CA2093924C - Acid bath for copper plating - Google Patents
Acid bath for copper plating Download PDFInfo
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- CA2093924C CA2093924C CA002093924A CA2093924A CA2093924C CA 2093924 C CA2093924 C CA 2093924C CA 002093924 A CA002093924 A CA 002093924A CA 2093924 A CA2093924 A CA 2093924A CA 2093924 C CA2093924 C CA 2093924C
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- bath
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- phenazonium
- naphthol
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention concerns an aqueous acid copper-electroplating bath and the use of the bath for the electrolytic deposition of copper.
Description
ACID BATH FOR COPPER PLATING
FIELD OF THE INVENTION
The invention relates to an acid bath for galvanic precipitation of bright and smooth copper coatings and their use.
BACKGROUND OF THE INVENTION
It has long been known that certain organic substances can be added in small quantities to acid, in particular the most widely used sulfuric acid, copper electrolytes in order to obtain bright copper coatings instead of a matte crystalline precipitation. For this purpose, for example, polyethylene glycol, thiourea, gelatins, molasses, instant coffee, "base" dyes and thiophosphoric acid ester have been used. However, such baths no longer have practical importance since the quality of the copper coatings obtained do not meet today's requirements. So these coatings are either too brittle or they are not bright enough or they precipitate in a relief formation in certain current density areas.
The addition of polyalkylimines in connection with organic thio compounds (DE-PS 1246347, February 15, 1968) and polyvinyl compounds in a mixture with oxygen-containing high-molecular compounds and organic, in particular aromatic thio compounds (DE-AS 1521062, November 18, 1971) is known. However, copper electrolytes of this type do not permit the use of high cathodic current densities and the precipitated copper coatings can also only be nickel-coated after a prior intermediate treatment. In the above named DE-AS 1521062, an acid copper bath is also described, which in addition to a polymer oxygen-containing compound with hydrophilic group, contains at least one substituted phenazonium compound dissolved in it. With these monomer phenazonium compounds, there is room for improvement in the current density that can be used and the aging behavior.
In addition, combinations of organic thio compounds and non-ionogenic wetting agents with other dyes, for example crystal violet (EP-PS 71512, June 5, 1985), amidene (DE-PS
2746938, April 9, 1987), phthalocyanine derivatives with aposafranine (DE-PS 3420999, October 15, 1987) are known.
Instead of dyes, undefined conversion products of polyamines with benzylchloride (DE-PS 2541897, January 21, 1982) and/or epichlorhydrine (EP-PS 68807, April 1, 1987) or those with thio compounds and acrylamide (EP-PS 107109, February 24, 1988) are used.
The previously known baths all produce non-uniform deposits; this is particularly true of the combination with thio compounds containing nitrogen.
FIELD OF THE INVENTION
The invention relates to an acid bath for galvanic precipitation of bright and smooth copper coatings and their use.
BACKGROUND OF THE INVENTION
It has long been known that certain organic substances can be added in small quantities to acid, in particular the most widely used sulfuric acid, copper electrolytes in order to obtain bright copper coatings instead of a matte crystalline precipitation. For this purpose, for example, polyethylene glycol, thiourea, gelatins, molasses, instant coffee, "base" dyes and thiophosphoric acid ester have been used. However, such baths no longer have practical importance since the quality of the copper coatings obtained do not meet today's requirements. So these coatings are either too brittle or they are not bright enough or they precipitate in a relief formation in certain current density areas.
The addition of polyalkylimines in connection with organic thio compounds (DE-PS 1246347, February 15, 1968) and polyvinyl compounds in a mixture with oxygen-containing high-molecular compounds and organic, in particular aromatic thio compounds (DE-AS 1521062, November 18, 1971) is known. However, copper electrolytes of this type do not permit the use of high cathodic current densities and the precipitated copper coatings can also only be nickel-coated after a prior intermediate treatment. In the above named DE-AS 1521062, an acid copper bath is also described, which in addition to a polymer oxygen-containing compound with hydrophilic group, contains at least one substituted phenazonium compound dissolved in it. With these monomer phenazonium compounds, there is room for improvement in the current density that can be used and the aging behavior.
In addition, combinations of organic thio compounds and non-ionogenic wetting agents with other dyes, for example crystal violet (EP-PS 71512, June 5, 1985), amidene (DE-PS
2746938, April 9, 1987), phthalocyanine derivatives with aposafranine (DE-PS 3420999, October 15, 1987) are known.
Instead of dyes, undefined conversion products of polyamines with benzylchloride (DE-PS 2541897, January 21, 1982) and/or epichlorhydrine (EP-PS 68807, April 1, 1987) or those with thio compounds and acrylamide (EP-PS 107109, February 24, 1988) are used.
The previously known baths all produce non-uniform deposits; this is particularly true of the combination with thio compounds containing nitrogen.
Baths that contain polymer phenazonium compounds (DE-PS 2,039,831, January 5, 1972) resulted in progress; these are mainly used in combination with non-ionogenic wetting agents and organic sulfur compounds.
In fact, it is the state of the art to add non-ionogenic wetting agents to the acid copper baths, however this did not eliminate the fine roughness.
The use of ~-naphthol-polyglycolether as an addition to a copper bath will be disclosed in DE-OS 37 21 985 (January 12, 1989) (Example 2) and GB-A-2075063 (November 11, 1981), but not in combination with polymer phenazonium compounds.
DE-PS 3104108 (February 5, 1987) describes a fluoroborate bath that contains ~-naphtholethoxylate in combination with a phthalocyanine dye. The electrolyte itself shows only a moderate smoothing in comparison to polymer phenazonium compounds. With high smoothing, the disadvantage of these baths is a fine roughness (pitting, nodules) on the coating, which seriously impairs the decorative appearance, particularly of large-surface parts.
