CN102119240B - Surface treating agent for copper or copper alloy and use thereof - Google Patents

Surface treating agent for copper or copper alloy and use thereof Download PDF

Info

Publication number
CN102119240B
CN102119240B CN200980131025.2A CN200980131025A CN102119240B CN 102119240 B CN102119240 B CN 102119240B CN 200980131025 A CN200980131025 A CN 200980131025A CN 102119240 B CN102119240 B CN 102119240B
Authority
CN
China
Prior art keywords
methyl
imidazoles
phenyl
methylimidazole
dichlorophenyl
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CN200980131025.2A
Other languages
Chinese (zh)
Other versions
CN102119240A (en
Inventor
平尾浩彦
山地范明
村井孝行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shikoku Chemicals Corp
Original Assignee
Shikoku Chemicals Corp
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 Corp filed Critical Shikoku Chemicals Corp
Publication of CN102119240A publication Critical patent/CN102119240A/en
Application granted granted Critical
Publication of CN102119240B publication Critical patent/CN102119240B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • 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
    • 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, thiol
    • H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan

Abstract

A surface treating agent for copper or a copper alloy contains an imidazole compound represented by the formula (I): wherein R represents a hydrogen atom or an alkyl group, X1 and X2 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. The surface treating agent is also used in surface treating methods, in making printed wiring boards and in soldering methods.

