WO2023173807A1 - Pâte de cuivre conductrice antioxydante, son procédé de préparation et son utilisation - Google Patents

Pâte de cuivre conductrice antioxydante, son procédé de préparation et son utilisation Download PDF

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WO2023173807A1
WO2023173807A1 PCT/CN2022/135155 CN2022135155W WO2023173807A1 WO 2023173807 A1 WO2023173807 A1 WO 2023173807A1 CN 2022135155 W CN2022135155 W CN 2022135155W WO 2023173807 A1 WO2023173807 A1 WO 2023173807A1
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diisocyanate
conductive copper
thiol
copper slurry
compound
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PCT/CN2022/135155
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Chinese (zh)
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WO2023173807A9 (fr
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李健
何博
董鑫
杨泽君
李鹏
徐希翔
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西安隆基乐叶光伏科技有限公司
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Publication of WO2023173807A9 publication Critical patent/WO2023173807A9/fr

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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
    • 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

Definitions

  • the present application relates to the field of battery technology, and in particular to an anti-oxidation conductive copper slurry, a preparation method and its application.
  • Silver paste and other precious metal pastes have been widely used in semiconductors, electronics, automobiles, new energy and other fields because of their excellent electrical conductivity.
  • silver and other precious metal pastes are expensive and the silver paste migrates during use. This phenomenon has prompted people to gradually turn to research on using base metals instead of precious metals to prepare conductive pastes.
  • the electrical conductivity of copper is second only to silver, has no migration phenomenon, and is cheap. Therefore, it has gradually attracted people's attention in the development of conductive paste technology.
  • copper is easily oxidized in the air, and its long-term stability faces challenges.
  • the copper slurry described in this application uses compounds with thiocarbamate structural units and uses them as cross-linking agents.
  • the thiols/thiophenols are released at the curing temperature, thus exerting their reducing properties. It protects copper powder from oxidation, achieves high conductivity, and can be quickly cured at low temperatures. It has stable conductivity in air atmosphere, and shows excellent performance in high-temperature oxidation experiments (200°C, 60min). of antioxidant properties.
  • An antioxidant conductive copper slurry includes a compound having a thiocarbamate structural unit.
  • the compound having a thiocarbamate structural unit is obtained by reacting thiol or thiophenol with a polyisocyanate compound.
  • the thiol or thiol phenol is an aliphatic thiol compound with a carbon number of 1-30 and/or an aromatic sulfur compound with a carbon number of 2-30. Phenolic compounds.
  • the polyisocyanate compound is selected from the group consisting of isocyanate, terephthalic diisocyanate, 1,3-diisocyanatotoluene, and 1,6-hexamethylene diisocyanate.
  • the compound having a thiocarbamate structural unit is 1-10 in terms of mass percentage in the anti-oxidation conductive copper slurry. %, preferably 2-7%.
  • the anti-oxidation conductive copper slurry further includes copper powder, resin, accelerator, auxiliary agent and conductive enhancement filler.
  • the particle size D50 of the copper powder is 0.1-10 ⁇ m.
  • the shape of the copper powder is flake, spherical and/or dendritic.
  • the resin is selected from one or more of epoxy resin, polyamide resin, saturated polyester resin, polyurethane resin, acrylic resin and silicone resin. .
  • the accelerator is selected from one of organic amines, imidazoles, boron trifluoride complexes, organic tin compounds and transition metal complexes. Or two or more.
  • the auxiliary agent is selected from one or more of a dispersant, a stabilizer, a thixotropic agent and a coupling agent.
  • the conductive enhancing filler is selected from nano or sub-micron carbon black, graphene, carbon nanotubes, nickel powder, tin powder, indium powder, silver powder and aluminum. One or more than two kinds of powders.
  • the anti-oxidation conductive copper slurry also contains a solvent.
  • the solvent is selected from the group consisting of hydroxyl-containing compounds with a carbon number of 2-16, carbon atoms It is one or more of an ether group-containing compound with 2 to 18 carbon atoms, a carbonyl group-containing compound with 3 to 12 carbon atoms, and an ester group-containing compound with 2 to 16 carbon atoms.
  • the copper powder is 75-85% and the resin is 3-11% in terms of mass percentage in the anti-oxidation conductive copper slurry,
  • the accelerator is 0.05-0.5%, the auxiliary is 0.05-0.5%, the conductive reinforcing filler is 0.1-1%, and the solvent is 2-5%.
