JPH07243054A - Surface treating agent for copper and copper alloy - Google Patents
Surface treating agent for copper and copper alloyInfo
- Publication number
- JPH07243054A JPH07243054A JP6550394A JP6550394A JPH07243054A JP H07243054 A JPH07243054 A JP H07243054A JP 6550394 A JP6550394 A JP 6550394A JP 6550394 A JP6550394 A JP 6550394A JP H07243054 A JPH07243054 A JP H07243054A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- acid
- compound
- treating agent
- weight
- 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
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
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、銅及び銅合金の表面に
化成被膜を形成する水溶液系表面処理剤に関するもので
あり、特に硬質プリント配線板及びフレキシブルプリン
ト配線板における銅回路部のプレフラックス処理剤とし
て好適なものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous surface treatment agent for forming a chemical conversion film on the surfaces of copper and copper alloys, and particularly to a pre-flux for a copper circuit portion in a hard printed wiring board and a flexible printed wiring board. It is suitable as a treating agent.
【０００２】[0002]
【従来の技術】銅あるいは銅合金の表面に、２位長鎖ア
ルキルイミダゾール化合物の被膜を形成する表面処理方
法としては、特公昭46-17046号、同48-11454号、同48-2
5621号、同49- 1983号、同49-26183号、同58-22545号、
同61-41988号及び特開昭61-90492号公報に記載されてい
る。また銅あるいは銅合金の表面に、２位アリール基置
換イミダゾール化合物の被膜を形成する処理方法として
は、特開平4-202780号及び同4-206681号公報に記載され
ている。2. Description of the Related Art Surface treatment methods for forming a film of a 2-position long-chain alkylimidazole compound on the surface of copper or a copper alloy are disclosed in Japanese Examined Patent Publication Nos. 46-17046, 48-11454, and 48-2.
No. 5621, No. 49-1983, No. 49-26183, No. 58-22545,
No. 61-41988 and JP-A No. 61-90492. Further, a treatment method for forming a film of a 2-position aryl group-substituted imidazole compound on the surface of copper or a copper alloy is described in JP-A-4-202780 and 4-206681.
【０００３】他に銅あるいは銅合金の表面にベンズイミ
ダゾール系化合物の化成被膜を形成する方法としては、
５−メチルベンズイミダゾールを用いる処理方法が特開
昭58-501281 号公報に、２−アルキルベンズイミダゾー
ル化合物、２−アリールベンズイミダゾール化合物、２
−アラルキルベンズイミダゾール化合物あるいは２−メ
ルカプトアルキルベンズイミダゾール化合物を用いる処
理方法が、特開平3-124395号、同3-236478号、同4-7207
2 号、同4-80375 号、同4-99285 号、同4-157174号、同
4-165083号、同4-173983号、同4-183874号、同4-202780
号、同4-206681号、同4-218679号、同5-25407 号、同5-
93280 号、同5-93281 号、同5-156475号、同5-163585
号、同5-175643号、同5-186880号、同5-186888号、同5-
202492号、同5-230674号、同5-237688号、同5-263275
号、同5-287562号、同5-291729号、同5-287563号及び同
5-291729号公報に記載されている。Another method for forming a chemical conversion coating film of a benzimidazole compound on the surface of copper or copper alloy is as follows.
A treatment method using 5-methylbenzimidazole is disclosed in JP-A-58-501281, which is a 2-alkylbenzimidazole compound, a 2-arylbenzimidazole compound, 2
-The treatment method using an aralkylbenzimidazole compound or a 2-mercaptoalkylbenzimidazole compound is disclosed in JP-A-3-124395, JP-A-3-236478 and JP-A-4-7207.
No. 2, No. 4-80375, No. 4-99285, No. 4-157174, No.
4-165083, 4-173983, 4-183874, 4-202780
No. 4, No. 4-206681, No. 4-218679, No. 5-25407, No. 5-
93280, 5-93281, 5-156475, 5-163585
No. 5, No. 5-175643, No. 5-186880, No. 5-186888, No. 5-
202492, 5-230674, 5-237688, 5-263275
No. 5, No. 5-287562, No. 5-219729, No. 5-275563, and No.
It is described in Japanese Patent Publication No. 5-291729.
【０００４】これらの他に、２−メルカプトベンズイミ
ダゾールを用いる銅あるいは銅合金の防錆方法が、特開
昭55-83157号、同62-77600号及び同63-118598 号公報に
開示されている。In addition to these, a method of preventing rust of copper or copper alloy using 2-mercaptobenzimidazole is disclosed in JP-A-55-83157, JP-A-62-77600 and JP-A-63-118598. .
【０００５】[0005]
【発明が解決しようとする課題】近時プリント配線板に
対する電子部品の接合方法として、表面実装法が多く採
用されるようになり、チップ部品の仮止め、部品装置の
両面装着あるいはチップ部品とディスクリート部品の混
載などにより、プリント配線板が高温下に曝されるよう
になった。Recently, as a method of joining electronic components to a printed wiring board, a surface mounting method has come to be widely used, and a chip component is temporarily fixed, both sides of a component device are mounted, or a chip component and a discrete component. Printed wiring boards have come to be exposed to high temperatures due to mixed components.