Description

For surface treatment agent and the application thereof of copper or copper alloy
Technical field
The present invention relates to the surface treatment agent and the application thereof that during the copper of printed-wiring board (PWB) or copper alloy, use electronic unit etc. is welded to.
Background technology
In recent years, extensively adopt and there is highdensity surface mounting technique using the installation method as printed-wiring board (PWB).Wherein, this surface mounting technique is divided into double-dial watch SMT and mixes field engineering etc., in described double-dial watch SMT, use soldering paste that chip type component is bonded together, and described mixing field engineering is to use the surface mounting technique of chip type component of soldering paste and the combination of the through hole mount technology of discrete parts.In any installation method, printed-wiring board (PWB) experiences more than twice welding step, is therefore exposed to the open air at high temperature, thereby causes serious thermal history.
As a result, form the copper of circuit block of printed-wiring board (PWB) or the surface of copper alloy (be hereinafter sometimes called for short and make copper) because heating has promoted the formation of oxide film, therefore the surface of circuit block can not keep good weldability.
In order to prevent the copper circuit parts generation atmospheric oxidation of printed-wiring board (PWB), conventionally use surface treatment agent to form chemical layer on the surface of circuit block.But, even must be by after copper circuit parts have the thermal history of multiple circulations, also prevent that chemical layer from worsening (, by deteriorated) and protecting copper circuit parts, thereby keep good weldability.
Conventionally that tin-lead alloy eutectic solder is first-class for electronic unit being installed to printed-wiring board (PWB).But, in recent years, produce following worry: the lead comprising in welding flux alloy produces injurious effects to human body, therefore expect to use lead-free solder.
Therefore, considering multiple lead-free solder.For example, propose following lead-free solder, wherein in the underlying metal of tin, added one or more metals as silver, zinc, bismuth, indium, antimony, copper etc.
Normally used tin-plumbous eutectic solder has excellent wettability on the surface of substrate, particularly copper, therefore can adhere on copper securely, thereby cause high reliability.
On the contrary, compared with normally used tin-lead solder, lead-free solder is poor in the lip-deep wettability of copper, and therefore, because space and other joint defects cause, weldability is poor and bond strength is low.
Therefore,, in the time using lead-free solder, must select to have the welding flux alloy and the soldering flux that is applicable to using of superior weldability together with lead-free solder.For preventing that the surface treatment agent that oxidation occurs on the surface of copper or copper alloy from also needing to have the raising wettability of lead-free solder and the function of weldability.
Many lead-free solders have high-melting-point, and its welding temperature is than high approximately 20 DEG C～approximately 50 DEG C of the temperature of normally used tin-plumbous eutectic solder.Therefore, for utilizing the surface treatment agent of the method that lead-free solder welds should there is the characteristic of the chemical layer that can form excellent heat resistance.
As the activeconstituents of this surface treatment agent, multiple imidazolium compounds is proposed.For example, respectively, patent documentation 1 discloses 2-alkyl imidazole compound as 2-undecyl imidazole; Patent documentation 2 discloses 2-Aryimidazole compound as 2-phenylimidazole and 2-phenyl-4-methylimidazole; Patent documentation 3 discloses 2-alkyl benzimidazole compound as 2-nonyl benzoglyoxaline; Patent documentation 4 discloses 2-aralkyl benzimidazole compound as 2-(4-Chlorophenylmethyl) benzoglyoxaline; And patent documentation 5 discloses 2-aralkyl imidazolium compounds as 2-(4-Chlorophenylmethyl) imidazoles and 2-(2,4 dichloro benzene ylmethyl)-4,5-diphenyl-imidazole.
But in the situation of the surface treatment agent that contains this imidazolium compounds in use, the thermotolerance of the chemical layer forming on copper surface is still undesirable.In addition,, in the time of welding, the wettability of scolder is not enough and therefore can not obtain good weldability.Especially, in the situation that replaces eutectic solder to weld with lead-free solder, be difficult to above-mentioned surface treatment agent to be put to actual use.
Reference listing
Patent documentation
Patent documentation 1:JP-B-46-17046
Patent documentation 2:JP-A-4-206681
Patent documentation 3:JP-A-5-25407
Patent documentation 4:JP-A-5-186888
Patent documentation 5:JP-A-7-243054
Summary of the invention
In view of the above problems, completed the present invention.An object of the present invention is to provide a kind of surface treatment agent and a kind of surface treatment method, wherein in the time using scolder that electronic unit etc. is installed on printed-wiring board (PWB), described surface treatment agent forms the chemical layer with excellent heat resistance forming on the copper of circuit block etc. of printed-wiring board (PWB) or copper alloy surface, meanwhile, described surface treatment agent has improved the wettability to described scolder and has made weldability good.
In addition, another object of the present invention is to provide a kind of printed-wiring board (PWB) and a kind of welding process is provided, described printed-wiring board (PWB), by contacting and obtain with above-mentioned surface treatment agent forming the copper of copper circuit parts or the surface of copper alloy, contacts the surface of copper or copper alloy and then uses lead-free solder to weld in described welding process with above-mentioned surface treatment agent.
In order to address the above problem, the inventor has carried out extensive and careful research.Found that, the surface treatment agent that contains the imidazolium compounds being represented by formula (I) by utilization is processed the printed-wiring board (PWB) with copper circuit parts, can on the surface of copper circuit parts, form and there is excellent heat resistance and can resist the chemical layer of the welding temperature of lead-free solder, simultaneously, by improve the wettability of scolder to copper or copper alloy surface in the welding that utilizes lead-free solder to carry out, can obtain good weldability, thereby complete the present invention.
, the present invention its most widely configuration comprise following aspect:
(1) for a surface treatment agent for copper or copper alloy, it comprises the imidazolium compounds being represented by formula (I):
Wherein R represents hydrogen atom or alkyl, X 1and X 2identical or different and represent chlorine atom or bromine atoms; M and n represent that at least one in 0～3 integer and m or n is more than 1.
(2), according to the surface treatment agent of above-mentioned (1), wherein each in m and n is more than 1.
(3), according to the surface treatment agent of above-mentioned (1), wherein at least one in m or n is more than 2.
(4), for a surface treatment method for copper or copper alloy, described method comprises the surface treatment agent described in any one in the surface of copper or described alloy and above-mentioned (1)～(3) is contacted.
(5) printed-wiring board (PWB), it comprises the copper or the copper alloy that form copper circuit parts, and the surface of wherein said copper or described alloy contacts with the surface treatment agent described in any one in above-mentioned (1)～(3).
(6) welding process, described method comprises the surface treatment agent described in any one in the surface of copper or copper alloy and above-mentioned (1)～(3) contact also and then utilizes lead-free solder to weld.
Surface treatment agent of the present invention not only can form the chemical layer with excellent heat resistance forming on the copper of circuit block etc. of printed-wiring board (PWB) or the surface of copper alloy, can also greatly improve the wettability of lead-free solder to body surface and good weldability is provided.
In addition, because welding process of the present invention makes to use not the scolder containing harmful metallic lead, so from the viewpoint of environment protection, described method is useful.
Embodiment
Imidazolium compounds for the present invention is represented by formula (I),, there is the imidazolium compounds of following basic framework, wherein phenmethyl be attached to (hereafter is made phenmethyl) on the 2-position of imidazole ring and phenyl be attached on 4 (5)-positions of imidazole ring (hereafter is made phenyl), and utilize one or more chlorine atoms and/or bromine atoms (hereinafter sometimes chlorine atom and bromine atoms being referred to as to halogen atom) in the phenyl ring of phenmethyl or phenyl at least any one replaces.
R, X in its Chinese style 1, X 2, m and n same as described above.
Replace according to halogen (being chlorine and/or bromine), this imidazolium compounds can be divided into following (A)～(E) several classes:
(A) imidazolium compounds that wherein only the hydrogen atom in any one in phenmethyl or phenyl is replaced by a halogen atom;
(B) imidazolium compounds that wherein hydrogen atom in phenmethyl and phenyl is all replaced by a halogen atom respectively;
(C) imidazolium compounds that wherein only the hydrogen atom in any one is replaced by more than two halogen atom in phenmethyl or phenyl;
(D) imidazolium compounds that wherein hydrogen atom in any one in phenmethyl or phenyl is replaced by more than two halogen atom and hydrogen atom in another is replaced by a halogen atom; With
(E) imidazolium compounds that wherein hydrogen atom in phenmethyl and phenyl is all replaced by more than two halogen atom respectively.
The discovery obtaining according to the inventor, in using containing the imidazolium compounds of above-mentioned classification (A)～(E), a kind of surface treatment agent of compound forms chemical layer and uses in the situation that lead-free solder welds on copper or copper alloy surface, and the order that weldability is improved is (A) < (B) < (C)～(E).; compared with forming the weldability in the situation of chemical layer with the surface treatment agent of the imidazolium compounds that contains (A) in use on copper surface, it is more excellent that the surface treatment agent of the imidazolium compounds that contains (B) in use forms weldability in the situation of chemical layer on copper surface.Similarly, compared with the situation of the imidazolium compounds of (B), in the situation of the imidazolium compounds of (C), weldability is more excellent.And, contain in use (C), (D) and (E) in any one surface treatment agent on copper surface, form in the situation of chemical layer, obtained almost identical weldability.