  • a method for preparing anti-oxidation conductive copper slurry including:
  • the first mixture and the second mixture are mixed to obtain an oxidation-resistant conductive copper slurry.
  • the first mixture and the second mixture are mixed and then subjected to primary dispersion and secondary dispersion to obtain the anti-oxidation conductive copper slurry.
  • the viscosity of the conductive copper slurry at room temperature is 150-350 Pa ⁇ s.
  • the resin, compounds having thiocarbamate structural units, accelerators, auxiliaries, copper powder and conductive reinforcing fillers are in the anti-oxidation conductive copper slurry. raw material.
  • An electrode comprising the anti-oxidation conductive copper slurry or the anti-oxidation conductive copper slurry prepared by the method.
  • a battery including the electrode A battery including the electrode.
  • the copper slurry described in this application contains a compound with a thiocarbamate structural unit and uses it as a cross-linking agent.
  • the thiol/thiol in the cross-linking agent is released,
  • the sulfhydryl groups of thiols/thiols are complexed with copper and adsorbed on the surface of copper powder, blocking the reaction between oxides and copper.
  • thiols/thiophenols are also reducing and can react with oxides preferentially, or will already Oxidized copper is reduced, thereby achieving excellent antioxidant effects.
  • the present application provides the use of compounds having thiocarbamate structural units as cross-linking agents.
  • This application also provides the use of compounds having thiocarbamate structural units in anti-oxidation conductive copper slurries.
  • the compound having a thiocarbamate structural unit is obtained by reacting thiol or thiophenol with a polyisocyanate compound.
  • the thiol or thiol is an aliphatic thiol compound having 1-30 carbon atoms and/or an aromatic thiol compound having 2-30 carbon atoms.
  • the polyisocyanate compound is selected from the group consisting of isocyanate, p-phenylene diisocyanate, 1,3-diisocyanatotoluene, 1,6-hexamethylene diisocyanate, 3,3'-dimethyl -4,4'-Biphenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, m-xylylene diisocyanate, o- Xylylene diisocyanate, 2,6-diisocyanate toluene, 2,4-diisocyanate toluene, 2,5-diisocyanate toluene, 1,4-cyclohexyl diisocyanate, 4,4-diisocyanate dicyclohexylmethane , 1,4-cyclohexane dimethyl diisocyanate
  • the mercaptan can be n-propyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, n-nonyl mercaptan, n-decyl mercaptan, n-11 mercaptan Mercaptan, n-dodecyl mercaptan, isobutyl mercaptan, isopentyl mercaptan, isooctyl mercaptan, sec-butyl mercaptan or sec-octyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, 2-methyltetrahydrofuran- 3-thiol, 2-thiophenethiol, benzylthio
  • the thiophenol can be thiophenol, 2-methylthiophenol, 3-methylthiophenol, 4-methylthiophenol, 4-fluorothiophenol, 2-naphthylthiophenol, 5-mercapto -1-Methyltetrazole, 3-mercapto-4-methyl-1,2,4-triazole, 2-mercapto-1-methylimidazole, 2-mercaptothiazoline, 2-mercaptopyridine, 2 -Mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoselenazole, 5-fluoro-2-mercaptobenzothiazole, etc.
  • the present application provides an oxidation-resistant conductive copper slurry, which contains a compound having a thiocarbamate structural unit.
  • the compound having a thiocarbamate structural unit is obtained by reacting thiol or thiophenol with a polyisocyanate compound.
  • the compound having a thiocarbamate structural unit serves as a cross-linking agent.
  • the thiol/thiol refers to an organic compound containing a -SH structure. If the -SH structure is directly connected to an aliphatic alkane, it is a thiol. If the -SH structure is directly connected to an aromatic hydrocarbon, it is a thiol. thiophenol.
  • the antioxidant conductive copper slurry described in this application contains compounds with thiocarbamate structural units, and the compounds with thiocarbamate structural units are formed by mercaptan or thiophenol and polyisocyanate.
  • the anti-oxidation conductive copper slurry is obtained by the reaction of compounds.
  • mercaptans or thiophenols are released, and the sulfhydryl groups of the mercaptan or thiophenol molecules are complexed with copper to be adsorbed on the surface of the copper powder, blocking It prevents oxides from reacting with copper.