【０００６】従来知られている２位長鎖アルキルイミダ
ゾール化合物を用いてプリント配線板の表面処理を行な
った場合、高温に曝されると表面処理された銅面が変色
し、その後のはんだ付けに際して支障を生じるおそれが
あった。特開昭58−501281号公報に記載の５−メチルベ
ンズイミダゾールを用いる処理方法では、この化合物が
水に比較的溶け易いため、好ましい膜厚と認められる
０．０８μｍ以上の化成被膜を形成することができず、
高温下において下地銅を保護し難く、酸化銅が発生する
欠点があった。When a surface treatment of a printed wiring board is carried out using a conventionally known 2-position long-chain alkylimidazole compound, the surface-treated copper surface is discolored when exposed to high temperature, and at the time of subsequent soldering. There was a risk of trouble. In the treatment method using 5-methylbenzimidazole described in JP-A-58-501281, since this compound is relatively soluble in water, a chemical conversion film of 0.08 μm or more, which is recognized as a preferable film thickness, should be formed. I can't
It was difficult to protect the base copper at high temperature, and there was a drawback that copper oxide was generated.
【０００７】また特開昭55-83157号及び同62-77600号公
報に記載の２−メルカプトベンズイミダゾールを用いた
防錆方法は、２−メルカプトベンズイミダゾールをメタ
ノール等の有機溶剤に溶かして、基材に塗布し乾燥する
方法であり、有機溶剤を使用するため人体に対する悪影
響や工場の保安面で問題があった。特開昭63-118598号
公報に記載の方法については２−メルカプトベンズイミ
ダゾールの薄膜を形成するのに、約３時間の浸漬処理を
必要としており、高生産性、高速処理を要求されるプリ
ント配線板業界の実情に適合しないものであった。Further, the anticorrosion method using 2-mercaptobenzimidazole described in JP-A-55-83157 and JP-A-62-77600 is a method of dissolving 2-mercaptobenzimidazole in an organic solvent such as methanol to prepare a base solution. It is a method of applying it to a material and drying it. Since it uses an organic solvent, it has a bad effect on the human body and has a problem in safety of the factory. According to the method described in Japanese Patent Laid-Open No. 63-118598, a printed wiring that requires a high productivity and a high-speed treatment requires a dipping treatment for about 3 hours to form a thin film of 2-mercaptobenzimidazole. It did not fit the actual situation of the board industry.
【０００８】一方、前記２−アルキルベンズイミダゾー
ル化合物、２−アリールベンズイミダゾール化合物、２
−アラルキルベンズイミダゾール化合物あるいは２−メ
ルカプトアルキルベンズイミダゾール化合物を用いた防
錆方法は耐熱性に優れ、充分実用に供するものである
が、さらに耐熱性の改善が求められていた。特開平4-20
6681号公報には、２位アリール基置換イミダゾール化合
物及び高級脂肪酸類化合物を含む水性液を用いたプリン
ト配線板の表面処理方法が記載されているが、この表面
処理方法は実用に供する程の耐熱性が得られないもので
あった。On the other hand, the 2-alkylbenzimidazole compound, the 2-arylbenzimidazole compound, 2
The rust-preventing method using an aralkylbenzimidazole compound or a 2-mercaptoalkylbenzimidazole compound has excellent heat resistance and can be sufficiently put into practical use, but further improvement in heat resistance has been required. JP 4-20
Japanese Patent No. 6681 describes a surface treatment method for a printed wiring board using an aqueous liquid containing a 2-position aryl group-substituted imidazole compound and a higher fatty acid compound. However, this surface treatment method has a heat resistance sufficient for practical use. It was something that was not obtained.
【０００９】このようにプリント配線板の表面実装法に
対応しうる、耐熱性が高く且つ作業環境を悪化させない
プレフラックス、即ち高温に曝されたのちもはんだ付け
性に優れた水溶液系のプレフラックスが望まれていた。As described above, the pre-flux that can be applied to the surface mounting method of the printed wiring board and has high heat resistance and does not deteriorate the working environment, that is, an aqueous solution-based pre-flux that is excellent in solderability even after being exposed to high temperature. Was desired.
【００１０】[0010]
【課題を解決するための手段】本発明者等は、このよう
な事情に鑑み鋭意研究を行なった結果、銅あるいは銅合
金の表面に、化２で示される２−アラルキルイミダゾー
ル化合物を有効成分として含有する水溶液系表面処理剤
を接触させることにより、防錆性・耐熱性に優れた化成
被膜が形成されることを見い出し、本発明を完遂するに
至った。Means for Solving the Problems As a result of intensive studies in view of such circumstances, the present inventors have found that a 2-aralkylimidazole compound represented by Chemical formula 2 is used as an active ingredient on the surface of copper or a copper alloy. It has been found that a chemical conversion coating film having excellent rust prevention and heat resistance is formed by contacting the contained aqueous surface treatment agent, and the present invention has been completed.
