CN114836744A - Chromium-free passivation solution for copper foil and preparation method thereof - Google Patents
Chromium-free passivation solution for copper foil and preparation method thereof Download PDFInfo
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- CN114836744A CN114836744A CN202210458345.6A CN202210458345A CN114836744A CN 114836744 A CN114836744 A CN 114836744A CN 202210458345 A CN202210458345 A CN 202210458345A CN 114836744 A CN114836744 A CN 114836744A
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- 238000002161 passivation Methods 0.000 title claims abstract description 83
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000011889 copper foil Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 23
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 60
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims abstract description 58
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 30
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 30
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 21
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 21
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 21
- 229940033123 tannic acid Drugs 0.000 claims abstract description 21
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 21
- 229920002258 tannic acid Polymers 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 125000005605 benzo group Chemical group 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007605 air drying Methods 0.000 abstract description 12
- 238000005406 washing Methods 0.000 abstract description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052804 chromium Inorganic materials 0.000 abstract description 7
- 239000011651 chromium Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000007336 electrophilic substitution reaction Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920001864 tannin Polymers 0.000 description 4
- 239000001648 tannin Substances 0.000 description 4
- 235000018553 tannin Nutrition 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- -1 oxygen free radical Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a chromium-free passivation solution for copper foil and a preparation method thereof. The chromium-free passivation solution comprises the following components: 0.1-5 parts of benzo, 0.1-3 parts of tannic acid, 0.2-4 parts of benzoic acid, 1-20 parts of n-propyl acetate and 100 parts of water. The preparation method of the chromium-free passivation solution comprises the following steps: at normal temperature, dissolving the benzene and the benzoic acid in n-propyl acetate to form a first solution, wherein the benzoic acid is easily dissolved in the n-propyl acetate, and the benzene in the solution generate electrophilic substitution reaction; mixing the first solution with tannic acid to form a second solution, wherein the tannic acid and benzoic acid jointly act on benzene to promote the benzene to form a polymer precursor; and dissolving the second solution in water, and uniformly mixing to form the chromium-free passivation solution. Passivating the copper foil by using the chromium-free passivation solution: immersing the copper foil into a chromium-free passivation solution for 0.1-10 s; and taking out the copper foil, washing with clear water, and air-drying to complete passivation. Compared with the conventional chromium-containing passivator, the chromium-containing passivator is more environment-friendly, and meanwhile, the passivation performance is improved.
Description
Technical Field
The invention belongs to the technical field of copper foil production, and particularly relates to a chromium-free passivation solution for a copper foil, a preparation method of the chromium-free passivation solution and a passivation method for the copper foil.
Technical Field
The prepared copper foil needs a passivation process, so that a passivation film is formed on the surface of the copper foil, and the storage time of the copper foil is prolonged by preventing the surface of the copper foil from being oxidized. The unprotected copper foil is oxidized to form local spots during the contact process with air, and the intrinsic performance and the subsequent processing of the copper foil are influenced.
Traditionally, the cost of forming a protective layer using chromate containing solutions has been low but the effectiveness has been controversial. Such as: the chromium oxide layer is cracked, and a layer of zinc or zinc alloy needs to be plated under the oxide layer to isolate the surface of the copper foil. Meanwhile, chromium-containing ions have certain toxicity and pollute the environment, and certain cost is needed if the chromium-containing ions in the sewage are treated.
Organic passivation solution is another way to solve the problem of passivation of copper foil. Unlike the complex passivation process of chromium-containing passivation solution, the copper foil can form a uniform and compact protective layer on the surface only by soaking in the organic passivation solution for a period of time.
But organic passivation solutions generally do not perform as well as chromium-containing passivation solutions. The organic passivation solution mainly takes water as a solvent, and has the problems of slow dissolution rate and strong volatilization of organic active substances in the preparation process, so that the preparation efficiency of the organic passivator and the concentration of active ingredients in the passivator are reduced.
Disclosure of Invention
The invention aims to provide a chromium-free organic passivation solution for copper foil and a preparation method thereof, which aim to realize passivation by adopting a specific organic solution, reduce the emission of pollutants and facilitate environmental protection, and simultaneously, organic components are selected to promote dissolution, so that the preparation efficiency of the passivation solution is accelerated, the passivation effect is improved, and the method has remarkable economic and social benefits.