According to above-mentioned discovery, about being applicable to implement imidazolium compounds of the present invention, with in m or n, at least one is compared with more than 1 situation, m and n are both preferably at least one more than 1 and in m or n more preferably more than 2.
R in formula (I) is that hydrogen atom or alkyl and described alkyl are preferably and have the straight chain of 1～8 carbon atom or the radical of saturated aliphatic group of branching.The example of this alkyl comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl and octyl group.
Can synthesize for implementing imidazolium compounds of the present invention by adopting the synthetic method shown in following reaction icon.In this, as phenylacetamidino compound, can suitably use phenylacetamidino hydrochloride compound.
Wherein R, X 1, X 2, m and n and above-mentioned identical and X 3represent chlorine atom, bromine atoms or iodine atom.
As for implement of the present invention by formula (I) represent imidazolium compounds, in the situation that is hydrogen atom at R, the example comprises: 2-phenmethyl-4-(2-chloro-phenyl-) imidazoles, 2-phenmethyl-4-(3-chloro-phenyl-) imidazoles, 2-phenmethyl-4-(4-chloro-phenyl-) imidazoles, 2-phenmethyl-4-(2-bromophenyl) imidazoles, 2-phenmethyl-4-(3-bromophenyl) imidazoles, 2-phenmethyl-4-(4-bromophenyl) imidazoles, 2-phenmethyl-4-(2,3-dichlorophenyl) imidazoles, 2-phenmethyl-4-(2,4 dichloro benzene base) imidazoles, 2-phenmethyl-4-(2,5-dichlorophenyl) imidazoles, 2-phenmethyl-4-(2,6-dichlorophenyl) imidazoles, 2-phenmethyl-4-(3,4-dichlorophenyl) imidazoles, 2-phenmethyl-4-(3,5-dichlorophenyl) imidazoles, 2-phenmethyl-4-(2,4-dibromo phenyl) imidazoles, 2-phenmethyl-4-(2,5-dibromo phenyl) imidazoles, 2-phenmethyl-4-(2,4,5-trichlorophenyl) imidazoles, 2-phenmethyl-4-(3,4,5-trichlorophenyl) imidazoles, 2-phenmethyl-4-(2,4,5-tribromo phenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-phenylimidazole, 2-(3-chlorophenylmethyl)-4-phenylimidazole, 2-(4-chlorophenylmethyl)-4-phenylimidazole, 2-(2-Brombenzyl)-4-phenylimidazole, 2-(3-Brombenzyl)-4-phenylimidazole, 2-(4-Brombenzyl)-4-phenylimidazole, 2-(2-chlorophenylmethyl)-4-(2-chloro-phenyl-) imidazoles, 2-(2-chlorophenylmethyl)-4-(4-chloro-phenyl-) imidazoles, 2-(4-chlorophenylmethyl)-4-(2-chloro-phenyl-) imidazoles, 2-(4-chlorophenylmethyl)-4-(4-chloro-phenyl-) imidazoles, 4-(4-bromophenyl)-2-(4-chlorophenylmethyl) imidazoles, 2-(4-Brombenzyl)-4-(2-chloro-phenyl-) imidazoles, 2-(4-Brombenzyl)-4-(4-chloro-phenyl-) imidazoles, 2-(4-Brombenzyl)-4-(4-bromophenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(2,3-dichlorophenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(2-chlorophenylmethyl)-4-(2,5-dichlorophenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(2,6-dichlorophenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(3,5-dichlorophenyl) imidazoles, 2-(3-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(3-chlorophenylmethyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2,3-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(4-chlorophenylmethyl)-4-(2,5-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2,6-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(3,5-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2,4-dibromo phenyl) imidazoles, 2-(2-Brombenzyl)-4-(2,5-dichlorophenyl) imidazoles, 2-(2-Brombenzyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(2-Brombenzyl)-4-(2,5-dibromo phenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(2,4,5-trichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2,4,5-tribromo phenyl) imidazoles, 2-(4-Brombenzyl)-4-(2,4,5-trichlorophenyl) imidazoles, 2-(2-Brombenzyl)-4-(2,4,6-tribromo phenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-phenylimidazole, 2-(2,4 dichloro benzene methyl)-4-phenylimidazole, 2-(2,5-dichlorobenzene methyl)-4-phenylimidazole, 2-(2,6-dichlorobenzene methyl)-4-phenylimidazole, 2-(3,4-dichlorobenzene methyl)-4-phenylimidazole, 2-(3,5-dichlorobenzene methyl)-4-phenylimidazole, 2-(2,4-dibromobenzene methyl)-4-phenylimidazole, 4-(2-chloro-phenyl-)-2-(2,3-dichlorobenzene methyl) imidazoles, 4-(2-chloro-phenyl-)-2-(2,4 dichloro benzene methyl) imidazoles, 4-(2-chloro-phenyl-)-2-(2,5-dichlorobenzene methyl) imidazoles, 4-(2-chloro-phenyl-)-2-(2,6-dichlorobenzene methyl) imidazoles, 4-(2-chloro-phenyl-)-2-(3,4-dichlorobenzene methyl) imidazoles, 4-(2-chloro-phenyl-)-2-(3,5-dichlorobenzene methyl) imidazoles, 4-(3-chloro-phenyl-)-2-(2,4 dichloro benzene methyl) imidazoles, 4-(3-chloro-phenyl-)-2-(2,6-dichlorobenzene methyl) imidazoles, 4-(3-chloro-phenyl-)-2-(3,4-dichlorobenzene methyl) imidazoles, 4-(4-chloro-phenyl-)-2-(2,3-dichlorobenzene methyl) imidazoles, 4-(4-chloro-phenyl-)-2-(2,4 dichloro benzene methyl) imidazoles, 4-(4-chloro-phenyl-)-2-(2,5-dichlorobenzene methyl) imidazoles, 4-(4-chloro-phenyl-)-2-(2,6-dichlorobenzene methyl) imidazoles, 4-(4-chloro-phenyl-)-2-(3,4-dichlorobenzene methyl) imidazoles, 4-(4-chloro-phenyl-)-2-(3,5-dichlorobenzene methyl) imidazoles, 4-(2-bromophenyl)-2-(2,4 dichloro benzene methyl) imidazoles, 4-(2-bromophenyl)-2-(3,4-dichlorobenzene methyl) imidazoles, 4-(4-chloro-phenyl-)-2-(2,5-dibromobenzene methyl) imidazoles, 4-(4-bromophenyl)-2-(2,5-dibromobenzene methyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(2,3-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(2,3-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(2,3-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(2,3-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(2,3-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(2,3-dichlorophenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(2,5-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(2,5-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(2,5-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(2,5-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(2,5-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(2,5-dichlorophenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(2,6-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(2,6-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(2,6-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(2,6-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(2,6-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(2,6-dichlorophenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(3,5-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(3,5-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(3,5-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(3,5-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(3,5-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(3,5-dichlorophenyl) imidazoles, 4-(2,5-dibromo phenyl)-2-(2,4 dichloro benzene methyl) imidazoles, 4-(2,5-dibromo phenyl)-2-(3,4-dichlorobenzene methyl) imidazoles, 2-(2,5-dibromobenzene methyl)-4-(3,4-dichlorophenyl) imidazoles, 2-(2,4-dibromobenzene methyl)-4-(3,4-dibromo phenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(3,4,5-trichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(2,4,6-tribromo phenyl) imidazoles, 2-(2,4-dibromobenzene methyl)-4-(3,4,5-trichlorophenyl) imidazoles, 2-(2,4-dibromobenzene methyl)-4-(2,4,5-tribromo phenyl) imidazoles, 4-phenyl-2-(3,4,5-trichlorobenzene methyl) imidazoles, 4-phenyl-2-(2,4,5-tribromo-benzene methyl) imidazoles, 4-(4-chloro-phenyl-)-2-(2,3,6-trichlorobenzene methyl) imidazoles, 4-(2-bromophenyl)-2-(3,4,5-trichlorobenzene methyl) imidazoles, 4-(4-chloro-phenyl-)-2-(2,3,5-tribromo-benzene methyl) imidazoles, 4-(4-bromophenyl)-2-(2,4,6-tribromo-benzene methyl) imidazoles, 4-(2,4 dichloro benzene base)-2-(3,4,5-trichlorobenzene methyl) imidazoles, 4-(2,4-dibromo phenyl)-2-(3,4,5-trichlorobenzene methyl) imidazoles, 4-(3,4-dichlorophenyl)-2-(2,4,5-tribromo-benzene methyl) imidazoles, 4-(2,5-dibromo phenyl)-2-(2,3,5-tribromo-benzene methyl) imidazoles, 2-(3,4,5-trichlorobenzene methyl)-4-(2,4,5-trichlorophenyl)-imidazoles, 4-(2,4,5-tribromo phenyl)-2-(3,4,5-trichlorobenzene methyl)-imidazoles, 2-(2,4,6-tribromo-benzene methyl)-4-(2,4,5-trichlorophenyl)-imidazoles and 2-(2,4,6-tribromo-benzene methyl)-4-(2,4,6-tribromo phenyl)-imidazoles.
Similarly, in the situation that is methyl at R, the example comprises: 2-benzyl-4-(2-chlorphenyl)-5-methylimidazole, 2-benzyl-4-(3-chlorphenyl)-5-methylimidazole, 2-benzyl-4-(4-chlorphenyl)-5-methylimidazole, 2-benzyl-4-(2-bromophenyl)-5-methylimidazole, 2-benzyl-4-(3-bromophenyl)-5-methylimidazole, 2-benzyl-4-(4-bromophenyl)-5-methylimidazole, 2-benzyl-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-benzyl-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-benzyl-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-benzyl-4-(2,6-dichlorophenyl)-5-methylimidazole, 2-benzyl-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-benzyl-4-(3,5-dichlorophenyl)-5-methylimidazole, 2-benzyl-4-(2,4-dibromo phenyl)-5-methylimidazole, 2-benzyl-4-(2,5-dibromo phenyl)-5-methylimidazole, 2-benzyl-5-methyl-4-(2,4,5-trichlorophenyl) imidazoles, 2-benzyl-5-methyl-4-(3,4,5-trichlorophenyl) imidazoles, 2-benzyl-5-methyl-4-(2,4,5-tribromo phenyl) imidazoles, 2-(2-chlorophenylmethyl)-5-methyl 4-phenyl imidazoles, 2-(3-chlorophenylmethyl)-5-methyl 4-phenyl imidazoles, 2-(4-chlorophenylmethyl)-5-methyl 4-phenyl imidazoles, 2-(2-Brombenzyl)-5-methyl 4-phenyl imidazoles, 2-(3-Brombenzyl)-5-methyl 4-phenyl imidazoles, 2-(4-Brombenzyl)-5-methyl 4-phenyl imidazoles, 2-(2-chlorophenylmethyl)-4-(2-chlorphenyl)-5-methylimidazole, 2-(2-chlorophenylmethyl)-4-(4-chlorphenyl)-5-methylimidazole, 2-(4-chlorophenylmethyl)-4-(2-chlorphenyl)-5-methylimidazole, 2-(4-chlorophenylmethyl)-4-(4-chlorphenyl)-5-methylimidazole, 4-(4-bromophenyl)-2-(2-chlorophenylmethyl)-5-methylimidazole, 2-(4-Brombenzyl)-4-(2-chlorphenyl)-5-methylimidazole, 2-(4-Brombenzyl)-4-(4-chlorphenyl)-5-methylimidazole, 2-(4-Brombenzyl)-4-(4-bromophenyl)-5-methylimidazole, 2-(2-chlorophenylmethyl)-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-(2-chlorophenylmethyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(2-chlorophenylmethyl)-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-(2-chlorophenylmethyl)-4-(2,6-dichlorophenyl)-5-methylimidazole, 