JPS5948874B2 - Citric acid-based bright tin or tin alloy plating bath - Google Patents
Citric acid-based bright tin or tin alloy plating bathInfo
- Publication number
- JPS5948874B2 JPS5948874B2 JP13673077A JP13673077A JPS5948874B2 JP S5948874 B2 JPS5948874 B2 JP S5948874B2 JP 13673077 A JP13673077 A JP 13673077A JP 13673077 A JP13673077 A JP 13673077A JP S5948874 B2 JPS5948874 B2 JP S5948874B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- citric acid
- plating bath
- alloy plating
- tin alloy
- 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
Links
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims description 33
- 238000007747 plating Methods 0.000 title claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 16
- 229910001128 Sn alloy Inorganic materials 0.000 title claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 229920003169 water-soluble polymer Polymers 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 4
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 4
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 claims description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- -1 aliphatic aldehydes Chemical class 0.000 claims description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 229940081310 piperonal Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012141 vanillin Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 5
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims 2
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 229940015043 glyoxal Drugs 0.000 claims 1
- 238000009713 electroplating Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WDHWFGNRFMPTQS-UHFFFAOYSA-N cobalt tin Chemical compound [Co].[Sn] WDHWFGNRFMPTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 1
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】
本発明は光沢錫または光沢錫合金のクエン酸系電気めつ
き浴に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a citric acid-based electroplating bath for bright tin or bright tin alloys.
錫または錫合金のクエン酸系電気めつき浴において光沢
性の錫または錫合金を得る、優れた光沢．添加剤は未だ
開発されていない。In a citric acid-based electroplating bath for tin or tin alloys, a bright tin or tin alloy is obtained with excellent gloss. Additives have not yet been developed.
本発明者等はクエン酸系電気めつき浴において析出する
錫または錫合金に優れた光沢を与える添加剤を得んとし
て種々研究した結果本発明に到達したものであつて、本
発明はクエン酸またはクエン酸塩およびアノンモニウム
塩を含有するＰＨ４〜８の錫または錫合金めつき浴に、
エポキシ化合物とエチレングリコール、プロピレングリ
コールまたはグリセリンとの重合反応によつて得られる
水溶性ポリマーを添加するか、あるいはこの合成水溶性
ポリマーと脂，肪族または芳香族アルデヒドとを添加し
たクエン酸系光沢錫または錫合金めつき浴である。本発
明においてエポキシ化合物としては、のうちの少くとも
一種類が使用される。The present inventors have arrived at the present invention as a result of various studies aimed at obtaining an additive that gives excellent gloss to tin or tin alloys deposited in a citric acid-based electroplating bath. or in a tin or tin alloy plating bath with a pH of 4 to 8 containing citrate and anonmonium salt;
Citric acid-based gloss with the addition of a water-soluble polymer obtained by the polymerization reaction of an epoxy compound with ethylene glycol, propylene glycol or glycerin, or with the addition of this synthetic water-soluble polymer and a fatty, aliphatic or aromatic aldehyde. This is a tin or tin alloy plating bath. In the present invention, at least one of the following is used as the epoxy compound.
そしてこのエポキシ化合物１モル当りエチレングリコー
ル、プロピレングリコールまたはグリセリンを１モルの
割合で添加し、温度６０〜９０℃で重合反応が行なう。
この際ＢＦ３またはＳｎｃｌ４を触媒として使用すれば
、さらに低い温度で合成することができる。このように
して合成した水溶性ポリマーの添加量はめつき浴１立当
り１〜２ｇである。次に脂肪族アルデヒドとしてはホル
ムアルデヒド、アセトアルデヒド、プロピオンアルデヒ
ド、グリオキサーノレ、スクシンジアノレデヒド、カプ
ロンアルデヒド、アルドールなどが少くとも１種類また
は芳香族アルデヒドとしてはベンズアルデヒド、Ｐ−ト
ルアルデヒド、サリチルアルデヒド、ベラトルアルデヒ
ド、アニスアルデヒド、ピペロナール、バニリンなどが
少くとも１種類使用され、その使用量は脂肪族の場合で
も、芳香族の場合でもめつき浴１立当り０．１〜０．５
ｇである。本発明のうち合成水溶性ポリマーのみを添加
したものを使用すれば半光沢性のある錫または錫合金が
めつきされ、かつめつき浴の老化性が少なく、浴の寿命
が長くなる利点があるが、さらにこの合成水溶性ポリマ
ーに上記アルデヒド類を添加しためつき浴を使用すれば
、鏡面光沢のある錫または錫合金がめつきされ、かつめ
つき液の寿命も一層長くなる。めつき条件はめつき浴温
１０〜４０℃、電流密度０．１〜６Ａ／Ｄｍ２である。
この電流密度範囲外では海綿状の析出物が出るかまたは
無光沢になる。本発明は錫は勿論錫一亜鉛合金、錫一鉛
合金、錫−コバルト合金、錫一銀合金、錫一銅合金など
の合金めつきに使用される。Then, ethylene glycol, propylene glycol or glycerin is added at a ratio of 1 mol per mol of this epoxy compound, and a polymerization reaction is carried out at a temperature of 60 to 90°C.
