WO2010016620A1 - Agent de traitement de surface pour cuivre ou alliage de cuivre et son utilisation - Google Patents

Agent de traitement de surface pour cuivre ou alliage de cuivre et son utilisation Download PDF

Info

Publication number
WO2010016620A1
WO2010016620A1 PCT/JP2009/064318 JP2009064318W WO2010016620A1 WO 2010016620 A1 WO2010016620 A1 WO 2010016620A1 JP 2009064318 W JP2009064318 W JP 2009064318W WO 2010016620 A1 WO2010016620 A1 WO 2010016620A1
Authority
WO
WIPO (PCT)
Prior art keywords
imidazole
dichlorophenyl
copper
methylimidazole
dichlorobenzyl
Prior art date
Application number
PCT/JP2009/064318
Other languages
English (en)
Inventor
Hirohiko Hirao
Noriaki Yamaji
Takayuki Murai
Original Assignee
Shikoku Chemicals Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shikoku Chemicals Corporation filed Critical Shikoku Chemicals Corporation
Priority to CN200980131025.2A priority Critical patent/CN102119240B/zh
Publication of WO2010016620A1 publication Critical patent/WO2010016620A1/fr

Links

Classifications

    • 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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • B23K35/3615—N-compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/12—Copper or alloys thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
    • H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan

Definitions

  • the present invention relates to a surface treating agent which is used during soldering electronic parts or the like to copper or a copper alloy of a printed wiring board, and use thereof.
  • surface mount technology with high density has been widely adopted as a mount method of a printed wiring board.
  • Such surface mount technology is classified, among others, into double-sided surface mount technology in which chip type parts are joined with use of solder paste, and hybrid mount technology which is a combination of surface mount technology of chip type parts using solder paste and through-hole mount technology of discrete parts.
  • a printed wiring board is subjected to two or more soldering steps, and thus it is exposed to high temperatures resulting in a severe thermal history.
  • oxide film formation is accelerated by heating the surface of copper or copper alloys (hereinafter sometimes simply referred to as copper) constituting the circuit part of a printed wiring board, and thus the surface of the circuit part cannot maintain good solderability .
  • a chemical layer is generally formed on the surface of the circuit part using a surface treating agent. It is necessary, however, that good solderability be maintained by preventing the chemical layer from degenerating (i.e., being degraded) to protect the copper circuit part even after the copper circuit part has a thermal history of multiple cycles.
  • Tin-lead alloy eutectic solders have been conventionally used for mounting electronic parts to a printed wiring board, etc. In recent years, however, concerns have developed that the lead contained in the solder alloy adversely affects the human body, and thus the use of a lead-free solder is desired. Accordingly, various lead-free solders are being considered.
  • solders have been suggested in which one or more metals, such as silver, zinc, bismuth, indium, antimony, copper, etc. , are added to a base metal of tin.
  • the conventionally used tin-lead eutectic solder is excellent in wettability on the surface of a substrate, particularly copper, and thus strongly adheres to copper, resulting in high reliability.
  • a lead-free solder is inferior to the conventionally used tin-lead solder in wettability on a copper surface, and thus exhibits poor solderability and low bonding strength due to voids and other bonding defects .
  • a surface treatment agent for use in preventing oxidation on the surface of copper or a copper alloy is also required to have functions for improving the wettability and solderability of the lead- free solder .
  • solders have a high melting point, and a soldering temperature that is about 20 to about 50°C higher than that of the conventionally used tin-lead eutectic solder.
  • the surface treatment agent for use in the process of soldering with the lead-free solder should have the characteristic of being able to form a chemical layer with excellent heat resistance.
  • Patent Document 1 discloses 2-alkylimidazole compounds such as 2-undecylimidazole; Patent Document 2 discloses 2-arylimidazole compounds such as 2- phenylimidazole and 2-phenyl-4-methylimidazole; Patent Document 3 discloses 2-alkylbenzimidazole compounds such as 2-nonylbenzimidazole; Patent Document 4 discloses 2- aralkylbenzimidazole compounds such as 2- (4- chlorophenylmeth ⁇ l)benzimidazole; and Patent Document 5 discloses 2-aralk ⁇ limidazole compounds such as 2- (4- chlorophenylmethyl) imidazole and 2- (2,4- dichlorophenylmethyl) -4 , 5-diphenylimidazole, respectively.
  • Patent Document 2 discloses 2-alkylimidazole compounds such as 2-undecylimidazole
  • Patent Document 2 discloses 2-arylimidazole compounds such as 2- phenylimidazole and 2-phenyl-4-
  • An object of the invention is to provide a surface treating agent, which in mounting electronic parts or the like to a printed wiring board using a solder, forms a chemical layer having excellent heat resistance on the surface of copper or a copper alloy constituting a circuit part of a printed wiring board or the like and at the same time, improves the wettability to the solder and makes the solderability good, and a surface treatment method.
  • another object of the invention is to provide a printed wiring board resulting from bringing the surface of copper or a copper alloy constituting a copper circuit part into contact with the foregoing surface treating agent and to provide a soldering method by bringing the surface of copper or a copper alloy into contact with the foregoing surface treating agent and then performing soldering using a lead-free solder.
  • the present inventors made extensive and intensive investigations.
  • a surface treating agent for copper or a copper alloy which comprises an imidazole compound represented by the formula (I) :
  • CD wherein R represents a hydrogen atom or an alkyl group, Xi and X 2 are the same or different and represent a chlorine atom or a bromine atom; m and n represent an integer of 0 to 3 and at least one of m or n is 1 or more.
