CN114927258A - Environment-friendly antioxidant conductive copper paste and preparation method and application thereof - Google Patents
Environment-friendly antioxidant conductive copper paste and preparation method and application thereof Download PDFInfo
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- CN114927258A CN114927258A CN202210646875.3A CN202210646875A CN114927258A CN 114927258 A CN114927258 A CN 114927258A CN 202210646875 A CN202210646875 A CN 202210646875A CN 114927258 A CN114927258 A CN 114927258A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- 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
- H05K1/00—Printed circuits
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- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
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Abstract
The invention relates to an environment-friendly antioxidant conductive copper paste and a preparation method thereof, wherein the conductive copper paste comprises the following raw materials in percentage by mass: copper powder 40-70 wt.%, organic binder 0.1-5 wt.%, bioreductive agent 3-10 wt.%, solvent 10-50 wt.%, and other additives 0.1-6 wt.%. The obtained environment-friendly anti-oxidation conductive copper paste can realize 180-fold low-temperature curing at 200 ℃, and after the copper paste product is stored for 45 days in the air atmosphere at room temperature, the volume resistivity of a copper wire or a copper film after sintering is still less than 5 multiplied by 10 ‑5 Omega cm, the conductivity of the copper paste can still be compared with that of the copper paste on the market. The environment-friendly antioxidant conductive copper paste prepared by the invention is suitable for circuit printing in flexible devices or electronic element preparation, and the used raw materials are environment-friendly, pollution-free and non-toxic, and meet the requirement of green production.
Description
Technical Field
The invention belongs to the field of material science, relates to a preparation method of conductive paste, and particularly relates to environment-friendly antioxidant conductive copper paste and a preparation method thereof.
Background
The conductive paste is widely applied to the fields of metallurgy, chemical engineering, electronic technology and the like as an important functional material, and generally mainly comprises three parts: a conductive phase, a binder phase and an organic vehicle. The conductive phase determines the basic properties of the conductive paste and affects the physical and mechanical properties of the paste product, and is typically metal particles, alloy particles, and mixtures thereof. The binder phase, which is used to bond the conductive paste film layer to the substrate material, is usually an organic binder or an inorganic binder, such as epoxy resin or a mixture of glass powder and oxide crystal, and affects the mechanical and dielectric properties of the formed film. The organic carrier is a mixture of organic polymer, surfactant, dispersant, thixotropic agent, etc. and solvent, and is a carrier for the conductive phase and the binding phase, and is used for wetting and dispersing the conductive phase particles and regulating and controlling the rheological property of the conductive paste.
The conductive phase of the conductive paste usually adopts noble metals such as silver and gold, and although the noble metals have excellent conductivity and excellent oxidation resistance, the noble metals are few in storage and high in cost, and the metal silver particles are easy to generate an electron transfer effect in the using process, so that the reliability of the product is poor. The metallic copper is an ideal substitute material for preparing the conductive paste, the copper reserves in China are rich, the price is much cheaper than that of silver and gold materials, and the conductivity is second to that of silver. However, copper is very active in chemical property, and is easily oxidized when exposed to air at normal temperature, an oxide film layer is formed on the surface of the copper, the resistivity of the oxide film layer is high, the conductivity is reduced, the practicability of the copper is greatly reduced, and the heat treatment temperature of the conductive slurry is greatly increased by the oxide film layer, so that the processing difficulty is increased.
In the prior art, in order to prevent copper powder from being oxidized, the commonly adopted method comprises the following steps: (1) silver or nickel is plated on the surface of the copper powder, the silver or the nickel is not easy to be oxidized in the air, and the copper is protected, but the uniformity and the coverage rate of a plating layer on the surface of the copper powder after the silver or the nickel plating are plated cannot be well ensured; (2) adding antioxidant components into an organic carrier, such as adding an antioxidant or a deoxidizing agent, wherein the antioxidant or the deoxidizing agent is oxidized before the copper powder is contacted with oxygen, so that the contact chance of the oxygen and the copper powder is reduced, the antioxidant hydrazine hydrate has toxicity, the deoxidizing agent comprises phosphorus-containing organic matters, rare earth elements and the like, but the addition of phosphorus seriously reduces the conductivity of the copper, so that the copper loses the function of serving as an electronic material, and the addition of the rare earth elements has the problem of environmental pollution; (3) the copper powder is wrapped by the organic high-molecular polymer, a protective shell layer is formed on the surface of the copper powder to isolate oxygen, but the shell layer structure is easy to break in the production and processing process, the risk of oxidation still exists when the shell layer structure is exposed in air, and the required amount of the surface coating agent is more than several times of the volume of copper, so that large-amplitude volume shrinkage during sintering can be caused, a high-density sintered body is difficult to obtain, and further the conductivity is deteriorated; (4) the problem of how to technically effectively avoid gas leakage is still solved by adopting a reducing sintering atmosphere, such as hydrogen and flammable and explosive reducing gas; (5) an organic corrosion inhibitor is added to form a protective coating on the surface of the copper powder, and the copper powder can be effectively prevented from being oxidized as a representative corrosion inhibitor such as an imidazole compound, but the heat resistance of the copper powder is poor, so that serious thermal history can occur when the temperature is over 150 ℃ in a heat treatment step, a surface oxidation film with poor conductivity of the copper powder is promoted to be formed, and the conductivity is greatly reduced; (6) copper powder oxidation is inhibited through low-temperature sintering, and the method can effectively solve the problem of copper powder oxidation.