【００１１】[0011]
【化２】 [Chemical 2]
【００１２】（式中Ａは炭素数１ないし１０の直鎖又は
分枝鎖のアルキレン基、Ｒ1 及びＲ2は同一又は異なっ
て水素原子、置換されていてもよい炭素数１ないし１０
のアルキル基、アルケニル基、アラルキル基あるいはア
リール基又はハロゲン原子、Ｒ3 及びＲ4 は同一又は異
なって水素原子、低級アルキル基、低級アルコキシ基又
はハロゲン原子を表す。）(Wherein A is a linear or branched alkylene group having 1 to 10 carbon atoms, R 1 and R 2 are the same or different hydrogen atoms, and optionally substituted 1 to 10 carbon atoms)
The alkyl group, alkenyl group, aralkyl group or aryl group or halogen atom, R 3 and R 4 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. )
【００１３】本発明の実施に適する２−アラルキルイミ
ダゾール化合物の代表的なものとしては、２−ベンジル
イミダゾール、２−ベンジル−４−メチルイミダゾー
ル、２−ベンジル−４，５−ジメチルイミダゾール、２
−ベンジル−４−ウンデシルイミダゾール、２−ベンジ
ル−４−メチル−５−クロロイミダゾール、２−（４−
クロロフェニルメチル）イミダゾール、２−（４−クロ
ロフェニルメチル）−４，５−ジメチルイミダゾール、
２，４−ジベンジル−５−メチルイミダゾール、２，
４，５−トリベンジルイミダゾール、２−ベンジル−
４，５−ジフェニルイミダゾール、２−ベンジル−４，
５−ビス（４−クロロフェニル）イミダゾール、２−
（２−フェニルエチル）イミダゾール、２−（３−フェ
ニルプロピル）イミダゾール、２−（４−フェニルブチ
ル）イミダゾール、２−（５−フェニルペンチル）イミ
ダゾール、２−（６−フェニルヘキシル）イミダゾー
ル、２−（７−フェニルヘプチル）イミダゾール、２−
（８−フェニルオクチル）イミダゾール、２−（９−フ
ェニルノニル）イミダゾール、２−（１０−フェニルデ
シル）イミダゾール、２−（２−フェニルエチル）−
４，５−ジフェニルイミダゾール、２−（３−フェニル
プロピル）−４−オクタデシルイミダゾール、２−（４
−フェニルブチル）−４−ベンジルイミダゾール、２−
〔５−（４−トリル）ペンチル〕イミダゾール、２−
〔６−（４−メトキシフェニル）ヘキシル〕イミダゾー
ル、２−〔７−（２−ブロモフェニル）ヘプチル〕−４
−ビニルイミダゾール、２−〔８−（２，４−ジクロロ
フェニル）オクチル〕−４−メチル−５−クロロイミダ
ゾール、２−（９−フェニルノニル）−４，５−ジブロ
モイミダゾール、２−（α−メチルベンジル）イミダゾ
ール及び２−（２−エチル−３−フェニルプロピル）−
４−フェニルイミダゾール等である。Typical examples of the 2-aralkylimidazole compound suitable for carrying out the present invention include 2-benzylimidazole, 2-benzyl-4-methylimidazole, 2-benzyl-4,5-dimethylimidazole, and 2-benzylimidazole.
-Benzyl-4-undecylimidazole, 2-benzyl-4-methyl-5-chloroimidazole, 2- (4-
Chlorophenylmethyl) imidazole, 2- (4-chlorophenylmethyl) -4,5-dimethylimidazole,
2,4-dibenzyl-5-methylimidazole, 2,
4,5-Tribenzylimidazole, 2-benzyl-
4,5-diphenylimidazole, 2-benzyl-4,
5-bis (4-chlorophenyl) imidazole, 2-
(2-Phenylethyl) imidazole, 2- (3-phenylpropyl) imidazole, 2- (4-phenylbutyl) imidazole, 2- (5-phenylpentyl) imidazole, 2- (6-phenylhexyl) imidazole, 2- (7-phenylheptyl) imidazole, 2-
(8-Phenyloctyl) imidazole, 2- (9-phenylnonyl) imidazole, 2- (10-phenyldecyl) imidazole, 2- (2-phenylethyl)-
4,5-diphenylimidazole, 2- (3-phenylpropyl) -4-octadecylimidazole, 2- (4
-Phenylbutyl) -4-benzylimidazole, 2-
[5- (4-tolyl) pentyl] imidazole, 2-
[6- (4-Methoxyphenyl) hexyl] imidazole, 2- [7- (2-bromophenyl) heptyl] -4
-Vinylimidazole, 2- [8- (2,4-dichlorophenyl) octyl] -4-methyl-5-chloroimidazole, 2- (9-phenylnonyl) -4,5-dibromoimidazole, 2- (α-methyl) Benzyl) imidazole and 2- (2-ethyl-3-phenylpropyl)-
4-phenylimidazole and the like.
【００１４】これらの２−アラルキルイミダゾール化合
物は、各種の公知方法を用いることにより合成すること
ができる。例えば、１，２−ジカルボニル化合物、アラ
ルキルアルデヒド化合物及び酢酸アンモニウムを酢酸
中、加熱して反応させることにより２−アラルキルイミ
ダゾール化合物を得ることができ、これを反応式で表せ
ば、化３に示すとおりである。These 2-aralkylimidazole compounds can be synthesized by using various known methods. For example, a 1,2-dicarbonyl compound, an aralkyl aldehyde compound, and ammonium acetate can be heated in acetic acid to react with each other to obtain a 2-aralkyl imidazole compound. It is as follows.