2-(2-chlorophenylmethyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(2-chlorophenylmethyl)-4-(3,5-dichlorophenyl)-5-methylimidazole,2-(3-chlorophenylmethyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(3-chlorophenylmethyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(4-chlorophenylmethyl)-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-(4-chlorophenylmethyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(4-chlorophenylmethyl)-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-(4-chlorophenylmethyl)-4-(2,6-dichlorophenyl)-5-methylimidazole, 2-(4-chlorophenylmethyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(4-chlorophenylmethyl)-4-(3,5-dichlorophenyl)-5-methylimidazole, 2-(4-chlorophenylmethyl)-4-(2,4-dibromo phenyl)-5-methylimidazole, 2-(4-Brombenzyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(4-Brombenzyl)-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-(4-Brombenzyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(4-Brombenzyl)-4-(2,5-dibromo phenyl)-5-methylimidazole, 2-(2-chlorophenylmethyl)-5-methyl-4-(2,4,5-trichlorophenyl)-imidazoles, 2-(4-chlorophenylmethyl)-5-methyl-4-(2,4,5-tribromo phenyl)-imidazoles, 2-(4-Brombenzyl)-5-methyl-4-(2,4,5-trichlorophenyl)-imidazoles, 2-(2-Brombenzyl)-5-methyl-4-(2,4,6-tribromo phenyl)-imidazoles, 2-(2,3-dichloro-benzenes methyl)-5-methyl 4-phenyl imidazoles, 2-(2,4-dichloro-benzenes methyl)-5-methyl 4-phenyl imidazoles, 2-(2,5-dichloro-benzenes methyl)-5-methyl 4-phenyl imidazoles, 2-(2,6-dichloro-benzenes methyl)-5-methyl 4-phenyl imidazoles, 2-(3,4-dichloro-benzenes methyl)-5-methyl 4-phenyl imidazoles, 2-(3,5-dichloro-benzenes methyl)-5-methyl 4-phenyl imidazoles, 2-(2,4-dibromobenzene methyl)-5-methyl 4-phenyl imidazoles, 4-(2-chlorphenyl)-2-(2,3-dichloro-benzenes methyl)-5-methylimidazole, 4-(2-chlorphenyl)-2-(2,4-dichloro-benzenes methyl)-5-methylimidazole, 4-(2-chlorphenyl)-2-(2,5-dichloro-benzenes methyl)-5-methylimidazole, 4-(2-chlorphenyl)-2-(2,6-dichloro-benzenes methyl)-5-methylimidazole, 4-(2-chlorphenyl)-2-(3,4-dichloro-benzenes methyl)-5-methylimidazole, 4-(2-chlorphenyl)-2-(3,5-dichloro-benzenes methyl)-5-methylimidazole, 4-(3-chlorphenyl)-2-(2,4-dichloro-benzenes methyl)-5-methylimidazole, 4-(3-chlorphenyl)-2-(2,6-dichloro-benzenes methyl)-5-methylimidazole, 4-(3-chlorphenyl)-2-(3,4-dichloro-benzenes methyl)-5-methylimidazole,4-(4-chlorphenyl)-2-(2,3-dichloro-benzenes methyl)-5-methylimidazole, 4-(4-chlorphenyl)-2-(2,4-dichloro-benzenes methyl)-5-methylimidazole, 4-(4-chlorphenyl)-2-(2,5-dichloro-benzenes methyl)-5-methylimidazole, 4-(4-chlorphenyl)-2-(2,6-dichloro-benzenes methyl)-5-methylimidazole, 4-(4-chlorphenyl)-2-(3,4-dichloro-benzenes methyl)-5-methylimidazole, 4-(4-chlorphenyl)-2-(3,5-dichloro-benzenes methyl)-5-methylimidazole, 4-(2-bromophenyl)-2-(2,4-dichloro-benzenes methyl)-5-methylimidazole, 4-(4-bromophenyl)-2-(3,4-dichloro-benzenes methyl)-5-methylimidazole, 4-(4-chlorphenyl)-2-(2,5-dibromobenzene methyl)-5-methylimidazole, 4-(4-bromophenyl)-2-(2,5-dibromobenzene methyl)-5-methylimidazole, 2-(2,3-dichloro-benzenes methyl)-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-(2,4-dichloro-benzenes methyl)-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-(2,5-dichloro-benzenes methyl)-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-(2,6-dichloro-benzenes methyl)-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-(3,4-dichloro-benzenes methyl)-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-(3,5-dichloro-benzenes methyl)-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-(2,3-dichloro-benzenes methyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(2,4-dichloro-benzenes methyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(2,5-dichloro-benzenes methyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(2,6-dichloro-benzenes methyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(3,4-dichloro-benzenes methyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(3,5-dichloro-benzenes methyl)-4-(2,4-dichlorophenyl)-5-methylimidazole, 2-(2,3-dichloro-benzenes methyl)-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-(2,4-dichloro-benzenes methyl)-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-(2,5-dichloro-benzenes methyl)-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-(2,6-dichloro-benzenes methyl)-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-(3,4-dichloro-benzenes methyl)-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-(3,5-dichloro-benzenes methyl)-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-(2,3-dichloro-benzenes methyl)-4-(2,6-dichlorophenyl)-5-methylimidazole, 2-(2,4-dichloro-benzenes methyl)-4-(2,6-dichlorophenyl)-5-methylimidazole, 2-(2,5-dichloro-benzenes methyl)-4-(2,6-dichlorophenyl)-5-methylimidazole, 2-(2,6-dichloro-benzenes methyl)-4-(2,6-dichlorophenyl)-5-methylimidazole, 2-(3,4-dichloro-benzenes methyl)-4-(2,6-dichlorophenyl)-5-methylimidazole, 2-(3,5-dichloro-benzenes methyl)-4-(2,6-dichlorophenyl)-5-methylimidazole, 2-(2,3-dichloro-benzenes methyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(2,4-dichloro-benzenes methyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(2,5-dichloro-benzenes methyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(2,6-dichloro-benzenes methyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(3,4-dichloro-benzenes methyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(3,5-dichloro-benzenes methyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(2,3-dichloro-benzenes methyl)-4-(3,5-dichlorophenyl)-5-methylimidazole, 2-(2,4-dichloro-benzenes methyl)-4-(3,5-dichlorophenyl)-5-methylimidazole, 2-(2,5-dichloro-benzenes methyl)-4-(3,5-dichlorophenyl)-5-methylimidazole, 2-(2,6-dichloro-benzenes methyl)-4-(3,5-dichlorophenyl)-5-methylimidazole, 2-(3,4-dichloro-benzenes methyl)-4-(3,5-dichlorophenyl)-5-methylimidazole, 2-(3,5-dichloro-benzenes methyl)-4-(3,5-dichlorophenyl)-5-methylimidazole, 4-(2,5-dibromo phenyl)-2-(2,4-dichloro-benzenes methyl)-5-methylimidazole, 4-(2,5-dibromo phenyl)-2-(3,4-dichloro-benzenes methyl)-5-methylimidazole, 2-(2,5-dibromobenzene methyl)-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-(2,4-dibromobenzene methyl)-4-(3,4-dibromo phenyl)-5-methylimidazole, 2-(2,4-dichloro-benzenes methyl)-5-methyl-4-(3,4,5-trichlorophenyl) imidazoles, 2-(3,4-dichloro-benzenes methyl)-5-methyl-4-(2,4,6-tribromo phenyl) imidazoles, 2-(2,4-dibromobenzene methyl)-5-methyl-4-(3,4,5-trichlorophenyl) imidazoles, 2-(2,4-dibromobenzene methyl)-5-methyl-4-(2,4,5-tribromo phenyl) imidazoles, 5-methyl 4-phenyl-2-(3,4,5-trichloro-benzenes methyl) imidazoles, 5-methyl 4-phenyl-2-(2,4,5-tribromo-benzene methyl) imidazoles, 4-(4-chlorphenyl)-5-methyl-2-(2,3,6-trichloro-benzenes methyl) imidazoles, 4-(4-bromophenyl)-5-methyl-2-(3,4,5-trichloro-benzenes methyl) imidazoles, 4-(4-chlorphenyl)-5-methyl-2-(2,3,5-tribromo-benzene methyl) imidazoles, 4-(4-bromophenyl)-5-methyl-2-(2,4,6-tribromo-benzene methyl) imidazoles, 4-(2, 4-dichlorophenyl)-5-methyl-2-(3, 4, 5-trichloro-benzenes methyl) imidazoles, 4-(2, 4-dibromo phenyl)-5-methyl-2-(3, 4, 5-trichloro-benzenes methyl) imidazoles, 4-(3, 4-dichlorophenyl)-5-methyl-2-(2, 4, 5-tribromo-benzene methyl) imidazoles, 4-(2, 5-dibromo phenyl)-5-methyl-2-(2, 3, 5-tribromo-benzene methyl) imidazoles, 5-methyl-2-(3, 4, 5-trichloro-benzenes methyl)-4-(2, 4, 5-trichlorophenyl) imidazoles, 5-methyl-4-(2, 4, 5-tribromo phenyl)-2-(3, 4, 5-trichloro-benzenes methyl) imidazoles, 5-methyl-2-(2, 4, 6-tribromo-benzene methyl)-4-(2, 4, 5-trichlorophenyl) imidazoles and 5-methyl-2-(2, 4, 6-tribromo-benzene methyl)-4-(2, 4, 6-tribromo phenyl) imidazoles.
Can be by imidazolium compounds as passing through the activeconstituents of its surface treatment agent of preparing soluble in water.Described imidazolium compounds can be for example with 0.01～10 % by weight, and preferably the ratio of 0.1～5 % by weight is included in surface treatment agent.In the time that the content of described imidazolium compounds is less than 0.01 % by weight, the film thickness of the chemical layer forming on described copper surface may be too thin, thereby make fully to prevent the oxidation on copper surface.On the other hand, in the time that it exceedes 10 % by weight, the imidazolium compounds in surface treatment agent may be difficult to dissolve completely, even or exist described compound completely dissolve after still may there is reppd problem, be therefore not preferred.
Incidentally, in the time that enforcement is of the present invention, in the imidazolium compounds being represented by formula (I), can only use its a kind of suitable imidazolium compounds, but also can use the not combination of imidazolium compounds of the same race.
In the time that enforcement is of the present invention, when by (the formation aqueous solution) soluble in water imidazolium compounds, conventionally organic acid or mineral acid can be used as to described acid, but can uses a small amount of organic solvent simultaneously.The organic acid representative example that will use in this case comprises formic acid, acetic acid, propionic acid, butyric acid, oxoethanoic acid, pyruvic acid, etheric acid, levulinic acid, enanthic acid, sad, capric acid, lauric acid, oxyacetic acid, R-Glyceric acid, lactic acid, vinylformic acid, methoxyacetic acid, ethoxyacetic acid, propoxy-acetic acid, butoxy acetic acid, 2-(2-methoxy ethoxy) acetic acid, 2-[2-(2-ethoxy ethoxy) oxyethyl group] acetic acid, 2-{2-[2-(2-ethoxy ethoxy) oxyethyl group] oxyethyl group } acetic acid, 3-methoxypropionic acid, 3-ethoxy-propionic acid, 3-propoxy-propionic acid, 3-butoxy propionic acid, phenylformic acid, p-nitrobenzoic acid, tosic acid, Whitfield's ointment, picric acid, oxalic acid, succsinic acid, toxilic acid, fumaric acid, tartrate and hexanodioic acid, and the example of mineral acid comprises hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid.Can be with 0.1～50 % by weight, preferably the ratio of 1～30 % by weight adds this acid in surface treatment agent.
In addition,, as organic solvent, suitable is that lower alcohol is as methyl alcohol, ethanol and Virahol; Or acetone, DMF, ethylene glycol etc., it can be freely miscible with water.
Can in surface treatment agent of the present invention, add copper compound to accelerate the formation speed of chemical layer on the surface of copper or copper alloy.In addition, can add zn cpds further to improve the thermotolerance of the chemical layer being formed.
