CN104080955A - Method for producing matt copper deposits - Google Patents

Method for producing matt copper deposits Download PDF

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Publication number
CN104080955A
CN104080955A CN201280068192.9A CN201280068192A CN104080955A CN 104080955 A CN104080955 A CN 104080955A CN 201280068192 A CN201280068192 A CN 201280068192A CN 104080955 A CN104080955 A CN 104080955A
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group
ionogen
copper coating
deposition
matt
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CN104080955B (en
Inventor
斯特凡·克雷奇默
飞利浦·哈特曼
贝恩德·罗夫斯
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The present invention relates to a method for deposition of a matt copper coating wherein a first copper layer is deposited from an aqueous copper electrolyte which does not contain an organic compound comprising divalent sulfur. A second copper layer is then deposited onto the first copper layer from an aqueous copper electrolyte comprising a first and a second water soluble sulfurcontaining additive wherein the first water soluble sulfur-containing compound is an alkyl sulfonic acid derivative and the second water soluble sulfur-containing additive is an aromatic sulfonic acid derivative. The method provides copper layers with a homogeneous and adjustable matt appearance for decorative applications.

Description

Manufacture the method for matt copper deposition
Technical field
The present invention relates to deposit the method for the matt copper deposition in decorative coating field.
Background technology
In decorative coating field, need matt copper coating as for example, coating materials for () sanitation.The Another Application of matt copper coating is that as the middle layer in ornamental multi-layer coating system, the toxicity to the demand in this middle layer because of nickel increases alternative matt nickel dam (" satin face nickel, satin nickel ") day by day.
Decorative metals layer needs even matt appearance.The homogeneity of matt appearance can easily realize on the substrate without complicated shape, because the electric current distribution of matt copper layer during electroplating is in close limit.Yet, at substrate to be coated, having under the situation of complicated shape, the current density of during electroplating is in wide region.The typical substrate with complicated shape of stand-by matt copper coating coating is (for example) shower nozzle and automotive interior part.
To another requirement of matt copper layer, be that its matt degree should be adjustable, can manufacture the copper layer with different matt degree.
For produce the plating bath composition that comprises at least one bound to polyglycerol compound of matt copper layer during printed circuit board (PCB) manufacture, be disclosed in US 2004/0020783A1.While using the ionogen wherein disclosed, can not obtain even matt copper deposition having on the substrate of complicated shape, can not regulate the matt degree of described copper deposition.
invention target
Target of the present invention is to provide especially has the method that deposits the copper layer with even and adjustable matt appearance on the substrate of complicated shape.
Summary of the invention
This target is to realize by depositing the method for matt copper coating, and described method comprises following steps in the following order
A., substrate is provided,
B. from the first aqueous electrolyte, the first bronze medal is deposited to described substrate, described the first aqueous electrolyte comprises copper ion source, at least one acid and at least one polyether compound, and wherein said the first ionogen is not containing the organic compound that comprises divalent sulfur
With
C. from the second aqueous electrolyte, the second bronze medal is deposited to described the first bronze medal layer to the first water-soluble sulfur-containing additive of group and the second water-soluble sulfur-containing additive of the group that the free aromatic sulfonic acid derivative of choosing forms that described the second aqueous electrolyte comprises copper ion source, at least one acid, selects free alkyl sulfonic acid derivative to form.
The copper coating obtaining by the inventive method has even matt appearance having on the substrate of complicated shape.In addition, the matt appearance of copper coating can regulate during the indivedual copper layers of deposition.
Embodiment
The method that deposits matt copper coating comprises from two kinds of indivedual copper electrolytes two indivedual copper is deposited to substrate, and described indivedual copper electrolytes represent in this article to deposit the first ionogen of the first bronze medal layer and the second bronze medal is deposited to the second ionogen on the first bronze medal layer.
The first ionogen comprises copper ion source, at least one acid and at least one polyether compound.The first ionogen is not for example, containing the organic compound that comprises divalent sulfur (, sulfide, disulphide, mercaptan and its derivative).
With water-soluble mantoquita or its aqueous solution form, add cupric ion to first ionogen.Preferably, copper ion source is selected from copper sulfate and methanesulfonic copper.The concentration of the cupric ion in the first ionogen preferably 15g/l to 75g/l, more preferably 40g/l within the scope of 60g/l.