In order to achieve the above purpose, the invention provides the following technical scheme.
The chromium-free passivation solution for the copper foil is an organic passivation solution, and comprises the following components in parts by mass:
and (3) benzene synthesis: 0.1-5 parts;
tannic acid: 0.1-3 parts;
benzoic acid: 0.2-4 parts;
n-propyl acetate: 1-20 parts;
water: 100 parts.
In the chromium-free passivation solution, benzo and copper atoms form covalent bonds and coordination bonds, and the covalent bonds and the coordination bonds are mutually replaced by chain polymers, so that a protective film is formed on the surface of copper, and the contact between the copper and oxygen molecules is avoided. Tannic acid has antioxidant effect, and can reduce oxygen content on copper surface through reduction reaction, and inhibit oxidation reaction by combining with oxygen free radical in environment via hydrogen donor to stop chain reaction initiated by free radical in polymer. Benzoic acid is not easy to be oxidized, electrophilic substitution reaction can occur on the benzene ring of the benzoic acid, and a meta-substitution product is mainly obtained. The n-propyl acetate can increase the solubility of the three organic matters, and compared with the traditional solvents of ethanol and glycerol, the n-propyl acetate can release active substances from the solution to be adsorbed on the surface of the copper foil more easily, so that the passivation efficiency is higher when the n-propyl acetate is used as a cosolvent. When benzene, tannin, benzoic acid and n-propyl acetate are organically mixed, the benzoic acid and the tannin and the benzene under the action of the n-propyl acetate cooperate to form a polymer with a complex configuration, pi bonds of the polymer and outer unsaturated empty orbitals of copper atoms form stable chelates, and the formed passivation film is colorless, transparent and compact, thereby achieving the purpose of preventing the copper parts from being oxidized, discolored and blackened.
Among them, it is preferable that,
and (3) benzene synthesis: 0.2-1.5 parts;
tannic acid: 0.3-1.1 parts;
benzoic acid: 0.4-1.6 parts;
n-propyl acetate: 1-10 parts;
water: 100 parts.
Among them, more preferably 0.5 part of benzo; 1 part of tannic acid; 0.8 part of benzoic acid; 5 parts of n-propyl acetate; 100 parts of water.
The invention also provides a preparation method of the chromium-free passivation solution for the copper foil, which comprises the following steps:
dissolving benzo and benzoic acid in n-propyl acetate at normal temperature to form a first solution; benzoic acid is easily dissolved in n-propyl acetate, and in the n-propyl acetate solution, benzoic acid and benzene generate electrophilic substitution reaction.
Mixing the first solution with tannic acid to form a second solution; the tannin is added to enable the tannin and the benzoic acid to jointly act on the benzene and promote the benzene to form a polymer precursor.
And dissolving the second solution in water, and uniformly mixing to form organic passivation solution containing different effective components, namely the chromium-free passivation solution.
The invention also provides a method for passivating the copper foil by using the chromium-free passivation solution of the copper foil, which comprises the following steps:
immersing the copper foil into the chromium-free passivation solution to fully soak the upper surface and the lower surface, and keeping for 0.1-10 s; and taking out the copper foil, washing the copper foil with clear water, and carrying out air drying treatment on the copper foil to finish the passivation process.
After extensive research, the inventor of the invention finds that the situation that the effective components of organic matters are difficult to dissolve can be effectively improved by adding the organic solvent into the formula of the passivating agent. In the research, the inventors tried various organic solvents such as ethanol, glycerol, n-propyl acetate, and the like. In experiments, the dissolution efficiency is greatly improved when organic solvents containing a large amount of hydroxyl groups, such as ethanol and glycerol, are used, but the passivation effect of the passivating agent is obviously influenced, and the method is presumably related to the generation of a large amount of hydrogen bonds between the solvents and the effective components to prevent the effective components from being adsorbed to the surface of the copper foil. For the organic matter of esters, the dissolution efficiency is not as good as that of alcohols, but the dissolution efficiency is still improved considerably compared with the single use of water as a solvent. In particular, when the n-propyl acetate is used as a solvent of the benzo and the benzoic acid and is combined with the benzo, the benzoic acid and the tannic acid for use, the copper is promoted to replace a hydrogen atom in an NH functional group of one benzo molecule at a solid-liquid interface, the hydrogen atom is connected with the hydrogen atom through a covalent bond, and the hydrogen atom is connected with a free electron of a nitrogen atom in another benzo molecule through a coordination bond to form a semi-permeable chelate, so that a good passivation effect is achieved.
Compared with the prior art, the method changes the conventional method for obtaining the copper foil oxide layer by using the chromium-containing passivator, improves the manufacturability and environmental protection in the passivation process, and simultaneously has better passivation performance compared with the passivator in the market. And due to the introduction of n-propyl acetate, the preparation efficiency of the passivation solution is obviously improved, the affinity of the effective components and the solvent is also obviously improved, and the loss of the effective components in the preparation process is reduced. Therefore, the cost is reduced, and the economic benefit is improved.
Drawings
FIG. 1 is a photograph showing the surface state of a copper foil sample of example 1 after heating at 130 ℃ for one hour, which still shows the natural color of copper without significant oxidation.
FIG. 2 is a photograph showing the surface state of a copper foil sample of comparative example 1 heated at 130 ℃ for one hour, and the surface was significantly oxidized and had non-uniform color.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
Dissolving 0.1 part of benzo and 0.2 part of benzoic acid in 1 part of n-propyl acetate, mixing with 0.1 part of tannic acid, dissolving in 100 parts of water, and uniformly mixing to obtain an organic passivation solution; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 10 s. And (5) washing the taken copper foil with clear water, and carrying out air drying treatment to complete the preparation.
Example 2
Dissolving 5 parts of benzo and 4 parts of benzoic acid in 20 parts of n-propyl acetate, mixing with 3 parts of tannic acid, dissolving in 100 parts of water, and uniformly mixing to obtain an organic passivation solution; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 0.1 s. And (5) washing the taken copper foil with clear water, and carrying out air drying treatment to complete the preparation.
Example 3
Dissolving 0.2 part of benzo and 0.4 part of benzoic acid in 1 part of n-propyl acetate, mixing with 0.3 part of tannic acid, dissolving in 100 parts of water, and uniformly mixing to obtain an organic passivation solution; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 10 s. And (5) washing the taken copper foil with clear water, and carrying out air drying treatment to complete the preparation.
Example 4
Dissolving 1.5 parts of benzo and 1.6 parts of benzoic acid in 10 parts of n-propyl acetate, mixing with 1.1 parts of tannic acid, dissolving in 100 parts of water, and uniformly mixing to obtain an organic passivation solution; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 0.1 s. And (5) washing the taken copper foil with clear water, and carrying out air drying treatment to complete the preparation.
Example 5
Dissolving 0.5 part of benzo and 1 part of benzoic acid in 5 parts of n-propyl acetate, mixing with 0.8 part of tannic acid, dissolving in 100 parts of water, and uniformly mixing to obtain an organic passivation solution; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 1 s. And (5) washing the taken copper foil with clear water, and carrying out air drying treatment to complete the preparation.
Comparative example 1
Dissolving 0.2 part of benzo, 0.3 part of benzoic acid and 0.4 part of tannic acid in 100 parts of water, and uniformly mixing to obtain an organic passivation solution; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 10 s. And (5) washing the taken copper foil with clear water, and carrying out air drying treatment to complete the preparation.
Comparative example 2
Dissolving 0.2 part of benzene in 1 part of n-propyl acetate, then dissolving the mixture and 0.3 part of tannic acid in 100 parts of water, and uniformly mixing to obtain an organic passivation solution; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 10 s. And (5) washing the taken copper foil with clear water, and carrying out air drying treatment to complete the preparation.
Comparative example 3
Dissolving 0.4 part of benzoic acid in 1 part of n-propyl acetate, then dissolving the benzoic acid and 0.3 part of tannic acid in 100 parts of water together, and uniformly mixing to obtain an organic passivation solution; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 10 s. And (5) washing the taken copper foil with clear water, and carrying out air drying treatment to complete the preparation.
Comparative example 4
Dissolving 0.2 part of benzo and 0.4 part of benzoic acid in 1 part of n-propyl acetate, then dissolving in 100 parts of water, and uniformly mixing to obtain an organic passivation solution; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 10 s. And (5) washing the taken copper foil with clear water, and carrying out air drying treatment to complete the preparation.
Comparative example 5
Purchasing a conventional hexavalent chromium passivation solution from the market; and immersing the copper foil into the passivation solution to fully soak the upper surface and the lower surface, and keeping for 2 s. And (5) washing the copper foil taken out with clear water, and performing air drying treatment to complete preparation.
The air-dried copper foils of the above examples and comparative examples were placed in an oven and heated at 130 c for one hour, and were subjected to chemical analysis to obtain a surface oxide film thickness, as shown in table 1. Referring to FIG. 1, a photograph showing the surface state of a copper foil sample of example 1 after heating at 130 ℃ for one hour still shows the natural color of copper which is not significantly oxidized. FIG. 2 is a photograph showing the surface state of the copper foil sample of comparative example 1 after heating at 130 ℃ for one hour, which was remarkably oxidized and non-uniform in color.
Table 1: thickness of surface oxide film after baking treatment after passivation of copper foil of each example and comparative example
| Copper foil sample | Thickness of oxide film (unit: micron) |
| Example 1 | 2.39 |
| Example 2 | 2.21 |
| Example 3 | 2.18 |
| Example 4 | 2.01 |
| Example 5 | 1.82 |
| Comparative example 1 | 4.92 |
| Comparative example 2 | 3.91 |
| Comparative example 3 | 6.35 |
| Comparative example 4 | 4.23 |
| Comparative example 5 | 2.51 |
As can be seen from the results of the thickness of the oxide films in the embodiments 1 to 5, when the passivation solution is used according to the proportion and the configuration mode of the technical scheme, the copper foil can obtain good oxidation resistance, and the thickness of the oxide film is even slightly lower than that of the copper foil treated by the conventional hexavalent chromium passivation solution (comparative example 5). The passivation solution in the optimized range can further reduce the oxide film and achieve more excellent antioxidant effect.
As can be seen from the thickness of the oxide films of the embodiment 1 and the comparative examples 1 to 4, when the proportion or the configuration mode of the technical scheme is not followed, the passivation effect of the solution is poor, and the thickness of the oxide film of the obtained copper foil is obviously thicker. According to the data, the copper foil chromium-free passivation solution disclosed by the embodiment of the invention has excellent performance and can completely meet the industrial requirements. Compared with the traditional chromate passivation process, the oxidation resistance is better; and because the paint does not contain heavy metal hexavalent chromium, no toxic and harmful substances are discharged. And the preparation and passivation process is simple, the operability is strong, and the method is green and nontoxic.
Claims (6)
1. The chromium-free passivation solution for the copper foil is an organic passivation solution and is characterized by comprising the following components:
and (3) benzene synthesis: 0.1-5 parts;
tannic acid: 0.1-3 parts;
benzoic acid: 0.2-4 parts;
n-propyl acetate: 1-20 parts;
water: 100 parts of (A);
wherein the mixture ratio is mass ratio.
2. The chromium-free passivation solution for copper foil according to claim 1, characterized in that it consists of the following components:
and (3) benzene synthesis: 0.2-1.5 parts;
tannic acid: 0.3-1.1 parts;
benzoic acid: 0.4-1.6 parts;
n-propyl acetate: 1-10 parts;
water: 100 parts of (A);
wherein the proportion of the components is mass ratio.
3. The chromium-free passivation solution for copper foil according to claim 2, characterized in that it consists of the following components: 0.5 part of benzene; 1 part of tannic acid; 0.8 part of benzoic acid; 5 parts of n-propyl acetate; 100 parts of water; wherein the proportion of the components is mass ratio.
4. The method for preparing the chromium-free passivation solution for copper foil according to any one of claims 1 to 3, characterized by comprising the steps of:
1) dissolving benzo and benzoic acid in n-propyl acetate at normal temperature to form a first solution;
2) mixing the first solution with tannic acid to form a second solution;
3) and dissolving the second solution in water, and uniformly mixing to form organic passivation solution containing different effective components, namely the chromium-free passivation solution.
5. The use of the chromium-free passivation solution for copper foil according to any one of claims 1 to 3, wherein the chromium-free passivation solution passivates the copper foil by: and the copper foil is immersed into the chromium-free passivation solution to fully infiltrate the upper surface and the lower surface, and then the copper foil is taken out to be washed by clear water and dried in the air.
6. The use of the chromium-free passivation solution for copper foil according to claim 5, characterized in that: and the copper foil is kept soaked in the chromium-free passivation solution for 0.1-10 s.
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