WO2017141799A1 - Agent de microgravure pour cuivre et procédé de production de panneau de câblage - Google Patents

Agent de microgravure pour cuivre et procédé de production de panneau de câblage Download PDF

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Publication number
WO2017141799A1
WO2017141799A1 PCT/JP2017/004653 JP2017004653W WO2017141799A1 WO 2017141799 A1 WO2017141799 A1 WO 2017141799A1 JP 2017004653 W JP2017004653 W JP 2017004653W WO 2017141799 A1 WO2017141799 A1 WO 2017141799A1
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Prior art keywords
copper
microetching agent
polymer
ion source
microetching
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PCT/JP2017/004653
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English (en)
Japanese (ja)
Inventor
啓佑 松本
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メック株式会社
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Priority claimed from JP2017011841A external-priority patent/JP6218000B2/ja
Application filed by メック株式会社 filed Critical メック株式会社
Priority to CN201780002281.6A priority Critical patent/CN107849705B/zh
Priority to KR1020177036688A priority patent/KR101861051B1/ko
Priority to US16/067,665 priority patent/US20190003062A1/en
Priority to EP17753057.3A priority patent/EP3388551B1/fr
Publication of WO2017141799A1 publication Critical patent/WO2017141799A1/fr
Priority to US16/736,154 priority patent/US11053594B2/en

