CN102119240A - 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 PDFInfo
- Publication number
- CN102119240A CN102119240A CN2009801310252A CN200980131025A CN102119240A CN 102119240 A CN102119240 A CN 102119240A CN 2009801310252 A CN2009801310252 A CN 2009801310252A CN 200980131025 A CN200980131025 A CN 200980131025A CN 102119240 A CN102119240 A CN 102119240A
- Authority
- CN
- China
- Prior art keywords
- imidazoles
- phenyl
- copper
- reference example
- chloro
- 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.)
- Granted
Links
- 0 C*C1NC(*c(c(Cl)c2)ccc2Cl)NC1C(C=CC(C1)Cl)=C1C1IC1 Chemical compound C*C1NC(*c(c(Cl)c2)ccc2Cl)NC1C(C=CC(C1)Cl)=C1C1IC1 0.000 description 2
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, thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (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
A surface treating agent for copper or a copper alloy, which 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
Technical field
The present invention relates to the surface treatment agent that during copper that electronic unit etc. is welded to printed-wiring board (PWB) or copper alloy, uses and use.
Background technology
In recent years, extensively adopted and had highdensity surface mounting technique with installation method as printed-wiring board (PWB).Wherein, this surface mounting technique is divided into two-sided surface mounting technique and mixes field engineering etc., in described two-sided surface mounting technique, use soldering paste that chip type component is bonded together, and described mixing field engineering is to use the combination of the through hole mount technology of the surface mounting technique of chip type component of soldering paste and discrete parts.In any installation method, therefore twice above welding step of printed-wiring board (PWB) experience expose it at high temperature to the open air, thereby cause serious thermal history.
As a result, constitute the surface of the copper of circuit block of printed-wiring board (PWB) or copper alloy (hereinafter be called for short sometimes and make copper) owing to heat the formation that has promoted oxide film, so 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), use surface treatment agent on the surface of circuit block, to form chemical layer usually.Yet, even must prevent that also chemical layer from worsening (that is, by deterioration) and protecting the copper circuit parts, thereby keep good weldability by having at the copper circuit parts after a plurality of round-robin thermal histories.
It is first-class the tin-lead alloy eutectic solder to be used for that conventionally electronic unit is installed to printed-wiring board (PWB).Yet in recent years, produced following worry: the lead that comprises in the welding flux alloy produces injurious effects to human body, and therefore lead-free solder is used in expectation.
Therefore, considering multiple lead-free solder.For example, proposed 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 the copper securely, thereby cause high reliability.
On the contrary, compare with normally used tin-lead solder, lead-free solder is relatively poor in the lip-deep wettability of copper, therefore, and owing to space and other joint defects cause weldability difference and bond strength low.
Therefore, when using lead-free solder, must select the soldering flux that has the welding flux alloy of superior weldability and be fit to use with lead-free solder.Be used to prevent that the surface treatment agent that oxidation takes place from also needing to have the wettability of raising lead-free solder and the function of weldability on the surface of copper or copper alloy.
Many lead-free solders have high-melting-point, and its welding temperature is than high about 20 ℃～about 50 ℃ of the temperature of normally used tin-plumbous eutectic solder.Therefore, be used for utilizing the surface treatment agent of the method that lead-free solder welds to have the characteristic of the chemical layer that can form excellent heat resistance.
As the activeconstituents of this surface treatment agent, multiple imidazolium compounds has been proposed.For example, respectively, patent documentation 1 discloses 2-alkyl imidazole compound such as 2-undecyl imidazole; Patent documentation 2 discloses 2-Aryimidazole compound such as 2-phenylimidazole and 2-phenyl-4-methylimidazole; Patent documentation 3 discloses 2-alkyl benzimidazole compound such as 2-nonyl benzoglyoxaline; Patent documentation 4 discloses 2-aralkyl benzimidazole compound such as 2-(4-Chlorophenylmethyl) benzoglyoxaline; And patent documentation 5 discloses 2-aralkyl imidazolium compounds such as 2-(4-Chlorophenylmethyl) imidazoles and 2-(2,4 dichloro benzene ylmethyl)-4,5-diphenyl-imidazole.
Yet, containing in the situation of surface treatment agent of this imidazolium compounds in use, the thermotolerance of the chemical layer that forms on the copper surface is still undesirable.In addition, when welding, the wettability of scolder is not enough and therefore can not obtain good weldability.Especially, in the situation of using lead-free solder replacement eutectic solder to weld, be difficult to above-mentioned surface treatment agent is 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, finished 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 when using scolder to be installed to electronic unit etc. on the printed-wiring board (PWB), described surface treatment agent forms the chemical layer with excellent heat resistance on the copper of the circuit block that constitutes printed-wiring board (PWB) etc. or copper alloy surface, simultaneously, described surface treatment agent has improved the wettability of described scolder and has made weldability good.
In addition, another object of the present invention provides a kind of printed-wiring board (PWB) and a kind of welding process is provided, copper or the surface of copper alloy of described printed-wiring board (PWB) by will constituting the copper circuit parts contacts with above-mentioned surface treatment agent and obtains, and in described welding process the surface of copper or copper alloy contacted with above-mentioned surface treatment agent and uses lead-free solder to weld then.
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 of being represented by formula (I) by utilization is handled the printed-wiring board (PWB) with copper circuit parts, can on the surface of copper circuit parts, form and have the chemical layer that excellent heat resistance promptly can be resisted the welding temperature of lead-free solder, simultaneously, by in the welding that utilizes lead-free solder to carry out, improving the wettability of scolder to copper or copper alloy surface, can obtain good weldability, thereby finish the present invention.
