present invention provides a method for forming an electronic circuit by etching a copper-clad laminate comprising a rolled copper foil or an electrolytic copper foil, wherein the rolled copper foil or electrolytic copper for an electronic circuit as described in 1 to 12 above.
- a method of forming an electronic circuit comprising: forming a copper circuit by etching the copper foil using a ferric chloride aqueous solution or a cupric chloride aqueous solution and removing unnecessary portions of copper. , Provide. In this method, any of the above-described rolled copper foil or electrolytic copper foil for electronic circuits can be used.
- Platinum group, gold, silver layer of any one of these metals or alloys containing them as a main component platinum-zinc alloy, platinum-phosphorus alloy, platinum-molybdenum alloy, platinum-tungsten alloy, platinum-iron alloy, platinum -Cobalt alloys and the like can all be formed by sputtering. Further, any of them may be a wet plating method such as electroplating or electroless plating.
- K 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ) Cr 40 to 300 g / L H 2 SO 4 : 0.5 to 10.0 g / L Bath temperature: 40-60 ° C Current density D k : 0.01 to 50 A / dm 2 Time: 1 to 100 seconds
- Anode Pt-plated Ti plate, stainless steel plate, lead plate, etc.
- silane treatment Select from various series of silanes such as: Concentration: 0.01 wt% to 5 wt% Type: Olefin-based silane, epoxy-based silane, acrylic-based silane, amino-based silane, mercapto-based silane A silane dissolved in alcohol is diluted with water to a predetermined concentration and applied to the copper foil surface.
- Platinum amount analysis method In order to analyze the platinum-treated surface, the opposite surface is press-made with FR-4 resin and masked. The sample is dissolved in aqua regia until the surface treatment film is dissolved, the solution in the beaker is diluted, and quantitative analysis of platinum is performed by atomic absorption spectrometry. Analysis of other platinum groups, gold, and silver can be similarly performed.
- the copper foil of the copper-clad laminate When etching the copper foil of the copper-clad laminate, after forming a metal or alloy layer having a slower etching rate than copper on the etching surface side of the copper foil, the copper foil is used with a cupric chloride aqueous solution or a ferric chloride aqueous solution. Etch the foil.
- the etching factor can be 3.7 or more, that is, the inclination angle of the circuit side surface between the etching side surface of the copper foil circuit and the resin substrate can be 75 degrees or more. Although a particularly desirable inclination angle is in the range of 80 to 95 degrees, the present invention can realize this, and thereby, a rectangular etching circuit without sagging can be formed.
- Example 1 A rolled copper foil having a foil thickness of 18 ⁇ m was used. The surface roughness Rz of this rolled copper foil was 0.7 ⁇ m. 200 ⁇ g / dm 2 of platinum was formed on the rolled copper foil under the above platinum sputtering conditions. Further, the copper foil was bonded to the resin substrate with the opposite side of the surface provided with the platinum layer as the bonding surface.
- Etching conditions Ferric chloride aqueous solution: (37 wt%, Baume degree: 40 °) Liquid temperature: 50 ° C Spray pressure: 0.15 MPa
- the etching factor is defined as the point of intersection between the perpendicular line from the upper surface of the copper foil and the resin substrate, assuming that the circuit is etched vertically when etching is performed in a divergent manner (when sagging occurs).
- the ratio of this a to the thickness b of the copper foil: b / a is shown.
- the larger this value the greater the inclination angle and the etching. It means that no residue remains and dripping is reduced.
- Etching was performed under the above conditions. As a result, etching progressed substantially vertically from the resist side of the side surface of the copper circuit toward the resin substrate side, and a rectangular copper foil circuit was formed. Next, the inclination angle of the etched copper foil was measured (note that this is the minimum value of the inclination angle at a circuit length of 100 ⁇ m). In addition, the etching factor was examined. The results are shown in Table 1. As shown in Table 1, the average value of the left and right inclination angles was 81 degrees, and a substantially rectangular copper foil circuit was formed. The etching factor was 6.2 at a pitch of 50 ⁇ m. As a result, a good etching circuit was obtained as shown in FIG.
- Example 2 Similarly to Example 1, a rolled copper foil having a foil thickness of 18 ⁇ m was used. The surface roughness Rz of this rolled copper foil was 0.7 ⁇ m. Platinum 500 ⁇ g / dm 2 was formed on the rolled copper foil under the platinum sputtering conditions. Further, the copper foil was bonded to the resin substrate with the opposite side of the surface provided with the platinum layer as the bonding surface.
- Etching conditions Ferric chloride aqueous solution: (37 wt%, Baume degree: 40 °) Liquid temperature: 50 ° C Spray pressure: 0.15 MPa
- the etching factor measurement conditions are the same as in Example 1 above, and are therefore omitted. Etching was performed under the above conditions. As a result, etching progressed substantially vertically from the resist side of the side surface of the copper circuit toward the resin substrate side, and a rectangular copper foil circuit was formed. Next, the inclination angle of the etched copper foil was measured (note that this is the minimum value of the inclination angle at a circuit length of 100 ⁇ m). In addition, the etching factor was examined. The results are shown in Table 1. As shown in Table 1, the average value of the left and right inclination angles was 82 degrees, and a substantially rectangular copper foil circuit was formed. The etching factor was 7 at a pitch of 50 ⁇ m. As a result, a good etching circuit was obtained.
- Example 3 In this example, a rolled copper foil having a foil thickness of 9 ⁇ m was used. The surface roughness Rz of this rolled copper foil was 0.7 ⁇ m. Platinum 900 ⁇ g / dm 2 was formed on the rolled copper foil under the platinum sputtering conditions. Further, the copper foil was bonded to the resin substrate with the opposite side of the surface provided with the platinum layer as the bonding surface.