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal

Definitions

  • the present invention relates to a method for manufacturing copper microetching and a wiring board.
  • a general multilayer wiring board is manufactured by laminating and pressing an inner layer substrate having a conductive layer made of copper, copper alloy or the like with another inner layer substrate, copper foil or the like with a prepreg interposed therebetween.
  • the conductive layers are electrically connected by a through-hole called a through-hole in which the hole wall is plated with copper.
  • a method of forming a fine uneven shape on the surface of the conductive layer with a microetching agent is used. When a microetching agent is brought into contact with the metal surface, uneven shapes are formed due to differences in the etching rate depending on the crystal orientation of the metal crystal grains and the etching rate between the metal crystal grains and the crystal grain boundary. And the surface is roughened.
  • microetching agents for copper or copper alloys examples include organic acid microetching agents (see Patent Document 1), sulfuric acid-hydrogen peroxide microetching agents (see Patent Document 2), and hydrochloric acid microetching agents (see Patent Document 3). ) Etc. are known. To these microetching agents, halogens, polymers, corrosion inhibitors, surfactants, and the like are added for the purpose of adjusting the roughening shape and etching rate.
  • Rolled copper foil and electrolytic copper foil are mainly used as the conductive layer of the printed wiring board. As shown in FIGS. 1A and 1B, rolled copper and electrolytic copper have different surface microscopic shapes. In addition, the crystal characteristics of the two are greatly different. Therefore, when the type of copper foil is different, the roughened shape formed on the surface by the etching process may be different. In particular, since the rolled copper foil has large crystal grains and high uniformity in crystal plane orientation, it tends to be difficult to form an uneven shape. Therefore, the conventional micro-etching agent can form a rough shape with excellent adhesion to the resin evenly on the surface of the electrolytic copper foil, but an appropriate rough shape is formed for the rolled copper foil. In some cases, roughening unevenness may occur. In such a case, it is necessary to change the microetching agent to be used according to the type of copper foil, which causes problems such as complicated process management.
  • the present invention has a small roughened shape difference due to the difference in crystallinity of copper, and has a roughened shape with excellent adhesion to a resin or the like for both electrolytic copper and rolled copper.
  • An object is to provide a microetching agent that can be formed.
  • the present invention relates to a copper microetching agent used for copper surface roughening.
  • "copper” in this specification includes copper and a copper alloy.
  • the “copper layer” also includes a copper wiring pattern layer.
  • the microetching agent is an acidic aqueous solution containing an inorganic acid, a cupric ion source, a halide ion source, a sulfate ion source, and a polymer.
  • the polymer contained in the microetching agent is a water-soluble polymer having an amino group or quaternary ammonium group in the side chain and having a weight average molecular weight of 1000 or more, and is preferably cationic.
  • this invention relates to the manufacturing method of the wiring board which manufactures the wiring board containing a copper layer.
  • the manufacturing method of a wiring board has the process (roughening process process) which makes the said microetching agent contact the surface of a copper layer, and roughens the surface of a copper layer.
  • a replenisher is preferably added to the microetching agent in order to keep the composition of the microetching agent within a predetermined range.
  • Scanning electron micrograph of the surface of rolled copper that has not been subjected to etching treatment (photographing angle: 45 °, magnification: 3500 times).
  • Scanning electron micrograph of the surface of the electrolytic copper that has not been etched (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper roughened with the microetching agent of the example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper roughened with the microetching agent of the example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 3500 times).
  • the scanning electron micrograph of the rolling copper surface roughened with the microetching agent of the Example (photographing angle 45 degrees, magnification 5000 times).
  • the scanning electron micrograph of the surface of the electrolytic copper roughened with the microetching agent of the example (photographing angle 45 °, magnification 5000 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the rolled copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the scanning electron micrograph of the surface of the electrolytic copper processed with the microetching agent of the comparative example (photographing angle 45 °, magnification 3500 times).
  • the microetching agent of the present invention is used for forming a roughened shape on the surface of copper.
  • the microetching agent is an acidic aqueous solution containing an inorganic acid, a cupric ion source, a halide ion source, a sulfate ion source and a polymer.
  • an inorganic acid a cupric ion source, a halide ion source, a sulfate ion source and a polymer.