【００１５】[0015]
【化３】 [Chemical 3]
【００１６】（式中、Ａ、Ｒ1 、Ｒ2 、Ｒ3 及びＲ4 は
前記と同じである） 本発明の実施においては、有効成分として２−アラルキ
ルイミダゾール化合物を０．０１〜１０重量％の割合、
好ましくは０．１〜５重量％の割合で含有する水溶液系
の表面処理剤を使用する。２−アラルキルイミダゾール
化合物は、水に対して難溶性であるため、有機酸または
無機酸を用いて水溶液化させる。また、水と混和するこ
とができる有機溶媒を有機酸または無機酸と併用して、
２−アラルキルイミダゾール化合物を水溶液化しても良
い。(In the formula, A, R 1 , R 2 , R 3 and R 4 are the same as above.) In the practice of the present invention, 0.01 to 10% by weight of a 2-aralkylimidazole compound is used as an active ingredient. Ratio of
It is preferable to use an aqueous solution type surface treatment agent which is contained in a proportion of 0.1 to 5% by weight. Since the 2-aralkylimidazole compound is poorly soluble in water, it is made an aqueous solution using an organic acid or an inorganic acid. In addition, an organic solvent that is miscible with water is used in combination with an organic acid or an inorganic acid,
You may make 2-aralkyl imidazole compound into an aqueous solution.
【００１７】この際に用いられる有機酸としては、ギ
酸、酢酸、プロピオン酸、酪酸、ヘプタン酸、カプリル
酸、カプリン酸、ラウリル酸、グリコール酸、乳酸、ア
クリル酸、安息香酸、パラニトロ安息香酸、パラトルエ
ンスルホン酸、サリチル酸、ピクリン酸、シュウ酸、コ
ハク酸、マレイン酸、フマール酸、酒石酸、アジピン酸
等であり、無機酸としては、塩酸、リン酸、硫酸、硝酸
等である。これらの酸は、水溶液に対し０．０１〜４０
重量％の割合、好ましくは０．２〜２０重量％の割合に
なるように添加すれば良い。Examples of the organic acid used in this case include formic acid, acetic acid, propionic acid, butyric acid, heptanoic acid, caprylic acid, capric acid, lauric acid, glycolic acid, lactic acid, acrylic acid, benzoic acid, paranitrobenzoic acid, and para-nitrobenzoic acid. Toluenesulfonic acid, salicylic acid, picric acid, oxalic acid, succinic acid, maleic acid, fumaric acid, tartaric acid, adipic acid and the like, and inorganic acids include hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid and the like. These acids are contained in an amount of 0.01-40
It may be added so as to be a ratio of wt%, preferably 0.2 to 20% by weight.
【００１８】また、この際に用いられる有機溶媒として
は、メタノール、エタノール、イソプロピルアルコール
などの低級アルコール類や、アセトン、Ｎ，Ｎ−ジメチ
ルホルムアミドなどの水と混和させることのできるもの
である。As the organic solvent used at this time, lower alcohols such as methanol, ethanol and isopropyl alcohol, and water such as acetone and N, N-dimethylformamide can be mixed.
【００１９】本発明の表面処理剤で銅あるいは銅合金の
表面を処理する条件としては、処理剤の液温を約２０℃
〜６０℃、接触時間を１秒ないし１０分間の範囲が適当
である。接触方法は、浸漬、噴霧、塗布などである。The condition for treating the surface of copper or copper alloy with the surface treating agent of the present invention is that the temperature of the treating agent is about 20.degree.
Appropriately, the contact time is from 1 second to 10 minutes at -60 ° C. The contact method includes dipping, spraying, coating and the like.
【００２０】本発明の表面処理剤に使用に際して、金属
表面における化成被膜の形成速度を高めるために銅化合
物を添加してもよく、また形成された化成被膜の耐熱性
をさらに向上させるために亜鉛化合物を添加してもよ
い。When used in the surface treatment agent of the present invention, a copper compound may be added to increase the rate of formation of a conversion coating on a metal surface, and zinc may be added to further improve the heat resistance of the formed conversion coating. A compound may be added.
【００２１】本発明において使用できる銅化合物の代表
的なものとしては、塩化第一銅、塩化第二銅、水酸化
銅、リン酸銅、酢酸銅、硫酸銅、硝酸銅、臭化銅等であ
り、また亜鉛化合物の代表的なものとしては、酸化亜
鉛、蟻酸亜鉛、酢酸亜鉛、蓚酸亜鉛、乳酸亜鉛、クエン
酸亜鉛、硫酸亜鉛、硝酸亜鉛、リン酸亜鉛等であり、い
ずれも水溶液に対して0.０１〜１０重量％の割合、好ま
しくは0.０２〜５重量％の割合で添加すれば良い。Typical copper compounds usable in the present invention include cuprous chloride, cupric chloride, copper hydroxide, copper phosphate, copper acetate, copper sulfate, copper nitrate, copper bromide and the like. There are zinc compounds such as zinc oxide, zinc formate, zinc acetate, zinc oxalate, zinc lactate, zinc citrate, zinc sulfate, zinc nitrate, and zinc phosphate. Therefore, it may be added in an amount of 0.01 to 10% by weight, preferably 0.02 to 5% by weight.
【００２２】このように、銅化合物あるいは亜鉛化合物
を用いる場合には、有機酸あるいは無機酸の他にアンモ
ニアあるいはアミン類等の緩衝作用を有する物質を添加
して溶液のｐＨを安定にすることが望ましい。また本発
明表面処理剤を使用する際には、化成被膜上に熱可塑性
樹脂の二重構造を形成し、耐熱性を向上させることも可
能である。As described above, when a copper compound or a zinc compound is used, it is possible to stabilize the pH of the solution by adding a substance having a buffering action such as ammonia or amines in addition to the organic acid or the inorganic acid. desirable. When the surface treatment agent of the present invention is used, it is also possible to improve the heat resistance by forming a double structure of a thermoplastic resin on the chemical conversion film.
