TWI393804B - Metal surface treatment agent and its use - Google Patents

Metal surface treatment agent and its use Download PDF

Info

Publication number
TWI393804B
TWI393804B TW096117828A TW96117828A TWI393804B TW I393804 B TWI393804 B TW I393804B TW 096117828 A TW096117828 A TW 096117828A TW 96117828 A TW96117828 A TW 96117828A TW I393804 B TWI393804 B TW I393804B
Authority
TW
Taiwan
Prior art keywords
phenyl
imidazole
naphthyl
methylimidazole
benzimidazole
Prior art date
Application number
TW096117828A
Other languages
Chinese (zh)
Other versions
TW200804622A (en
Inventor
Hirao Hirohiko
Kikukawa Yoshimasa
Murai Takayuki
Original Assignee
Shikoku Chem
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 Chem filed Critical Shikoku Chem
Publication of TW200804622A publication Critical patent/TW200804622A/en
Application granted granted Critical
Publication of TWI393804B publication Critical patent/TWI393804B/en

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
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
    • 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
    • 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
    • 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
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/36—Electric or electronic devices
    • B23K2101/42—Printed circuits
    • 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

Description

金屬之表面處理劑及其用途Metal surface treatment agent and use thereof

本發明係關於將電子零件等焊接於構成印刷佈線板之電路部的金屬製導電部表面時，所使用之表面處理劑及其用途。The present invention relates to a surface treatment agent used for soldering an electronic component or the like to the surface of a metal conductive portion constituting a circuit portion of a printed wiring board, and a use thereof.

作為目前印刷佈線板之安裝方法，係廣泛使用使安裝密度提升之表面安裝。此種表面安裝方法，區分為以焊料膏接合晶片零件之兩面表面安裝、晶片零件以焊料膏進行之表面安裝與分立零件組合了通孔安裝的混載安裝等。任一種安裝方法中，印刷佈線板皆進行複數次之焊接，故屆時將曝露於高溫下而受到嚴苛的熱歷程。As a method of mounting a printed wiring board, surface mounting for increasing the mounting density is widely used. Such a surface mounting method is divided into a surface mounting of a solder paste bonding wafer surface, a surface mounting of a wafer component with a solder paste, and a hybrid mounting of a discrete component combined with a via mounting. In any of the mounting methods, the printed wiring board is soldered several times, so that it will be exposed to high temperatures and subjected to severe heat history.

結果，構成印刷佈線板之電路部的金屬製導電部之銅、銅合金或銀等之金屬表面，將因加熱而促進氧化皮膜的形成，故無法良好地保持該導電部表面的焊接性。As a result, the surface of the metal such as copper, copper alloy or silver constituting the metal conductive portion of the circuit portion of the printed wiring board promotes the formation of the oxide film by heating, so that the weldability of the surface of the conductive portion cannot be satisfactorily maintained.

為了保護此種印刷佈線板之金屬製導電部免於空氣氧化，已提案有使用以各種之咪唑化合物作為有效成分之防銹劑，於該導電部表面形成化成皮膜的表面處理方法(例如，專利文獻1~4)In order to protect the metal conductive portion of such a printed wiring board from air oxidation, a surface treatment method for forming a film on the surface of the conductive portion using a rust inhibitor containing various imidazole compounds as an active ingredient has been proposed (for example, a patent) Literature 1~4)

然而，習知以來，於將電子零件接合至印刷佈線板等時，係廣泛使用錫－鉛合金之共結晶焊料，但近年來，因顧慮到該焊料合金中所含之鉛對人體之有害性，而要求使用未含鉛之焊料。因此，研討了各種無鉛焊料，例如已提案有以錫作為糊料金屬，並添加銀、鋅、鉍、銦、銻或銅等之金屬的無鉛焊料。However, conventionally, when a electronic component is bonded to a printed wiring board or the like, a tin-lead alloy co-crystal solder is widely used, but in recent years, it has been considered that the lead contained in the solder alloy is harmful to the human body. It is required to use solder without lead. Therefore, various lead-free solders have been studied. For example, a lead-free solder using tin as a paste metal and adding a metal such as silver, zinc, bismuth, indium, antimony or copper has been proposed.

前者之共結晶焊料，係對於金屬表面之濕潤性優良，對於金屬可牢固地進行接合，故可得到高可靠性。相對於此，後者之無鉛焊料若相較於共結晶焊料，則對於金屬表面之濕潤性差劣，故焊接性惡化而容易發生空隙(void)等之接合不良，故有與金屬之焊料接合強度較弱的難處。The former co-crystallized solder is excellent in wettability to a metal surface, and can be firmly bonded to a metal, so that high reliability can be obtained. On the other hand, when the lead-free solder of the latter is inferior to the eutectic solder, the wettability to the metal surface is deteriorated, so that the solderability is deteriorated and the bonding defects such as voids are likely to occur, so that the solder joint strength with the metal is higher. Weak difficulties.

因此，當使用無鉛焊料時，將要求焊接性更良好之焊料合金及選擇適合無鉛焊料之助熔劑(flux)，對於用於防止金屬表面氧化而使用之表面處理劑，亦要求可改善無鉛焊料之濕潤性並使焊料性良好的功能。Therefore, when a lead-free solder is used, a solder alloy having better solderability and a flux suitable for lead-free solder are required, and a surface treatment agent for preventing oxidation of a metal surface is required to improve lead-free solder. A function of wettability and good solderability.

專利文獻1：日本專利特公昭46－17046號公報專利文獻2：日本專利特開平4－206681號公報專利文獻3：日本專利特開平5－25407號公報專利文獻4：日本專利特開平5－186888號公報Patent Document 1: Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin

本發明係有鑑於上述情事而完成者，其目的在於提供一種金屬之表面處理劑，係在將電子零件焊接至構成印刷佈線板之電路部之金屬製導電部表面時，對於該導電部之表面的焊料濕潤性良好。The present invention has been made in view of the above circumstances, and an object thereof is to provide a surface treatment agent for a metal, which is a surface of the conductive portion when the electronic component is soldered to the surface of the metal conductive portion constituting the circuit portion of the printed wiring board. The solder has good wettability.

另外，其目的在於提供一種藉由使上述表面處理劑接觸於金屬製導電部表面，而於金屬製導電部表面形成化成皮膜之印刷佈線板，以及，提供一種藉由使上述表面處理劑接觸於金屬製導電部表面，而於金屬製導電部表面形成化成皮膜後，使用焊料進行焊接的印刷佈線板之製造方法。Further, it is an object of the invention to provide a printed wiring board having a film formed on a surface of a metal conductive portion by contacting the surface treatment agent with a surface of a metal conductive portion, and providing a surface treatment agent by contacting the surface treatment agent A method of manufacturing a printed wiring board in which a surface of a metal conductive portion is formed on a surface of a metal conductive portion and then soldered using solder.

本發明者等人為解決上述課題而重覆研究，結果發現，藉由作成以含有咪唑化合物與葡萄糖酸化合物為特徵之金屬之表面處理劑，將達成所期望之目的，遂完成本發明。The inventors of the present invention have repeatedly studied in order to solve the above problems, and as a result, have found that a desired surface is achieved by preparing a surface treatment agent containing a metal characterized by containing an imidazole compound and a gluconic acid compound.

另外，第2發明之金屬之表面處理劑，係於第1發明中，以0.01~10重量%之比例含有咪唑化合物，以0.01~50重量%之比例含有葡萄糖酸化合物。In the first aspect of the invention, the metal surface treatment agent according to the second aspect of the invention contains the imidazole compound in an amount of 0.01 to 10% by weight, and the gluconic acid compound in an amount of 0.01 to 50% by weight.

第3發明之印刷佈線板，係於第1發明或第2發明中，藉由使金屬之表面處理劑接觸於金屬製導電部，於金屬製導電部表面形成化成皮膜。In the printed wiring board according to the third aspect of the invention, the metal surface treatment agent is brought into contact with the metal conductive portion to form a chemical conversion film on the surface of the metal conductive portion.

第4發明之印刷佈線板之製造方法，係於第1發明或第2發明中，藉由使金屬之表面處理劑接觸於金屬製導電部，於金屬製導電部表面形成化成皮膜後，使用無鉛焊料進行焊接。In the method of manufacturing a printed wiring board according to the first aspect of the invention, the metal surface treatment agent is brought into contact with the metal conductive portion to form a film on the surface of the metal conductive portion, and then lead-free is used. Solder is soldered.

本發明之金屬之表面處理劑，係組合咪唑化合物與葡萄糖酸化合物而使用，藉此在將電子零件焊接至構成印刷佈線板之電路部的金屬製導電部表面時，可形成對於該導電部表面之濕潤性良好的化成皮膜。於使用本發明之印刷佈線板的情況下，或根據本發明之印刷佈線板之製造方法，將可藉由使用無鉛焊料之焊接而確實地接合金屬製導電部與電子零件。The metal surface treatment agent of the present invention is used by combining an imidazole compound and a gluconic acid compound, whereby when the electronic component is soldered to the surface of the metal conductive portion constituting the circuit portion of the printed wiring board, the surface of the conductive portion can be formed. The film is formed into a film with good wettability. In the case of using the printed wiring board of the present invention or the method of manufacturing a printed wiring board according to the present invention, the metal conductive portion and the electronic component can be surely joined by soldering using lead-free solder.

以下，針對本發明進行詳細說明。Hereinafter, the present invention will be described in detail.

本發明之表面處理劑，係含有咪唑化合物與葡萄糖酸化合物之水溶性液體。本發明實施中所使用之咪唑化合物並無限制，較佳為使用例如下述化1~8之一般式(I)~(VIII)所示之咪唑化合物。又，此等咪唑化合物可組合2種以上使用。The surface treatment agent of the present invention is a water-soluble liquid containing an imidazole compound and a gluconic acid compound. The imidazole compound used in the practice of the present invention is not limited, and for example, an imidazole compound represented by the general formulas (I) to (VIII) of the following formulas 1 to 8 is preferably used. Further, these imidazole compounds may be used in combination of two or more kinds.

(式中，R1 為氫原子、或碳數1~25之可具有取代基之直鏈狀或分枝鏈狀的烷基或烯基。R2 及R3 為氫原子、鹵原子或碳數1~8之直鏈狀或分枝鏈狀之烷基。) (wherein R 1 is a hydrogen atom or a linear or branched alkyl group or alkenyl group having a carbon number of 1 to 25 and may have a substituent ; and R 2 and R 3 are a hydrogen atom, a halogen atom or a carbon. a linear or branched chain of 1 to 8 alkyl groups.)