  • cupric ion source generates cupric ions in an aqueous solution.
  • Cupric ion acts as an oxidizing agent for oxidizing copper.
  • copper halides such as cupric chloride and cupric bromide
  • inorganic acid salts such as cupric sulfate and cupric nitrate
  • cupric formate and cupric acetate etc.
  • Organic acid salt cupric hydroxide
  • cupric oxide since cupric halide produces cupric ions and halide ions in an aqueous solution, it can be used as having both functions of a halide ion source and a cupric ion source.
  • cupric sulfate produces cupric ions, sulfate ions and hydrogen sulfate ions in an aqueous solution, it can be used as having both functions of a sulfate ion source and a cupric ion source.
  • a cupric ion source may use 2 or more types together.
  • the molar concentration of the cupric ion source is preferably 0.05 mol / L or more.
  • the molar concentration of the cupric ion source is the molar concentration of copper atoms contained in the cupric ion source, and is equal to the concentration of cupric ions in the etching agent.
  • the molar concentration of the cupric ion source is preferably 3 mol / L or less.
  • the molar concentration of the cupric ion source is more preferably 0.1 to 2 mol / L, still more preferably 0.3 to 1.5 mol / L.
  • the acid has a function of dissolving copper oxidized by cupric ions in an aqueous solution and also has a pH adjusting function.
  • the inorganic acid is preferably a hydrohalic acid such as hydrochloric acid or hydrobromic acid, or a strong acid such as sulfuric acid or nitric acid.
  • Hydrohalic acid can be used as having the action of both a halide ion source and an acid.
  • Sulfuric acid can be used as having both the action of a sulfate ion source and an acid. Therefore, the microetching agent of the present invention preferably contains sulfuric acid and / or hydrohalic acid as the inorganic acid.
  • hydrohalic acids hydrochloric acid (aqueous hydrogen chloride solution) is preferred.
  • the pH of the microetching agent is preferably 3 or less, and more preferably 2 or less, from the viewpoint of suppressing the precipitation of other components when the cupric ion concentration is increased and improving the stability of the etching agent.
  • the concentration of the inorganic acid in the microetching agent is preferably adjusted so that the pH is in the above range.
  • the halide ion source generates halide ions in an aqueous solution.
  • Halide ions assist the dissolution of copper and have a function of forming a copper layer surface with excellent adhesion.
  • Examples of halide ions include chloride ions and bromide ions. Among these, chloride ions are preferable from the viewpoint of uniformly forming a roughened shape having excellent adhesion. Two or more halide ions may be contained.
  • Halide ion sources include: hydrohalic acids such as hydrochloric acid and hydrobromic acid; sodium chloride, calcium chloride, potassium chloride, ammonium chloride, potassium bromide, sodium bromide, copper chloride, copper bromide, zinc chloride, Examples thereof include metal salts such as iron chloride and tin bromide. Two or more halide ion sources may be used in combination. As described above, hydrohalic acid has the action of both a halide ion source and an acid, and copper halide has the action of both a halide ion source and a cupric ion source.
  • the concentration of halide ions in the microetching agent that is, the concentration of halide ions ionized in the etching agent is 0.01 mol / L or more.
  • 0.05 mol / L or more is more preferable, and 0.1 mol / L or more is more preferable.
  • the upper limit of the halide ion concentration is not particularly limited, but is preferably 4 mol / L or less and more preferably 2 mol / L or less from the viewpoint of solubility.
  • the molar concentration of the cupric ion source is preferably at least 0.2 times the molar concentration of the halide ion source, more preferably at least 0.3 times, and even more preferably at least 0.5 times.
  • the concentration ratio between the cupric ion and the halogen By adjusting the concentration ratio between the cupric ion and the halogen, a uniform roughened shape having excellent adhesion to a resin or the like tends to be easily formed on both electrolytic copper and rolled copper.
  • the molar concentration of the cupric ion source is preferably 10 times or less, more preferably 7 times or less, more preferably 5 times the molar concentration of the halide ion source. The following is more preferable.
  • the sulfate ion source generates sulfate ions (SO 4 2 ⁇ ) and / or hydrogen sulfate ions (HSO 4 ⁇ ) in an aqueous solution.
  • the sulfate ion source include sulfates such as potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate, cupric sulfate, ferric sulfate, and ammonium sulfate, sulfuric acid, sodium hydrogen sulfate, and the like.
  • cupric sulfate has the action of both a sulfate ion source and a cupric ion source
  • sulfuric acid has the action of both a sulfate ion source and an acid.
  • sulfate ions and hydrogen sulfate ions are present, so that the copper surface has a fine shape suitable for adhesion to resins, etc. There is a tendency that irregularities are easily formed. Further, the presence of sulfate ions and hydrogen sulfate ions can keep the pH of the solution low and increase the stability of the aqueous solution.
  • the concentration of the sulfate ion source that is, the sum of the sulfate ion concentration and the hydrogen sulfate ion concentration in the microetching agent is preferably 0.02 mol / L or more.