【００２３】即ち銅あるいは銅合金の表面に２−アラル
キルイミダゾール化合物の化成被膜を形成したのち、ロ
ジン、ロジンエステル等のロジン誘導体、テルペン樹
脂、テルペンフェノール樹脂等のテルペン樹脂誘導体ま
たは芳香族炭化水素樹脂、脂肪族炭化水素樹脂、脂環族
炭化水素樹脂等の炭化水素樹脂あるいはこれらの混合物
等からなる耐熱性に優れた熱可塑性樹脂をトルエン、酢
酸エチル、ＩＰＡ等の溶媒に溶解し、ロールコーター法
等により化成被膜上に膜厚１〜30μｍの厚みになるよう
に均一に塗布して化成被膜と熱可塑性樹脂の二層構造を
形成すれば良い。That is, after forming a conversion coating of a 2-aralkylimidazole compound on the surface of copper or a copper alloy, rosin, a rosin derivative such as a rosin ester, a terpene resin derivative such as a terpene resin or a terpene phenol resin, or an aromatic hydrocarbon resin. A thermoplastic resin having excellent heat resistance, which is composed of a hydrocarbon resin such as an aliphatic hydrocarbon resin or an alicyclic hydrocarbon resin, or a mixture thereof, is dissolved in a solvent such as toluene, ethyl acetate or IPA, and then the roll coater method is used. It is sufficient to form a two-layer structure of the chemical conversion coating and the thermoplastic resin by uniformly coating the chemical conversion coating with a film thickness of 1 to 30 μm.
【００２４】[0024]
【作用】銅あるいは銅合金の表面に有効成分として２−
アラルキルイミダゾール化合物を含有する水溶液系表面
処理剤を接触させると、２−アラルキルイミダゾール化
合物と銅との錯体形成反応及び２−アラルキルイミダゾ
ール化合物間の水素結合とファンデルワールス力の両作
用により、局部的に銅錯体となった２−アラルキルイミ
ダゾール化合物の化成被膜が銅あるいは銅合金表面上に
形成される。[Function] As an active ingredient on the surface of copper or copper alloy, 2-
When an aqueous surface treatment agent containing an aralkyl imidazole compound is brought into contact with the aralkyl imidazole compound, a complex formation reaction between the 2-aralkyl imidazole compound and copper and a hydrogen bond between the 2-aralkyl imidazole compound and a van der Waals force both act locally, A chemical conversion coating of the 2-aralkylimidazole compound that has become a copper complex is formed on the surface of copper or copper alloy.
【００２５】前記の化成被膜を放置あるいは加熱するこ
とにより銅表面から銅の移行が起こり、２−アラルキル
イミダゾール化合物の大部分は２−アラルキルイミダゾ
ール化合物の銅錯体になる。前記の銅錯体からなる化成
被膜は、熱的にもまた化学的にも安定であり、下地の銅
あるいは銅合金を高温に曝すことによる酸化、また長期
放置による錆の発生から保護しうるものである。When the above chemical conversion coating is left standing or heated, copper is transferred from the copper surface, and most of the 2-aralkylimidazole compound becomes a copper complex of the 2-aralkylimidazole compound. The chemical conversion coating consisting of the above copper complex is both thermally and chemically stable, and can protect the underlying copper or copper alloy from oxidation due to exposure to high temperatures and from rust due to long-term storage. is there.
【００２６】２−アラルキルイミダゾール化合物を含有
する水溶液系表面処理剤を用いて表面処理した銅板ある
いは銅合金板は、２−アルキルイミダゾール化合物、２
−アリールイミダゾール化合物又は２−アルキルベンズ
イミダゾール化合物を含有する表面処理剤を用いて表面
処理した場合と比べて、長期放置後に高温に曝されたの
ちのはんだ濡れ性が良好であり、さらに長期放置後のク
リームはんだ広がり性も良好である。The copper plate or the copper alloy plate surface-treated with the aqueous surface treatment agent containing the 2-aralkylimidazole compound is a 2-alkylimidazole compound, 2
-Solder wettability after exposure to high temperature for a long period of time is better than when surface-treated with a surface-treating agent containing an aryl imidazole compound or a 2-alkylbenzimidazole compound, and after long-term exposure The cream solder spreadability is also good.
【００２７】[0027]
【実施例】以下、実施例及び比較例によって、本発明を
具体的に説明する。なお、これらの試験において金属表
面における化成被膜の厚さは、実際にプリント配線板と
して用いられている硬質銅張積層板を所定の大きさに切
断した試験片を用いて所定の浸漬処理を行い、金属表面
に化成被膜を形成したのち、０．５％の塩酸水溶液に浸
漬して、２−アラルキルイミダゾール化合物を抽出し、
紫外分光光度計を用いて、この抽出液中に含まれる２−
アラルキルイミダゾール化合物の濃度を測定し、化成被
膜の厚さに換算したものである。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In these tests, the thickness of the chemical conversion coating on the metal surface was determined by dipping the hard copper clad laminate, which is actually used as a printed wiring board, into a predetermined size. After forming a conversion coating on the metal surface, it is immersed in a 0.5% aqueous solution of hydrochloric acid to extract the 2-aralkylimidazole compound,
Using an ultraviolet spectrophotometer, 2-
The concentration of the aralkylimidazole compound was measured and converted into the thickness of the chemical conversion film.
