CN112095109A - Electrolytic copper foil antioxidant - Google Patents
Electrolytic copper foil antioxidant Download PDFInfo
- Publication number
- CN112095109A CN112095109A CN202010803247.2A CN202010803247A CN112095109A CN 112095109 A CN112095109 A CN 112095109A CN 202010803247 A CN202010803247 A CN 202010803247A CN 112095109 A CN112095109 A CN 112095109A
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- Prior art keywords
- copper foil
- electrolytic copper
- antioxidant
- surfactant
- sodium
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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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
Abstract
The invention relates to an electrolytic copper foil antioxidant which comprises, by mass, 0.1-10 parts of carboxylic acid, 0.1-5 parts of inorganic salt or silane coupling agent, 0.1-10 parts of surfactant mixture and 0.1-10 parts of film forming agent, wherein the surfactant mixture comprises: at least one surfactant having an HLB value of less than 14 and at least one surfactant having an HLB value of greater than 14. The electrolytic copper foil antioxidant provided by the invention does not contain heavy metal, does not need to be electrified or washed by water, and is safe and environment-friendly, thus being a new generation of electrolytic copper foil antioxidant.
Description
Technical Field
The invention relates to an antioxidant, in particular to an electrolytic copper foil antioxidant, and belongs to the technical field of electrolytic copper foil surface treatment.
Background
Copper foil is a negative electrolyte material that is deposited as a thin, continuous metal foil on the substrate layer of a circuit board that serves as the electrical conductor for the PCB. It is easy to adhere to the insulating layer, receive the printing protective layer, form the circuit pattern after corroding. Copper does not react with oxygen at normal temperature and is relatively stable metal, but under the condition that oxygen, carbon dioxide and water exist simultaneously, copper is easy to oxidize, and the copper foil antioxidant in the prior art has the defects of heavy metal content, environmental protection deficiency and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the antioxidant for the electrolytic copper foil, which does not contain heavy metal, does not need to be electrified or washed, is safe and environment-friendly and is a new generation of antioxidant for the electrolytic copper foil.
The purpose of the invention is realized by the following technical scheme:
an electrolytic copper foil antioxidant comprises the following components: comprises the following components: according to the mass parts, 0.1-10 parts of carboxylic acid, 0.1-5 parts of inorganic salt or silane coupling agent, 0.1-10 parts of surfactant mixture and 0.1-10 parts of film forming agent, wherein the surfactant mixture comprises: at least one surfactant having an HLB value of less than 14 and at least one surfactant having an HLB value of greater than 14.
Based on the technical scheme, the carboxylic acid is used as a chelating agent to be chelated with copper, has strong chelating ability and high temperature resistance, and wraps copper in the carboxylic acid to enhance the stability of the copper, so that the further oxidation of the copper is prevented. The inorganic salt and the carboxylic acid can form an inorganic-organic hybrid material, the silane coupling agent can combine organic and inorganic matrixes to form a stable solution system, the surfactant with the HLB value of less than 14 has good wettability, the surfactant with the HLB value of more than 14 has good emulsibility, and the surfactant and the carboxylic acid can be combined in a proper proportion to improve the wettability and the emulsifying and dispersing performance of the whole solution. The film forming agent enables the substance of the whole system to form a film, and can better wrap copper, prevent copper oxidation and improve the surface roughness.
Further, the sol also comprises 0.1-5 parts of sol.
Further, the carboxylic acid is selected from one or more of S-carboxyethyl sulfosuccinic acid, citric acid and tartaric acid.
Further, the inorganic salt is selected from one or more of sodium metaaluminate, potassium metaaluminate, sodium silicate, potassium silicate, ammonium silicate, sodium tungstate, potassium tungstate, ammonium tungstate, sodium molybdate, potassium molybdate and ammonium molybdate.
Further, the silane coupling agent is selected from one or a mixture of more of 3-aminopropyltriethoxysilane, gamma-diethylenetriamine propyl methyldimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3- (2, 3-glycidoxy) propyl methyldimethoxysilane and gamma-mercaptopropyl trimethoxysilane.
Further, the surfactant with HLB value less than 14 is selected from one or more of castor oil polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyethylene glycol, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
Further, the surfactant with HLB value larger than 14 is selected from one or more of fatty alcohol-polyoxyethylene ether, polyoxyethylene stearate and propylene glycol block polyether.