  • the concentration of the sulfate ion source is more preferably 0.05 to 5 mol / L, still more preferably 0.1 to 3 mol / L.
  • the microetching agent of the present invention contains a water-soluble polymer having an amino group or a quaternary ammonium group in the side chain and having a weight average molecular weight of 1000 or more.
  • a polymer has the effect
  • the weight average molecular weight of the polymer is preferably 2000 or more, and more preferably 5000 or more.
  • the polymer weight average molecular weight is preferably 5 million or less, and more preferably 2 million or less.
  • the weight average molecular weight is a value obtained in terms of polyethylene glycol by gel permeation chromatograph (GPC) analysis.
  • Examples of the polymer having a quaternary ammonium group in the side chain include a polymer having a repeating unit represented by the following formula (I).
  • R 1 to R 3 each independently represents a chain or cyclic hydrocarbon group which may have a substituent, and two or more of R 1 to R 3 are bonded to each other. Thus, a ring structure may be formed.
  • R 4 is a hydrogen atom or a methyl group
  • X 1 is a single bond or a divalent linking group
  • Z ⁇ is a counter anion.
  • polymer having a repeating unit represented by the formula (I) examples include a quaternary ammonium salt type styrene polymer, a quaternary ammonium salt type aminoalkyl (meth) acrylate polymer, and the like.
  • the polymer having a quaternary ammonium group in the side chain includes a repeating unit in which the main chain carbon atom and the side chain quaternary ammonium group form a cyclic structure, as represented by the following formula (II). You may have.
  • R 5 and R 6 are chain or cyclic hydrocarbon groups which may have a substituent, and R 5 and R 6 are bonded to each other to form a cyclic structure. Also good. m is an integer of 0-2. X 2 and X 3 are each independently a single bond or a divalent linking group. Specific examples of the polymer having a repeating unit of the formula (II) include a quaternary ammonium salt type diallylamine polymer obtained by polymerization of a diallyldialkylammonium salt represented by the formula (IIa).
  • R 7 and R 8 are each independently a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and preferably a hydrogen atom.
  • the quaternary ammonium group in the side chain may have a double bond between the nitrogen atom and the carbon atom, and the nitrogen atom of the quaternary ammonium group may be included as a ring constituent atom. Further, as in the repeating unit represented by the following formula (III), two polymer chains may be cross-linked by a quaternary ammonium group.
  • X 4 to X 7 are each independently a single bond or a divalent linking group.
  • the counter anion Z ⁇ of the quaternary ammonium salt includes Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , PF 6 ⁇ , HSO 4 ⁇ , C 2 H 5 SO 4 ⁇ . Is mentioned.
  • X 1 to X 7 are divalent linking groups, specific examples thereof include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R— group, a —COO—R— group ( R represents a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms.
  • Examples of the polymer having an amino group in the side chain include a polymer having a repeating unit represented by the following formula (IV).
  • R 11 and R 12 are each independently a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and R 11 and R 12 are bonded to each other.
  • An annular structure may be formed.
  • R 13 is a hydrogen atom or a methyl group
  • X 11 is a single bond or a divalent linking group.
  • the amino group may be primary, secondary or tertiary, and may form an ammonium salt. Examples of the counter anion of the ammonium salt include those described above as the counter anion Z ⁇ of the quaternary ammonium salt.
  • the polymer having an amino group in the side chain may have a repeating unit in which the main chain carbon atom and the side chain amino group form a cyclic structure, as represented by the following formula (V).
  • R 14 is a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent.
  • m is an integer of 0-2.
  • X 12 and X 13 are each independently a single bond or a divalent linking group.
  • Specific examples of the polymer having a repeating unit of the formula (V) include diallylamine polymers obtained by polymerization of diallylamine or diallylamine salts.
  • the polymer containing an amino group or a quaternary ammonium group in the side chain may be a copolymer.
  • the copolymer may contain a repeating unit containing an amino group or a quaternary ammonium group and a repeating unit containing neither an amino group nor a quaternary ammonium group.
  • the arrangement of the repeating units in the copolymer is not particularly limited, and any of an alternating copolymer, a block copolymer, and a random copolymer may be used.
  • the ratio of the repeating unit containing an amino group or a quaternary ammonium group to the monomer units of the whole polymer is preferably 20 mol% or more, more preferably 30 mol% or more. Is more preferable, and 40 mol% or more is more preferable.
  • a polymer having a structure derived from a quaternary ammonium salt type diallylamine represented by the general formula (II) and a polymer having a structure derived from diallylamine represented by the general formula (IV) are: It is preferable to have a structural unit derived from sulfur dioxide represented by the following formula as a repeating unit.
