SU452107A3 - Bleaching agent - Google Patents

Description

one

The invention relates to the field of electroplating, in particular to the application of bright copper coatings.

It is known to use selenium organic compounds in organic compounds, for example, thiophenol selenium analogues, as a brightening agent in cyanide electrolytes of copper.

It is proposed to use selenium-containing compounds of the general formula as a gloss-forming additive in acidic electrolytes of copper plating;

Ri (Se) -Rs,

where RI and Na may be the same or different and are phenyl, nitrophenyl, methylphenyl, methoxyphenyl, carboxyphenyl, carbomethoxyphenyl, dimethylamino Coz8 (CH), 8e, Coz8 (CH,), 8e, Coz8 (CH,), i8e, NOz8 (CH,) ,, 8e, KN, Oz5 (CH,) from 5e2M (C, H,), BUT, 5СНз, 8e, CH

7. Na, O8-CH-CHj-CH2 j8e., Fennl, methylmercaptophenyl, aminophenyl, alkyl with 2-8 carbon atoms, benzyl, phenoxyethyl, sulfolanyl, furyl, cyclohexylmethyl, pyridylmethyl, carboxyethyl, dihydroxy5 propyl, sulfoalkyl with 2-6 carbon atoms, sulfophenyl, methoxysulfophenyl, methyl mercaptosulfophenyl, halogensulfophenyl, sulfonaphthyl, disulfonaphthyl, sulphobenzyl, and R2 can also be a 10 guanide group and a sulfonic acid group, n 1-2.

The proposed selenium-containing compounds can also be used in the form of their salts, for example sodium, potassium, ammonium 15 or triethylammonium.

The following selenium-containing compounds are recommended as a brightening agent in acidic electrolytes of copper plating:

-di- (6-sulfohexyl potassium) -delenide

-di- (4-sulfobutyl potassium) -delenide

-di- (3-sulfopropyl potassium) -delenide

-di- (3-sulfopropyl) -dpselenide

-di- (3-sulfopropyl ammonium) -dikelenide

-di- (3-triethylammonium sulfopropyl) -delenide

-di- (3-methyl-3-sulfopropyl sodium) -diselenide 8. NaOjS - CHa - -

9- 1 Se J-t

di- (4-sulfophenyl sodium) -didelenide di- (2-sulfoethyl sodium) -dielenide

, ,

10. KaO.S

Se,

/ SO, Na

eleven.

Se $ 0 ,, M

12. iCHbOnfV- / Se

13.

SNL

$ e,

 UttOiS

5e,

 // / g

15. (-fYY her x /

If.

SObNa

Se,

sixteen.

, NaOt, S

17. / -ае-ССНгН ОьШ

18. -SelCHOb ObK

19. CHb- {Se (CHObeO ,, K

di- (4-sulfophenyl sodium) -delenide

- di- (3-sulfophenyl sodium) -didelenide

- di- (4-methoxy-3-sulfophenyl sodium) -delenide

di- (5-methylmercapto-3-sulfophenyl sodium) -delenide

day- (4-sodium sulfo - 3-chlorophenyl) -diskelenide

- di- {7-sodium sulfonaphthyl-2) -delenide

di- (6.8 - disodiumsulfonaphthyl-2) -delenide

3- (phenylseleno) -propyl sulphate sodium

3 - (p - nitrophenylseleno) - potassium propylsulfonate

3- (p - methylphenylseleno) -propylsulfonate potassium

20. SNOCH - $ e- (

21- HOOC- - $ e (SNG) О ,, ,, Ma

22. / L-CH1-e1SNg)

23. 4 -o JH - lH: i $ ei iH) 0

24. Ng1 chGuye1CH, 1.0,, and

25. SNOOP-4) -Je1SNg)., $ 0,, K

26. iCHb) / -SeiCHjl ObK

27. 4) -SeiCH),

28. 4 -SeCH -CH SObNo

29.

thirty.

Q -CH-i-SeiCH2) SObKa

rSelCHOb O K

31. //

32. (H) -CHr- $ e (CHg) le05 a33

 V

34., S (CH,)

35., S. (CH,), Se

36.IKO, (CH,), lSe

- З- (p-methoxyphenylseleno) - potassium propylsulfonate

3- (p - carboxyphenylseleno) - propylsulfonate sodium

 3- (benzyl seleno) -propyl sulphate sodium

3 - (benzyl seleno) - sodium propyl sulfate

3 - (4 - aminophenylseleno) - propylsulfonate sodium

3 - (p-carbomethoxyphenylseleno) - potassium propylsulfonate.