- Etching conditions Ferric chloride aqueous solution: (37 wt%, Baume degree: 40 °) Liquid temperature: 50 ° C Spray pressure: 0.15 MPa
- the average value of the left and right inclination angles was 81 degrees, and a substantially rectangular copper foil circuit was formed.
- the etching factor was 6.5 at a pitch of 30 ⁇ m. As a result, a good etching circuit was obtained.
- Example 4 an electrolytic copper foil having a foil thickness of 5 ⁇ m was used.
- the surface roughness Rz of this electrolytic copper foil was 3 ⁇ m.
- Platinum 75 ⁇ g / dm 2 was formed on the electrolytic copper foil under the platinum sputtering conditions. Further, the copper foil was bonded to the resin substrate with the opposite side of the surface provided with the platinum layer as the bonding surface.
- Etching conditions Ferric chloride aqueous solution: (37 wt%, Baume degree: 40 °) Liquid temperature: 50 ° C Spray pressure: 0.15 MPa
- the average value of the left and right inclination angles was 81 degrees, and a substantially rectangular copper foil circuit was formed.
- the etching factor was 6.5 at a pitch of 30 ⁇ m. As a result, a good etching circuit was obtained.
- Example 5 Similarly to Example 1, a rolled copper foil having a foil thickness of 18 ⁇ m was used. The surface roughness Rz of this rolled copper foil was 0.7 ⁇ m. On this rolled copper foil, gold 450 ⁇ g / dm 2 was formed under the above gold sputtering conditions. Further, the copper foil was bonded to the resin substrate with the opposite side of the surface provided with the gold layer as the bonding surface.
- Etching conditions Ferric chloride aqueous solution: (37 wt%, Baume degree: 40 °) Liquid temperature: 50 ° C Spray pressure: 0.15 MPa
- the etching factor measurement conditions are the same as in Example 1 above, and are therefore omitted. Etching was performed under the above conditions. As a result, etching progressed substantially vertically from the resist side of the side surface of the copper circuit toward the resin substrate side, and a rectangular copper foil circuit was formed. Next, the inclination angle of the etched copper foil was measured (note that this is the minimum value of the inclination angle at a circuit length of 100 ⁇ m). In addition, the etching factor was examined. The results are shown in Table 1. As shown in Table 1, the average value of the left and right inclination angles was 82 degrees, and a substantially rectangular copper foil circuit was formed. The etching factor was 6.9 at a pitch of 50 ⁇ m. As a result, a good etching circuit was obtained.
- Example 6 Similarly to Example 1, a rolled copper foil having a foil thickness of 18 ⁇ m was used. The surface roughness Rz of this rolled copper foil was 0.7 ⁇ m. Palladium 550 ⁇ g / dm 2 was formed on the rolled copper foil under the above palladium sputtering conditions. Further, the copper foil was bonded to the resin substrate with the opposite side of the surface provided with the palladium layer as the bonding surface.
- Etching conditions Ferric chloride aqueous solution: (37 wt%, Baume degree: 40 °) Liquid temperature: 50 ° C Spray pressure: 0.15 MPa
- the etching factor measurement conditions are the same as in Example 1 above, and are therefore omitted. Etching was performed under the above conditions. As a result, etching progressed substantially vertically from the resist side of the side surface of the copper circuit toward the resin substrate side, and a rectangular copper foil circuit was formed. Next, the inclination angle of the etched copper foil was measured (note that this is the minimum value of the inclination angle at a circuit length of 100 ⁇ m). In addition, the etching factor was examined. The results are shown in Table 1. As shown in Table 1, the average value of the left and right inclination angles was 82 degrees, and a substantially rectangular copper foil circuit was formed. The etching factor was 6.8 at a pitch of 50 ⁇ m. As a result, a good etching circuit was obtained.
- Example 7 Similarly to Example 1, a rolled copper foil having a foil thickness of 18 ⁇ m was used. The surface roughness Rz of this rolled copper foil was 0.7 ⁇ m. 95% Pt-5% Pd 300 ⁇ g / dm 2 was formed on the rolled copper foil under the above 95% Pt-5% Pd sputtering conditions. Further, the copper foil was bonded to the resin substrate with the opposite side of the surface provided with the 95% Pt-5% Pd layer as the bonding surface.
- Etching conditions Ferric chloride aqueous solution: (37 wt%, Baume degree: 40 °) Liquid temperature: 50 ° C Spray pressure: 0.15 MPa
- the etching factor measurement conditions are the same as in Example 1 above, and are therefore omitted. Etching was performed under the above conditions. As a result, etching progressed substantially vertically from the resist side of the side surface of the copper circuit toward the resin substrate side, and a rectangular copper foil circuit was formed. Next, the inclination angle of the etched copper foil was measured (note that this is the minimum value of the inclination angle at a circuit length of 100 ⁇ m). In addition, the etching factor was examined. The results are shown in Table 1. As shown in Table 1, the average value of the left and right inclination angles was 82 degrees, and a substantially rectangular copper foil circuit was formed. The etching factor was 6.8 at a pitch of 50 ⁇ m. As a result, a good etching circuit was obtained.
- Example 8 Similarly to Example 1, a rolled copper foil having a foil thickness of 18 ⁇ m was used. The surface roughness Rz of this rolled copper foil was 0.7 ⁇ m. On this rolled copper foil, an Au 190 ⁇ g / dm 2 (bilayer) sputter layer was formed on Pt 210 ⁇ g / dm 2 under the above sputtering conditions. Further, the copper foil was bonded to the resin substrate with the opposite side of the surface provided with the two layers of sputter layers as the bonding surface.