  • the polymer may have both an amino group and a quaternary ammonium group in the side chain. Two or more polymers may be used in combination, and a polymer having an amino group in the side chain and a polymer having a quaternary ammonium group in the side chain may be used in combination.
  • the concentration of the polymer in the microetching agent is preferably from 0.002 to 2 g / L, more preferably from 0.005 to 1 g / L, from the viewpoint of forming a copper layer surface having excellent adhesion.
  • 0.5 g / L is more preferable, and 0.01 to 0.2 g / L is particularly preferable.
  • the content of cupric ions in the microetching agent is preferably 50 to 20000 times, more preferably 100 to 10,000 times, and even more preferably 200 to 6000 times by weight with respect to the polymer.
  • the microetching agent of the present invention can be prepared by dissolving each of the above components in ion exchange water or the like.
  • the microetching agent may contain components other than those described above.
  • a nonionic surfactant as an antifoaming agent or a complexing agent such as pyridine may be added to improve the dissolution stability of copper.
  • the microetching agent contains hydrogen peroxide
  • the copper will be dissolved by the oxidizing power of hydrogen peroxide, so a copper layer with large crystal grains and high uniformity of crystal plane orientation like rolled copper In some cases, the formation of the roughened shape is hindered.
  • the hydrogen peroxide concentration in the microetching agent is most preferably 0.
  • mixing of a trace amount of hydrogen peroxide contained in the raw material is acceptable.
  • the hydrogen peroxide concentration of the microetching agent is preferably 0.1% by weight or less, and more preferably 0.01% by weight or less.
  • microetching agent can be widely used for roughening the copper layer surface. Fine irregularities are uniformly formed on the surface of the treated copper layer, and adhesion to a resin such as a prepreg, a plating resist, an etching resist, a solder resist, an electrodeposition resist, or a coverlay is good. Further, since the surface is excellent in solderability, it is particularly useful for manufacturing various wiring boards including those for pin grid arrays (PGA) and ball grid arrays (BGA). It is also useful for surface treatment of lead frames.
  • PGA pin grid arrays
  • BGA ball grid arrays
  • the microetching agent of the present invention has a small difference in roughened shape due to the difference in crystallinity of copper, and has a roughened shape excellent in adhesiveness with resin or the like for both electrolytic copper and rolled copper. Can be formed. Therefore, even when the copper foil to be processed is different, it is not necessary to replace the etching agent, and the same etching agent can be used repeatedly.
  • the surface of copper is roughened by bringing the above-mentioned microetching agent into contact with the surface of the copper layer.
  • the microetching agent of the present invention can be suitably used for roughening a copper layer whose surface to be treated (surface to be brought into contact with the microetching agent) is made of rolled copper.
  • the method of bringing the microetching agent into contact with the surface of the copper layer is not particularly limited.
  • the method of spraying the microetching agent on the surface of the copper layer to be treated or the copper layer to be treated in the microetching agent And so on it is preferable to perform etching under conditions of a microetching agent temperature of 10 to 40 ° C. and a spray pressure of 0.03 to 0.3 MPa for 5 to 120 seconds.
  • the temperature of the microetching agent is 10 to 40 ° C. and etching is performed for 5 to 120 seconds.
  • the microetching agent does not substantially contain hydrogen peroxide, waste liquid treatment after use is easy, and for example, it can be treated by a general simple method using neutralization, a polymer flocculant or the like.
  • the etching amount in the roughening treatment is not particularly limited, but is preferably 0.05 ⁇ m or more and more preferably 0.1 ⁇ m or more from the viewpoint of forming a uniform uneven shape regardless of the crystallinity of copper. If the etching amount is excessively large, problems such as disconnection due to complete etching of the copper layer and increase in resistance due to a reduction in the wiring cross-sectional area may occur. Therefore, the etching amount is preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less.
  • the “etching amount” refers to the average etching amount (dissolution amount) in the depth direction, and is calculated from the weight and specific gravity of copper dissolved by the microetching agent and the front projected area of the copper surface.
  • the surface of the roughened copper layer is preferably washed with an acidic aqueous solution in order to remove the generated smut.
  • an acidic aqueous solution used for washing hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution and the like can be used.
  • Hydrochloric acid is preferred because it has little effect on the roughened shape and has high smut removability.
  • the acid concentration of the acidic aqueous solution is preferably 0.3 to 35% by weight, and more preferably 1 to 10% by weight.
  • the cleaning method is not particularly limited, and examples thereof include a method of spraying an acidic aqueous solution on the roughened copper layer surface, a method of immersing the roughened copper layer in the acidic aqueous solution, and the like.