This roughness does not result from floating particles in the electrolyte, rather it is a result of a defective precipitation in the cathodic double layer. This occurs especially with nitrogen-containing sulfur compounds (so-3a called thiourea derivatives) and with phenazonium compounds.
The task of this invention is to prevent the disadvantages described and additionally not to impair the advantageous smoothing.
SiJMMARY OF THE INVENTION
According to one aspect, the invention an aqueous acid bath for galvanic deposition of bright and smooth copper coatings, said bath comprising: a (3-naphtholalkoxylate of the formula I
~0(CHZCH20)n(CH-CH20)m-H I
in which n = 0 to 50 and m = 0 to 50, wherein n + m > 3;
at least one nitrogen-containing thio compound selected from the group consisting of thiourea, thiourea derivatives, or heterocyclic compounds containing S and N;
and a polymer phenazonium compound.
In another aspect, the invention provides a process for galvanic deposition of bright and smooth copper coatings comprising the steps of: a) providing an electrolyte bath comprising an aqueous acid bath as described herein; and b) applying a cathodic current density of from about 0.5 to about 12 A/dm2.
In fact, it is the state of the art to add non-ionogenic wetting agents to the acid copper baths, however this did not eliminate the fine roughness.
The use of ~-naphthol-polyglycolether as an addition to a copper bath will be disclosed in DE-OS 37 21 985 (January 12, 1989) (Example 2) and GB-A-2075063 (November 11, 1981), but not in combination with polymer phenazonium compounds.
DE-PS 3104108 (February 5, 1987) describes a fluoroborate bath that contains ~-naphtholethoxylate in combination with a phthalocyanine dye. The electrolyte itself shows only a moderate smoothing in comparison to polymer phenazonium compounds. With high smoothing, the disadvantage of these baths is a fine roughness (pitting, nodules) on the coating, which seriously impairs the decorative appearance, particularly of large-surface parts.
This roughness does not result from floating particles in the electrolyte, rather it is a result of a defective precipitation in the cathodic double layer. This occurs especially with nitrogen-containing sulfur compounds (so-3a called thiourea derivatives) and with phenazonium compounds.
The task of this invention is to prevent the disadvantages described and additionally not to impair the advantageous smoothing.
SiJMMARY OF THE INVENTION
According to one aspect, the invention an aqueous acid bath for galvanic deposition of bright and smooth copper coatings, said bath comprising: a (3-naphtholalkoxylate of the formula I
~0(CHZCH20)n(CH-CH20)m-H I
in which n = 0 to 50 and m = 0 to 50, wherein n + m > 3;
at least one nitrogen-containing thio compound selected from the group consisting of thiourea, thiourea derivatives, or heterocyclic compounds containing S and N;
and a polymer phenazonium compound.
In another aspect, the invention provides a process for galvanic deposition of bright and smooth copper coatings comprising the steps of: a) providing an electrolyte bath comprising an aqueous acid bath as described herein; and b) applying a cathodic current density of from about 0.5 to about 12 A/dm2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Compounds of Table 1 ~-Naphthol-tetracosa (ethoxylate) n = m =
24; 0 ~-Naphthol-eicosa (ethoxylate) n = m =
20; 0 ~-Naphthol-octadeca (ethoxylate) n = m =
18; 0 ~-Naphthol-hexadeca (ethoxylate) n = m =
16; 0 ~-Naphthol-tetradeca (ethoxylate) n = m =
14; 0 Q-Naphthol-trideca (ethoxylate) n = m =
13; 0 Q-Naphthol-dodeca (ethoxylate) n = m =
12; 0 ~-Naphthol-deca (ethoxylate) n = m =
10; 0 ~-Naphthol-octa (ethoxylate) n = 8; m 0 =
~-Naphthol-hexa (ethoxylate) n = 6; m 0 =
b-Naphthol-tetracosa (propoxylate) n = 0; m 24 =
~-Naphthol-tetracosa (ethoxy) n = 24; m =
-mono (propoxylate)*) B-Naphthol-octadeca (ethoxy)- n = 20; m =
di(proproxylate)*) ~-Naphthol-mono (propoxy)- n = 24; m =
tetracosa (ethoxylate)*) ~-Naphthol-di (propoxy)- n = 20; m =
octadeca (ethoxylate)*) +) mixed or block polymeride are particularly suited as B-naphtolalkoxylate of the general formula I.
Thiourea and thiourea derivatives and heterocyclic compounds containing S and N are used as nitrogen containing thiocompounds.
Table 2 contains examples of nitrogen-containing thio compounds (so-called thiourea derivatives) or heterocyclic compounds containing S and N and Table 3 of polymer phenazonium compounds.
~~~3~~~
Table 2 Thiourea N-Acetylthiourea 5 N-Trifluorocetylthiourea N-Ethylthiourea N-Cyanoacetylthiourea N-Allylthiourea 0-Tolylthiourea N,N'-Butylenethiourea Thiazolidinethiol (2) ~-Thiazolinethiol (2) Imidazolidinethiol (2) (N, N'-Ethylenethiourea) 4-Methyl-2-pyrimidinethiol 2-Thiouracil Table 3 Poly(6-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate) Poly(2-methyl-7-diethylamino-5-phenyl-phenazonium chloride) Poly(2-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate) Poly(5-methyl-7-dimethylamino-phenazonium acetate) Poly(2-methyl-7-anilino-5-phenyl-phenazonium sulfate) Poly(2-methyl-7-dimethylamino-phenazonium sulfate) Poly(7-methylamino-5-phenyl-phenazonium acetate) Poly(7-ethylamino-2, S-diphenyl-phenazonium chloride) Poly(2,8-dimethyl-7-diethylamino-5-p-tolyl-phenazonium chloride) Poly(2,5,8-triphenyl-7-dimethylamino-phenazonium sulfate) Poly(2,8-dimethyl-7-amino-5-phenyl-phenazonium sulfate) Poly(7-Dimethylamino-5-phenyl-phenazonium chloride) For the solutions according to the invention, mixtures of the compounds listed in Tables 1, 2 and 3 are used.
The preferred quantity of the ~-naphtholethoxylate that must be added in order to achieve a clear improvement in copper precipitation is about 0.005 to 3 g/liter, preferably 0.01 to 0.25 g/liter.
The ~-naphtholoethoxylates are known or can be produced using methods known in and of themselves from ~-naphthol with ethylene oxide and/or propylene oxide.
The individual components of the copper bath according to the invention can generally contain the following, advantageously within the following limit concentrations in the ready-to-use bath:
l0 Standard oxygen-containing high-molecular weight compounds (referred to herein as oxygen-containing high-molecular compounds) 0.005 - 20 g/liter preferably 0.01 - 5 g/liter Standard organic thio compounds with hydrophilic 2o groups 0.0005 - 0.2 g/liter preferably 0.001 - 0.03 g/1 Standard nitrogen-containing thio compounds (so-called thiourea derivatives) and/or polymer phenazonium compounds 0.0001 - 0.50 g/liter preferably 0.0005 - 0.04 g/liter The basic composition of the bath according to the invention can vary within wide limits. In general, an aqueous solution of the following composition is used:
Compounds of Table 1 ~-Naphthol-tetracosa (ethoxylate) n = m =
24; 0 ~-Naphthol-eicosa (ethoxylate) n = m =
20; 0 ~-Naphthol-octadeca (ethoxylate) n = m =
18; 0 ~-Naphthol-hexadeca (ethoxylate) n = m =
16; 0 ~-Naphthol-tetradeca (ethoxylate) n = m =
14; 0 Q-Naphthol-trideca (ethoxylate) n = m =
13; 0 Q-Naphthol-dodeca (ethoxylate) n = m =
12; 0 ~-Naphthol-deca (ethoxylate) n = m =
10; 0 ~-Naphthol-octa (ethoxylate) n = 8; m 0 =
~-Naphthol-hexa (ethoxylate) n = 6; m 0 =
b-Naphthol-tetracosa (propoxylate) n = 0; m 24 =
~-Naphthol-tetracosa (ethoxy) n = 24; m =
-mono (propoxylate)*) B-Naphthol-octadeca (ethoxy)- n = 20; m =
di(proproxylate)*) ~-Naphthol-mono (propoxy)- n = 24; m =
tetracosa (ethoxylate)*) ~-Naphthol-di (propoxy)- n = 20; m =
octadeca (ethoxylate)*) +) mixed or block polymeride are particularly suited as B-naphtolalkoxylate of the general formula I.
Thiourea and thiourea derivatives and heterocyclic compounds containing S and N are used as nitrogen containing thiocompounds.
Table 2 contains examples of nitrogen-containing thio compounds (so-called thiourea derivatives) or heterocyclic compounds containing S and N and Table 3 of polymer phenazonium compounds.
~~~3~~~
Table 2 Thiourea N-Acetylthiourea 5 N-Trifluorocetylthiourea N-Ethylthiourea N-Cyanoacetylthiourea N-Allylthiourea 0-Tolylthiourea N,N'-Butylenethiourea Thiazolidinethiol (2) ~-Thiazolinethiol (2) Imidazolidinethiol (2) (N, N'-Ethylenethiourea) 4-Methyl-2-pyrimidinethiol 2-Thiouracil Table 3 Poly(6-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate) Poly(2-methyl-7-diethylamino-5-phenyl-phenazonium chloride) Poly(2-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate) Poly(5-methyl-7-dimethylamino-phenazonium acetate) Poly(2-methyl-7-anilino-5-phenyl-phenazonium sulfate) Poly(2-methyl-7-dimethylamino-phenazonium sulfate) Poly(7-methylamino-5-phenyl-phenazonium acetate) Poly(7-ethylamino-2, S-diphenyl-phenazonium chloride) Poly(2,8-dimethyl-7-diethylamino-5-p-tolyl-phenazonium chloride) Poly(2,5,8-triphenyl-7-dimethylamino-phenazonium sulfate) Poly(2,8-dimethyl-7-amino-5-phenyl-phenazonium sulfate) Poly(7-Dimethylamino-5-phenyl-phenazonium chloride) For the solutions according to the invention, mixtures of the compounds listed in Tables 1, 2 and 3 are used.
The preferred quantity of the ~-naphtholethoxylate that must be added in order to achieve a clear improvement in copper precipitation is about 0.005 to 3 g/liter, preferably 0.01 to 0.25 g/liter.
The ~-naphtholoethoxylates are known or can be produced using methods known in and of themselves from ~-naphthol with ethylene oxide and/or propylene oxide.
The individual components of the copper bath according to the invention can generally contain the following, advantageously within the following limit concentrations in the ready-to-use bath:
l0 Standard oxygen-containing high-molecular weight compounds (referred to herein as oxygen-containing high-molecular compounds) 0.005 - 20 g/liter preferably 0.01 - 5 g/liter Standard organic thio compounds with hydrophilic 2o groups 0.0005 - 0.2 g/liter preferably 0.001 - 0.03 g/1 Standard nitrogen-containing thio compounds (so-called thiourea derivatives) and/or polymer phenazonium compounds 0.0001 - 0.50 g/liter preferably 0.0005 - 0.04 g/liter The basic composition of the bath according to the invention can vary within wide limits. In general, an aqueous solution of the following composition is used:
Copper sulfate (CuS04 5H20) 20 - 250 g/liter preferably 60 - 80 g/liter or 180 - 220 g/liter Sulfuric acid 50 - 350 g/liter preferably 180 - 220 g/liter ox 50 - 90 g/liter Sodium chloride 0.02 - 0.25 g/liter preferably 0.05 - 0.12 g/liter Instead of copper sulfate, other copper salts can also be used, at least in part. Sulfuric acid can also be partially or completely replaced by fluoroboric acid, methane sulfonic acid or other acids. The addition of sodium chloride can be omitted partially or entirely if halogen ions are already contained in the additives.
In addition, standard brighteners, smoothing agents or wetting agents can also be contained in the bath.
To produce the bath according to the invention, the individual components are added to the basic composition.
The operating conditions of the bath are as follows:
pH value:
< 1 Temperature: ' 15°C - 45°C, preferably 20°C - 30°C
Cathodic current density: 0.5 - 12 A/dm2, preferably 2-4 A/dm2 The electrolyte motion is caused by blowing in air.
Copper with a 0.02 to 0.067% phosphorous content is used as the anode.
In addition, standard brighteners, smoothing agents or wetting agents can also be contained in the bath.
To produce the bath according to the invention, the individual components are added to the basic composition.
The operating conditions of the bath are as follows:
pH value:
< 1 Temperature: ' 15°C - 45°C, preferably 20°C - 30°C
Cathodic current density: 0.5 - 12 A/dm2, preferably 2-4 A/dm2 The electrolyte motion is caused by blowing in air.
Copper with a 0.02 to 0.067% phosphorous content is used as the anode.
The invention also includes processes using the baths according to the invention.
The following examples are used to explain the invention:
0.2 g/liter polyethylene glycol and 0.01 g/liter bis-(w-sulfopropyl)-disulfide, disodium salt as a brightening agent and 0.02 g/liter polymer 7-dimethylamino-5-phenyl-phenazonium chloride are added to a copper bath of the composition 200.0 g/liter copper sulfate (CuS04 ~ 5Hz0) 65.0 g/liter sulfuric acid 0.2 g/liter sodium chloride.
At an electrolyte temperature of 27°C, with a current density of 4 A/dmz and air blown in, a well smoothed, bright copper coating is obtained that shows fine roughness (pitting) on polished brass sheet metal when closely examined.
If 0.025 g/liter of f3-naphtolalkoxylate of the general formula I with n = 12 and m = 0 is also added to the bath, the plating has a mirror finish and is well smoothed. No voids can be found.
2~~3~~4 0.6 g/liter polyethylene glycol and 0.02 g/liter 3-mercaptopropane-1-sulfonic acid, sodium salt as a brightener and 0.003 g/liter N-acetylthiourea are added to a copper bath of the composition 80.0 g/liter copper sulfate (CuS04 ~ 5H20) 180.0 g/liter conc. sulfuric acid 0.08 g/liter sodium chloride.
At an electrolyte temperature of 30°C, with a current density of 2 A/dm2, a bright copper coating is obtained on scratched copper laminate, on which fine roughness (pitting) is visible.
If 0.05 g/liter of the substance according to the invention of the general formula I with n = 24 and m = 0 is also added to the bath, the copper costing is bright and contains no faults.
The following examples are used to explain the invention:
0.2 g/liter polyethylene glycol and 0.01 g/liter bis-(w-sulfopropyl)-disulfide, disodium salt as a brightening agent and 0.02 g/liter polymer 7-dimethylamino-5-phenyl-phenazonium chloride are added to a copper bath of the composition 200.0 g/liter copper sulfate (CuS04 ~ 5Hz0) 65.0 g/liter sulfuric acid 0.2 g/liter sodium chloride.
At an electrolyte temperature of 27°C, with a current density of 4 A/dmz and air blown in, a well smoothed, bright copper coating is obtained that shows fine roughness (pitting) on polished brass sheet metal when closely examined.
If 0.025 g/liter of f3-naphtolalkoxylate of the general formula I with n = 12 and m = 0 is also added to the bath, the plating has a mirror finish and is well smoothed. No voids can be found.
2~~3~~4 0.6 g/liter polyethylene glycol and 0.02 g/liter 3-mercaptopropane-1-sulfonic acid, sodium salt as a brightener and 0.003 g/liter N-acetylthiourea are added to a copper bath of the composition 80.0 g/liter copper sulfate (CuS04 ~ 5H20) 180.0 g/liter conc. sulfuric acid 0.08 g/liter sodium chloride.
At an electrolyte temperature of 30°C, with a current density of 2 A/dm2, a bright copper coating is obtained on scratched copper laminate, on which fine roughness (pitting) is visible.
If 0.05 g/liter of the substance according to the invention of the general formula I with n = 24 and m = 0 is also added to the bath, the copper costing is bright and contains no faults.
Claims (33)
1. An aqueous acid bath for galvanic deposition of bright and smooth copper coatings, said bath comprising:
a .beta.-naphtholalkoxylate of the formula I
in which n = 0 to 50 and m = 0 to 50, wherein n + m > 3;
at least one nitrogen-containing thio compound selected from the group consisting of thiourea, thiourea derivatives, and heterocyclic compounds containing S and N;
and a polymer phenazonium compound.
a .beta.-naphtholalkoxylate of the formula I
in which n = 0 to 50 and m = 0 to 50, wherein n + m > 3;
at least one nitrogen-containing thio compound selected from the group consisting of thiourea, thiourea derivatives, and heterocyclic compounds containing S and N;
and a polymer phenazonium compound.
2. The bath according to claim 1, wherein the nitrogen-containing thio compound is selected from the group consisting of:
N-Acetylthiourea;
N-Trifluoroacetylthiourea;
N-Ethylthiourea;
N-Cyanoacetylthiourea;
N-Allylthiourea;
O-Tolylthiourea;
N,N'-Butylenethiourea;
Thiazolidinethiol (2);
4-Thiazolinethiol (2);
Imidazolidinethiol (2) (N, N'-Ethylenethiourea);
4-Methyl-2-pyrimidinethiol;
2-Thiouracil; and mixtures thereof.
N-Acetylthiourea;
N-Trifluoroacetylthiourea;
N-Ethylthiourea;
N-Cyanoacetylthiourea;
N-Allylthiourea;
O-Tolylthiourea;
N,N'-Butylenethiourea;
Thiazolidinethiol (2);
4-Thiazolinethiol (2);
Imidazolidinethiol (2) (N, N'-Ethylenethiourea);
4-Methyl-2-pyrimidinethiol;
2-Thiouracil; and mixtures thereof.
3. The bath according to claim 1 or 2, wherein the nitrogen-containing thio compound is present in a concentration of 0.0001 to 0.5 g/liter.
4. The bath according to claim 1, 2, or 3, further comprising an organic nitrogen-free thio compound.
5. The bath according to claim 4, wherein the organic nitrogen-free thio compound has water-soluble hydrophilic groups.
6. The bath according to claim 4 or 5, wherein the organic nitrogen-free thio compound is selected from the group consisting of:
3-Mercaptopropane-1-sulfonic acid, sodium salt;
Thiophosphoric acid-O-ethyl-bis-(w-sulfopropyl)-ester, disodium salt;
Thiophosphoric acid-tris-(w-sulfopropyl)-ester, trisodium salt;
Ethylenedithio-dipropylsulfonic acid, sodium salt;
Di-n-propylthioether-di-w-sulfonic acid, disodium salt;
Bis-(w-sulfopropyl)disulfide, disodium salt;
Bis-(w-sulfohydroxypropyl)disulfide, disodium salt;
Bis-(w-sulfobutyl)disulfide, disodium salt;
Methyl-(w-sulfopropyl)disulfide, sodium salt;
Methyl-(w-sulfobutyl)trisulfide, sodium salt; and mixtures thereof.
3-Mercaptopropane-1-sulfonic acid, sodium salt;
Thiophosphoric acid-O-ethyl-bis-(w-sulfopropyl)-ester, disodium salt;
Thiophosphoric acid-tris-(w-sulfopropyl)-ester, trisodium salt;
Ethylenedithio-dipropylsulfonic acid, sodium salt;
Di-n-propylthioether-di-w-sulfonic acid, disodium salt;
Bis-(w-sulfopropyl)disulfide, disodium salt;
Bis-(w-sulfohydroxypropyl)disulfide, disodium salt;
Bis-(w-sulfobutyl)disulfide, disodium salt;
Methyl-(w-sulfopropyl)disulfide, sodium salt;
Methyl-(w-sulfobutyl)trisulfide, sodium salt; and mixtures thereof.
7. The bath according to claim 4, 5, or 6, wherein the organic nitrogen-free thio compound is present in a concentration from 0.0005 to 0.2 g/liter.
8. The bath according to any one of claims 1 to 7, further comprising an oxygen-containing high-molecular compound.
9. The bath according to claim 8, wherein the oxygen-containing high-molecular compound is selected from the group consisting of:
Polyvinylalcohol;
Carboxymethylcellulose;
Polyethyleneglycol;
Polypropyleneglycol;
Stearic acid-polyglycolester;
Oleic acid-polyglycolester;
Stearic acid-polyglycolester;
Oleic acid-polyglycolester;
Stearylalcohol-polyglycolether;
Nonylphenyol-polyglycolether;
Octonalpolyalkylene-glycolether;
Octandiol-bis(polyalkyleneglycolether);
Polyoxypropyleneglycol;
Polyethylene-propyleneglycol; and mixtures thereof.
Polyvinylalcohol;
Carboxymethylcellulose;
Polyethyleneglycol;
Polypropyleneglycol;
Stearic acid-polyglycolester;
Oleic acid-polyglycolester;
Stearic acid-polyglycolester;
Oleic acid-polyglycolester;
Stearylalcohol-polyglycolether;
Nonylphenyol-polyglycolether;
Octonalpolyalkylene-glycolether;
Octandiol-bis(polyalkyleneglycolether);
Polyoxypropyleneglycol;
Polyethylene-propyleneglycol; and mixtures thereof.
10. The bath according to claim 8 or 9, wherein the oxygen-containing high-molecular compound is present in a concentration from 0.005 to 20 g/litre.
11. The bath according to claim 8 or 9, wherein the oxygen-containing high-molecular compound is present in a concentration from 0.05 to 5 g/liter.
12. An aqueous acid bath for galvanic deposition of bright and smooth copper coatings, said bath comprising:
a) a .beta.-naphtholalkoxylate of the formula I
wherein n = 0 to 50, m = 0 to 50, and n + m = > 3;
b) at least one polymer phenazonium compound;
c) copper sulfate;
d) one or more of an organic nitrogen-free thio compound;
and e) at least one oxygen-containing high-molecular compound present in a concentration from 0.005 to 20 g/liter.
a) a .beta.-naphtholalkoxylate of the formula I
wherein n = 0 to 50, m = 0 to 50, and n + m = > 3;
b) at least one polymer phenazonium compound;
c) copper sulfate;
d) one or more of an organic nitrogen-free thio compound;
and e) at least one oxygen-containing high-molecular compound present in a concentration from 0.005 to 20 g/liter.
13. The bath according to claim 12, wherein the organic nitrogen-free thio compound has water-soluble hydrophilic groups.
14. The bath according to claim 12 or 13, wherein the organic nitrogen-free thio compound is selected from the group consisting of:
3-Mercaptopropane-1-sulfonic acid, sodium salt;
Thiophosphoric acid-O-ethyl-bis-(w-sulfopropyl)-ester, disodium salt;
Thiophosphoric acid-tris-(w-sulfopropyl)-ester, trisodium salt;
Ethylenedithio-dipropylsulfonic acid, sodium salt;
Di-n-propylthioether-di-w-sulfonic acid, disodium salt;
Bis-(w-sulfopropyl)disulfide, disodium salt;
Bis(w-sulfohydroxypropyl)disulfide, disodium salt;
Bis(w-sulfobutyl)disulfide, disodium salt;
Methyl-(w-sulfopropyl)disulfide, sodium salt;
Methyl-(w-sulfobutyl)trisulfide, sodium salt; and mixtures thereof.
3-Mercaptopropane-1-sulfonic acid, sodium salt;
Thiophosphoric acid-O-ethyl-bis-(w-sulfopropyl)-ester, disodium salt;
Thiophosphoric acid-tris-(w-sulfopropyl)-ester, trisodium salt;
Ethylenedithio-dipropylsulfonic acid, sodium salt;
Di-n-propylthioether-di-w-sulfonic acid, disodium salt;
Bis-(w-sulfopropyl)disulfide, disodium salt;
Bis(w-sulfohydroxypropyl)disulfide, disodium salt;
Bis(w-sulfobutyl)disulfide, disodium salt;
Methyl-(w-sulfopropyl)disulfide, sodium salt;
Methyl-(w-sulfobutyl)trisulfide, sodium salt; and mixtures thereof.
15. The bath according to claim 12, 13, or 14, wherein the organic nitrogen-free thio compound is present in a concentration from 0.0005 to 0.2 g/liter.
16. The bath according to any one of claims 12 to 15, wherein the oxygen-containing high-molecular compound is selected from the group consisting of:
Polyvinylalcohol;
Carboxymethylcellulose;
Polyethyleneglycol;
Polypropyleneglycol;
Stearic acid-polyglycolester;
Oleic acid-polyglycolester;
Stearic acid-polyglycolester;
Oleic acid-polyglycolester;
Stearylalcohol-polyglycolether;
Nonylphenyol-polyglycolether;
Octonalpolyalkylene-glycolether;
Octandiol-bis (polyalkyleneglycolether);
Polyoxypropyleneglycol;
Polyethylene-propyleneglycol; and mixtures thereof.
Polyvinylalcohol;
Carboxymethylcellulose;
Polyethyleneglycol;
Polypropyleneglycol;
Stearic acid-polyglycolester;
Oleic acid-polyglycolester;
Stearic acid-polyglycolester;
Oleic acid-polyglycolester;
Stearylalcohol-polyglycolether;
Nonylphenyol-polyglycolether;
Octonalpolyalkylene-glycolether;
Octandiol-bis (polyalkyleneglycolether);
Polyoxypropyleneglycol;
Polyethylene-propyleneglycol; and mixtures thereof.
17. The bath according to any one of claims 12 to 16, wherein the oxygen-containing high-molecular compound is present in a concentration from 0.01 to 5 g/liter.
18. The bath according to any one of claims 12 to 16, wherein the oxygen-containing high-molecular compound is present in a concentration from 0.05 to 5 g/liter.
19. The bath according to any one of claims 12 to 18, further comprising at least one nitrogen-containing thio compound selected from the group consisting of thiourea, thiourea derivatives, and heterocyclic compounds containing S and N.
20. The bath according to claim 19, wherein the nitrogen-containing thio compound is selected from the group consisting of:
N-Acetylthiourea;
N-Trifluoroacetylthiourea;
N-Ethylthiourea;
N-Cyanoacetylthiourea;
N-Allylthiourea;
O-Tolylthiourea;
N,N'-Butylenethiourea;
Thiazolidinethiol (2);
4-Thiazolinethiol (2);
Imidazolidinethiol (2) (N, N'-Ethylenethiourea);
4-Methyl-2-pyrimidinethiol;
2-Thiouracil; and mixtures thereof.
N-Acetylthiourea;
N-Trifluoroacetylthiourea;
N-Ethylthiourea;
N-Cyanoacetylthiourea;
N-Allylthiourea;
O-Tolylthiourea;
N,N'-Butylenethiourea;
Thiazolidinethiol (2);
4-Thiazolinethiol (2);
Imidazolidinethiol (2) (N, N'-Ethylenethiourea);
4-Methyl-2-pyrimidinethiol;
2-Thiouracil; and mixtures thereof.
21. The bath according to claim 19 or 20, wherein the nitrogen-containing thio compound is present in a concentration of 0.0001 to 0.5 g/liter.
22. The bath according to any one of claims 1 to 21, wherein the .beta.-naphtholalkoxylate is selected from the group consisting of:
.beta.-Naphthol-tetracosa(ethoxylate);
.beta.-Naphthol-eicosa(ethoxylate);
.beta.-Naphthol-octadeca(ethoxylate);
.beta.-Naphthol-hexadeca(ethoxylate);
.beta.-Naphthol-tetradeca(ethoxylate);
.beta.-Naphthol-trideca(ethoxylate);
.beta.-Naphthol-dodeca(ethoxylate);
.beta.-Naphthol-deca(ethoxylate);
.beta.-Naphthol-octa(ethoxylate);
.beta.-Naphthol-hexa(ethoxylate);
.beta.-Naphthol-tetracosa(propoxylate);
.beta.-Naphthol-tetracosa(ethoxy)-mono(propoxylate);
.beta.-Naphthol-octadeca(ethoxy)-di(propoxylate);
.beta.-Naphthol-mono(propoxy)-tetracosa(ethoxylate);
.beta.-Naphthol-di(propoxy)-octadeca(ethoxylate); and mixtures thereof.
.beta.-Naphthol-tetracosa(ethoxylate);
.beta.-Naphthol-eicosa(ethoxylate);
.beta.-Naphthol-octadeca(ethoxylate);
.beta.-Naphthol-hexadeca(ethoxylate);
.beta.-Naphthol-tetradeca(ethoxylate);
.beta.-Naphthol-trideca(ethoxylate);
.beta.-Naphthol-dodeca(ethoxylate);
.beta.-Naphthol-deca(ethoxylate);
.beta.-Naphthol-octa(ethoxylate);
.beta.-Naphthol-hexa(ethoxylate);
.beta.-Naphthol-tetracosa(propoxylate);
.beta.-Naphthol-tetracosa(ethoxy)-mono(propoxylate);
.beta.-Naphthol-octadeca(ethoxy)-di(propoxylate);
.beta.-Naphthol-mono(propoxy)-tetracosa(ethoxylate);
.beta.-Naphthol-di(propoxy)-octadeca(ethoxylate); and mixtures thereof.
23. The bath according to any one of claims 1 to 22, wherein the .beta.-naphtolalkoxylate is present in a concentration from 0.005 to 3 g/liter.
24. The bath according to any one of claims 1 to 23, wherein the polymer phenazonium compound is selected from the group consisting of:
Poly(6-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate);
Poly(2-methyl-7-diethylamino-5-phenyl-phenazonium chloride);
Poly(2-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate);
Poly(5-methyl-7-dimethylamino-phenazonium acetate);
Poly(2-methyl-7-anilino-5-phenyl-phenazonium sulfate);
Poly(2-methyl-7-dimethylamino-phenazonium sulfate);
Poly(7-methylamino-5-phenyl-phenazonium acetate);
Poly(7-ethylamino-2, 5-diphenyl-phenazonium chloride);
Poly(2,8-dimethyl-7-diethylamino-5-p-tolyl-phenazonium chloride);
Poly(2,5,8-triphenyl-7-dimethylamino-phenazonium sulfate);
Poly(2,8-dimethyl-7-amino-5-phenyl-phenazonium sulfate);
Poly(7-Dimethylamino-5-phenyl-phenazonium chloride); and mixtures thereof.
Poly(6-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate);
Poly(2-methyl-7-diethylamino-5-phenyl-phenazonium chloride);
Poly(2-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate);
Poly(5-methyl-7-dimethylamino-phenazonium acetate);
Poly(2-methyl-7-anilino-5-phenyl-phenazonium sulfate);
Poly(2-methyl-7-dimethylamino-phenazonium sulfate);
Poly(7-methylamino-5-phenyl-phenazonium acetate);
Poly(7-ethylamino-2, 5-diphenyl-phenazonium chloride);
Poly(2,8-dimethyl-7-diethylamino-5-p-tolyl-phenazonium chloride);
Poly(2,5,8-triphenyl-7-dimethylamino-phenazonium sulfate);
Poly(2,8-dimethyl-7-amino-5-phenyl-phenazonium sulfate);
Poly(7-Dimethylamino-5-phenyl-phenazonium chloride); and mixtures thereof.
25. The bath according to any one of claims 1 to 24, wherein the polymer phenazonium compound is present in a concentration from 0.0001 to 0.5 g/liter.
26. The bath according to any one of claims 1 to 11, further comprising copper sulfate.
27. An aqueous acid bath for galvanic deposition of bright, and smooth copper coatings which avoids fine pitting comprising:
a) a .beta.-naphtholalkoxylate of the formula I
wherein n = 0 to 50, m = 0 to 50, and n + m > 3 b) at least one polymer phenazonium compound;
c) copper sulfate;
d) one or more of an organic nitrogen-free thio compound;
and e) polyethylene glycol present in a concentration from 0.05 to 5 g/liter.
a) a .beta.-naphtholalkoxylate of the formula I
wherein n = 0 to 50, m = 0 to 50, and n + m > 3 b) at least one polymer phenazonium compound;
c) copper sulfate;
d) one or more of an organic nitrogen-free thio compound;
and e) polyethylene glycol present in a concentration from 0.05 to 5 g/liter.
28. A process for galvanic deposition of bright and smooth copper coatings comprising the steps of:
a) providing an electrolyte bath comprising an aqueous acid bath according to any one of claims 1 to 27; and b) applying a cathodic current density of from 0.5 to 12 A/dm2.
a) providing an electrolyte bath comprising an aqueous acid bath according to any one of claims 1 to 27; and b) applying a cathodic current density of from 0.5 to 12 A/dm2.
29. The process of claim 28, further including the step of agitating the electrolyte bath.
30. The process of claim 29, wherein the step of agitating said electrolyte bath further includes the step of administering a current of air in the bath.
31. The process of claim 28, 29 or 30, wherein the cathodic current applied in step (b) is from 2 to 4 A/dm2.
32. The process according to any one of claims 28 to 31, further including the step of maintaining said electrolyte bath at a temperature of from 15°C to 45°C.
33. A process for galvanic deposition of bright and smooth copper coatings which avoids fine pitting, comprising the steps of:
a) providing an electrolyte bath comprising an aqueous acid bath according to any one of claims 1 to 27;
b) applying a cathodic current density of from 0.5 to 12 A/dm2 ;
c) maintaining a temperature of the bath of from 15°C to 45°C; and d) maintaining the pH of the bath at a value of 1 or less.
a) providing an electrolyte bath comprising an aqueous acid bath according to any one of claims 1 to 27;
b) applying a cathodic current density of from 0.5 to 12 A/dm2 ;
c) maintaining a temperature of the bath of from 15°C to 45°C; and d) maintaining the pH of the bath at a value of 1 or less.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4032864.3 | 1990-10-13 | ||
| DE4032864A DE4032864A1 (en) | 1990-10-13 | 1990-10-13 | ACIDIC BATH FOR THE GALVANIC DEPOSITION OF COPPER COVERS AND METHODS USING THIS COMBINATION |
| PCT/DE1991/000811 WO1992007116A1 (en) | 1990-10-13 | 1991-10-11 | Acid bath for copper plating, and a process using a bath of this type for this purpose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2093924A1 CA2093924A1 (en) | 1992-04-14 |
| CA2093924C true CA2093924C (en) | 2002-02-05 |
Family
ID=6416407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002093924A Expired - Lifetime CA2093924C (en) | 1990-10-13 | 1991-10-11 | Acid bath for copper plating |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0554275B1 (en) |
| JP (1) | JPH06501986A (en) |
| AT (1) | ATE115651T1 (en) |
| CA (1) | CA2093924C (en) |
| DE (2) | DE4032864A1 (en) |
| ES (1) | ES2066477T3 (en) |
| WO (1) | WO1992007116A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10261852B3 (en) * | 2002-12-20 | 2004-06-03 | Atotech Deutschland Gmbh | Mixture of di-, tri- and other oligomeric phenazinium compounds, used in copper electroplating bath for decorative plating or plating circuit board or semiconductor substrate, is prepared from monomer by diazotization and boiling |
| DE10337669B4 (en) * | 2003-08-08 | 2006-04-27 | Atotech Deutschland Gmbh | Aqueous, acid solution and process for the electrodeposition of copper coatings and use of the solution |
| DE102004041701A1 (en) * | 2004-08-28 | 2006-03-02 | Enthone Inc., West Haven | Process for the electrolytic deposition of metals |
| US7282602B2 (en) * | 2004-09-21 | 2007-10-16 | Bionumerik Pharmaceuticals, Inc. | Medicinal disulfide salts |
| JP5659411B2 (en) * | 2006-01-27 | 2015-01-28 | 奥野製薬工業株式会社 | Additive for electrolytic copper plating solution using phosphorous copper as anode, electrolytic copper plating solution and electrolytic copper plating method |
| DE102014208733A1 (en) | 2014-05-09 | 2015-11-12 | Dr. Hesse Gmbh & Cie Kg | Process for the electrolytic deposition of copper from water-based electrolytes |
| JP7064115B2 (en) | 2016-08-15 | 2022-05-10 | アトテック ドイチュラント ゲー・エム・ベー・ハー ウント コー． カー・ゲー | Acidic aqueous composition for electrolytic copper plating |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL291575A (en) * | 1962-04-16 | |||
| DE1246347B (en) * | 1966-03-08 | 1967-08-03 | Schering Ag | Acid galvanic copper bath |
| DE2039831C3 (en) * | 1970-06-06 | 1979-09-06 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Acid bath for the galvanic deposition of shiny copper coatings |
| ES440918A1 (en) * | 1975-03-11 | 1977-06-01 | Oxy Metal Industries Corp | Electrodeposition of copper |
| DE2721985A1 (en) * | 1977-05-14 | 1978-11-16 | Bayer Ag | PROCESS FOR THE PRODUCTION OF POLYISOCYANATE POLYADDITION PRODUCTS CONTAINING URETHANE AND / OR UREA GROUPS |
| DE2746938A1 (en) * | 1977-10-17 | 1979-04-19 | Schering Ag | ACID GALVANIC COPPER BATH |
| US4272335A (en) * | 1980-02-19 | 1981-06-09 | Oxy Metal Industries Corporation | Composition and method for electrodeposition of copper |
| US4374709A (en) * | 1980-05-01 | 1983-02-22 | Occidental Chemical Corporation | Process for plating polymeric substrates |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| FR2510145B1 (en) * | 1981-07-24 | 1986-02-07 | Rhone Poulenc Spec Chim | ADDITIVE FOR AN ACID ELECTROLYTIC COPPER BATH, ITS PREPARATION METHOD AND ITS APPLICATION TO COPPER PRINTED CIRCUITS |
| WO1984001393A1 (en) * | 1982-09-30 | 1984-04-12 | Learonal Inc | Electrolytic copper plating solutions |
| DE3402999A1 (en) * | 1984-01-28 | 1985-08-01 | Skw Trostberg Ag, 8223 Trostberg | Fertiliser solutions |
| DE3721985A1 (en) * | 1987-06-30 | 1989-01-12 | Schering Ag | AQUEOUS ACID BATH FOR GALVANIC DEPOSITION OF GLOSSY AND LEVELED COPPER COATINGS |
-
1990
- 1990-10-13 DE DE4032864A patent/DE4032864A1/en active Granted
-
1991
- 1991-10-11 JP JP3516095A patent/JPH06501986A/en active Pending
- 1991-10-11 CA CA002093924A patent/CA2093924C/en not_active Expired - Lifetime
- 1991-10-11 EP EP91917496A patent/EP0554275B1/en not_active Expired - Lifetime
- 1991-10-11 DE DE59103933T patent/DE59103933D1/en not_active Expired - Lifetime
- 1991-10-11 ES ES91917496T patent/ES2066477T3/en not_active Expired - Lifetime
- 1991-10-11 WO PCT/DE1991/000811 patent/WO1992007116A1/en active IP Right Grant
- 1991-10-11 AT AT91917496T patent/ATE115651T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992007116A1 (en) | 1992-04-30 |
| EP0554275B1 (en) | 1994-12-14 |
| DE59103933D1 (en) | 1995-01-26 |
| DE4032864C2 (en) | 1993-01-07 |
| CA2093924A1 (en) | 1992-04-14 |
| ES2066477T3 (en) | 1995-03-01 |
| DE4032864A1 (en) | 1992-04-16 |
| ATE115651T1 (en) | 1994-12-15 |
| EP0554275A1 (en) | 1993-08-11 |
| JPH06501986A (en) | 1994-03-03 |
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| EEER | Examination request | ||
| MKLA | Lapsed | ||
| MKEC | Expiry (correction) |
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