  • thiols/thiophenols also have reducing properties and can react preferentially with oxides or reduce oxidized copper. Therefore, by adding thiols/thiophenols to the conductive copper slurry, Compounds can achieve excellent antioxidant effects.
  • mercaptans/thiophenols since mercaptans/thiophenols contain active hydrogen, they can quickly react with epoxy resins at room temperature, thereby reducing the curing performance of the resin system and shortening the application period of the conductive slurry. This results in poor stability of the slurry and is difficult to produce on a large scale, and a compound with a thiocarbamate structural unit is generated by reacting a thiol/thiophenol compound with a polyisocyanate compound, which has a thiocarbamate structure. The compound of the unit is obtained by reacting thiol or thiol with a polyisocyanate compound.
  • the thiol or thiol is released, and the thiol or thiol molecules
  • the thiol group complexes with copper and is adsorbed on the surface of copper powder, blocking the reaction between oxide and copper.
  • thiol/thiol also has reducing properties and can react with oxides preferentially or reduce oxidized copper to avoid
  • the thiol or thiol is an aliphatic thiol compound having 1-30 carbon atoms and/or an aromatic thiol compound having 2-30 carbon atoms.
  • the aliphatic thiol compound with a value of 1-30 can be n-propyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, n-nonyl mercaptan, n-decyl mercaptan , n-undecanethiol, n-dodecanethiol, isobutylthiol, isopentylthiol, isooctylthiol, sec-butylthiol or sec-octylthiol, cyclopentylthiol, cyclohexanethiol, 2- Methyltetrahydrofuran-3-thiol, 2-thiophenethiol, benzylthiol, 2-pheny
  • the polyisocyanate compound is selected from the group consisting of isocyanate, p-phenylene diisocyanate, 1,3-diisocyanatotoluene, 1,6-hexamethylene diisocyanate, 3,3'-dimethyl -4,4'-Biphenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, m-xylylene diisocyanate, o- Xylylene diisocyanate, 2,6-diisocyanate toluene, 2,4-diisocyanate toluene, 2,5-diisocyanate toluene, 1,4-cyclohexyl diisocyanate, 4,4-diisocyanate dicyclohexylmethane , 1,4-cyclohexane dimethyl diisocyanate
  • the compound having a thiocarbamate structural unit is 1-10%, preferably 2-7%, in terms of mass percentage in the anti-oxidation conductive copper slurry.
  • the compound having a thiocarbamate structural unit may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.
  • the antioxidant conductive copper slurry also contains copper powder, resin, accelerator, auxiliary agent and conductive enhancement filler.
  • the particle size D50 of the copper powder is 0.1-10 ⁇ m, and further preferably , the shape of the copper powder is flake, spherical and/or dendritic.
  • the copper powder plays a conductive role, and the copper particles contact each other to form a charge transfer path.
  • the resin forms a skeleton. After curing, the resin molecules are connected to each other, so that between the copper powder and between the copper powder and the matrix Form close contact; the conductive enhancement filler fills the gaps between copper powders (carbon black), enhances the contact between copper powders and the matrix (indium powder), and increases the conductivity of the copper slurry (silver powder) ,
  • the auxiliary agent is at least one of a dispersant, a stabilizer, a thixotropic agent and a coupling agent, wherein the dispersant acts to reduce the surface tension of the resin system so that the solid and liquid phases form a uniform mixture; the stabilizer acts as To form electrostatic repulsion between copper powders, thereby slowing down the settling of copper powder in the slurry; the thixotropic agent provides hydrogen bonding force to slow down the fluidity of the slurry when it is static, and during operation (such as
  • the accelerator is at least one of organic amines, imidazoles, boron trifluoride complexes, organic tin compounds and transition metal complexes, which catalyzes the curing reaction, lowers the curing temperature and shortens the curing time. role.
  • the particle size D50 of the copper powder may be 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, etc.
  • the resin is selected from one or more of epoxy resin, polyamide resin, saturated polyester resin, polyurethane resin, acrylic resin and silicone resin.
  • it can be one or more of them. Two, three, four or more than five types.
  • the accelerator is selected from one or more of organic amines, imidazoles, boron trifluoride complexes, organotin complexes and transition metal complexes, for example, it can be one of the following One, two, three, four or more types of organic amines, imidazoles, boron trifluoride complexes, organotin complexes and transition metal complexes, this application Without any limitation, it can be selected according to needs.
  • the organic amines can be tripropylamine or triethanolamine, etc.
  • the imidazoles can be 2-methylimidazole, 2-methyl-4-ethylimidazole, etc.
  • the boron trifluoride complexes can be boron trifluoride ethylamine complex
  • the organic tin compounds can be stannous isooctanoate, dibutyltin dilaurate, etc.
  • the transition metal complexes can be For nickel acetylacetonate, cobalt acetylacetonate, etc.
  • the auxiliary agent is selected from one or more of dispersants, stabilizers, thixotropic agents and coupling agents.
  • the auxiliary agent can be one, two, three or four of them. .
  • dispersant can be oleic acid
  • the stabilizer can be phosphite
  • the thixotropic agent can be polyamide wax
  • the coupling agent may be isobutyltriethoxysilane.
  • the conductive enhancing filler is selected from one or more of nano or sub-micron carbon black, graphene, carbon nanotubes, nickel powder, tin powder, indium powder, silver powder and aluminum powder. , for example, it can be one, two, three, four or more than five of them.
  • the antioxidant conductive copper slurry also contains a solvent.
  • the solvent is selected from a hydroxyl-containing compound with a carbon number of 2-16 and an ether group-containing compound with a carbon number of 2-18. , one or more of a carbonyl group-containing compound with a carbon number of 3-12 and an ester group-containing compound with a carbon number of 2-16.
  • the solvent is to disperse the above other components in the solvent to form a slurry with a certain viscosity.
  • the specific types of carbonyl-containing compounds with carbon atoms of 3-12 and ester-containing compounds with carbon atoms of 2-16 are not limited in this application, and they can be selected according to needs.
  • carbon atoms of 2 The -16 hydroxyl-containing compound can be ⁇ -terpineol; the ether group-containing compound with 2-18 carbon atoms can be ethylene glycol monomethyl ether or propylene glycol phenyl ether; the carbonyl-containing compound with 3-12 carbon atoms
  • the compound can be dipropyl ketone; the ester group-containing compound with a carbon number of 2-16 can be butyl acetate or diethylene glycol butyl ether acetate.
  • the copper powder in terms of mass percentage in the anti-oxidation conductive copper slurry, the copper powder is 75-85%, the resin is 3-11%, and the accelerator is 0.05-0.5% , the additive is 0.05-0.5%, the conductive reinforcing filler is 0.1-1%, and the solvent is 2-5%.
  • the oxidation-resistant conductive copper slurry includes compounds having thiocarbamate structural units.
  • the compound having a thiocarbamate structural unit is obtained by reacting thiol or thiophenol with a polyisocyanate compound.
  • the oxidation-resistant conductive copper slurry includes compounds having thiocarbamate structural units.
  • the compound having a thiocarbamate structural unit is obtained by reacting thiol or thiophenol with a polyisocyanate compound.
  • the thiol or thiol is an aliphatic thiol compound having 1-30 carbon atoms and/or an aromatic thiol compound having 2-30 carbon atoms.
  • the polyisocyanate compound is selected from the group consisting of isocyanate, p-phenylene diisocyanate, 1,3-diisocyanatotoluene, 1,6-hexamethylene diisocyanate, 3,3'-dimethyl -4,4'-Biphenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, m-xylylene diisocyanate, o- Xylylene diisocyanate, 2,6-diisocyanate toluene, 2,4-diisocyanate toluene, 2,5-diisocyanate toluene, 1,4-cyclohexyl diisocyanate, 4,4-diisocyanate dicyclohexylmethane , 1,4-cyclohexane dimethyl diisocyanate
  • the oxidation-resistant conductive copper slurry includes compounds having thiocarbamate structural units.
  • the compound having a thiocarbamate structural unit is obtained by reacting thiol or thiophenol with a polyisocyanate compound.
  • the thiol or thiol is an aliphatic thiol compound having 1-30 carbon atoms and/or an aromatic thiol compound having 2-30 carbon atoms.
  • the polyisocyanate compound is selected from the group consisting of isocyanate, p-phenylene diisocyanate, 1,3-diisocyanatotoluene, 1,6-hexamethylene diisocyanate, 3,3'-dimethyl -4,4'-Biphenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, m-xylylene diisocyanate, o- Xylylene diisocyanate, 2,6-diisocyanate toluene, 2,4-diisocyanate toluene, 2,5-diisocyanate toluene, 1,4-cyclohexyl diisocyanate, 4,4-diisocyanate dicyclohexylmethane , 1,4-cyclohexane dimethyl diisocyanate
  • the compound having a thiocarbamate structural unit is 1-10%, preferably 2-7%, in terms of mass percentage in the anti-oxidation conductive copper slurry.
  • the antioxidant conductive copper slurry further includes copper powder, resin, accelerator, auxiliary agent and conductive enhancement filler.
  • the particle size D50 of the copper powder is 0.1-10 ⁇ m.
  • the shape of the copper powder is flake, spherical and/or dendritic.
  • the resin is selected from one or more of epoxy resin, polyamide resin, saturated polyester resin, polyurethane resin, acrylic resin and silicone resin.
  • the accelerator is selected from one or more than two types of organic amines, imidazoles, boron trifluoride complexes, organotin complexes and transition metal complexes.
  • the auxiliary agent is selected from one or more of dispersants, stabilizers, thixotropic agents and coupling agents.
  • the conductive enhancing filler is selected from one of nanometer or sub-micron carbon black, graphene, carbon nanotubes, metal nickel powder, metal tin powder, metal indium powder, metal silver powder and metal aluminum powder.
  • the antioxidant conductive copper slurry also contains a solvent.
  • the solvent is selected from a hydroxyl-containing compound with a carbon number of 2-16 and an ether group-containing compound with a carbon number of 2-18. , one or more of a carbonyl group-containing compound with a carbon number of 3-12 and an ester group-containing compound with a carbon number of 2-16.
  • the copper powder in terms of mass percentage in the anti-oxidation conductive copper slurry, the copper powder is 75-85%, the resin is 3-11%, and the accelerator is 0.05-0.5% , the additive is 0.05-0.5%, the conductive reinforcing filler is 0.1-1%, and the solvent is 2-5%.
  • the antioxidant conductive copper slurry described in the present application has excellent oxidation resistance and good stability because it contains compounds with thiocarbamate structural units.
  • This application provides a method for preparing oxidation-resistant conductive copper slurry, which includes:
  • the first mixture and the second mixture are mixed to obtain an oxidation-resistant conductive copper slurry.
  • the first mixture and the second mixture are mixed and then subjected to primary dispersion and secondary dispersion to obtain the anti-oxidation conductive copper slurry.
  • the conductive copper slurry has a viscosity of 150-350 Pa ⁇ s at room temperature.
  • the resin, compounds having thiocarbamate structural units, accelerators, auxiliaries, copper powder and conductive reinforcing fillers are raw materials in the above-mentioned antioxidant conductive copper slurry.
  • the present application provides an electrode, which contains the above-mentioned anti-oxidation conductive copper slurry or the above-mentioned anti-oxidation conductive copper slurry prepared by the above-mentioned method.
  • the present application provides a battery, which includes the electrode described above.
  • the antioxidant conductive copper slurry described in the present application contains a compound with a thiocarbamate structural unit.
  • the compound with a thiocarbamate structural unit is formed by thiol or thiophenol and a polyisocyanate compound.
  • the reaction results in the release of thiol or thiol phenol at the curing temperature of the anti-oxidation conductive copper slurry, and the mercapto group of the thiol or thiol phenol molecule complexes with the copper and is adsorbed on the surface of the copper powder, blocking the oxides.
  • thiol/thiol also has reducing properties, and can react preferentially with oxides, or reduce oxidized copper, so that the anti-oxidation conductive copper slurry has a high conductivity effect, and at low temperatures It solidifies quickly and has stable conductivity in air atmosphere. After being placed at room temperature for 6 months, its conductivity has almost no change. And after the anti-oxidation conductive copper slurry is oxidized in air at 200°C for 60 minutes, its conductivity Although the conductivity decreases, it still has good conductivity.
  • % means wt%, that is, weight percentage. If the manufacturer of the reagents or instruments used is not indicated, they are all conventional reagent products that can be purchased commercially.
  • resin carrier mixture of resin and solvent: Weigh bisphenol F epoxy resin 170, hydrogenated bisphenol A epoxy resin YDH3000, and diethylene glycol butyl ether according to the mass ratio of 45:25:20:10 Acetate and terpineol were mixed with magnetic stirring to make the mixture uniform to obtain a resin carrier.
  • An antioxidant conductive copper slurry was prepared according to the same method as Example 1, wherein the cross-linking agent was prepared according to the method described in Example 1 using 2-mercaptobenzothiazole and diphenylmethane diisocyanate.
  • the viscosity of the anti-oxidation conductive copper slurry is measured by the method described in 1, which is 250-350 Pa ⁇ s (25°C).
  • An antioxidant conductive copper slurry was prepared according to the same method as Example 1, wherein the cross-linking agent was prepared using 2-mercaptobenzimidazole and 1,6-hexamethylene diisocyanate according to the method described in Example 1, according to The viscosity of the anti-oxidation conductive copper slurry was measured using the method described in Example 1, which was 150-250 Pa ⁇ s (25°C).
  • Example 2 Prepare antioxidant conductive copper slurry according to the same method as Example 1. The difference from Example 2 is that the cross-linking agent used in Comparative Example 1 is Trixene BI7982.
  • the antioxidant conductive copper slurry is measured according to the method described in Example 1. The viscosity of the slurry is 180-230 Pa ⁇ s (25°C).
  • the anti-oxidation conductive copper paste obtained in the Examples and Comparative Examples was screen-printed on an ultra-white glass substrate with a size of 200mm*150mm through a screen with a mesh size of 100 to 500.
  • the sample was heated under a nitrogen atmosphere. Pre-cure at 140°C for 5 minutes on the table, and cure at 180°C for 20 minutes. After cooling, measure the sheet resistance; place it at room temperature (environment: 25 ⁇ 2°C, humidity 45 ⁇ 5%) for 6 months, and then measure the sheet resistance. Oxidize in a general blast oven at 200°C for 60 minutes, and then measure the sheet resistance.
  • the test results are shown in Table 2, where A and B represent parallel tests; the sheet resistance measurement method: adopt the test method of Guangzhou Four Probe Technology Co., Ltd. RTS-8 type four-probe tester can obtain direct readings.
  • the antioxidant conductive copper slurry described in this application has excellent conductivity and stable oxidation resistance. After six months of natural storage at room temperature, the conductivity of the antioxidant conductive copper slurry has improved. There is almost no change, indicating that it is almost not oxidized; after the above-mentioned anti-oxidation conductive copper slurry is oxidized in air at 200°C for 60 minutes, although its conductivity decreases, it still has good conductivity. As for Comparative Example 1, the slurry obtained by using the cross-linking agent in the prior art has a higher initial sheet resistance after curing.

Abstract

Une pâte de cuivre conductrice antioxydante, son procédé de préparation et son utilisation. La pâte de cuivre conductrice antioxydante contient un composé contenant une unité structurale de thiocarbamate, lequel composé est utilisé en tant qu'agent de réticulation. À la température de durcissement, le thiol/thiophénol dans l'agent de réticulation est libéré, et les groupes mercapto du thiol/thiophénol sont complexés avec du cuivre de façon à être adsorbés sur la surface d'une poudre de cuivre, de telle sorte que la réaction d'un oxyde avec le cuivre est bloquée ; de plus, le thiol/thiophénol présente également une réductibilité et peut de préférence réagir avec un oxyde ou réduire le cuivre oxydé, de telle sorte qu'un excellent effet anti-oxydation peut être obtenu ; en outre, étant donné qu'à la température de durcissement, le thiol/thiophénol dans l'agent de réticulation est libéré, et les groupes mercapto du thiol/thiophénol sont complexés avec du cuivre de façon à être adsorbés sur la surface de la poudre de cuivre, la réaction d'un oxyde avec du cuivre est bloquée ; en outre, le thiol/thiophénol présente également une réductibilité et peut de préférence réagir avec un oxyde ou réduire le cuivre oxydé, et par conséquent un excellent effet anti-oxydation peut être obtenu.
PCT/CN2022/135155 2022-03-17 2022-11-29 Pâte de cuivre conductrice antioxydante, son procédé de préparation et son utilisation WO2023173807A1 (fr)

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