CN110373672A - A kind of winged target chucking surface attachment Copper treatment liquid - Google Patents
A kind of winged target chucking surface attachment Copper treatment liquid Download PDFInfo
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- CN110373672A CN110373672A CN201910705020.1A CN201910705020A CN110373672A CN 110373672 A CN110373672 A CN 110373672A CN 201910705020 A CN201910705020 A CN 201910705020A CN 110373672 A CN110373672 A CN 110373672A
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- parts
- treatment liquid
- copper
- chucking surface
- winged target
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Classifications
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present invention relates to a kind of winged target chucking surfaces to adhere to Copper treatment liquid, includes following components by mass fraction: 4-8 parts of 50-65 parts of dilution heat of sulfuric acid, 8-12 parts of hydrogenperoxide steam generator, 8-12 parts of stabilizer, 10-15 parts of citric acid solution and sodium citrate powder and neopelex or 3-6 parts of methenamine；The stabilizer is by mass fraction including at least deionized water 75-85 parts, 3-6 parts of ethanol solution and 2-5 parts of sulfonic acid based compound.The present invention has the volatility for reducing treatment fluid, it is avoided to endanger the effect of operator's health.
Description
Technical field
The present invention relates to the technical fields of Treatment of Metal Surface, adhere to Copper treatment more particularly, to a kind of winged target chucking surface
Liquid.
Background technique
PCB circuit board is also known as printed circuit board, is the supplier of electronic component electrical connection.Industrially prepare pcb board
When usually require to carry out electro-coppering operation, it is to form PCB conductive path plate face figure that copper, which is used to interconnect component on pcb board,
A kind of good conductor material.It usually requires to clamp pcb board using dartlike weapon fixture in pcb board electroplating process, due to dartlike weapon
The end of fixture is often immersed in electroplate liquid, and surface metallic copper easy to attach forms one layer of copper attachment surface.When dartlike weapon fixture
Again when lower piece of not electroplated pcb board of de-clamping, the attachment copper on surface becomes easily infected by pcb board and influences pcb board
Electroplating effect, the pcb board quality for causing plating to be completed reduces, or even is not available.
To solve the above-mentioned problems, at industrially frequently with concentrated nitric acid solution to the attachment copper of dartlike weapon chucking surface
Redox reaction occurs for reason, concentrated nitric acid and copper, so that metallic copper be made to peel off from dartlike weapon chucking surface.But concentrated nitric acid property
It is not sufficiently stable, easily emits nitrogen dioxide, and concentrated nitric acid can also generate nitrogen dioxide, dioxy during reacting with metallic copper
Changing nitrogen is brownish red toxic gas, has strong impulse.Therefore, this method endangers pole to the health of operator
Greatly.
Summary of the invention
The object of the present invention is to provide a kind of winged target chucking surfaces to adhere to Copper treatment liquid, has the volatilization for reducing treatment fluid
Property, avoid it from endangering the effect of operator's health.
Above-mentioned technical purpose of the invention has the technical scheme that a kind of winged target chucking surface attachment
Copper treatment liquid, includes following components by mass fraction: 50-65 parts of dilution heat of sulfuric acid, 8-12 parts of hydrogenperoxide steam generator, stabilizer 8-
12 parts, 10-15 parts of citric acid solution and 4-8 parts of sodium citrate powder.
By using above-mentioned technical proposal, dilution heat of sulfuric acid does not react directly with metallic copper, and hydrogen peroxide is first by metallic copper
It is oxidized to copper oxide, copper oxide is reacted with dilution heat of sulfuric acid generates copper ion, thus peel off metallic copper from dartlike weapon chucking surface,
Since non-volatility toxic gas generates dilute sulfuric acid-hydrogen peroxide system during the reaction, the system avoids to operator
The damage of member's health；Citric acid is weak acid, contains hydrogen ion in weak acid, has facilitation effect to the reaction of the system；Lemon
Lemon acid sodium has demineralized water, prevents excessive copper ion the reaction was continued the effect for generating precipitating；And citric acid and sodium citrate
Compound use also have the function of raising system reaction stability, increase the molten amount of copper of solution；It is anti-in copper sulphate-hydrogen peroxide
It answers in system, with the raising of copper ion concentration in system, chain reaction can occur between copper ion and hydrogen peroxide, to accelerate
The decomposition rate of hydrogen peroxide, stabilizer is added into solution, to slow down the decomposition rate of hydrogen peroxide, so as to improve the body
The stability of system.