For example, patent CN200810142382.6, three mixed copper powders with different particle sizes, glass powder and organic carrier are weighed in proportion, and then are mixed, ground, dispersed and rolled to obtain copper slurry, although the invention obtains a copper film with good conductivity by sintering, the sintering peak temperature is as high as 700 ℃, the glass transition temperature of most of high molecular materials is known to be lower than 200 ℃, and the glass transition temperature of the commonly used flexible substrates of PET and PI films is in the range of 200-300 ℃, so that the technical scheme is not suitable for flexible substrates and can limit the application scenarios.
At present, low-temperature sintering of copper paste is also reported, for example, patent CN201710534066.2 reports an electronic paste based on low-melting-point metal micro-nano powder and a preparation method thereof, low-melting-point metal or alloy (melting point is-78-232 ℃) is adopted as a conductive phase to reduce the sintering temperature, but metals such as chromium, mercury and the like are not environment-friendly and easily cause environmental pollution; in the patent CN202110392854.9, the copper paste with the particle size of 1-20 μm is adopted to realize 180-DEG C low-temperature curing at 300 ℃, but the used reagents such as phenyl glycidyl ether, cyclohexanone and the like have toxic and harmful effects on the environment or human body and are not environment-friendly; patent CN201910315885.7 reports a low-temperature conductive copper paste and a preparation method thereof, silver-coated copper powder with the particle size of 5-15 μm is adopted, the curing temperature is high and cannot reach below 200 ℃, in addition, cracks often exist on the surface of the silver-coated copper powder, the oxidation of a copper core is still caused finally, and the cost of the conductive paste is increased by the use of silver and a copper plating process; in patent CN201910727885.8, low-melting point SnAgCu alloy powder with the melting point of 218 ℃ is added into micron copper powder, the SnAgCu alloy powder is melted to form an intermetallic compound with the micron copper powder, and low-temperature sintering and solidification can be carried out at 180-250 ℃, but the alloy powder contains metallic silver, so that the cost is increased, and the used reducing agent sodium phosphate is not environment-friendly and has pollution risk.
In summary, the oxidation problem and the low temperature heat treatment problem of the copper powder greatly limit the application of the copper powder in the field of conductive paste, so that there is a need to develop an oxidation-resistant conductive copper paste which is environment-friendly and can be sintered at 180-.
Disclosure of Invention
In order to solve the technical problems in the prior art, one of the objectives of the present invention is to provide an environment-friendly anti-oxidation conductive copper paste, which can be sintered and cured at a low temperature of 180-200 ℃ and has excellent oxidation resistance and oxidation resistanceAfter the conductive and environment-friendly anti-oxidation conductive copper paste product is stored for 45 days in the air atmosphere at room temperature, the volume resistivity of the copper wire or the copper film after sintering is still less than 5 multiplied by 10 -5 Omega cm, the conductivity is superior to most of the copper conductive paste in the market.
The environment-friendly antioxidant conductive copper paste comprises the following raw materials: copper powder 40-70 wt.%, organic binder 0.1-5 wt.%, bioreductive agent 3-10 wt.%, other additives 0.1-6 wt.%, and solvent 10-50 wt.%, wherein the total ratio of the raw material components is 100%.