(式中，R1 為氫原子、或碳數1~25之可具有取代基之直鏈狀或分枝鏈狀的烷基或烯基。R2 及R3 可為相同或相異，表示氫原子、鹵原子或碳數1~8之直鏈狀或分枝鏈狀之烷基。) (wherein R 1 is a hydrogen atom or a linear or branched alkyl group or alkenyl group having a carbon number of 1 to 25 and may have a substituent; R 2 and R 3 may be the same or different, and a hydrogen atom, a halogen atom or a linear or branched chain alkyl group having 1 to 8 carbon atoms.)

[化3] (式中，R1 為氫原子、鹵原子或碳數1~17之直鏈狀或分枝鏈狀的烷基。R2 、R3 、R4 及R5 可為相同或相異，表示氫原子、鹵原子或碳數1~8之直鏈狀或分枝鏈狀之烷基。)[Chemical 3] (wherein R 1 is a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 17 carbon atoms; and R 2 , R 3 , R 4 and R 5 may be the same or different, and a hydrogen atom, a halogen atom or a linear or branched chain alkyl group having 1 to 8 carbon atoms.)

(式中，R1 為氫原子、鹵原子或碳數1~17之直鏈狀或分枝鏈狀的烷基。R2 、R3 、R4 及R5 可為相同或相異，表示氫原子、鹵原子或碳數1~8之直鏈狀或分枝鏈狀之烷基。) (wherein R 1 is a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 17 carbon atoms; and R 2 , R 3 , R 4 and R 5 may be the same or different, and a hydrogen atom, a halogen atom or a linear or branched chain alkyl group having 1 to 8 carbon atoms.)

(式中，R1 為氫原子、鹵原子或碳數1~17之直鏈狀或分枝鏈狀的烷基。R2 、R3 、R4 及R5 可為相同或相異，表示氫原子、鹵原子或碳數1~8之直鏈狀或分枝鏈狀之烷基。) (wherein R 1 is a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 17 carbon atoms; and R 2 , R 3 , R 4 and R 5 may be the same or different, and a hydrogen atom, a halogen atom or a linear or branched chain alkyl group having 1 to 8 carbon atoms.)

(式中，R1 、R2 、R3 及R4 可為相同或相異，表示氫原子、鹵原子或碳數1~8之直鏈狀或分枝鏈狀之烷基。n為0~6之整數。) (wherein R 1 , R 2 , R 3 and R 4 may be the same or different and each represents a hydrogen atom, a halogen atom or a linear or branched chain alkyl group having 1 to 8 carbon atoms. n is 0 An integer of ~6.)

(式中，R1 、R2 、R3 及R4 可為相同或相異，表示氫原子、鹵原子或碳數1~8之直鏈狀或分枝鏈狀之烷基。n為0~6之整數。) (wherein R 1 , R 2 , R 3 and R 4 may be the same or different and each represents a hydrogen atom, a halogen atom or a linear or branched chain alkyl group having 1 to 8 carbon atoms. n is 0 An integer of ~6.)

(式中，R1 及R2 可為相同或相異，表示氫原子、鹵原子或碳數1~8之直鏈狀或分枝鏈狀之烷基。n為0~6之整數。) (wherein R 1 and R 2 may be the same or different and each represents a hydrogen atom, a halogen atom or a linear or branched chain alkyl group having 1 to 8 carbon atoms. n is an integer of 0 to 6.)

作為化1之一般式(I)所示之咪唑化合物，可例示如：咪唑、2－甲基咪唑、2－乙基咪唑、2－丙基咪唑、2－異丙基咪唑、2－丁基咪唑、2－第三丁基咪唑、2－戊基咪唑、2－己基咪唑、2－庚基咪唑、2－(1－乙基戊基)咪唑、2－辛基咪唑、2－壬基咪唑、2－癸基咪唑、2－十一基咪唑、2－十二基咪唑、2－十三基咪唑、2－十四基咪唑、2－十五基咪唑、2－十六基咪唑、2－十七基咪唑、2－十八基咪唑、2－十九基咪唑、2－二十基咪唑、2－二十一基咪唑、2－二十二基咪唑、2－二十三基咪唑、2－二十四基咪唑、2－二十五基咪唑、2－(1－甲基戊基)咪唑、2－(1－乙基戊基)咪唑、2－(1－庚基癸基)咪唑、2－(5－己烯基)咪唑、2－(9－辛烯基)咪唑、2－(8－十七烯基)咪唑、2－(4－氯丁基)咪唑、2－(9－羥壬基)咪唑、2－乙基－4－甲基咪唑、2－十一基－4－甲基咪唑、2－十七基－4－甲基咪唑、4－甲基咪唑、4－異丙基咪唑、4－辛基咪唑、2,4,5－三甲基咪唑、4,5－二甲基－2－辛基咪唑、2－十一基－4－甲基－5－溴咪唑、4,5－二氯－2－乙基咪唑等之烷基咪唑化合物。As the imidazole compound represented by the general formula (I) of the formula 1, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2-butyl group can be exemplified. Imidazole, 2-tert-butylimidazole, 2-pentylimidazole, 2-hexylimidazole, 2-heptyl imidazole, 2-(1-ethylpentyl)imidazole, 2-octylimidazole, 2-mercaptoimidazole , 2-mercaptopimidazole, 2-undecylimidazole, 2-dodecylimidazole, 2-tridecylimidazole, 2-tetradecylimidazole, 2-pentadecylimidazole, 2-hexadecylimidazole, 2 -heptadecylimidazole, 2-octadecyl imidazole, 2-nonylimidazole, 2-eicosyl imidazole, 2-episoimidazole, 2-docosylimidazole, 2-docosyl imidazole , 2-tetrakisyl imidazole, 2-tetradecylimidazole, 2-(1-methylpentyl)imidazole, 2-(1-ethylpentyl)imidazole, 2-(1-heptyldecyl) Imidazole, 2-(5-hexenyl)imidazole, 2-(9-octenyl)imidazole, 2-(8-heptadecenyl)imidazole, 2-(4-chlorobutyl)imidazole, 2- (9-hydroxyindenyl)imidazole, 2-ethyl-4-methylimidazole, 2-undecyl-4-methylimidazole, 2-ten 4-methylimidazole, 4-methylimidazole, 4-isopropylimidazole, 4-octylimidazole, 2,4,5-trimethylimidazole, 4,5-dimethyl-2-octyl Alkyl imidazole compound such as imidazole, 2-undecyl-4-methyl-5-bromoimidazole or 4,5-dichloro-2-ethylimidazole.

作為化2之一般式(II)所示之咪唑化合物，可例示如：2－甲基苯并咪唑、2－乙基苯并咪唑、2－丙基苯并咪唑、2－異丙基苯并咪唑、2－丁基苯并咪唑、2－第三丁基苯并咪唑、2－戊基苯并咪唑、2－己基苯并咪唑、2－(1－甲基戊基)苯并咪唑、2－庚基苯并咪唑、2－(1－乙基戊基)苯并咪唑、2－辛基苯并咪唑、2－(2,4,4－三甲基戊基)苯并咪唑、2－壬基苯并咪唑、2－癸基苯并咪唑、2－十一基苯并咪唑、2－十二基苯并咪唑、2－十三基苯并咪唑、2－十四基苯并咪唑、2－十五基苯并咪唑、2－十六基苯并咪唑、2－十七基苯并咪唑、2－(1－庚基癸基)苯并咪唑、2－十八基苯并咪唑、2－十九基苯并咪唑、2－二十基苯并咪唑、2－二十一基苯并咪唑、2－二十二基苯并咪唑、2－二十三基苯并咪唑、2－二十四基苯并咪唑、2－二十五基苯并咪唑、2－(8－辛基十六基)苯并咪唑、2－(9－辛烯基)苯并咪唑、2－(8－庚烯基)苯并咪唑、2－(4－氯丁基)苯并咪唑、2－(9－羥壬基)苯并咪唑、2－己基－5－甲基苯并咪唑、2－庚基－5,6－二甲基苯并咪唑、2－辛基－5－氯苯并咪唑、2－乙基－5－辛基－6－溴苯并咪唑、2－戊基－5,6－二氯苯并咪唑、4－氟苯并咪唑、2－戊基－5－碘苯并咪唑等之烷基苯并咪唑化合物。As the imidazole compound represented by the general formula (II) of the formula 2, for example, 2-methylbenzimidazole, 2-ethylbenzimidazole, 2-propylbenzimidazole, 2-isopropylbenzone can be exemplified. Imidazole, 2-butylbenzimidazole, 2-tert-butylbenzimidazole, 2-pentylbenzimidazole, 2-hexylbenzimidazole, 2-(1-methylpentyl)benzimidazole, 2 -heptylbenzimidazole, 2-(1-ethylpentyl)benzimidazole, 2-octylbenzimidazole, 2-(2,4,4-trimethylpentyl)benzimidazole, 2- Mercaptobenzimidazole, 2-mercaptobenzimidazole, 2-undecylbenzimidazole, 2-dodecylbenzimidazole, 2-tridecylbenzimidazole, 2-tetradecylbenzimidazole, 2-pentylbenzimidazole, 2-hexadebenzimidazole, 2-heptylbenzimidazole, 2-(1-heptyldecyl)benzimidazole, 2-octadecylbenzimidazole, 2-nonylbenzimidazole, 2-icosylbenzimidazole, 2-isopropenylbenzimidazole, 2-docosylbenzimidazole, 2-docosylbenzimidazole,2- Tetrakilylbenzimidazole, 2-tetradecylbenzimidazole, 2-(8-octylhexadecyl)benzo Oxazole, 2-(9-octenyl)benzimidazole, 2-(8-heptenyl)benzimidazole, 2-(4-chlorobutyl)benzimidazole, 2-(9-hydroxydecyl) Benzimidazole, 2-hexyl-5-methylbenzimidazole, 2-heptyl-5,6-dimethylbenzimidazole, 2-octyl-5-chlorobenzimidazole, 2-ethyl-5 - alkyl benzoyl such as octyl-6-bromobenzimidazole, 2-pentyl-5,6-dichlorobenzimidazole, 4-fluorobenzimidazole, 2-pentyl-5-iodobenzimidazole Imidazole compound.