At least one acid in the first ionogen is selected from the group that comprises sulfuric acid, fluoroboric acid and methanesulfonic.At least one sour concentration in the first ionogen preferably 20g/l to 400g/l and more preferably 40g/l within the scope of 300g/l.
Use sulfuric acid as sour situation under, it preferably adds to the solution form of 96wt.-% with 50wt.-%.More preferably, as 50wt.-% aqueous sulfuric acid, add sulfuric acid to first ionogen.
The group that at least one polyether compound in the first ionogen selects free polyalkylene ether and bound to polyglycerol compound to form.
Suitable polyalkylene ether choosing is the following group forming freely: polyoxyethylene glycol, polypropylene glycol, stearyl alcohol polyglycol ether, nonyl phenol polyglycol ether, octanol polyalkylene glycol ethers, ethohexadiol-bis--(polyalkylene glycol ethers), poly-(ethylene glycol-random-propylene glycol), PEG-block-poly-(propylene glycol)-block-PEG and poly-(propylene glycol)-block-PEG-block-poly-(propylene glycol).
Suitable bound to polyglycerol compound choosing freely gathers the group that (Glycerin), poly-(2,3-epoxy group(ing)-1-propyl alcohol) and its derivative form, and it is by formula (1), (2) and (3) representative:
Wherein
N is 1 to 80, preferred 2 to 30 integer;
R 6, R 7and R 8identical or different, and the group that selects free hydrogen, alkyl, acyl group, phenyl and benzyl to form, preferably straight chain or tool side chain C of alkyl wherein 1to C 18alkyl, and acyl group R preferably 10-CO, wherein R 10straight chain or tool side chain C 1to C 18alkyl, phenyl or benzyl; Alkyl phenyl and benzyl in formula (1) can be substituted;
Wherein
N is the integer of > 1, and m is the integer of > 1, and prerequisite is n+m≤30;
R 6, R 7, R 8and R 9identical or different, and the group that selects free hydrogen, alkyl, acyl group, phenyl and benzyl to form, preferably straight chain or tool side chain C of alkyl wherein 1to C 18alkyl, and acyl group R preferably 10-CO, wherein R 10straight chain or tool side chain C 1to C 18alkyl, phenyl or benzyl; Alkyl phenyl and benzyl in formula (2) can be substituted;
Wherein
N is 1 to 80, preferred 2 to 20 integer;
And R wherein 6, R 7the group that selects free hydrogen, alkyl, acyl group, phenyl and benzyl to form, wherein preferably straight chain or tool side chain C of alkyl 1to C 18alkyl, and acyl group R preferably 10-CO, wherein R 10straight chain or tool side chain C 1to C 18alkyl, phenyl or benzyl; Alkyl phenyl and benzyl in formula (3) can be substituted.
Bound to polyglycerol compound is to produce according to currently known methods.About producing the indication of condition, be for example disclosed in, in () following publication: cosmetic science and technology book series (Cosmet.Sci.Technol.Ser.), glycerine (glycerines), the 106th page and US 3,945,894.Other synthetic details about the bound to polyglycerol compound of formula (1), (2) and (3) is disclosed in US2004/0020783A1.
More preferably, at least one polyether compound in the first ionogen is selected from the compound of formula (1), (2) and (3).
At least one polyether compound or all polyether compounds together (add surpassing under a kind of situation of polyether compound) concentration preferably 0.005g/l to 20g/l, more preferably 0.01g/l within the scope of 5g/l.
During operation, preferably the first electrolytical temperature is adjusted to 30 ℃ to 60 ℃, the more preferably value within the scope of 40 ℃ to 50 ℃.
In the current density that is applied to substrate during the first aqueous electrolyte deposited copper preferably at 0.5A/dm 2to 5A/dm 2, more preferably 1A/dm 2to 3A/dm 2in scope.
Optionally, water rinses substrate, then from second electrolyte deposition the second bronze medal layer.
Using cupric ion as water-soluble mantoquita or its aqueous solution add the second ionogen to.Preferably, copper ion source is selected from copper sulfate and methanesulfonic copper.The concentration of the cupric ion in the second ionogen preferably 15g/l to 75g/l, more preferably 40g/l within the scope of 60g/l.
At least one acid in the second ionogen is selected from the group that comprises sulfuric acid, fluoroboric acid and methanesulfonic.At least one sour concentration in the second ionogen preferably 20g/l to 400g/l and more preferably 40g/l within the scope of 300g/l.