  • spraying it is preferable to wash the acidic aqueous solution at a temperature of 15 to 35 ° C. under a spray pressure of 0.03 to 0.3 MPa for 3 to 30 seconds.
  • immersion it is preferable that the temperature of the acidic aqueous solution is 15 to 35 ° C. and the cleaning is performed for 3 to 30 seconds.
  • the replenisher is an aqueous solution containing an inorganic acid, a cupric ion source, a halide ion source, a sulfate ion source, and the polymer.
  • the amount of the replenisher added and the timing of the replenisher added can be appropriately set according to the concentration control range of each component.
  • Each component in the replenisher is the same as the component contained in the above-described microetching agent.
  • the concentration of each component in the replenisher is appropriately adjusted according to the initial concentration of the microetching agent used for the treatment.
  • the treatment may be performed with an aqueous solution of an azole or an alcohol solution. Further, after the treatment with the microetching agent, an oxidation treatment called brown oxide treatment or black oxide treatment may be performed.
  • a base material having a rolled copper foil (JX metal HA foil) was prepared as a test substrate. Each of these substrates was sprayed on the copper foil of the test substrate under the condition of a spray pressure of 0.1 MPa using each microetching agent (25 ° C.) shown in Table 1, and the etching amount of copper was 0.5 ⁇ m. Etching was carried out by adjusting the etching time so that Subsequently, it was washed with water, and the etched surface was immersed in hydrochloric acid (hydrogen chloride concentration: 3.5 wt%) at a temperature of 25 ° C. for 15 seconds. Thereafter, it was washed with water and dried.
  • hydrochloric acid hydrochloric acid
  • a glass cloth epoxy resin-impregnated copper clad laminate obtained by bonding an electrolytic copper foil having a thickness of 35 ⁇ m on both sides of an insulating base material. 0.2 mm) using a test substrate plated with 18 ⁇ m of copper, and using the etching agents of Examples 1, 2, 11 and Comparative Examples 3 and 4, etching, acid cleaning, water washing and drying were performed in the same manner as described above. Carried out.
  • Polymer A Diallyldialkylammonium (quaternary ammonium) hydrochloride / sulfur dioxide alternating copolymer (weight average molecular weight of about 5000) having the following repeating units
  • Polymer B diallylamine (secondary amine) hydrochloride / sulfur dioxide alternating copolymer having the following repeating units (weight average molecular weight of about 5000)
  • Polymer C diallylamine (secondary amine) acetate / sulfur dioxide alternating copolymer having the following repeating units (weight average molecular weight: about 5000)
  • Polymer D Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylamide diethyl sulfate random copolymer having the following structure (weight average molecular weight: about 800,000)
  • Polymer E Dicyandiamide / formaldehyde condensation polymer having the following structure
  • ⁇ Evaluation criteria> 1 The surface has no irregularities 2: The surface has irregularities but is not roughened 3: The surface has irregularities and is roughened, but the irregularities are large and rough unevenness is observed Some 4: Fine irregularities are formed on the entire surface 5: Fine irregularities are formed on the entire surface, and in-plane uniformity is high
  • Comparative Example 2 using an organic acid-based microetching agent, a uniform roughened shape was formed on the surface of the electrolytic copper (FIG. 14B), but the surface of the rolled copper was not roughened ( FIG. 14A). Even in Comparative Example 3 using a sulfuric acid-hydrogen peroxide microetching agent, a uniform roughened shape was formed on the surface of the electrolytic copper (FIG. 15B), but the surface of the rolled copper was roughened. (FIG. 15A).
  • Example 1 using the microetching agent containing hydrochloric acid, copper sulfate, and a polymer, the adhesiveness to the resin is improved on any surface of rolled copper (FIG. 2A) and electrolytic copper (FIG. 2B). An excellent uniform roughened shape was formed.
  • Example 2 as well, a uniform roughened shape with excellent adhesion to the resin was formed on the surfaces of both rolled copper (FIG. 3A) and electrolytic copper (FIG. 3B). Even in Examples 3 to 6 in which the blending amounts of hydrochloric acid, copper sulfate, and polymer were changed, a uniform roughened shape was formed on the surface of the rolled copper.
  • Example 11 using a microetching agent containing sulfuric acid, copper sulfate, copper chloride and a polymer, similarly to Examples 1 and 2, the surfaces of both rolled copper (FIG. 12A) and electrolytic copper (FIG. 12B) were used. A uniform roughened shape was formed.
  • Polymer F Poly (oxyethyleneoxypropylene (5E.O., 5P.O.)) glycol monoether (number average molecular weight of about 510)
  • Polymer G Polyethyleneimine (weight average molecular weight 70000)
  • Polymer H Polyethyleneimine (weight average molecular weight 300)
  • Polymer I Polyoxyethylene-polyoxypropylene block polymer adduct of ethylenediamine represented by the following formula
  • an aqueous solution containing an inorganic acid, cupric ion, halide ion, sulfate ion, and a polymer having a quaternary ammonium group or amino group in the side chain is not only rolled, but also electrolytic copper. It can be seen that fine irregularities can be uniformly formed on the surface of copper.