作為化3之一般式(III)所示之咪唑化合物，可例示如：2,4－二苯基咪唑、2－(2－甲基苯基)－4－苯基咪唑、2－(3－辛基苯基)－4－苯基咪唑、2－(2,4－二甲基苯基)－4－苯基咪唑、2－苯基－4－(4－己基苯基)咪唑、2－苯基－4－(2－甲基－5－丁基苯基)咪唑、2,4－二苯基－5－甲基咪唑、2,4－二苯基－5－己基咪唑、2－(2,4－二乙基)－4－(3－丙基－5－辛基)－5－異丁基咪唑、2－(2－氯苯基)－4－苯基咪唑、2－(3－氯苯基)－4－苯基咪唑、2－(4－氯苯基)－4－苯基咪唑、2－(2－溴苯基)－4－苯基咪唑、2－(3－溴苯基)－4－苯基咪唑、2－(4－溴苯基)－4－苯基咪唑、2－(2－碘苯基)－4－苯基咪唑、2－(3－碘苯基)－4－苯基咪唑、2－(4－碘苯基)－4－苯基咪唑、2－(2－氟苯基)－4－苯基咪唑、2－(3－氟苯基)－4－苯基咪唑、2－(4－氟苯基)－4－苯基咪唑、2－(2,3－二氯苯基)－4－苯基咪唑、2－(2,4－二氯苯基)－4－苯基咪唑、2－(2,5－二氯苯基)－4－苯基咪唑、2－(2,6－二氯苯基)－4－苯基咪唑、2－(3,4－二氯苯基)－4－苯基咪唑、2－(3,5－二氯苯基)－4－苯基咪唑、2－(2,4－二溴苯基)－4－苯基咪唑、2－(2－甲基－4－氯苯基)－4－苯基咪唑、2－(3－溴－5－辛基苯基)－4－苯基咪唑、2－(2－氯苯基)－4－苯基－5－甲基咪唑、2－(3－氯苯基)－4－苯基－5－甲基咪唑、2－(4－氯苯基)－4－苯基－5－甲基咪唑、2－(2－溴苯基)－4－苯基－5－甲基咪唑、2－(3－溴苯基)－4－苯基－5－甲基咪唑、2－(4－溴苯基)－4－苯基－5－甲基咪唑、2－(2－碘苯基)－4－苯基－5－甲基咪唑、2－(3－碘苯基)－4－苯基－5－甲基咪唑、2－(4－碘苯基)－4－苯基－5－甲基咪唑、2－(2－氟苯基)－4－苯基－5－甲基咪唑、2－(3－氟苯基)－4－苯基－5－甲基咪唑、2－(4－氟苯基)－4－苯基－5－甲基咪唑、2－(2,3－二氯苯基)－4－苯基－5－甲基咪唑、2－(2,4－二氯苯基)－4－苯基－5－甲基咪唑、2－(2,5－二氯苯基)－4－苯基－5－甲基咪唑、2－(2,6－二氯苯基)－4－苯基－5－甲基咪唑、2－(3,4－二氯苯基)－4－苯基－5－甲基咪唑、2－(3,5－二氯苯基)－4－苯基－5－甲基咪唑、2－(2,4－二氯苯基)－4－苯基－5－乙基咪唑、2－(2,3－二氯苯基)－4－苯基－5－癸基咪唑、2－(3,4－二氯苯基)－4－苯基－5－十七基咪唑、2－(2,4－二溴苯基)－4－苯基－5－異丙基咪唑、2－(2－庚基－4－氯苯基)－4－苯基－5－異丁基咪唑、2－苯基－4－(2－氯苯基)咪唑、2－苯基－4－(3－氯苯基)咪唑、2－苯基－4－(4－氯苯基)咪唑、2－苯基－4－(2－溴苯基)咪唑、2－苯基－4－(3－溴苯基)咪唑、2－苯基－4－(4－溴苯基)咪唑、2－苯基－4－(2－碘苯基)咪唑、2－苯基－4－(3－碘苯基)咪唑、2－苯基－4－(4－碘苯基)咪唑、2－苯基－4－(2－氟苯基)咪唑、2－苯基－4－(3－氟苯基)咪唑、2－苯基－4－(4－氟苯基)咪唑、2－苯基－4－(2,3－二氯苯基)咪唑、2－苯基－4－(2,4－二氯苯基)咪唑、2－苯基－4－(2,5－二氯苯基)咪唑、2－苯基－4－(2,6－二氯苯基)咪唑、2－苯基－4－(3,4－二氯苯基)咪唑、2－苯基－4－(3,5－二氯苯基)咪唑、2－苯基－4－(2,3－二溴苯基)咪唑、2－苯基－4－(2－溴－3－氯苯基)咪唑、2－苯基－4－(3－溴－4－庚基苯基)咪唑、2－苯基－4－(2－氯苯基)－5－甲基咪唑、2－苯基－4－(3－氯苯基)－5－甲基咪唑、2－苯基－4－(4－氯苯基)－5－甲基咪唑、2－苯基－4－(2－溴苯基)－5－甲基咪唑、2－苯基－4－(3－溴苯基)－5－甲基咪唑、2－苯基－4－(4－溴苯基)－5－甲基咪唑、2－苯基－4－(2－碘苯基)－5－甲基咪唑、2－苯基－4－(3－碘苯基)－5－甲基咪唑、2－苯基－4－(4－碘苯基)－5－甲基咪唑、2－苯基－4－(2－氟苯基)－5－甲基咪唑、2－苯基－4－(3－氟苯基)－5－甲基咪唑、2－苯基－4－(4－氟苯基)－5－甲基咪唑、2－苯基－4－(2,3－二氯苯基)－5－甲基咪唑、2－苯基－4－(2,4－二氯苯基)－5－甲基咪唑、2－苯基－4－(2,5－二氯苯基)－5－甲基咪唑、2－苯基－4－(2,6－二氯苯基)－5－甲基咪唑、2－苯基－4－(3,4－二氯苯基)－5－甲基咪唑、2－苯基－4－(3,5二氯苯基)－5－甲基咪唑、2－苯基－4－(2,3－二氯苯基)－5－丙基咪唑、2－苯基－4－(2,4－二氯苯基)－5－十一基咪唑、2－苯基－4－(2,4－二溴苯基)－5－(1－甲基丁基)咪唑、2－苯基－4－(2－己基－4－碘苯基)－5－丙基咪唑、2,4－雙(4－氯苯基)咪唑、2－(2,4－二氯苯基)－4－(3,4－二氯苯基)－5－甲基咪唑、2－(2－溴－4－辛基苯基)－4－(2－甲基－4－碘苯基)－5－辛基咪唑、2,4－二苯基－5－氟咪唑、2,4－二苯基－5－氯咪唑、2,4－二苯基－5－溴咪唑、2,4－二苯基－5－碘咪唑、2－(4－甲基苯基)－4－苯基－5－氯咪唑、2－(4－氯苯基)－4－苯基－5－溴咪唑、2－苯基－4－(2－氯苯基)－5－碘咪唑等。As the imidazole compound represented by the general formula (III) of the formula 3, for example, 2,4-diphenylimidazole, 2-(2-methylphenyl)-4-phenylimidazole, 2-(3- Octylphenyl)-4-phenylimidazole, 2-(2,4-dimethylphenyl)-4-phenylimidazole, 2-phenyl-4-(4-hexylphenyl)imidazole, 2- Phenyl-4-(2-methyl-5-butylphenyl)imidazole, 2,4-diphenyl-5-methylimidazole, 2,4-diphenyl-5-hexylimidazole, 2-( 2,4-Diethyl)-4-(3-propyl-5-octyl)-5-isobutylimidazole, 2-(2-chlorophenyl)-4-phenylimidazole, 2-(3 -Chlorophenyl)-4-phenylimidazole, 2-(4-chlorophenyl)-4-phenylimidazole, 2-(2-bromophenyl)-4-phenylimidazole, 2-(3-bromo Phenyl)-4-phenylimidazole, 2-(4-bromophenyl)-4-phenylimidazole, 2-(2-iodophenyl)-4-phenylimidazole, 2-(3-iodophenyl) )-4-phenylimidazole, 2-(4-iodophenyl)-4-phenylimidazole, 2-(2-fluorophenyl)-4-phenylimidazole, 2-(3-fluorophenyl)- 4-phenylimidazole, 2-(4-fluorophenyl)-4-phenylimidazole, 2-(2,3-dichlorophenyl) 4-phenylimidazole, 2-(2,4-dichlorophenyl)-4-phenylimidazole, 2-(2,5-dichlorophenyl)-4-phenylimidazole, 2-(2,6 -dichlorophenyl)-4-phenylimidazole, 2-(3,4-dichlorophenyl)-4-phenylimidazole, 2-(3,5-dichlorophenyl)-4-phenylimidazole , 2-(2,4-dibromophenyl)-4-phenylimidazole, 2-(2-methyl-4-chlorophenyl)-4-phenylimidazole, 2-(3-bromo-5- Octylphenyl)-4-phenylimidazole, 2-(2-chlorophenyl)-4-phenyl-5-methylimidazole, 2-(3-chlorophenyl)-4-phenyl-5- Methylimidazole, 2-(4-chlorophenyl)-4-phenyl-5-methylimidazole, 2-(2-bromophenyl)-4-phenyl-5-methylimidazole, 2-(3 -Bromophenyl)-4-phenyl-5-methylimidazole, 2-(4-bromophenyl)-4-phenyl-5-methylimidazole, 2-(2-iodophenyl)-4- Phenyl-5-methylimidazole, 2-(3-iodophenyl)-4-phenyl-5-methylimidazole, 2-(4-iodophenyl)-4-phenyl-5-methylimidazole , 2-(2-fluorophenyl)-4-phenyl-5-methylimidazole, 2-(3-fluorophenyl)-4-phenyl-5-methylimidazole, 2 -(4-fluorophenyl)-4-phenyl-5-methylimidazole, 2-(2,3-dichlorophenyl)-4-phenyl-5-methylimidazole, 2-(2,4 -dichlorophenyl)-4-phenyl-5-methylimidazole, 2-(2,5-dichlorophenyl)-4-phenyl-5-methylimidazole, 2-(2,6-di Chlorophenyl)-4-phenyl-5-methylimidazole, 2-(3,4-dichlorophenyl)-4-phenyl-5-methylimidazole, 2-(3,5-dichlorobenzene 4-phenyl-5-methylimidazole, 2-(2,4-dichlorophenyl)-4-phenyl-5-ethylimidazole, 2-(2,3-dichlorophenyl) 4-phenyl-5-mercaptoimidazole, 2-(3,4-dichlorophenyl)-4-phenyl-5-heptadecylimidazole, 2-(2,4-dibromophenyl)- 4-phenyl-5-isopropylimidazole, 2-(2-heptyl-4-chlorophenyl)-4-phenyl-5-isobutylimidazole, 2-phenyl-4-(2-chloro Phenyl)imidazole, 2-phenyl-4-(3-chlorophenyl)imidazole, 2-phenyl-4-(4-chlorophenyl)imidazole, 2-phenyl-4-(2-bromophenyl) Imidazole, 2-phenyl-4-(3-bromophenyl)imidazole, 2-phenyl-4-(4-bromophenyl)imidazole, 2-phenyl-4-(2-iodophenyl)imide Oxazole, 2-phenyl-4-(3-iodophenyl)imidazole, 2-phenyl-4-(4-iodophenyl)imidazole, 2-phenyl-4-(2-fluorophenyl)imidazole, 2-phenyl-4-(3-fluorophenyl)imidazole, 2-phenyl-4-(4-fluorophenyl)imidazole, 2-phenyl-4-(2,3-dichlorophenyl)imidazole , 2-phenyl-4-(2,4-dichlorophenyl)imidazole, 2-phenyl-4-(2,5-dichlorophenyl)imidazole, 2-phenyl-4-(2,6 -dichlorophenyl)imidazole, 2-phenyl-4-(3,4-dichlorophenyl)imidazole, 2-phenyl-4-(3,5-dichlorophenyl)imidazole, 2-phenyl 4-(2,3-dibromophenyl)imidazole, 2-phenyl-4-(2-bromo-3-chlorophenyl)imidazole, 2-phenyl-4-(3-bromo-4-glybdenum Phenyl)imidazole, 2-phenyl-4-(2-chlorophenyl)-5-methylimidazole, 2-phenyl-4-(3-chlorophenyl)-5-methylimidazole, 2- Phenyl-4-(4-chlorophenyl)-5-methylimidazole, 2-phenyl-4-(2-bromophenyl)-5-methylimidazole, 2-phenyl-4-(3- Bromophenyl)-5-methylimidazole, 2-phenyl-4-(4-bromophenyl)-5-methylimidazole, 2-phenyl-4-(2-iodophenyl)-5 Methylimidazole, 2-phenyl-4-(3-iodophenyl)-5-methylimidazole, 2-phenyl-4-(4-iodophenyl)-5-methylimidazole, 2-phenyl 4-(2-fluorophenyl)-5-methylimidazole, 2-phenyl-4-(3-fluorophenyl)-5-methylimidazole, 2-phenyl-4-(4-fluorobenzene 5-methylimidazole, 2-phenyl-4-(2,3-dichlorophenyl)-5-methylimidazole, 2-phenyl-4-(2,4-dichlorophenyl) -5-methylimidazole, 2-phenyl-4-(2,5-dichlorophenyl)-5-methylimidazole, 2-phenyl-4-(2,6-dichlorophenyl)-5 -methylimidazole, 2-phenyl-4-(3,4-dichlorophenyl)-5-methylimidazole, 2-phenyl-4-(3,5-dichlorophenyl)-5-methyl Imidazole, 2-phenyl-4-(2,3-dichlorophenyl)-5-propylimidazole, 2-phenyl-4-(2,4-dichlorophenyl)-5-undecylimidazole , 2-phenyl-4-(2,4-dibromophenyl)-5-(1-methylbutyl)imidazole, 2-phenyl-4-(2-hexyl-4-iodophenyl)- 5-propylimidazole, 2,4-bis(4-chlorophenyl)imidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dichlorophenyl)-5-methyl Imidazole 2-(2-Bromo-4-octylphenyl)-4-(2-methyl-4-iodophenyl)-5-octyl imidazole, 2,4-diphenyl-5-fluoroimidazole, 2 , 4-diphenyl-5-chloroimidazole, 2,4-diphenyl-5-bromoimidazole, 2,4-diphenyl-5-iodoimidazole, 2-(4-methylphenyl)-4 -Phenyl-5-chloroimidazole, 2-(4-chlorophenyl)-4-phenyl-5-bromoimidazole, 2-phenyl-4-(2-chlorophenyl)-5-iodoimidazole, and the like.