That is, the present invention its comprise in configuration the most widely following aspect:
(1) a kind of surface treatment agent that is used for copper or copper alloy, it comprises the imidazolium compounds by formula (I) expression:
Wherein R represents hydrogen atom or alkyl, X
1And X
2Identical or different and expression chlorine atom or bromine atoms; M and n represent that 0～3 integer and at least one among m or the n are more than 1.
(2) according to the surface treatment agent of above-mentioned (1), wherein each among m and the n all is more than 1.
(3) according to the surface treatment agent of above-mentioned (1), wherein at least one among m or the n is more than 2.
(4) a kind of surface treatment method that is used for copper or copper alloy, described method comprise that the surface with copper or described alloy contacts with each described surface treatment agent in above-mentioned (1)～(3).
(5) a kind of printed-wiring board (PWB), it comprises copper or the copper alloy that constitutes the copper circuit parts, and the surface of wherein said copper or described alloy contacts with each described surface treatment agent in above-mentioned (1)～(3).
(6) a kind of welding process, described method comprise that the surface with copper or copper alloy contacts with each described surface treatment agent in above-mentioned (1)～(3) and utilizes lead-free solder to weld then.
Surface treatment agent of the present invention not only can form the chemical layer with excellent heat resistance on the surface of the copper of the circuit block that constitutes printed-wiring board (PWB) etc. or copper alloy, can also improve lead-free solder greatly to the wettability of body surface and good weldability is provided.
In addition,, welding process of the present invention can use the scolder that does not contain harmful metallic lead, so from the viewpoint of environment protection, described method is useful because making.
Embodiment
The imidazolium compounds that is used for the present invention is represented by formula (I), promptly, imidazolium compounds with following basic framework, wherein phenmethyl is attached to (hereafter is made phenmethyl) on the 2-position of imidazole ring and phenyl is 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 halogen atom) in the phenyl ring of phenmethyl or phenyl any one replaces at least.
R in its Chinese style, X
1, X
2, m and n be 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 replaced by a halogen atom of the hydrogen atom in any one in phenmethyl or phenyl only wherein;
(B) imidazolium compounds that all replaced by halogen atom respectively of the hydrogen atom in phenmethyl and phenyl wherein;
(C) imidazolium compounds that wherein only the hydrogen atom in any one is replaced by two above halogen atoms in phenmethyl or phenyl;
(D) imidazolium compounds that wherein hydrogen atom in any one in phenmethyl or phenyl is replaced by two above halogen atoms and the hydrogen atom in another is replaced by a halogen atom; With
(E) imidazolium compounds that all replaced by two above halogen atoms respectively of the hydrogen atom in phenmethyl and phenyl wherein.
Discovery according to inventor's acquisition, form chemical layer and use in the situation that lead-free solder welds on copper or copper alloy surface at the surface treatment agent that use contains a kind of compound in the imidazolium compounds of above-mentioned classification (A)～(E), the order that weldability is improved is (A)＜(B)＜(C)～(E).Promptly, compare with the weldability that the surface treatment agent of the imidazolium compounds that contains (A) in use forms on the copper surface in the situation of chemical layer, the weldability that the surface treatment agent that contains the imidazolium compounds of (B) in use forms on the copper surface in the situation of chemical layer is more excellent.Similarly, compare with the situation of the imidazolium compounds of (B), weldability is more excellent in the situation of the imidazolium compounds of (C).And, contain in use (C), (D) and (E) in any one surface treatment agent on the copper surface, form in the situation of chemical layer, obtained weldability much at one.
According to above-mentioned discovery, implement imidazolium compounds of the present invention about being applicable to, with at least one is that situation more than 1 is compared among m or the n, m and n both are preferably more than 1 and among m or the n at least one more preferably more than 2.
R in the formula (I) is that hydrogen atom or alkyl and described alkyl are preferably the straight chain with 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.
Be used to implement imidazolium compounds of the present invention by adopting the synthetic method shown in the following reaction icon to synthesize.In this, as phenyl ethanamidine compound, can suitably use phenyl B amidine hydrochloric acid salt compound.
Wherein R, X
1, X
2, m and n and above-mentioned identical and X
3Expression chlorine atom, bromine atoms or iodine atom.
As being used to implement the imidazolium compounds by formula (I) expression of the present invention, be that the example comprises in the situation of hydrogen atom at R: 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, the 3-dichlorophenyl) imidazoles, 2-phenmethyl-4-(2, the 4-dichlorophenyl) imidazoles, 2-phenmethyl-4-(2, the 5-dichlorophenyl) imidazoles, 2-phenmethyl-4-(2, the 6-dichlorophenyl) imidazoles, 2-phenmethyl-4-(3, the 4-dichlorophenyl) imidazoles, 2-phenmethyl-4-(3, the 5-dichlorophenyl) imidazoles, 2-phenmethyl-4-(2, the 4-dibromo phenyl) imidazoles, 2-phenmethyl-4-(2, the 5-dibromo phenyl) imidazoles, 2-phenmethyl-4-(2,4, the 5-trichlorophenyl) imidazoles, 2-phenmethyl-4-(3,4, the 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, the 3-dichlorophenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(2-chlorophenylmethyl)-4-(2, the 5-dichlorophenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(2, the 6-dichlorophenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(3, the 5-dichlorophenyl) imidazoles, 2-(3-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(3-chlorophenylmethyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2, the 3-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles, 2-(4-chlorophenylmethyl)-4-(2, the 5-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2, the 6-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(3, the 5-dichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2, the 4-dibromo phenyl) imidazoles, 2-(2-Brombenzyl)-4-(2, the 5-dichlorophenyl) imidazoles, 2-(2-Brombenzyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(2-Brombenzyl)-4-(2, the 