Further, the film forming agent is selected from one or more of glucose, maltose, galactose, lactose, fructose, saccharin sodium and acesulfame potassium.
Further, the sol is selected from one or more of zirconia sol, silica sol, alumina sol and titania sol.
The invention has the beneficial effects that:
the antioxidant provided by the invention does not contain heavy metals such as chromium, zinc and the like, does not need to be electrified, does not need to be washed to cause water pollution, is safe and environment-friendly, is a new generation of electrolytic copper foil antioxidant, can better infiltrate the surface of copper to prevent the copper from being oxidized, has strong chelating capacity with the copper, further prevents the copper from being oxidized by wrapping the copper in a chelating agent, can also improve the roughness of the surface of the copper, resists high temperature, and can play a good role in oxidation resistance without limiting the temperature application range of the electrolytic copper foil.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Stirring and uniformly mixing 10g of citric acid, 10g of sodium metaaluminate, 1g of fatty alcohol-polyoxyethylene ether, 9g of sodium dodecyl benzene sulfonate and 10g of glucose to obtain the antioxidant.
Example 2
1kg of tartaric acid, 1kg of sodium tungstate, 100g of fatty alcohol-polyoxyethylene ether, 900g of octyl phenol-polyoxyethylene ether and 1kg of maltose are stirred and mixed uniformly to obtain the antioxidant.
Example 3
10g of citric acid, 10g of 3-aminopropyltriethoxysilane, 1g of polyethylene glycol, 9g of propylene glycol block polyether and 10g of glucose are stirred and mixed uniformly to obtain the antioxidant.
Example 4
1kg of tartaric acid, 1kg of gamma-mercaptopropyl-trimethoxysilane, 100g of propylene glycol block polyether, 900g of octylphenol polyoxyethylene ether and 1kg of maltose are stirred and mixed uniformly to obtain the antioxidant.
Example 5
Stirring and mixing 10g of citric acid, 10g of sodium metaaluminate, 1g of polyethylene glycol, 9g of propylene glycol block polyether, 10g of glucose and 10g of zirconia sol uniformly to obtain the antioxidant.
Example 6
1kg of tartaric acid, 1kg of sodium tungstate, 100g of fatty alcohol-polyoxyethylene ether, 900g of octylphenol-polyoxyethylene ether, 1kg of maltose and 500g of silica sol are stirred and mixed uniformly to obtain the antioxidant.
Example 7
Stirring and uniformly mixing 10g of citric acid, 10g of sodium metaaluminate, 1g of polyethylene glycol, 9g of sodium dodecyl benzene sulfonate and 10g of saccharin sodium to obtain the antioxidant.
Example 8
1kg of tartaric acid, 1kg of sodium tungstate, 100g of fatty alcohol-polyoxyethylene ether, 900g of polyoxyethylene stearate and 1kg of acesulfame potassium are stirred and mixed uniformly to obtain the antioxidant.
Example 9
And (3) uniformly stirring and mixing 750g of citric acid, 600g of sodium metaaluminate, 200g of polyethylene glycol, 700g of polyoxyethylene stearate and 550g of glucose to obtain the antioxidant.
Comparative example 1
0.5g of chromium trioxide, 0.3g of sodium methyl disulfate, 0.2g of potassium methyl disulfonate and 999g of pure water were formulated as a composite antioxidant.
The heavy metals used in comparative example 1 are not environmentally friendly and are not conducive to sustainable development.
Comparative example 2
1kg of methylbenzotriazole, 1kg of gamma-mercaptopropyltrimethoxysilane, 100g of fatty alcohol-polyoxyethylene ether, 900g of polyoxyethylene stearate and 1kg of maltose are stirred and mixed uniformly to obtain the antioxidant.
The chelating agent used in comparative example 2 is an azole compound, and the chelating ability with copper is weak, so that the copper wrapping ability is weak, and the oxidation preventing effect is poor.
Any one of the antioxidants of examples 1 to 9 and comparative examples 1 to 2 was used for the treatment of the copper foil by the following process:
1. the temperature of the antioxidant in the antioxidant groove is controlled.
2. And stripping the electrolytic copper foil from the foil forming machine, leading the electrolytic copper foil to enter an anti-oxidation tank through a guide roller, and immersing the copper foil into an antioxidant through the anti-oxidation tank.
3. And extruding the soaked copper foil by an extrusion guide roller to clean the antioxidant remained on the surface of the copper foil, and then drying by hot air and rolling.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150 ℃ for 150mm by 150mm, preserving the heat for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil. The test results are shown in the following table.
Table 1 copper foil antioxidant test results
Compared with the examples, the comparative examples not only contain heavy metal ions, but also have poor oxidation prevention effect, and need to be baked in an oven.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. An electrolytic copper foil antioxidant is characterized by comprising the following components: according to the mass portion, 0.1-10 portions of carboxylic acid, 0.1-5 portions of inorganic salt or silane coupling agent, 0.1-10 portions of surfactant mixture and 0.1-10 portions of film-forming agent,
the surfactant mixture includes: at least one surfactant having an HLB value of less than 14 and at least one surfactant having an HLB value of greater than 14.
2. The copper foil dotting oxidation inhibitor as claimed in claim 1, further comprising 0.1-5 parts of sol.
3. The electrolytic copper foil antioxidant as claimed in claim 1, wherein the carboxylic acid is selected from one or more of S-carboxyethylthiosuccinic acid, citric acid and tartaric acid.
4. The electrolytic copper foil antioxidant as set forth in claim 1, wherein the inorganic salt is selected from one or more of sodium metaaluminate, potassium metaaluminate, sodium silicate, potassium silicate, ammonium silicate, sodium tungstate, potassium tungstate, ammonium tungstate, sodium molybdate, potassium molybdate and ammonium molybdate.
5. The electrolytic copper foil antioxidant as claimed in claim 1, wherein the silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, gamma-diethylenetriaminepropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, and gamma-mercaptopropyltrimethoxysilane.
6. The electrolytic copper foil antioxidant as claimed in claim 1, wherein the surfactant having an HLB value of less than 14 is selected from one or more of castor oil polyoxyethylene ether, isotridecanol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyethylene glycol, sodium dodecylsulfonate, and sodium dodecylbenzenesulfonate.
7. The electrolytic copper foil antioxidant as claimed in claim 1, wherein the surfactant having an HLB value of more than 14 is selected from the group consisting of fatty alcohol-polyoxyethylene ether, polyoxyethylene stearate, and propylene glycol block polyether.
8. The electrolytic copper foil antioxidant as set forth in claim 1, wherein said film-forming agent is selected from one or more of glucose, maltose, galactose, lactose, fructose, saccharin sodium and acesulfame potassium.
9. The electrolytic copper foil antioxidant as claimed in claim 2, wherein the sol is selected from one or more of zirconia sol, silica sol, alumina sol and titania sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010803247.2A CN112095109A (en) | 2020-08-11 | 2020-08-11 | Electrolytic copper foil antioxidant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010803247.2A CN112095109A (en) | 2020-08-11 | 2020-08-11 | Electrolytic copper foil antioxidant |
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| CN112095109A true CN112095109A (en) | 2020-12-18 |
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| CN202010803247.2A Pending CN112095109A (en) | 2020-08-11 | 2020-08-11 | Electrolytic copper foil antioxidant |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113463078A (en) * | 2021-08-04 | 2021-10-01 | 武汉轻工大学 | Preparation method and application of anti-oxidation liquid containing polyhydroxy organic matter |
| CN113564572A (en) * | 2021-08-04 | 2021-10-29 | 武汉轻工大学 | Preparation and application of novel electrolytic copper foil anti-oxidation liquid |
| CN113755829A (en) * | 2021-08-16 | 2021-12-07 | 深圳市志凌伟业光电有限公司 | Blackening-treated copper film surface anticorrosion protective liquid medicine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113463078A (en) * | 2021-08-04 | 2021-10-01 | 武汉轻工大学 | Preparation method and application of anti-oxidation liquid containing polyhydroxy organic matter |
| CN113564572A (en) * | 2021-08-04 | 2021-10-29 | 武汉轻工大学 | Preparation and application of novel electrolytic copper foil anti-oxidation liquid |
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| CN113755829A (en) * | 2021-08-16 | 2021-12-07 | 深圳市志凌伟业光电有限公司 | Blackening-treated copper film surface anticorrosion protective liquid medicine |
| CN113755829B (en) * | 2021-08-16 | 2024-05-07 | 深圳市志凌伟业技术股份有限公司 | Blackening-treated copper film surface anti-corrosion protection liquid medicine |
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