  • a surface treatment method for copper or a copper alloy which comprises bringing a surface of the copper or the alloy into contact with the surface treating agent according to any one of the above (1) to (3) .
  • a printed wiring board which comprises copper or a copper alloy constituting a copper circuit part, wherein a surface of the copper or the alloy has been brought into contact with the surface treating agent according to any one of the above (1) to (3) .
  • a soldering method which comprises bringing a surface of copper or a copper alloy into contact with the surface treating agent according to any one of the above (1) to (3) and then performing soldering with a lead-free solder.
  • the surface treating agent according to the invention is not only able to form a chemical layer having excellent heat resistance on the surface of copper or a copper alloy constituting a circuit part of a printed wiring board or the like, but is also able to greatly improve the wettability of a lead-free solder to the subject surface and provide for good solderability. Also, since the soldering method according to the invention makes it possible to use a solder not containing lead, which is a harmful metal, it is useful from the viewpoint of environmental protection.
  • the imidazole compound for use in the invention is represented by the formula (I), i.e., an imidazole compound having a fundamental skeleton wherein a benzyl group is bonded to the 2-position of the imidazole ring (hereinafter simply referred to as benzyl group) and a phenyl group is bonded to the 4 (5) -position of the imidazole ring (hereinafter simply referred to as phenyl group) , and at least either one of the benzene ring of the benzyl group or the phenyl group is substituted with one or more chlorine atom(s) and/or bromine atom(s) (hereinafter a chlorine atom and a bromine atom are sometimes collectively referred to as a halogen atom) .
  • imidazole compounds can be classified into the following categories (A) to (E) , based on halogen (i .e. , chlorine and/or bromine) substitution:
  • solderability improves on the order of (A) ⁇ (B) ⁇ (C) to (E). That is, as compared with the solderability in the case where a chemical layer is formed on the copper surface using a surface treating agent containing the imidazole compound of (A) , the solderability in the case where a chemical layer is formed on the copper surface using a surface treating agent containing the imidazole compound of (B) is more excellent.
  • R in the formula (I) is a hydrogen atom or an alkyl group and the alkyl group is preferably a linear or branched saturated aliphatic group having 1 to 8 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group.
  • the imidazole compound for use in carrying out the invention can be synthesized by adopting the synthetic method shown in the following reaction scheme. In this connection, as a phenylacetamidine compound, a phenylacetamidine hydrochloride compound can be suitably used.
  • R, X 1 , X 2 , m and n are the same as described above and X 3 represents a chlorine atom, a bromine atom or an iodine atom.
  • examples thereof in the case where R is a hydrogen atom include: 2-benzyl-4- (2-chlorophenyl) imidazole, 2-benzyl-4- (3-chlorophenyl) imidazole, 2-benzyl-4- (4 -chlorophenyl) imidazole, 2-benzyl-4- (2-bromophenyl ) imidazole, 009/064318
  • R is a methyl group
  • examples thereof in the case where R is a methyl group include : 2-benzyl-4- (2-chlorophenyl) -5-meth ⁇ limidazole, 2-benzyl-4- (3-chlorophenyl) -5-methylimidazole, 2-benzyl-4- (4-chlorophenyl) -5-methylimidazole, 2-benzyl-4- (2-bromophenyl) -5-methylimidazole, 2-benzyl-4- (3-bromophenyl) -5-methylimidazole, 2-benzyl-4- (4 -bromophenyl ) -5-methylimidazole,
  • the imidazole compound is used as an active ingredient of a surface treating agent prepared by dissolving it in water.
  • the imidazole compound may be contained, for example, in a proportion of from 0.01 to 10% by weight, and preferably from 0.1 to 5% by weight in the surface treating agent.
  • the content of the imidazole compound is less than 0.01% by weight, the film thickness of the chemical layer as formed on the surface of copper may be too thin, so that the oxidation of the surface of copper cannot be sufficiently prevented.
  • the imidazole compound in the surface treating agent may fail to be completely dissolved, or there is a concern that the compound may be reprecipitated even after it has been completely dissolved, and is therefore not preferred.
  • an organic acid or an inorganic acid may be generally used as the acid, but a small amount of an organic solvent may be used simultaneously.
  • Representative examples of the organic acid to be used on this occasion include formic acid, acetic acid, propionic acid, butyric acid, glyoxylic acid, pyruvic acic, acetoacetic acid, levulinic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, glycolic acid, glyceric acid, lactic acid, acrylic acid, methoxyacetic acid, ethoxyacetic acid, propoxyacetic acid, butoxyacetic acid, 2-(2 ⁇ methoxyethoxy) acetic acid, 2-[2-(2- ethoxyethoxy) ethoxy] acetic acid, 2- ⁇ 2-[2-(2- ethoxyethoxy) ethoxy] ethoxy ⁇ acetic acid,