【００２８】はんだ濡れ性の測定は次のようにして行っ
た。まず、試験片として５mm×５０mm×０．３mmの大き
さの銅板を用い、この試験片を脱脂、ソフトエッチング
及び水洗を行ったのち、所定の液温に保持した各実施例
あるいは比較例に記載の組成からなる表面処理剤に夫々
所定時間浸漬し、次いで水洗、乾燥して試験片表面に厚
さ約０．１０〜０．２５μｍの化成被膜を夫々形成させ
た。The solder wettability was measured as follows. First, a copper plate having a size of 5 mm x 50 mm x 0.3 mm was used as a test piece, and the test piece was degreased, soft-etched and washed with water, and then described in each Example or Comparative Example held at a predetermined liquid temperature. Each of them was dipped in a surface treatment agent having the above composition for a predetermined time, then washed with water and dried to form a chemical conversion coating having a thickness of about 0.10 to 0.25 μm on the surface of the test piece.
【００２９】被膜形成処理がなされた試験片を表１に示
す条件で放置し、２００℃の熱風オーブン中で１０分間
加熱処理を行った。次いで、この試験片にポストフラッ
クス（商品名：ＪＳ−６４、（株）弘輝製）を浸漬付着
させ、はんだ濡れ時間を測定した。測定に当たっては、
はんだ濡れ性試験器（製品名：ＷＥＴ−３０００、
（株）レスカ製）を用い、その測定条件ははんだ温度２
５０℃、浸漬深さ２mm、浸漬スピード１６mm／秒とし
た。The film-forming test piece was left standing under the conditions shown in Table 1 and heat-treated in a hot air oven at 200 ° C. for 10 minutes. Then, post flux (trade name: JS-64, manufactured by Hiroki Co., Ltd.) was dipped and adhered to the test piece, and the solder wetting time was measured. When measuring
Solder wettability tester (Product name: WET-3000,
(Manufactured by RESCA Co., Ltd.) and the measurement conditions are solder temperature 2
The temperature was 50 ° C., the immersion depth was 2 mm, and the immersion speed was 16 mm / sec.
【００３０】またクリームはんだ広がり性の試験につい
ては、次のようにして行った。試験片としては絶縁抵抗
試験に用いられるくし形電極Ｉ形〔ＪＩＳ Ｚ−３１９
７６．８〕を用い、この試験片を脱脂、ソフトエッチン
グ及び水洗を行ったのち、前記はんだ濡れ性の測定と同
様にして表面処理剤に浸漬し、水洗、乾燥して試験片表
面に厚さ約０．２５μｍの化成被膜を夫々形成させたの
ち、室温で１０日間放置した。The cream solder spreadability test was conducted as follows. As a test piece, a comb-shaped electrode I type [JIS Z-319 used for an insulation resistance test is used.
76.8], the test piece is degreased, soft-etched and washed with water, and then immersed in a surface treatment agent in the same manner as in the measurement of the solder wettability, washed with water and dried to give a thickness on the surface of the test piece. After forming a chemical conversion coating of about 0.25 μm each, it was left at room temperature for 10 days.
【００３１】被膜形成処理がなされ、１０日間放置した
後の前記試験片にクリームはんだ（商品名：ＡＥ−５３
ＨＧＩ、四国化成工業（株）製）を印刷幅３mmで一文
字印刷し、赤外線リフロー装置（製品名：ＭＵＬＴＩ−
ＰＲＯ−３０６、ヴィトロニクス社製）を用いてリフロ
ー加熱（ピーク温度２３０℃）を行い、広がったはんだ
の広がり長さを測定した。A cream solder (trade name: AE-53) was applied to the test piece after a film-forming treatment and leaving it for 10 days.
HGI, manufactured by Shikoku Kasei Kogyo Co., Ltd., prints one character with a printing width of 3 mm, and uses an infrared reflow device (product name: MULTI-
Reflow heating (peak temperature of 230 ° C.) was performed using PRO-306, manufactured by Vitronics Co., Ltd., and the spread length of the spread solder was measured.
【００３２】（実施例１）はんだ濡れ時間及びクリーム
はんだ広がり性測定用試験片を、表面処理剤が２−（４
−クロロフェニルメチル）イミダゾール０．５０重量
％、酢酸２．０重量％及び臭化銅０．０５重量％からな
る水溶液に、液温５０℃で６０秒間浸漬したのち、水
洗、乾燥した。Example 1 A test piece for measuring solder wetting time and cream solder spreadability was tested with a surface treatment agent of 2- (4).
-Chlorophenylmethyl) imidazole was immersed in an aqueous solution containing 0.50% by weight of acetic acid, 2.0% by weight of acetic acid and 0.05% by weight of copper bromide at a liquid temperature of 50 ° C for 60 seconds, washed with water and dried.
【００３３】次いで、はんだ濡れ時間の測定は、試験片
を表１に示す条件で放置し、加熱処理を行なったのち測
定を行い、その結果は表１に示すとおりであった。また
クリームはんだ広がり性は、測定用試験片を１０日間室
温で放置したのち測定を行い、その測定結果は表１に示
すとおりであった。Next, the solder wetting time was measured by leaving the test piece under the conditions shown in Table 1 and subjecting it to heat treatment, and then the results were as shown in Table 1. The cream solder spreadability was measured after leaving the test piece for measurement for 10 days at room temperature, and the measurement results are shown in Table 1.