The present invention is further arranged to: further including neopelex or 3-6 parts of methenamine in the component.
By using above-mentioned technical proposal, neopelex and methenamine all have infiltration, emulsification, dispersion
The effects of, one of the two is added in solution, to clean to the surface of adhesion metal copper, attachment is improved with this
The surface-active of copper promotes the reaction rate of attachment copper and solution, peels off metallic copper to improve dilute sulfuric acid-hydrogen peroxide system
Rate.
The present invention is further arranged to: the stabilizer by mass fraction include at least deionized water 75-85 parts, ethyl alcohol it is molten
3-6 parts of liquid and 2-5 parts of sulfonic acid based compound.
By using above-mentioned technical proposal, hydrogen peroxide can generate living radical in decomposable process, inhibit peroxide
Change the decomposition of hydrogen it is necessary to reduce the activity of living radical, the O-H key containing easy fracture in living radical, after the fracture of O-H key
Free H is generated, contains sulfo group in sulfonic acid based compound, sulfo group is the strong negative group containing S, H, O element, can be with free H again
Secondary formation hydrogen bond, so that a possibility that reinforcing the connective stability of O-H key, reducing its fracture, reduces living radical with this
Activity, play the role of inhibit hydrogen peroxide decompose.
The present invention is further arranged to: the stabilizer further includes 10-15 parts of Amine Solutions.
By using above-mentioned technical proposal, amido is contained in Amine Solutions, amido is the strong negative proup containing N, O element
A possibility that group is conducive to the connective stability for reinforcing O-H key, reduces living radical scission of link, reduces living radical with this
Activity, play the role of inhibit hydrogen peroxide decompose.
The present invention is further arranged to: the stabilizer further includes 3-5 parts of EDTA.
By using above-mentioned technical proposal, contain ammonia carboxyl in EDTA, ammonia carboxyl is the strong negative proup containing N, H, O element
A possibility that group is conducive to the connective stability for reinforcing O-H key, reduces living radical scission of link, reduces living radical with this
Activity, play the role of inhibit hydrogen peroxide decompose.
The present invention is further arranged to: the stabilizer further includes 3-5 parts of HA.
By using above-mentioned technical proposal, the basic structure of HA is aromatic ring and alicyclic ring, be connected on ring carboxyl, hydroxyl, carbonyl,
The functional groups such as quinonyl, methoxyl group, wherein carboxyl, hydroxyl are the functional group with strong negativity, therefore have the company for reinforcing O-H key
The effect for a possibility that connecing stability, reducing living radical scission of link reduces the activity of living radical with this, inhibits peroxidating
The decomposition of hydrogen.
The present invention is further arranged to: the sulfonic acid based compound is p-methyl benzenesulfonic acid, methane sulfonic acid or sulfamic acid
In any one.
By using above-mentioned technical proposal, toluenesulfonic acid, methane sulfonic acid and sulfamic acid structure are simple, inexpensive easy
, and cost is relatively low for preparation process, selects one of three kinds to be added in component, is conducive to control cost, while preventing from drawing
Into more impurity elements.
The present invention is further arranged to: the Amine Solutions are in 2 hydroxy ethylamine, 3- Propanolamine or isopropanolamine
Any one.
By using above-mentioned technical proposal, 2 hydroxy ethylamine, 3- Propanolamine and isopropanolamine structure are simple, are added to group
It avoids introducing extra impurity element and influencing system reaction in point, and three kinds of elements are cheap and easy to get, effectively reduce and are produced into
This.
In conclusion advantageous effects of the invention are as follows:
1. the system avoids right since non-volatility toxic gas generates dilute sulfuric acid-hydrogen peroxide system during the reaction
The damage of operator's health；
2. the compound use of the citric acid and sodium citrate also work with raising system reaction stability, the increase molten amount of copper of solution
With；
3. neopelex and methenamine all have the effects of infiltration, emulsification, dispersion, one of the two is added
It adds in solution, to clean to the surface of adhesion metal copper, improves the surface-active of attachment copper with this, promote attachment copper
With the reaction rate of solution, to improve the rate that dilute sulfuric acid-hydrogen peroxide system peels off metallic copper；
A possibility that being added with the connective stability for being conducive to reinforce O-H key, reduce living radical scission of link of 4.EDTA or HA, with
This reduces the activity of living radical, plays the role of that hydrogen peroxide is inhibited to decompose.
Specific embodiment
Embodiment 1, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 2, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 3, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 4, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 5, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 6, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 7, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 8, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 9, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 10, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 11, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Embodiment 12, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Comparative example 1, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Comparative example 2, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Comparative example 3, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Comparative example 4, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Comparative example 5, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Comparative example 6, a kind of winged target chucking surface attachment Copper treatment liquid, including following components.
Solution prepared by embodiment 1-4, comparative example 1 and comparative example 3 is sampled, every group of embodiment sampling 20
Part, and attachment copper-stripping efficiency test test is carried out to sample, adhere to copper-stripping efficiency test test principle are as follows: adhere to surface
The dartlike weapon fixture of same thickness metallic copper is placed in sample solution, and the required time is completely exfoliated in record attachment copper, and attachment copper is complete
It is shorter the time required to fully stripped, illustrate that the charge stripping efficiency for adhering to copper is higher, log is as shown in table 1.
The time is completely exfoliated in the attachment copper of sample in table 1- embodiment 1-4, comparative example 1 and comparative example 3
| The time (s) is completely exfoliated | |
| Embodiment 1 | 35 |
| Embodiment 2 | 45 |
| Embodiment 3 | 41 |
| Embodiment 4 | 43 |
| Comparative example 1 | 49 |
| Comparative example 3 | 56 |
The data comparison of time is completely exfoliated according to the attachment copper of embodiment 1-4: the ratio between component is different, right
Certain influence can be generated in the charge stripping efficiency of attachment copper, therefore, when carrying out attachment copper-stripping operation using the solution, is needed
Suitable proportion is chosen to improve the charge stripping efficiency of attachment copper.
The data comparison of time is completely exfoliated according to the attachment copper of embodiment 1 and comparative example 1: it is molten to delete citric acid
Liquid, that adheres to copper is completely exfoliated time extension, illustrates that the addition of citric acid solution has the charge stripping efficiency for improving attachment copper
Certain facilitation.
The data comparison of time is completely exfoliated according to the attachment copper of embodiment 1 and comparative example 3: deleting detergent alkylate
Sodium sulfonate, that adheres to copper is completely exfoliated time extension, illustrates that the stripping of copper is adhered in the addition of neopelex for improving
There is certain facilitation from efficiency.
Solution prepared by embodiment 1,5-12 and comparative example 2,4-6 is sampled, every group of embodiment samples 20 parts,
And system stability testing experiment, system stability testing experiment principle are carried out to sample are as follows: by surface attachment same thickness gold
The dartlike weapon fixture for belonging to copper, which is placed in sample solution, carries out stripping process, is completely exfoliated to first dartlike weapon chucking surface attachment copper
Afterwards, second dartlike weapon fixture is placed, and so on, when to be placed to the 5th dartlike weapon fixture, record the 5th dartlike weapon fixture
The extent of exfoliation of surface attachment copper when 1min, extent of exfoliation is higher, illustrates that system stability is stronger, log such as table 2
It is shown.
The attachment copper 1min extent of exfoliation of sample in table 2- embodiment 1,5-12 and comparative example 1,4-6
| Extent of exfoliation (%) | |
| Embodiment 1 | 87 |
| Embodiment 5 | 86 |
| Embodiment 6 | 87 |
| Embodiment 7 | 89 |
| Embodiment 8 | 85 |
| Embodiment 9 | 90 |
| Embodiment 10 | 91 |
| Embodiment 11 | 92 |
| Embodiment 12 | 80 |
| Comparative example 2 | 81 |
| Comparative example 4 | 79 |
| Comparative example 5 | 80 |
| Comparative example 6 | 79 |
According to the attachment copper 1min extent of exfoliation data comparison of embodiment 1 and comparative example 4: addition Amine Solutions
Afterwards, adhere to extent of exfoliation in copper 1min to improve, illustrate that the addition of Amine Solutions for improving system stability, reduces peroxidating
Hydrogen decomposition rate has positive effect.
According to embodiment 1 and the attachment copper 1min extent of exfoliation data comparison of embodiment 7-12: in addition methyl
One or both of on the basis of benzene sulfonic acid, then be superimposed Amine Solutions, EDTA and HA, adhere to the removing journey in copper 1min
Degree increases, and illustrates to be superimposed one or both of Amine Solutions, EDTA and HA for improving system stability, drop
Low hydrogen peroxide decomposition rate has positive effect；But on the basis of adding toluenesulfonic acid, then simultaneously added with machine amine
Solution, EDTA and HA can reduce instead attachment copper 1min in extent of exfoliation, this may be because, adding ingredient is excessive, at
/ can have certain inhibition and influence the stability of system.
According to embodiment 1 and the attachment copper 1min extent of exfoliation data comparison of embodiment 5-6: 2 hydroxy ethylamine,
3- Propanolamine or isopropanolamine have facilitation, and stripping in the attachment copper 1min of three to reduction hydrogen peroxide decomposition rate
It is little from degree difference, it is contemplated that one of optional three of the other factors such as cost is added in component；
According to the attachment copper 1min extent of exfoliation data comparison of embodiment 1 and comparative example 2: while deleting citric acid sodium powder
End and citric acid solution, the extent of exfoliation adhered in copper 1min reduce, illustrate sodium citrate powder and citric acid solution is compound makes
There is facilitation with to raising system stability.
According to the attachment copper 1min extent of exfoliation data comparison of comparative example 4-6: p-methyl benzenesulfonic acid, methane sulfonic acid or
Sulfamic acid has facilitation, and extent of exfoliation difference in the attachment copper 1min of three to reduction hydrogen peroxide decomposition rate
Less, it is contemplated that one of optional three of the other factors such as cost is added in component.
The embodiment of present embodiment is presently preferred embodiments of the present invention, not limits protection of the invention according to this
Range, therefore: the equivalence changes that all structures under this invention, shape, principle are done, should all be covered by protection scope of the present invention it
It is interior.
Claims (8)
- Include following components by mass fraction 1. a kind of winged target chucking surface adheres to Copper treatment liquid: 50-65 parts of dilution heat of sulfuric acid, 8-12 parts of hydrogenperoxide steam generator, 8-12 parts of stabilizer, 10-15 parts of citric acid solution and 4-8 parts of sodium citrate powder.
- 2. a kind of winged target chucking surface according to claim 1 adheres to Copper treatment liquid, it is characterised in that: in the component also Including neopelex or 3-6 parts of methenamine.
- 3. a kind of winged target chucking surface according to claim 1 adheres to Copper treatment liquid, it is characterised in that: the stabilizer is pressed Mass fraction is including at least deionized water 75-85 parts, 3-6 parts of ethanol solution and 2-5 parts of sulfonic acid based compound.
- 4. a kind of winged target chucking surface according to claim 2 adheres to Copper treatment liquid, it is characterised in that: the stabilizer is also Including 10-15 parts of Amine Solutions.
- 5. a kind of winged target chucking surface according to claim 3 or 4 adheres to Copper treatment liquid, it is characterised in that: the stabilization Agent further includes 3-5 parts of EDTA.
- 6. a kind of winged target chucking surface attachment Copper treatment liquid according to claim 3 or 4 or 5, it is characterised in that: described steady Determining agent further includes 3-5 parts of HA.
- 7. a kind of winged target chucking surface according to claim 3 adheres to Copper treatment liquid, it is characterised in that: the sulfonic group Conjunction object is any one in p-methyl benzenesulfonic acid, methane sulfonic acid or sulfamic acid.
- 8. a kind of winged target chucking surface according to claim 4 adheres to Copper treatment liquid, it is characterised in that: the organic amine is molten Liquid is any one in 2 hydroxy ethylamine, 3- Propanolamine or isopropanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910705020.1A CN110373672B (en) | 2019-08-01 | 2019-08-01 | Treatment liquid for attaching copper to surface of target-flying clamp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910705020.1A CN110373672B (en) | 2019-08-01 | 2019-08-01 | Treatment liquid for attaching copper to surface of target-flying clamp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110373672A true CN110373672A (en) | 2019-10-25 |
| CN110373672B CN110373672B (en) | 2021-09-03 |
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ID=68257408
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910705020.1A Active CN110373672B (en) | 2019-08-01 | 2019-08-01 | Treatment liquid for attaching copper to surface of target-flying clamp |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106330A (en) * | 2022-06-27 | 2022-09-27 | 湖北金禄科技有限公司 | Stripping and hanging groove for vertical continuous electroplating of circuit board and cleaning method thereof |
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| CN1730728A (en) * | 2005-08-09 | 2006-02-08 | 广东省石油化工研究院 | Copper or copper alloy surface tiny-etching treatment fluid for smoothing |
| US20080224092A1 (en) * | 2007-03-15 | 2008-09-18 | Samsung Electronics Co., Ltd. | Etchant for metal |
| JP2011202242A (en) * | 2010-03-26 | 2011-10-13 | Mec Kk | Etchant of copper and method of manufacturing substrate |
| KR20140108795A (en) * | 2013-02-28 | 2014-09-15 | 동우 화인켐 주식회사 | Echaing composition for copper-based metal layer and multiful layer of copper-based metal layer and metal oxide layer and method of preparing metal line |
| CN109735845A (en) * | 2019-02-23 | 2019-05-10 | 上海富柏化工有限公司 | It is a kind of that hole is prevented to enclose the micro-corrosion liquid to whiten |
-
2019
- 2019-08-01 CN CN201910705020.1A patent/CN110373672B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730728A (en) * | 2005-08-09 | 2006-02-08 | 广东省石油化工研究院 | Copper or copper alloy surface tiny-etching treatment fluid for smoothing |
| US20080224092A1 (en) * | 2007-03-15 | 2008-09-18 | Samsung Electronics Co., Ltd. | Etchant for metal |
| JP2011202242A (en) * | 2010-03-26 | 2011-10-13 | Mec Kk | Etchant of copper and method of manufacturing substrate |
| KR20140108795A (en) * | 2013-02-28 | 2014-09-15 | 동우 화인켐 주식회사 | Echaing composition for copper-based metal layer and multiful layer of copper-based metal layer and metal oxide layer and method of preparing metal line |
| CN109735845A (en) * | 2019-02-23 | 2019-05-10 | 上海富柏化工有限公司 | It is a kind of that hole is prevented to enclose the micro-corrosion liquid to whiten |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106330A (en) * | 2022-06-27 | 2022-09-27 | 湖北金禄科技有限公司 | Stripping and hanging groove for vertical continuous electroplating of circuit board and cleaning method thereof |
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|---|---|
| CN110373672B (en) | 2021-09-03 |
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