According to an embodiment of the present invention, the bioreductive agent is capsaicin or a combination of capsaicin and one or more of chitin, resveratrol, tannic acid, chlorogenic acid, caffeic acid and piperine;
preferably, the bioreductive agent is capsaicin, capsaicin: chitin 1:1 (mass ratio), capsaicin: 1:1 (mass ratio), capsaicin: chlorogenic acid 1:1 (mass ratio), capsaicin: caffeic acid 1:1 (mass ratio);
furthermore, the capsaicin is trans-8-methyl-N-vanillyl-6-nonenamide, is colorless and tasteless crystal powder, has hydroxyl, methoxy, alkenyl and acylamino in the molecular structure, and is adsorbed and interacted with copper powder, and hetero atoms and pi bonds in the capsaicin can transfer electrons to the surface of the copper powder to inhibit the oxidation of the copper powder and play a role in corrosion inhibition, and the capsaicin has a large steric hindrance in the molecular structure, can protect and stabilize the copper powder and also plays a certain role in dispersing the copper powder;
furthermore, the chitin, the resveratrol, the tannic acid, the chlorogenic acid, the caffeic acid and the piperine all contain N, O heteroatoms, and structures such as unsaturated bonds, hydroxyl groups and the like, so that electrons can be given out to play a role in reduction, and the prepared environment-friendly antioxidant conductive copper paste has the antioxidant property.
Preferably, the other additives include antifoaming agents, thixotropic agents and dispersing agents; wherein, the first and the second end of the pipe are connected with each other,
the defoaming agent is a polyether defoaming agent or an organic silicon defoaming agent, the polyether defoaming agent comprises a polyether defoaming agent GP-330, a polyether defoaming agent GPE-3000 or a polyether defoaming agent PPG-1000, and the organic silicon defoaming agent comprises an organic silicon defoaming agent FAG-470, an organic silicon defoaming agent BYK-065, an organic silicon defoaming agent BYK-066N or a polysiloxane defoaming agent YCK-615; the addition amount of the defoaming agent accounts for 0.1-2 wt% of the environment-friendly antioxidant conductive copper paste, and the defoaming agent is used for reducing bubbles in the process of mixing and stirring the paste, so that the environment-friendly antioxidant conductive copper paste reduces pores in the sintering process, ensures compact sintering and reduces resistance;
the thixotropic agent is hydrogenated castor oil, oxidized polyethylene wax, polyamide wax, palmitol, span-85 or ethylene glycol, and the addition amount of the thixotropic agent accounts for 0.1-3 wt% of the environment-friendly antioxidant conductive copper paste; the thixotropic agent has the function of ensuring that the slurry obtains necessary thixotropy, has fluidity when being subjected to shearing force and recovers the original state of the slurry when not being subjected to shearing force; when the addition amount of the thixotropic agent is too large, the environment-friendly copper conductive paste is difficult to remove in the sintering and curing process, and when the addition amount is too small, the thixotropic property of the environment-friendly copper conductive paste cannot be effectively provided.
The dispersing agent is amino clay or attapulgite clay, wherein the amino clay is a layered silicate, and the addition amount of the dispersing agent accounts for 0.1-1 wt% of the environmentally-friendly antioxidant conductive copper paste;
wherein, the amino clay is a self-made product, and the specific preparation method comprises the following steps: dissolving magnesium chloride hexahydrate in 200mL of absolute ethyl alcohol, fully stirring for 30min, dropwise adding gamma-aminopropyltriethoxysilane, continuously stirring until the reaction is complete, centrifuging the obtained white suspension at 5000rpm for 5min, drying in a vacuum drying oven at 45 ℃ for 24h, grinding into powder, and putting into a dryer for later use, wherein the mass ratio of gamma-aminopropyltriethoxysilane: the mass ratio of magnesium chloride hexahydrate is 1.25-1.35, and the required amino clay can be prepared in the ratio range; the structure of the amino clay is a layered structure, so that oxygen in the air can be shielded, and the amino group on the surface of the amino clay is reduced, so that the oxidation resistance of copper in the copper slurry can be improved;
the attapulgite is a commercially available product, preferably 1200-mesh attapulgite sold by Tianke mineral company Limited in the bright market, the attapulgite is grey white and has multiple pores inside, the structure can reduce the heat dissipation of the environment-friendly copper conductive paste during sintering, the sintering and curing temperature is reduced, and the surface of the attapulgite also contains hydroxyl, so that a certain antioxidation effect can be achieved during sintering; the amino clay or the attapulgite has a dispersing effect due to the structural characteristics thereof, and also has the effect of adjusting the viscosity of the environment-friendly copper conductive paste.