At this time, if BF3 or Sncl4 is used as a catalyst, synthesis can be performed at an even lower temperature. The amount of the water-soluble polymer thus synthesized is 1 to 2 g per plating bath. Next, examples of aliphatic aldehydes include formaldehyde, acetaldehyde, propionaldehyde, glyoxanole, succindianoledehyde, capronaldehyde, and aldol, and examples of aromatic aldehydes include benzaldehyde, P-tolualdehyde, salicylaldehyde, and veratraldehyde. , anisaldehyde, piperonal, vanillin, etc., are used in an amount of 0.1 to 0.5 per plating bath, whether aliphatic or aromatic.
It is g. If the synthetic water-soluble polymer of the present invention is used, semi-glossy tin or tin alloy can be plated, and the plating bath has the advantage of less aging and a longer bath life. Furthermore, by using a plating bath in which the above-mentioned aldehydes are added to this synthetic water-soluble polymer, tin or a tin alloy with a specular luster can be plated, and the life of the plating solution can be further extended. The plating conditions are a plating bath temperature of 10 to 40°C and a current density of 0.1 to 6 A/Dm2.
Outside this current density range, spongy precipitates appear or become matte. The present invention is used for plating not only tin but also alloys such as tin-zinc alloy, tin-lead alloy, tin-cobalt alloy, tin-silver alloy, tin-copper alloy.
次に実施例を示すが実施例に使用しためつき浴の組成は
次の如きものである。Next, examples will be shown, and the composition of the tempering bath used in the examples is as follows.
合成した水溶性ポリマー
一ＣＨ２−ＣＨ−ＣＨ２
＼ノ
１モルとＣＨ２−０Ｈ２モル
とをＢＦ３を触媒として９０℃で合成した水溶性ポリマ
ュ（ＥＰ−６）：ＣＨ２−ＣＨ−ＣＨ２−０ＣＨ３１モ
＼ノルとＣＨ２−０Ｈ
１モルとをＢＦ３を触媒として
６０℃で合成した水溶性ポリマー
（ＥＰ−７）：ＣＨ２−ＣＨ−ＣＨ２−０Ｈ１モルとＣ
Ｈ２−０Ｈ１モルとをＢＦｌを触媒として
８０℃で合成した水溶性ポリマー
一ＣＨ＝ＣＨ２
ｌモルとＣＨ２−０Ｈ１モルとを
Ｓｎｃｔ４を触媒として９０℃
Ｃで合成した水溶性ポリマー。Water-soluble polymer (EP-6) synthesized from 1 mol of CH2-CH-CH2 and 2 mol of CH2-0H at 90°C using BF3 as a catalyst: CH2-CH-CH2-0CH3 1 mol Water-soluble polymer (EP-7) synthesized with 1 mol of CH2-0H and 1 mol of CH2-0H at 60°C using BF3 as a catalyst: 1 mol of CH2-CH-CH2-0H and C
A water-soluble polymer synthesized from 1 mol of CH=CH2 and 1 mol of CH2-0H at 90°C using Snct4 as a catalyst.
次にめつき条件は次の如くである。Next, the plating conditions are as follows.
これらの実施結果を次表に示す。The results of these implementations are shown in the table below.