The representative example of copper compound comprises venus crystals, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cupric iodide, copper hydroxide, cupric phosphate, copper sulfate and cupric nitrate; And the representative example of zn cpds comprises zinc oxide, zinc formate, zinc acetate, zinc oxalate, zinc lactate, zinc citrate, zinc sulfate, zinc nitrate and zinc phosphate.Described both can be with 0.01～10 % by weight, preferably the ratio of 0.02～5 % by weight is included in tensio-active agent.
Using in the situation of this copper compound or zn cpds, except organic acid or mineral acid, the material, aminated compounds that can expect to have a shock absorption by interpolation carrys out the pH of stabilizing solution as ammonia, monoethanolamine, diethanolamine or trolamine.
In order further to improve the formation speed of chemical layer and the thermotolerance of described layer, can be with 0.001～1 % by weight, preferably the ratio of 0.01～0.1 % by weight is added halogen compounds (using " halogen " in its more general implication) in surface treatment agent.The example of halogen compounds comprises Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, sodium-chlor, Repone K, ammonium chloride, Sodium Bromide, Potassium Bromide, brometo de amonio, sodium iodide, potassiumiodide and ammonium iodide.
About the condition that uses surface treatment agent of the present invention to process copper or copper alloy surface, the fluid temperature of described surface treatment agent can be preferably 10 DEG C～70 DEG C, can be preferably 1 second duration of contact～10 minutes.The example of contact method comprises dipping, spraying and coating method.
In addition, after carrying out surface treatment of the present invention, can further improve thermotolerance by forming bilayer structure, described bilayer structure comprises the chemical layer that is coated with thermoplastic resin.
, form chemical layer on the surface of copper or copper alloy after, for example, by the thermoplastic resin with excellent heat resistance being dissolved in to solvent (toluene, ethyl acetate or Virahol) in, and use the solution that even coating thickness is for example 1～30 μ m on described chemical layer such as roller coating machine can form the bilayer structure of chemical layer and thermoplastic resin, described thermoplastic resin can for example, by rosin derivative (rosin or rosin ester), terpine resin derivative (for example terpine resin or terpene-phenolic resin), hydrocarbon resin (for example aromatic hydrocarbon resin or aliphatic hydrocarbon resin), or its mixture forms.
The example that is applicable to enforcement lead-free solder of the present invention comprises that lead-free solder is as Sn-Ag-Cu base, Sn-Ag-Bi base, Sn-Bi base, Sn-Ag-Bi-In base, Sn-Zn base and Sn-Cu parent metal.
Welding process of the present invention is applicable to flow soldering or reflow soldering, described flow soldering is included on the fused solution scolder in welding groove mobile printed-wiring board (PWB) so that the junction surface between electronic unit and printed-wiring board (PWB) is welded, described reflow soldering comprises prints paste shape scolder, mounting electronic parts whole printed-wiring board (PWB) is heated with melting solder thereon in advance on printed-wiring board (PWB) according to circuit pattern, thereby completes welding.
Embodiment
Below with reference to embodiment and comparative example, the present invention is specifically described, but should not be construed, the present invention is limited to this.
Incidentally, as follows for imidazolium compounds and the evaluation test method of embodiment and comparative example.
Imidazolium compounds
Following and in reference example 2～20, synthesis example has been shown for the imidazolium compounds of embodiment.Incidentally, reference example 1 has shown the synthesis example of (4-chloro-phenyl-) B amidine hydrochloric acid salt, and it is the raw material of the imidazolium compounds of reference example 2.
2-(4-chlorophenylmethyl)-4-phenylimidazole (being called " A-1 ")
2-phenmethyl-4-(4-chloro-phenyl-)-5-Methylimidazole (being called " A-2 ")
2-(2-chlorophenylmethyl)-5-methyl 4-phenyl imidazoles (being called " A-3 ")
2-(2-chlorophenylmethyl)-4-(4-chloro-phenyl-)-5-Methylimidazole (being called " B-1 ")
2-(4-chlorophenylmethyl)-4-(2-chloro-phenyl-)-5-Methylimidazole (being called " B-2 ")
2-(4-chlorophenylmethyl)-4-(4-chloro-phenyl-)-5-Methylimidazole (being called " B-3 ")
2-(2,4 dichloro benzene methyl)-4-phenylimidazole (being called " C-1 ")
2-phenmethyl-4-(2,4 dichloro benzene base)-5-Methylimidazole (being called " C-2 ")
5-hexyl-4-phenyl-2-(3,4,5-trichlorobenzene methyl) imidazoles (being called " C-3 ")
4-(4-chloro-phenyl-)-2-(2,4 dichloro benzene methyl)-5-Methylimidazole (being called " D-1 ")
4-(4-bromophenyl)-2-(2,4 dichloro benzene methyl)-5-Methylimidazole (being called " D-2 ")
2-(2-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles (being called " D-3 ")
2-(4-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles (being called " D-4 ")
2-(4-Brombenzyl)-4-(2,4 dichloro benzene base)-5-Methylimidazole (being called " D-5 ")
2-(4-Brombenzyl)-4-(3,4-dichlorophenyl)-5-Methylimidazole (being called " D-6 ")
2-(4-chlorophenylmethyl)-5-methyl-4-(3,4,5-trichlorophenyl) imidazoles (being called " D-7 ")
2-(2,4 dichloro benzene methyl)-4-(2,4 dichloro benzene base)-5-Methylimidazole (being called " E-1 ")
2-(2,4 dichloro benzene methyl)-4-(3,4-dichlorophenyl)-5-Methylimidazole (being called " E-2 ")
2-(3,4-dichlorobenzene methyl)-4-(3,4-dichlorophenyl)-5-Methylimidazole (being called " E-3 ")
In this, as mentioned above, symbol A～E represents respectively following (A)～(E) class.
(A) imidazolium compounds that wherein only the hydrogen atom in any one in phenmethyl or phenyl is replaced by a halogen atom;
(B) imidazolium compounds that wherein hydrogen atom in phenmethyl and phenyl is all replaced by a halogen atom respectively;
(C) imidazolium compounds that wherein only the hydrogen atom in any one in phenmethyl or phenyl is replaced by more than two halogen atom;
(D) imidazolium compounds that wherein hydrogen atom in any one in phenmethyl or phenyl is replaced by more than two halogen atom and hydrogen atom in another is replaced by a halogen atom; With
(E) imidazolium compounds that wherein hydrogen atom in phenmethyl and phenyl is all replaced by two halogen atoms respectively.
Reference example 1
Synthetic (4-chloro-phenyl-) B amidine hydrochloric acid salt
The solution of the dehydrated alcohol that preparation contains 137.2g's (0.905mol) (4-chloro-phenyl-) acetonitrile and 51.1g (1.11mol) also adds 36.7g (1.01mol) hydrogen chloride gas under cooling at 15～20 DEG C in 2 hours.In adding hydrogen chloride gas, form solid.In the time at room temperature reaction mixture sat being spent the night, as white solid, obtain ethyl (4-chloro-phenyl-) acetimidate hydrochloride salt.After solid is crushed, the solution that portion-wise addition is made up of 28.4g (1.67mol) ammonia and 250g dehydrated alcohol wherein in vibration under ice-cooled.After completing interpolation, lower mixture is stirred 1 hour and at room temperature spend the night ice-cooled.After filtering out insoluble white solid matter, in a vacuum filtrate is concentrated and is dried, thereby obtain 178g (0.868mol, yield is 96%) (4-chloro-phenyl-) B amidine hydrochloric acid salt white crystal.
Reference example 2
Synthetic A-1
To the sodium methylate that adds 16.2g (0.30mol) in the solution that contains 61.5g (0.30mol) (4-chloro-phenyl-) B amidine hydrochloric acid salt and 250mL tetrahydrofuran (THF), then at 50 DEG C, heat 1 hour.Then, add wherein 83g (0.60mol) salt of wormwood.At 50～55 DEG C, in gained suspension, drip the solution being formed by 59.7g (0.30mol) 2-bromoacetophenone and 200mL tetrahydrofuran (THF).After completing dropping, to described mixture reflux 2 hours.Then, reaction mixture is cooled to room temperature, insoluble substance is filtered, and in a vacuum filtrate is concentrated and is dried.After washing with water, enriched material is stirred together with toluene, thus crystallize out.After the crystal of by gac, filtration being collected in methyl alcohol decolours, carry out recrystallization, thereby obtain 25g (0.093mol, yield: 31%) pale pink crystal.
Reference example 3
Synthetic A-2
First,, according to the method synthesis of phenyl B amidine hydrochloric acid salt of reference example 1, wherein change benzyl cyanide into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to synthetic 2-phenmethyl-4-(4-the chloro-phenyl-)-5-Methylimidazole of the method for reference example 2, wherein change phenylacetamidino hydrochloride into and change 2-bromoacetophenone into 2-bromo-4 '-chlorophenyl acetone with reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2.
Reference example 4
Synthetic A-3
First,, according to synthetic (2-chloro-phenyl-) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (2-chloro-phenyl-) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to synthetic 2-(2-the chlorophenylmethyl)-5-methyl 4-phenyl imidazoles of the method for reference example 2, wherein change (2-chloro-phenyl-) B amidine hydrochloric acid salt into and change 2-bromoacetophenone into 2-brom-acetophenone with reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2.
Reference example 5
Synthetic B-1
First,, according to synthetic (2-chloro-phenyl-) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (2-chloro-phenyl-) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to synthetic 2-(2-chlorophenylmethyl)-4-(4-the chloro-phenyl-)-5-Methylimidazole of the method for reference example 2, wherein change (2-chloro-phenyl-) B amidine hydrochloric acid salt into and change 2-bromoacetophenone into 2-bromo-4 '-chlorophenyl acetone with reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2.
Reference example 6
Synthetic B-2
According to synthetic 2-(4-chlorophenylmethyl)-4-(2-the chloro-phenyl-)-5-Methylimidazole of the method for reference example 2, wherein change the bromo-2 '-chlorophenyl acetone of 2-into reference to the 2-bromoacetophenone of example 2.
Reference example 7
Synthetic B-3
According to synthetic 2-(4-chlorophenylmethyl)-4-(4-the chloro-phenyl-)-5-Methylimidazole of the method for reference example 2, wherein change the bromo-4 '-chlorophenyl acetone of 2-into reference to the 2-bromoacetophenone of example 2.
Reference example 8
Synthetic C-1
First,, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (2,4 dichloro benzene base) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then,, according to synthetic 2-(2,4 dichloro benzene the methyl)-4-phenylimidazole of the method for reference example 2, wherein change (2,4 dichloro benzene base) B amidine hydrochloric acid salt into reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2.