化4之一般式(IV)所示之咪唑化合物，可例示如：2－苯基－4－(1－萘基)咪唑、2－苯基－4－(2－萘基)咪唑、2－(4－甲基苯基)－4－(4－氯－6－丁基－1－萘基)咪唑、2－(2－辛基－4－乙基苯基)－4－(5－氯－7－庚基－1－萘基)咪唑、2－(2,4二氯苯基)－4－(2－異丁基－6－溴－2－萘基)咪唑、2－苯基－4－(1－萘基)－5－甲基咪唑、2－(4－碘苯基)－4－(5,6－二甲基－1－萘基)－5－癸基咪唑、2－苯基－4－(2－萘基)－5－甲基咪唑、2－(2,3－二氟苯基)－4－(7－辛基－2－萘基)－5－十七基咪唑、2－苯基－4－(1－萘基)－5－氟咪唑、2－苯基－4－(1－萘基)－5－氯咪唑、2－苯基－4－(1－萘基)－5－溴咪唑、2－苯基－4－(1－萘基)－5－碘咪唑、2－苯基－4－(2－萘基)－5－氟咪唑、2－苯基－4－(2－萘基)－5－氯咪唑、2－苯基－4－(2－萘基)－5－溴咪唑、2－苯基－4－(2－萘基)－5－碘咪唑、2－(4－甲基苯基)－4－(5－氯－1－萘基)－5－氯咪唑等。The imidazole compound represented by the general formula (IV) of 4 may, for example, be 2-phenyl-4-(1-naphthyl)imidazole, 2-phenyl-4-(2-naphthyl)imidazole, 2- (4-methylphenyl)-4-(4-chloro-6-butyl-1-naphthyl)imidazole, 2-(2-octyl-4-ethylphenyl)-4-(5-chloro -7-heptyl-1-naphthyl)imidazole, 2-(2,4-dichlorophenyl)-4-(2-isobutyl-6-bromo-2-naphthyl)imidazole, 2-phenyl- 4-(1-naphthyl)-5-methylimidazole, 2-(4-iodophenyl)-4-(5,6-dimethyl-1-naphthyl)-5-nonylimidazole, 2- Phenyl-4-(2-naphthyl)-5-methylimidazole, 2-(2,3-difluorophenyl)-4-(7-octyl-2-naphthalenyl)-5-heptyl Imidazole, 2-phenyl-4-(1-naphthyl)-5-fluoroimidazole, 2-phenyl-4-(1-naphthyl)-5-chloroimidazole, 2-phenyl-4-(1- Naphthyl)-5-bromoimidazole, 2-phenyl-4-(1-naphthyl)-5-iodoimidazole, 2-phenyl-4-(2-naphthyl)-5-fluoroimidazole, 2-benzene 4-(2-naphthyl)-5-chloroimidazole, 2-phenyl-4-(2-naphthyl)-5-bromoimidazole, 2-phenyl-4-(2-naphthyl) 5-iodo-imidazole, 2- (4-methylphenyl) -4- (5-chloro-1-naphthyl) -5-chloro-imidazole.

化5之一般式(V)所示之咪唑化合物，可例示如：2－(1－萘基)－4－苯基咪唑、2－(2－萘基)－4－苯基咪唑、2－(2－甲基－5－氯－1－萘基)－4－(4－己基苯基)咪唑、2－(2－異丁基－5－碘－2－萘基)－4－(2－戊基－5－氟苯基)咪唑、2－(1－萘基)－4－苯基－5－甲基咪唑、2－(3,6二氯－2－萘基)－4－(2－異丙基－5－氟苯基)－5－癸基咪唑、2－(6－丙基－7－1－萘基)－4－(3－己基－6－溴苯基)－5－十七基咪唑、2－(1－萘基)－4－苯基－5－氟咪唑、2－(1－萘基)－4－苯基－5－氯咪唑、2－(1－萘基)－4－苯基－5－溴咪唑、2－(1－萘基)－4－苯基－5－碘咪唑、2－(2－萘基)－4－苯基－5－氟咪唑、2－(2－萘基)－4－苯基－5－氯咪唑、2－(2－萘基)－4－苯基－5－溴咪唑、2－(2－萘基)－4－苯基－5－碘咪唑、2－(4－氯－2－萘基)－4－(2－己基苯基)－5－氯咪唑等。The imidazole compound represented by the general formula (V) of 5 may, for example, be 2-(1-naphthyl)-4-phenylimidazole, 2-(2-naphthyl)-4-phenylimidazole, 2- (2-methyl-5-chloro-1-naphthalenyl)-4-(4-hexylphenyl)imidazole, 2-(2-isobutyl-5-iodo-2-naphthyl)-4-(2 -pentyl-5-fluorophenyl)imidazole, 2-(1-naphthyl)-4-phenyl-5-methylimidazole, 2-(3,6-dichloro-2-naphthyl)-4-( 2-isopropyl-5-fluorophenyl)-5-mercaptoimidazole, 2-(6-propyl-7-1-naphthyl)-4-(3-hexyl-6-bromophenyl)-5 -heptadecylimidazole, 2-(1-naphthyl)-4-phenyl-5-fluoroimidazole, 2-(1-naphthyl)-4-phenyl-5-chloroimidazole, 2-(1-naphthalene) 4-phenyl-5-bromoimidazole, 2-(1-naphthyl)-4-phenyl-5-iodoimidazole, 2-(2-naphthyl)-4-phenyl-5-fluoroimidazole , 2-(2-naphthyl)-4-phenyl-5-chloroimidazole, 2-(2-naphthyl)-4-phenyl-5-bromoimidazole, 2-(2-naphthyl)-4- Phenyl-5-iodoimidazole, 2-(4-chloro-2-naphthyl)-4-(2-hexylphenyl)-5-chloroimidazole, and the like.