Claims (1)
するｐＨ４〜８の錫または錫合金めつき浴に、エポキシ
化合物とエチレングリコール、プロピレングリコールま
たはグリセリンとの重合反応によつて得られる水溶性ポ
リマを添加したクエン酸系光沢錫または錫合金めつき浴
。 ２ エポキシ化合物１モル当りエチレングリコール、プ
ロピレングリコールまたはグリセリンはエポキシ基１個
に対し１モルを６０〜９０℃で触媒の存在下で重合反応
せしめる特許請求の範囲第１項記載のクエン酸系光沢錫
または錫合金めつき浴。 ３ エポキシ化合物として （１）▲数式、化学式、表等があります▼（２）▲数式
、化学式、表等があります▼（３）▲数式、化学式、表
等があります▼（４）▲数式、化学式、表等があります
▼（５）▲数式、化学式、表等があります▼のうちの少
くとも１種類を使用する特許請求の範囲第１〜２項記載
のクエン酸系光沢錫または錫合金めつき浴。 ４ クエン酸またはその塩およびアンモニウム塩を含有
するｐＨ４〜８の錫または錫合金めつき浴に、エポキシ
化合物とエチレングリコール、プロピレングリコールま
たはグリセリンとの重合反応によつて得られる水溶性ポ
リマーと、脂肪族およびまたは芳香族アルデヒドを添加
したクエン酸系光沢錫または錫合金めつき浴。 ５ 脂肪族アルデヒドとしてホルムアルデヒド、アセト
アルデヒド、プロピオンアルデヒド、グリオキサール、
スクシンジアルデヒド、カプロンアルデヒドおよびアル
ドールのうちの少くとも１種類を使用する特許請求の範
囲第４項記載のクエン酸系光沢錫または錫合金めつき浴
。 ６ 芳香族アルデヒドとしてベンズアルデヒド、Ｐ−ト
ルアルデヒド、サリチルアルデヒド、ベラトルアルデヒ
ド、アニスアルデヒド、ピペロナールおよびバニリンの
うちの少くとも１種類を使用する特許請求の範囲第４項
記載のクエン酸系光沢錫または錫合金めつき浴。[Scope of Claims] 1. Obtained by polymerization reaction of an epoxy compound and ethylene glycol, propylene glycol or glycerin in a tin or tin alloy plating bath of pH 4 to 8 containing citric acid or a salt thereof and an ammonium salt. A citric acid-based bright tin or tin alloy plating bath containing a water-soluble polymer. 2. Citric acid-based shiny tin according to claim 1, wherein 1 mole of ethylene glycol, propylene glycol or glycerin per 1 mole of epoxy compound is polymerized for each epoxy group at 60 to 90°C in the presence of a catalyst. Or tin alloy plating bath. 3 As epoxy compounds, (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ (5) ▲ Numerical formulas, chemical formulas, tables, etc. bath. 4. A water-soluble polymer obtained by a polymerization reaction of an epoxy compound with ethylene glycol, propylene glycol or glycerin, and a fat A citric acid-based bright tin or tin alloy plating bath to which group and/or aromatic aldehydes are added. 5 As aliphatic aldehydes, formaldehyde, acetaldehyde, propionaldehyde, glyoxal,
The citric acid-based bright tin or tin alloy plating bath according to claim 4, which uses at least one of succindialdehyde, capronaldehyde and aldol. 6. The citric acid-based shiny tin according to claim 4, wherein at least one of benzaldehyde, P-tolualdehyde, salicylaldehyde, veratraldehyde, anisaldehyde, piperonal, and vanillin is used as the aromatic aldehyde, or Tin alloy plating bath.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13673077A JPS5948874B2 (en) | 1977-11-16 | 1977-11-16 | Citric acid-based bright tin or tin alloy plating bath |
| GB7844297A GB2013241B (en) | 1977-11-16 | 1978-11-13 | Electroplating bath for depositing tin or tin alloy with brightness |
| DE2849502A DE2849502C2 (en) | 1977-11-16 | 1978-11-15 | Bath for the galvanic deposition of semi-glossy to glossy coatings made of tin or a tin alloy |
| US05/960,944 US4168223A (en) | 1977-11-16 | 1978-11-15 | Electroplating bath for depositing tin or tin alloy with brightness |
| FR7832240A FR2409327A1 (en) | 1977-11-16 | 1978-11-15 | ELECTROPLACING BATHS FOR THE GLOSSY DEPOSIT OF TIN OR TIN ALLOYS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13673077A JPS5948874B2 (en) | 1977-11-16 | 1977-11-16 | Citric acid-based bright tin or tin alloy plating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5469533A JPS5469533A (en) | 1979-06-04 |
| JPS5948874B2 true JPS5948874B2 (en) | 1984-11-29 |
Family
ID=15182153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13673077A Expired JPS5948874B2 (en) | 1977-11-16 | 1977-11-16 | Citric acid-based bright tin or tin alloy plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5948874B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62500667A (en) * | 1984-10-11 | 1987-03-19 | リ−ロ−ナル インコ−ポレ−テツド | Plating bath for tin/lead alloy of composite substrate and its plating method |
-
1977
- 1977-11-16 JP JP13673077A patent/JPS5948874B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5469533A (en) | 1979-06-04 |
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