Reference example 9
Synthetic C-2
First,, according to the method synthesis of phenyl B amidine hydrochloric acid salt of reference example 1, wherein change benzyl cyanide into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to the synthetic 2-phenmethyl-4-(2 of the method for reference example 2,4-dichlorophenyl)-5-Methylimidazole, wherein with reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2 change into phenylacetamidino hydrochloride and by 2-bromoacetophenone change into 2-bromo-2 ', 4 '-dichloropropiophenone.
Reference example 10
Synthetic C-3
First,, according to synthetic (3,4, the 5-trichlorophenyl) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (3,4,5-trichlorophenyl) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to the synthetic 5-hexyl-4-phenyl-2-(3 of the method for reference example 2,4,5-trichlorobenzene methyl) imidazoles, wherein change (3 into reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2,4,5-trichlorophenyl) B amidine hydrochloric acid salt change 2-bromoacetophenone into 2-bromobenzene octanone.
Reference example 11
Synthetic D-1
First,, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (2,4 dichloro benzene base) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to synthetic 4-(4-the chloro-phenyl-)-2-(2 of the method for reference example 2,4-dichlorobenzene methyl)-5-Methylimidazole, wherein change (2,4 dichloro benzene base) B amidine hydrochloric acid salt into and change 2-bromoacetophenone into 2-bromo-4 '-chlorophenyl acetone with reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2.
Reference example 12
Synthetic D-2
First,, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (2,4 dichloro benzene base) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to synthetic 4-(4-the bromophenyl)-2-(2 of the method for reference example 2,4-dichlorobenzene methyl)-5-Methylimidazole, wherein change (2 into reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2,4-dichlorophenyl) B amidine hydrochloric acid salt change 2-bromoacetophenone into 2,4 '-dibromobenzene acetone.
Reference example 13
Synthetic D-3
First,, according to synthetic (2-chloro-phenyl-) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (2-chloro-phenyl-) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to synthetic 2-(2-the chlorophenylmethyl)-4-(2 of the method for reference example 2,4-dichlorophenyl) imidazoles, wherein with reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2 change into (2-chloro-phenyl-) B amidine hydrochloric acid salt and by 2-bromoacetophenone change into 2-bromo-2 ', 4 '-dichloroacetophenone.
Reference example 14
Synthetic D-4
According to synthetic 2-(4-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles of the method for reference example 2, wherein with reference to the 2-bromoacetophenone of example 2 change into 2-bromo-2 ', 4 '-dichloroacetophenone.
Reference example 15
Synthetic D-5
First,, according to synthetic (4-bromophenyl) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (4-bromophenyl) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to synthetic 2-(4-the Brombenzyl)-4-(2 of the method for reference example 2,4-dichlorophenyl)-5-Methylimidazole, wherein with reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2 change into (4-bromophenyl) B amidine hydrochloric acid salt and by 2-bromoacetophenone change into 2-bromo-2 ', 4 '-dichloropropiophenone.
Reference example 16
Synthetic D-6
First,, according to synthetic (4-bromophenyl) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (4-bromophenyl) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to synthetic 2-(4-the Brombenzyl)-4-(3 of the method for reference example 2,4-dichlorophenyl)-5-Methylimidazole, wherein with reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2 change into (4-bromophenyl) B amidine hydrochloric acid salt and by 2-bromoacetophenone change into 2-bromo-3 ', 4 '-dichloropropiophenone.
Reference example 17
Synthetic D-7
According to synthetic 2-(4-chlorophenylmethyl)-5-methyl-4-(3,4, the 5-trichlorophenyl) imidazoles of the method for reference example 2, wherein with reference to the 2-bromoacetophenone of example 2 change into 2-bromo-3 ', 4 ', 5 '-trichlorobenzene acetone.
Reference example 18
Synthetic E-1
First,, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (2,4 dichloro benzene base) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to the synthetic 2-(2 of the method for reference example 2,4-dichlorobenzene methyl)-4-(2,4-dichlorophenyl)-5-Methylimidazole, wherein change (2 into reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2,4-dichlorophenyl) B amidine hydrochloric acid salt and by 2-bromoacetophenone change into 2-bromo-2 ', 4 '-dichloropropiophenone.
Reference example 19
Synthetic E-2
First,, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (2,4 dichloro benzene base) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to the synthetic 2-(2 of the method for reference example 2,4-dichlorobenzene methyl)-4-(3,4-dichlorophenyl)-5-Methylimidazole, wherein change (2 into reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2,4-dichlorophenyl) B amidine hydrochloric acid salt and by 2-bromoacetophenone change into 2-bromo-3 ', 4 '-dichloropropiophenone.
Reference example 20
Synthetic E-3
First,, according to synthetic (3, the 4-dichlorophenyl) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (3,4-dichlorophenyl) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to the synthetic 2-(3 of the method for reference example 2,4-dichlorobenzene methyl)-4-(3,4-dichlorophenyl)-5-Methylimidazole, wherein change (3 into reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2,4-dichlorophenyl) B amidine hydrochloric acid salt and by 2-bromoacetophenone change into 2-bromo-3 ', 4 '-dichloropropiophenone.
Imidazolium compounds for comparative example is as follows.
2-phenmethyl-4-phenylimidazole (being called " Z-1 ")
The chloro-4-methylimidazole of 2-phenmethyl-5-(being called " Z-2 ")
2-(4-chlorophenylmethyl) imidazoles (being called " Z-3 ")
2-(2,4 dichloro benzene methyl)-4,5-diphenyl-imidazole (being called " Z-4 ")
4-methyl-2-phenylimidazole (being called " Z-5 ")
2-(4-chlorophenylmethyl) benzoglyoxaline (being called " Z-6 ")
The synthesis example of Z-1, Z-2, Z-3 and Z-4 has been shown in reference example 21～24.About Z-5 and Z-6, use respectively the trade name " Curesol 2P4MZ " of being manufactured by Shikoku Chem (Shikoku Chemicals Corporation) and the reagent of being manufactured by Wako Pure Chemical Industries, Ltd. (Wako Pure Chemical Industries, Ltd.).
Reference example 21
Synthetic Z-1
First,, according to the method synthesis of phenyl B amidine hydrochloric acid salt of reference example 1, wherein change benzyl cyanide into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then,, according to the synthetic 2-phenmethyl-4-phenylimidazole of the method for reference example 2, wherein change phenylacetamidino hydrochloride into reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2.
Reference example 22
Synthetic Z-2
At room temperature, to the N-chlorosuccinimide of portion-wise addition 13.3g (0.1mol) in the solution by 16g (0.093mol) 2-phenmethyl-4-methylimidazole (being manufactured " 2B4MI " by POLYORGANIX) and 100mL ethanol composition.Mixture was stirred after 1 hour, reaction mixture is concentrated and be dried in a vacuum, and the material of drying is washed with hot water.Then, by its recrystallization and obtain 8.5g (0.041mol, yield: the chloro-4-methylimidazole of 2-phenmethyl-5-44%), it is light beige needle-like crystal in acetonitrile.
Reference example 23
Synthetic Z-3
The solution under agitation sulphur of (4-chloro-phenyl-) acetonitrile, 22.8g (0.38mol) quadrol and 0.21g (6.5mmol) by 52.0g (0.343mol) being formed heats and in 2 hours, temperature is risen to 280 DEG C from 150 DEG C.After mixture is cooling, add wherein the solution being formed by 1.0g sodium hydroxide and 10mL methyl alcohol, then reflux 3 hours.After in a vacuum reaction mixture being concentrated, in a vacuum enriched material distilled and obtain 43g (0.22mol, yield: 2-(4-chlorophenylmethyl) tetrahydroglyoxaline 64%), it is the cut with 163 DEG C～170 DEG C/4mmHg boiling point.
Then, at room temperature 27g (0.17mol) potassium permanganate is added in the solution being made up of the above-mentioned 2-of 21g (0.108mol) (4-chlorophenylmethyl) tetrahydroglyoxaline and 250mL diox in batches.After to mixture reflux 8 hours, insoluble substance is filtered, and in a vacuum filtrate is concentrated and is dried.After water washs the product of drying, from water-acetonitrile, product is carried out recrystallization and obtains 13.5g (0.070mol, yield: 2-(4-chlorophenylmethyl) imidazoles 65%), it is oyster white crystal.
Reference example 24
Synthetic Z-4
First,, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein change (2,4 dichloro benzene base) acetonitrile into reference to (4-chloro-phenyl-) acetonitrile of example 1.
Then, according to the synthetic 2-(2 of the method for reference example 2,4-dichlorobenzene methyl)-4,5-diphenyl-imidazole, wherein change (2,4 dichloro benzene base) B amidine hydrochloric acid salt into and change 2-bromoacetophenone into the bromo-2-phenyl of 2-methyl phenyl ketone with reference to (4-chloro-phenyl-) B amidine hydrochloric acid salt of example 2.
The chemical formula of the imidazolium compounds for embodiment is shown in as follows:
The chemical formula of the imidazolium compounds for comparative example is shown in as follows.
Evaluation test method for embodiment and comparative example is as follows.
For the upwards evaluation test of the performance of turnover rate (flow-up rate) of scolder
By the printed-wiring board (PWB) of being made up of glass epoxy resin, as test film, described printed-wiring board (PWB) is of a size of 120mm (length) × 150mm (width) × 1.6mm (thickness) and has 300 copper vias that internal diameter is 0.80mm.To this test film carry out degreasing, soft erosion and then water wash., test film immersed remain in the surface treatment agent of specifying fluid temperature under and continue the time cycle of specifying, wash with water, and be then dried, thereby on copper surface, form the chemical layer that thickness is approximately 0.10～0.50 μ m thereafter.
Use infrared reflow stove (trade name: MULTI-PRO-306, by (the Vetronix Co. of Wei Teni company, Ltd.) manufacture) test film processed of the effects on surface reflux that carries out three circulations, wherein peak temperature is 240 DEG C, and utilizes subsequently jet soldering apparatus to weld (line speed: 1.0m/ minute).