  • organic solvent suitable are lower alcohols such as methanol, ethanol , and isopropyl alcohol, or acetone, N,N-dimethylfofmamide, ethylene glycol and the like, which are freely miscible with water.
  • lower alcohols such as methanol, ethanol , and isopropyl alcohol, or acetone, N,N-dimethylfofmamide, ethylene glycol and the like, which are freely miscible with water.
  • a copper compound may be added in order to hasten the formation rate of the chemical layer on the surface of copper or a copper alloy.
  • a zinc compound may be added in order to further enhance the heat resistance of the chemical layer formed.
  • Representative examples of the copper compound include copper acetate, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, copper iodide, copper hydroxide, copper phosphate, copper sulfate, and copper nitrate; and representative examples of the zinc compound include zinc oxide, zinc formate, zinc acetate, zinc oxalate, zinc lactate, zinc citrate, zinc sulfate, zinc nitrate, and zinc phosphate. Both of them may be contained in a proportion of from 0.01 to 10% by weight, and preferably from 0.02 to 5% by weight in the surface treating agent.
  • a halogen compound (using "halogen” in its more general sense) may be added into the surface treating agent in a proportion of from 0.001 to 1% by weight, and preferably from 0.01 to 0.1% by weight.
  • halogen compound examples include sodium fluoride, potassium fluoride, ammonium fluoride, sodium chloride, potassium chloride, ammonium chloride, sodium bromide, potassium bromide, ammonium bromide, sodium iodide, potassium iodide, and ammonium iodide.
  • the liquid temperature of the surface treating agent may be preferably from 10 to 70°C, and the contact time may be preferably from 1 second to 10 minutes .
  • Examples of the contact method include dipping, spraying, and coating methods .
  • thermoplastic resin After performing the surface treatment according to the invention, it is possible to further enhance the heat resistance by forming a double layer structure comprising the chemical layer coated with a thermoplastic resin.
  • thermoplastic resin having excellent heat resistance which may be composed of a rosin derivative (for example, rosin or a rosin ester) , a terpene resin derivative (for example, a terpene resin or a terpene phenol resin) , a hydrocarbon resin (for example, an aromatic hydrocarbon resin or an aliphatic hydrocarbon resin) , or a mixture thereof in a solvent (for example, toluene, ethyl acetate, or isopropyl alcohol) and uniformly coating the solution in a thickness of, for example, from 1 to 30 ⁇ m on the chemical layer using a roll ⁇ oater or the like.
  • a rosin derivative for example, rosin or a rosin ester
  • terpene resin derivative for example, a terpene resin or a terpene phenol resin
  • hydrocarbon resin for example, an aromatic hydrocarbon resin or an aliphatic hydrocarbon resin
  • solvent for example, toluene,
  • the soldering method of the invention is applicable to flow soldering which comprises moving a printed wiring board over a molten liquid-state solder in a solder bath to solder junctions between electronic parts and the printed wiring board or reflow soldering which comprises printing in advance a paste cream solder on the printed wiring board according to a circuit pattern, mounting electronic parts thereon, and heating the whole printed wiring board to melt the solder to complete the soldering.
  • imidazole compounds and evaluating test methods used in Examples and Comparative Examples are as follows .
  • Imidazole compounds used in Examples are as follows and Synthesis Examples are shown in Reference Examples 2 to 20.
  • Reference Example 1 shows a synthesis example of (4-chlorophenyl) acetamidine hydrochloride which is a raw material for the imidazole compound of Reference Example 2.
  • C-2 5-hexyl-4-phenyl-2- (3 , 4 , 5-trichlorobenzyl) imidazole
  • ⁇ D-4 -2- (4 -bromobenzyl ) -4- (2 ,4-dichlorophenyl) -5- methylimidazole
  • 2-benzyl-4- (4-chlorophenyl) -5-methylimidazole was synthesized in accordance with the method of Reference Example 2, changing (4-chlorophen ⁇ l) acetamidine hydrochloride of Reference Example 2 to phenylacetamidine hydrochloride and 2-bromoacetophenone to 2-bromo-4 T - chloropropiophenone .
  • (2-chlorophen ⁇ l) acetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4- chlorophenyl) acetonitrile of Reference Example 1 to (2- chlorophenyl) acetonitrile .
  • 2- (2-chlorobenzyl) -5-methyl-4-phen ⁇ limidazole was synthesized in accordance with the method of Reference Example 2, changing (4 -chlorophenyl) acetamidine hydrochloride of Reference Example 2 to (2- chlorophenyl) acetamidine hydrochloride and 2- bromoacetophenone to 2-bromopropiophenone.
  • (2 , 4-dichlorophenyl) acetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4- chlorophenyl) acetonitrile of Reference Example 1 to (2,4- dichlorophenyl) acetonitrile.
  • phenylacetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4 -chlorophenyl) acetonitrile of Reference Example 1 to phenylacetonitrile.