5-dibromo phenyl) imidazoles, 2-(2-chlorophenylmethyl)-4-(2,4, the 5-trichlorophenyl) imidazoles, 2-(4-chlorophenylmethyl)-4-(2,4,5-tribromo phenyl) imidazoles, 2-(4-Brombenzyl)-4-(2,4, the 5-trichlorophenyl) imidazoles, 2-(2-Brombenzyl)-4-(2,4,6-tribromo phenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-the 4-phenylimidazole, 2-(2,4 dichloro benzene methyl)-4-phenylimidazole, 2-(2,5-dichlorobenzene methyl)-4-phenylimidazole, 2-(2,6-dichlorobenzene methyl)-the 4-phenylimidazole, 2-(3,4-dichlorobenzene methyl)-4-phenylimidazole, 2-(3,5-dichlorobenzene methyl)-4-phenylimidazole, 2-(2,4-dibromobenzene methyl)-the 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, the 3-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(2, the 3-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(2, the 3-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(2, the 3-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(2, the 3-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(2, the 3-dichlorophenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(2, the 4-dichlorophenyl) 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, the 4-dichlorophenyl) 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, the 5-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(2, the 5-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(2, the 5-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(2, the 5-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(2, the 5-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(2, the 5-dichlorophenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(2, the 6-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(2, the 6-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(2, the 6-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(2, the 6-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(2, the 6-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(2, the 6-dichlorophenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(2,3-dichlorobenzene methyl)-4-(3, the 5-dichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(3, the 5-dichlorophenyl) imidazoles, 2-(2,5-dichlorobenzene methyl)-4-(3, the 5-dichlorophenyl) imidazoles, 2-(2,6-dichlorobenzene methyl)-4-(3, the 5-dichlorophenyl) imidazoles, 2-(3,4-dichlorobenzene methyl)-4-(3, the 5-dichlorophenyl) imidazoles, 2-(3,5-dichlorobenzene methyl)-4-(3, the 5-dichlorophenyl) imidazoles, 4-(2, the 5-dibromo phenyl)-2-(2,4-dichlorobenzene methyl) imidazoles, 4-(2, the 5-dibromo phenyl)-2-(3,4-dichlorobenzene methyl) imidazoles, 2-(2,5-dibromobenzene methyl)-4-(3, the 4-dichlorophenyl) imidazoles, 2-(2,4-dibromobenzene methyl)-4-(3, the 4-dibromo phenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(3,4, the 5-trichlorophenyl) imidazoles, 2-(2,4 dichloro benzene methyl)-4-(2,4,6-tribromo phenyl) imidazoles, 2-(2,4-dibromobenzene methyl)-4-(3,4, the 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, the 4-dibromo phenyl)-2-(3,4,5-trichlorobenzene methyl) imidazoles, 4-(3, the 4-dichlorophenyl)-2-(2,4,5-tribromo-benzene methyl) imidazoles, 4-(2, the 5-dibromo phenyl)-2-(2,3,5-tribromo-benzene methyl) imidazoles, 2-(3,4,5-trichlorobenzene methyl)-4-(2,4, the 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, the 5-trichlorophenyl)-imidazoles and 2-(2,4,6-tribromo-benzene methyl)-4-(2,4,6-tribromo phenyl)-imidazoles.
Can be with imidazolium compounds as the activeconstituents that passes through its surface treatment agent for preparing soluble in water.Described imidazolium compounds can be for example with 0.01～10 weight %, and the ratio of preferred 0.1～5 weight % is included in the surface treatment agent.When the content of described imidazolium compounds during less than 0.01 weight %, the film thickness of the chemical layer that forms on described copper surface may be too thin, thereby make and can not fully prevent the oxidation on copper surface.On the other hand, when it surpassed 10 weight %, the imidazolium compounds in the surface treatment agent may be difficult to dissolve fully, still reppd problem may take place after the dissolving fully even perhaps exist at described compound, was not preferred therefore.
Incidentally, when enforcement is of the present invention, in imidazolium compounds, can only use its a kind of suitable imidazolium compounds, but also can use the not combination of imidazolium compounds of the same race by formula (I) expression.
When enforcement is of the present invention, with imidazolium compounds (the formation aqueous solution) soluble in water the time, organic acid or mineral acid can be used as described acid usually, but can uses a small amount of organic solvent simultaneously.The organic acid representative example that will use in this case comprises formic acid, acetate, 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-acetate, butoxy acetic acid, 2-(2-methoxy ethoxy) acetate, 2-[2-(2-ethoxy ethoxy) oxyethyl group] acetate, 2-{2-[2-(2-ethoxy ethoxy) oxyethyl group] oxyethyl group } acetate, the 3-methoxypropionic acid, the 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 representative examples of mineral pigments comprises hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid.Can this acid be added in the surface treatment agent with the ratio of 0.1～50 weight %, preferred 1～30 weight %.
In addition, as organic solvent, suitable is lower alcohol such as methyl alcohol, ethanol and Virahol; Or acetone, N, dinethylformamide, ethylene glycol etc., it can be miscible with the water freedom.
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 the thermotolerance of zn cpds with the formed chemical layer of further raising.
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 weight %, and the ratio of preferred 0.02～5 weight % is included in the tensio-active agent.
In the situation of using this copper compound or zn cpds, except organic acid or mineral acid, can expect to come the pH of stabilizing solution by material, aminated compounds such as ammonia, monoethanolamine, diethanolamine or trolamine that interpolation has a shock absorption.
For the further formation speed of chemical layer and the thermotolerance of described layer of improving, can in surface treatment agent, add halogen compounds (using " halogen " in its more general implication) with the ratio of 0.001～1 weight %, preferred 0.01～0.1 weight %.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 of using surface treatment agent of the present invention that copper or copper alloy surface are handled, the fluid temperature of described surface treatment agent can be preferably 10 ℃～70 ℃, 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.