The scolder using is for consisting of tin-plumbous eutectic solder (trade name: H63A of 63% tin and 37% lead (% by weight), by (the Senju Metal Industry Co. of Senju Metal Industry Co., Ltd, Ltd.) manufacture), be JS-64MSS (being manufactured by Hong Hui Co., Ltd. (Koki Co., Ltd.)) for the soldering flux welding.Welding temperature is 240 DEG C.
In addition, to use lead-free solder to welding by above-mentioned test film surface of processing with the mode that tin-plumbous eutectic solder is identical.The scolder using is lead-free solder (trade name: H705 " ECOSOLDER ", manufactured by Senju Metal Industry Co., Ltd), it consists of 96.5% tin, 3.0% silver and 0.5% copper (% by weight), and is JS-E-09 (being manufactured by Hong Hui Co., Ltd.) for the soldering flux welding.The peak temperature of described reflux is 245 DEG C, and welding temperature is also 245 DEG C.
About the test film of welding, calculate the ratio (%) of the copper vias number of (welding) with respect to copper vias sum (300 holes), in described (welding) copper vias, scolder is filled until the top (upper land) of copper vias.
When scolder is in the time that the lip-deep wettability of copper is large, fusion welding penetrates in each copper vias, and fusion welding is easy to through hole to be filled to through hole top thus.That is, in the time that the ratio of the soldered via count in top and through hole sum is large, should be by scolder the wettability to copper and weldability be judged to be excellence.
For the evaluation test of scolder spreadability
The printed-wiring board (PWB) of the 50mm being made up of glass epoxy resin (length) × 50mm (width) × 1.2mm (thickness) is used as to test film.This printed-wiring board (PWB) has a kind of circuit pattern, wherein on width, forms the 10 slice copper foil circuits of conductor width as 0.80mm and length as 20mm taking the interval of 1.0mm.To test film carry out degreasing, soft erosion and then water wash., test film immersed remain in the surface treatment agent of specifying fluid temperature under and continue the time cycle of specifying, wash with water, and be then dried, thereby on copper surface, form the chemical layer that thickness is approximately 0.10～0.50 μ m thereafter.
The reflux that the test film that uses infrared reflow stove (trade name: MULTI-PRO-306 is manufactured by Wei Teni company) effects on surface to process carries out a circulation, wherein peak temperature is 240 DEG C.Thereafter, use the metal mask with 1.2mm aperture and 150 μ m thickness by tin-lead welding cream be printed on copper circuit parts in the heart, and carry out under these conditions reflux, and weld.The eutectic solder (trade name: OZ-63-330F-40-10 by Senju Metal Industry Co., Ltd manufactured) of the tin-lead welding cream using for being formed by 63% tin and 37% lead (% by weight).
In addition, also use lead-free solder paste to welding by the above-mentioned surface-treated test film that carries out in the mode identical with tin-lead welding cream.The lead-free solder using forms (trade name: M705-221BM5-42-11, is manufactured by Senju Metal Industry Co., Ltd) by 96.5% tin, 3.0% copper (% by weight) silver-colored and 0.5%.The peak temperature of the reflux obtaining before printing with paste and is afterwards set as to 245 DEG C.
Length (mm) wetting on the copper circuit parts at the test film obtaining and scolder that sprawl is measured.
In the time that length is longer, solder wettability and weldability are judged to be to excellence.
Embodiment 1
Using as 2-(4-the chlorophenylmethyl)-4-phenylimidazole of imidazolium compounds, be dissolved in deionized water and after making to have the composition described in table 1 as sour levulinic acid with as the venus crystals of metal-salt and zinc chloride, utilize ammoniacal liquor by pH regulator to 3.6, thereby prepared surface treatment agent.
Then, the test film of printed-wiring board (PWB) is immersed and is controlled in 40 DEG C of surface treatment agents at temperature and continues 30 seconds, water washs, then dry, thereby has measured the upwards turnover rate performance of scolder and the spreadability of scolder.These test-results are shown in Table 1.
Embodiment 2～19
Use imidazolium compounds, acid, metal-salt and halogen compounds described in table 1 or 2, prepare the various surface treatment agents with composition described in table 1 or 2 in mode in the same manner as in Example 1, and carried out surface treatment under the treatment condition described in table 1 or 2.About gained test film, the upwards turnover rate performance of scolder and the spreadability of scolder are measured.These test-results are shown in table 1 or 2.
Comparative example 1～6
Use imidazolium compounds, acid, metal-salt and halogen compounds described in table 3, prepared the various surface treatment agents with composition described in table 3 in mode in the same manner as in Example 1, and under the treatment condition described in table 3, carried out surface treatment.About gained test film, the upwards turnover rate performance of scolder and the spreadability of scolder are measured.These test-results are shown in Table 3.
Can be clear according to the test-results shown in table 1 (embodiment 1～9) and table 2 (embodiment 10～19), can improve eutectic solder or the solder wettability of lead-free solder to printed-wiring board (PWB) copper surface by surface treatment agent of the present invention and copper Surface Contact are formed to chemical layer, and eutectic solder or the weldability (the upwards turnover rate performance of scolder, the spreadability of scolder) of lead-free solder to copper surface become excellent.
In embodiment 1～19, find in the upwards turnover rate performance that uses scolder in the situation of eutectic solder in the top and bottom almost, to be all 100% (being only 98% in embodiment 3) and not observe difference in embodiment 1～19.But, about the upwards turnover rate performance of scolder in the situation that uses lead-free solder with in the spreadability that uses scolder in eutectic solder or lead-free solder situation, observe some difference at embodiment 1～3 (being hereinafter called situation A), embodiment 4～6 (being hereinafter called situation B) and embodiment 7～19 (being hereinafter called situation C)., in using the upwards turnover rate performance of scolder in the situation of lead-free solder and using the situation of eutectic solder or lead-free solder, the spreadability of scolder is improved with the order of situation A < situation B < situation C.
As mentioned above, be those imidazolium compoundss that wherein only the hydrogen atom in any one group in phenmethyl or phenyl is replaced by a halogen atom for the imidazolium compounds of situation A.Imidazolium compounds in situation B is those imidazolium compoundss that wherein hydrogen atom in phenmethyl and phenyl is all replaced by a halogen atom respectively.For the imidazolium compounds of situation C be (i) those compounds (embodiment 7～9) that wherein only the hydrogen atom in any one group in phenmethyl or phenyl is replaced by more than two halogen atom, (ii) wherein in phenmethyl or phenyl the hydrogen atom in any one group replaced by more than two halogen atom and another group in those compounds (embodiment 10～16) of being replaced by a halogen atom of hydrogen atom and (iii) wherein the hydrogen atom in phenmethyl and phenyl all respectively by those compounds (embodiment 17～19) of two halogen atoms replacements.
According to the test-results shown in table 3 (comparative example 1～6), in the situation of surface treatment agent that uses comparative example 4, weldability is better.For the imidazolium compounds (Z-4) of this surface treatment agent be wherein two hydrogen atoms in phenmethyl by the compound of two halogen atoms replacements, but described imidazolium compounds is compared with being applicable to implement the imidazolium compounds of formula of the present invention (I), be attached to the substituent kind difference on imidazole ring 5-position.; in the test-results of comparative example 4; can say that it has implied, the effect that weldability is improved is derived from and is attached on imidazole ring 2-position and phenyl is attached to the chemical structure on its 4-position by phenmethyl, and wherein in described phenmethyl, two hydrogen atoms are replaced by two halogen atoms.But, be applicable to implement imidazolium compounds of the present invention and there is the above-mentioned chemical structure different from Z-4, wherein hydrogen atom or alkyl instead of phenyl are attached on the 5-position of imidazole ring.This point is the feature that is applicable to implement imidazolium compounds of the present invention, and causes above-mentioned improved result.
Even if in the time using eutectic solder to weld, also can use easily surface treatment agent of the present invention, but using in the welding of the lead-free solder that shows poor weldability compared with eutectic solder, also can use suitably described surface treatment agent.
Industrial applicibility
The present invention relates to a kind of surface treatment agent and corresponding surface treatment method, described surface treatment agent forms the chemical layer with excellent heat resistance using scolder forming when electronic unit etc. is installed on printed-wiring board (PWB) on the copper of circuit block etc. of printed-wiring board (PWB) or copper alloy surface, meanwhile, improved wettability, the weldability to scolder.
In addition, the present invention can provide a kind of by contacting the printed-wiring board (PWB) obtaining with above-mentioned surface treatment agent and can provide a kind of by the welding process that the surface of copper or copper alloy is contacted with above-mentioned surface treatment agent and then use lead-free solder to weld forming the copper of copper circuit parts or the surface of copper alloy.
Although the present invention be have been described in detail with reference to its embodiment, it should be apparent to those skilled in the art that in the case without departing from the scope of the present invention, can carry out therein variations and modifications.
The application is the Japanese patent application 2008-295619 submitting to taking Japanese patent application 2008-206119, on November 19th, 2008 that on August 8th, 2008 submits to and the Japanese patent application 2009-124003 submitting on May 22nd, 2009 as basis, hereby by reference to its full content is incorporated herein.