The copper powder comprises: one or the combination of two of spherical copper powder, flake copper powder, dendritic copper powder, rod copper powder, fibrous copper powder or polyhedral copper powder,
wherein the average particle size of spherical copper powder is 0.05-0.5 μm, the average particle size of flake copper powder is 2-10 μm, the average thickness is 0.05-0.2 μm, the average particle size of dendritic copper powder is 3-5 μm, the average diameter of rod copper powder is 0.05-0.1 μm, the average length is 1-2.5 μm, the average diameter of fiber copper powder is 0.03-0.05 μm, the average length is 10-30 μm, and the average particle size of polyhedron copper powder is 0.1-2 μm;
preferably, the copper powder can be spherical copper powder and flake copper powder according to the mass ratio of 1:0.1-0.5, the spherical copper powder and dendritic copper powder according to the mass ratio of 1:0.1-0.5, the spherical copper powder and rod copper powder according to the mass ratio of 1:0.1-0.5, the spherical copper powder and fibrous copper powder according to the mass ratio of 1:0.1-0.5, and the polyhedral copper powder and dendritic copper powder according to the mass ratio of 1: 0.1-0.5; copper powder with different shapes is compounded to promote effective contact and connection between copper powders, and the conductive performance of the environment-friendly anti-oxidation conductive copper slurry after sintering can be ensured on the basis of reducing the consumption of the copper powders.
Preferably, the organic binder is polyvinyl alcohol resin (molecular weight 5000-; the selected organic binder can enhance the decomposability of the environment-friendly anti-oxidation conductive copper paste during sintering, and a compact conductor path with low resistance is obtained.
Preferably, the solvent is one or more of terpineol, carbitol, butyl carbitol, diethylene glycol ether acetate, dibutyl phthalate, tributyl citrate, ethylene glycol, propylene glycol, aminomethyl propanol, diethylene glycol, triethylene glycol, diethylene glycol methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, monoethanolamine, diethanolamine, and triethanolamine.
The invention also aims to provide a preparation method of the environment-friendly antioxidant conductive copper paste, which comprises the following steps:
(1) dissolving an organic binder in a solvent, adding a defoaming agent, a thixotropic agent and a dispersing agent, heating in a water bath at 30-60 ℃, stirring until the organic binder is completely dissolved, and sieving to remove impurities to obtain an organic carrier;
(2) uniformly ultrasonically dispersing copper powder, a biological reducing agent and the solvent, mixing with the organic carrier, and dispersing to obtain uniform first slurry; fully stirring and dispersing the first slurry in a high-speed mixer or a planetary stirrer for 10-30min, then rolling and dispersing for 3-5 times in a three-roll mill, wherein the rolling speed is 400 plus materials at 500rpm, the rolling time is 2-5h, the rolling fineness is ensured to be less than 1 mu m, obtaining a second slurry, and finally filtering through a 5-10 mu m filter screen to obtain the environment-friendly antioxidant conductive copper slurry.
Wherein, the step (1) of sieving is to adopt a 300-mesh stainless steel net or a polyester net for filtering and impurity removal, so as to ensure that the slurry is uniform and fine.
In the step (1), the addition amount of each component in the organic carrier is as follows by mass ratio: organic binder: solvent: defoaming agent: thixotropic agent: dispersant 0.1-8: 10-50: 0.1-2: 0.1-3: 0.1-1.
The viscosity of the first slurry in the step (2) is controlled within the range of 15-65 pas, if the viscosity is too high, the copper slurry is not easy to mix uniformly and the fluidity is poor, operations such as spreading and filling of the environment-friendly antioxidant conductive copper slurry can be adversely affected, and if the viscosity is too low, shrinkage failure of the environment-friendly antioxidant conductive copper slurry during drying can be increased disadvantageously, a compact conductive path cannot be formed, the resistance is increased, and the conductivity is reduced.
In addition, the invention also provides application of the environment-friendly anti-oxidation conductive copper paste in a flexible device.
Specifically, the environment-friendly anti-oxidation conductive copper paste is applied to circuit printing in flexible devices or preparation of electronic components.
Furthermore, the environment-friendly antioxidant conductive copper paste prepared by the invention is suitable for circuit printing in flexible devices or electronic element preparation, and the used raw materials are environment-friendly, pollution-free and non-toxic, and meet the requirement of green production.