Promptly, on the surface of copper or copper alloy, form after the chemical layer, be dissolved in solvent (toluene for example by the thermoplastic resin that will have excellent heat resistance, ethyl acetate or Virahol) in, and use roller coating machine etc. on described chemical layer evenly coating thickness can form the bilayer structure of chemical layer and thermoplastic resin for for example solution of 1～30 μ m, described thermoplastic resin can be by rosin derivative (for example 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 constitutes.
The example that is fit to enforcement lead-free solder of the present invention comprises lead-free solder such 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 the welding groove mobile printing wiring board so that the junction surface between electronic unit and the printed-wiring board (PWB) is welded, described reflow soldering comprises in advance according to circuit pattern prints paste shape scolder, electronic unit and whole printed-wiring board (PWB) heated with melting solder is installed thereon on printed-wiring board (PWB), thereby finishes welding.
Embodiment
Below with reference to embodiment and comparative example the present invention is specifically described, the present invention is limited to this but should not be construed.
Incidentally, it is as follows to be used for the imidazolium compounds and the evaluation test method of embodiment and comparative example.
Imidazolium compounds
It is following and in reference example 2～20 synthesis example has been shown to be used 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-phenylimidazole (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, the 4-dichlorophenyl)-5-Methylimidazole (being called " D-6 ")
2-(4-chlorophenylmethyl)-5-methyl-4-(3,4, the 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, the 4-dichlorophenyl)-5-Methylimidazole (being called " E-2 ")
2-(3,4-dichlorobenzene methyl)-4-(3, the 4-dichlorophenyl)-5-Methylimidazole (being called " E-3 ")
In this, as mentioned above, symbol A～E represents following (A)～(E) class respectively.
(A) imidazolium compounds that replaced by a halogen atom of the hydrogen atom in any one in phenmethyl or phenyl only wherein;
(B) imidazolium compounds that all replaced by halogen atom respectively of the hydrogen atom in phenmethyl and phenyl wherein;
(C) imidazolium compounds that replaced by two above halogen atoms of the hydrogen atom in any one in phenmethyl or phenyl only wherein;
(D) imidazolium compounds that wherein hydrogen atom in any one in phenmethyl or phenyl is replaced by two above halogen atoms and the hydrogen atom in another is replaced by a halogen atom; With
(E) imidazolium compounds that all replaced by two halogen atoms respectively of the hydrogen atom in phenmethyl and phenyl wherein.
Reference example 1
Synthetic (4-chloro-phenyl-) B amidine hydrochloric acid salt
Preparation contain 137.2g's (0.905mol) (4-chloro-phenyl-) acetonitrile and 51.1g (1.11mol) dehydrated alcohol solution and under cooling in 2 hour time, adding 36.7g (1.01mol) hydrogen chloride gas under 15～20 ℃.When adding hydrogen chloride gas, form solid.When at room temperature reaction mixture sat being spent the night,, obtained ethyl (4-chloro-phenyl-) acetimidate hydrochloride salt as white solid.With after the solid crushing, at the ice-cooled solution that in vibration, constitutes by 28.4g (1.67mol) ammonia and 250g dehydrated alcohol down to portion-wise addition wherein.After finishing interpolation, also at room temperature spent the night in 1 hour ice-cooled down mixture the stirring.After filtering out insoluble white solid matter, in a vacuum filtrate is concentrated and drying, thereby obtain 178g (0.868mol, yield are 96%) (4-chloro-phenyl-) B amidine hydrochloric acid salt white crystal.
Reference example 2
Synthetic A-1
In the solution that contains 61.5g (0.30mol) (4-chloro-phenyl-) B amidine hydrochloric acid salt and 250mL tetrahydrofuran (THF), add the sodium methylate of 16.2g (0.30mol), heated 1 hour down at 50 ℃ then.Then, to wherein adding 83g (0.60mol) salt of wormwood.In gained suspension, dripping the solution that constitutes by 59.7g (0.30mol) 2-bromoacetophenone and 200mL tetrahydrofuran (THF) under 50～55 ℃.After finishing dropping, described mixture heating up was refluxed 2 hours.Then, reaction mixture is cooled to room temperature, insoluble substance is filtered, and in a vacuum filtrate is concentrated and drying.After washing with water, enriched material is stirred with toluene, thereby separate out crystal.After the crystal of by gac filtration being collected in methyl alcohol decolours, carry out recrystallization, thereby obtain 25g (0.093mol, yield: pale pink crystal 31%).
Reference example 3
Synthetic A-2
At first, according to the method synthesis of phenyl B amidine hydrochloric acid salt of reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes benzyl cyanide into.
Then, according to method Synthetic 2-phenmethyl-4-(4-the chloro-phenyl-)-5-Methylimidazole of reference example 2, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt of reference example 2 is changed into the phenyl B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-4 '-chlorophenyl acetone.
Reference example 4
Synthetic A-3
At first, according to synthetic (2-chloro-phenyl-) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (2-chloro-phenyl-) acetonitrile into.
Then, according to method Synthetic 2-(2-the chlorophenylmethyl)-5-methyl-4-phenylimidazole of reference example 2, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt with reference example 2 changes (2-chloro-phenyl-) B amidine hydrochloric acid salt into and changes the 2-bromoacetophenone into the 2-brom-acetophenone.
Reference example 5
Synthetic B-1
At first, according to synthetic (2-chloro-phenyl-) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (2-chloro-phenyl-) acetonitrile into.
Then, according to method Synthetic 2-(2-chlorophenylmethyl)-4-(4-the chloro-phenyl-)-5-Methylimidazole of reference example 2, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt of reference example 2 is changed into (2-chloro-phenyl-) B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-4 '-chlorophenyl acetone.
Reference example 6
Synthetic B-2
According to method Synthetic 2-(4-chlorophenylmethyl)-4-(2-the chloro-phenyl-)-5-Methylimidazole of reference example 2, wherein the 2-bromoacetophenone of reference example 2 is changed into 2-bromo-2 '-chlorophenyl acetone.