化6之一般式(VI)所示之咪唑化合物，可例示如：2－苯基苯并咪唑、2－(4－甲基苯基)苯并咪唑、2－(2,4－二氯苯基)苯并咪唑、2－(2－己基苯基)－5－氯苯并咪唑、2－(苯基甲基)苯并咪唑、2－(4－乙基苯基甲基)苯并咪唑、2－(4－氯苯基甲基)苯并咪唑、2－(2,4－二氯苯基甲基)苯并咪唑、2－(3,4－二氯苯基甲基)苯并咪唑、2－(4－溴苯基甲基)－5－乙基苯并咪唑、2－(3－碘苯基甲基)－4－氯苯并咪唑、2－(2－苯基乙基)苯并咪唑、2－[2－(3－異丙基苯基)乙基]苯并咪唑、2－[2－(4－氯苯基)乙基]苯并咪唑、2－[2－(4－氯苯基)乙基]－4,5－二甲基苯并咪唑、2－(3－苯基丙基)苯并咪唑、2－[3－(4－第三丁基苯基)丙基]苯并咪唑、2－[3－(2－氯苯基)丙基]苯并咪唑、2－[3－(4－溴苯基)丙基]－5－丁基苯并咪唑、2－(4－苯基甲基)苯并咪唑、2－[4－(4－氯苯基)丁基]苯并咪唑、2－[4－(2,4－二氯苯基)丁基]－4,7－二氯苯并咪唑、2－(5－苯基戊基)苯并咪唑、2－[5－(2－辛基苯基)戊基]苯并咪唑、2－[5－(3,4－二氯苯基)戊基]－5－庚基苯并咪唑、2－(6－苯基己基)苯并咪唑、2－[6－(3－己基苯基)己基]苯并咪唑、2－[6－(2－乙基－3－氟苯基)己基]4－丁基－5－辛基苯并咪唑等。The imidazole compound represented by the general formula (VI) of 6 can be exemplified by 2-phenylbenzimidazole, 2-(4-methylphenyl)benzimidazole, 2-(2,4-dichlorobenzene Benzimidazole, 2-(2-hexylphenyl)-5-chlorobenzimidazole, 2-(phenylmethyl)benzimidazole, 2-(4-ethylphenylmethyl)benzimidazole , 2-(4-chlorophenylmethyl)benzimidazole, 2-(2,4-dichlorophenylmethyl)benzimidazole, 2-(3,4-dichlorophenylmethyl)benzo Imidazole, 2-(4-bromophenylmethyl)-5-ethylbenzimidazole, 2-(3-iodophenylmethyl)-4-chlorobenzimidazole, 2-(2-phenylethyl Benzimidazole, 2-[2-(3-isopropylphenyl)ethyl]benzimidazole, 2-[2-(4-chlorophenyl)ethyl]benzimidazole, 2-[2- (4-chlorophenyl)ethyl]-4,5-dimethylbenzimidazole, 2-(3-phenylpropyl)benzimidazole, 2-[3-(4-t-butylphenyl) )propyl]benzimidazole, 2-[3-(2-chlorophenyl)propyl]benzimidazole, 2-[3-(4-bromophenyl)propyl]-5-butylbenzimidazole , 2-(4-phenylmethyl)benzimidazole, 2-[4-(4-chlorophenyl)butyl]benzimidazole, 2 [4-(2,4-Dichlorophenyl)butyl]-4,7-dichlorobenzimidazole, 2-(5-phenylpentyl)benzimidazole, 2-[5-(2-octyl) Phenyl)pentyl]benzimidazole, 2-[5-(3,4-dichlorophenyl)pentyl]-5-heptylbenzimidazole, 2-(6-phenylhexyl)benzimidazole ,2-[6-(3-hexylphenyl)hexyl]benzimidazole, 2-[6-(2-ethyl-3-fluorophenyl)hexyl]4-butyl-5-octylbenzimidazole Wait.

化7之一般式(VII)所示之咪唑化合物，可例示如：2－(1－萘基)苯并咪唑、2－(1－萘基)－4－甲基苯并咪唑、2－(2－萘基)苯并咪唑、2－(1－氯－2－萘基)－5,6－二氯苯并咪唑、2－(1－萘基甲基)苯并咪唑、2－(4,6－二甲基－1－萘基甲基)－5－乙基苯并咪唑、2－(7－溴－1－萘基甲基)－5－溴苯并咪唑、2－(2－萘基甲基)苯并咪唑、2－(4－異丙基－2－萘基甲基)－5－第三丁基苯并咪唑、2－[2－(1－萘基)乙基]苯并咪唑、2－[2－(5－戊基－1－萘基)乙基]－5－氯苯并咪唑、2－[2－(2－萘基)乙基]苯并咪唑、2－[2－(6－庚基－2－萘基)乙基]－4－甲基－5－己基苯并咪唑、2－[3－(1－萘基)丙基]苯并咪唑、2－[3－(4－碘－1－萘基)丙基]5,6－二溴苯并咪唑、2－[3－(2－萘基)丙基]苯并咪唑、2－[3－(8－異丙基－2－萘基)丙基]－5－(2－甲基戊基)苯并咪唑、2－[4－(1－萘基)丁基]苯并咪唑、2－[4－(5－氟－1－萘基)丁基]－4－(2－丙基丁基)苯并咪唑、2－[4－(2－萘基)丁基]苯并咪唑、2－[4－(7－辛基－2－萘基)丁基]－4,6－二乙基苯并咪唑、2－[5－(1－萘基)戊基]苯并咪唑、2－[5－(6－戊基－7－氟－1－萘基)戊基]4,7－二丙基苯并咪唑、2－[5－(2－萘基)戊基]苯并咪唑、2－[5－(6,7－二甲基－2－萘基)戊基]－5,6－二氯苯并咪唑、2－[6－(6,7－二乙基－1－萘基)己基]－5－辛基苯并咪唑、2－[6－(2－萘基)己基]苯并咪唑、2－[6－(7－乙基－8－溴－2－萘基)己基]－4－己基－6－氟苯并咪唑等。The imidazole compound represented by the general formula (VII) of the formula 7 may, for example, be 2-(1-naphthyl)benzimidazole, 2-(1-naphthyl)-4-methylbenzimidazole, 2-( 2-naphthyl)benzimidazole, 2-(1-chloro-2-naphthyl)-5,6-dichlorobenzimidazole, 2-(1-naphthylmethyl)benzimidazole, 2-(4 ,6-Dimethyl-1-naphthylmethyl)-5-ethylbenzimidazole, 2-(7-bromo-1-naphthylmethyl)-5-bromobenzimidazole, 2-(2- Naphthylmethyl)benzimidazole, 2-(4-isopropyl-2-naphthylmethyl)-5-tert-butylbenzimidazole, 2-[2-(1-naphthyl)ethyl] Benzimidazole, 2-[2-(5-pentyl-1-naphthalenyl)ethyl]-5-chlorobenzimidazole, 2-[2-(2-naphthyl)ethyl]benzimidazole, 2 -[2-(6-heptyl-2-naphthalenyl)ethyl]-4-methyl-5-hexylbenzimidazole, 2-[3-(1-naphthyl)propyl]benzimidazole, 2 -[3-(4-iodo-1-naphthyl)propyl]5,6-dibromobenzimidazole, 2-[3-(2-naphthyl)propyl]benzimidazole, 2-[3- (8-isopropyl-2-naphthyl)propyl]-5-(2-methylpentyl)benzimidazole, 2-[4-(1-naphthyl)butyl]benzo Oxazole, 2-[4-(5-fluoro-1-naphthalenyl)butyl]-4-(2-propylbutyl)benzimidazole, 2-[4-(2-naphthyl)butyl]benzene Imidazole, 2-[4-(7-octyl-2-naphthalenyl)butyl]-4,6-diethylbenzimidazole, 2-[5-(1-naphthyl)pentyl]benzo Imidazole, 2-[5-(6-pentyl-7-fluoro-1-naphthalenyl)pentyl]4,7-dipropylbenzimidazole, 2-[5-(2-naphthyl)pentyl] Benzimidazole, 2-[5-(6,7-dimethyl-2-naphthyl)pentyl]-5,6-dichlorobenzimidazole, 2-[6-(6,7-diethyl 1-naphthyl)hexyl]-5-octylbenzimidazole, 2-[6-(2-naphthyl)hexyl]benzimidazole, 2-[6-(7-ethyl-8-bromo-2 -Naphthyl)hexyl]-4-hexyl-6-fluorobenzimidazole and the like.

化8之一般式(VIII)所示之咪唑化合物，可例示如：2－環己基苯并咪唑、2－環己基－5,6－二甲基苯并咪唑、2－環己基－5－氯苯并咪唑、2－環己基－4－異丙基苯并咪唑、2－(環己基甲基)苯并咪唑、2－(環己基甲基)－5－乙基苯并咪唑、2－(環己基甲基)－5－溴苯并咪唑、2－(2－環己基乙基)苯并咪唑、2－(2－環己基乙基)－5－氯－6－甲基苯并咪唑、2－(3－環己基丙基)苯并咪唑、2－(3－環己基丙基)－5－丁基苯并咪唑、2－(3－環己基丙基)－4,7－二甲基苯并咪唑、2－(4－環己基丁基)苯并咪唑、2－(4－環己基丁基)－5－碘苯并咪唑、2－(4－環己基丁基)－4－氯－5－乙基苯并咪唑、2－(4－環己基丁基)－5－辛基苯并咪唑、2－(5－環己基戊基)苯并咪唑、2－(5－環己基戊基)－5－己基苯并咪唑、2－(5－環己基戊基)－5,6－二溴苯并咪唑、2－(6－環己基己基)苯并咪唑、2－(6－環己基己基)－5－庚基苯并咪唑、2－(6－環己基己基)－4－氯－5－(2－丙基丁基)苯并咪唑等。The imidazole compound represented by the general formula (VIII) of the formula 8 can be exemplified by 2-cyclohexylbenzimidazole, 2-cyclohexyl-5,6-dimethylbenzimidazole, 2-cyclohexyl-5-chloro Benzimidazole, 2-cyclohexyl-4-isopropylbenzimidazole, 2-(cyclohexylmethyl)benzimidazole, 2-(cyclohexylmethyl)-5-ethylbenzimidazole, 2-( Cyclohexylmethyl)-5-bromobenzimidazole, 2-(2-cyclohexylethyl)benzimidazole, 2-(2-cyclohexylethyl)-5-chloro-6-methylbenzimidazole, 2-(3-cyclohexylpropyl)benzimidazole, 2-(3-cyclohexylpropyl)-5-butylbenzimidazole, 2-(3-cyclohexylpropyl)-4,7-dimethyl Benzimidazole, 2-(4-cyclohexylbutyl)benzimidazole, 2-(4-cyclohexylbutyl)-5-iodobenzimidazole, 2-(4-cyclohexylbutyl)-4- Chloro-5-ethylbenzimidazole, 2-(4-cyclohexylbutyl)-5-octylbenzimidazole, 2-(5-cyclohexylpentyl)benzimidazole, 2-(5-cyclohexyl Pentyl)-5-hexylbenzimidazole, 2-(5-cyclohexylpentyl)-5,6-dibromobenzimidazole, 2-(6-cyclohexylhexyl)benzimidazole, 2 -(6-Cyclohexylhexyl)-5-heptylbenzimidazole, 2-(6-cyclohexylhexyl)-4-chloro-5-(2-propylbutyl)benzimidazole, and the like.