  • 2-benzyl-4- (2 ,4-dichlorophen ⁇ l) -5- methylimidazole was synthesized in accordance with the method of Reference Example 2, changing (4- chlorophenyl) acetamidine hydrochloride of Reference Example 2 to phenylacetamidine hydrochloride and 2- bromoacetophenone to 2-bromo-2 ' ,4 ' -dichloropropiophenone .
  • Reference Example 10 Synthesis of C-3
  • 5-hexyl-4-phen ⁇ l-2- (3,4,5- trichlorobenzyl) imidazole was synthesized in accordance with the method of Reference Example 2, changing (4- chlorophenyl) acetamidine hydrochloride of Reference Example 2 to (3 ,4 ,5-trichlorophenyl) acetamidine hydrochloride and 2-bromoacetophenone to 2- bromooctanophenone .
  • (2, 4-dichlorophenyl) acetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4- chlorophenyl) acetonitrile of Reference Example 1 to (2,4- dichlorophenyl) acetonitrile.
  • (2, 4-dichlorophenyl) acetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4- chlorophenyl) acetonitrile of Reference Example 1 to (2,4- dichlorophenyl) acetonitrile .
  • (2-chlorophenyl) acetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4- chlorophenyl) acetonitrile of Reference Example 1 to (2- chlorophenyl) acetonitrile.
  • (4-bromophenyl) acetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4 -chlorophenyl) acetonitrile of Reference Example 1 to (4 -bromophenyl) acetonitrile.
  • (2 , 4-dichlorophenyl) acetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4- chlorophenyl) acetonitrile of Reference Example 1 to (2,4- dichlorophenyl) acetonitrile.
  • (2,4-dichlorophenyl ) acetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4- chlorophenyl) acetonitrile of Reference Example 1 to (2,4- dichlorophenyl) acetonitrile.
  • 2-benz ⁇ l-4-phenylimidazole was synthesized in accordance with the method of Reference Example 2, changing (4-chlorophen ⁇ l) acetamidine hydrochloride of Reference Example 2 to phenylacetamidine hydrochloride.
  • (2 , 4-dichlorophenyl) acetamidine hydrochloride was synthesized in accordance with the method of Reference Example 1, changing (4- chlorophenyl) a ⁇ etonitrile of Reference Example 1 to (2,4- dichlorophenyl) acetonitrile.
  • 2- (2 ,4-dichlorobenzyl) -4 ,5-diphenylimidazole was synthesized in accordance with the method of Reference Example 2, changing (4-chlorophenyl) acetamidine hydrochloride of Reference Example 2 to (2,4- dichlorophenyl) acetamidine hydrochloride and 2- bromoacetophenone to 2-bromo-2-phenylacetophenone.
  • a printed wiring board made of a glass epoxy resin of 120 mm (length) x 150 mm (width) x 1.6 mm (thickness) and having 300 copper through-holes having an inner diameter of 0.80 iron was used as a test piece.
  • This test piece was degreased, subjected to soft etching, and then washed with water. Thereafter, the test piece was dipped in a surface treating agent kept at a prescribed liquid temperature for a prescribed period of time, washed with water, and then dried to form a chemical layer having a thickness of from about 0.10 to 0.50 ⁇ m on the copper surface .
  • the surface-treated test piece was subjected to three cycles of reflow-heating in which the peak temperature was 240°C using an infrared reflow oven (trade name: MULTI-PRO-306, manufactured by Vetronix Co., Ltd.) and subsequently soldering was performed with a flow soldering device (conveyor speed: 1.0 m/min) .
  • the solder used was a tin-lead eutectic solder with a composition of 63% tin and 37% lead (% by weight) (trade name: H63A, manufactured by Senju Metal Industry Co., Ltd.), and the flux used for soldering was JS-64MSS (manufactured by Koki Co., Ltd.).
  • the soldering temperature was 240°C.
  • the test piece surface treated as above was also soldered using a lead-free solder in the same manner as for the tin-lead eutectic solder.
  • the solder used was a lead-free solder (trade name: H705 ⁇ ECOSOLDER” , manufactured by Senju Metal Industry Co., Ltd.) with a composition of 96.5% tin, 3.0% silver and 0.5% copper (% by weight) , and the flux used for soldering was JS-E-09 (manufactured by Koki Co., Ltd.).
  • the reflow-heating peak temperature was 245°C
  • the soldering temperature was also 245°C.
  • the proportion (%) of the number of (soldered) copper through-holes in which the solder was filled up to the upper land of the copper through-holes with respect to the total number of copper through-holes (300 holes) was calculated.
  • solder wettability on the copper surface When the solder wettability on the copper surface is large, the molten solder penetrates inside each copper through-hole, whereby the molten solder readily fills it to the upper land of the through-hole. That is, when a ratio of the number of through-holes whose upper lands were soldered to the total number of through-holes was large, solder wettability and solderability to the copper would be judged to be excellent.
  • a printed wiring board made of a glass epoxy resin of 50 mm (length) x 50 mm (width) x 1.2 mm (thickness) was used as a test piece.
  • This printed wiring board had a circuit pattern in which 10 pieces of a copper-foiled circuit with a conductor width of 0.80 mm and a length of 20 mm were formed in a width direction at intervals of 1.0 mm.