- Etching conditions Ferric chloride aqueous solution: (37 wt%, Baume degree: 40 °) Liquid temperature: 50 ° C Spray pressure: 0.15 MPa
- the etching factor measurement conditions are the same as in Example 1 above, and are therefore omitted. Etching was performed under the above conditions. As a result, etching progressed substantially vertically from the resist side of the side surface of the copper circuit toward the resin substrate side, and a rectangular copper foil circuit was formed. Next, the inclination angle of the etched copper foil was measured (note that this is the minimum value of the inclination angle at a circuit length of 100 ⁇ m). In addition, the etching factor was examined. The results are shown in Table 1. As shown in Table 1, the average value of the left and right inclination angles was 82 degrees, and a substantially rectangular copper foil circuit was formed. The etching factor was 6.9 at a pitch of 50 ⁇ m. As a result, a good etching circuit was obtained.
- Example 2 45 ⁇ g / dm 2 and 900 ⁇ g / dm 2 are formed on the same rolled copper foil as in Example 1 (platinum is 200 ⁇ g / dm 2 under platinum sputtering conditions on 18 ⁇ m rolled copper foil) under the galvanizing conditions, and oxidation resistance
- the property (discoloration improvement) was confirmed by the following test method, and good results were obtained.
- (Yake test) In an air atmosphere, hold at 240 ° C. for 10 minutes and check for discoloration. This is a condition assuming a condition in which the copper foil provided with the zinc plating layer and the nickel plating layer is bonded to the resin substrate as an etching side to form a copper-clad laminate.
- Example 1 An 18 ⁇ m rolled copper foil was used. The surface roughness Rz of this rolled copper foil was 0.7 ⁇ m. A 1200 ⁇ g / dm 2 nickel plating layer was formed on the rolled copper foil under the above nickel plating conditions and adhered to the resin substrate. Next, in the same manner as in Example 1, ten circuits were printed by a resist coating and exposure process, and an etching process for removing unnecessary portions of the copper foil was performed. Except for the circuit formation conditions, the etching conditions, the measurement conditions for the etching factor, and the burn test were performed in the same manner as in Example 1. Description of the same conditions as in Example 1 is omitted.
- Etching was performed under the above conditions. As a result, the etching progressed from the resist side to the resin substrate side of the side surface of the copper circuit, but a copper foil circuit was formed spreading out at the end. Next, the inclination angle of the etched copper foil was measured (note that this is the minimum value of the inclination angle at a circuit length of 100 ⁇ m). The above results are similarly shown in Table 2. As shown in Table 2, the average value of the left and right inclination angles was 52 degrees, and a trapezoidal copper foil circuit with poor etching properties was formed. The etching factor was 1.3 at a 50 ⁇ m pitch, resulting in failure.