3- (p - dimethylaminophenylseleno) -propyl sulphate potassium

4- (phenylseleno) -butyl sulphate sodium

2- (Phenylseleno) -ethyl sulphate sodium

- 3 - (sulfolanilidene) -propyl sulphate potassium

- 3 - (furilseleno) - propylsulfonate sodium

3 - (w - methylmercaptophenylseleno) - propyl sulphate sodium

3- (cyclohexylmethyl seleno) - propylsulfonate sodium

3- (3 - pyridylmethyl seleno) -propylsulfonate potassium

bis (4-sulfobutyl sodium) -selenide

bis (3-sulfopropyl sodium) -selenide

bis- (2-sulfoethyl potassium) -selenide

37.С2Н55е (СН,) з80зМа

38.С, Н, 8е {СН,) з80зМа

39.СН „5е (СН,) З80зК

40.HOOS (CH), 8E (CH,), 80ZK

OH 41. HOCHj -CH-CHs-8e (CH3) 58 Hazard -

The proposed compounds are recommended to be added to acid electrolytes of copper in an amount of from 0.0005 to 0.5 g / l, preferably from 0.0005 to 0.1 g / l.

Copper sulfate is usually used as an electrolyte to precipitate a copper coating with the addition of a selenium-containing compound at the following ratios of components, g / l:

Copper sulfate 125-260

Sulfuric acid 20-85.

Instead of copper sulfate, other copper salts may also be used in part. Sulfuric acid can be replaced in part or in whole with borfluoride acid, phosphoric acid or other acids. The electrolyte may also contain chlorides, such as alkali metal chlorides or hydrochloric acid, in an amount of 0.001 to 0.24 l to improve gloss and leveling.

In addition, other known brighteners can be added to the electrolyte. first of all, oxygen-containing high-molecular compounds, which include: polyvinyl alcohol, pe- ri, pep, pec, polyethylene glycol, polypropylene glycol, polyglycol. alkylene with amines, as well as polymers of phenazine compounds, polyalkylenes, polyvinylamines, polyvinylimidazole, polyviiiylpyrrolone, phenene and other dyes and organic thio compounds.

Example 1. The deposition was carried out from the electrolyte s. Leading composition, g / l:

Copper sulfate220

Sulfuric acid (concentrated) 50

Di- (3-sulfopropyl potassium) -delenide 0.05 at a temperature of 25 ° C. current density of 4.0 a / dm and mixing.

Fine crystalline copper deposits with a Vickers hardness of 105 kg / mm and a stress of 80 kg / cm were obtained.

Z- (eth.tseleno) - sodium propyl sulfate

3 - (piopilseleno) - sodium propyl sulfate

S- (octylseleno) -propyl sulphate sodium

3 - (carboxyethyl seleno) - potassium propylsulfonate

Example 2. Copper plating was carried out from the electrolyte following the composition, g / l:

Fluoroborate copper300

Hydrofluoric acid 20 2 - (phenylseleno) -ethylsulfate sodium0.3

at a temperature of 25 ° C, a current density of 8.0 a / dm and stirring of the electrolyte by blowing air.

Fine crystalline precipitates of copper with a Vickers hardness of PO kg / cm and a stress upon stretching of 60 kg / cm were obtained.

Example 3. Copper plating was carried out from the electrolyte composition, g / l:

Copper sulfate200

Sulfuric acid (concentrated) 60 Chloride ions 0.03 DI- (3-sulfopropyl) -di0, 08 selenide

at a temperature of 22 ° C

current

density 4.0 a / dm and mixing.

Meln fine crystalline precipitates were obtained with a Vickers hardness of PO kg / mm and a stress upon stretching of 80 kg / cm.

Example 4. Copper plating was carried out from the electrolyte composition, g / l:

Copper sulfate220

Sulfuric acid (concentrated) 60 Chloride ions 0.05 Di- (3-sulfopropyl ka0 .01 li) -delenide

0.5 Polypropylene glycol at a temperature of 26 ° C,

current density

5.0 a / dm and mixing by blowing air.

Mirror-bright copper sediments with a Vickers hardness of 170 kg / mm yr were obtained by stretching 240 kg / cm.

Example 5. Coppering was carried out from the electrolyte composition, g / l:

Copper sulfate220

Sulfuric acid (concentrated) 60 Chloride ions 0.05 Di- (4-sulfophenyl sodium) -dihelenide 0.03 Nonyl phenol-polyglycol ether 4.0 3- (2,3-dihydroxypropyl seleno) -propyl sulfonic acid