Reference example 7
Synthetic B-3
According to method Synthetic 2-(4-chlorophenylmethyl)-4-(4-the chloro-phenyl-)-5-Methylimidazole of reference example 2, wherein the 2-bromoacetophenone of reference example 2 is changed into 2-bromo-4 '-chlorophenyl acetone.
Reference example 8
Synthetic C-1
At first, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (2,4 dichloro benzene base) acetonitrile into.
Then, according to method Synthetic 2-(2,4 dichloro benzene the methyl)-4-phenylimidazole of reference example 2, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt with reference example 2 changes (2,4 dichloro benzene base) B amidine hydrochloric acid salt into.
Reference example 9
Synthetic C-2
At first, according to the method synthesis of phenyl B amidine hydrochloric acid salt of reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes benzyl cyanide into.
Then, method Synthetic 2-phenmethyl-4-(2 according to reference example 2, the 4-dichlorophenyl)-the 5-Methylimidazole, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt of reference example 2 is changed into the phenyl B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-2 ', 4 '-dichloropropiophenone.
Reference example 10
Synthetic C-3
At first, according to synthetic (3,4, the 5-trichlorophenyl) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (3,4, the 5-trichlorophenyl) acetonitrile into.
Then, according to the synthetic 5-hexyl of the method for reference example 2-4-phenyl-2-(3,4,5-trichlorobenzene methyl) imidazoles, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt with reference example 2 changes (3,4, the 5-trichlorophenyl) B amidine hydrochloric acid salt into and changes the 2-bromoacetophenone into 2-bromobenzene octanone.
Reference example 11
Synthetic D-1
At first, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (2,4 dichloro benzene base) acetonitrile into.
Then, according to the synthetic 4-(4-chloro-phenyl-) of the method for reference example 2-2-(2,4-dichlorobenzene methyl)-the 5-Methylimidazole, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt of reference example 2 is changed into (2,4 dichloro benzene base) B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-4 '-chlorophenyl acetone.
Reference example 12
Synthetic D-2
At first, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (2,4 dichloro benzene base) acetonitrile into.
Then, according to the synthetic 4-(4-bromophenyl) of the method for reference example 2-2-(2,4 dichloro benzene methyl)-5-Methylimidazole, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt with reference example 2 changes (2 into, the 4-dichlorophenyl) B amidine hydrochloric acid salt and change the 2-bromoacetophenone into 2,4 '-dibromobenzene acetone.
Reference example 13
Synthetic D-3
At first, according to synthetic (2-chloro-phenyl-) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (2-chloro-phenyl-) acetonitrile into.
Then, method Synthetic 2-(2-chlorophenylmethyl)-4-(2 according to reference example 2, the 4-dichlorophenyl) imidazoles, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt of reference example 2 is changed into (2-chloro-phenyl-) B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-2 ', 4 '-dichloroacetophenone.
Reference example 14
Synthetic D-4
According to method Synthetic 2-(4-chlorophenylmethyl)-4-(2,4 dichloro benzene base) imidazoles of reference example 2, wherein the 2-bromoacetophenone of reference example 2 is changed into 2-bromo-2 ', 4 '-dichloroacetophenone.
Reference example 15
Synthetic D-5
At first, according to synthetic (4-bromophenyl) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (4-bromophenyl) acetonitrile into.
Then, method Synthetic 2-(4-Brombenzyl)-4-(2 according to reference example 2, the 4-dichlorophenyl)-the 5-Methylimidazole, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt of reference example 2 is changed into (4-bromophenyl) B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-2 ', 4 '-dichloropropiophenone.
Reference example 16
Synthetic D-6
At first, according to synthetic (4-bromophenyl) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (4-bromophenyl) acetonitrile into.
Then, method Synthetic 2-(4-Brombenzyl)-4-(3 according to reference example 2, the 4-dichlorophenyl)-the 5-Methylimidazole, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt of reference example 2 is changed into (4-bromophenyl) B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-3 ', 4 '-dichloropropiophenone.
Reference example 17
Synthetic D-7
According to method Synthetic 2-(4-chlorophenylmethyl)-5-methyl-4-(3,4, the 5-trichlorophenyl) imidazoles of reference example 2, wherein the 2-bromoacetophenone of reference example 2 is changed into 2-bromo-3 ', 4 ', 5 '-trichlorobenzene acetone.
Reference example 18
Synthetic E-1
At first, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (2,4 dichloro benzene base) acetonitrile into.
Then, method Synthetic 2-(2 according to reference example 2,4-dichlorobenzene methyl)-4-(2, the 4-dichlorophenyl)-the 5-Methylimidazole, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt with reference example 2 changes (2 into, the 4-dichlorophenyl) B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-2 ', 4 '-dichloropropiophenone.
Reference example 19
Synthetic E-2
At first, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (2,4 dichloro benzene base) acetonitrile into.
Then, method Synthetic 2-(2 according to reference example 2,4-dichlorobenzene methyl)-4-(3, the 4-dichlorophenyl)-the 5-Methylimidazole, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt with reference example 2 changes (2 into, the 4-dichlorophenyl) B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-3 ', 4 '-dichloropropiophenone.
Reference example 20
Synthetic E-3
At first, according to synthetic (3, the 4-dichlorophenyl) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (3, the 4-dichlorophenyl) acetonitrile into.
Then, method Synthetic 2-(3 according to reference example 2,4-dichlorobenzene methyl)-4-(3, the 4-dichlorophenyl)-the 5-Methylimidazole, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt with reference example 2 changes (3 into, the 4-dichlorophenyl) B amidine hydrochloric acid salt and with the 2-bromoacetophenone change into 2-bromo-3 ', 4 '-dichloropropiophenone.