- Etching was performed under the above conditions. As a result, the average value of the left and right inclination angles was 74 degrees, and a substantially rectangular copper foil circuit was formed.
- the etching factor was 3.5 at a 30 ⁇ m pitch. (It is the minimum value of the tilt angle at a circuit length of 100 ⁇ m). The results are shown in Table 2. Thus, an etching circuit having a substantially rectangular shape but a slightly small inclination angle and a slightly small etching factor was obtained.
- the present invention has an effect that a circuit with a desired circuit width can be formed more uniformly when forming a circuit by etching a copper foil, preventing the occurrence of sagging due to etching, and reducing the time for circuit formation by etching. It is possible to shorten the etching rate, and pattern etching is performed by a metal layer composed of at least one of platinum group, gold, and silver having a lower etching rate than copper or an alloy layer containing these as a main component. Since the etching property can be improved and the occurrence of short circuits and circuit width defects can be prevented, it can be used as a copper-clad laminate (for rigid and flexible) and used for forming electronic circuits on printed circuit boards.
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Abstract
Description
これらの銅箔は、樹脂基材と接着される面と非接着面があり、それぞれ特殊な表面処理(トリート処理)が施されている。また、多層プリント配線板の内層に使用する銅箔のように両面に樹脂との接着機能をもつようにされる(ダブルトリート処理)場合もある。
さらに、このような凹凸を増強した上に銅粒子の脱落を防止するために薄いめっき層を形成する場合もある。これらの一連の工程を粗化処理と呼んでいる。このような粗化処理は、電解銅箔に限らず圧延銅箔でも要求されることであり、同様な粗化処理が圧延銅箔においても実施されている。
それは、エッチング後の銅箔回路の銅部分が、銅箔の表面から下に向かって、すなわち樹脂層に向かって、末広がりにエッチングされる(ダレを発生する)ことである。通常は、回路側面の角度が50°前後の「ダレ」となり、特に大きな「ダレ」が発生した場合には、樹脂基板近傍で銅回路が短絡し、不良品となる場合もある(後述する図2参照)。
しかし、この場合は、すでに所定の幅寸法に至っている箇所があると、そこがさらにエッチングされることになるので、その銅箔部分の回路幅がそれだけ狭くなり、回路設計上目的とする均一な線幅(回路幅)が得られず、特にその部分(細線化された部分)で発熱し、場合によっては断線するという問題が発生する。
電子回路のファインパターン化がさらに進行する中で、現在もなお、このようなエッチング不良による問題がより強く現れ、回路形成上で、大きな問題となっている。
回路設計に際しては、レジスト塗布側、すなわち銅箔の表面からエッチング液が浸透するので、レジスト直下にエッチング速度が遅い金属又は合金層があれば、その近傍の銅箔部分のエッチングが抑制され、他の銅箔部分のエッチングが進行するので、「ダレ」が減少し、より均一な幅の回路が形成できるという効果をもたらし、回路側面の角度が63°~75°という、従来技術と比較して急峻な回路形成が可能となり、大きな進歩があったと言える。
また、さらに改良を進める段階で、問題がいくつか浮上した。それは回路を形成した後、レジンの除去、さらには「ダレ」防止用に形成したエッチング速度が遅い金属又は合金層をソフトエッチングにより除去する必要があること、さらには前記エッチング速度が遅い金属又は合金層付き銅箔を、銅張積層板とし電子回路を形成する工程で、樹脂の貼付けなどの工程で銅箔を、高温処理する必要があることである。
特許文献2:特開2006-261270号公報
1.エッチングにより回路形成を行う電子回路用の圧延銅箔又は電解銅箔において、該圧延銅箔又は電解銅箔のエッチング面側に形成された銅よりもエッチングレートの低い白金族、金、銀のいずれか1種以上からなる金属の層又はこれらを主成分とする合金の層を備えていることを特徴とする電子回路用の圧延銅箔又は電解銅箔
2.前記銅よりもエッチングレートの低い層(A)が、白金又は白金合金であることを特徴とする上記1記載の電子回路用の圧延銅箔又は電解銅箔
3.前記銅よりもエッチングレートの低い層(A)が白金合金であって、該白金合金の白金比率が50wt%を超えることを特徴とする上記1記載の電子回路用の圧延銅箔又は電解銅箔
4.前記銅よりもエッチングレートの低い層(A)が白金合金であって、該白金合金に含まれる合金成分が亜鉛、リン、ホウ素、モリブデン、タングステン、ニッケル、鉄又はコバルトから選ばれる少なくとも一種以上の元素であることを特徴とする上記1又は2記載の電子回路用の圧延銅箔又は電解銅箔、を提供する。
5.前記層(A)の上または下に、さらに耐熱層(B)を備えることを特徴とする上記1~4のいずれか一項に記載の電子回路用の圧延銅箔又は電解銅箔
6.前記耐熱層(B)は、亜鉛又は亜鉛合金のいずれかからなる層であり、該亜鉛合金は、白金族元素、金、パラジウム族元素及び銀の群から選択した一種又は二種以上を合金元素として含有することを特徴とする上記1~5のいずれか一項に記載の電子回路用の圧延銅箔又は電解銅箔、を提供する。