  • the test piece was degreased, subjected to soft etching, and then washed with water.
  • test piece was dipped in a surface treating agent kept at a prescribed liquid temperature for a prescribed period of time, washed with water, and then dried to form a chemical layer having a thickness of from about 0.10 to 0.50 ⁇ m on the copper surface.
  • the surface-treated test piece was subjected to one cycle of reflow-heating in which the peak temperature was 240°C using an infrared reflow oven (trade name: MULTI- PRO-306, manufactured by Vetronix Co., Ltd.).
  • a tin-lead solder paste was printed on the center of the copper circuit parts using a metal mask having an aperture diameter of 1.2 mm and a thickness of 150 ⁇ m, and reflow-heating was conducted under the above- described conditions and soldering was conducted.
  • the tin-lead solder paste used was an eutectic solder (trade name: OZ-63-330F-40-10 , manufactured by Senju Metal
  • Test pieces surface treated as above were also soldered using a lead-free solder paste in the same manner for the tin-lead solder paste.
  • the lead-free solder used was composed of 96.5% tin, 3.0% silver and 0.5% copper (% by weight) (trade name: M705-221BM5-42-11 , manufactured by Senju Metal Industry Co., Ltd.) .
  • the peak temperature of reflow-heating attained before and after the solder paste printing was set to 245°C.
  • the length (mm) of solder which wet and spread over the copper circuit part of the obtained test piece was measured.
  • solder wettability and solderability would be judged to be excellent.
  • Example 1 and subjected to a surface treatment under the treatment conditions as described in Table 1 or 2. With respect to the resulting test pieces, the solder flow-up rate properties and solder spreadability were measured. These test results are shown in Table 1 or 2.
  • Example 1 to 19 the solder flow-up rate properties in the case of using an eutectic solder are found to be 100% in just about all cases (98% only in Example 3) and no difference is observed among Examples 1 to 19.
  • some differences are observed among Examples 1 to 3 (hereinafter referred to Case A) , Examples 4 to 6 (hereinafter referred to Case B) and Examples 7 to 19 (hereinafter referred to Case C) .
  • solder flow-up rate properties in the case of using a lead-free solder and the solder spreadability in the case of using an eutectic solder or a lead-free solder are improved in the order of Case A ⁇ Case B ⁇ Case C .
  • the imidazole compounds used in Case A are those wherein a hydrogen atom in only either one of the benzyl group or the phenyl group is substituted with one halogen atom.
  • the imidazole compounds used in Case B are those wherein hydrogen atoms in both of the benzyl group and the phenyl group are substituted with one halogen atom, respectively.
  • the imidazole compounds used in Case C are (i) those wherein hydrogen atoms in only either one of the benzyl group or the phenyl group is substituted with two or more halogen atoms (Examples 7 to 9) , (ii) those wherein hydrogen atoms in either one of the benzyl group or the phenyl group is substituted with two or more halogen atoms and a hydrogen atom in another one is substituted with one halogen atom (Examples 10 to 16) , and (iii) those wherein hydrogen atoms in both of the benzyl group and the phenyl group are substituted with two halogen atoms, respectively (Examples 17 to 19) .
  • the imidazole compound (Z- 4) for use in the surface treating agent is one wherein two hydrogen atoms in the benzyl group are substituted with two halogen atoms but the imidazole compound is different in the kind of the substituent bonded to 5- position of the imidazole ring from the imidazole compounds of formula (I) suitable for carrying out the invention.
  • the surface treating agent according to the invention may be conveniently used even in soldering using an eutectic solder, but can also be suitably used in soldering using a lead-free solder which shows poor solderability as compared with an eutectic solder.
  • the present invention is directed to a surface treating agent, which in mounting electronic parts or the like to a printed wiring board using a solder, forms a chemical layer having excellent heat resistance on the surface of copper or a copper alloy constituting a circuit part of a printed wiring board or the like and at the same time, improves the wettability to the solder, the solderability, and a corresponding surface treatment method.
  • the invention can provide a printed wiring board resulting from bringing the surface of copper or a copper alloy constituting a copper circuit part into contact with the foregoing surface treating agent and can provide a soldering method by bringing the surface of copper or a copper alloy into contact with the foregoing surface treating agent and then performing soldering using a lead-free solder.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Epoxy Resins (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