The imidazolium compounds that is used for comparative example is as follows.
2-phenmethyl-4-phenylimidazole (being called " Z-1 ")
2-phenmethyl-5-chloro-4-methylimidazole (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 by the trade name " Curesol 2P4MZ " of Shikoku Chem (Shikoku Chemicals Corporation) manufacturing with by Wako Pure Chemical Industries, Ltd. (Wako Pure Chemical Industries, the Ltd.) reagent of Zhi Zaoing.
Reference example 21
Synthetic Z-1
At first, according to the method synthesis of phenyl B amidine hydrochloric acid salt of reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes benzyl cyanide into.
Then, according to the method Synthetic 2-phenmethyl-4-phenylimidazole of reference example 2, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt with reference example 2 changes the phenyl B amidine hydrochloric acid salt into.
Reference example 22
Synthetic Z-2
At room temperature, the N-chlorosuccinimide of portion-wise addition 13.3g (0.1mol) in the solution of forming by 16g (0.093mol) 2-phenmethyl-4-methylimidazole (making " 2B4MI " by POLYORGANIX) and 100mL ethanol.After mixture stirring 1 hour, in a vacuum reaction mixture is concentrated and drying, and wash with the material of hot water to drying.Then, with its recrystallization and obtain 8.5g (0.041mol, yield: 2-phenmethyl 44%)-5-chloro-4-methylimidazole, it is the light beige needle-like crystal in acetonitrile.
Reference example 23
Synthetic Z-3
Under agitation the solution of being made up of the sulphur of (4-chloro-phenyl-) acetonitrile, 22.8g (0.38mol) quadrol and the 0.21g (6.5mmol) of 52.0g (0.343mol) is heated and in 2 hour time, temperature is risen to 280 ℃ from 150 ℃.After with the mixture cooling, to wherein adding the solution of being made up of 1.0g sodium hydroxide and 10mL methyl alcohol, reflux is 3 hours then.After in a vacuum reaction mixture being concentrated, in a vacuum enriched material is distilled and obtain 43g (0.22mol, yield: 2-64%) (4-chlorophenylmethyl) tetrahydroglyoxaline, it is the cut with 163 ℃～170 ℃/4mmHg boiling point.
Then, at room temperature 27g (0.17mol) potassium permanganate is added in the solution of being made up of the above-mentioned 2-of 21g (0.108mol) (4-chlorophenylmethyl) tetrahydroglyoxaline and 250mL diox in batches.After mixture heating up was refluxed 8 hours, insoluble substance is filtered, and in a vacuum filtrate is concentrated and drying.After water washs the product of drying, from water-acetonitrile, product carried out recrystallization and obtain 13.5g (0.070mol, yield: 2-65%) (4-chlorophenylmethyl) imidazoles, it is the oyster white crystal.
Reference example 24
Synthetic Z-4
At first, according to synthetic (2,4 dichloro benzene base) B amidine hydrochloric acid salt of the method for reference example 1, wherein (4-chloro-phenyl-) acetonitrile with reference example 1 changes (2,4 dichloro benzene base) acetonitrile into.
Then, according to method Synthetic 2-(the 2,4 dichloro benzene methyl)-4 of reference example 2,5-diphenyl-imidazole, wherein (4-chloro-phenyl-) B amidine hydrochloric acid salt with reference example 2 changes (2,4 dichloro benzene base) B amidine hydrochloric acid salt into and changes the 2-bromoacetophenone into 2-bromo-2-phenyl methyl phenyl ketone.
The chemical formula that will be used for the imidazolium compounds of embodiment is shown in as follows:
The chemical formula that will be used for the imidazolium compounds of comparative example is shown in as follows.
The evaluation test method that is used for embodiment and comparative example is as follows.
Be used for the make progress evaluation test of performance of turnover rate (flow-up rate) of scolder
To be used as test film by the printed-wiring board (PWB) that glass epoxy resin is made, 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.Thereafter, immersing in the surface treatment agent that remains under the appointment fluid temperature test film and the lasting specified time cycle, wash with water, and carry out drying then, is the chemical layer of about 0.10～0.50 μ m thereby form thickness on the copper surface.
Use infrared reflow stove (trade name: MULTI-PRO-306, by (the Vetronix Co. of Wei Teni company, Ltd.) make) surface-treated test film is carried out three round-robin reflux, wherein peak temperature is 240 ℃, and utilizes the flow soldering device to weld (line speed: 1.0m/ minute) subsequently.
Employed scolder is for consisting of tin-plumbous eutectic solder (trade name: H63A of 63% tin and 37% lead (weight %), by (the Senju Metal Industry Co. of Senju Metal Industry Co., Ltd, Ltd.) make), the soldering flux that is used to weld is that JS-64MSS is (by great brightness Co., Ltd. (Koki Co. Ltd.) makes).Welding temperature is 240 ℃.
In addition, to use lead-free solder to welding by above-mentioned test film surface of handling with the mode that tin-plumbous eutectic solder is identical.Employed scolder is lead-free solder (trade name: H705 " ECOSOLDER ", make by Senju Metal Industry Co., Ltd), it consists of 96.5% tin, 3.0% silver and 0.5% copper (weight %), and the soldering flux that is used to weld is JS-E-09 (by the manufacturing of great brightness Co., Ltd.).The peak temperature of described reflux is 245 ℃, and welding temperature also is 245 ℃.
Test film about welding has calculated the ratio (%) of the copper vias number of (welding) with respect to copper vias sum (300 holes), and in described (welding) copper vias, scolder is filled until the top of copper vias (upper land).
When scolder when the lip-deep wettability of copper is big, fusion welding penetrates in each copper vias, fusion welding is easy to through hole is filled to through hole top thus.That is, when the ratio of the soldered via count in top and through hole sum is big, scolder should be judged to be excellence to the wettability and the weldability of copper.
Be used for the evaluation test of scolder spreadability
The printed-wiring board (PWB) of 50mm (length) * 50mm (the width) * 1.2mm (thickness) that will be made by glass epoxy resin is as test film.This printed-wiring board (PWB) has a kind of circuit pattern, and wherein the interval formation conductor width with 1.0mm is that 0.80mm and length are 10 copper foil circuits of 20mm on width.To test film carry out degreasing, soft erosion and then water wash.Thereafter, immersing in the surface treatment agent that remains under the appointment fluid temperature test film and the lasting specified time cycle, wash with water, and carry out drying then, is the chemical layer of about 0.10～0.50 μ m thereby form thickness on the copper surface.
Use infrared reflow stove (trade name: MULTI-PRO-306 is made by Wei Teni company) that surface-treated test film is carried out a round-robin reflux, wherein peak temperature is 240 ℃.Thereafter, use metal mask with 1.2mm aperture and 150 μ m thickness with tin-lead welding cream be printed on the copper circuit parts in the heart, and carry out reflux under these conditions, and weld.Employed tin-lead welding cream is the eutectic solder (trade name: OZ-63-330F-40-10 is made by Senju Metal Industry Co., Ltd) that is made of 63% tin and 37% lead (weight %).
In addition, also use lead-free solder paste to welding in the mode identical by the above-mentioned surface-treated test film that carries out with tin-lead welding cream.Employed lead-free solder constitutes (trade name: M705-221BM5-42-11 is made by Senju Metal Industry Co., Ltd) by 96.5% tin, 3.0% copper (weight %) silver-colored and 0.5%.The peak temperature of the reflux of will be before printing with paste and obtaining afterwards is set at 245 ℃.
Wetting length (mm) with the scolder of sprawling on the copper circuit parts of the test film that obtains is measured.
When length is longer, solder wettability and weldability are judged to be excellence.
Embodiment 1
Make being dissolved in deionized water as 2-(4-the chlorophenylmethyl)-4-phenylimidazole of imidazolium compounds, as the levulinic acid of acid with as the venus crystals of metal-salt and zinc chloride have the composition described in the table 1 after, utilize ammoniacal liquor with pH regulator to 3.6, thereby prepared surface treatment agent.
Then, the test film of printed-wiring board (PWB) immersed be controlled in 40 ℃ of surface treatment agents under the temperature and continue 30 seconds, water washs, and is dry then, thereby 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, with with embodiment 1 in identical mode prepared and variously had the surface treatment agents of described in table 1 or 2, forming, and under the treatment condition described in table 1 or 2, carry out surface treatment.About the gained test film, the upwards turnover rate performance of scolder and the spreadability of scolder have been measured.These test-results are shown in table 1 or 2.
Comparative example 1～6
Use imidazolium compounds, acid, metal-salt and halogen compounds as table 3 described in, with embodiment 1 in identical mode prepared various surface treatment agents with composition described in table 3, and under the treatment condition described in table 3, carry out surface treatment.About the gained test film, the upwards turnover rate performance of scolder and the spreadability of scolder have been 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 the table 2 (embodiment 10～19), forms chemical layer and can improve eutectic solder or lead-free solder solder wettability by surface treatment agent of the present invention and copper surface contact printed-wiring board (PWB) copper surface, and eutectic solder or lead-free solder excellence becomes to the weldability (spreadability of make progress turnover rate performance, the scolder of scolder) on copper surface.
In embodiment 1～19, the upwards turnover rate performance of finding scolder in the situation of using eutectic solder all is 100% (only being 98% in embodiment 3) in the top and bottom almost and does not observe difference in embodiment 1～19.Yet, about the upwards turnover rate performance of scolder in using the situation of lead-free solder and in using eutectic solder or lead-free solder situation the spreadability of scolder, observe some difference at embodiment 1～3 (hereinafter being called situation A), embodiment 4～6 (hereinafter being called situation B) and embodiment 7～19 (hereinafter being called situation C).That is, in using the situation of lead-free solder the upwards turnover rate performance of scolder and in the situation of using eutectic solder or lead-free solder the spreadability of scolder improve with the order of situation A＜situation B＜situation C.
As mentioned above, the imidazolium compounds that is used for situation A is those imidazolium compoundss of being replaced by a halogen atom of the hydrogen atom in any one group in phenmethyl or phenyl only wherein.Imidazolium compounds among the situation B is those imidazolium compoundss of all being replaced by a halogen atom respectively of the hydrogen atom in phenmethyl and the phenyl wherein.The imidazolium compounds that is used for situation C is (i) those compounds (embodiment 7～9) of being replaced by two above halogen atoms of the hydrogen atom in any one group in phenmethyl or phenyl only wherein, (ii) wherein in phenmethyl or phenyl the hydrogen atom in any one group replaced by two above halogen atoms and another group in those compounds (embodiment 10～16) of being replaced by a halogen atom of hydrogen atom, (iii) those compounds (embodiment 17～19) of all being replaced by two halogen atoms respectively of the hydrogen atom in phenmethyl and phenyl wherein.
According to the test-results shown in the table 3 (comparative example 1～6), weldability is better in the situation of the surface treatment agent that uses comparative example 4.The compound that the imidazolium compounds (Z-4) that is used for this surface treatment agent is replaced by two halogen atoms for two hydrogen atoms in the phenmethyl wherein, but described imidazolium compounds is compared with being applicable to the imidazolium compounds of implementing formula of the present invention (I), is attached to the substituent kind difference on the imidazole ring 5-position.Promptly, in the test-results of comparative example 4, we can say that it has hinted, the effect that weldability is improved is derived from and is attached on the imidazole ring 2-position and phenyl is attached to chemical structure on its 4-position by phenmethyl, and wherein two hydrogen atoms are replaced by two halogen atoms in described phenmethyl.Yet, be applicable to that implementing imidazolium compounds of the present invention has the above-mentioned chemical structure different with Z-4, wherein hydrogen atom or alkyl rather than phenyl are attached on the 5-position of imidazole ring.This point is to be applicable to the feature of implementing imidazolium compounds of the present invention, and causes above-mentioned improved result.