Use sulfuric acid as sour situation under, it is to add to the solution form of 96wt.-% with 50wt.-%.Preferably, sulfuric acid is to add the second ionogen to as 50wt.-% aqueous sulfuric acid.
The second ionogen further comprises the first water-soluble sulfur-containing additive and the second water-soluble sulfur-containing additive.
The first water-soluble sulfocompound is alkyl sulfonic acid derivative.Preferably, alkyl sulfonic acid derivative comprises divalent sulfur.
The second water-soluble sulfocompound is aromatic sulfonic acid derivative.Preferably, aromatic sulfonic acid derivative comprises divalent sulfur.
The group that the first sulfur-containing additive more preferably selects the compound of free style (4) and (5) to form:
R 1S-(CH 2) n-SO 3R 2 (4)
R 3SO 3-(CH 2) m-S-S-(CH 2) m-SO 3R 3 (5)
Wherein
R 1choosing is the following group forming freely: hydrogen, methyl, ethyl, propyl group, butyl, lithium, sodium, potassium and ammonium, more preferably, R 1choosing is the following group forming freely: hydrogen, methyl, ethyl, propyl group, sodium and potassium;
N is 1 to 6 integer, and more preferably, n is 2 to 4 integer;
R 2choosing is the following group forming freely: hydrogen, methyl, ethyl, propyl group, butyl, lithium, sodium, potassium and ammonium, more preferably, R 2the group that selects free hydrogen, sodium and potassium to form;
R 3choosing is the following group forming freely: hydrogen, methyl, ethyl, propyl group, butyl, lithium, sodium, potassium and ammonium, more preferably, R 3select the group of free hydrogen, sodium, potassium and composition
M is 1 to 6 integer, and more preferably, m is 2 to 4 integer.
The concentration of the first sulfur-containing additive in the second ionogen preferably 0.0001g/l to 0.05g/l, more preferably 0.0002g/l within the scope of 0.025g/l.
The group that the second sulfur-containing additive in the second ionogen more preferably selects the compound of free style (6) and (7) to form:
R 4S y-X-SO 3M (6)
R wherein 4choosing is the following group forming freely
and hydrogen;
X choosing is the following group forming freely
with
Y is 1 to 4 integer, and M selects the group of free hydrogen, sodium, potassium and ammonium composition; With
R wherein 5select free hydrogen, SH and SO 3the group that M forms, and M selects the group of free hydrogen, sodium, potassium and ammonium composition.
More preferably, the second sulfur-containing additive is selected from formula (6) compound.
The concentration of the second sulfur-containing additive in the second ionogen preferably 0.0051g/l to 1g/l, more preferably 0.01g/l within the scope of 0.25g/l.
Optionally, the second ionogen further comprises the freely supporting agent additive of the following group forming of one or more choosing: polyvinyl alcohol, carboxymethyl cellulose, polyoxyethylene glycol, polypropylene glycol, stearic acid polyglycol ester, alkoxylate naphthols, oleic acid polyglycol ester, stearyl alcohol polyglycol ether, nonyl phenol polyglycol ether, octanol polyalkylene glycol ethers, ethohexadiol-bis--(polyalkylene glycol ethers), poly-(ethylene glycol-random-propylene glycol), PEG-block-poly-(propylene glycol)-block-PEG and poly-(propylene glycol)-block-PEG-block-poly-(propylene glycol).
The concentration of the optional supporting agent additive in the second ionogen preferably 0.005g/l to 5g/l, more preferably 0.01g/l within the scope of 3g/l.
During operation, preferably the second electrolytical temperature is adjusted to 20 ℃ to 50 ℃, the value within the scope of 25 ℃ to 30 ℃ most preferably.
In the current density that is applied to substrate during the second aqueous electrolyte deposited copper preferably at 0.5A/dm 2to 5A/dm 2, more preferably 1A/dm 2to 3A/dm 2in scope.
The matt degree on copper surface can regulate the thickness of the first bronze medal layer and the second bronze medal layer to adjust by simple experiment.The stronger outward appearance of tarnish can utilize thinner the second bronze medal layer to realize, and the weak outward appearance of tarnish can utilize thicker the second bronze medal layer to realize.
Following instance is further explained the present invention.
Example
Substrate:
In all examples, use have ABS (acrylonitrile-butadiene-styrene (ABS)-multipolymer) substrate of complicated shape and brass substrate the two.
By the etching in chromic acid of ABS substrate, through activating containing palladium colloid, and metallize by the ionogen electroless plating nickel from based on acid phosphinates, then deposited copper.
By brass substrate degreasing, subsequently deposited copper.
Testing method:
In all examples, by visual inspection copper facing substrate, carry out the matt appearance of copper test coating.
example 1 (comparison)
From aqueous acidic ionogen, copper is deposited on the ABS substrate and brass substrate with complicated shape, described aqueous acidic ionogen comprises 80g/l CuSO 45H 2the mixture (wherein n=2 to 7) of O, 240g/l sulfuric acid and 1g/l formula (1) bound to polyglycerol compound.
Obtain evenly strong matt copper surface, its tarnish is excessively strong for decorative applications.
example 2 (comparison)
From aqueous acidic ionogen, copper is deposited on the ABS substrate and brass substrate with complicated shape, described aqueous acidic ionogen comprises 80g/l CuSO 45H 2o, 240g/l sulfuric acid and 0.5mg/l formula (5) first sulfur-containing additives (wherein m=3 and R 3=sodium) and 80mg/l formula (6) second sulfur-containing additives (R wherein 4= x y=2 and M=sodium) and 200mg/l polyoxyethylene glycol.
The even technology glossiness on gained copper surface is not that decorative applications is required.
example 3 (comparison)
From example 2, ionogen used is deposited to the first bronze medal on the ABS substrate and brass substrate with complicated shape.Thereon, electrolyte deposition the second bronze medal layer used from example 1.
Obtain evenly strong matt copper surface, its tarnish is excessively strong for decorative applications.
example 4 (comparison)
From example 1, ionogen used is deposited to the first bronze medal on the ABS substrate and brass substrate with complicated shape.Next, from the second ionogen, the second bronze medal layer is deposited thereon, described the second ionogen comprises 80g/lCuSO 45H 2o, 240g/l sulfuric acid and 0.5mg/l formula (5) sulfur-containing additive (wherein m=3 and R 3=sodium).The second ionogen is not containing the second sulfur-containing additive that is selected from formula (6) and (7) compound.
Gained copper surface has the unacceptable inhomogeneous matt appearance of decorative applications.
example 5 (comparison)
From example 1, ionogen used is deposited to the first bronze medal on the ABS substrate and brass substrate with complicated shape.Next, from the second ionogen, the second bronze medal layer is deposited thereon, described the second ionogen comprises 80g/lCuSO 45H 2o, 240g/l sulfuric acid and 80mg/l formula (6) sulfur-containing additive (R wherein 4= x= y=2 and M=sodium).The second ionogen is not containing the first sulfur-containing additive that is selected from the compound of formula (4) and (5).
Gained copper surface has that decorative applications is unacceptable has a matt appearance of burning region (furvous outward appearance).
example 6
From example 1, ionogen used is deposited to the first bronze medal in ABS substrate and brass substrate.From example 2, ionogen used is deposited thereon by the second bronze medal layer.
Gained copper surface has the desired even matt appearance of decorative applications.
example 7
From comprising 80g/l CuSO 45H 2first electrolyte deposition the first bronze medal layer of O, 240g/l sulfuric acid and 1g/l polyoxyethylene glycol.From example 2, ionogen used is deposited thereon by the second bronze medal layer.
Gained copper surface has the desired even matt appearance of decorative applications.

Claims (12)

1. deposit a method for matt copper coating, it comprises following steps in the following order
A, provide substrate,
B, from the first aqueous electrolyte, the first bronze medal is deposited to described substrate, described the first aqueous electrolyte comprises copper ion source, at least one acid and at least one polyether compound, and wherein said the first ionogen is containing the organic compound that comprises divalent sulfur
With
C, from the second aqueous electrolyte, the second bronze medal is deposited to described the first bronze medal layer, described the second aqueous electrolyte comprises copper ion source, at least one acid, select the first water-soluble sulfur-containing additive of group that free alkyl sulfonic acid derivative forms and the second water-soluble sulfur-containing additive of the group of the free aromatic sulfonic acid derivative composition of choosing
Wherein current density is applied to described substrate during step b and c.
2. the method for the matt copper coating of deposition according to claim 1, the group that described at least one polyether compound in wherein said the first ionogen selects free polyalkylene glycol and Polyglycerine to form.
3. according to the method for the matt copper coating of the deposition described in arbitrary claim in aforementioned claim, described at least one polyether compound choosing in wherein said the first ionogen freely gathers (1,2,3-glycerol), the group that poly-(2,3-epoxy group(ing)-1-propyl alcohol) and its derivative form.
4. according to the method for the matt copper coating of the deposition described in arbitrary claim in aforementioned claim, described at least one polyether compound in wherein said the first ionogen selects the group of the compound composition of free style (1), (2) and (3):
Wherein n is 1 to 80 integer;
Wherein n is the integer of > 1, and m is the integer of > 1, and prerequisite is n+m≤30;
Wherein n is 1 to 80 integer;
And wherein
R 6, R 7, R 8and R 9identical or different, and be selected from the group that comprises hydrogen, alkyl, acyl group, phenyl and benzyl.
5. the method for the matt copper coating of deposition according to claim 4, the molecular weight of the compound of wherein said formula (1), (2) and (3) at 160g/mol within the scope of 6000g/mol.
6. according to the method for the matt copper coating of the deposition described in arbitrary claim in aforementioned claim, the concentration of described at least one polyether compound in wherein said the first ionogen arrives within the scope of 5g/l at 0.005g/l.
7. according to the method for the matt copper coating of the deposition described in arbitrary claim in aforementioned claim, described the first water-soluble sulfur-containing additive in wherein said the second ionogen selects the group of the compound composition of free style (4) and (5):
R 1S-(CH 2) n-SO 3R 2 (4)
R 3SO 3-(CH 2) m-S-S-(CH 2) m-SO 3R 3 (5)
Wherein
R 1choosing is the following group forming freely: hydrogen, methyl, ethyl, propyl group, butyl, lithium, sodium, potassium and ammonium, n in 1 to 6 scope,
R 2choosing is the following group forming freely: hydrogen, methyl, ethyl, propyl group, butyl, lithium, sodium, potassium and ammonium,
R 3choosing is the following group forming freely: hydrogen, methyl, ethyl, propyl group, butyl, lithium, sodium, potassium and ammonium, and m is in 1 to 6 scope.
8. according to the method for the matt copper coating of the deposition described in arbitrary claim in aforementioned claim, the concentration of described the first water-soluble sulfur-containing additive in wherein said the second ionogen arrives within the scope of 0.05g/l at 0.0001g/l.
8, according to the method for the matt copper coating of the deposition described in arbitrary claim in aforementioned claim, the group that described the second water-soluble sulfur-containing additive in wherein said the second ionogen selects the compound of free style (6) and (7) to form:
R 4S y-X-SO 3M (6)
R wherein 4choosing is the following group forming freely
and hydrogen;
X choosing is the following group forming freely
with
Y is 1 to 4 integer, and M selects the group of free hydrogen, sodium, potassium and ammonium composition; With
R wherein 5select free H, SH and SO 3the group that M forms, and M selects the group of free hydrogen, sodium, potassium and ammonium composition.
9. according to the method for the matt copper coating of the deposition described in arbitrary claim in aforementioned claim, the concentration of described the second water-soluble sulfur-containing additive in wherein said the second ionogen arrives within the scope of 1g/l at 0.005g/l.
10. according to the method for the matt copper coating of the deposition described in arbitrary claim in aforementioned claim, wherein said the second ionogen further comprises at least one supporting agent additive.
The method of the matt copper coating of 11. deposition according to claim 10, wherein said at least one supporting agent additive choosing is the following group forming freely: polyvinyl alcohol, carboxymethyl cellulose, polyoxyethylene glycol, polypropylene glycol, stearic acid polyglycol ester, alkoxylate naphthols, oleic acid polyglycol ester, stearyl alcohol polyglycol ether, nonyl phenol polyglycol ether, octanol polyalkylene glycol ethers, ethohexadiol-bis--(polyalkylene glycol ethers), poly--(ethylene glycol-random-propylene glycol), PEG-block-poly--(propylene glycol)-block-PEG and poly-(propylene glycol)-block-PEG-block-poly-(propylene glycol).
12. according to the method for the matt copper coating of the deposition described in claim 10 and 11, and the concentration of described at least one the supporting agent additive in wherein said the second ionogen arrives within the scope of 5g/l at 0.005g/l.
CN201280068192.9A 2012-01-25 2012-11-27 Manufacture the method for matt copper deposition Active CN104080955B (en)

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EP12152390.6A EP2620529B1 (en) 2012-01-25 2012-01-25 Method for producing matt copper deposits
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PCT/EP2012/073688 WO2013110373A2 (en) 2012-01-25 2012-11-27 Method for producing matt copper deposits

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