7.前記耐熱層(B)の上に、さらにクロム層若しくはクロメート層及び/又はシラン処理層を備えていることを特徴とする上記1~6のいずれか一項に記載の電子回路用の圧延銅箔又は電解銅箔
8.圧延銅箔又は電解銅箔からなる銅張り積層板の、該銅箔をエッチングし電子回路を形成する方法において、銅箔のエッチング面側に銅よりもエッチングレートの低い白金族、金、銀のいずれか1種の金属の層又はこれらを主成分とする合金の層を形成し、塩化第二鉄水溶液又は塩化第二銅水溶液を用いて該銅箔をエッチングし、銅の不必要部分を除去して、銅の回路を形成することを特徴とする電子回路の形成方法
9.圧延銅箔又は電解銅箔からなる銅張り積層板の、該銅箔をエッチングし電子回路を形成する方法において、上記1~12の電子回路用の圧延銅箔又は電解銅箔を用い、エッチングレートの低い層(A)をエッチング面として銅張積層板を作製し、塩化第二鉄水溶液又は塩化第二銅水溶液を用いて該銅箔をエッチングし、銅の不必要部分を除去して、銅の回路を形成することを特徴とする電子回路の形成方法、を提供する。
これによってショートや回路幅の不良の発生を防止できる電子回路用の圧延銅箔又は電解銅箔を提供することができ、優れた電子回路の形成方法を提供することができるという効果を有する。
このようにして作製した銅箔を用いて銅張り積層板とする。この銅箔は、電解銅箔及び圧延銅箔のいずれにも適用できる。また、電解銅箔の場合、粗面(M面)又は光沢面(S面)にも同様に適用できるが、エッチングされる面は、通常光沢面側を使用する。圧延銅箔の中には高純度銅箔又は強度を向上させた合金銅箔も存在するが、本件発明はこれらの銅箔の全てを包含する。
エッチングを抑制する白金族、金、銀のいずれか1種以上からなる金属の層又はこれらを主成分とする合金は、銅箔上のレジスト部分に近い位置にあり、レジスト側の銅箔のエッチングは、この白金族、金、銀のいずれか1種以上からなる金属の層又はこれらを主成分とする合金の層近傍がエッチングされていく速度よりも速い速度でこの層から離れた部位の銅層のエッチングが進行することにより、銅回路がほぼ垂直にエッチングが進行し、矩形の銅箔回路が形成される。
白金合金に含まれる合金成分は通常知られている合金であれば何れも使用できる。例えば、亜鉛、リン、ホウ素、モリブデン、タングステン、ニッケル、鉄又はコバルトから選ばれる少なくとも一種以上の元素との合金は、エッチング速度が銅より遅く、エッチングファクターを改善する効果があることを確認できる。
前記白金族、金、銀のいずれか1種以上からなる金属の層又はこれらを主成分とする合金の層(A)上には、さらにクロム層若しくはクロメート層及び又はシラン処理層を形成することができる。
30μg/dm2未満では、耐酸化性(ヤケ性改善)に効果がない。また、1000μg/dm2を超えると、効果が飽和すると共に、前記層(A)の効果を減殺させてしまうので、金属亜鉛換算で、30μg/dm2~1000μg/dm2とすることが好ましい。
エッチング液は、いずれも使用可能であるが、特に塩化第二鉄水溶液が有効である。これは、微細回路はエッチングに時間が掛かるが、塩化第二鉄水溶液の方が塩化第二銅水溶液よりもエッチング速度が早いという理由による。
白金族、金、銀のいずれか1種の金属の層又はこれらを主成分とする合金(白金-亜鉛合金、白金-リン合金、白金-モリブデン合金、白金-タングステン合金、白金-鉄合金、白金-コバルト合金等)については、いずれもスパッタリング法により成膜することができる。また、いずれも、電気めっき、無電解めっき等の湿式めっき法でもよい。
装置:HITACHI製、E-102イオンスパッタ装置
真空度:0.01~0.1Torr
電流:5~30mA
時間:5~150秒
Zn:1~20g/L
pH:3~3.7
温度:常温~60°C
電流密度Dk:1~15A/dm2
時間:1~10秒
K2Cr2O7(Na2Cr2O7或いはCrO3)
Cr:40~300g/L
H2SO4 :0.5~10.0g/L
浴温:40~60°C
電流密度Dk :0.01~50A/dm2
時間:1~100秒
アノード:PtめっきTi 板、ステンレス鋼板、鉛板等
(a)電解クロメート処理の例
CrO3又はK2Cr2O7:1~12g/L
Zn(OH)2又はZnSO4・7H2O:0(0.05)~10g/L
Na2SO4:0(0.05)~20g/L
pH:2.5~12.5
温度:20~60°C
電流密度:0.5~5A/dm2
時間:0.5~20秒
Ni:10~40g/L
pH:2.5~3.5
温度:常温~60°C
電流密度Dk:2~50A/dm2
時間:1~4秒
下記のような色々な系列のシランから選択。
濃度:0.01wt%~5wt%
種類:オレフィン系シラン、エポキシ系シラン、アクリル系シラン、アミノ系シラン、メルカプト系シラン
アルコールに溶解したシランを所定の濃度まで水で希釈し、銅箔表面へ塗布するもの。
白金処理面を分析するため、反対面をFR-4樹脂でプレス作製し、マスキングする。そのサンプルを王水にて表面処理被膜が溶けるまで溶解させ、ビーカー中の溶解液を稀釈し、原子吸光分析により白金の定量分析を行う。
その他の白金族、金、銀の分析も同様に行うことができる。
処理面を分析するため、反対面をFR-4樹脂でプレス作製し、マスキングする。そのサンプルを濃度30%硝酸にて3分間煮沸して処理層を溶解させ、その溶液を原子吸光分析により亜鉛、クロムの定量分析を行う。
銅張り積層板(CCL)の製造の段階で、銅箔に熱がかかる。この熱によって、銅箔表層に設けられたエッチング改善処理層は銅層へ拡散する。そのため、当初期待したエッチング改善効果が減退し、エッチングファクターは減少する傾向がある。このことから、拡散していない状態と同等の効果を出すには、CCL作製時の銅箔にかかる熱量を考慮して、改善処理層の付着量を1.1~2倍程度増やすことが必要である。
上記の条件でエッチングすることにより、エッチングファクターを3.7以上、すなわち銅箔回路のエッチング側面と樹脂基板との間の回路側面の傾斜角を75度以上とすることができる。特に望ましい傾斜角は80~95度の範囲であるが、本願発明はこれを実現することが可能であり、これによって、ダレのない矩形のエッチング回路が形成できる。
箔厚18μmの圧延銅箔を用いた。この圧延銅箔の表面粗さRzは0.7μmであった。この圧延銅箔に、上記白金スパッタ条件で、白金200μg/dm2を形成した。
さらに、この白金層を設けた面の逆側を接着面として銅箔を樹脂基板に接着した。
(エッチング条件)
塩化第二鉄水溶液:(37wt%、ボーメ度:40°)
液温:50°C
スプレー圧:0.15MPa
回路ピッチ:30μmピッチ、50μmピッチの2種であるが、銅箔の厚みによって変更する。本実施例1の場合は、18μm厚の銅箔を用いたので、次の条件である。
(50μmピッチ回路形成)
レジストL/S=33μm/17μm、仕上がり回路トップ(上部)幅:15μm、エッチング時間:105秒前後
