CN108753197B - Thermosetting conductive adhesive and preparation method thereof - Google Patents
Thermosetting conductive adhesive and preparation method thereof Download PDFInfo
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- CN108753197B CN108753197B CN201810301822.1A CN201810301822A CN108753197B CN 108753197 B CN108753197 B CN 108753197B CN 201810301822 A CN201810301822 A CN 201810301822A CN 108753197 B CN108753197 B CN 108753197B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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Abstract
The invention discloses a thermosetting conductive adhesive, which comprises the following components in percentage by weight: 50-70% of conductive filler, 1-20% of thermosetting resin, 0-20% of volatile organic compound and 1-30% of nano-silver cross-linking agent; the nano silver cross-linking agent is nano silver particles with oligomers adsorbed on the surfaces, the particle size of the nano silver particles is 1-100nm, one end group of the oligomers is selected from carboxyl, sulfydryl and amino, and the other end group of the oligomers is selected from carboxyl, sulfydryl and amino; the two ends of the thermosetting resin contain reactive epoxy groups. The invention also provides a preparation method of the conductive adhesive. The conductive adhesive has the advantages of stable system at normal temperature, convenient storage, excellent ageing resistance, excellent conductivity and the like.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a thermosetting conductive adhesive and a preparation method thereof.
Background
The conductive adhesive is an adhesive with certain conductivity after being cured or dried, and can connect a plurality of conductive materials together to form a conductive path between the connected materials. Typically, the conductive filler is made by dispersing a conductive filler such as gold powder, silver powder, copper powder, etc. in a resin carrier. In the electronics industry, conductive adhesives have become an indispensable new material.
The conductivity of the conductive adhesive is derived from contact conduction between conductive particles and electron tunneling. The stable contact between the particles in the glue layer is caused by the curing or drying of the conductive glue. Before the conductive adhesive is cured or dried, the conductive particles are separated in the adhesive and are not in continuous contact with each other, so that the conductive adhesive is in an insulating state. After the conductive paste is cured or dried, the volume of the adhesive shrinks due to the volatilization of the solvent and the curing of the adhesive, so that the conductive particles are contacted with each other to form a stable continuous state, thereby showing conductivity.
At present, the middle-temperature curing conductive adhesive (lower than 150 ℃) is mostly applied at home and abroad, the curing temperature is moderate, the curing temperature is matched with the temperature resistance and the use temperature of electronic components, the mechanical property is excellent, and the application is wide. In principle, the resin for the conductive adhesive can be a resin matrix of various adhesive types, and generally, thermosetting resins such as epoxy resin, silicone resin, polyimide resin, phenol resin, polyurethane, acrylic resin, and the like are used. The thermosetting resin forms a molecular skeleton structure of the conductive adhesive after being cured, guarantees mechanical property and bonding property and enables conductive filler particles to form channels.
Thermosetting conductive adhesives typically require a curing agent to cure, which can cause storage and handling inconvenience. During storage, the double-component type cold storage food is stored at normal temperature or the single-component type ultra-low temperature; this causes inconvenience in use because the use is under normal temperature conditions, resulting in gelation. Generally, the service life at normal temperature is only 24-48h, and some service lives are even shorter.
Disclosure of Invention
Aiming at the problem that the existing thermosetting conductive adhesive is inconvenient to store and use, the invention aims to provide the conductive adhesive which can be stored and used at normal temperature and has excellent heat resistance, ageing resistance and conductivity.
A thermosetting conductive adhesive comprises the following components in percentage by weight: 50-70% of conductive filler, 1-20% of thermosetting resin, 0-20% of volatile organic compound and 1-30% of nano-silver cross-linking agent; the nano silver cross-linking agent is nano silver particles with oligomers adsorbed on the surfaces, the particle size of the nano silver particles is 1-100nm, one end group of the oligomers is selected from carboxyl, sulfydryl and amino, and the other end group of the oligomers is selected from carboxyl, sulfydryl and amino; the two ends of the thermosetting resin contain reactive epoxy groups.
In the invention, the preferable scheme is that the average molecular weight of the oligomer is 200-3000 g/mol.
In the present invention, it is preferable that the conductive filler is composed of conductive fillers having different particle diameters between 100nm and 10 um.
In the invention, the preferable scheme is that the conductive filler is composed of silver powder with the particle diameters of 100-300nm, 1-5um and 5-10um respectively.
In the present invention, it is preferable that the thermosetting resin is an epoxy resin having reactive epoxy groups at both ends.
In the invention, the preferable scheme is that the thermosetting resin is epoxy resin, epoxy modified phenolic resin, epoxy modified acrylic resin, epoxy modified polyurethane resin and epoxy modified organic silicon resin, both ends of which contain reactive epoxy groups.
In the present invention, the volatile organic compound is one or a mixture of two or more of a medium-high boiling point solvent, a reactive monomer and an auxiliary agent.
In the present invention, the medium-high boiling point solvent is one or a mixture of two or more of ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, terpineol, butyl acetate and amyl acetate;
the reactable monomer is one or the mixture of more than two of acrylic acid alkyl ester, methacrylic acid alkyl ester and glycidyl ether;
the auxiliary agent is one or the mixture of more than two of polyoxyethylene and polyoxypropylene copolymer, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene polyester fatty alcohol ether, polyglycerol fatty acid ester, polysiloxane and polyether modified siloxane.
The invention also provides a preparation method of the thermosetting conductive adhesive, which comprises the following steps:
A. mixing 38-63 wt% of conductive filler and 5-15 wt% of thermosetting resin, and stirring and mixing uniformly to obtain a composition A;
B. mixing the nano-silver cross-linking agent with the rest of the conductive filler and the thermosetting resin; stirring and mixing uniformly to obtain a composition B;
C. and mixing the composition A and the composition B uniformly to obtain the composition.
Further, the preparation method of the solid conductive adhesive comprises the following steps:
A. mixing 38-63 wt% of conductive filler with 5-15 wt% of thermosetting resin, adding 38-63 wt% of volatile organic compound, and stirring and mixing uniformly to obtain a composition A;
B. mixing the nano-silver cross-linking agent with the rest of the conductive filler and the thermosetting resin; then adding the residual volatile organic compounds, and uniformly stirring and mixing to obtain a composition B;
C. and mixing the composition A and the composition B uniformly to obtain the composition.
The invention has the beneficial effects that: the nano-silver cross-linking agent is added, so that the prepared conductive adhesive can be stored stably at normal temperature, and the storage and the use of the conductive adhesive are greatly facilitated; in addition, the obtained conductive adhesive has excellent conductivity, heat resistance, curing shrinkage performance and ageing resistance.
Detailed Description
The invention will be further described with reference to specific embodiments:
a thermosetting conductive adhesive comprises the following components in percentage by weight: 50-70% of conductive filler, 1-20% of thermosetting resin, 0-20% of volatile organic compound and 1-30% of nano-silver cross-linking agent; the nano silver cross-linking agent is nano silver particles with oligomers adsorbed on the surfaces, the particle size of the nano silver particles is 1-100nm, one end group of the oligomers is selected from carboxyl, sulfydryl and amino, and the other end group of the oligomers is selected from carboxyl, sulfydryl and amino; the two ends of the thermosetting resin contain reactive epoxy groups.
Because carboxyl, sulfydryl and amino have strong coordination and recombination effects with the surface of the high-activity silver nano particle, oligomers containing carboxyl, sulfydryl and amino at two ends can be strongly adsorbed on the surface of the nano silver through carboxyl, sulfydryl and amino functional groups at the end. At the moment, the nano-silver cross-linking agent with the structure is dispersed in thermosetting resin with reactive epoxy groups at two ends, and carboxyl, amino and sulfhydryl functional groups capable of reacting with the epoxy groups are strongly adsorbed and coordinated on the surfaces of the silver nanoparticles and lose reaction activity, so that the system cannot be gelated at normal temperature, and can be stored at the normal temperature better without being stored separately. When the system is heated to 120-180 ℃, at least one terminal functional group is released, and then the epoxy group reaction can be initiated to achieve curing.
In the invention, the preferable scheme is that the average molecular weight of the oligomer is 200-3000g/mol, and the molecular formula of part of the oligomer is as follows:
HOOC-(CH2-CH2)n-COOH；HOOC-(CH2-CH2-O)n-CH2COOH；HOOC-(CH2-CH(CH2)-O)n-CH2COOH；NH2-(CH2-CH2)n-NH2；NH2-(CH2-CH2-O)n-CH2NH2；NH2-(CH2-CH(CH2)-O)n-CH2NH2；SH2-(CH2-CH2)n-NH2；SH2-(CH2-CH2-O)n-CH2NH2；SH2-(CH2-CH(CH2)-O)n-CH2NH2；SH2-(CH2-CH2)n-COOH；SH2-(CH2-CH2-O)n-CH2COOH；SH2-(CH2-CH(CH2)-O)n-CH2COOH。
in order to improve the conductivity of the conductive adhesive, the conductive filler is composed of conductive fillers with different particle sizes between 100nm and 10 um; due to the arrangement, the conductive fillers with different particle sizes are combined, so that the conductive fillers can be in better and more stable contact in a conductive adhesive system, and the conductivity is improved. In order to further improve the conductivity of the conductive adhesive, the conductive filler is composed of silver powder with the particle sizes of 100-300nm, 1-5um and 5-10um respectively.
In the present invention, it is preferable that the thermosetting resin is an epoxy resin having reactive epoxy groups at both ends.
In the invention, the preferable scheme is that the thermosetting resin is epoxy resin, epoxy modified phenolic resin, epoxy modified acrylic resin, epoxy modified polyurethane resin and epoxy modified organic silicon resin, both ends of which contain reactive epoxy groups.
In the invention, the preferable scheme is that the volatile organic compound is one or a mixture of more than two of medium and high boiling point solvent (boiling point range is 100-250 ℃), reactive monomer and auxiliary agent.
In the present invention, the medium-high boiling point solvent is one or a mixture of two or more of ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, terpineol, butyl acetate and amyl acetate;
the reactable monomer is one or the mixture of more than two of acrylic acid alkyl ester, methacrylic acid alkyl ester and glycidyl ether;
the auxiliary agent is one or the mixture of more than two of polyoxyethylene and polyoxypropylene copolymer, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene polyester fatty alcohol ether, polyglycerol fatty acid ester, polysiloxane and polyether modified siloxane.
The invention also provides a preparation method of the thermosetting conductive adhesive, which comprises the following steps:
A. mixing 38-63 wt% of conductive filler and 5-15 wt% of thermosetting resin, and stirring and mixing uniformly to obtain a composition A;
B. mixing the nano-silver cross-linking agent with the rest of the conductive filler and the thermosetting resin; stirring and mixing uniformly to obtain a composition B;
C. and mixing the composition A and the composition B uniformly to obtain the composition.
Further, the preparation method of the solid conductive adhesive comprises the following steps:
A. mixing 38-63 wt% of conductive filler with 5-15 wt% of thermosetting resin, adding 38-63 wt% of volatile organic compound, and stirring and mixing uniformly to obtain a composition A;
B. mixing the nano-silver cross-linking agent with the rest of the conductive filler and the thermosetting resin; then adding the residual volatile organic compounds, and uniformly stirring and mixing to obtain a composition B;
C. and mixing the composition A and the composition B uniformly to obtain the composition.
The stirring and mixing in the invention can be carried out by adopting a three-roller machine, a high-speed shearing machine, a sand mill and other equipment.
Example 1:
a preparation method of a solid conductive adhesive comprises the following steps:
A. mixing 35g of silver flake powder with the particle size of 1-5um and 14g of silver flake powder with the particle size of 5-10um into 15g of epoxy modified acrylic resin, diluting with 5g of reactive diluent butyl acrylate, mechanically stirring for 30-60min, and rolling for three times by using a three-roll mill to obtain a component A;
B. taking 21g of silver powder with the particle size of 100-300nm and 1g of nano-silver cross-linking agent with the particle size of 10nm, wherein the surface of the nano-silver cross-linking agent contains NH with the molecular structure2-(CH2-CH2-O)n-CH2NH2Mixing low molecular weight oligomer with average molecular weight of 200g/mol into 5g of epoxy modified acrylic resin, diluting with 4g of reactive diluent butyl acrylate, mechanically stirring for 30-60min, rolling for three times by using a three-roll mill, and continuously dispersing for 5-15min by using a high-speed shearing machine and a sand mill to prepare a component B;
C. mixing the component A and the component B, mechanically stirring and dispersing for 30-60min, and rolling for three times by a three-roll mill for dispersing to obtain the conductive adhesive which can be stored at normal temperature.
The conductive adhesive can be cured by baking at 150 deg.C for 30min, and the resistivity can reach 5-6 × 10-6Ωm。
The initial viscosity of the conductive adhesive is 10000-15000cps, and the viscosity of the conductive adhesive becomes larger by less than 50 percent after the conductive adhesive is placed in an environment at 25 ℃ for 6 months. The viscosity values were measured at 10rpm in a 25 ℃ environment using a Brookfield DV3T viscometer with a CP2-52Z spindle. For comparison, for example, the Hangao CA3556HF needs to be stored at the temperature of-25 to-18 ℃, and the service life of the product is within 48h at the temperature of 25 ℃; the Hangao ICP 4001 needs to be stored at the low temperature of 40 ℃ below zero, the service life is within 24 hours at the temperature of 25 ℃, and the viscosity is increased by nearly 50% when the product is placed at the normal temperature for 24 hours; the Hitachi CP-300-D needs to be stored at-13 ℃, and the service life is within 24h after being sealed at 25 ℃. The gradual increase of the viscosity of the conductive adhesive in the room temperature environment is caused by the chemical gelation reaction inside the conductive adhesive, namely, the high-activity curing agent and the thermosetting resin in the system are slowly subjected to the chemical crosslinking reaction. The conductive adhesive is generally applied by a dispensing process, and the increase of the viscosity of the conductive adhesive affects the stability of the dispensing process, thereby causing a plurality of problems such as needle blockage, reduced dispensing amount and the like. The invention seals the high-activity curing agent on the surface of the nano-silver to realize the sealing of the reaction group at normal temperature and the release of the sealed reaction group at high temperature, thereby realizing the stable storage at normal temperature. In addition, the existence of the nano silver has the advantage of improving the electrical property of the conductive adhesive.
After the conductive adhesive is baked for 30min at 150 ℃, and cured, a damp-heat aging test is carried out for 1000h at 85 ℃ and 85% humidity, and the shear strength before and after aging is less than 10%. The Test was carried out using the international standard ISO 16525-1-2014 additives-Test Methods For Isotropic electric Conductive additives-Part 1: General Test Methods.
Example 2:
A. mixing 14g of silver flake powder with the particle size of 1-5um and 49g of silver flake powder with the particle size of 5-10um into 15g of epoxy modified acrylic resin, diluting with 6g of reactive diluent, namely butyl methacrylate, mechanically stirring for 30-60min, and then rolling for three times by using a three-roll mill to obtain a component A;
B. taking 7g of silver powder with the particle size of 100-300nm and 1g of nano-silver cross-linking agent with the particle size of 10nm, wherein the surface of the nano-silver cross-linking agent contains a molecular structure of HOOC- (CH)2-CH2)n-COOH, a low molecular weight oligomer with an average molecular weight of 400g/mol, is mixed into 5g of epoxy modified acrylic resin, diluted with 3g of butyl methacrylate as an active diluent, mechanically stirred for 30-60min, rolled for three times by a three-roll mill, and then continuously dispersed for 5-15min by a high-speed shearing machine and a sand mill to obtain a component B;
C. mixing the component A and the component B, mechanically stirring and dispersing for 30-60min, and rolling for three times by a three-roll mill for dispersing to obtain the conductive adhesive which can be stored at normal temperature.
The conductive adhesive can be cured by baking at 150 deg.C for 30min, and the resistivity can reach 0.8-1 × 10-6Ωm。
The initial viscosity of the conductive adhesive is 10000-15000cps, and the viscosity of the conductive adhesive is increased to 15-30% after being placed in an environment at 25 ℃ for 6 months. The viscosity values were measured at 10rpm in a 25 ℃ environment using a Brookfield DV3T viscometer with a CP2-52Z spindle.
After the conductive adhesive is baked for 30min at 150 ℃, and cured, a damp-heat aging test is carried out for 1000h at 85 ℃ and 85% humidity, and the shear strength before and after aging is less than 10%. The Test was carried out using the international standard ISO 16525-1-2014 additives-Test Methods For Isotropic electric Conductive additives-Part 1: General Test Methods.
Example 3:
A. mixing 35g of silver flake powder with the particle size of 1-5um and 14g of silver flake powder with the particle size of 5-10um into 5g of epoxy resin, diluting with 5g of glycidyl ether serving as an active diluent, mechanically stirring for 30-60min, and rolling for three times by using a three-roll mill to obtain a component A;
B. taking 21g of silver powder with the particle size of 100-300nm and 10g of nano-silver cross-linking agent with the particle size of 10nm, wherein the surface of the nano-silver cross-linking agent contains a molecular structure of HOOC- (CH)2-CH2-O)n-CH2COOH, a low molecular weight oligomer with an average molecular weight of 600g/mol, in 5g of an epoxy resinDiluting with 4.9g of glycidyl ether serving as an active diluent, adding 0.10g of polyether modified siloxane serving as an auxiliary agent, mechanically stirring for 30-60min, rolling for three times by using a three-roll mill, and continuously dispersing for 5-15min by using a high-speed shearing machine and a sand mill to obtain a component B;
C. mixing the component A and the component B, mechanically stirring and dispersing for 30-60min, and rolling for three times by a three-roll mill for dispersing to obtain the conductive adhesive which can be stored at normal temperature.
The conductive adhesive can be cured by baking at 150 deg.C for 30min, and the resistivity can reach 1-2 × 10-7Ωm。
The initial viscosity of the conductive adhesive is 15000-. The viscosity values were measured at 10rpm in a 25 ℃ environment using a Brookfield DV3T viscometer with a CP2-52Z spindle.
After the conductive adhesive is baked for 30min at 150 ℃, and cured, a damp-heat aging test is carried out for 1000h at 85 ℃ and 85% humidity, and the shear strength before and after aging is less than 10%. The Test was carried out using the international standard ISO 16525-1-2014 additives-Test Methods For Isotropic electric Conductive additives-Part 1: General Test Methods.
Example 4:
A. mixing 10g of silver flake powder with the particle size of 1-5um and 35g of silver flake powder with the particle size of 5-10um into 10g of epoxy modified polyurethane resin, diluting with 10g of glycidyl ether serving as an active diluent, mechanically stirring for 30-60min, and rolling for three times by using a three-roll mill to obtain a component A;
B. taking 5g of silver powder with the particle size of 100-300nm and 10g of nano-silver cross-linking agent with the particle size of 10nm, wherein the surface of the nano-silver cross-linking agent contains NH with the molecular structure2-(CH2-CH(CH2)-O)n-CH2NH2Mixing low molecular weight oligomer with average molecular weight of 1000g/mol into 10g of epoxy modified polyurethane resin, diluting with 10g of active diluent glycidyl ether, mechanically stirring for 30-60min, rolling for three times by a three-roll mill, and continuously dispersing for 5-15min by a high-speed shearing machine and a sand mill to obtain a component B;
C. mixing the component A and the component B, mechanically stirring and dispersing for 30-60min, and rolling for three times by a three-roll mill for dispersing to obtain the conductive adhesive which can be stored at normal temperature.
The conductive adhesive can be cured by baking at 150 deg.C for 30min, and the resistivity can reach 5-6 × 10-6Ωm。
The initial viscosity of the conductive adhesive is 20000-25000cps, and the viscosity of the conductive adhesive is increased to 30-50% after being placed in an environment at 25 ℃ for 6 months. The viscosity values were measured at 10rpm in a 25 ℃ environment using a Brookfield DV3T viscometer with a CP2-52Z spindle.
After the conductive adhesive is baked for 30min at 150 ℃, and cured, a damp-heat aging test is carried out for 1000h at 85 ℃ and 85% humidity, and the shear strength before and after aging is less than 20%. The Test was carried out using the international standard ISO 16525-1-2014 additives-Test Methods For Isotropic electric Conductive additives-Part 1: General Test Methods.
Example 5:
A. mixing 42g of silver flake powder with the particle size of 1-5um and 6g of silver flake powder with the particle size of 5-10um into 0.5g of epoxy modified phenolic resin, diluting with 5g of glycidyl ether serving as an active diluent, mechanically stirring for 30-60min, and rolling for three times by using a three-roll mill to obtain a component A;
B. taking 12g of silver powder with the particle size of 100-300nm and 30g of nano-silver cross-linking agent with the particle size of 100nm, wherein the surface of the nano-silver cross-linking agent contains a molecular structure SH2-(CH2-CH2-O)n-CH2COOH, a low molecular weight oligomer with the average molecular weight of 3000g/mol, is mixed into 0.5g of epoxy modified phenolic resin, diluted by 4g of active diluent glycidyl ether, mechanically stirred for 30-60min, rolled for three times by a three-roll mill, and continuously dispersed for 5-15min by a high-speed shearing machine and a sand mill to prepare a component B;
C. mixing the component A and the component B, mechanically stirring and dispersing for 30-60min, and rolling for three times by a three-roll mill for dispersing to obtain the conductive adhesive which can be stored at normal temperature.
The conductive adhesive can be cured by baking at 180 deg.C for 30min, and the resistivity can reach 0.8-1.0 × 10-7Ωm。
The initial viscosity of the conductive adhesive is 8000-12000cps, and the viscosity of the conductive adhesive is increased to 15-30% after being placed in an environment at 25 ℃ for 6 months. The viscosity values were measured at 10rpm in a 25 ℃ environment using a Brookfield DV3T viscometer with a CP2-52Z spindle.
After the conductive adhesive is baked for 30min at 180 ℃, and cured, a damp-heat aging test is carried out for 1000h at 85 ℃ and 85% humidity, and the shear strength before and after aging is less than 10%. The Test was carried out using the international standard ISO 16525-1-2014 additives-Test Methods For Isotropic electric Conductive additives-Part 1: General Test Methods.
Example 6:
A. mixing 10g of silver flake powder with the particle size of 1-5um and 35g of silver flake powder with the particle size of 5-10um into 10g of epoxy modified organic silicon resin, mechanically stirring for 30-60min, and rolling for three times by using a three-roll mill to obtain a component A;
B. taking 5g of silver powder with the particle size of 100-300nm and 30g of nano-silver cross-linking agent with the particle size of 80nm, wherein the surface of the nano-silver cross-linking agent contains a molecular structure SH2-(CH2-CH(CH2)-O)n-CH2NH2Mixing low molecular weight oligomer with average molecular weight of 2000g/mol into epoxy modified organic silicon resin of 9.9g, adding auxiliary agent polyether modified siloxane of 0.10g, mechanically stirring for 30-60min, rolling for three times by a three-roll mill, and continuously dispersing for 5-15min by a high-speed shearing machine and a sand mill to prepare a component B;
C. mixing the component A and the component B, mechanically stirring and dispersing for 30-60min, and rolling for three times by a three-roll mill for dispersing to obtain the conductive adhesive which can be stored at normal temperature.
The conductive adhesive can be cured by baking at 180 deg.C for 30min, and the resistivity can reach 1-2 × 10-7Ωm。
The initial viscosity of the conductive adhesive is 20000-25000cps, and the viscosity of the conductive adhesive is increased to 30-50% after being placed in an environment at 25 ℃ for 6 months. The viscosity values were measured at 10rpm in a 25 ℃ environment using a Brookfield DV3T viscometer with a CP2-52Z spindle.
After the conductive adhesive is baked for 30min at 180 ℃, and cured, a damp-heat aging test is carried out for 1000h at 85 ℃ and 85% humidity, and the shear strength before and after aging is less than 10%. The Test was carried out using the international standard ISO 16525-1-2014 additives-Test Methods For Isotropic electric Conductive additives-Part 1: General Test Methods.
It will be apparent to those skilled in the art that other various changes and modifications can be made in the above-described embodiments and concepts and all such changes and modifications are intended to be within the scope of the invention.
Claims (4)
1. The thermosetting conductive adhesive is characterized by comprising the following components in percentage by weight: 50-70% of conductive filler, 1-20% of thermosetting resin, 0-20% of volatile organic compound and 1-30% of nano-silver cross-linking agent; the content of the volatile organic compound is not 0; the nano silver cross-linking agent is nano silver particles with oligomers adsorbed on the surfaces, the particle size of the nano silver particles is 1-100nm, one end group of the oligomers is selected from carboxyl, sulfydryl and amino, and the other end group of the oligomers is selected from carboxyl, sulfydryl and amino; both ends of the thermosetting resin contain reactive epoxy groups; the average molecular weight of the oligomer is 200-3000 g/mol; the conductive filler is composed of silver powder with the particle size of 100-300nm, 1-5um and 5-10um respectively;
the volatile organic compound is one or a mixture of more than two of a medium-high boiling point solvent, a reactive monomer and an auxiliary agent;
the medium-high boiling point solvent is one or the mixture of more than two of ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, terpineol, butyl acetate and amyl acetate;
the reactable monomer is one or the mixture of more than two of acrylic acid alkyl ester, methacrylic acid alkyl ester and glycidyl ether;
the auxiliary agent is one or a mixture of more than two of polyoxyethylene and polyoxypropylene copolymer, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty alcohol ether, polyglycerol fatty acid ester, polysiloxane and polyether modified siloxane.
2. The thermosetting conductive adhesive according to claim 1, characterized in that: the thermosetting resin is epoxy resin with two ends containing reactive epoxy groups.
3. The thermosetting conductive adhesive according to claim 1, characterized in that: the thermosetting resin is epoxy resin, epoxy modified phenolic resin, epoxy modified acrylic resin, epoxy modified polyurethane resin and epoxy modified organic silicon resin, both ends of which contain reactive epoxy groups.
4. The method for preparing a thermosetting conductive adhesive according to any one of claims 1 to 3, characterized by comprising the steps of:
A. mixing 38-63 wt% of conductive filler with 5-15 wt% of thermosetting resin, adding 38-63 wt% of volatile organic compound, and stirring and mixing uniformly to obtain a composition A;
B. mixing the nano-silver cross-linking agent with the rest of the conductive filler and the thermosetting resin; then adding the residual volatile organic compounds, and uniformly stirring and mixing to obtain a composition B;
C. and mixing the composition A and the composition B uniformly to obtain the composition.
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| CN112080240A (en) * | 2020-09-17 | 2020-12-15 | 镝普材料(深圳)有限公司 | Low-resistance conductive adhesive and manufacturing method of conductive adhesive tape |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1478285A (en) * | 2000-10-25 | 2004-02-25 | ��ĥ������ʽ���� | Electroconductive metal paste |
| CN101175994A (en) * | 2004-10-21 | 2008-05-07 | 药品诊断学公司 | Stable metal/conductive polymer composite colloids and methods for making and using the same |
| US20150282330A1 (en) * | 2012-10-31 | 2015-10-01 | Mitsuboshi Belting Ltd. | Conductive adhesive for screen printing, joined body of inorganic material, and method for producing same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1478285A (en) * | 2000-10-25 | 2004-02-25 | ��ĥ������ʽ���� | Electroconductive metal paste |
| CN101175994A (en) * | 2004-10-21 | 2008-05-07 | 药品诊断学公司 | Stable metal/conductive polymer composite colloids and methods for making and using the same |
| US20150282330A1 (en) * | 2012-10-31 | 2015-10-01 | Mitsuboshi Belting Ltd. | Conductive adhesive for screen printing, joined body of inorganic material, and method for producing same |
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