CN111205806A - High-conductivity conductive adhesive and synthesis process thereof - Google Patents
High-conductivity conductive adhesive and synthesis process thereof Download PDFInfo
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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
- C09J175/06—Polyurethanes from polyesters
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/085—Copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention relates to a high-conductivity conductive adhesive and a synthesis process thereof, relating to the technical field of conductive adhesives, and the high-conductivity conductive adhesive is prepared from the following raw materials in percentage by weight: 30-40% of polyurethane adhesive; 40-50% of conductive filler; 10-30% of reinforcing filler; the polyurethane adhesive is prepared from the following raw materials in percentage by weight: 6-10% of trimethylolpropane triacrylate; 16-20% of isooctyl acrylate; benzoin ethyl ether 1-1.4%; 0.6 to 1 percent of benzophenone; 0.6 to 1 percent of benzoyl peroxide; the balance of modified polyurethane prepolymer. The invention is used for improving the adhesion effect of the conductive adhesive on the conductive material, thereby improving the conductivity of the conductive adhesive.
Description
Technical Field
The invention relates to the technical field of conductive adhesives, in particular to a high-conductivity conductive adhesive and a synthesis process thereof.
Background
The conductive adhesive is an adhesive which has certain conductivity after being cured or dried. It can connect multiple conductive materials together to form an electrical path between the connected materials. In the electronic industry, conductive adhesive has become an indispensable new material
However, the existing conductive adhesive has poor adhesion on objects, and is easy to separate from the surface of the conductive material to be adhered in the long-term use process, so that the connection tightness between the conductive adhesive and the conductive material is reduced, and the conductive effect of the conductive adhesive is influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-conductivity conductive adhesive and a synthesis process thereof, which are used for improving the adhesion effect of the conductive adhesive on a conductive material so as to improve the conductivity of the conductive adhesive.
The above object of the present invention is achieved by the following technical solutions:
the high-conductivity conductive adhesive is prepared from the following raw materials in percentage by weight:
30-40% of polyurethane adhesive;
40-50% of conductive filler;
10-30% of reinforcing filler;
the polyurethane adhesive is prepared from the following raw materials in percentage by weight:
by adopting the technical scheme, the modified polyurethane prepolymer is added to endow the conductive adhesive with good bonding effect and water resistance and endow the conductive adhesive with good heat resistance. The reinforced filler is added, so that the strength of the conductive adhesive can be improved, the mechanical property of the conductive adhesive is improved, the conductive adhesive is endowed with good strength and toughness, the durability and the wear resistance of the conductive adhesive are improved, and the service life of the conductive adhesive is prolonged.
Trimethylolpropane triacrylate is used as a crosslinking monomer and an active diluent, and isooctyl acrylate is used as an active monomer to modify polyurethane to prepare acrylate-polyurethane composite emulsion, so that the polyurethane adhesive is endowed with good heat resistance. The trimethylolpropane triacrylate has higher curing shrinkage rate, so that the curing shrinkage rate of polyurethane can be improved, and the curing shrinkage rate of a polymer matrix is increased to cause the contact between the conductive fillers in the conductive compound to be more sufficient, so that the volume resistivity of the conductive compound is reduced, and the conductivity of the conductive adhesive is improved.
The benzoin ethyl ether and the benzophenone are used as the photoinitiator, the benzoyl peroxide is used as the thermal initiator, and the photoinitiator and the thermal initiator are added, so that when the conductive adhesive is used, the conductive adhesive can be quickly cured under the irradiation of ultraviolet rays, and the surface of the conductive adhesive is quickly dried. And then, the conductive adhesive is subjected to thermosetting to be completely cured, and the adhesion effect of the conductive adhesive on the conductive material is improved through the combined action of the two curing modes of photocuring and thermosetting, so that the conductivity of the conductive adhesive is improved.
The invention is further configured to: the modified polyurethane prepolymer is prepared from the following raw materials in percentage by weight:
by adopting the technical scheme, the polyester polyol and the toluene diisocyanate are common raw materials for preparing polyurethane. The gamma-methacryloxypropyltrimethoxysilane can perform addition reaction with polyurethane to introduce siloxane into the polyurethane so as to modify the polyurethane and endow the polyurethane with good water resistance. The monoethanolamine is used as a chain extender and a blocking agent, and can expose hydroxyl during blocking, and the hydroxyl can be in chemical bond connection with the surface of a metal conductive material, so that the adhesion effect of the conductive adhesive on the conductive material is improved, and the conductivity of the conductive adhesive is improved. Dibutyl tin dilaurate is used as a catalyst to improve the reaction rate, optimize the reaction environment and facilitate the actual operation. The ethyl acetate is used as a solvent, is a safe and pollution-free environment-friendly solvent, and improves the physical health of workers.
The invention is further configured to: the polyester polyol is prepared from the following raw materials in percentage by weight:
by adopting the technical scheme, three diacids of terephthalic acid, isophthalic acid and sebacic acid are compounded for use, and the three diacids make up for each other, so that the polyurethane prepared by using the polyester polyol prepared in the invention can have good heat-resistant and water-resistant effects, and the conductive adhesive can have good adhesive force. Tetrabutyl titanate is used as a catalyst, so that the reaction rate can be improved.
The invention is further configured to: the conductive filler comprises the following raw materials in percentage by weight:
30-50% of nano silver particles;
50-70% of silver-plated copper powder.
By adopting the technical scheme, in order to store the silver-plated copper powder, the surface of the silver-plated copper powder is generally coated with a layer of insulating organic matter, the insulating organic matter is generally an organic lubricant, the silver-plated copper powder is directly added into a polyurethane adhesive, and larger tunnel resistance exists between conductive fillers which are in physical contact, so that the conductivity of the conductive adhesive is influenced. The nano silver particles are added, and the nano silver particles have larger surface energy, so that the melting phenomenon, namely low-temperature sintering, can occur at the temperature lower than the melting point of the body. When the conductive adhesive is thermally cured, the nano silver particles can be sintered in situ on the surface of the silver-plated copper powder, so that alloy bond connection is formed between the silver-plated copper powder, a pure physical contact form between fillers is changed, the whole conductive adhesive system forms a high-efficiency conductive path, and the conductive adhesive is endowed with good conductivity. The silver-plated copper powder has the conductive effect of the silver powder, is low in price and is a good conductive adhesive filler, and the silver-plated copper powder is dendritic, so that the contact area between the silver-plated copper powder and each raw material can be increased, and the conductive performance of the conductive adhesive is improved.
The invention is further configured to: the silver-plated copper powder is pretreated by a modifier, and the volume ratio of the modifier to the silver-plated copper powder is as follows: 2: 1;
the modifier comprises the following raw materials in percentage by weight:
the pretreatment comprises the following process steps: putting the silver-plated copper powder into the prepared modifier in proportion, and performing ultrasonic dispersion treatment for 1-2h to obtain slurry; and (3) putting the slurry into a ball mill for ball milling for 1-2h, and then putting the ball mill into a vacuum drying oven at 90-100 ℃ for drying for 1-2h to obtain the pretreated silver-plated copper powder.
By adopting the technical scheme, the malonic acid and the adipic acid are both straight-chain binary acids, and both can react with insulating organic matters on the surface of the silver-plated copper powder to replace organic lubricants on the surface of the silver-plated copper powder in situ, so that the conductivity of the conductive adhesive is improved. And both ends of the dicarboxylic acid can be ionized into carboxylate radicals with negative electricity, so that the dicarboxylic acid can be effectively anchored on the surface of the silver powder, and the short-chain structure of the dicarboxylic acid is favorable for electron transmission, so that the conductivity of the conductive adhesive is improved. And although the malonic acid and the adipic acid have certain acidity and certain removal capability on the insulating lubricant on the surface of the silver powder, the malonic acid and the adipic acid are not strong in acidity, so that the agglomeration phenomenon caused by the rapid removal of the organic substances on the surface of the silver powder can be avoided. Meanwhile, malonic acid and adipic acid can also react with amino and hydroxyl in polyurethane, so that the binding force of the silver-plated copper powder and resin is improved, and the conductive adhesive is endowed with good conductivity and mechanical properties.
The vinyl trimethoxy silane is used as a silane coupling agent to reduce the surface energy of the surface of the silver-plated copper powder, so that the surface of the silver-plated copper powder can be conveniently removed by malonic acid and adipic acid, and the dispersion effect of the silver-plated copper powder in the polyurethane adhesive is improved. And when the conductive adhesive is cured, the vinyltrimethoxysilane and the modified polyurethane prepolymer are subjected to Michael addition reaction, so that the binding force of the silver-plated copper powder and the resin is improved, and the conductive adhesive is endowed with good conductive performance and mechanical performance. Absolute ethyl alcohol is used as a solvent.
The invention is further configured to: the reinforcing filler comprises the following raw materials in percentage by weight:
by adopting the technical scheme, acrylic acid is added to modify the multi-walled carbon nanotube, and carboxyl is introduced on the surface of the multi-walled carbon nanotube. The periphery of the multi-wall carbon nano-tube grafted with acrylic acid becomes an environment with negative electricity, and the negative electricity environment can offset Van der Waals force between the multi-wall carbon nano-tubes through electrostatic repulsion, thereby improving the dispersion effect of the reinforcing filler in the polyurethane adhesive and improving the conductivity and mechanical property of the conductive adhesive. And the carboxyl can react with the modified polyurethane prepolymer, so that the bonding force of the reinforced filler and the resin is improved, and the conductive adhesive has good conductivity and mechanical properties. Meanwhile, the multi-walled carbon nanotube is modified by acrylic acid, so that the adhesion effect of the silver-plated copper powder on the multi-walled carbon nanotube can be improved. Because the multi-wall carbon nano-tube and the silver-plated copper powder are both acidic and the surface is provided with carboxyl, the silver-plated copper powder can be uniformly attached to the multi-wall carbon nano-tube, and the conductivity of the conductive adhesive is improved.
The vinyl triethoxysilane is used as a silane coupling agent to reduce the surface energy of the surface of the multi-walled carbon nanotube, so that acrylic acid is grafted on the surface of the multi-walled carbon nanotube conveniently, and the dispersion effect of the reinforcing filler in the polyurethane adhesive is improved. And when the conductive adhesive is cured, the vinyltriethoxysilane and the modified polyurethane prepolymer generate Michael addition reaction, so that the binding force of the reinforcing filler and the resin is improved, and the conductive adhesive is endowed with good conductive performance and mechanical performance. Azodiisobutyronitrile is used as an initiator to promote acrylic acid to be grafted on the multi-wall carbon nanotube, so that the reaction rate is increased and the reaction process is accelerated. Acetone is used as a solvent.
The invention is further configured to: the polyurethane emulsion also comprises the following raw materials in percentage by weight:
20-30% of bisphenol A epoxy acrylate;
3-7% of hydroxyethyl methacrylate phosphate.
By adopting the technical scheme, the bisphenol A type epoxy acrylate is added and can be used as a crosslinking monomer to modify polyurethane, so that the adhesion effect of the polyurethane adhesive on metal is improved, two conductive materials can be better connected, and the conductive effect of the conductive adhesive is improved. And during curing, the cured epoxy resin and the cured polyurethane are interlaced and wound together to form a three-dimensional network structure, so that the confidentiality and the strength of the film layer are improved, and the film layer is endowed with good toughness. Meanwhile, the connection tightness between the conductive fillers is improved, the contact area between the conductive fillers is increased, and therefore the conductivity of the conductive adhesive is improved. And endows the polyurethane adhesive with good strength, wear resistance and corrosion resistance. The hydroxyethyl methacrylate phosphate is added and can be used as a crosslinking monomer to introduce the phosphate, so that the conductive adhesive has good flame retardance, and meanwhile, the adhesion effect of the polyurethane adhesive on metal is improved, so that two conductive materials can be better connected, and the conductive effect of the conductive adhesive is improved.
The above object of the present invention is achieved by the following technical solutions:
a synthesis process of a high-conductivity conductive adhesive comprises the following process steps:
1) synthesizing and preparing polyester polyol: adding 1, 4-butanediol into a stirring reaction kettle according to a proportion, adding terephthalic acid, isophthalic acid, sebacic acid and tetrabutyl titanate according to a proportion under the condition of starting stirring, heating to 140 ℃ at the speed of 0.5 ℃/min, introducing nitrogen, reacting for 1h while keeping the temperature, heating to 240 ℃ within 7 h, keeping the temperature under the nitrogen atmosphere, and sampling and analyzing; measuring the acid value, measuring the hydroxyl value if the acid value is less than 0.5mgKOH/g, and cooling to room temperature when the hydroxyl value is 12 +/-1 mgKOH/g to obtain polyester polyol; if the hydroxyl value is not reached, continuously discharging alcohol until the hydroxyl value is qualified;
2) synthesizing and preparing a modified polyurethane prepolymer: dropwise adding toluene diisocyanate into the polyester polyol prepared in the step 1) at a constant speed according to a proportion, completing dropwise adding within 20-30min, heating to 70-80 ℃, carrying out heat preservation reaction for 3h, then adding monoethanolamine, gamma-methacryloxypropyltrimethoxysilane and dibutyltin dilaurate according to a proportion, heating to 80-90 ℃, carrying out heat preservation reaction for 2h, heating to 90-100 ℃, carrying out heat preservation reaction until NCO% is less than 0.05%, then cooling to 70-80 ℃, adding ethyl acetate, stirring for 0.5h, and cooling to room temperature to prepare a modified polyurethane prepolymer;
3) synthesizing and preparing a polyurethane adhesive: adding trimethylolpropane triacrylate, isooctyl acrylate, benzoin ethyl ether, benzophenone, benzoyl peroxide, hydroxyethyl methacrylate phosphate and bisphenol A type epoxy acrylate into the modified polyurethane prepolymer prepared in the step 2) according to the proportion, and stirring for 20-30min under the condition that the rotating speed is 1000-2000r/min to prepare a polyurethane adhesive;
4) synthesizing and preparing the conductive adhesive: adding the conductive filler and the reinforcing filler into the polyurethane adhesive prepared in the step 3) according to the proportion, and stirring for 10-20min under the condition that the rotating speed is 2000-3000r/min to prepare the high-conductivity conductive adhesive.
The invention is further configured to: the reinforcing filler comprises the following preparation processes: adding the multi-walled carbon nano-tubes into acetone according to a proportion, ultrasonically dispersing for 10-20min, adding acrylic acid, vinyl triethoxysilane and azobisisobutyronitrile according to a proportion, introducing nitrogen for 30min, stirring for 8h at 50-60 ℃, then carrying out vacuum filtration, washing solid particles with ethanol, and obtaining the reinforcing filler after washing.
By adopting the technical scheme, the multi-wall carbon nano-tube is added into acetone, and ultrasonic dispersion is carried out for 10-20min to remove impurities and treating agents on the surface of the multi-wall carbon nano-tube, so that acrylic acid is grafted on the surface of the multi-wall carbon nano-tube conveniently, and the grafting efficiency and effect of the acrylic acid are improved.
In summary, the invention includes at least one of the following beneficial technical effects:
1. the modified polyurethane prepolymer is added to endow the conductive adhesive with good bonding effect and water resistance and endow the conductive adhesive with good heat resistance;
2. the reinforcing filler is added, so that the strength of the conductive adhesive can be improved, the mechanical property of the conductive adhesive is improved, the conductive adhesive is endowed with good strength and toughness, the durability and the wear resistance of the conductive adhesive are improved, and the service life of the conductive adhesive is prolonged;
3. the silver-plated copper powder is pretreated to remove the organic lubricant on the surface of the silver-plated copper powder, so that the binding force between the silver-plated copper powder and resin is improved, and the conductivity and mechanical properties of the conductive adhesive are improved.
Detailed Description
Example 1: the invention discloses a high-conductivity conductive adhesive, which comprises the following process steps:
1) synthesizing and preparing polyester polyol:
the process for preparing the polyester polyol comprises the following steps: adding 1, 4-butanediol into a stirring reaction kettle, adding terephthalic acid, isophthalic acid, sebacic acid and tetrabutyl titanate under the condition of starting stirring, heating to 140 ℃ at the speed of 0.5 ℃/min, introducing nitrogen, reacting for 1h while keeping the temperature, heating to 240 ℃ within 7 h, keeping the temperature in a nitrogen atmosphere, sampling and analyzing; measuring the acid value, measuring the hydroxyl value when the acid value is less than 0.5mgKOH/g, and cooling to room temperature when the hydroxyl value is 12mgKOH/g to prepare polyester polyol;
the polyester polyol is prepared from the following raw materials in percentage by weight:
2) synthesizing and preparing a modified polyurethane prepolymer:
the process for preparing the modified polyurethane prepolymer comprises the following steps: dropwise adding toluene diisocyanate into the polyester polyol prepared in the step 1) at a constant speed, completing dropwise adding within 25min, heating to 75 ℃, carrying out heat preservation reaction for 3h, then adding monoethanolamine, gamma-methacryloxypropyltrimethoxysilane and dibutyltin dilaurate, heating to 85 ℃, carrying out heat preservation reaction for 2h, heating to 95 ℃, carrying out heat preservation reaction until the NCO% is equal to 0.04%, then cooling to 75 ℃, adding ethyl acetate, stirring for 0.5h, and cooling to room temperature to prepare a modified polyurethane prepolymer;
the modified polyurethane prepolymer is prepared from the following raw materials in percentage by weight:
3) synthesizing and preparing a polyurethane adhesive:
the process for preparing the polyurethane adhesive comprises the following steps: adding trimethylolpropane triacrylate, isooctyl acrylate, benzoin ethyl ether, benzophenone, benzoyl peroxide, hydroxyethyl methacrylate phosphate and bisphenol A epoxy acrylate into the modified polyurethane prepolymer prepared in the step 2), and stirring at the rotation speed of 1500r/min for 25min to prepare a polyurethane adhesive;
the polyurethane adhesive is prepared from the following raw materials in percentage by weight:
4) synthesizing and preparing the conductive adhesive:
the process for preparing the high-conductivity conductive adhesive comprises the following steps: adding a conductive filler and a reinforcing filler into the polyurethane adhesive prepared in the step 3), and stirring for 15min at the rotating speed of 2500r/min to prepare a high-conductivity conductive adhesive;
the high-conductivity conductive adhesive is prepared from the following raw materials in percentage by weight:
35% of polyurethane adhesive;
45% of conductive filler;
20% of reinforcing filler;
the conductive filler comprises the following raw materials in percentage by weight:
40% of nano silver particles;
60% of silver-plated copper powder;
the silver-plated copper powder is pretreated by a modifier, and the volume ratio of the modifier to the silver-plated copper powder is as follows: 2: 1;
wherein, the pretreatment comprises the following process steps: putting the silver-plated copper powder into the prepared modifier, and performing ultrasonic dispersion treatment for 1.5h to obtain slurry; respectively putting the slurry into a ball mill for ball milling for 1.5h, and then putting the ball mill into a vacuum drying oven at 95 ℃ for drying for 1.5h to prepare pretreated silver-plated copper powder;
wherein, the modifier comprises the following raw materials in percentage by weight:
the reinforcing filler is prepared from the following raw materials in percentage by weight:
wherein, the process for preparing the reinforced filler comprises the following steps: adding the multi-walled carbon nanotube into acetone, dispersing for 15min by ultrasonic waves, adding acrylic acid, vinyl triethoxysilane and azobisisobutyronitrile, introducing nitrogen for 30min, stirring for 8h at 55 ℃, then carrying out vacuum filtration, washing and filtering the obtained solid particles by using ethanol with the mass concentration of 50%, and washing the solid particles to obtain the reinforced filler.
When the conductive adhesive is applied, the conductive adhesive is coated on an object to be adhered, and then the object is cured for 3min under the UV irradiation at the temperature of 140 ℃, wherein the power of a UV lamp is 1000W, and the irradiation distance is 13 cm.
Examples 2 to 5 are different from example 1 in that the highly conductive adhesive is prepared from the following raw materials in percentage by weight:
examples 6 to 9 differ from the examples in that the polyurethane adhesive is prepared from the following raw materials in percentage by weight:
examples 10 to 13 are different from example 1 in that the modified polyurethane prepolymer is prepared from the following raw materials in percentage by weight:
examples 14-17 differ from example 1 in that the polyester polyol is made from the following raw materials in weight percent:
examples 18-21 differ from example 1 in that the conductive filler comprises the following raw materials in weight percent:
examples 22-25 differ from example 1 in that the modifier comprises the following raw materials in weight percent:
examples 26 to 29 differ from example 1 in that the reinforcing filler comprises the following raw materials in weight percent:
comparative example:
comparative example 1 is different from example 1 in that the highly conductive paste does not include a reinforcing filler;
comparative example 2 differs from example 1 in that the reinforcing filler is a multi-walled carbon nanotube;
comparative example 3 differs from example 1 in that the polyurethane adhesive does not include bisphenol a type epoxy acrylate;
comparative example 4 differs from example 1 in that hydroxyethyl methacrylate phosphate is not included in the polyurethane adhesive;
comparative example 5 differs from example 1 in that the polyurethane adhesive does not include trimethylolpropane triacrylate;
comparative example 6 differs from example 1 in that the modified polyurethane prepolymer does not include gamma-methacryloxypropyltrimethoxysilane;
comparative example 7 differs from example 1 in that the conductive filler is silver-plated copper powder;
comparative example 8 differs from example 1 in that the silver-plated copper powder was not pretreated with a modifier;
comparative example 9 is different from example 1 in that the conductive paste is applied by coating the conductive paste on an object to be adhered and then curing it by UV irradiation for 3min, wherein the power of the UV lamp is 1000W and the irradiation distance is 13 cm.
The detection method comprises the following steps:
the following tests were carried out on the conductive pastes prepared in examples 1 to 29 and comparative examples 1 to 10:
1) and (3) measuring the adhesion force: according to the national standard GB/T13217-. Using an adhesion tester to scratch the surface of a tested coating into small grids, using an adhesive tape to stick the scratched small grids, wiping the adhesive tape for about 30-90 seconds, tearing the adhesive tape along the vertical direction of a test surface, checking the falling degree of the coating, wherein 5B indicates that the grids do not fall, 4B indicates that the grids fall within 5%, 3B indicates that the grids fall within 5%, 2B indicates that the grids fall within 15% -35%, 1B indicates that the grids fall within 35% -65%, and 0B indicates that the grids fall within more than 65%.
2) Determination of Water resistance: the water absorption of the coating film is measured according to GB/T1034-1998, the cured film is cut into 4cm multiplied by 4cm, the mass of the film is weighed after the film is dried to be constant, the film is put into water to be soaked for 48 hours and then taken out, the surface water is sucked by filter paper and then the film is weighed, and the water absorption Wm is calculated according to the formula:
Wm＝(Wt-Wi)/Wi；
wm: mass water absorption (%) of the conductive paste sample; wt: mass (g) of the coating before immersion; and Wi: mass (g) before coating film immersion.
3) Measurement of Heat resistance: curing the PVC synthetic leather sample strip coated with the conductive adhesive, placing the sample strip at room temperature for 24 hours, cutting the sample strip into a sample of 100mmx25mm, separating the part of the sample which is not bonded into 180 ℃, fixing a chuck of a drying oven at the upper end, and hanging a weight of 0.5kg on a chuck at the lower end; heating in a circulating blower for 30min, and observing the separation condition of the adhesive joint surface; if the glue is glued, sold and peeled, the temperature of the oven is the heat-resistant temperature of the glue film.
4) Measurement of conductive Properties: preparing a conductive adhesive standard sample and testing the volume resistivity by adopting a four-point probe method according to the standard of ASTM D257-2007 Standard test method for direct current resistance or conductivity of insulating materials;
the specific process is as follows: two parallel strips of 3M patch 810 (4 mm apart) were attached to a standard 2.54cm x7.62cm glass slide, a small amount of the prepared conductive adhesive was placed in the gap between the two strips and coated flat with a scalpel, and the strips were removed. The volume resistance of the cured conductive adhesive is tested by using an HTS-8 type four-point probe tester, 5 points are measured on each sample, the average value of the points is taken as the resistance of the conductive adhesive, and the volume resistivity rho is calculated according to the formula:
ρ＝Rx(bxd)/L；
l, b, d: length, width and thickness (cm) of the conductive adhesive sample; r: resistance (Ω) of the electric glue sample; ρ: volume resistivity (Ω · cm) of the sample.
From the above table, it can be seen that:
1. compared with the comparative examples 1 and 2, the reinforced filler is added, and the acrylic acid, the vinyltriethoxysilane, the azobisisobutyronitrile and the acetone are added to modify the multi-walled carbon nanotube, so that the carboxyl is introduced to the surface of the multi-walled carbon nanotube, the dispersion effect of the reinforced filler in the polyurethane adhesive is improved, and the conductivity and the mechanical property of the conductive adhesive are improved;
2. as can be seen from the comparison between the example 1 and the comparative examples 3 to 4, the addition of the bisphenol A type epoxy acrylate and the hydroxyethyl methacrylate phosphate can modify polyurethane and improve the adhesion effect of the polyurethane adhesive on metal, so that two conductive materials can be better connected and the conductive effect of the conductive adhesive can be improved;
3. compared with the comparative example 5, the embodiment 1 shows that the curing shrinkage of polyurethane can be improved by adding the trimethylolpropane triacrylate, and the increase of the curing shrinkage of the polymer matrix leads to more sufficient contact between the conductive fillers in the conductive compound, so that the volume resistivity of the conductive compound is reduced, and the conductivity of the conductive adhesive is improved;
4. as can be seen from comparison between example 1 and comparative example 6, gamma-methacryloxypropyltrimethoxysilane was added to introduce siloxane into the polyurethane to modify the polyurethane, thereby imparting good water resistance to the polyurethane;
5. compared with the comparative example 7, the embodiment 1 shows that the added nano silver particles and the silver-plated copper powder are compounded for use, so that the nano silver particles can be sintered in situ on the surface of the silver-plated copper powder during thermosetting, alloy bonds are formed between the silver-plated copper powders, the simple physical contact form between fillers is changed, the whole conductive colloid system forms a high-efficiency conductive path, and the conductive adhesive is endowed with good conductive performance;
6. compared with the comparative example 8, the conductive performance of the conductive adhesive is improved by pretreating the silver-plated copper powder to remove the organic lubricant on the surface of the silver-plated copper powder, and meanwhile, carboxylate with negative electricity is introduced to the surface of the silver-plated copper powder to improve the conductive performance of the conductive adhesive;
7. as can be seen from comparison between example 1 and comparative example 9, the adhesion effect of the conductive adhesive on the conductive material is improved by the combined action of the two curing methods of photo-curing and thermal-curing, so that the conductivity of the conductive adhesive is improved.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (9)
1. The high-conductivity conductive adhesive is characterized in that: the material is prepared from the following raw materials in percentage by weight:
30-40% of polyurethane adhesive;
40-50% of conductive filler;
10-30% of reinforcing filler;
the polyurethane adhesive is prepared from the following raw materials in percentage by weight:
2. the highly conductive adhesive according to claim 1, wherein: the modified polyurethane prepolymer is prepared from the following raw materials in percentage by weight:
3. the highly conductive adhesive according to claim 2, wherein: the polyester polyol is prepared from the following raw materials in percentage by weight:
4. the highly conductive adhesive according to claim 1, wherein: the conductive filler comprises the following raw materials in percentage by weight:
30-50% of nano silver particles;
50-70% of silver-plated copper powder.
5. The highly conductive adhesive according to claim 2, wherein: the silver-plated copper powder is pretreated by a modifier, and the volume ratio of the modifier to the silver-plated copper powder is as follows: 2: 1;
the modifier comprises the following raw materials in percentage by weight:
the pretreatment comprises the following process steps: putting the silver-plated copper powder into the prepared modifier in proportion, and performing ultrasonic dispersion treatment for 1-2h to obtain slurry; and (3) putting the slurry into a ball mill for ball milling for 1-2h, and then putting the ball mill into a vacuum drying oven at 90-100 ℃ for drying for 1-2h to obtain the pretreated silver-plated copper powder.
6. The highly conductive adhesive according to claim 1, wherein: the reinforcing filler comprises the following raw materials in percentage by weight:
7. the highly conductive adhesive according to claim 1, wherein: the polyurethane emulsion also comprises the following raw materials in percentage by weight:
20-30% of bisphenol A epoxy acrylate;
3-7% of hydroxyethyl methacrylate phosphate.
8. A synthesis process of high-conductivity conductive adhesive is characterized by comprising the following steps: the method comprises the following process steps:
1) synthesizing and preparing polyester polyol: adding 1, 4-butanediol into a stirring reaction kettle according to a proportion, adding terephthalic acid, isophthalic acid, sebacic acid and tetrabutyl titanate according to a proportion under the condition of starting stirring, heating to 140 ℃ at the speed of 0.5 ℃/min, introducing nitrogen, reacting for 1h while keeping the temperature, heating to 240 ℃ within 7 h, keeping the temperature under the nitrogen atmosphere, and sampling and analyzing; measuring the acid value, measuring the hydroxyl value if the acid value is less than 0.5mgKOH/g, and cooling to room temperature when the hydroxyl value is 12 +/-1 mgKOH/g to obtain polyester polyol; if the hydroxyl value is not reached, continuously discharging alcohol until the hydroxyl value is qualified;
2) synthesizing and preparing a modified polyurethane prepolymer: dropwise adding toluene diisocyanate into the polyester polyol prepared in the step 1) at a constant speed according to a proportion, completing dropwise adding within 20-30min, heating to 70-80 ℃, carrying out heat preservation reaction for 3h, then adding monoethanolamine, gamma-methacryloxypropyltrimethoxysilane and dibutyltin dilaurate according to a proportion, heating to 80-90 ℃, carrying out heat preservation reaction for 2h, heating to 90-100 ℃, carrying out heat preservation reaction until NCO% is less than 0.05%, then cooling to 70-80 ℃, adding ethyl acetate, stirring for 0.5h, and cooling to room temperature to prepare a modified polyurethane prepolymer;
3) synthesizing and preparing a polyurethane adhesive: adding trimethylolpropane triacrylate, isooctyl acrylate, benzoin ethyl ether, benzophenone, benzoyl peroxide, hydroxyethyl methacrylate phosphate and bisphenol A epoxy acrylate into the modified polyurethane prepolymer prepared in the step 2) according to the proportion, and stirring for 20-30min under the condition that the rotating speed is 1000-2000r/min to prepare a polyurethane adhesive;
4) synthesizing and preparing the conductive adhesive: adding the conductive filler and the reinforcing filler into the polyurethane adhesive prepared in the step 3) according to the proportion, and stirring for 10-20min under the condition that the rotating speed is 2000-3000r/min to prepare the high-conductivity conductive adhesive.
9. The process for synthesizing a highly conductive adhesive according to claim 8, wherein: the reinforcing filler comprises the following preparation processes: adding the multi-walled carbon nano-tube into acetone according to a proportion, ultrasonically dispersing for 10-20min, adding acrylic acid, vinyl triethoxysilane and azobisisobutyronitrile according to a proportion, introducing nitrogen for 30min, stirring for 8h at 50-60 ℃, then carrying out vacuum filtration, washing with ethanol, and washing to obtain the reinforcing filler.
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| CN113436782A (en) * | 2021-04-29 | 2021-09-24 | 哈工大机器人集团(无锡)科创基地研究院 | Light high-conductivity aqueous conductive slurry and preparation method thereof |
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| CN113436782B (en) * | 2021-04-29 | 2023-01-24 | 哈工大机器人集团(无锡)科创基地研究院 | Light high-conductivity aqueous conductive slurry and preparation method thereof |
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