本發明之實施中，可於表面處理劑中含有此等咪唑化合物0.01~10重量%之比例、較佳0.1~5重量%之比例。若咪唑化合物之含有比例少於0.01重量%，則形成於金屬表面之化成皮膜變薄，無法充分防止金屬表面之氧化。又，在咪唑化合物之含有比例多於10重量%時，將難以控制用於得到適合焊接條件之所需膜厚的表面處理。In the practice of the present invention, the proportion of the imidazole compound in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, may be contained in the surface treatment agent. When the content ratio of the imidazole compound is less than 0.01% by weight, the film formed on the surface of the metal becomes thin, and oxidation of the metal surface cannot be sufficiently prevented. Further, when the content ratio of the imidazole compound is more than 10% by weight, it is difficult to control the surface treatment for obtaining a desired film thickness suitable for the welding conditions.

本發明之實施中所使用的葡萄糖酸化合物，係指具有下述化9所示構造之葡萄糖酸或其銨鹽及金屬鹽。作為葡萄糖酸之銨鹽，可舉例如葡萄糖酸銨和葡萄糖酸三甲基銨葡萄糖酸三乙醇銨等之胺鹽等。作為葡萄糖酸之金屬鹽，可舉例如葡萄糖酸銨、葡萄糖酸鋅、葡萄糖酸鐵、葡萄糖酸鋁等。The gluconic acid compound used in the practice of the present invention means gluconic acid or an ammonium salt thereof and a metal salt having the structure shown in the following formula 9. Examples of the ammonium salt of gluconic acid include an ammonium salt such as ammonium gluconate and trimethylammonium gluconate glucosamine triacetate. Examples of the metal salt of gluconic acid include ammonium gluconate, zinc gluconate, iron gluconate, and aluminum gluconate.

此等葡萄糖酸化合物，可於表面處理劑中含有0.01~50重量%之比例、較佳0.1~30重量%之比例。在葡萄糖酸化合物之含有比例少於0.01重量%時，焊料濕潤性之改善效果將不足，又，即使使其比例多於50重量%，亦無法期待焊料濕潤性之改善效果增加。These gluconic acid compounds may be contained in the surface treatment agent in a proportion of 0.01 to 50% by weight, preferably 0.1 to 30% by weight. When the content ratio of the gluconic acid compound is less than 0.01% by weight, the effect of improving the wettability of the solder is insufficient, and even if the ratio is more than 50% by weight, the effect of improving the solder wettability cannot be expected to increase.

己知葡萄糖酸化合物具有配位於金屬之化用(鉗合能)，但可認為其在咪唑化合物於金屬表面形成錯合體之下，藉由分子間鍵結而凝集沉澱形成化成皮膜時，將發揮某種作用。It is known that the gluconic acid compound has a compounding property for the metal (clamping energy), but it is considered that when the imidazole compound forms a complex under the metal surface and is agglomerated by intermolecular bonding to form a film into a film, it will be exerted. Some kind of effect.

本發明之實施中，當將咪唑化合物予以水溶液化時，可使用習知之有機酸、無機酸或有機溶劑作為可溶化劑。In the practice of the present invention, when the imidazole compound is aqueousally solutioned, a conventional organic acid, inorganic acid or organic solvent can be used as the solubilizing agent.

此時所使用之代表性有機酸，可舉例如：蟻酸、醋酸、丙酸、酪酸、乙醛酸、丙酮酸、乙醯乙酸、乙醯丙酸、庚酸、辛酸、癸酸、月桂酸、乙醇酸、甘油酸、乳酸、丙烯酸、苯甲酸、對硝基苯甲酸、對甲苯磺酸、甲磺酸、水楊酸、苦味酸、草酸、琥珀酸、順丁醯二酸、反丁醯二酸、酒石酸、己二酸等；作為無機酸，可舉例如：鹽酸、磷酸、硫酸、硝酸等。Typical organic acids used at this time include, for example, formic acid, acetic acid, propionic acid, butyric acid, glyoxylic acid, pyruvic acid, acetoacetic acid, acetyl propionic acid, heptanoic acid, octanoic acid, citric acid, lauric acid, Glycolic acid, glyceric acid, lactic acid, acrylic acid, benzoic acid, p-nitrobenzoic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, picric acid, oxalic acid, succinic acid, cis-sebacic acid, anti-butyric acid An acid, tartaric acid, adipic acid, etc., and a mineral acid, for example, hydrochloric acid, a phosphoric acid, a sulfuric acid, a nitric acid, etc. are mentioned.

另外，作為有機酸，亦可使用化10一般式所示之羧酸化合物。Further, as the organic acid, a carboxylic acid compound represented by the general formula 10 may be used.

[化10] (式中，R1 表示碳數1~4之直鏈狀或分枝鏈狀烷基，R2 表示氫原子或甲基。m表示0或3之整數，n表示1或2。)[化10] (wherein R 1 represents a linear or branched chain alkyl group having 1 to 4 carbon atoms, and R 2 represents a hydrogen atom or a methyl group. m represents an integer of 0 or 3, and n represents 1 or 2.)

此等酸化合物可單獨使用或組合使用，可於表面處理劑中含有0.1~50重量%之比例、較佳為1~30重量%之比例。在酸化合物之含有比例少於0.1重量%時，將無法使咪唑化合物充分可溶化，又，即使多於50重量%，亦無法期待咪唑化合物之可溶化效果的增加，僅不過增加酸化合物之藥劑成本。These acid compounds may be used singly or in combination, and may be contained in the surface treatment agent in a proportion of 0.1 to 50% by weight, preferably 1 to 30% by weight. When the content ratio of the acid compound is less than 0.1% by weight, the imidazole compound cannot be sufficiently solubilized, and even if it is more than 50% by weight, an increase in the solubilization effect of the imidazole compound cannot be expected, but the agent for increasing the acid compound is not provided. cost.

另外，作為有機溶劑，可舉例如可與水自由混合之甲醇、乙醇、異丙醇等之低級醇或丙酮、N,N－二甲基甲醯胺、乙二醇等。Further, examples of the organic solvent include a lower alcohol such as methanol, ethanol or isopropyl alcohol or acetone, N,N-dimethylformamide or ethylene glycol which can be freely mixed with water.

本發明之表面處理劑中，可添加用於使金屬製導電部表面之化成皮膜之形成速度加快的銅化合物，或可添加使所形成之化成皮膜之耐熱性更加提升之鋅化合物。In the surface treatment agent of the present invention, a copper compound for increasing the formation speed of the surface of the metal conductive portion into a film may be added, or a zinc compound for further improving the heat resistance of the formed film into a film may be added.

作為上述銅化合物之代表者，有如醋酸銅、氯化銅、氯化亞銅、溴化銅、溴化亞銅、碘化銅、氫氧化銅、磷酸銅、硫酸銅、硝酸銅等，又，作為上述鋅化合物之代表者，可舉例如氧化鋅、氯化鋅、溴化鋅、碘化鋅、蟻酸鋅、醋酸鋅、草酸鋅、乳酸鋅、檸檬酸鋅、硫酸鋅、硝酸鋅、磷酸鋅等，任一者均於表面處理劑中可含有0.01~10重量%、較佳0.02~5重量%之比例。Representative examples of the copper compound include copper acetate, copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, copper hydroxide, copper phosphate, copper sulfate, copper nitrate, and the like. Representative examples of the zinc compound include zinc oxide, zinc chloride, zinc bromide, zinc iodide, zinc formate, zinc acetate, zinc oxalate, zinc lactate, zinc citrate, zinc sulfate, zinc nitrate, and zinc phosphate. Any of these may be contained in the surface treatment agent in a proportion of 0.01 to 10% by weight, preferably 0.02 to 5% by weight.

於使用此等銅化合物和鋅化合物的情況下，最好於表面處理劑中，添加氨、或單乙醇胺、二乙醇胺、三乙醇胺等之胺類等之具有緩衝作用的物質，以使表面處理劑之pH穩定。When such a copper compound and a zinc compound are used, it is preferable to add a buffering substance such as ammonia or an amine such as monoethanolamine, diethanolamine or triethanolamine to the surface treatment agent to prepare a surface treatment agent. The pH is stable.

本發明之表面處理劑中，為了更加提升化成皮膜之形成速度及該皮膜之耐熱性，可依0.001~1重量%、較佳0.01~0.5重量%之比例含有鹵化合物。作為鹵化合物，可舉例如氟化銨、氟化鉀、氟化銨氯化銨、氯化鉀、氯化銨、溴化鈉、溴化鉀、溴化銨、碘化銨、碘化鉀、碘化銨等。In the surface treatment agent of the present invention, in order to further increase the formation rate of the chemical conversion film and the heat resistance of the film, the halogen compound may be contained in an amount of 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight. The halogen compound may, for example, be ammonium fluoride, potassium fluoride, ammonium fluoride ammonium chloride, potassium chloride, ammonium chloride, sodium bromide, potassium bromide, ammonium bromide, ammonium iodide, potassium iodide or iodinated. Ammonium, etc.

作為使用本發明之表面處理劑而對印刷佈線板之金屬製導電部表面進行處理時的條件，較佳係將表面處理劑之液溫設為10~70℃，將接觸時間設為1秒~10分鐘。作為接觸方法，可舉例如浸漬、噴霧、塗佈等方法。When the surface of the metal conductive portion of the printed wiring board is treated by using the surface treatment agent of the present invention, the liquid temperature of the surface treatment agent is preferably set to 10 to 70 ° C, and the contact time is set to 1 second. 10 minutes. Examples of the contact method include a method such as dipping, spraying, and coating.

另外，於進行本發明之表面處理後，亦可於化成皮膜上藉由熱可塑性樹脂形成雙重構造，以使耐熱性更加提升。Further, after the surface treatment of the present invention, a double structure can be formed on the chemical conversion resin by the thermoplastic resin to further improve the heat resistance.

亦即，於金屬製導電部表面上生成化成皮膜後，將由松香、松香酯等之松香衍生體，萜樹脂、萜苯酚樹脂等之萜樹脂衍生體，芳香族烴樹脂、脂肪族烴樹脂等之烴樹脂和此等之混合物所組成之耐熱性優越的熱可塑性樹脂，溶解於甲苯、醋酸乙酯、異丙基醇等之溶媒中，藉由輥塗機等於化成皮膜上均勻地塗佈成膜厚1~30 μm之厚度，而形成化成皮膜與熱可塑性樹脂之雙重構造。In other words, a rosin derivative such as rosin or rosin ester, an oxime resin derivative such as an anthracene resin or a phenol resin, an aromatic hydrocarbon resin or an aliphatic hydrocarbon resin, etc., are formed on the surface of the metal conductive portion. A thermoplastic resin having a heat resistance superior in composition of a hydrocarbon resin and a mixture thereof is dissolved in a solvent such as toluene, ethyl acetate or isopropyl alcohol, and uniformly coated on the film by a roll coater. It has a thickness of 1 to 30 μm and forms a dual structure of a chemical film and a thermoplastic resin.