エッチングファクターは、末広がりにエッチングされた場合(ダレが発生した場合)、回路が垂直にエッチングされたと仮定した場合の、銅箔上面からの垂線と樹脂基板との交点をP点とし、このP点からのダレの長さの距離をaとした場合において、このaと銅箔の厚さbとの比:b/aを示すものであり、この数値が大きいほど、傾斜角は大きくなり、エッチング残渣が残らず、ダレが小さくなることを意味する。
エッチングファクター(EF)の計算方法の概略を図1に示す。この図1に示すように、EF=b/aとして計算する。このエッチングファクターを用いることにより、エッチング性の良否を簡単に判定できる。
表1に示すように、左右の傾斜角の平均値は81度となり、ほぼ矩形の銅箔回路が形成された。エッチングファクターは50μmピッチで6.2となった。
この結果、図3に示すように、良好なエッチング回路が得られた。
実施例1と同様に、箔厚18μmの圧延銅箔を用いた。この圧延銅箔の表面粗さRzは0.7μmであった。この圧延銅箔に、上記白金スパッタ条件で、白金500μg/dm2を形成した。
さらに、この白金層を設けた面の逆側を接着面として銅箔を樹脂基板に接着した。
(エッチング条件)
塩化第二鉄水溶液:(37wt%、ボーメ度:40°)
液温:50°C
スプレー圧:0.15MPa
レジストL/S=33μm/17μm、仕上がり回路トップ(上部)幅:15μm、エッチング時間:105秒前後
エッチングファクターの測定条件は、上記実施例1と同様なので省略する。そして、上記の条件でエッチングを行った。この結果、銅回路の側面のレジスト側から樹脂基板側に向かって、ほぼ垂直にエッチングが進行し、矩形の銅箔回路が形成された。
次に、エッチングした銅箔の傾斜角度を測定した(なお、回路長100μmにおける傾斜角の最小値である)。また、エッチングファクターを調べた。以上の結果を、表1に示す。
表1に示すように、左右の傾斜角の平均値は82度となり、ほぼ矩形の銅箔回路が形成された。エッチングファクターは50μmピッチで7となった。
この結果、良好なエッチング回路が得られた。
本実施例においては箔厚9μmの圧延銅箔を用いた。この圧延銅箔の表面粗さRzは0.7μmであった。この圧延銅箔に、上記白金スパッタ条件で、白金900μg/dm2を形成した。
さらに、この白金層を設けた面の逆側を接着面として銅箔を樹脂基板に接着した。
(エッチング条件)
塩化第二鉄水溶液:(37wt%、ボーメ度:40°)
液温:50°C
スプレー圧:0.15MPa
本実施例3の場合は、9μm厚の銅箔を用いたので、次の条件である。
レジストL/S=25μm/5μm、仕上がり回路トップ(上部)幅:10μm、エッチング時間:76秒前後
この結果、良好なエッチング回路が得られた。
本実施例においては箔厚5μmの電解銅箔を用いた。この電解銅箔の表面粗さRzは3μmであった。この電解銅箔に、上記白金スパッタ条件で、白金75μg/dm2を形成した。
さらに、この白金層を設けた面の逆側を接着面として銅箔を樹脂基板に接着した。
(エッチング条件)
塩化第二鉄水溶液:(37wt%、ボーメ度:40°)
液温:50°C
スプレー圧:0.15MPa
本実施例4の場合は、5μm厚の銅箔を用いたので、次の条件である。
レジストL/S=25μm/5μm、仕上がり回路トップ(上部)幅:10μm、エッチング時間:48秒前後
この結果、良好なエッチング回路が得られた。
実施例1と同様に、箔厚18μmの圧延銅箔を用いた。この圧延銅箔の表面粗さRzは0.7μmであった。この圧延銅箔に、上記金スパッタ条件で、金450μg/dm2を形成した。
さらに、この金層を設けた面の逆側を接着面として銅箔を樹脂基板に接着した。
(エッチング条件)
塩化第二鉄水溶液:(37wt%、ボーメ度:40°)
液温:50°C
スプレー圧:0.15MPa
レジストL/S=33μm/17μm、仕上がり回路トップ(上部)幅:15μm、エッチング時間:105秒前後
エッチングファクターの測定条件は、上記実施例1と同様なので省略する。そして、上記の条件でエッチングを行った。この結果、銅回路の側面のレジスト側から樹脂基板側に向かって、ほぼ垂直にエッチングが進行し、矩形の銅箔回路が形成された。
次に、エッチングした銅箔の傾斜角度を測定した(なお、回路長100μmにおける傾斜角の最小値である)。また、エッチングファクターを調べた。以上の結果を、表1に示す。
表1に示すように、左右の傾斜角の平均値は82度となり、ほぼ矩形の銅箔回路が形成された。エッチングファクターは50μmピッチで6.9となった。
この結果、良好なエッチング回路が得られた。
実施例1と同様に、箔厚18μmの圧延銅箔を用いた。この圧延銅箔の表面粗さRzは0.7μmであった。この圧延銅箔に、上記パラジウムスパッタ条件で、パラジウム550μg/dm2を形成した。
さらに、このパラジウム層を設けた面の逆側を接着面として銅箔を樹脂基板に接着した。
(エッチング条件)
塩化第二鉄水溶液:(37wt%、ボーメ度:40°)
液温:50°C
スプレー圧:0.15MPa
レジストL/S=33μm/17μm、仕上がり回路トップ(上部)幅:15μm、エッチング時間:105秒前後
エッチングファクターの測定条件は、上記実施例1と同様なので省略する。そして、上記の条件でエッチングを行った。この結果、銅回路の側面のレジスト側から樹脂基板側に向かって、ほぼ垂直にエッチングが進行し、矩形の銅箔回路が形成された。
次に、エッチングした銅箔の傾斜角度を測定した(なお、回路長100μmにおける傾斜角の最小値である)。また、エッチングファクターを調べた。以上の結果を、表1に示す。
表1に示すように、左右の傾斜角の平均値は82度となり、ほぼ矩形の銅箔回路が形成された。エッチングファクターは50μmピッチで6.8となった。
この結果、良好なエッチング回路が得られた。
実施例1と同様に、箔厚18μmの圧延銅箔を用いた。この圧延銅箔の表面粗さRzは0.7μmであった。この圧延銅箔に、上記95%Pt-5%Pdスパッタ条件で、95%Pt-5%Pd300μg/dm2を形成した。
さらに、この95%Pt-5%Pd層を設けた面の逆側を接着面として銅箔を樹脂基板に接着した。
(エッチング条件)
塩化第二鉄水溶液:(37wt%、ボーメ度:40°)
液温:50°C
スプレー圧:0.15MPa
レジストL/S=33μm/17μm、仕上がり回路トップ(上部)幅:15μm、エッチング時間:105秒前後
エッチングファクターの測定条件は、上記実施例1と同様なので省略する。そして、上記の条件でエッチングを行った。この結果、銅回路の側面のレジスト側から樹脂基板側に向かって、ほぼ垂直にエッチングが進行し、矩形の銅箔回路が形成された。
次に、エッチングした銅箔の傾斜角度を測定した(なお、回路長100μmにおける傾斜角の最小値である)。また、エッチングファクターを調べた。以上の結果を、表1に示す。
表1に示すように、左右の傾斜角の平均値は82度となり、ほぼ矩形の銅箔回路が形成された。エッチングファクターは50μmピッチで6.8となった。
