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JP4277954B2 - Discoloration removal / prevention agent for tin or tin alloy plating - Google Patents

Discoloration removal / prevention agent for tin or tin alloy plating Download PDF

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Publication number
JP4277954B2
JP4277954B2 JP2004012601A JP2004012601A JP4277954B2 JP 4277954 B2 JP4277954 B2 JP 4277954B2 JP 2004012601 A JP2004012601 A JP 2004012601A JP 2004012601 A JP2004012601 A JP 2004012601A JP 4277954 B2 JP4277954 B2 JP 4277954B2
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acid
tin
discoloration
alloy plating
tin alloy
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JP2005206860A (en
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香苗 時尾
玲子 川畑
弘樹 安田
芳明 村松
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JCU Corp
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Ebara Udylite Co Ltd
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Description

本発明は、スズまたはスズ合金めっきの変色除去・防止剤に関し、更に詳細には、めっき後の水洗不足や、高温・高湿などにより生じるめっき被膜の変色を除去ないしは防止し、はんだ濡れ性の劣化を防ぐスズまたはスズ合金めっきの変色除去・防止剤に関する。   The present invention relates to a discoloration removal / prevention agent for tin or tin alloy plating, and more specifically, removes or prevents discoloration of a plating film caused by lack of water washing after plating or high temperature / high humidity. The present invention relates to a discoloration removing / preventing agent for tin or tin alloy plating which prevents deterioration.

コネクタやリードフレーム等の多くの電子部品用部材には、従来、耐蝕性、はんだ付け性改良のために、スズめっきやスズ−鉛めっき等のスズ合金めっきが施されてきた。   Conventionally, many electronic component members such as connectors and lead frames have been subjected to tin alloy plating such as tin plating or tin-lead plating in order to improve corrosion resistance and solderability.

しかし、スズやスズ合金めっきを行った部品は、その後の水洗いが不十分であったり、高温や高湿の条件におかれた場合、その表面が変色するという問題があった。この変色は、単に外観が悪くなるだけでなく、はんだ濡れ性が低下し、最終的に電子部品の性能に影響を与えることもあるので、その防止が強く求められている。   However, parts subjected to tin or tin alloy plating have a problem that the surface thereof is discolored when the subsequent washing with water is insufficient, or when the parts are subjected to high temperature or high humidity. This discoloration not only deteriorates the appearance but also lowers the solder wettability and may ultimately affect the performance of the electronic component.

従来、このようなスズやスズ合金めっきの変色は、第三リン酸ナトリウムを含有する変色防止剤に浸漬することにより除去しているが、その効果が十分でない場合があり、より優れた方法の開発が求められていた。また、更に、高温や高湿の条件におかれた場合や、リフロー処理が行われた場合であってもスズやスズ合金めっきの変色を防ぐことのできる方法が求められていた。   Conventionally, such discoloration of tin or tin alloy plating has been removed by immersing it in a discoloration inhibitor containing trisodium phosphate, but the effect may not be sufficient, Development was required. Furthermore, there is a need for a method that can prevent discoloration of tin or tin alloy plating even when subjected to high temperature and high humidity conditions or when reflow treatment is performed.

従って本発明の課題は、従来使用されていたものよりも優れた変色除去効果を有し、更には積極的に変色を防止することのできる変色除去・防止剤を提供することである。   Accordingly, an object of the present invention is to provide a discoloration removing / preventing agent that has a discoloration removing effect superior to those conventionally used and that can positively prevent discoloration.

本発明者らは、上記課題を解決すべく鋭意検討を行っていた結果、特定の酸成分とチオ尿素誘導体を組み合わせることにより、スズまたはスズ合金めっきの変色を有効に除去しうることを見出した。また、これらを組み合わせた溶液にスズまたはスズ合金めっきを行った製品を浸漬すれば、その後、高温・高湿の条件下においたり、リフロー処理した場合であっても変色が起こりにくいことを見出した。   As a result of intensive studies to solve the above problems, the present inventors have found that discoloration of tin or tin alloy plating can be effectively removed by combining a specific acid component and a thiourea derivative. . In addition, it was found that if a product plated with tin or tin alloy is immersed in a solution that combines these, discoloration is unlikely to occur even under high temperature and high humidity conditions or after reflow treatment. .

本発明は、上記知見に基づき完成されたものであり、次の成分(a)および(b)
(a)ホスホン酸、アミノアルキレンホスホン酸、ヒドロキシアルキルホスホン酸、ア ルカンスルホン酸、アルカノールスルホン酸、硫酸、塩酸、硝酸、リン酸またはそれ らの塩から選ばれる酸成分の一種または二種以上
(b)チオ尿素、アルキルチオ尿素、フェニルチオ尿素およびアリルチオ尿素から選ば れるチオ尿素誘導体の一種または二種以上
を含有するスズまたはスズ合金めっきの変色除去・防止剤である。
The present invention has been completed based on the above findings, and the following components (a) and (b)
(A) One or more acid components selected from phosphonic acid, aminoalkylenephosphonic acid, hydroxyalkylphosphonic acid, alkanesulfonic acid, alkanolsulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or salts thereof b) A discoloration removing / preventing agent for tin or tin alloy plating containing one or more thiourea derivatives selected from thiourea, alkylthiourea, phenylthiourea and allylthiourea.

本発明のスズまたはスズ合金めっきの変色除去・防止剤によれば、一旦生成したスズまたはスズ合金めっき皮膜上の変色を簡単に除去することができる。また、変色前のスズまたはスズ合金めっきを浸漬すれば、高温・高湿の条件下においたり、リフロー処理した場合の変色を抑制することができる。   According to the tin or tin alloy plating discoloration removing / preventing agent of the present invention, the discoloration on the tin or tin alloy plating film once formed can be easily removed. Moreover, if tin or tin alloy plating before discoloration is immersed, discoloration at the time of high temperature and high humidity or when reflow treatment is performed can be suppressed.

本発明のスズまたはスズ合金めっきの変色除去・防止剤(以下、「変色除去・防止剤」という)において、成分(a)である酸成分は、ホスホン酸、アミノアルキレンホスホン酸、ヒドロキシアルキルホスホン酸、アルカンスルホン酸、アルカノールスルホン酸、硫酸、塩酸、硝酸、リン酸およびそれらの塩から選ばれるものである。   In the tin or tin alloy plating discoloration removing / inhibiting agent of the present invention (hereinafter referred to as “discoloring removing / inhibiting agent”), the acid component as component (a) is phosphonic acid, aminoalkylenephosphonic acid, hydroxyalkylphosphonic acid , Alkane sulfonic acid, alkanol sulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and salts thereof.

このうち、アミノホスホン酸としては、例えば、下記式(I)または(II)で表されるアミノトリ(メチレンホスホン酸)や、アルキレンジアミンテトラ(メチレンホスホン酸)等が挙げられ、アルキレンジアミンテトラ(メチレンホスホン酸)の例としては、エチレンジアミンテトラ(メチレンホスホン酸)(式(II)中、n=2)等が挙げられる。   Among these, examples of aminophosphonic acid include aminotri (methylenephosphonic acid) represented by the following formula (I) or (II), alkylenediaminetetra (methylenephosphonic acid), and the like. Examples of phosphonic acid include ethylenediaminetetra (methylenephosphonic acid) (in formula (II), n = 2).

また、ヒドロキシアルキルホスホン酸としては、下記式(III)で表されるものが挙げられる。このヒドロキシアルキルホスホン酸の例としては、1−ヒドロキシエチリデン−1,1−ジホスホン酸(式(III)中、m=0)等が挙げられる。   Moreover, as hydroxyalkyl phosphonic acid, what is represented by following formula (III) is mentioned. Examples of this hydroxyalkylphosphonic acid include 1-hydroxyethylidene-1,1-diphosphonic acid (m = 0 in formula (III)) and the like.

Figure 0004277954
(式中、nは1以上の整数を、mは0または1以上の整数を示し、Mは水素原子またはア ルカリ金属を示す)
Figure 0004277954
(In the formula, n represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and M represents a hydrogen atom or an alkali metal)

また、本発明の変色除去・防止剤の成分(a)のうち、アルカンスルホン酸としては、例えば、メタンスルホン酸、エタンスルホン酸等が挙げられ、アルカノールスルホン酸としては、例えば、イソプロパノールスルホン酸等が挙げられる。   Further, among the component (a) of the discoloration removing / inhibiting agent of the present invention, examples of the alkane sulfonic acid include methane sulfonic acid and ethane sulfonic acid, and examples of the alkanol sulfonic acid include isopropanol sulfonic acid and the like. Is mentioned.

一方、成分(b)であるチオ尿素誘導体は、チオ尿素、アルキルチオ尿素、フェニルチオ尿素およびアリルチオ尿素から選ばれるものである。このうち、アルキルチオ尿素の例としては、ジエチルチオ尿素等が挙げられる。   On the other hand, the component (b) thiourea derivative is selected from thiourea, alkylthiourea, phenylthiourea and allylthiourea. Among these, examples of alkylthiourea include diethylthiourea and the like.

本発明の変色除去・防止剤は、常法に従い、上記成分(a)および成分(b)を混合することにより調製することができる。   The discoloration removing / preventing agent of the present invention can be prepared by mixing the component (a) and the component (b) according to a conventional method.

上記変色除去・防止剤の調製に当たっての、成分(a)および成分(b)の配合量は、その使用時における濃度として、成分(a)が1ないし200g/l程度、成分(b)が1ないし100g/l程度とすることが好ましく、特に、成分(a)が10ないし100g/、成分(b)が2ないし50g/lであることが好ましい。また、これらの配合比率は、成分(a)と成分(b)の重量比で、2:1ないし20:1とすることが好ましい。   In the preparation of the discoloration removing / preventing agent, the amount of the component (a) and the component (b) is about 1 to 200 g / l for the component (a) and 1 for the component (b). The component (a) is preferably 10 to 100 g / l, and the component (b) is preferably 2 to 50 g / l. The blending ratio of these components is preferably 2: 1 to 20: 1 in terms of the weight ratio of the component (a) to the component (b).

なお、本発明の変色除去・防止剤においては、成分(a)として、ホスホン酸、アミノアルキレンホスホン酸、ヒドロキシアルキルホスホン酸およびそれらの塩から選ばれるホスホン酸系酸成分(以下、「成分(a−1)」ということがある)と、それ以外のアルカンスルホン酸、アルカノールスルホン酸、硫酸、塩酸、硝酸、リン酸およびそれらの塩から選ばれる酸成分(以下、「成分(a−2)」ということがある)の両者を使用することが望ましい。   In the discoloration removing / inhibiting agent of the present invention, as the component (a), a phosphonic acid-based acid component (hereinafter referred to as “component (a) selected from phosphonic acid, aminoalkylenephosphonic acid, hydroxyalkylphosphonic acid and salts thereof” is used. -1) ") and other acid components selected from alkane sulfonic acid, alkanol sulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and salts thereof (hereinafter referred to as" component (a-2) ") It is desirable to use both.

この場合の成分(a−1)と成分(a−2)の配合比は、それらの重量比として、5:1ないし1:5とすることが好ましい。   In this case, the mixing ratio of the component (a-1) and the component (a-2) is preferably 5: 1 to 1: 5 as a weight ratio thereof.

更に、本発明の変色除去・防止剤の調製に当たっては、必要により上記成分(a)および(b)の他、通常の表面処理剤に用いられる添加剤を使用することができる。   Furthermore, in preparing the discoloration removing / preventing agent of the present invention, additives used in ordinary surface treatment agents can be used as necessary in addition to the components (a) and (b).

これらの添加剤としては、種々の界面活性剤、トリアゾール誘導体等を挙げることができる。   Examples of these additives include various surfactants and triazole derivatives.

かくして得られる本発明の変色除去・防止剤は、スズまたはスズ合金めっき皮膜上の変色を簡単に除去できるが、これは、成分(a)である酸成分と、成分(b)であるチオ尿素誘導体の相乗的な作用によるものと考えられる。また、変色前のスズまたはスズ合金めっきの、高温・高湿の条件下や、リフロー処理での変色を防止、抑制することができるが、これは特に成分(a−1)であるホスホン酸系酸成分が特に作用する結果と判断される。   The discoloration removing / preventing agent of the present invention thus obtained can easily remove discoloration on the tin or tin alloy plating film. This is because the component (a) is an acid component and the component (b) is a thiourea. This is thought to be due to the synergistic action of the derivatives. Moreover, tin or tin alloy plating before discoloration can prevent or suppress discoloration in high-temperature and high-humidity conditions or reflow treatment, but this is particularly the phosphonic acid-based component (a-1) It is judged that the acid component is particularly effective.

以下実施例を挙げ本発明を更に詳しく説明するが、本発明はこれら実施例により何ら制約されるものではない。   Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

実 施 例 1
変色除去・防止剤の調製:
以下に示す組成で、変色除去防止剤を調製した。
Example 1
Preparation of discoloration removal / prevention agent:
A discoloration removal inhibitor was prepared with the composition shown below.

(組成1)
硫 酸 50g/l
チオ尿素 20g/l
精製水 残 部
(Composition 1)
Sulfuric acid 50g / l
Thiourea 20g / l
Purified water balance

(組成2)
メタンスルホン酸 50g/l
チオ尿素 10g/l
精製水 残 部
(Composition 2)
Methanesulfonic acid 50g / l
Thiourea 10g / l
Purified water balance

(組成3)
アミノトリ(メチレンホスホン酸) 50g/l
チオ尿素 5g/l
精製水 残 部
(Composition 3)
Aminotri (methylenephosphonic acid) 50 g / l
Thiourea 5g / l
Purified water balance

(組成4)
1−ヒドロキシエチリデン−
1,1−ジホスホン酸 100g/l
チオ尿素 5g/l
精製水 残 部
(Composition 4)
1-hydroxyethylidene
1,1-diphosphonic acid 100 g / l
Thiourea 5g / l
Purified water balance

(組成5)
硝 酸 10g/l
エチレンジアミンテトラ(メチレン
ホスホン酸)4ナトリウム塩 10g/l
チオ尿素 2g/l
精製水 残 部
(Composition 5)
Nitric acid 10g / l
Ethylenediaminetetra (methylene
Phosphonic acid) tetrasodium salt 10 g / l
Thiourea 2g / l
Purified water balance

(組成6)
リ ン 酸 50g/l
1−ヒドロキシエチリデン−
1,1−ジホスホン酸 10g/l
チオ尿素 10g/l
精製水 残 部
(Composition 6)
Phosphoric acid 50g / l
1-hydroxyethylidene
1,1-diphosphonic acid 10 g / l
Thiourea 10g / l
Purified water balance

(組成7)
塩 酸 10g/l
1−ヒドロキシエチリデン−1,1−
ジホスホン酸4ナトリウム塩 20g/l
ジエチルチオ尿素 2g/l
精製水 残 部
(Composition 7)
Hydrochloric acid 10g / l
1-hydroxyethylidene-1,1-
Diphosphonic acid tetrasodium salt 20 g / l
Diethylthiourea 2g / l
Purified water balance

(組成8)
メタンスルホン酸 25g/l
アミノトリ(メチレンホスホン酸) 25g/l
チオ尿素 15g/l
精製水 残 部
(Composition 8)
Methanesulfonic acid 25g / l
Aminotri (methylenephosphonic acid) 25 g / l
Thiourea 15g / l
Purified water balance

(組成9)
硫 酸 50g/l
アミノトリ(メチレンホスホン酸)
5ナトリウム塩 20g/l
アリルチオ尿素 2g/l
精製水 残 部
(Composition 9)
Sulfuric acid 50g / l
Aminotri (methylenephosphonic acid)
5 sodium salt 20g / l
Allylthiourea 2g / l
Purified water balance

実 施 例 2
スズめっき皮膜上での変色防止・除去効果およびはんだ濡れ性試験:
試験板(黄銅基板上にニッケルめっきを2μm施したもの;1cm×3cm )上に、一般的なすずめっきプロセスにより平均膜厚が4μmとなるようにすずめっきを行なった。このすずめっき試験板について、以下に示す方法により、実施例1の組成1、3、5、6および7の処理による変色除去効果、変色防止効果およびはんだ濡れ性を試験した。この結果を表1に示す。なお、1−ヒドロキシエチリデン−1,1−ジホスホン酸を50g/lで精製水に溶解したもの(参考組成1)およびリン酸三ナトリウムを60g/lで精製水に溶解したもの(比較組成1)並びにまったく処理を行わなかったものの結果並びに処理条件も表1中に示す。
Example 2
Discoloration prevention / removal effect and solder wettability test on tin plating film:
Tin was plated on a test plate (brass substrate with 2 μm of nickel plating; 1 cm × 3 cm 2) by a general tin plating process so that the average film thickness was 4 μm. With respect to this tin plating test plate, the discoloration removing effect, the discoloration preventing effect and the solder wettability by the treatment of the compositions 1, 3, 5, 6 and 7 of Example 1 were tested by the following methods. The results are shown in Table 1. 1-hydroxyethylidene-1,1-diphosphonic acid dissolved in purified water at 50 g / l (reference composition 1) and trisodium phosphate dissolved in purified water at 60 g / l (comparative composition 1) In addition, Table 1 also shows the results and processing conditions of the samples that were not processed at all.

すずめっき浴組成;
エバソルダSN * 400 g/l
エバソルダA * 100 g/l
エバソルダHS−220S * 40 ml/l
* いずれも荏原ユージライト株式会社製
Tin plating bath composition;
Eva Solder SN * 400 g / l
Evasolda A * 100 g / l
Evasolda HS-220S * 40 ml / l
* Both are made by Ebara Eugene Corporation.

すずめっき条件;
陰極電流密度 10 A/dm
めっき温度 40 ℃
めっき時間 50 秒
撹拌 陰極揺動撹拌(2m/min)
Tin plating conditions;
Cathode current density 10 A / dm 2
Plating temperature 40 ℃
Plating time 50 seconds
Agitation Cathodic rocking agitation (2m / min)

( 変色除去試験 )
めっき直後の試験板を、水洗前に60秒間空中に放置し、外観ムラを発生させた。ついで、所定の処理条件で各組成に浸漬し、その後、水洗、乾燥させて外観ムラの有無を下記基準により評価した。
評 価 : 評 価 内 容
◎ : 外観ムラ、変色等なし。
○ : 極淡い外観ムラ残りあり。変色なし。
△ : 外観ムラあり。変色なし。
× : 外観ムラ、変色あり。
(Discoloration removal test)
The test plate immediately after plating was left in the air for 60 seconds before washing with water to cause appearance unevenness. Subsequently, it was immersed in each composition under predetermined processing conditions, then washed with water and dried, and the presence or absence of appearance irregularities was evaluated according to the following criteria.
Evaluation: Evaluation content ◎: No appearance irregularity, discoloration, etc.
○: Very pale appearance unevenness remains. No discoloration.
Δ: Appearance unevenness. No discoloration.
×: Appearance unevenness and discoloration.

( 変色防止試験 )
めっき直後の試験板を水洗後、所定の処理条件で各組成に浸漬し、その後、水洗、乾燥させた。更に、乾燥後の試験板を、ホットプレート(260℃)上で30秒間リフロー処理し、目視にて外観を下記基準により評価した。
評 価 : 評 価 内 容
○ : 均一な光沢外観。
△ : やや外観に曇りあり。
× : 黄色の変色あり。
(Discoloration prevention test)
The test plate immediately after plating was washed with water, then immersed in each composition under predetermined processing conditions, and then washed and dried. Furthermore, the test plate after drying was subjected to reflow treatment on a hot plate (260 ° C.) for 30 seconds, and the appearance was visually evaluated according to the following criteria.
Evaluation: Evaluation content ○: Uniform gloss appearance.
Δ: Slightly cloudy in appearance.
×: Yellow discoloration.

( はんだ濡れ性試験 )
めっき直後の試験板を、所定の処理条件で各組成に浸漬し、その後、水洗、乾燥させた。このものについて、はんだ槽平衡法によりゼロクロスタイムの測定を行った。
(Solder wettability test)
The test plate immediately after plating was immersed in each composition under predetermined processing conditions, and then washed with water and dried. About this thing, the zero crossing time was measured by the solder tank equilibrium method.

( 結 果 )

Figure 0004277954
(Result)
Figure 0004277954

この結果から明らかなように、本発明の変色除去・防止剤により、すずめっき皮膜上の変色が除去され、また、予め浸漬することによりすずめっき皮膜の変色が防止された。また、本発明の変色除去・防止剤によって、はんだ濡れ性の劣化が防止された。   As is apparent from this result, the discoloration removing / preventing agent of the present invention removed the discoloration on the tin plating film, and the discoloration of the tin plating film was prevented by immersing in advance. Further, the deterioration of solder wettability was prevented by the discoloration removing / preventing agent of the present invention.

実 施 例 3
スズ合金めっき皮膜上での変色防止・除去効果およびはんだ濡れ性試験:
実施例2と同様にして、試験板上に平均膜厚が2μmとなるようにすず合金めっきを行なった。得られたすず合金めっきの皮膜組成は、すず−銀合金めっきの場合、銀を2%含むものであり、すず−銅合金めっきの場合、銅を2%含むものであった。このすず合金めっき試験板について、実施例2と同様な方法により、実施例1の組成2、4、5、8およびの処理による変色除去効果、変色防止効果およびはんだ濡れ性を試験した。この結果を表2に示す。
Example 3
Discoloration prevention / removal effect and solder wettability test on tin alloy plating film:
In the same manner as in Example 2, tin alloy plating was performed on the test plate so that the average film thickness was 2 μm. The resulting tin alloy plating film composition contained 2% silver in the case of tin-silver alloy plating and 2% copper in the case of tin-copper alloy plating. This tin alloy plating test plate was tested in the same manner as in Example 2 for the discoloration removing effect, discoloration preventing effect, and solder wettability by the treatment of compositions 2, 4, 5, and 8 of Example 1. The results are shown in Table 2.

すず−銀合金めっき浴組成;
エバソルダSN * 300 g/l
エバソルダAG * 10 ml/l
エバソルダA * 150 g/l
エバソルダSE * 100 ml/l
* いずれも荏原ユージライト株式会社製
Tin-silver alloy plating bath composition;
Eva Solder SN * 300 g / l
Evasolda AG * 10 ml / l
Eva Solder A * 150 g / l
Evasolda SE * 100 ml / l
* Both are made by Ebara Eugene Corporation.

すず−銀合金めっき条件;
陰極電流密度 10 A/dm
めっき温度 25 ℃
めっき時間 30 秒
撹拌 陰極揺動撹拌(2m/min)
Tin-silver alloy plating conditions;
Cathode current density 10 A / dm 2
Plating temperature 25 ℃
Plating time 30 seconds
Agitation Cathodic rocking agitation (2m / min)

すず−銅合金めっき浴組成;
エバソルダSN * 300 g/l
エバソルダCU * 16 ml/l
エバソルダA * 150 g/l
エバソルダSC * 100 ml/l
* いずれも荏原ユージライト株式会社製
Tin-copper alloy plating bath composition;
Eva Solder SN * 300 g / l
Evasolda CU * 16 ml / l
Eva Solder A * 150 g / l
Eva Solder SC * 100 ml / l
* Both are made by Ebara Eugene Corporation.

すず−銅合金めっき条件;
陰極電流密度 10 A/dm
めっき温度 25 ℃
めっき時間 30 秒
撹拌 陰極揺動撹拌(2m/min)
Tin-copper alloy plating conditions;
Cathode current density 10 A / dm 2
Plating temperature 25 ℃
Plating time 30 seconds
Agitation Cathodic rocking agitation (2m / min)

( 結 果 )


Figure 0004277954
(Result)


Figure 0004277954

この結果から明らかなように、本発明の変色除去・防止剤により、すず合金めっき皮膜上の変色が除去され、また、予め浸漬することによりすず合金めっき皮膜の変色が防止された。また、本発明の変色除去・防止剤によって、はんだ濡れ性の劣化が防止された。   As is clear from this result, the discoloration removing / preventing agent of the present invention removed the discoloration on the tin alloy plating film, and also prevented the discoloration of the tin alloy plating film by dipping in advance. Further, the deterioration of solder wettability was prevented by the discoloration removing / preventing agent of the present invention.

本発明の変色除去・防止剤を使用することにより、作業途中で生成したスズまたはスズ合金めっき皮膜上の変色を簡単に除去することができる。また、予め、これにスズまたはスズ合金めっきを浸漬すれば、高温・高湿の条件下においたり、リフロー処理した場合の変色を抑制することができる。   By using the discoloration removing / preventing agent of the present invention, discoloration on the tin or tin alloy plating film generated during the work can be easily removed. In addition, if tin or tin alloy plating is immersed in advance, discoloration can be suppressed under high temperature and high humidity conditions or when reflow treatment is performed.

従って、変色除去・防止剤は、すずあるいはすず合金めっきを必要とする電子部品用部材の製造工程等において、有利に使用することができるものである。

以 上
Therefore, the discoloration removing / preventing agent can be advantageously used in a manufacturing process of a member for electronic parts that requires tin or tin alloy plating.

more than

Claims (5)

次の成分(a)および(b)
(a)ホスホン酸、アミノアルキレンホスホン酸、ヒドロキシアルキルホスホン酸、ア
ルカンスルホン酸、アルカノールスルホン酸、硫酸、塩酸、硝酸、リン酸または
それらの塩から選ばれる酸成分の一種または二種以上
(b)チオ尿素、アルキルチオ尿素、フェニルチオ尿素およびアリルチオ尿素から選ば
れるチオ尿素誘導体の一種または二種以上
を含有するスズまたはスズ合金めっきの変色除去・防止剤。
The following components (a) and (b)
(A) One or more acid components selected from phosphonic acid, aminoalkylenephosphonic acid, hydroxyalkylphosphonic acid, alkanesulfonic acid, alkanolsulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or salts thereof (b) ) A discoloration removing / preventing agent for tin or tin alloy plating containing one or more thiourea derivatives selected from thiourea, alkylthiourea, phenylthiourea and allylthiourea.
使用時の酸成分の濃度が1ないし200g/l、チオ尿素誘導体の濃度が1ないし100g/lである請求項第1項記載のスズまたはスズ合金めっきの変色除去・防止剤。   The tin or tin alloy plating discoloration removal / prevention agent according to claim 1, wherein the concentration of the acid component during use is 1 to 200 g / l and the concentration of the thiourea derivative is 1 to 100 g / l. 成分(a)として、ホスホン酸、アミノアルキレンホスホン酸、ヒドロキシアルキルホスホン酸およびそれらの塩から選ばれるホスホン酸系酸成分と、それ以外のアルカンスルホン酸、アルカノールスルホン酸、硫酸、塩酸、硝酸、リン酸およびそれらの塩から選ばれる酸成分の両者を含有する請求項第1項または第2項記載のスズまたはスズ合金めっきの変色除去・防止剤。   As component (a), a phosphonic acid-based acid component selected from phosphonic acid, aminoalkylenephosphonic acid, hydroxyalkylphosphonic acid and salts thereof, and other alkanesulfonic acid, alkanolsulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphorus The discoloration removing / preventing agent for tin or tin alloy plating according to claim 1 or 2, comprising both an acid and an acid component selected from salts thereof. スズまたはスズ合金めっき皮膜上に生じた変色を除去するものである請求項第1項ないし第3項記載の何れかの項記載のスズまたはスズ合金めっきの変色除去・防止剤。   The discoloration removing / preventing agent for tin or tin alloy plating according to any one of claims 1 to 3, wherein the discoloration produced on the tin or tin alloy plating film is removed. すずまたはすず合金めっきを施した部材を浸漬し、変色の発生を防止するものである請求項第1項ないし第3項記載の何れかの項記載のスズまたはスズ合金めっきの変色除去・防止剤。

The tin or tin alloy plating discoloration removing / preventing agent according to any one of claims 1 to 3, wherein a member subjected to tin or tin alloy plating is immersed to prevent discoloration. .

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WO2007029589A1 (en) * 2005-09-07 2007-03-15 Nippon Mining & Metals Co., Ltd. Aqueous antioxidant for tin or tin alloy
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US7883738B2 (en) * 2007-04-18 2011-02-08 Enthone Inc. Metallic surface enhancement
CN108315789A (en) * 2018-03-01 2018-07-24 深圳市盛元半导体有限公司 A kind of copper-based tin plating high temperature resistant protective agent
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