作為可適應本發明之焊接方法，可舉例如：於裝入了經加熱熔融之液體狀焊料的焊料槽上使印刷佈線板流動，而於電子零件與印刷佈線板之接合部進行焊接的流動法；或預先於印刷佈線板上配合電路圖案印刷糊狀的焊料膏，於其安裝電子零件，將印刷佈線板加熱使焊料熔融，而進行焊接之迴焊法。The welding method which can be adapted to the present invention is, for example, a flow method in which a printed wiring board is placed on a solder bath in which a liquid solder which is heated and melted is placed to be welded to a joint portion between an electronic component and a printed wiring board. Or pre-printing a paste-like solder paste on a printed wiring board, mounting an electronic component thereon, heating the printed wiring board to melt the solder, and performing a solder reflow method.

作為適合本發明焊接之焊料，可舉例如Sn－Ag－Cu系、Sn－Ag－Bi系、Sn－Bi系、Sn－Ag－Bi－In系、Sn－Zn系、Sn－Cu系等之無鉛焊料，亦可使用習知所使用之錫－鉛合金的共結晶焊料。Examples of the solder suitable for the welding of the present invention include a Sn-Ag-Cu system, a Sn-Ag-Bi system, a Sn-Bi system, a Sn-Ag-Bi-In system, a Sn-Zn system, and a Sn-Cu system. For lead-free solders, it is also possible to use a tin-lead alloy co-crystal solder which is conventionally used.

(實施例)(Example)

以下，藉由實施例及比較例更具體地說明本發明，但本發明並不限定於此等。又，實施例及比較例所使用之原料及評價試驗方法係如下述。未記載之原料，係使用市售試藥。Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto. Moreover, the raw materials and evaluation test methods used in the examples and comparative examples are as follows. For the undocumented raw materials, commercially available reagents are used.

[咪唑化合物][Imidazole compound]

．2,4－二苯基－5－甲基咪唑(依照日本專利特開平7－243053號公報所記載之方法進行合成)．2－(2,4－二氯苯基)－4－苯基－5－甲基咪唑(依照日本專利特開2004－277386號公報所記載之方法進行合成)．2－苯基－4－(3,4－二氯苯基)咪唑(依照日本專利特開2005－104878號公報所記載之方法進行合成)．2－(1－萘基)－4－苯基－5－甲基咪唑(依照日本專利特開2006－36683號公報所記載之方法進行合成)．2－苯基－4－(2－萘基)咪唑(依照日本專利特開2006－36683號公報所記載之方法進行合成)．2－(4－氯苯基甲基)咪唑(依照Science of Synthesis,12 ,529(2002)所記載之方法進行合成)．2－(1－萘基甲基)咪唑(依照Biochemical Pharmacology,36 ,463(1987)所記載之方法進行合成). 2,4-diphenyl-5-methylimidazole (synthesized according to the method described in JP-A-H07-243053). 2-(2,4-Dichlorophenyl)-4-phenyl-5-methylimidazole (synthesized according to the method described in JP-A-2004-277386). 2-Phenyl-4-(3,4-dichlorophenyl)imidazole (synthesized according to the method described in JP-A-2005-104878). 2-(1-Naphthyl)-4-phenyl-5-methylimidazole (synthesized according to the method described in JP-A-2006-36683). 2-phenyl-4-(2-naphthyl)imidazole (synthesized according to the method described in JP-A-2006-36683). 2-(4-Chlorophenylmethyl)imidazole (synthesized according to the method described in Science of Synthesis, 12 , 529 (2002)). 2-(1-Naphthylmethyl)imidazole (synthesized according to the method described in Biochemical Pharmacology, 36 , 463 (1987))

[葡萄糖酸化合物][gluconic acid compound]

．葡萄糖酸(50%水溶液，和光純藥工業公司製試藥). Gluconic acid (50% aqueous solution, manufactured by Wako Pure Chemical Industries, Ltd.)

[焊料上升性之評價試驗][Testing test for solder rise]

作為試驗片，係使用具有300孔之內徑0.80mm銅通孔之120mm(縱)×150mm(橫)×1.6mm(厚)之玻璃環氧樹脂製之印刷佈線板。將此試驗片進行脫脂、軟蝕刻及水洗後，浸漬於保持在既定溫液之表面處理劑中既定時間，接著進行水洗、乾燥，而於銅表面上形成厚度約0.10~0.50 μm之化成皮膜。As the test piece, a printed wiring board made of a glass epoxy resin having 120 mm (longitudinal) × 150 mm (horizontal) × 1.6 mm (thickness) of a 300-hole inner diameter 0.80 mm copper through hole was used. After the test piece is degreased, soft-etched, and washed with water, it is immersed in a surface treatment agent held in a predetermined temperature liquid for a predetermined period of time, followed by washing with water and drying to form a film having a thickness of about 0.10 to 0.50 μm on the copper surface.

針對經該表面處理之試驗片，使用紅外線迴焊裝置(製品名：MULTI－PRO－306，Vetronix公司製)，進行波峰溫度為245℃之迴焊加熱3次，其次，使用流動焊接裝置(輸送帶速度1.0m/分)進行焊接。For the test piece subjected to the surface treatment, an infrared reflow soldering apparatus (product name: MULTI-PRO-306, manufactured by Vetronix Co., Ltd.) was used, and reflow soldering was performed at a peak temperature of 245 ° C for 3 times, and second, using a flow soldering apparatus (conveying) Welding with a belt speed of 1.0 m/min).

尚且，所使用之焊料為具有96.5錫－3.0銀－0.5銅(重量%)之組成的無鉛焊料(商品名：H705「Ecosolder」千住金屬工業製)，於焊接時所使用之助熔劑為JS－E－09(弘輝製)。又，焊料溫度設為245℃。Further, the solder used is a lead-free solder having a composition of 96.5 tin-3.0 silver-0.5 copper (% by weight) (trade name: H705 "Ecosolder", manufactured by Senju Metal Industry Co., Ltd.), and the flux used in soldering is JS- E-09 (Hongfa system). Further, the solder temperature was set to 245 °C.

針對進行了焊接之試驗片，計測焊料上升至銅通孔之上部台(land)部分(經焊接)之通孔數，算出相對於總通孔數(300孔)之比例(%)。With respect to the test piece which was welded, the number of through holes in which the solder was raised to the land portion (welded) of the copper through hole was measured, and the ratio (%) to the total number of through holes (300 holes) was calculated.

焊料對於銅表面之濕潤性越大，則經熔融之焊料越容易浸透於銅通孔內而上升至該通孔之上部台部分。亦即，相對於總通孔數之焊料上升至上部台部分的通孔數比例越大，則對於銅之焊料濕潤性越優越，將判定為焊接性良好。The greater the wettability of the solder to the copper surface, the more easily the molten solder penetrates into the copper via and rises to the upper portion of the via. In other words, the larger the ratio of the number of through holes in which the solder is increased to the upper stage portion with respect to the total number of through holes, the superior the wettability to the solder of copper, and it is judged that the weldability is good.

[焊料延廣性之評價試驗][Testing test for solder extension]

使用500mm(縱)×50mm(橫)×1.2mm(厚)之玻璃環氧樹脂製之印刷佈線板(作為電路圖案，係將由銅箔所形成之導體寬0.80mm、長20mm之電路部，依1.0mm之間隔於寬度方向上形成10根者)作為試驗片。將此試驗片進行脫脂、軟蝕刻及水洗後，浸漬於保持在既定液溫之表面處理劑中既定時間，其次進行水洗、乾燥，於銅表面上形成厚度約0.10~0.50 μm之化成皮膜。A printed wiring board made of glass epoxy resin of 500 mm (vertical) × 50 mm (horizontal) × 1.2 mm (thickness) is used as a circuit pattern, and a circuit portion made of a copper foil having a width of 0.80 mm and a length of 20 mm is used. A test piece was formed by forming 10 pieces of 1.0 mm in the width direction. After the test piece is degreased, soft-etched, and washed with water, it is immersed in a surface treatment agent maintained at a predetermined liquid temperature for a predetermined period of time, and then washed with water and dried to form a film having a thickness of about 0.10 to 0.50 μm on the copper surface.

針對經該表面處理之試驗片，使用紅外線迴焊裝置(製品名：MULTI－PRO－306，Vetronix公司製)，進行波峰溫度為245℃之迴焊加熱1次。其後，使用開口徑1.2mm、厚150 μm之金屬遮置於銅電路部中央印刷焊料膏，依上述條件進行迴焊加熱，進行焊接。For the test piece subjected to the surface treatment, an infrared reflow soldering apparatus (product name: MULTI-PRO-306, manufactured by Vetronix Co., Ltd.) was used, and reflow soldering at a peak temperature of 245 ° C was performed once. Thereafter, the solder paste was placed in the center of the copper circuit portion by using a metal having an opening diameter of 1.2 mm and a thickness of 150 μm, and reflow soldering was performed under the above conditions to perform soldering.

尚且，所使用之焊料為具有96.5錫－3.0銀－0.5銅(重量%)之組成的無鉛焊料(商品名：M705－221BM5－42－11，千住金屬工業製)。Further, the solder used was a lead-free solder having a composition of 96.5 tin-3.0 silver-0.5 copper (% by weight) (trade name: M705-221BM5-42-11, manufactured by Senju Metal Industry Co., Ltd.).

針對所得之試驗片，測定濕潤延展於銅電路表面之焊料長度(mm)。For the obtained test piece, the length (mm) of the solder which spreads on the surface of the copper circuit was measured.

此長度越大，判定為焊料濕潤性越優越，焊接性越良好。The larger the length, the more excellent the wettability of the solder, and the better the weldability.

[實施例1][Example 1]

將作為咪唑化合物之2,4－二苯基－5－甲基咪唑、作為可溶化劑之醋酸及葡萄糖酸、作為金屬鹽之醋酸銅、作為鹵化合物之碘化銨，分別依表1記載之組成溶解於離子交換水後，以氨水調整為pH3.6，而調製表面處理劑。2,4-diphenyl-5-methylimidazole as an imidazole compound, acetic acid and gluconic acid as a solubilizing agent, copper acetate as a metal salt, and ammonium iodide as a halogen compound, respectively, as described in Table 1 After the composition was dissolved in ion-exchanged water, the surface treatment agent was prepared by adjusting the ammonia water to pH 3.6.

