CN111962081A - Organic phosphonic acid and derivative thereof based copper foil anti-oxidation additive and preparation method thereof - Google Patents
Organic phosphonic acid and derivative thereof based copper foil anti-oxidation additive and preparation method thereof Download PDFInfo
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- CN111962081A CN111962081A CN202010803217.1A CN202010803217A CN111962081A CN 111962081 A CN111962081 A CN 111962081A CN 202010803217 A CN202010803217 A CN 202010803217A CN 111962081 A CN111962081 A CN 111962081A
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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
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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
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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Abstract
The invention belongs to the technical field of electrolytic copper foil surface treatment, and particularly relates to an organic phosphonic acid and derivative thereof based copper foil anti-oxidation additive and a preparation method thereof. The organic phosphonic acid and the derivative thereof based copper foil anti-oxidation additive provided by the invention comprise: the organic phosphonic acid film forming agent comprises organic phosphonic acid and derivatives thereof, a film forming auxiliary agent, a surfactant, a reducing agent and water, wherein the concentration of the organic phosphonic acid and the derivatives thereof is 0.01-5 g/L, the concentration of the film forming auxiliary agent is 0.05-5 g/L, the concentration of the surfactant is 0.05-5 g/L, and the concentration of the reducing agent is 0.05-5 g/L. The antioxidant provided by the invention does not contain heavy metal ions, does not need to be electrified or washed by water, is convenient to use, is safe and environment-friendly, and is a new generation of electrolytic copper foil antioxidant.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil surface treatment, and particularly relates to an organic phosphonic acid and derivative thereof based copper foil anti-oxidation additive.
Background
In recent years, the technology of electronic copper foil has been rapidly developed, and particularly, great technological progress has been made on copper foil for Printed Circuit Boards (PCBs) and lithium ion batteries, but an important problem in the industry is the technology of oxidation prevention treatment of the surface of electrolytic copper foil. At present, the common method mainly uses chromate antioxidant, nickel salt, zinc salt and cobalt salt to prevent forming oxidation liquid, or combines the two oxidation liquids, and a layer of oxidation-resistant film is plated on the surface of the copper foil through the electroplating of an oxidation-resistant tank, so that the purpose of oxidation resistance is achieved. However, with the stricter environmental requirements, the heavy metal ion antioxidant, especially the chromium ion antioxidant with high carcinogenicity, will rapidly exit the historical stage, and the development of a new electrolytic copper foil antioxidant which does not contain heavy metal ions and is safe and environment-friendly has important significance.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method. The invention aims to provide an electrolytic copper foil antioxidant and a preparation method thereof, and the antioxidant provided by the invention does not contain heavy metal ions, does not need to be electrified or washed by water, is convenient to use, is safe and environment-friendly, and is a new generation of electrolytic copper foil antioxidant.
The technical scheme provided by the invention is as follows:
an organic phosphonic acid and derivative thereof based copper foil anti-oxidation additive comprises: the organic phosphonic acid film forming agent comprises organic phosphonic acid and derivatives thereof, a film forming auxiliary agent, a surfactant, a reducing agent and water, wherein the concentration of the organic phosphonic acid and the derivatives thereof is 0.01-5 g/L, the concentration of the film forming auxiliary agent is 0.05-5 g/L, the concentration of the surfactant is 0.05-5 g/L, and the concentration of the reducing agent is 0.05-5 g/L.
In the above technical scheme:
organic phosphonic acid and derivatives thereof are used as chelating agents to be chelated with copper on the surface of the copper foil to form a stable chelated anti-oxidation layer; the organic phosphonic acid and the derivatives thereof are selected as the chelating agent, the organic phosphonic acid and the derivatives thereof have many chelating sites, strong chelating capacity, strong chelate stability and high temperature resistance, and the anti-oxidation high temperature resistance of the copper foil can be obviously improved. Compared with the organic carboxylic acid chelating agent, the organic carboxylic acid chelating agent has better solubility and is easy to improve the film forming property.
The film forming auxiliary agent can form a compact structure, fills up a chelating anti-oxidation layer and further enhances the anti-oxidation function;
the surfactant promotes the dispersion of each component in the system;
the reducing agent has antioxidant effect.
Based on the technical scheme, the copper foil anti-oxidation additive based on the organic phosphonic acid and the derivatives thereof can form a chelating anti-oxidation layer on the surface of the copper foil and a compact anti-oxidation layer composed of a compact structure formed by the film forming auxiliary agent, thereby realizing the anti-oxidation of the copper foil.
Specifically, the organic phosphonic acid and the derivatives thereof are selected from any one or a combination of several of amino trimethylene phosphonic Acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP), ethylene diamine tetra methylene phosphonic acid (EDTMP), Ethylene Diamine Tetra Methylene Phosphonic Acid (EDTMPA), diethylene triamine penta methylene phosphonic acid (DTPMP), 2-phosphonic butane-1, 2, 4-tricarboxylic acid (PBTCA), polyol phosphate ester (PAPE), 2-hydroxyphosphonoacetic acid (HPAA), inositol hexaphosphoric acid (PHA), inositol hexaphosphate ester (PHAA), hexamethylenediamine tetramethylmethylene phosphonic acid (HDTMPA), polyamino poly ether methylene Phosphonic Acid (PAPEMP), bis 1, 6-hexylidene triamine pentamethylene phosphonic acid (bhpmpa).
In the technical scheme, each organic phosphonic acid and the derivatives thereof are used as chelating agents to be chelated with copper on the surface of the copper foil to form a stable chelated anti-oxidation layer; the organic phosphonic acid and the derivatives thereof are selected as the chelating agent, the organic phosphonic acid and the derivatives thereof have many chelating sites, strong chelating capacity, strong chelate stability and high temperature resistance, and the anti-oxidation high temperature resistance of the copper foil can be obviously improved. Compared with the organic carboxylic acid chelating agent, the organic carboxylic acid chelating agent has better solubility and is easy to improve the film forming property.
Specifically, the film-forming assistant is a sol precursor, a sol or a silane coupling agent.
In the technical scheme, the sol precursor and the sol can form compact structures on the smooth surface and the rough surface of the copper foil, so that the anti-oxidation effect on the copper foil is further enhanced; the silane coupling agent is easy to form a compact structure on the rough surface of the copper foil, and the anti-oxidation effect on the copper foil is further enhanced.
Specifically, the sol precursor is selected from one or more of sodium metaaluminate, potassium metaaluminate, sodium silicate, potassium silicate and ammonium silicate.
The sol precursors can form compact structures on the smooth surface and the rough surface of the copper foil as film forming aids, so that a chelating anti-oxidation layer is filled, and the anti-oxidation function is further enhanced.
Specifically, the sol is selected from any one or a combination of several of zirconia sol, alumina sol, silica sol or titania sol.
The sol can be used as a film forming aid to form a compact structure on the smooth surface and the rough surface of the copper foil, so that a chelating anti-oxidation layer is filled, and the anti-oxidation function is further enhanced.
Specifically, the silane coupling agent is selected from any one or a combination of more of 3-aminopropyltriethoxysilane, gamma-diethylenetriamine propyl methyldimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3- (2, 3-glycidoxy) propyl methyldimethoxysilane or gamma-mercaptopropyltrimethoxysilane.
The silane coupling agents can form a compact structure on the rough surface of the copper foil as a film forming aid, so that a chelating anti-oxidation layer is filled, and the anti-oxidation function is further enhanced.
Specifically, the surfactant is selected from fatty alcohol polyoxyethylene ether (common trade marks: AEO-15, AEO-20 and AEO-23), polyoxyethylene stearate (common trade marks: SG-40 and SG-50), alkylphenol polyoxyethylene ether (common trade marks: nonylphenol polyoxyethylene ether, common trade marks: NP-9 and NP-10), octylphenol polyoxyethylene ether (common trade mark OP-20), castor oil polyoxyethylene ether (common trade marks: EL-30, EL-40 and HEL-40), isotridecanol polyoxyethylene ether (common trade marks: 1303 and 1305), polyethylene glycol (common trade marks: PEG400, PEG6000 and PEG10000), propylene glycol block polyether (common trade marks: L45 and F68), and any one or a combination of a plurality of sodium dodecyl sulfonate or sodium dodecyl benzene sulfonate. Preferably, a mixture of the plurality is used.
The surfactants described above can facilitate the dispersion of the components in the system.
Preferably, the reducing agent is a reducing sugar.
Based on the technical scheme, the reducing sugar can supplement the antioxidant effect on one hand, and has certain decocting capability on the other hand, and can supplement the chelating capability of the organic phosphonic acid and the derivatives thereof on the surface of the copper foil.
Specifically, the reducing sugar is selected from one or more of glucose, maltose, galactose, lactose, fructose, and saccharin sodium.
The invention also provides a preparation method of the copper foil anti-oxidation additive based on the organic phosphonic acid and the derivatives thereof, which comprises the following steps: dissolving organic phosphonic acid and derivatives thereof, film forming auxiliary agent, surfactant and reducing agent in water.
The organic phosphonic acid and the derivative thereof based copper foil anti-oxidation additive provided by the invention can be prepared by the method. The preparation method is simple, efficient and convenient for industrial production.
The organic phosphonic acid and the derivative thereof based copper foil anti-oxidation additive provided by the invention can be used according to the following method:
1. preparing an antioxidant, and controlling the temperature of the antioxidant in the anti-oxidation tank.
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.
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.
Copper foil anti-oxidation additive based on organic phosphonic acid and derivatives thereof
The copper foil anti-oxidation additive based on organic phosphonic acid and derivatives thereof prepared by the preparation method provided by the invention
Use of copper foil anti-oxidation additive based on organic phosphonic acid and derivatives thereof
Immersing the copper foil produced by the foil producing machine into the additive for 6-20 seconds (the temperature of the additive is 20-40 ℃), extruding by a roller, and drying and rolling by hot air at 50-120 ℃.
Example 1
1) And dissolving A, B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 0.1 g/L; concentration of the agent B: 5 g/L; the concentration of the agent C is 2 g/L; concentration of agent D: 1 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the agent B comprises the following components: potassium metaaluminate and sodium silicate in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Example 2
1) And dissolving A, B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 5 g/L; concentration of the agent B: 5 g/L; the concentration of the agent C is 2 g/L; concentration of agent D: 1 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the agent B comprises the following components: potassium metaaluminate and sodium silicate in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Example 3
1) And dissolving A, B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 10 g/L; concentration of the agent B: 5 g/L; the concentration of the agent C is 2 g/L; concentration of agent D: 1 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the agent B comprises the following components: potassium metaaluminate and sodium silicate in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Example 4
1) And dissolving A, B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 0.1 g/L; concentration of the agent B: 5 g/L; the concentration of the agent C is 2 g/L; concentration of agent D: 1 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and 2-hydroxyphosphonoacetic acid in a mass ratio of 1: 3.
the agent B comprises the following components: potassium metaaluminate and sodium silicate in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Example 5
1) And dissolving A, B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 0.1 g/L; concentration of the agent B: 5 g/L; the concentration of the agent C is 2 g/L; concentration of agent D: 1 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the agent B comprises the following components: zirconia sol and alumina sol in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Example 6
1) And dissolving A, B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 0.1 g/L; concentration of the agent B: 5 g/L; the concentration of the agent C is 2 g/L; concentration of agent D: 1 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the agent B comprises the following components: n-2-aminoethyl-3-aminopropylmethyldimethoxysilane and 3- (2, 3-glycidoxy) propylmethyldimethoxysilane in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Example 7
1) And dissolving A, B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 10 g/L; concentration of the agent B: 2.5 g/L; the concentration of the agent C is 0.1 g/L; concentration of agent D: 10 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the agent B comprises the following components: potassium metaaluminate and sodium silicate in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Example 8
1) And dissolving A, B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 5 g/L; concentration of the agent B: 0.1 g/L; the concentration of the agent C is 10 g/L; concentration of agent D: 5 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the agent B comprises the following components: potassium metaaluminate and sodium silicate in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Example 9
1) And dissolving A, B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 0.1 g/L; concentration of the agent B: 5 g/L; the concentration of the agent C is 5 g/L; concentration of agent D: 0.1 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the agent B comprises the following components: potassium metaaluminate and sodium silicate in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Comparative example 1
1) And dissolving B, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent B: 5 g/L; the concentration of the agent C is 2 g/L; concentration of agent D: 1 g/L.
The agent B comprises the following components: potassium metaaluminate and sodium silicate in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the copper foil.
Comparative example 2
1) And dissolving A, C, D agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 0.1 g/L; the concentration of the agent C is 2 g/L; concentration of agent D: 1 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
The agent D comprises the following components: fructose, saccharin sodium and glucose in a mass ratio of 1:2: 5.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
Placing the copper foil subjected to anti-oxidation treatment at 150mm to 150mm in an oven, setting the treatment temperature, respectively keeping the temperature for 15 minutes and 30 minutes, and observing the surface condition of the copper foil
Comparative example 3
1) And dissolving A, B, C agent in deionized water according to the mass ratio to form the copper foil antioxidant. Wherein: concentration of the agent A: 0.1 g/L; concentration of the agent B: 5 g/L; the concentration of the agent C is 2 g/L; concentration of agent D: 1 g/L.
The agent A comprises the following components: amino trimethylene phosphonic acid and hydroxy ethylidene diphosphonic acid, the mass ratio is 1: 3.
the agent B comprises the following components: potassium metaaluminate and sodium silicate in a mass ratio of 10: 1.
The component of the agent C is as follows: polyethylene glycol (PEG400) and propylene glycol block polyether (F68) in a mass ratio of 5: 1.
2) And (3) injecting the copper foil antioxidant into an antioxidant tank after passing through a fine filtration pump, and controlling the temperature of the tank liquor to be 30 ℃. And stripping the electrolytic copper foil from a crude foil machine, enabling the electrolytic copper foil to enter an anti-oxidation groove through a guide roller, immersing the copper foil in an antioxidant for 7s through the anti-oxidation groove, extruding the immersed copper foil through an extrusion guide roller to completely remove the antioxidant remained on the surface of the copper foil, drying the copper foil by hot air, and winding the copper foil.
Test of copper foil anti-oxidation effect
And (3) placing the copper foil subjected to the anti-oxidation treatment in an oven at 150mm to 150mm, setting the treatment temperature, keeping the temperature for 15 minutes and 30 minutes respectively, and observing the surface condition of the smooth surface of the copper foil.
The copper foil oxidation resistance test data of each example and comparative example are shown in the following table:
the data of each embodiment show that the azole compound-based copper foil has high stability in oxidation prevention, and the formed oxidation-resistant film can be stable at the temperature of 180 ℃ and has an obvious effect.
According to the respective proportions, it can be seen that the absence of the agent A, the absence of the agent B or the absence of the agent D causes the oxidation resistance of the copper foil to be lowered. The reduction in the absence of agent A is greater than the reduction in the absence of agent B.
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 (10)
1. An organic phosphonic acid and derivative thereof based copper foil anti-oxidation additive is characterized by comprising: the organic phosphonic acid film forming agent comprises organic phosphonic acid and derivatives thereof, a film forming auxiliary agent, a surfactant, a reducing agent and water, wherein the concentration of the organic phosphonic acid and the derivatives thereof is 0.01-5 g/L, the concentration of the film forming auxiliary agent is 0.05-5 g/L, the concentration of the surfactant is 0.05-5 g/L, and the concentration of the reducing agent is 0.05-5 g/L.
2. The organic phosphonic acid and its derivative based copper foil anti-oxidation additive of claim 1, characterized in that: the organic phosphonic acid and the derivatives thereof are selected from any one or the combination of several of amino trimethylene phosphonic acid, hydroxy ethylidene diphosphonic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine penta methylene phosphonic acid, 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid, polyalcohol phosphate ester, 2-hydroxy phosphoric acid radical acetic acid, inositol hexaphosphoric acid, inositol hexaphosphate ester, hexamethylene diamine tetramethylmethylene phosphonic acid, polyamino polyether methylene phosphonic acid and bis 1, 6-hexamethylene triamine penta methylene phosphonic acid.
3. The copper foil oxidation preventing additive based on organic phosphonic acid and derivatives thereof as claimed in claim 1, wherein: the film-forming auxiliary agent is a sol precursor, a sol or a silane coupling agent.
4. The organic phosphonic acid and its derivative based copper foil anti-oxidation additive of claim 3, characterized in that: the sol precursor is selected from one or more of sodium metaaluminate, potassium metaaluminate, sodium silicate, potassium silicate and ammonium silicate.
5. The organic phosphonic acid and its derivative based copper foil anti-oxidation additive of claim 3, characterized in that: the sol is selected from any one or combination of more of zirconia sol, alumina sol, silica sol or titania sol.
6. The organic phosphonic acid and its derivative based copper foil anti-oxidation additive of claim 3, characterized in that: the silane coupling agent is selected from any one or a combination of more of 3-aminopropyltriethoxysilane, gamma-diethylenetriamine propyl methyldimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3- (2, 3-glycidoxy) propyl methyldimethoxysilane or gamma-mercaptopropyltrimethoxysilane.
7. The organic phosphonic acid and its derivative based copper foil anti-oxidation additive of claim 1, characterized in that: the surfactant is selected from any one or a combination of a plurality of fatty alcohol polyoxyethylene ether, stearic acid polyoxyethylene ester, alkylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether, castor oil polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, polyethylene glycol, propylene glycol block polyether, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
8. The copper foil oxidation preventing additive based on organic phosphonic acid and its derivative as set forth in any one of claims 1 to 7, wherein: the reducing agent is reducing sugar.
9. The organic phosphonic acid and its derivatives as claimed in claim 8, wherein the copper foil oxidation preventing additive is characterized in that: the reducing sugar is selected from one or more of glucose, maltose, galactose, lactose, fructose and saccharin sodium.
10. A method for preparing copper foil oxidation preventing additive based on organic phosphonic acid and derivatives thereof according to any one of claims 1 to 9, characterized by comprising the following steps: dissolving organic phosphonic acid and derivatives thereof, film forming auxiliary agent, surfactant and reducing agent in water.
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