La présente invention concerne un agent de traitement de surface pour cuivre ou alliage de cuivre, l’agent contenant un composé imidazole représenté par la formule (I) : dans laquelle R représente un atome d’hydrogène ou un groupe alkyle, X1 et X2 sont identiques ou différents et représentent un atome de chlore ou un atome de brome ; m et n représentent un entier de 0 à 3 et m et/ou n vaut 1 ou plus. L’agent de traitement de surface est également utilisé dans des procédés de traitement de surface, dans la fabrication de cartes de circuits imprimés et dans des procédés de soudage.
PCT/JP2009/064318 2008-08-08 2009-08-07 Agent de traitement de surface pour cuivre ou alliage de cuivre et son utilisation WO2010016620A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200980131025.2A CN102119240B (zh) 2008-08-08 2009-08-07 用于铜或铜合金的表面处理剂及其应用

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2008206119 2008-08-08
JP2008-206119 2008-08-08
JP2008295619 2008-11-19
JP2008-295619 2008-11-19
JP2009124003A JP5313044B2 (ja) 2008-08-08 2009-05-22 銅または銅合金の表面処理剤及びその利用
JP2009-124003 2009-05-22

Publications (1)

Publication Number Publication Date
WO2010016620A1 true WO2010016620A1 (fr) 2010-02-11

Family

ID=41259797

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/064318 WO2010016620A1 (fr) 2008-08-08 2009-08-07 Agent de traitement de surface pour cuivre ou alliage de cuivre et son utilisation

Country Status (6)

Country Link
JP (1) JP5313044B2 (fr)
KR (1) KR101540143B1 (fr)
CN (1) CN102119240B (fr)
MY (1) MY162495A (fr)
TW (1) TWI464298B (fr)
WO (1) WO2010016620A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012161341A1 (fr) * 2011-05-23 2012-11-29 Shikoku Chemicals Corporation Composition de traitement de surface pour du cuivre et un alliage du cuivre et son utilisation
WO2012176591A1 (fr) * 2011-06-20 2012-12-27 Shikoku Chemicals Corporation Composition de traitement de surface pour du cuivre et un alliage de cuivre et son utilisation

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5301218B2 (ja) * 2008-08-25 2013-09-25 四国化成工業株式会社 銅または銅合金の表面処理剤及びその利用
JP5260357B2 (ja) * 2008-09-17 2013-08-14 四国化成工業株式会社 ２−（２，４−ジクロロベンジル）−４−フェニル−５−アルキルイミダゾール化合物
JP5260208B2 (ja) * 2008-09-22 2013-08-14 四国化成工業株式会社 ２−（２，４−ジクロロベンジル）−４−（ハロゲン化フェニル）イミダゾール化合物
JP5260367B2 (ja) * 2008-09-26 2013-08-14 四国化成工業株式会社 ２−（クロロベンジル）−４−フェニルイミダゾール化合物
KR101555753B1 (ko) 2013-11-18 2015-09-30 서울대학교산학협력단 단일 공정의 부식 방지된 구리 페이스트 제조와 다이폴 태그 안테나로의 응용
CN109048019B (zh) * 2018-09-13 2021-01-26 烟台孚信达双金属股份有限公司 一种用于铜铝复合排的焊接工艺
JP6681567B1 (ja) * 2019-05-27 2020-04-15 千住金属工業株式会社 はんだペースト及びフラックス
JP6681566B1 (ja) * 2019-05-27 2020-04-15 千住金属工業株式会社 はんだペースト及びフラックス

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06322551A (ja) * 1993-05-10 1994-11-22 Shikoku Chem Corp 銅及び銅合金の表面処理剤
JPH06329635A (ja) * 1993-05-24 1994-11-29 Shikoku Chem Corp 新規イミダゾール化合物
EP0627499A1 (fr) * 1993-05-10 1994-12-07 Shikoku Chemicals Corporation Agent de traitement de surfaces en cuivre ou ses alliages
JPH07243054A (ja) * 1994-03-08 1995-09-19 Shikoku Chem Corp 銅及び銅合金の表面処理剤
WO2000071120A1 (fr) * 1999-05-25 2000-11-30 Smithkline Beecham Corporation Composes antibacteriens
JP2005068530A (ja) * 2003-08-28 2005-03-17 Tamura Kaken Co Ltd 表面処理剤、プリント回路基板およびプリント回路基板の金属の表面処理方法
EP1605078A1 (fr) * 2003-03-19 2005-12-14 Shikoku Chemicals Corporation Nouveau compose imidazole et utilisation
WO2007135930A1 (fr) * 2006-05-19 2007-11-29 Shikoku Chemicals Corporation Agent de traitement de surfaces mÉtalliques et sON utilisation

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08183776A (ja) * 1994-12-28 1996-07-16 Hideaki Yamaguchi 金属の表面保護剤ならびにそれを用いた製造方法
US6524644B1 (en) * 1999-08-26 2003-02-25 Enthone Inc. Process for selective deposition of OSP coating on copper, excluding deposition on gold
JP4181888B2 (ja) * 2003-02-04 2008-11-19 四国化成工業株式会社 銀及び銀合金の防食処理剤
JP4546163B2 (ja) * 2004-06-10 2010-09-15 四国化成工業株式会社 銅または銅合金の表面処理剤及び半田付け方法
JP2007297685A (ja) * 2006-05-01 2007-11-15 Shikoku Chem Corp 金属の表面処理剤およびその利用