【００３４】（実施例２）試験片を表面処理剤が２−ベ
ンジル−４−メチル−５−クロロイミダゾール０．３０
重量％、酢酸１０．０重量％及び臭化銅０．０５重量％
からなる水溶液に、液温５０℃で８０秒間浸漬したの
ち、取り出し水洗、乾燥した。実施例１と同様にはんだ
濡れ性試験及びクリームはんだ広がり性試験を行ったと
ころ、その測定結果は表１に示すとおりであった。Example 2 A test piece was treated with a surface treatment agent of 2-benzyl-4-methyl-5-chloroimidazole 0.30.
% By weight, 10.0% by weight acetic acid and 0.05% by weight copper bromide
The sample was immersed in an aqueous solution consisting of the above for 80 seconds at a liquid temperature of 50 ° C., taken out, washed with water and dried. When the solder wettability test and the cream solder spreadability test were performed in the same manner as in Example 1, the measurement results were as shown in Table 1.
【００３５】（実施例３）試験片を表面処理剤が２，４
−ジベンジル−５−メチルイミダゾール０．５０重量
％、ギ酸３．０重量％及び塩化銅０．０９重量％からな
る水溶液に、液温５０℃で８０秒間浸漬したのち、取り
出し水洗、乾燥した。実施例１と同様にはんだ濡れ性試
験及びクリームはんだ広がり性試験を行ったところ、そ
の測定結果は表１に示すとおりであった。(Example 3) The test piece was treated with a surface treatment agent of 2,4.
It was immersed in an aqueous solution of 0.50% by weight of dibenzyl-5-methylimidazole, 3.0% by weight of formic acid and 0.09% by weight of copper chloride at a liquid temperature of 50 ° C. for 80 seconds, taken out, washed with water and dried. When the solder wettability test and the cream solder spreadability test were performed in the same manner as in Example 1, the measurement results were as shown in Table 1.
【００３６】（実施例４）試験片を表面処理剤が２−
（２，４−ジクロロフェニルメチル）−４，５−ジフェ
ニルイミダゾール０．４０重量％、ギ酸５．０重量％及
び塩化銅０．０９重量％からなる水溶液に、液温４５℃
で４０秒間浸漬したのち、取り出し水洗、乾燥した。実
施例１と同様にはんだ濡れ性試験及びクリームはんだ広
がり性試験を行ったところ、その測定結果は表１に示す
とおりであった。Example 4 A test piece was treated with a surface treatment agent of 2-
(2,4-Dichlorophenylmethyl) -4,5-diphenylimidazole 0.40% by weight, formic acid 5.0% by weight and copper chloride 0.09% by weight in an aqueous solution at a liquid temperature of 45 ° C.
After soaking for 40 seconds, it was taken out, washed with water and dried. When the solder wettability test and the cream solder spreadability test were performed in the same manner as in Example 1, the measurement results were as shown in Table 1.
【００３７】（実施例５）試験片を表面処理剤が２−
（２−フェニルエチル）−４−メチルイミダゾール０．
５０重量％、酢酸２．０重量％及び臭化銅０．１０重量
％からなる水溶液に、液温５０℃で６０秒間浸漬したの
ち、取り出し水洗、乾燥した。実施例１と同様にはんだ
濡れ性試験及びクリームはんだ広がり性試験を行ったと
ころ、その測定結果は表１に示すとおりであった。Example 5 A test piece was treated with a surface treatment agent of 2-
(2-Phenylethyl) -4-methylimidazole 0.
It was immersed in an aqueous solution of 50% by weight, acetic acid 2.0% by weight and copper bromide 0.10% by weight at a liquid temperature of 50 ° C. for 60 seconds, taken out, washed with water and dried. When the solder wettability test and the cream solder spreadability test were performed in the same manner as in Example 1, the measurement results were as shown in Table 1.
【００３８】（実施例６）試験片を表面処理剤が２−
（７−パラトリルヘプチル）−４，５−ジメチルイミダ
ゾール０．３５重量％、酢酸５．０重量％及び臭化銅
０．１０重量％からなる水溶液に、液温４０℃で２０秒
間浸漬したのち、取り出し水洗、乾燥した。実施例１と
同様にはんだ濡れ性試験及びクリームはんだ広がり性試
験を行ったところ、その測定結果は表１に示すとおりで
あった。Example 6 A test piece was treated with a surface treatment agent of 2-
(7-Paratolylheptyl) -4,5-dimethylimidazole 0.35% by weight, 5.0% by weight of acetic acid and 0.10% by weight of copper bromide were immersed in an aqueous solution at a liquid temperature of 40 ° C. for 20 seconds and then immersed. It was taken out, washed with water and dried. When the solder wettability test and the cream solder spreadability test were performed in the same manner as in Example 1, the measurement results were as shown in Table 1.
【００３９】（実施例７）真鍮製の試験片を脱脂、ソフ
トエッチング及び水洗したのち、実施例１と同じ処理剤
を用いて実施例１と全く同じ処理を行ったところ、厚さ
０．２０μｍの化成皮膜の形成が確認できた。(Example 7) A brass test piece was degreased, soft-etched and washed with water, and then the same treatment as in Example 1 was performed using the same treatment agent as in Example 1. The thickness was 0.20 μm. The formation of a chemical conversion film was confirmed.
【００４０】（比較例１）試験片を表面処理剤が２−フ
ェニルイミダゾール１．０重量％、酢酸２．０重量％、
ラウリン酸０．１重量％及び臭化第二銅０．０５重量％
からなる水溶液に、液温５０℃で３０秒間浸漬した後、
取り出し水洗、乾燥した。その後実施例１と同様にはん
だ濡れ性試験及びクリームはんだ広がり性試験を行った
ところ、その測定結果は表１に示すとおりであった。(Comparative Example 1) A test piece was treated with a surface treatment agent of 2-phenylimidazole 1.0% by weight, acetic acid 2.0% by weight,
Lauric acid 0.1% by weight and cupric bromide 0.05% by weight
After immersing in an aqueous solution consisting of
It was taken out, washed with water and dried. Then, a solder wettability test and a cream solder spreadability test were conducted in the same manner as in Example 1, and the measurement results were as shown in Table 1.
【００４１】（比較例２）試験片を表面処理剤が２−ノ
ニルベンズイミダゾール０．２重量％、酢酸５．０重量
％及び塩化第二銅０．０３５重量％からなる水溶液に、
液温４０℃で３０秒間浸漬した後、取り出し水洗、乾燥
した。その後実施例１と同様にはんだ濡れ性試験及びク
リームはんだ広がり性試験を行ったところ、その測定結
果は表１に示すとおりであった。Comparative Example 2 A test piece was treated with an aqueous solution containing 0.2% by weight of 2-nonylbenzimidazole, 5.0% by weight of acetic acid and 0.035% by weight of cupric chloride as a surface treatment agent.
After dipping for 30 seconds at a liquid temperature of 40 ° C., it was taken out, washed with water and dried. Then, a solder wettability test and a cream solder spreadability test were conducted in the same manner as in Example 1, and the measurement results were as shown in Table 1.
【００４２】（比較例４）試験片を表面処理剤が２−
（４−クロロフェニルメチル）ベンズイミダゾール０．
５重量％、ギ酸３．０重量％、ペンタン酸０．０４重量
％及び塩化第二銅０．０９重量％からなる水溶液に、液
温５０℃で６０秒間浸漬した後、取り出し水洗、乾燥し
た。その後実施例１と同様にはんだ濡れ性試験及びクリ
ームはんだ広がり性試験を行ったところ、その測定結果
は表１に示すとおりであった。(Comparative Example 4) The test piece was treated with 2-
(4-chlorophenylmethyl) benzimidazole 0.
The sample was immersed in an aqueous solution containing 5% by weight, formic acid 3.0% by weight, pentanoic acid 0.04% by weight and cupric chloride 0.09% by weight at a liquid temperature of 50 ° C. for 60 seconds, taken out, washed with water and dried. Then, a solder wettability test and a cream solder spreadability test were conducted in the same manner as in Example 1, and the measurement results were as shown in Table 1.
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【発明の効果】銅あるいは銅合金を２−アラルキルイミ
ダゾール化合物を主成分とする水溶液に浸漬処理するこ
とにより、その表面に撥水性に優れ、長期保存安定性に
富み、且つ耐湿性及び耐熱性に優れた化成被膜を形成す
ることができるので、プリント配線板の表面実装法にお
けるはんだ付け性を向上させることができる。EFFECTS OF THE INVENTION By dipping copper or a copper alloy in an aqueous solution containing a 2-aralkylimidazole compound as a main component, its surface is excellent in water repellency, has long-term storage stability, and has excellent moisture resistance and heat resistance. Since an excellent chemical conversion film can be formed, the solderability in the surface mounting method of the printed wiring board can be improved.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年５月２４日[Submission date] May 24, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４３[Correction target item name] 0043
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４３】[0043]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 村井 孝行 香川県仲多度郡多度津町大字東白方498番 地 (72)発明者 吉岡 隆 香川県丸亀市津森町382番地15 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takayuki Murai 498 Totashikata, Tatsutsu, Nakatado-gun, Kagawa Prefecture (72) Takashi Yoshioka 382-15, Tsumori-cho, Marugame, Kagawa Prefecture 15
Claims (1)
ール化合物を有効成分として含有することを特徴とする
銅及び銅合金の表面処理剤。 【化１】 （式中Ａは炭素数１ないし１０の直鎖又は分枝鎖のアル
キレン基、Ｒ1 及びＲ2は同一又は異なって水素原子、
置換されていてもよい炭素数１ないし１０のアルキル
基、アルケニル基、アラルキル基あるいはアリール基又
はハロゲン原子、Ｒ3 及びＲ4 は同一又は異なって水素
原子、低級アルキル基、低級アルコキシ基又はハロゲン
原子を表す。）1. A surface treating agent for copper and copper alloys, which contains a 2-aralkylimidazole compound represented by Chemical formula 1 as an active ingredient. [Chemical 1] (In the formula, A is a linear or branched alkylene group having 1 to 10 carbon atoms, R 1 and R 2 are the same or different and are hydrogen atoms,
Alkyl group, alkenyl group, aralkyl group or aryl group or halogen atom having 1 to 10 carbon atoms which may be substituted, and R 3 and R 4 are the same or different and are hydrogen atom, lower alkyl group, lower alkoxy group or halogen atom. Represents )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06550394A JP3311858B2 (en) | 1994-03-08 | 1994-03-08 | Copper and copper alloy surface treatment agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06550394A JP3311858B2 (en) | 1994-03-08 | 1994-03-08 | Copper and copper alloy surface treatment agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07243054A true JPH07243054A (en) | 1995-09-19 |
| JP3311858B2 JP3311858B2 (en) | 2002-08-05 |
Family
ID=13288950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06550394A Expired - Lifetime JP3311858B2 (en) | 1994-03-08 | 1994-03-08 | Copper and copper alloy surface treatment agent |
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| Country | Link |
|---|---|
| JP (1) | JP3311858B2 (en) |
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