Even when using eutectic solder to weld, also can use surface treatment agent of the present invention easily, but in the welding of using the lead-free solder of comparing the weldability that shows difference with eutectic solder, also can use described surface treatment agent suitably.
Industrial applicibility
The present invention relates to a kind of surface treatment agent and corresponding surface treatment method, described surface treatment agent is constituting when using scolder to be installed to electronic unit etc. on the printed-wiring board (PWB) on the copper of the circuit block of printed-wiring board (PWB) etc. or the copper alloy surface and is forming the chemical layer with excellent heat resistance, simultaneously, wettability, weldability have been improved to scolder.
In addition, the present invention can provide a kind of by will constituting the copper circuit parts copper or the surface of copper alloy contact the printed-wiring board (PWB) that obtains with above-mentioned surface treatment agent and a kind of welding process that contacts with above-mentioned surface treatment agent and use lead-free solder to weld then by the surface with copper or copper alloy can be provided.
Although the present invention is 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 variations and modifications therein.
The application is based on Japanese patent application 2008-295619 that submits in the Japanese patent application 2008-206119 that submitted on August 8th, 2008, on November 19th, 2008 and the Japanese patent application 2009-124003 that submitted on May 22nd, 2009, by reference its full content is incorporated herein hereby.
Claims (6)
1. surface treatment agent that is used for copper or copper alloy, it comprises the imidazolium compounds by formula (I) expression:
Wherein R represents hydrogen atom or alkyl, X
1And X
2Identical or different and expression chlorine atom or bromine atoms; M and n represent that 0～3 integer and at least one among m or the n are more than 1.
2. surface treatment agent as claimed in claim 1, wherein each among m and the n all is more than 1.
3. surface treatment agent as claimed in claim 1, wherein at least one among m or the n is more than 2.
4. surface treatment method that is used for copper or copper alloy, described method comprises that the surface with described copper or described alloy contacts with each described surface treatment agent in the claim 1～3.
5. printed-wiring board (PWB), it comprises copper or the copper alloy that constitutes the copper circuit parts, and the surface of wherein said copper or described alloy contacts with each described surface treatment agent in the claim 1～3.
6. welding process, described method comprise that the surface with copper or copper alloy contacts with each described surface treatment agent in the claim 1～3 and utilizes lead-free solder to weld then.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-206119 | 2008-08-08 | ||
| JP2008206119 | 2008-08-08 | ||
| JP2008-295619 | 2008-11-19 | ||
| JP2008295619 | 2008-11-19 | ||
| JP2009-124003 | 2009-05-22 | ||
| JP2009124003A JP5313044B2 (en) | 2008-08-08 | 2009-05-22 | Surface treatment agent for copper or copper alloy and use thereof |
| 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 true CN102119240A (en) | 2011-07-06 |
| CN102119240B 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109048019A (en) * | 2018-09-13 | 2018-12-21 | 烟台孚信达双金属股份有限公司 | A kind of welding procedure for Copper-Aluminum compound row |
Families Citing this family (9)
| 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 |
| JP6681566B1 (en) * | 2019-05-27 | 2020-04-15 | 千住金属工業株式会社 | Solder paste and flux |
| JP6681567B1 (en) * | 2019-05-27 | 2020-04-15 | 千住金属工業株式会社 | Solder paste and flux |
Citations (4)
| 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 |
| JPH07243054A (en) * | 1994-03-08 | 1995-09-19 | Shikoku Chem Corp | Surface treating agent for copper and copper alloy |
| 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 (9)
| 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 |
| 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 |
-
2009
- 2009-05-22 JP JP2009124003A patent/JP5313044B2/en active Active
- 2009-08-06 TW TW098126511A patent/TWI464298B/en active
- 2009-08-07 CN CN200980131025.2A patent/CN102119240B/en active Active
- 2009-08-07 KR KR1020117002997A patent/KR101540143B1/en active IP Right Grant
- 2009-08-07 WO PCT/JP2009/064318 patent/WO2010016620A1/en active Application Filing
- 2009-08-07 MY MYPI2011000452A patent/MY162495A/en unknown
Patent Citations (5)
| 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 |
| JPH07243054A (en) * | 1994-03-08 | 1995-09-19 | Shikoku Chem Corp | Surface treating agent for copper and copper alloy |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109048019A (en) * | 2018-09-13 | 2018-12-21 | 烟台孚信达双金属股份有限公司 | A kind of welding procedure for Copper-Aluminum compound row |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110073421A (en) | 2011-06-29 |
| TW201009117A (en) | 2010-03-01 |
| TWI464298B (en) | 2014-12-11 |
| CN102119240B (en) | 2014-07-30 |
| JP5313044B2 (en) | 2013-10-09 |
| WO2010016620A1 (en) | 2010-02-11 |
| KR101540143B1 (en) | 2015-07-28 |
| MY162495A (en) | 2017-06-15 |
| JP2010150651A (en) | 2010-07-08 |
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 | |
| CN103547706B (en) | Surface treating composition and utilization thereof for copper and copper alloy | |
| CN101228000B (en) | Water-soluble preflux and use thereof | |
| CN101448978A (en) | Metal surface treatment agent and use of same | |
| TWI431157B (en) | Phenylnaphthylimidazole compound and usage of the same | |
| 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 |