この結果、良好なエッチング回路が得られた。
実施例1と同様に、箔厚18μmの圧延銅箔を用いた。この圧延銅箔の表面粗さRzは0.7μmであった。この圧延銅箔に、上記スパッタ条件で、Pt210μg/dm2上にAu190μg/dm2(二層)スパッタ層を形成した。
さらに、この二層のスパッタ層を設けた面の逆側を接着面として銅箔を樹脂基板に接着した。
(エッチング条件)
塩化第二鉄水溶液:(37wt%、ボーメ度:40°)
液温:50°C
スプレー圧:0.15MPa
レジストL/S=33μm/17μm、仕上がり回路トップ(上部)幅:15μm、エッチング時間:105秒前後
エッチングファクターの測定条件は、上記実施例1と同様なので省略する。そして、上記の条件でエッチングを行った。この結果、銅回路の側面のレジスト側から樹脂基板側に向かって、ほぼ垂直にエッチングが進行し、矩形の銅箔回路が形成された。
次に、エッチングした銅箔の傾斜角度を測定した(なお、回路長100μmにおける傾斜角の最小値である)。また、エッチングファクターを調べた。以上の結果を、表1に示す。
表1に示すように、左右の傾斜角の平均値は82度となり、ほぼ矩形の銅箔回路が形成された。エッチングファクターは50μmピッチで6.9となった。
この結果、良好なエッチング回路が得られた。
(ヤケ試験)
大気雰囲気下で、240°Cに10分間保持して、変色の有無で確認する。この亜鉛めっき層及びニッケルめっき層を設けた銅箔をエッチング側として樹脂基板に接着し、銅張り積層板とする条件を想定した条件である。
18μm圧延銅箔を用いた。この圧延銅箔の表面粗さRz:0.7μmであった。この圧延銅箔に、上記ニッケルめっき条件で、1200μg/dm2のニッケルめっき層を形成し、樹脂基板に接着した。
次に、実施例1と同様に、レジスト塗布及び露光工程により10本の回路を印刷し、さらに銅箔の不要部分を除去するエッチング処理を実施した。
回路形成条件を除き、エッチング条件、エッチングファクターの測定条件、ヤケ試験は、実施例1と同様にして実施した。実施例1と同様の条件については、記載を省略する。
レジストL/S=33μm/17μm、仕上がり回路トップ(上部)幅:15μm、エッチング時間:105秒前後
上記の条件でエッチングを行った。この結果、左右の傾斜角の平均値は73度となり、ほぼ矩形の銅箔回路が形成された。エッチングファクターは50μmピッチで3.3となった。この結果、図4に示すように、ほぼ矩形ではあるが、傾斜角がやや小さく、エッチングファクターがやや小さいエッチング回路が得られた。
18μm圧延銅箔を用いた。この圧延銅箔の表面粗さRz:0.7μmであった。この圧延銅箔に、上記白金スパッタ条件で、25μg/dm2の白金層を形成した。そのまま白金層の逆側の面を接着面として銅箔を樹脂基板に接着した。
回路形成条件を除き、エッチング条件、エッチングファクターの測定条件、ヤケ試験は、実施例1と同様にして実施した。実施例1と同様の条件については、記載を省略する。
(50μmピッチ回路形成)
レジストL/S=33μm/17μm、仕上がり回路トップ(上部)幅:15μm、エッチング時間:105秒前後
以上の結果を、同様に表2に示す。表2に示すように、左右の傾斜角の平均値は52度となり、エッチング性が悪い台形状の銅箔回路が形成された。エッチングファクターは50μmピッチで1.3となり、不良となった。
5μm電解銅箔を用いた。この電解銅箔の表面粗さRz:3μmであった。この電解銅箔の光沢(S)面に、上記ニッケルめっき条件で、580μg/dm2のニッケルめっき層を形成した。さらに、このニッケルめっき層を設けた面の逆側を接着面として銅箔を樹脂基板に接着した。
回路形成条件を除き、エッチング条件、エッチングファクターの測定条件、は、実施例1と同様にして実施した。実施例1と同様の条件については、記載を省略する。
(30μmピッチ回路形成)
レジストL/S=25μm/5μm、仕上がり回路トップ(上部)幅:15μm、エッチング時間:48秒前後
結果を表2に示す。このように、ほぼ矩形ではあるが、傾斜角がやや小さく、エッチングファクターがやや小さいエッチング回路が得られた。
これに対して、本願発明の条件に合わないものは、ほぼ矩形であっても、エッチングファクターがやや小さく急峻でなくなり、ダレが大きく台形状の銅箔回路が形成された。
このような、回路側面の傾斜角75度以上を実現する効果は、白金又は白金合金だけでなく、他の白金族、金、銀のいずれか1種以上からなる金属の層又はこれらを主成分とする合金の層においても同様に得られた。
Claims (9)
- エッチングにより回路形成を行う電子回路用の圧延銅箔又は電解銅箔において、該圧延銅箔又は電解銅箔のエッチング面側に形成された銅よりもエッチングレートの低い白金族、金、銀のいずれか1種以上からなる金属の層又はこれらを主成分とする合金の層を備えていることを特徴とする電子回路用の圧延銅箔又は電解銅箔。
- 前記銅よりもエッチングレートの低い層(A)が、白金又は白金合金であることを特徴とする請求項1記載の電子回路用の圧延銅箔又は電解銅箔。
- 前記銅よりもエッチングレートの低い層(A)が白金合金であって、該白金合金の白金比率が50wt%を超えることを特徴とする請求項1記載の電子回路用の圧延銅箔又は電解銅箔。
- 前記銅よりもエッチングレートの低い層(A)が白金合金であって、該白金合金に含まれる合金成分が亜鉛、リン、ホウ素、モリブデン、タングステン、ニッケル、鉄又はコバルトから選ばれる少なくとも一種以上の元素であることを特徴とする請求項1又は2記載の電子回路用の圧延銅箔又は電解銅箔。
- 前記銅層の上または下に、さらに耐熱層(B)を備えることを特徴とする請求項1~4のいずれか一項に記載の電子回路用の圧延銅箔又は電解銅箔。
- 前記耐熱層(B)は、亜鉛又は亜鉛合金のいずれかからなる層であり、該亜鉛合金は、白金族元素、金、パラジウム族元素及び銀の群から選択した一種又は二種以上を合金元素として含有することを特徴とする請求項1~5のいずれか一項に記載の電子回路用の圧延銅箔又は電解銅箔。
- 前記耐熱層(B)の上に、さらにクロム層若しくはクロメート層及び/又はシラン処理層を備えていることを特徴とする請求項1~6のいずれか一項に記載の電子回路用の圧延銅箔又は電解銅箔。
- 圧延銅箔又は電解銅箔からなる銅張り積層板の、該銅箔をエッチングし電子回路を形成する方法において、銅箔のエッチング面側に銅よりもエッチングレートの低い白金族、金、銀のいずれか1種の金属の層又はこれらを主成分とする合金の層を形成し、塩化第二鉄水溶液又は塩化第二銅水溶液を用いて該銅箔をエッチングし、銅の不必要部分を除去して、銅の回路を形成することを特徴とする電子回路の形成方法。
- 圧延銅箔又は電解銅箔からなる銅張り積層板の、該銅箔をエッチングし電子回路を形成する方法において、請求項1~12の電子回路用の圧延銅箔又は電解銅箔を用い、エッチングレートの低い層(A)をエッチング面として銅張積層板を作製し、塩化第二鉄水溶液又は塩化第二銅水溶液を用いて該銅箔をエッチングし、銅の不必要部分を除去して、銅の回路を形成することを特徴とする電子回路の形成方法。