Claims (6)

1. for a surface treatment agent for copper or copper alloy, it comprises the imidazolium compounds being represented by formula (I):
Wherein R represents hydrogen atom or alkyl, X 1and X 2identical or different and represent chlorine atom or bromine atoms; M and n represent that at least one in 0～3 integer and m or n is more than 1.
2. surface treatment agent as claimed in claim 1, wherein each in m and n is more than 1.
3. surface treatment agent as claimed in claim 1, wherein at least one in m or n is more than 2.
4. for a surface treatment method for copper or copper alloy, described method comprises carries out surface treatment by the surface treatment agent described in any one in the surface employing claim 1～3 of described copper or described alloy.
5. a printed-wiring board (PWB), it comprises the copper or the copper alloy that form copper circuit parts, and the surface of wherein said copper or described alloy has adopted the surface treatment agent described in any one in claim 1～3 to carry out surface treatment.
6. a welding process, described method comprises carries out the surface treatment agent described in any one in the surface employing claim 1～3 of copper or copper alloy surface treatment and then utilizes lead-free solder to weld.
CN200980131025.2A 2008-08-08 2009-08-07 Surface treating agent for copper or copper alloy and use thereof Active CN102119240B (en)

Applications Claiming Priority (7)

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 (en) 2008-08-08 2009-05-22 Surface treatment agent for copper or copper alloy and use thereof
JP2009-124003 2009-05-22
PCT/JP2009/064318 WO2010016620A1 (en) 2008-08-08 2009-08-07 Surface treating agent for copper or copper alloy and use thereof

Publications (2)

Publication Number Publication Date
CN102119240A CN102119240A (en) 2011-07-06
CN102119240B true CN102119240B (en) 2014-07-30

Family

ID=41259797

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200980131025.2A Active CN102119240B (en) 2008-08-08 2009-08-07 Surface treating agent for copper or copper alloy and use thereof

Country Status (6)

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

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5301218B2 (en) * 2008-08-25 2013-09-25 四国化成工業株式会社 Surface treatment agent for copper or copper alloy and use thereof
JP5260357B2 (en) * 2008-09-17 2013-08-14 四国化成工業株式会社 2- (2,4-dichlorobenzyl) -4-phenyl-5-alkylimidazole compound
JP5260208B2 (en) * 2008-09-22 2013-08-14 四国化成工業株式会社 2- (2,4-Dichlorobenzyl) -4- (halogenated phenyl) imidazole compound
JP5260367B2 (en) * 2008-09-26 2013-08-14 四国化成工業株式会社 2- (Chlorobenzyl) -4-phenylimidazole compound
JP5615227B2 (en) 2011-05-23 2014-10-29 四国化成工業株式会社 Surface treatment agent for copper or copper alloy and use thereof
JP5615233B2 (en) 2011-06-20 2014-10-29 四国化成工業株式会社 Surface treatment agent for copper or copper alloy and use thereof
KR101555753B1 (en) 2013-11-18 2015-09-30 서울대학교산학협력단 one-step method for preparation of corrosion preventive copper paste and its flexible dipole tag antenna application
CN109048019B (en) * 2018-09-13 2021-01-26 烟台孚信达双金属股份有限公司 Welding process for copper-aluminum composite bar
JP6681567B1 (en) * 2019-05-27 2020-04-15 千住金属工業株式会社 Solder paste and flux
JP6681566B1 (en) * 2019-05-27 2020-04-15 千住金属工業株式会社 Solder paste and flux

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0627499A1 (en) * 1993-05-10 1994-12-07 Shikoku Chemicals Corporation Agent for treating surfaces of copper and copper alloys
CN1391618A (en) * 1999-08-26 2003-01-15 恩索恩－Omi公司 Process for selective deposition of copper substrates
CN1761773A (en) * 2003-03-19 2006-04-19 四国化成工业株式会社 Novel imidazole compound and usage thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3277025B2 (en) * 1993-05-10 2002-04-22 四国化成工業株式会社 Copper and copper alloy surface treatment agent
JPH06329635A (en) * 1993-05-24 1994-11-29 Shikoku Chem Corp New imidazole compound
JP3311858B2 (en) * 1994-03-08 2002-08-05 四国化成工業株式会社 Copper and copper alloy surface treatment agent
JPH08183776A (en) * 1994-12-28 1996-07-16 Hideaki Yamaguchi Surface-protecting agent of metal and production using the same
AR024077A1 (en) * 1999-05-25 2002-09-04 Smithkline Beecham Corp ANTIBACTERIAL COMPOUNDS
JP4181888B2 (en) * 2003-02-04 2008-11-19 四国化成工業株式会社 Anticorrosive treatment for silver and silver alloys
JP2005068530A (en) * 2003-08-28 2005-03-17 Tamura Kaken Co Ltd Surface-treating agent, printed circuit board, and method for surface-treating metal on printed circuit board
JP4546163B2 (en) * 2004-06-10 2010-09-15 四国化成工業株式会社 Copper or copper alloy surface treatment agent and soldering method
JP2007297685A (en) * 2006-05-01 2007-11-15 Shikoku Chem Corp Surface treatment agent for metal, and its utilization
JP5036216B2 (en) * 2006-05-19 2012-09-26 四国化成工業株式会社 Metal surface treatment agent and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0627499A1 (en) * 1993-05-10 1994-12-07 Shikoku Chemicals Corporation Agent for treating surfaces of copper and copper alloys
US5498301A (en) * 1993-05-10 1996-03-12 Shikoku Chemicals Corporation Agent for treating surfaces of copper and copper alloys
CN1391618A (en) * 1999-08-26 2003-01-15 恩索恩－Omi公司 Process for selective deposition of copper substrates
CN1761773A (en) * 2003-03-19 2006-04-19 四国化成工业株式会社 Novel imidazole compound and usage thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开平7-243054A 1995.09.19

Also Published As

Publication number Publication date
KR20110073421A (en) 2011-06-29
JP5313044B2 (en) 2013-10-09
KR101540143B1 (en) 2015-07-28
WO2010016620A1 (en) 2010-02-11
TWI464298B (en) 2014-12-11
JP2010150651A (en) 2010-07-08
CN102119240A (en) 2011-07-06
MY162495A (en) 2017-06-15
TW201009117A (en) 2010-03-01

Similar Documents

Publication Publication Date Title
CN102119240B (en) Surface treating agent for copper or copper alloy and use thereof
EP2721195B1 (en) Surface treating composition for copper and copper alloy and utilization thereof
US10398028B2 (en) Surface treating composition for copper and copper alloy and utilization thereof
EP1753728B1 (en) Phenylnaphthylimidazoles for use on copper surfaces during soldering
CN101228000A (en) Water-soluble preflux and use thereof
CN1761773B (en) Novel imidazole compound and usage thereof
CN102131959B (en) Surface treating agent for copper or copper alloy and use thereof
CN102137953B (en) Surface treating agent for copper or copper alloy and use thereof
CN1964949B (en) Phenylnaphthylimidazoles for use on copper surfaces during soldering

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant