JPH0362793B2 - - Google Patents
Info
- Publication number
- JPH0362793B2 JPH0362793B2 JP58245408A JP24540883A JPH0362793B2 JP H0362793 B2 JPH0362793 B2 JP H0362793B2 JP 58245408 A JP58245408 A JP 58245408A JP 24540883 A JP24540883 A JP 24540883A JP H0362793 B2 JPH0362793 B2 JP H0362793B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- filtration
- powder
- treatment
- sensitization
- 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.)
- Expired - Lifetime
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000007772 electroless plating Methods 0.000 claims description 8
- 230000001235 sensitizing effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 229940079877 pyrogallol Drugs 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 25
- 206010070834 Sensitisation Diseases 0.000 description 19
- 230000008313 sensitization Effects 0.000 description 19
- 239000000843 powder Substances 0.000 description 18
- 238000001914 filtration Methods 0.000 description 15
- 239000008187 granular material Substances 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001994 activation Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- UWPPADMWQVNQFC-UHFFFAOYSA-J tetrachlorostannane;hydrochloride Chemical compound Cl.Cl[Sn](Cl)(Cl)Cl UWPPADMWQVNQFC-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
Description
本発明は、粉粒体の表面に無電解めつきで金属
被覆する際に、めつき前処理として触媒作用のあ
る物質を密着させるために行なわれる感受性化・
活性化処理工程の中の感受性化処理液の安定性の
改良に関する。
従来無電解めつきを行なうには塩化第一錫と塩
酸とからなる水溶液で被めつき物を感受性化処理
し水洗し、次に塩化パラジウムと塩酸とからなる
水溶液で活性化処理し、水洗したのち、無電解め
つきを行なつてきた。しかしこの方法を粉粒体特
に微粉（ミクロン級）、極微粉（サブミクロン級）
に適用する場合、次のような欠点がある。
(1) 感受性化処理液中の塩化第一錫が空気酸化を
受け、感受性化処理液が老化し、無電解めつき
において全面的あるいは部分的に未析出が起こ
る。
(2) 粉粒体を感受性化処理すると処理中に液が分
解し、処理後に粉粒体をろ別分離する際、感受
性化処理液の分解生成物によりフイルターが目
詰りし、ろ別分離ができなくなる。
(3) 感受性化処理し、粉粒体を水洗する際に粉粒
体に付着している感受性化処理液が分解し、分
解生成物によりフイルターが目詰りし、粉粒体
のろ別分離の支障をきたす。
本発明の目的はこれらの欠点を除いた無電解め
つきの前処理における安定性の優れた感受性化処
理液を提供することである。
感受性化処理液の安定性を改良する物質につい
て種々検討した結果、或る種の還元性物質が添加
されると感受性化処理液の安定性が飛躍的に向上
することを見出した。
本発明によれば、塩化第一錫と塩酸を含む無電
解めつきのための感受性化処理液であつて、合計
で0.001〜５ｇ／のチオ尿素、ピロガロールお
よびヒドロキノンの中の１種以上を含有すること
を特徴とする処理液が提供される。
本発明の処理液は、好ましい実施態様におい
て、さらに金属錫を含む。
本発明の感受性化処理液は使用時に各成分を混
合して調製してもよいが、あらかじめ各種濃度に
調製した原液として充分に保存可能である。
通常の塩化錫−塩酸感受性化処理液は塩化錫を
0.1〜100ｇ／含み、PHが２以下である。このよ
うな処理液に対してチオ尿素、ピロガロールおよ
びヒドロキノンの１種以上の合計が0.001〜５
ｇ／となるように添加される。
金属錫を添加する場合、錫は塊であつても粒
状、片状であつてもよい。処理液の保存ないし使
用期間中溶解してしまわない量で存在すればよ
い。
感受性化処理液の安定性に与える各種還元性物
質の影響を表１に示す。
The present invention deals with sensitization and sensitization, which is carried out as a pre-plating treatment in order to adhere a catalytic substance to the surface of powder particles by electroless plating.
This invention relates to improving the stability of a sensitizing solution during an activation process. Conventionally, to perform electroless plating, the object to be plated was sensitized with an aqueous solution of stannous chloride and hydrochloric acid and washed with water, then activated with an aqueous solution of palladium chloride and hydrochloric acid, and washed with water. Later, he started performing electroless plating. However, this method cannot be applied to powders, especially fine powders (micron class) and ultrafine powders (submicron class).
When applied, there are the following drawbacks. (1) The stannous chloride in the sensitizing treatment solution undergoes air oxidation, the sensitization treatment solution ages, and non-precipitation occurs entirely or partially during electroless plating. (2) When powder and granules are sensitized, the liquid decomposes during the treatment, and when the powder and granules are separated by filtration after treatment, the filter is clogged by the decomposition products of the sensitized solution, which prevents filtration and separation. become unable. (3) When sensitizing the powder and granular material is washed with water, the sensitizing solution adhering to the granular material decomposes, and the decomposition products clog the filter, making it difficult to separate the granular material by filtration. cause trouble. The object of the present invention is to provide a sensitizing solution that eliminates these drawbacks and has excellent stability in pretreatment for electroless plating. As a result of various studies on substances that improve the stability of the sensitized solution, it was discovered that the stability of the sensitized solution can be dramatically improved when a certain type of reducing substance is added. According to the present invention, the sensitizing solution for electroless plating contains stannous chloride and hydrochloric acid, and contains a total of 0.001 to 5 g/at least of one or more of thiourea, pyrogallol, and hydroquinone. A processing liquid is provided. In a preferred embodiment, the treatment liquid of the present invention further contains metal tin. The sensitization treatment solution of the present invention may be prepared by mixing the components at the time of use, but it can be sufficiently stored as a stock solution prepared in advance at various concentrations. Ordinary tin chloride-hydrochloric acid sensitization treatment solution contains tin chloride.
Contains 0.1-100g/PH is 2 or less. For such a treatment solution, the total amount of one or more of thiourea, pyrogallol and hydroquinone is 0.001 to 5.
g/. When metallic tin is added, tin may be in the form of lumps, granules, or flakes. It is sufficient that it is present in an amount that does not dissolve during storage or use of the processing solution. Table 1 shows the influence of various reducing substances on the stability of the sensitized treatment solution.
【表】
使用した感受性化処理液はSnCl210ｇ／、PH
1.05（HClで調製）である。表１よりヒドロキノ
ン、ピロガロールおよびチオ尿素の中の１種以上
の添加により感受性化処理液の安定性が改善され
ることがわかる。またこれらの還元性物質と金属
錫が同時に共存すると感受性化処理液の安定性は
一段と向上する。安定化剤の好ましい添加量は、
0.001〜５ｇ／であり、0.001ｇ／以下では効
果が少なく、５ｇ／以上では、感受性化処理液
の安定性が逆に低下する傾向が認められたためで
ある。かくして感受性化処理液の長期保存が可能
となる。また前記の安定化剤を添加した感受性化
処理液による粉粒体の感受性化処理においても感
受性化処理液の液成分の分解がなく、処理後のフ
イルターによる粉粒体のろ別分離が容易に行なわ
れることを確認すると共に感受性化処理に続く水
洗後の粉粒体のろ別分離の際にも錫塩の分解によ
るフイルターの目詰りの問題も解消される。
感受性化処理液に安定化剤が添加されることに
よつて液中のSn2+イオンの粉粒体への密着析出
が妨げられることはなく、その後パラジウム塩に
よる活性化処理で粉粒体表面に充分な触媒活性が
付与され、無電解めつきによりめつき欠陥のない
均一な金属被膜が得られる。
次に本発明を実施例により具体的に説明する。
実施例および比較例は以下に示す工程で行なつ
た。
感受性化処理（常温５分）→ろ過→水洗→ろ過
→活性化処理（PdCl20.2ｇ／、HCl2.5ml／、
常温、５分）→ろ過→水洗→ろ過→無電解Niめ
つき（日本カニゼン社SB−55、60℃、１分）→
ろ過→水洗→ろ過→乾燥
粉粒体には立法晶窒化硼素CBN（平均粉径3μ）
１ｇを用い、ろ過はメンブレンフイルター（孔径
0.4μｍ）によつて行なつた。
実施例 １
感受性化処理液にはSnCl210ｇ／、ピロガロ
ール0.05ｇ／を含みPH1.05（HClで調製）を用い
た。感受性化処理後のCBN粉のろ別分離は容易
にでき、無電解Niめつきにより0.23ｇの重量増が
得られ、Niめつきは均一であつた。
実施例 ２
感受性化処理液にはSnCl210ｇ／、チオ尿素
0.5ｇ／PH1.05（HClで調製）を用いた。感受性
化処理後のろ別分離は容易にでき、無電解Niめ
つきにより0.15ｇの重量増が得られNiめつきは均
一であつた。
比較例 １
感受性化処理液にはSnCl210ｇ／、PH1.05
（HClで調製）を用いた。感受性化処理後のCBN
粉のろ別分離には３時間かかり、その後の水洗で
も支障をきたした。無電解Niめつき後のCBN粉
の重量は、試験開始時に比べて0.03ｇ減つてお
り、Niの析出は局部的に僅か見られるだけであ
つた。尚、無電解Niめつき後の秤量で重量減少
となつたのは、各工程でCBN粉が槽壁に付着し、
それらの回収が100％でなかつたために起こつた。[Table] The sensitization solution used was SnCl 2 10g/, PH
1.05 (prepared with HCl). Table 1 shows that the stability of the sensitized solution is improved by adding one or more of hydroquinone, pyrogallol, and thiourea. Furthermore, when these reducing substances and metallic tin coexist at the same time, the stability of the sensitization treatment solution is further improved. The preferred amount of stabilizer added is:
This is because when the amount is 0.001 to 5 g/, the effect is small, and when it is 5 g/ or more, the stability of the sensitized treatment liquid tends to decrease. In this way, the sensitized solution can be stored for a long period of time. In addition, even in the sensitization treatment of powder and granular material using the sensitization treatment solution containing the above-mentioned stabilizer, there is no decomposition of the liquid components of the sensitization treatment solution, and the filtration separation of the powder and granule material after treatment is easy. This also eliminates the problem of filter clogging due to the decomposition of tin salts during the filtration separation of the powder after washing with water following the sensitization treatment. Adding a stabilizer to the sensitization treatment solution does not prevent Sn 2+ ions in the solution from adhering to the powder and granule, and then the activation treatment with palladium salt improves the surface of the powder. Sufficient catalytic activity is imparted to the metal, and a uniform metal coating without plating defects can be obtained by electroless plating. Next, the present invention will be specifically explained using examples. Examples and comparative examples were carried out using the steps shown below. Sensitization treatment (5 minutes at room temperature) → Filtration → Water washing → Filtration → Activation treatment (PdCl 2 0.2g/, HCl 2.5ml/,
Room temperature, 5 minutes) → Filtration → Water washing → Filtration → Electroless Ni plating (Nippon Kanigen SB-55, 60℃, 1 minute) →
Filtration → Water washing → Filtration → Drying Powder contains cubic boron nitride CBN (average powder diameter 3μ)
1 g, and filtration is done using a membrane filter (pore size
0.4 μm). Example 1 A sensitization treatment solution containing 10 g of SnCl 2 and 0.05 g of pyrogallol and having a pH of 1.05 (prepared with HCl) was used. After the sensitization treatment, the CBN powder could be easily separated by filtration, and the electroless Ni plating increased the weight by 0.23 g, and the Ni plating was uniform. Example 2 Sensitization treatment solution contains 10 g of SnCl 2 /thiourea
0.5g/PH1.05 (prepared with HCl) was used. Filtration separation after sensitization treatment was easy, and electroless Ni plating increased the weight by 0.15 g, and the Ni plating was uniform. Comparative Example 1 Sensitization treatment solution contains SnCl 2 10g/, PH1.05
(prepared with HCl) was used. CBN after sensitization treatment
It took three hours to separate the powder by filtration, and the subsequent washing with water also caused problems. The weight of the CBN powder after electroless Ni plating was 0.03 g less than at the start of the test, and Ni precipitation was only slightly observed locally. The weight decrease after electroless Ni plating was due to CBN powder adhering to the tank wall during each process.
This happened because their recovery was not 100%.
Claims (1)
の感受性化処理液であつて、合計で0.001〜５
ｇ／のチオ尿素、ピロガロールおよびヒドロキ
ノンの中の１種以上を含有することを特徴とする
処理液。 ２ 特許請求の範囲第１項に記載の感受性化処理
液であつて、さらに金属錫を含有する処理液。[Scope of Claims] 1. A sensitizing treatment solution for electroless plating containing stannous chloride and hydrochloric acid, the total amount of which is 0.001 to 5.
A processing liquid characterized in that it contains one or more of thiourea, pyrogallol and hydroquinone in an amount of 1.5 g/g/g/g/g of thiourea, pyrogallol and hydroquinone. 2. A sensitizing treatment liquid according to claim 1, which further contains metal tin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24540883A JPS60141875A (en) | 1983-12-28 | 1983-12-28 | Sensitizing solution for electroless plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24540883A JPS60141875A (en) | 1983-12-28 | 1983-12-28 | Sensitizing solution for electroless plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60141875A JPS60141875A (en) | 1985-07-26 |
| JPH0362793B2 true JPH0362793B2 (en) | 1991-09-27 |
Family
ID=17133205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24540883A Granted JPS60141875A (en) | 1983-12-28 | 1983-12-28 | Sensitizing solution for electroless plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60141875A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2866676B2 (en) * | 1989-09-18 | 1999-03-08 | 株式会社日立製作所 | Electroless gold plating solution and gold plating method using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5237971A (en) * | 1975-09-22 | 1977-03-24 | Hakusui Purasuchitsuku Kougiyo | Method of molding hollow nonnporous plastic product |
-
1983
- 1983-12-28 JP JP24540883A patent/JPS60141875A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5237971A (en) * | 1975-09-22 | 1977-03-24 | Hakusui Purasuchitsuku Kougiyo | Method of molding hollow nonnporous plastic product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60141875A (en) | 1985-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4420401A (en) | Solution waste treatment | |
| US4260493A (en) | Solution waste treatment | |
| DE3000526C2 (en) | Bath for the electroless deposition of palladium and autocatalytic palladium deposition process | |
| US2945757A (en) | Recovery of noble metals from catalytic composites | |
| JPH0293076A (en) | Production of fine metal body utilized for electroless plating | |
| JPH0362793B2 (en) | ||
| JP4111768B2 (en) | Water treatment catalyst and water treatment method | |
| JP3826544B2 (en) | Catalyst composition for electroless plating | |
| Froment et al. | Structural and Analytical Characteristics of Adsorbed Pd‐Sn Colloids | |
| US2871139A (en) | Silvering process and materials | |
| JP6336890B2 (en) | Electroless platinum plating bath | |
| JPS5932542B2 (en) | Method for controlling copper ion concentration and salt-forming anion concentration in electroless copper deposition bath | |
| JPH04227058A (en) | Platinum/graphite catalyst and its application method | |
| JP2004097893A (en) | Catalyst for water treatment and water treatment method | |
| EP0066123B1 (en) | Electroless application of a silver coating to diamond particles | |
| JPS6182811A (en) | Waste solution treatment module | |
| EP0059350A1 (en) | Waste solution treatment module | |
| US1617353A (en) | Extraction of gold from dilute solutions | |
| US2847327A (en) | Processes of chemical nickel plating and baths therefor | |
| JP2500936B2 (en) | Powder plating method | |
| JP3939887B2 (en) | Regeneration method of electroless nickel plating solution | |
| JPH05222543A (en) | Electroless platinum plating bath and production of platinum plated product using the same | |
| JPH1112753A (en) | Electroless gold plating method | |
| JPH0247546B2 (en) | ||
| JPH0657314A (en) | Production of fine palladium powder |