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Abstract

La présente invention concerne : un agent de microgravure formant des formes rugueuses moins affecté par des différences de cristallinité du cuivre et avec lequel des formes rugueuses excellentes en termes d'adhésivité aux résines, etc. peuvent être formées sur cuivre électrolytique ou sur cuivre laminé ; et un procédé de production d'un panneau de câblage qui comprend une étape dans laquelle une surface de cuivre rugosifiée utilisant l'agent de microgravure. L'agent de microgravure pour cuivre selon la présente invention est une solution aqueuse acide contenant un acide inorganique, une source d'ions cupriques, une source d'ions halogénure et un polymère. Le polymère possède un groupe fonctionnel contenant un atome d'azote. Il est préférable que l'agent de microgravure contienne une source d'ions sulfate.
PCT/JP2017/004653 2016-02-19 2017-02-08 Agent de microgravure pour cuivre et procédé de production de panneau de câblage WO2017141799A1 (fr)

Priority Applications (5)

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CN201780002281.6A CN107849705B (zh) 2016-02-19 2017-02-08 铜的微蚀刻剂及电路基板的制造方法
KR1020177036688A KR101861051B1 (ko) 2016-02-19 2017-02-08 구리의 마이크로 에칭제 및 배선 기판의 제조 방법
US16/067,665 US20190003062A1 (en) 2016-02-19 2017-02-08 Microetchant for copper and method for producing wiring board
EP17753057.3A EP3388551B1 (fr) 2016-02-19 2017-02-08 Agent de microgravure pour cuivre et procédé de production de panneau de câblage
US16/736,154 US11053594B2 (en) 2016-02-19 2020-01-07 Microetchant for copper and method for producing wiring board

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JP2017011841A JP6218000B2 (ja) 2016-02-19 2017-01-26 銅のマイクロエッチング剤および配線基板の製造方法
JP2017-011841 2017-01-26

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US16/736,154 Continuation US11053594B2 (en) 2016-02-19 2020-01-07 Microetchant for copper and method for producing wiring board

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11230644B1 (en) * 2020-07-20 2022-01-25 Mec Company Ltd. Coating film-forming composition, method for producing surface-treated metal member, and method for producing metal-resin composite

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JPH0941163A (ja) 1995-08-01 1997-02-10 Mec Kk 銅および銅合金のマイクロエッチング剤
JP2002047583A (ja) 2000-07-28 2002-02-15 Mec Kk 銅または銅合金のマイクロエッチング剤およびそれを用いるマイクロエッチング法
JP2006028556A (ja) * 2004-07-13 2006-02-02 Nippon Refine Kk 金属含有酸廃液の再生装置
JP2006299359A (ja) * 2005-04-22 2006-11-02 Asahi Kagaku Kogyo Co Ltd エッチング組成液中の添加剤の定量方法
WO2007024312A1 (fr) 2005-08-23 2007-03-01 Macdermid, Incorporated Solution de microgravure amelioree
WO2010071078A1 (fr) * 2008-12-17 2010-06-24 三菱製紙株式会社 Solution de gravure pour cuivre ou alliage de cuivre, procédé de gravure, et procédé de gestion du renouvellement d'une solution de gravure
JP2010525175A (ja) * 2007-04-27 2010-07-22 マクダーミッド インコーポレーテッド 金属表面処理組成物

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Publication number Priority date Publication date Assignee Title
JPH0941163A (ja) 1995-08-01 1997-02-10 Mec Kk 銅および銅合金のマイクロエッチング剤
JP2002047583A (ja) 2000-07-28 2002-02-15 Mec Kk 銅または銅合金のマイクロエッチング剤およびそれを用いるマイクロエッチング法
JP2006028556A (ja) * 2004-07-13 2006-02-02 Nippon Refine Kk 金属含有酸廃液の再生装置
JP2006299359A (ja) * 2005-04-22 2006-11-02 Asahi Kagaku Kogyo Co Ltd エッチング組成液中の添加剤の定量方法
WO2007024312A1 (fr) 2005-08-23 2007-03-01 Macdermid, Incorporated Solution de microgravure amelioree
JP2010525175A (ja) * 2007-04-27 2010-07-22 マクダーミッド インコーポレーテッド 金属表面処理組成物
WO2010071078A1 (fr) * 2008-12-17 2010-06-24 三菱製紙株式会社 Solution de gravure pour cuivre ou alliage de cuivre, procédé de gravure, et procédé de gestion du renouvellement d'une solution de gravure

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11230644B1 (en) * 2020-07-20 2022-01-25 Mec Company Ltd. Coating film-forming composition, method for producing surface-treated metal member, and method for producing metal-resin composite

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