Based on the above, compared with the prior art, the environment-friendly antioxidant conductive copper paste provided by the invention has the following advantages:
(1) the environment-friendly anti-oxidation conductive copper paste prepared by the invention can be sintered and solidified at a low temperature of 200 ℃ at 180- -5 Omega cm, the conductivity is superior to most of copper conductive slurry on the market;
(2) according to the invention, a biological reducing agent is selected, and hetero atoms (N, O) and pi bonds in the biological reducing agent can transfer electrons to the surface of copper powder to inhibit the oxidation of the copper powder, so that a corrosion inhibition effect is achieved, the capsaicin has large molecular structure steric hindrance, the copper powder can be protected and stabilized, and a dispersion effect is achieved; the used raw materials are environment-friendly and pollution-free.
(3) According to the invention, the organic carrier is self-prepared, so that the cost is low, the volatility is good, the anti-oxidation sintering of the environment-friendly anti-oxidation conductive copper paste can be realized under the protection of nitrogen atmosphere, the process for preparing the environment-friendly anti-oxidation conductive copper paste is simple, and the biological antioxidant is environment-friendly and economical.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an environment-friendly antioxidant conductive copper paste which comprises the following raw materials in percentage by mass: 40-70 wt.% of copper powder, 0.1-5 wt.% of organic binder, 3-10 wt.% of biological reducing agent, 0.1-6 wt.% of other additives and 10-50 wt.% of solvent, wherein the sum of the raw material components is 100%.
And printing the prepared environment-friendly anti-oxidation conductive copper paste on an alumina ceramic substrate by a screen printing technology, then placing the alumina ceramic substrate in a muffle furnace at 180 ℃ for sintering and curing, and testing the resistivity of the obtained sample by adopting a four-probe tester.
The invention will now be further illustrated, but is not limited, by the following specific examples.
Example 1
The preparation method of the environment-friendly antioxidant conductive copper paste comprises the following steps:
(1) dissolving polyvinyl alcohol resin in carbitol, adding a polyether defoamer GP-330, hydrogenated castor oil and amino clay, heating in a water bath at 60 ℃, stirring until the polyether defoamer GP-330, the hydrogenated castor oil and the amino clay are completely dissolved, and sieving by a screen to remove impurities to obtain an organic carrier; the addition amount of each component in the organic carrier is as follows according to the mass ratio: organic binder: solvent: defoaming agent: thixotropic agent: dispersant 5: 38.5: 1.5: 1: 1;
(2) uniformly mixing spherical copper powder and flake copper powder according to the mass ratio of 1:0.4, wherein the average particle size of the spherical copper powder is 0.1-0.5 mu m, the average particle size of the flake copper powder is 2-10 mu m, the average thickness of the flake copper powder is 0.05-0.2 mu m, and uniformly dispersing the flake copper powder, capsaicin and diethylene glycol ether acetate by ultrasonic, and then mixing and dispersing the flake copper powder with an organic carrier to obtain uniform first slurry; fully stirring and dispersing the first slurry in a high-speed mixer for 30min, then rolling and dispersing for 5 times in a three-roll mill, wherein the rolling speed is 400rpm, the rolling time is 4h, the rolling fineness is ensured to be less than 1 mu m, so as to obtain a second slurry, and finally filtering the second slurry through a filter screen with the thickness of 10 mu m, so as to obtain environment-friendly antioxidant conductive copper slurry;
the environment-friendly antioxidant conductive copper paste is characterized in that the additive amount of each component in the environment-friendly antioxidant conductive copper paste is as follows by mass percent: copper powder 45 wt.%, organic binder 5 wt.%, bioreductive agent 8 wt.%, other additives 3.5 wt.%, and solvent 38.5 wt.%.
And storing the environment-friendly anti-oxidation conductive copper paste product in the air atmosphere at room temperature for 45 days, and taking the average value of three groups of parallel samples of the volume resistivity of the copper film obtained after sintering as 4.5 multiplied by 10 -5 Ω·cm。
Example 2
A preparation method of environment-friendly antioxidant conductive copper paste specifically comprises the following steps:
(1) dissolving polyvinylpyrrolidone K-30 in butyl carbitol, adding a polyether defoamer PPG-1000, polyamide wax and attapulgite clay, heating in a water bath at 55 ℃, stirring until the mixture is completely dissolved, and sieving by a screen to remove impurities to obtain an organic carrier; the addition amount of each component in the organic carrier is as follows according to the mass ratio: organic binder: solvent: defoaming agent: thixotropic agent: dispersant 7: 25: 2: 2: 1;
(2) the mass ratio of spherical copper powder to dendritic copper powder is 1:0.5, the average particle size of the spherical copper powder is 0.1-0.5 mu m, the average particle size of the dendritic copper powder is 3-5 mu m, and capsaicin: ultrasonically dispersing resveratrol (mass ratio) 1:1 and butyl carbitol solvent uniformly, mixing with an organic carrier, and dispersing to obtain uniform first slurry; fully stirring and dispersing the first slurry in a planetary stirrer for 25min, then rolling and dispersing for 5 times in a three-roll mill, wherein the rolling speed is 500rpm, the rolling time is 3.5h, the rolling fineness is ensured to be less than 1 mu m, so as to obtain a second slurry, and finally filtering the second slurry through a filter screen with the diameter of 8 mu m, so as to obtain environment-friendly antioxidant conductive copper slurry;
the environment-friendly antioxidant conductive copper paste is characterized in that the additive amount of each component in the environment-friendly antioxidant conductive copper paste is as follows by mass percent: 53 wt.% copper powder, 7 wt.% organic binder, 10 wt.% bioreductive agent, 5 wt.% other additives, 25 wt.% solvent.
And storing the environment-friendly anti-oxidation conductive copper paste product in the air atmosphere at room temperature for 45 days, and taking the average value of three groups of parallel samples as 4.1 multiplied by 10 for the volume resistivity of the copper film obtained after sintering -5 Ω·cm。
Example 3
A preparation method of environment-friendly antioxidant conductive copper paste specifically comprises the following steps:
(1) dissolving acrylic resin in ethylene glycol monoethyl ether, adding an organic silicon defoamer FAG-470, oxidized polyethylene wax and amino clay, heating in a water bath at 45 ℃, stirring until the mixture is completely dissolved, and sieving by using a screen to remove impurities to obtain an organic carrier; the addition amount of each component in the organic carrier is as follows according to the mass ratio: organic binder: solvent: defoaming agent: thixotropic agent: dispersant 5: 36: 2: 1.5: 0.5;
(2) the method comprises the following steps of mixing spherical copper powder and rod-shaped copper powder according to the mass ratio of 1:0.5, capsaicin: uniformly ultrasonically dispersing chlorogenic acid and a monoethanolamine solvent in a mass ratio of 1:1, mixing with an organic carrier, and dispersing to obtain uniform first slurry; fully stirring and dispersing the first slurry in a planetary stirrer for 30min, then carrying out rolling dispersion in a three-roll mill for 3 times at the rolling speed of 500rpm for 2h, ensuring that the rolling fineness is less than 1 mu m to obtain a second slurry, and finally filtering the second slurry through a 5 mu m filter screen to obtain environment-friendly antioxidant conductive copper slurry;
the environment-friendly antioxidant conductive copper paste is characterized in that the additive amount of each component is ensured to be as follows by mass percent: copper powder 50 wt.%, organic binder 5 wt.%, bioreductive agent 5 wt.%, other additives 4 wt.%, and solvent 36 wt.%.
And storing the environment-friendly anti-oxidation conductive copper paste product in the air atmosphere at room temperature for 45 days, and taking the average value of three groups of parallel samples of the volume resistivity of the copper film obtained after sintering as 4.8 multiplied by 10 -5 Ω·cm。
Comparative example 1
The difference between the comparative example 1 and the example 1 is that no biological reducing agent is added, and the others are kept unchanged, and the preparation steps of the environment-friendly antioxidant conductive copper paste prepared in the comparative example 1 are as follows:
(1) dissolving polyvinyl alcohol resin in carbitol, adding a polyether defoamer GP-330, hydrogenated castor oil and amino clay, heating in a water bath at 60 ℃, stirring until the polyether defoamer is completely dissolved, and sieving by using a screen to remove impurities to obtain an organic carrier; the addition amount of each component in the organic carrier is as follows according to the mass ratio: organic binder: solvent: defoaming agent: thixotropic agent: dispersant 5: 38.5: 1.5: 1: 1;
(2) uniformly mixing spherical copper powder and flake copper powder according to the mass ratio of 1:0.4, wherein the average particle size of the spherical copper powder is 0.1-0.5 mu m, the average particle size of the flake copper powder is 2-10 mu m, the average thickness of the flake copper powder is 0.05-0.2 mu m, and uniformly dispersing the flake copper powder with capsaicin and diethylene glycol ether acetate in an ultrasonic manner, and then mixing and dispersing the flake copper powder with an organic carrier to obtain uniform first slurry; fully stirring and dispersing the first slurry in a high-speed mixer for 30min, then rolling and dispersing for 5 times in a three-roll mill, wherein the rolling speed is 400rpm, the rolling time is 4h, the rolling fineness is ensured to be less than 1 mu m, so as to obtain a second slurry, and finally filtering the second slurry through a filter screen with the thickness of 10 mu m, so as to obtain environment-friendly antioxidant conductive copper slurry;
the environment-friendly copper slurry comprises the following components in percentage by mass: copper powder 45 wt.%, organic binder 5 wt.%, other additives 3.5 wt.%, solvent 38.5 wt.%.
And after the environment-friendly copper paste product is stored for 45 days in the air atmosphere at room temperature, the volume resistivity of the sintered copper film is 7.3 multiplied by 10 -5 Omega cm, which is larger than the resistivity of the copper film in example 1, shows that compared with the environment-friendly copper paste without capsaicin, the environment-friendly anti-oxidation conductive copper paste with capsaicin can effectively improve the anti-oxidation capability and further improve the conductivity.
Comparative example 2
The difference between the comparative example 2 and the example 1 is that the sintering temperature is different, and the preparation of copper paste of the comparative example 1 is carried out according to the formula described in patent CN109979686A, and the concrete steps are as follows:
(1) adding 45 mass percent of solid high-molecular polyester resin into 65 mass percent of diethylene glycol ethyl ether acetate solvent, and dissolving to obtain a high-molecular polyester resin carrier;
(2) taking silver-coated copper powder with the average particle size of 5-15 mu m, wherein the silver-coated copper powder is flaky, adding 45% of the silver-coated copper powder and 52% of the macromolecular polyester resin carrier in the step (1) into a high-speed dispersion machine, dispersing by the high-speed dispersion machine to obtain a primary uniform carrier, pouring the carrier into a three-roller machine, grinding and dispersing to obtain a secondary carrier, adding the secondary carrier, 2% of the closed isocyanate curing agent and 1% of the macromolecular dispersing agent into a planetary stirring machine, vacuumizing, and removing bubbles to obtain the conductive copper slurry.
Storing the conductive paste product containing the silver-coated copper powder obtained in the step (2) in the air atmosphere at room temperature for 45 days, and then sintering and curing at 380 ℃, wherein the volume resistivity of a copper film after sintering is 2.6 multiplied by 10 -5 Omega cm, the composite copper powder with smaller average particle size used in the embodiment 1 of the invention greatly reduces the sintering temperature, and can realize effective contact between the copper powder and the copper powder under the condition of reducing the using amount of the copper powder, and the biological reducing agent in the invention plays an effective antioxidation role, and the obtained environment-friendly type antioxidation conductive copper slurry has strong antioxidation capability, so that the resistivity of the obtained copper film product is low, and the conductivity is good.
The above analysis is combined to show that, compared with comparative example 1 and comparative example 2, in examples 1 to 3 of the present invention, compared with the prior art, the technical scheme of the present invention has the advantages of simple process, environmental protection, high efficiency, good oxidation resistance, realization of low temperature sintering and curing, etc.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The environment-friendly antioxidant conductive copper paste is characterized by comprising the following raw materials in percentage by mass: 40-70 wt.% of copper powder, 0.1-5 wt.% of organic binder, 3-10 wt.% of biological reducing agent, 0.1-6 wt.% of other additives and 10-50 wt.% of solvent, wherein the sum of the raw material components is 100%.
2. The environment-friendly antioxidant conductive copper paste as claimed in claim 1, wherein the bioreductive agent is capsaicin or a combination of capsaicin and one or more of chitin, resveratrol, tannic acid, chlorogenic acid, caffeic acid and piperine.
3. The environment-friendly antioxidant conductive copper paste as claimed in claim 1, wherein said other additives include an antifoaming agent, a thixotropic agent and a dispersing agent; wherein the content of the first and second substances,
the defoaming agent is a polyether defoaming agent or an organic silicon defoaming agent, and the defoaming agent accounts for 0.1-2 wt% of the environment-friendly antioxidant conductive copper paste;
the thixotropic agent is hydrogenated castor oil, oxidized polyethylene wax, polyamide wax, palmitol, span-85 or ethylene glycol, and the thixotropic agent accounts for 0.1-3 wt% of the environment-friendly antioxidant conductive copper paste;
the dispersant is amino clay or attapulgite clay, and the dispersant accounts for 0.1 to 1 weight percent of the environment-friendly antioxidant conductive copper paste;
and, the preparation method of the amino clay is as follows:
dissolving magnesium chloride hexahydrate in 200mL of absolute ethyl alcohol, fully stirring for 30min, dropwise adding gamma-aminopropyltriethoxysilane, continuously stirring until the reaction is complete, centrifuging the obtained white suspension at 5000rpm for 5min, drying in a vacuum drying oven at 45 ℃ for 24h, grinding into powder to obtain the amino clay, and putting into a dryer for later use;
wherein, gamma-aminopropyltriethoxysilane: the mass ratio of magnesium chloride hexahydrate is 1.25-1.35.
4. The environment-friendly antioxidant conductive copper paste as claimed in claim 3, wherein the polyether defoamer is polyether defoamer GP-330, polyether defoamer GPE-3000 or polyether defoamer PPG-1000, and the silicone defoamer is silicone defoamer FAG-470, silicone defoamer BYK-065, silicone defoamer BYK-066N or polysiloxane defoamer YCK-615.
5. The environment-friendly antioxidant conductive copper paste as claimed in claim 1, wherein the copper powder is at least one of spherical copper powder, flake copper powder, dendritic copper powder, rod copper powder, fibrous copper powder and polyhedral copper powder,
the average grain diameter of the spherical copper powder is 0.05-0.5 μm; the average grain diameter of the flake copper powder is 2-10 μm, and the average thickness is 0.05-0.2 μm; the average grain diameter of the dendritic copper powder is 3-5 μm; the average diameter of the rod-shaped copper powder is 0.05-0.1 μm, and the average length of the rod-shaped copper powder is 1-2.5 μm; the average diameter of the fibrous copper powder is 0.03-0.05 μm, and the average length is 10-30 μm; the average grain diameter of the polyhedral copper powder is 0.1-2 mu m.
6. The environment-friendly antioxidant conductive copper paste as claimed in claim 1, wherein the organic binder is polyvinyl alcohol resin, polyvinylpyrrolidone K-30, polyethylene glycol-400, acrylic resin, hydroxyethyl cellulose, hydroxypropyl cellulose, gelatin, shellac or gum arabic.
7. The environment-friendly antioxidant conductive copper paste as claimed in claim 1, wherein the solvent is at least one of terpineol, carbitol, butyl carbitol, diethylene glycol ether acetate, dibutyl phthalate, tributyl citrate, ethylene glycol, propylene glycol, aminomethyl propanol, diethylene glycol, triethylene glycol, diethylene glycol methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, monoethanolamine, diethanolamine, and triethanolamine.
8. The preparation method of the environment-friendly anti-oxidation conductive copper paste as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
(1) dissolving an organic binder in a solvent, adding a defoaming agent, a thixotropic agent and a dispersing agent, heating in a water bath at 30-60 ℃, stirring until the organic binder is completely dissolved, and filtering and removing impurities by using a 300-mesh stainless steel net or a polyester net to obtain an organic carrier; the organic carrier comprises the following components in addition amount by mass: organic binder: solvent: defoaming agent: thixotropic agent: 0.1-8% of dispersant: 10-50: 0.1-2: 0.1-3: 0.1 to 1;
(2) uniformly ultrasonically dispersing copper powder, a biological reducing agent and the solvent, mixing with the organic carrier, and dispersing to obtain uniform first slurry; controlling the viscosity of the first slurry to be 15-65 Pa.s, fully stirring and dispersing the first slurry in a high-speed mixer or a planetary stirrer for 10-30min, then carrying out rolling dispersion in a three-roll mill for 3-5 times at the rolling speed of 400 plus materials of 500rpm for 2-5h, ensuring the rolling fineness to be less than 1 mu m to obtain a second slurry, and finally filtering the second slurry through a filter screen of 5-10 mu m to obtain the environment-friendly antioxidant conductive copper slurry.
9. The method as claimed in claim 8, wherein the environmentally friendly anti-oxidation conductive copper paste can be cured at a temperature of 180-200 ℃, and the volume resistivity of the sintered copper wire or copper film is still less than 5 x 10 after the environmentally friendly anti-oxidation conductive copper paste product is stored in the room temperature air atmosphere for 45 days -5 Ω·cm。
10. The use of the environment-friendly antioxidant conductive copper paste as defined in claims 1-7 or the environment-friendly antioxidant conductive copper paste prepared by the method as defined in claim 8 in a flexible device.
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