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06322551A (ja) * 1993-05-10 1994-11-22 Shikoku Chem Corp 銅及び銅合金の表面処理剤
EP0627499A1 (fr) * 1993-05-10 1994-12-07 Shikoku Chemicals Corporation Agent de traitement de surfaces en cuivre ou ses alliages
US5560785A (en) * 1993-05-10 1996-10-01 Shikoku Chemicals Corporation Method for forming a protective chemical layer on copper and copper alloy surfaces
JPH06329635A (ja) * 1993-05-24 1994-11-29 Shikoku Chem Corp 新規イミダゾール化合物
JPH07243054A (ja) * 1994-03-08 1995-09-19 Shikoku Chem Corp 銅及び銅合金の表面処理剤
WO2000071120A1 (fr) * 1999-05-25 2000-11-30 Smithkline Beecham Corporation Composes antibacteriens
JP2003500357A (ja) * 1999-05-25 2003-01-07 スミスクライン・ビーチャム・コーポレイション 抗菌性化合物
EP1605078A1 (fr) * 2003-03-19 2005-12-14 Shikoku Chemicals Corporation Nouveau compose imidazole et utilisation
JP2005068530A (ja) * 2003-08-28 2005-03-17 Tamura Kaken Co Ltd 表面処理剤、プリント回路基板およびプリント回路基板の金属の表面処理方法
WO2007135930A1 (fr) * 2006-05-19 2007-11-29 Shikoku Chemicals Corporation Agent de traitement de surfaces mÉtalliques et sON utilisation

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012161341A1 (fr) * 2011-05-23 2012-11-29 Shikoku Chemicals Corporation Composition de traitement de surface pour du cuivre et un alliage du cuivre et son utilisation
US9532493B2 (en) 2011-05-23 2016-12-27 Shikoku Chemicals Corporation Surface treating composition for copper and copper alloy and utilization thereof
US10398028B2 (en) 2011-05-23 2019-08-27 Shikoku Chemicals Corporation Surface treating composition for copper and copper alloy and utilization thereof
WO2012176591A1 (fr) * 2011-06-20 2012-12-27 Shikoku Chemicals Corporation Composition de traitement de surface pour du cuivre et un alliage de cuivre et son utilisation
CN103620088A (zh) * 2011-06-20 2014-03-05 四国化成工业株式会社 用于铜和铜合金的表面处理组合物及其利用
US9649713B2 (en) 2011-06-20 2017-05-16 Shikoku Chemicals Corporation Surface treating composition for copper and copper alloy and utilization thereof

Also Published As

Publication number Publication date
TW201009117A (en) 2010-03-01
JP5313044B2 (ja) 2013-10-09
JP2010150651A (ja) 2010-07-08
KR20110073421A (ko) 2011-06-29
KR101540143B1 (ko) 2015-07-28
TWI464298B (zh) 2014-12-11
CN102119240B (zh) 2014-07-30
MY162495A (en) 2017-06-15
CN102119240A (zh) 2011-07-06

Similar Documents

Publication Publication Date Title
KR101540143B1 (ko) 구리 또는 구리 합금용 표면 처리제 및 그 용도
US10398028B2 (en) Surface treating composition for copper and copper alloy and utilization thereof
EP1886759B1 (fr) Preflux hydrosoluble et son utilisation
EP2721195B1 (fr) Composition de traitement de surface pour du cuivre et un alliage de cuivre et son utilisation
KR101074640B1 (ko) 납땜 동안 구리 표면에 사용하기 위한 페닐나프틸이미다졸
JP4546163B2 (ja) 銅または銅合金の表面処理剤及び半田付け方法
KR101540144B1 (ko) 구리 또는 구리 합금용 표면 처리제 및 그 용도
JP5985367B2 (ja) 銅または銅合金の表面処理方法およびその利用
TWI448581B (zh) 銅或銅合金之表面處理劑及其用途

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980131025.2

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09788032

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20117002997

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 960/DELNP/2011

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09788032

Country of ref document: EP

Kind code of ref document: A1