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JP4955105B2 (ja) | 2008-12-26 | 2012-06-20 | Jx日鉱日石金属株式会社 | 電子回路用の圧延銅箔又は電解銅箔及びこれらを用いた電子回路の形成方法 |
WO2014175850A2 (en) * | 2012-10-26 | 2014-10-30 | Applied Materials, Inc. | Combinatorial masking |
KR101420543B1 (ko) * | 2012-12-31 | 2014-08-13 | 삼성전기주식회사 | 다층기판 |
US9960135B2 (en) * | 2015-03-23 | 2018-05-01 | Texas Instruments Incorporated | Metal bond pad with cobalt interconnect layer and solder thereon |
EP3786315A4 (en) | 2018-04-27 | 2022-04-20 | JX Nippon Mining & Metals Corporation | SURFACE TREATED COPPER FOIL, COPPER COATED LAMINATE AND CIRCUIT BOARD |
RU2747969C1 (ru) * | 2020-07-21 | 2021-05-18 | Акционерное Общество "Нииэфа Им. Д.В. Ефремова" | Устройство для формирования антикоррозионных слоев на поверхности тепловыделяющих элементов |
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Cited By (13)
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JP2013254961A (ja) * | 2009-01-29 | 2013-12-19 | Jx Nippon Mining & Metals Corp | 電子回路用の圧延銅箔又は電解銅箔及びこれらを用いた電子回路の形成方法 |
JP2011211008A (ja) * | 2010-03-30 | 2011-10-20 | Jx Nippon Mining & Metals Corp | エッチング性に優れたプリント配線板用銅箔及びそれを用いた積層体 |
JP2012169547A (ja) * | 2011-02-16 | 2012-09-06 | Jx Nippon Mining & Metals Corp | プリント配線板用銅箔及びそれを用いた積層板 |
JP2012167354A (ja) * | 2011-02-16 | 2012-09-06 | Jx Nippon Mining & Metals Corp | プリント配線板用銅箔、積層体及びプリント配線板 |
JP2012186211A (ja) * | 2011-03-03 | 2012-09-27 | Jx Nippon Mining & Metals Corp | プリント配線板用銅箔及びそれを用いた積層板 |
CN103430635A (zh) * | 2011-03-18 | 2013-12-04 | Jx日矿日石金属株式会社 | 印刷布线板用铜箔及使用它的层叠体 |
WO2012128009A1 (ja) * | 2011-03-18 | 2012-09-27 | Jx日鉱日石金属株式会社 | プリント配線板用銅箔及びそれを用いた積層体 |
JP2013045881A (ja) * | 2011-08-24 | 2013-03-04 | Jx Nippon Mining & Metals Corp | プリント配線板用銅箔及びそれを用いた積層板 |
CN103262665A (zh) * | 2011-08-24 | 2013-08-21 | Jx日矿日石金属株式会社 | 印刷布线板用铜箔及使用它的层叠体 |
WO2013027444A1 (ja) * | 2011-08-24 | 2013-02-28 | Jx日鉱日石金属株式会社 | プリント配線板用銅箔及びそれを用いた積層体 |
KR101507290B1 (ko) * | 2011-08-24 | 2015-03-30 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 프린트 배선판용 구리박 및 그것을 사용한 적층체 |
CN103262665B (zh) * | 2011-08-24 | 2016-03-09 | Jx日矿日石金属株式会社 | 铜箔、层叠体、印刷布线板及电子电路的形成方法 |
JP2013080735A (ja) * | 2011-09-30 | 2013-05-02 | Jx Nippon Mining & Metals Corp | 生産性に優れたプリント配線板用銅箔及びそれを用いた積層板 |
Also Published As
Publication number | Publication date |
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TW201032685A (en) | 2010-09-01 |
CN102301838B (zh) | 2015-12-09 |
TWI539875B (zh) | 2016-06-21 |
JPWO2010087268A1 (ja) | 2012-08-02 |
MY164452A (en) | 2017-12-15 |
JP5694453B2 (ja) | 2015-04-01 |
EP2384101A1 (en) | 2011-11-02 |
US20130270218A1 (en) | 2013-10-17 |
CN102301838A (zh) | 2011-12-28 |
JP5937652B2 (ja) | 2016-06-22 |
EP2384101A4 (en) | 2012-08-29 |
JP2013254961A (ja) | 2013-12-19 |
KR101412795B1 (ko) | 2014-06-27 |
JP2015019107A (ja) | 2015-01-29 |
US20110300401A1 (en) | 2011-12-08 |
KR20110099765A (ko) | 2011-09-08 |
JP5457374B2 (ja) | 2014-04-02 |
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