其次，將印刷佈線板之試驗片浸漬於調溫為40℃之水溶性預助熔劑中60秒後，進行水洗、乾燥，測定焊料上升性及焊料延廣性。此等試驗結果係如表1所示。Next, the test piece of the printed wiring board was immersed in the water-soluble preflux adjusted to 40 ° C for 60 seconds, and then washed with water and dried to measure solder ascending property and solder extension property. The results of these tests are shown in Table 1.

[實施例2~9、比較例1~9][Examples 2 to 9 and Comparative Examples 1 to 9]

與實施例1相同地，調製具有表1記載之組成及pH的表面處理劑，依表1記載之處張條件進行表面處理，實施評價試驗。將所得之試驗結果示於表1。In the same manner as in Example 1, a surface treatment agent having the composition and pH shown in Table 1 was prepared, and surface treatment was carried out under the conditions described in Table 1, and an evaluation test was carried out. The test results obtained are shown in Table 1.

以上雖參照詳細且特定之實施態樣說明了本發明，但在不脫離本發明精神與範圍之下，從業者自當明白可進行各種變化和修正。The present invention has been described with reference to the detailed and specific embodiments thereof. It is understood that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the invention.

本申請案係根據2006年5月19日申請之日本專利申請(特願2006－140229)，將其內容參照於此並予以援用。The present application is based on Japanese Patent Application No. 2006-140229, filed on Jan.

(產業上之可利用性)(industrial availability)

根據本發明，可提供在將電子零件焊接於構成印刷佈線板之電路部之金屬製導電部表面時，對於該導電部表面之焊料濕潤性良好之金屬之表面處理劑。According to the present invention, it is possible to provide a metal surface treatment agent which is excellent in solder wettability to the surface of the conductive portion when the electronic component is soldered to the surface of the metal conductive portion constituting the circuit portion of the printed wiring board.

另外，根據本發明，可提供一種藉由使上述表面處理劑接觸於金屬製導電部表面，而於金屬製導電部表面形成化成皮膜之印刷佈線板，以及，提供一種藉由使上述表面處理劑接觸於金屬製導電部表面，而於金屬製導電部表面形成化成皮膜後，使用焊料進行焊接的印刷佈線板之製造方法。Further, according to the present invention, it is possible to provide a printed wiring board which is formed into a film on the surface of a metal conductive portion by bringing the surface treating agent into contact with the surface of the metal conductive portion, and to provide a surface treating agent by using the surface treating agent A method of manufacturing a printed wiring board that is soldered using solder after forming a film on the surface of the metal conductive portion by contacting the surface of the metal conductive portion.

Claims (4)

一種金屬之表面處理劑，其特徵為含有咪唑化合物與葡萄糖酸。 A metal surface treatment agent characterized by containing an imidazole compound and gluconic acid. 如申請專利範圍第1項之金屬之表面處理劑，其中，以0.01~10重量%之比例含有咪唑化合物，以0.01~50重量%之比例含有葡萄糖酸。 The surface treatment agent for a metal according to the first aspect of the invention, wherein the imidazole compound is contained in an amount of 0.01 to 10% by weight, and the gluconic acid is contained in a ratio of 0.01 to 50% by weight. 一種印刷佈線板，其特徵為，藉由使申請專利範圍第1或2項之金屬之表面處理劑接觸於金屬製導電部表面，於金屬製導電部表面形成化成皮膜。 A printed wiring board characterized in that a surface treatment agent for a metal of the first or second aspect of the invention is brought into contact with a surface of a metal conductive portion to form a film on the surface of the metal conductive portion. 一種印刷佈線板之製造方法，其特徵為，藉由使申請專利範圍第1或2項之金屬之表面處理劑接觸於金屬製導電部表面，於金屬製導電部表面形成化成皮膜後，使用無鉛焊料進行焊接。 A method of manufacturing a printed wiring board, characterized in that a surface treatment agent for a metal according to claim 1 or 2 is brought into contact with a surface of a metal conductive portion to form a film on the surface of the metal conductive portion, and then lead-free is used. Solder is soldered.
TW096117828A 2006-05-19 2007-05-18 Metal surface treatment agent and its use TWI393804B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2006140229A JP5036216B2 (en) 2006-05-19 2006-05-19 Metal surface treatment agent and use thereof

Publications (2)

Publication Number Publication Date
TW200804622A TW200804622A (en) 2008-01-16
TWI393804B true TWI393804B (en) 2013-04-21

Family

ID=38723243

Family Applications (1)

Application Number Title Priority Date Filing Date
TW096117828A TWI393804B (en) 2006-05-19 2007-05-18 Metal surface treatment agent and its use

Country Status (5)

Country Link
JP (1) JP5036216B2 (en)
KR (1) KR101298386B1 (en)
CN (1) CN101448978B (en)
TW (1) TWI393804B (en)
WO (1) WO2007135930A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5313044B2 (en) * 2008-08-08 2013-10-09 四国化成工業株式会社 Surface treatment agent for copper or copper alloy and use thereof
JP5457814B2 (en) 2009-12-17 2014-04-02 コーア株式会社 Electronic component mounting structure
CN102153514B (en) * 2011-02-23 2013-02-20 广东东硕科技有限公司 Method for preparing fluorine-containing benzyl benzimidazole compound
CN102121108B (en) * 2011-02-23 2012-11-21 广东东硕科技有限公司 Compound OSP treating agent for lead-free printed circuit board
CN102775351B (en) * 2011-05-12 2015-09-30 比亚迪股份有限公司 A kind of diimidazole compounds and preparation method thereof soldering flux treatment solution organic with one
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
JP5985367B2 (en) * 2012-11-20 2016-09-06 四国化成工業株式会社 Method for surface treatment of copper or copper alloy and use thereof
CN103058931B (en) * 2012-12-31 2015-07-01 广东东硕科技有限公司 Four 2-(3', 5'-dihalo-benzyl) benzimidazole type novel compounds and preparation method thereof
JP6243792B2 (en) * 2014-05-12 2017-12-06 花王株式会社 Manufacturing method of circuit board on which solder is solidified, manufacturing method of circuit board on which electronic parts are mounted, and cleaning composition for flux
WO2019006628A1 (en) * 2017-07-03 2019-01-10 深圳市盈恒科技有限公司 Chromium-free passivator, aluminum part and surface passivation process therefor
CN110230048A (en) * 2019-07-18 2019-09-13 广东超华科技股份有限公司 A kind of anti-oxidation liquid of Chrome-free Non-water washing of lithium ion battery electrolytic copper foil and anti-oxidation technique
US11676926B2 (en) 2020-08-24 2023-06-13 Schlumberger Technology Corporation Solder joints on nickel surface finishes without gold plating
CN114134493A (en) * 2021-11-23 2022-03-04 沈阳加克科技有限公司 Metal surface passivation solution
CN115011956A (en) * 2022-06-28 2022-09-06 南通赛可特电子有限公司 Organic copper surface protective agent and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005179765A (en) * 2003-12-24 2005-07-07 Nikko Materials Co Ltd Surface treatment agent for copper and copper alloy
US20050217757A1 (en) * 2004-03-30 2005-10-06 Yoshihiro Miyano Preflux, flux, solder paste and method of manufacturing lead-free soldered body

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6192778A (en) * 1984-10-09 1986-05-10 C Uyemura & Co Ltd Parts to be soldered
JP2558982B2 (en) * 1991-12-25 1996-11-27 日鉱金属株式会社 Sealing method for precious metal plating
JPH1046385A (en) * 1996-08-02 1998-02-17 Daiwa Kasei Kenkyusho:Kk Electric and electronic circuit parts
JP3579550B2 (en) * 1996-09-30 2004-10-20 株式会社大和化成研究所 Electrical and electronic circuit components
DE10050862C2 (en) * 2000-10-06 2002-08-01 Atotech Deutschland Gmbh Bath and method for electroless deposition of silver on metal surfaces
JP2003328182A (en) * 2002-05-13 2003-11-19 Yutaka Fujiwara Tin-silver alloy plating bath for rackless plating
JP2004176179A (en) * 2002-11-15 2004-06-24 Chubu Kiresuto Kk Water soluble treatment agent for improving solder wettability of electronic component terminal, and treatment method therefor
TW200512196A (en) * 2003-03-19 2005-04-01 Shikoku Chem Novel imidazole compound and usage thereof
JP2005008975A (en) * 2003-06-20 2005-01-13 Nippon Paint Co Ltd Metal surface treatment method, surface-treated aluminum based metal and pretreatment method to hydrophilic treatment
JP2005169495A (en) * 2003-11-18 2005-06-30 Yoshihiro Miyano Pre-flux, flux, solder paste and fabrication method of structure joined with lead-free solder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005179765A (en) * 2003-12-24 2005-07-07 Nikko Materials Co Ltd Surface treatment agent for copper and copper alloy
US20050217757A1 (en) * 2004-03-30 2005-10-06 Yoshihiro Miyano Preflux, flux, solder paste and method of manufacturing lead-free soldered body

Also Published As

Publication number Publication date
JP2007308776A (en) 2007-11-29
CN101448978A (en) 2009-06-03
KR101298386B1 (en) 2013-08-20
KR20090009249A (en) 2009-01-22
WO2007135930A1 (en) 2007-11-29
TW200804622A (en) 2008-01-16
CN101448978B (en) 2012-06-13
JP5036216B2 (en) 2012-09-26

Similar Documents

Publication Publication Date Title
TWI393804B (en) Metal surface treatment agent and its use
TWI464298B (en) Surface treating agent for copper or copper alloy and use thereof
JP4883996B2 (en) Water-soluble preflux and its use
US10398028B2 (en) Surface treating composition for copper and copper alloy and utilization thereof
JP2007297685A (en) Surface treatment agent for metal, and its utilization
US9649713B2 (en) Surface treating composition for copper and copper alloy and utilization thereof
JP4694251B2 (en) Copper or copper alloy surface treatment agent for lead-free soldering and use thereof
JP2002105662A (en) Surface treating agent and surface treating method for copper and copper alloy
KR101540144B1 (en) Surface treating agent for copper or copper alloy and use thereof
JP5985367B2 (en) Method for surface treatment of copper or copper alloy and use thereof
KR101520992B1 (en) Surface treating agent for copper or copper alloy and use thereof
JP2009057596A (en) Sealing agent for gold-plated film, and its use
JP2014101554A (en) Surface treatment liquid of copper or copper alloy and its utilization
TW202346639A (en) Surface treatment agent for copper or copper alloy

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees