WO2022188504A1 - Heat-cured conductive adhesive and preparation method therefor - Google Patents

Heat-cured conductive adhesive and preparation method therefor Download PDF

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Publication number
WO2022188504A1
WO2022188504A1 PCT/CN2021/139775 CN2021139775W WO2022188504A1 WO 2022188504 A1 WO2022188504 A1 WO 2022188504A1 CN 2021139775 W CN2021139775 W CN 2021139775W WO 2022188504 A1 WO2022188504 A1 WO 2022188504A1
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WIPO (PCT)
Prior art keywords
conductive adhesive
parts
epoxy resin
thermally cured
cured conductive
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PCT/CN2021/139775
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French (fr)
Chinese (zh)
Inventor
崔会旺
卢春晖
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无锡帝科电子材料股份有限公司
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Publication of WO2022188504A1 publication Critical patent/WO2022188504A1/en

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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
    • 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
    • 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
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver

Definitions

  • the present application relates to the field of conductive adhesives, and in particular, to a thermally cured conductive adhesive and a preparation method thereof.
  • Conductive adhesive is a lead-free, green electronic packaging material suitable for micro-nano electronic packaging and interconnection of semiconductor components.
  • the conductive adhesive is mainly composed of conductive fillers, matrix resins, diluents and additives. It is thermally cured to form a conductive colloid with a three-dimensional network structure. It has the advantages of high bonding strength, high thermal stability, and low volume resistivity. However, its impact resistance The performance and crack resistance are low, and it is often difficult to meet the high reliability requirements of electronic products.
  • the purpose of the embodiments of the present application is to provide a thermally cured conductive adhesive and a preparation method thereof, which are intended to improve the impact resistance of the conductive adhesive.
  • the present application provides a method for preparing a thermally cured conductive adhesive, which mainly includes the following steps: thermally curing raw materials at 150-200° C. for 30-60 minutes; wherein, the raw materials include the following components in parts by weight: epoxy resin 5-14.5 parts of resin, 3-10 parts of diluent, 0.5-1 part of curing agent, 1.5-4.5 parts of flexibility auxiliary and 70-90 parts of micron silver powder.
  • the thermally cured conductive adhesive obtained by the above preparation method has better rheological properties and mechanical properties, and also has the advantages of low volume resistance, high bonding strength, high impact strength, low glass transition temperature and low storage modulus.
  • the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, acrylic modified epoxy resin, polyurethane modified epoxy resin, silicone At least one of modified epoxy resin, organic titanium modified epoxy resin and organic boron modified epoxy resin.
  • the diluent is selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, styrene, At least one of bisphenol A acrylate, ethoxylated bisphenol A diacrylate, and bisphenol A dimethacrylate.
  • the curing agent is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyano-2-ethyl-4-methylimidazole, blocked type At least one of hexafluoroantimonate, triaryliodonium salt, alkyl iodonium salt, and cumene ferrocene hexafluorophosphate.
  • the flexibilizer is selected from poly[(4-vinylphenol)-co-(methyl methacrylate)], poly(dimethylsiloxane-diphenylsiloxane) ), at least one of polydimethylsiloxane diglycidyl ether, 1,3-propanediol bis(4-aminobenzoate), and vinyl ether.
  • the particle size of the micron silver powder D50 is 3-5 ⁇ m
  • the bulk density is 3-5 g ⁇ cm ⁇ 3
  • the specific surface area is 0.5-1 m 2 ⁇ g ⁇ 1 .
  • the raw material before the raw material is thermally cured at 150-200° C. for 30-60 min, it further includes:
  • the raw material is prepared by mixing the epoxy resin, the diluent, the curing agent, the flexibility assistant and the micron silver powder, and then grinding and defoaming.
  • the thermal curing temperature of the raw material is 150-175°C.
  • the present application also provides a heat-curable conductive adhesive, which is prepared by the above-mentioned preparation method of the heat-curable conductive adhesive.
  • the present application also provides a heat-curing conductive adhesive, the volume resistance of the heat-curing conductive adhesive is 9-31 ⁇ cm, the bonding strength is 6.8-9.1 MPa, the impact strength is 2.7-4.0 kJ ⁇ m -2 , and the glass transition temperature is 6.8-9.1 MPa.
  • the storage modulus at room temperature is 6.1-7.6GPa, the storage modulus at 175°C is 0.7-2.4GPa, and the storage modulus at 240°C is 0.5-1.1GPa.
  • thermally curable conductive adhesive and the preparation method thereof of the embodiments of the present application will be specifically described below.
  • a preparation method of a thermally cured conductive adhesive mainly comprises the following steps:
  • the raw material includes the following components in parts by weight:
  • the raw materials containing the above-mentioned substances are thermally cured at 150-200 ° C for 30-60 minutes to obtain a thermally cured conductive adhesive.
  • the conductive adhesive has low volume resistance, high bonding strength, high impact strength, low glass transition temperature and storage. Low energy modulus and other properties.
  • the temperature of thermal curing may be 150°C, 152°C, 155°C, 161°C, 165°C, 172°C, 180°C, 191°C, 195°C, or 200°C, and the like.
  • the heating method can be, for example, heating with an oven or heating with an infrared furnace, and so on.
  • the time of thermal curing can be, for example, 30 min, 32 min, 38 min, 41 min, 47 min, 50 min, 52 min, 59 min or 60 min, and the like.
  • the raw materials include epoxy resin, diluent, curing agent, flexibilizer and micron silver powder.
  • the epoxy resin accounts for 5-14.5 parts by weight of the raw material, for example, it can be 5 parts, 6 parts, 7 parts, 7.5 parts, 8 parts, 9 parts, 9.5 parts, 10 parts, 11 parts, 12 parts servings, 12.5 servings, 12.7 servings, 13 servings, or 14.5 servings, etc.
  • the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, cycloaliphatic epoxy resin, acrylic modified epoxy resin, polyurethane modified epoxy resin, silicone modified epoxy resin At least one of oxygen resin, organic titanium modified epoxy resin and organic boron modified epoxy resin.
  • the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, acrylic modified epoxy resin or polyurethane Modified epoxy resin. For example, 6 parts by weight of acrylic modified epoxy resin is selected.
  • the diluent accounts for 3-10 parts by weight of the raw material, for example, it can be 3 parts, 3.1 parts, 3.5 parts, 3.7 parts, 4 parts, 4.9 parts, 5.5 parts, 5.6 parts, 6 parts, 6.25 parts , 6.8, 7.5, 8, 8.2, 9.1, 9.9, or 10, etc.
  • the diluent is selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, styrene, bisphenol A At least one of acrylate, ethoxylated bisphenol A diacrylate, and bisphenol A dimethacrylate.
  • the diluent is selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, trimethylol Propane triacrylate, bisphenol A acrylate or bisphenol A dimethacrylate. For example, 5.5 parts by weight of bisphenol A acrylate is selected.
  • the curing agent accounts for 0.5-1 part by weight of the raw material, such as 0.5 part, 0.6 part, 0.7 part, 0.75 part, 0.8 part, 0.9 part or 1.0 part and so on.
  • the curing agent is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyano-2-ethyl-4-methylimidazole, blocked hexafluoroantimonate , one or more of triaryliodonium salts, alkyl iodonium salts, and cumene ferrocene hexafluorophosphate.
  • the curing agent is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyano-2-ethyl-4-methylimidazole, blocked hexafluoroantimonate , one or more of triaryliodonium salts, alkyl iodonium salts, and cumene ferrocene hexafluorophosphate.
  • triaryliodonium salt 0.65 parts by weight of triaryliodonium salt is selected.
  • the above curing agent is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyano-2-ethyl-4- Methylimidazole, blocked hexafluoroantimonate, triaryliodonium or cumene ferrocene hexafluorophosphate.
  • the weight part of the softening aid is 1.5-4.5 parts of the raw material, for example, it can be 1.5 parts, 1.8 parts, 2 parts, 2.3 parts, 2.6 parts, 3 parts, 3.2 parts, 3.5 parts, 4 parts or 4.5 parts and so on.
  • the above-mentioned flexibilizer is a flexibilizer containing a flexible ether bond.
  • the -C-C- chemical bond length in the flexible additive is long, the -C-C- chemical bond angle is large, the short-range repulsion inside the molecular chain is small, and the rotation or twist of the main chain of the molecular chain can give the conductive adhesive excellent flexibility; softness in the flexible additive
  • the ether bond segment can be grafted into the network structure of the matrix resin cross-linked in the conductive adhesive to form an orderly and spaced network structure to improve the flexibility of the conductive adhesive; when the thermally cured conductive adhesive is used to bond electronic components, it can be Reduce the thermal stress in the bonding of the conductive adhesive and electronic components, and reduce the cracking and delamination of the conductive adhesive and electronic components caused by thermal stress.
  • the flexibility assistant is selected from poly[(4-vinylphenol)-co-(methyl methacrylate)], poly(dimethylsilicon) One or more of oxane-diphenylsiloxane), polydimethylsiloxane diglycidyl ether, 1,3-propanediol bis(4-aminobenzoate) and vinyl ether.
  • polydimethylsiloxane diglycidyl ether 2.5 parts by weight of polydimethylsiloxane diglycidyl ether is selected.
  • the micron silver powder accounts for 70-90 parts by weight of the raw material.
  • it can be 70, 72, 75, 80, 82, 85, 86, 89, or 90, and the like.
  • the particle size of the micron silver powder D50 is 3-5 ⁇ m
  • the bulk density is 3-5 g.cm ⁇ 3
  • the specific surface area is 0.5-1 m 2 .g ⁇ 1 .
  • the particle size of the micron silver powder D50 may be 3 ⁇ m, 4 ⁇ m, or 5 ⁇ m, and so on.
  • the bulk density of the micron silver powder is 3-5 g.cm -3 , for example, it can be 3 g.cm -3 , 4 g.cm -3 or 5 g.cm -3 and so on.
  • the specific surface area can be, for example, 0.5m 2 .g -1 , 0.7m 2 .g -1 , 0.8m 2 .g -1 , 0.9m 2 .g -1 , 1m 2 .g -1 , and the like.
  • the raw materials are obtained by mixing, grinding and then defoaming of the above-mentioned raw materials in various proportions. After the raw material is obtained, the raw material is thermally cured to obtain a flexible conductive adhesive. While improving the flexibility of the thermally cured conductive adhesive, the rheological properties and mechanical properties of the conductive adhesive are guaranteed, and the micron silver powder is used as a conductive filler to ensure the electrical properties of the conductive adhesive.
  • the present application also provides a thermally curable conductive adhesive, which has low volume resistance, high bonding strength, high impact strength, low glass transition temperature and low storage modulus.
  • the present application also provides a heat-curable conductive adhesive, the volume resistance of the heat-cured conductive adhesive is 9-31 ⁇ cm, the bonding strength is 6.8-9.1 MPa, the impact strength is 2.7-4.0 kJ ⁇ m -2 , the vitrification
  • the transition temperature is 151-161°C
  • the storage modulus at room temperature is 6.1-7.6GPa
  • the storage modulus at 175°C is 0.7-2.4GPa
  • the storage modulus at 240°C is 0.5-1.1GPa.
  • room temperature refers to the indoor temperature during measurement, which is usually 20-30°C.
  • Example 11 The micron silver powder used in Example 1-Example 11 was purchased from Japan Fukuda Metal Foil Powder Industry Co., Ltd., AgC-201 silver powder: solid density 3.43g ⁇ cm -3 , specific surface area 0.72m 2 ⁇ g -1 , average particle size 4.3 ⁇ m.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 150° C., and the curing time is 30 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 150° C., and the thermal curing time is 60 min.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • Cicyclic epoxy resin (CVC resin Epalloy 5200) 10 parts, 1,6-hexanediol diacrylate (MacLean reagent) 6.25 parts, 1-cyano-2-ethyl-4-methylimidazole (MacLean reagent) Reagent) 0.75 parts, 3 parts of polydimethylsiloxane diglycidyl ether (MacLean reagent), 80 parts of micron silver powder (Foton Metal AgC-201).
  • CVC resin Epalloy 5200 10 parts, 1,6-hexanediol diacrylate (MacLean reagent) 6.25 parts, 1-cyano-2-ethyl-4-methylimidazole (MacLean reagent) Reagent) 0.75 parts, 3 parts of polydimethylsiloxane diglycidyl ether (MacLean reagent), 80 parts of micron silver powder (Foton Metal AgC-201).
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 200° C., and the thermal curing time is 30 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 200° C., and the thermal curing time is 60 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • Cicyclic epoxy resin (CVC resin Epalloy 5200) 9.5 parts, bisphenol A dimethacrylate (MacLean reagent) 6 parts, cumyl ferrocene hexafluorophosphate (MacLean reagent) 0.5 parts, 1,3 - 4 parts of propylene glycol bis(4-aminobenzoate) (MacLean reagent), 80 parts of micron silver powder (Foton Metal AgC-201).
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 60 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • polyurethane modified epoxy resin bisphenol A acrylate, triaryliodonium salt, poly(dimethylsiloxane-diphenylsiloxane), and micron silver powder are fully stirred and dispersed, and then ground and defoamed. , that is, the conductive adhesive raw material is obtained.
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • polyurethane modified epoxy resin bisphenol A acrylate, triaryl iodonium salt, polydimethylsiloxane diglycidyl ether, and micron silver powder are fully stirred and dispersed, and then ground and deaerated to obtain conductive adhesive. raw material.
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
  • the embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
  • the above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
  • Volume resistance Print the thermally cured conductive adhesives of Examples 1 to 11 and commercially available products on a glass sheet to obtain a conductive adhesive film with a size of 30mm ⁇ 10mm ⁇ 0.05mm. After thermal curing, use the four-point probe method to test the resistance , and calculate the volume resistance.
  • Adhesion strength The thermally cured conductive adhesive of Example 1-Example 11 and commercially available products were printed on the glass sheet to obtain a conductive adhesive film with a size of 5mm ⁇ 5mm ⁇ 0.05mm, and then placed on the glass sheet (5mm ⁇ 5mm ⁇ 1mm) On the conductive adhesive film, two layers of glass sheets and one layer of conductive adhesive film form a "sandwich" structure; after thermal curing, it is tested by a multifunctional mechanical testing machine.
  • the thermally cured conductive adhesives of Examples 1 to 11 and commercially available products were printed on glass sheets to obtain a conductive adhesive film with a size of 50 mm ⁇ 3 mm ⁇ 0.7 mm. After thermal curing, a dynamic mechanical thermal analyzer was used. The storage modulus of the conductive adhesive was tested at room temperature (RT), 175°C, and 240°C. During the test, the room temperature (RT) was 26°C.
  • Glass transition temperature The thermally cured conductive adhesives of Examples 1 to 11 and commercially available products were printed on the glass sheet to obtain a conductive adhesive film with a size of 50 mm ⁇ 3 mm ⁇ 0.7 mm. After thermal curing, a dynamic mechanical thermal analyzer was used. test.
  • the thermally cured conductive adhesive provided by the application has low volume resistance, about 9-31 ⁇ cm, high bonding strength, about 6.8-9.1 MPa, and high impact strength, about 2.7- 4.0kJ ⁇ m -2 , low glass transition temperature, about 151-161°C, low storage modulus, about 6.1-7.6GPa at RT, about 0.7-2.4GPa at 175°C, about 240°C 0.5-1.1GPa, which are better than commercially available products. It is illustrated that the thermally cured conductive adhesive obtained by the preparation method of the thermally cured conductive adhesive provided in the embodiment of the present application has the advantages of low volume resistance, high bonding strength, high impact strength, low glass transition temperature, and low storage modulus.

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Abstract

The present application relates to the field of conductive adhesives, and specifically relates to a heat-cured conductive adhesive and a preparation method therefor. The preparation method for the heat-cured conductive adhesive mainly comprises the following step: heat-curing raw materials at 150-200ºC for 30-60 min, wherein the raw materials comprise the following components in parts by weight: 5-14.5 parts of an epoxy resin, 3-10 parts of a diluent, 0.5-1 parts of a curing agent, 1.5-4.5 parts of a flexible auxiliary agent and 70-90 parts of a micron silver powder. The heat-cured conductive adhesive prepared by means of the preparation method has good rheological and mechanical properties, and also has the advantages of a low volume resistance, a high bonding strength, a high impact strength, a low glass transition temperature, a low storage modulus, etc.

Description

一种热固化导电胶及其制备方法A kind of thermosetting conductive adhesive and preparation method thereof 技术领域technical field
本申请涉及导电胶领域，具体而言，涉及一种热固化导电胶及其制备方法。The present application relates to the field of conductive adhesives, and in particular, to a thermally cured conductive adhesive and a preparation method thereof.
背景技术Background technique
导电胶是一种无铅化、绿色型电子封装材料，适用于微-纳米电子封装和半导体元器件互连。导电胶主要有导电填料、基体树脂、稀释剂和添加剂组成，经热固化形成具有三维网络结构的导电胶体，具有粘接强度高、热稳定性高、体积电阻率低等优点，但其抗冲击性能和抗开裂性能较低，往往难以满足电子产品的高可靠性要求。Conductive adhesive is a lead-free, green electronic packaging material suitable for micro-nano electronic packaging and interconnection of semiconductor components. The conductive adhesive is mainly composed of conductive fillers, matrix resins, diluents and additives. It is thermally cured to form a conductive colloid with a three-dimensional network structure. It has the advantages of high bonding strength, high thermal stability, and low volume resistivity. However, its impact resistance The performance and crack resistance are low, and it is often difficult to meet the high reliability requirements of electronic products.
发明内容SUMMARY OF THE INVENTION
本申请实施例的目的在于提供一种热固化导电胶及其制备方法，其旨在提高导电胶的抗冲击性能。The purpose of the embodiments of the present application is to provide a thermally cured conductive adhesive and a preparation method thereof, which are intended to improve the impact resistance of the conductive adhesive.
本申请提供一种热固化导电胶的制备方法，主要包括以下步骤：将原料在150-200℃下热固化30-60min；其中，所述原料包括按重量份数计的以下组分：环氧树脂5-14.5份、稀释剂3-10份、固化剂0.5-1份、柔性助剂1.5-4.5份以及微米银粉70-90份。The present application provides a method for preparing a thermally cured conductive adhesive, which mainly includes the following steps: thermally curing raw materials at 150-200° C. for 30-60 minutes; wherein, the raw materials include the following components in parts by weight: epoxy resin 5-14.5 parts of resin, 3-10 parts of diluent, 0.5-1 part of curing agent, 1.5-4.5 parts of flexibility auxiliary and 70-90 parts of micron silver powder.
上述制备方法得到的热固化导电胶具有较佳的流变性能和力学性能，还具有体积电阻低，粘接强度高，冲击强度高，玻璃化转变温度低以及储能模量低等优点。The thermally cured conductive adhesive obtained by the above preparation method has better rheological properties and mechanical properties, and also has the advantages of low volume resistance, high bonding strength, high impact strength, low glass transition temperature and low storage modulus.
在本申请的一些实施例中，环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、脂环环氧树脂、丙烯酸改性环氧树脂、聚氨酯改性环氧树脂、有机硅改性环氧树脂、有机钛改性环氧树脂以及有机硼改性环氧树脂中的至少一种。In some embodiments of the present application, the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, acrylic modified epoxy resin, polyurethane modified epoxy resin, silicone At least one of modified epoxy resin, organic titanium modified epoxy resin and organic boron modified epoxy resin.
在本申请的一些实施例中，稀释剂选自甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、1,6-己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、苯乙烯、双酚A丙烯酸酯、乙氧基化双酚A二丙烯酸酯以及双酚A二甲基丙烯酸酯中的至少一种。In some embodiments of the present application, the diluent is selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, styrene, At least one of bisphenol A acrylate, ethoxylated bisphenol A diacrylate, and bisphenol A dimethacrylate.
在本申请的一些实施例中，所述固化剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、1-氰基-2-乙基-4-甲基咪唑、封闭型六氟锑酸盐、三芳基碘鎓盐、烷基碘鎓盐以及异丙苯茂铁六氟磷酸盐中的至少一种。In some embodiments of the present application, the curing agent is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyano-2-ethyl-4-methylimidazole, blocked type At least one of hexafluoroantimonate, triaryliodonium salt, alkyl iodonium salt, and cumene ferrocene hexafluorophosphate.
在本申请的一些实施例中，柔性助剂选自聚[(4-乙烯基苯酚)-co-(甲基丙烯酸甲酯)]、聚(二甲基硅氧烷-二苯基硅氧烷)、聚二甲基硅氧烷二缩水甘油醚、1,3-丙二醇双(4-氨基苯甲酸酯)以及乙烯基醚中的至少一种。In some embodiments of the present application, the flexibilizer is selected from poly[(4-vinylphenol)-co-(methyl methacrylate)], poly(dimethylsiloxane-diphenylsiloxane) ), at least one of polydimethylsiloxane diglycidyl ether, 1,3-propanediol bis(4-aminobenzoate), and vinyl ether.
在本申请的一些实施例中，所述微米银粉D50的粒径为3-5μm，敦实密度为3-5g·cm -3，比表面积为0.5-1m 2·g -1。在本申请的一些实施例中，将原料在150-200℃下热固化30-60min之前还包括： In some embodiments of the present application, the particle size of the micron silver powder D50 is 3-5 μm, the bulk density is 3-5 g·cm −3 , and the specific surface area is 0.5-1 m 2 ·g −1 . In some embodiments of the present application, before the raw material is thermally cured at 150-200° C. for 30-60 min, it further includes:
将所述环氧树脂、所述稀释剂、所述固化剂、所述柔性助剂以及所述微米银粉混合后研磨、脱泡制备所述原料。The raw material is prepared by mixing the epoxy resin, the diluent, the curing agent, the flexibility assistant and the micron silver powder, and then grinding and defoaming.
在本申请的一些实施例中，原料的热固化温度为150-175℃。In some embodiments of the present application, the thermal curing temperature of the raw material is 150-175°C.
本申请还提供一种热固化导电胶，热固化导电胶通过上述的热固化导电胶的制备方法制得。The present application also provides a heat-curable conductive adhesive, which is prepared by the above-mentioned preparation method of the heat-curable conductive adhesive.
本申请还提供一种热固化导电胶，热固化导电胶的体积电阻为9-31μΩ·cm，粘接强度为6.8-9.1MPa，冲击强度为2.7-4.0kJ·m -2，玻璃化转变温度为151-161℃，室温时的储能模量为6.1-7.6GPa，175℃时的储能模量为0.7-2.4GPa，240℃时的储能模量为0.5-1.1GPa。 The present application also provides a heat-curing conductive adhesive, the volume resistance of the heat-curing conductive adhesive is 9-31 μΩ·cm, the bonding strength is 6.8-9.1 MPa, the impact strength is 2.7-4.0 kJ·m -2 , and the glass transition temperature is 6.8-9.1 MPa. The storage modulus at room temperature is 6.1-7.6GPa, the storage modulus at 175°C is 0.7-2.4GPa, and the storage modulus at 240°C is 0.5-1.1GPa.
具体实施方式Detailed ways
为使本申请实施例的目的、技术方案和优点更加清楚，下面将对本申请实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。To make the purposes, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be described clearly and completely below. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.
下面对本申请实施例的热固化导电胶及其制备方法进行具体说明。The thermally curable conductive adhesive and the preparation method thereof of the embodiments of the present application will be specifically described below.
一种热固化导电胶的制备方法，主要包括以下步骤：A preparation method of a thermally cured conductive adhesive mainly comprises the following steps:
将原料在150-200℃下热固化30-60min；Heat the raw material at 150-200℃ for 30-60min;
其中，所述原料包括按重量份数计的以下组分：Wherein, the raw material includes the following components in parts by weight:
环氧树脂5-14.5份、稀释剂3-10份、固化剂0.5-1份、柔性助剂1.5-4.5份以及微米银粉70-90份。5-14.5 parts of epoxy resin, 3-10 parts of diluent, 0.5-1 part of curing agent, 1.5-4.5 parts of flexibility auxiliary and 70-90 parts of micron silver powder.
将含有上述配比的物质的原料在150-200℃下热固化30-60min得到热固化导电胶，该导电胶具有体积电阻低，粘接强度高，冲击强度高，玻璃化转变温度低以及储能模量低等性能。The raw materials containing the above-mentioned substances are thermally cured at 150-200 ° C for 30-60 minutes to obtain a thermally cured conductive adhesive. The conductive adhesive has low volume resistance, high bonding strength, high impact strength, low glass transition temperature and storage. Low energy modulus and other properties.
作为示例性地，热固化的温度可以为150℃、152℃、155℃、161℃、165℃、172℃、180℃、191℃、195℃或者200℃等等。As an example, the temperature of thermal curing may be 150°C, 152°C, 155°C, 161°C, 165°C, 172°C, 180°C, 191°C, 195°C, or 200°C, and the like.
加热的方式例如可以为采用烘箱加热或采用红外炉加热等等。The heating method can be, for example, heating with an oven or heating with an infrared furnace, and so on.
热固化的时间例如可以为30min、32min、38min、41min、47min、50min、52min、59min或者60min等等。The time of thermal curing can be, for example, 30 min, 32 min, 38 min, 41 min, 47 min, 50 min, 52 min, 59 min or 60 min, and the like.
原料包括环氧树脂、稀释剂、固化剂、柔性助剂以及微米银粉。The raw materials include epoxy resin, diluent, curing agent, flexibilizer and micron silver powder.
作为示例性地，环氧树脂占原料的重量份为5-14.5份，例如可以为5份、6份、7份、7.5份、8份、9份、9.5份、10份、11份、12份、12.5份、12.7份、13份或者14.5份等等。As an example, the epoxy resin accounts for 5-14.5 parts by weight of the raw material, for example, it can be 5 parts, 6 parts, 7 parts, 7.5 parts, 8 parts, 9 parts, 9.5 parts, 10 parts, 11 parts, 12 parts servings, 12.5 servings, 12.7 servings, 13 servings, or 14.5 servings, etc.
在一些实施例中，环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、脂环环氧树脂、丙烯酸改性环氧树脂、聚氨酯改性环氧树脂、有机硅改性环氧树脂、有机钛改性环氧树脂以及有机硼改性环氧树脂中的至少一种。为了进一步提高热固化导电胶的抗冲击性能，更优选地，上述环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、脂环环氧树脂、丙烯酸改性环氧树脂或聚氨酯改性环氧树脂。例如选用6重量份的丙烯酸改性环氧树脂。In some embodiments, the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, cycloaliphatic epoxy resin, acrylic modified epoxy resin, polyurethane modified epoxy resin, silicone modified epoxy resin At least one of oxygen resin, organic titanium modified epoxy resin and organic boron modified epoxy resin. In order to further improve the impact resistance of the thermally cured conductive adhesive, more preferably, the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, acrylic modified epoxy resin or polyurethane Modified epoxy resin. For example, 6 parts by weight of acrylic modified epoxy resin is selected.
作为示例性地，稀释剂占原料的重量份为3-10份，例如可以为3份、3.1份、3.5份、3.7份、4份、4.9份、5.5份、5.6份、6份、6.25份、6.8份、7.5份、8份、8.2份、9.1份、9.9份或者10份等等。As an example, the diluent accounts for 3-10 parts by weight of the raw material, for example, it can be 3 parts, 3.1 parts, 3.5 parts, 3.7 parts, 4 parts, 4.9 parts, 5.5 parts, 5.6 parts, 6 parts, 6.25 parts , 6.8, 7.5, 8, 8.2, 9.1, 9.9, or 10, etc.
在一些实施例中，稀释剂选自甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、1,6-己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、苯乙烯、双酚A丙烯酸酯、乙氧基化双酚A二丙烯酸酯以及双酚A二甲基丙烯酸酯中的至少一种。为了进一步提高热固化导电胶的抗冲击性能，更优选地，上述稀释剂选自甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、1,6-己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、双酚A丙烯酸酯或双酚A二甲基丙烯酸酯。例如选用5.5重量份的双酚A丙烯酸酯。In some embodiments, the diluent is selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, styrene, bisphenol A At least one of acrylate, ethoxylated bisphenol A diacrylate, and bisphenol A dimethacrylate. In order to further improve the impact resistance of the thermally curable conductive adhesive, more preferably, the diluent is selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, trimethylol Propane triacrylate, bisphenol A acrylate or bisphenol A dimethacrylate. For example, 5.5 parts by weight of bisphenol A acrylate is selected.
作为示例性地，固化剂占原料的重量份为0.5-1份，例如可以为0.5份、0.6份、0.7份、0.75份、0.8份、0.9份或者1.0份等等。As an example, the curing agent accounts for 0.5-1 part by weight of the raw material, such as 0.5 part, 0.6 part, 0.7 part, 0.75 part, 0.8 part, 0.9 part or 1.0 part and so on.
在一些实施例中，固化剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、1-氰基-2-乙基-4-甲基咪唑、封闭型六氟锑酸盐、三芳基碘鎓盐、烷基碘鎓盐、异丙苯茂铁六氟磷酸盐中的一种或几种。例如选用0.65重量份的三芳基碘鎓盐。为了进一步提高热固化导电胶的抗冲击性能，更优选地，上述固化剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、1-氰基-2-乙基-4-甲基咪唑、封闭型六氟锑酸盐、三芳基碘鎓盐或异丙苯茂铁六氟磷酸盐。In some embodiments, the curing agent is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyano-2-ethyl-4-methylimidazole, blocked hexafluoroantimonate , one or more of triaryliodonium salts, alkyl iodonium salts, and cumene ferrocene hexafluorophosphate. For example, 0.65 parts by weight of triaryliodonium salt is selected. In order to further improve the impact resistance of the thermally cured conductive adhesive, more preferably, the above curing agent is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyano-2-ethyl-4- Methylimidazole, blocked hexafluoroantimonate, triaryliodonium or cumene ferrocene hexafluorophosphate.
作为示例性地，柔性助剂占原料的重量份为1.5-4.5份，例如可以为1.5份、1.8份、2份、2.3份、2.6份、3份、3.2份、3.5份、4份或者4.5份等等。As an example, the weight part of the softening aid is 1.5-4.5 parts of the raw material, for example, it can be 1.5 parts, 1.8 parts, 2 parts, 2.3 parts, 2.6 parts, 3 parts, 3.2 parts, 3.5 parts, 4 parts or 4.5 parts and so on.
优选地，上述柔性助剂为含有柔性醚键的柔性助剂。柔性助剂中的-C-C-化学键长较长、-C-C-化学键角大，分子链内部短程排斥小，分子链主链的旋转或扭转可以赋予导电胶优异的柔韧性；柔性助剂中的柔软醚键链段可接枝到导电胶中基体树脂交联的网络结构中，形成有序、间隔的网络结构以提高导电胶柔韧性；该热固化导电胶用于粘接电子元器件时，可以减小导电胶与电子元器件粘接中的热应力，减少由热应力引起的导电胶与电子元器件开裂、分层等不良现象。为了进一步提高热固化导电胶的抗冲击性能，在一些实施例中，柔性助剂选自聚[(4-乙烯基苯酚)-co-(甲基丙烯酸甲酯)]、聚(二甲基硅氧烷-二苯基硅氧烷)、聚二甲基硅氧烷二缩水甘油醚、1,3-丙二醇双(4-氨基苯甲酸酯)以及乙烯基醚中的一种或几种。例如选用2.5重量份的聚二甲基硅氧烷二缩水甘油醚。Preferably, the above-mentioned flexibilizer is a flexibilizer containing a flexible ether bond. The -C-C- chemical bond length in the flexible additive is long, the -C-C- chemical bond angle is large, the short-range repulsion inside the molecular chain is small, and the rotation or twist of the main chain of the molecular chain can give the conductive adhesive excellent flexibility; softness in the flexible additive The ether bond segment can be grafted into the network structure of the matrix resin cross-linked in the conductive adhesive to form an orderly and spaced network structure to improve the flexibility of the conductive adhesive; when the thermally cured conductive adhesive is used to bond electronic components, it can be Reduce the thermal stress in the bonding of the conductive adhesive and electronic components, and reduce the cracking and delamination of the conductive adhesive and electronic components caused by thermal stress. In order to further improve the impact resistance of the thermally curable conductive adhesive, in some embodiments, the flexibility assistant is selected from poly[(4-vinylphenol)-co-(methyl methacrylate)], poly(dimethylsilicon) One or more of oxane-diphenylsiloxane), polydimethylsiloxane diglycidyl ether, 1,3-propanediol bis(4-aminobenzoate) and vinyl ether. For example, 2.5 parts by weight of polydimethylsiloxane diglycidyl ether is selected.
微米银粉占原料的重量份为70-90份。例如可以为70份、72份、75份、80份、82份、85份、86份、89份或者90份等等。The micron silver powder accounts for 70-90 parts by weight of the raw material. For example, it can be 70, 72, 75, 80, 82, 85, 86, 89, or 90, and the like.
在一些实施例中，所述微米银粉D50的粒径为3-5μm，敦实密度为3-5g.cm -3，比表面积为0.5-1m 2.g -1。作为示例性地，微米银粉D50的粒径可以为3μm、4μm或者5μm等等。微米银粉的敦实密度为3-5g.cm -3，例如可以为3g.cm -3、4g.cm -3或者5g.cm -3等等。比表面积例如可以为0.5m 2.g -1、0.7m 2.g -1、0.8m 2.g -1、0.9m 2.g -1、1m 2.g -1等等。 In some embodiments, the particle size of the micron silver powder D50 is 3-5 μm, the bulk density is 3-5 g.cm −3 , and the specific surface area is 0.5-1 m 2 .g −1 . As an example, the particle size of the micron silver powder D50 may be 3 μm, 4 μm, or 5 μm, and so on. The bulk density of the micron silver powder is 3-5 g.cm -3 , for example, it can be 3 g.cm -3 , 4 g.cm -3 or 5 g.cm -3 and so on. The specific surface area can be, for example, 0.5m 2 .g -1 , 0.7m 2 .g -1 , 0.8m 2 .g -1 , 0.9m 2 .g -1 , 1m 2 .g -1 , and the like.
在制备过程中，原料通过各个配比的上述原料经过混合、研磨然后脱泡得到。得到该原料后再对该原料进行热固化得到柔性导电胶。提高该热固化导电胶柔韧性的同时保障该导电胶的流变性能和力学性能，以微米银粉为导电填料，保障该导电胶的电学性能。In the preparation process, the raw materials are obtained by mixing, grinding and then defoaming of the above-mentioned raw materials in various proportions. After the raw material is obtained, the raw material is thermally cured to obtain a flexible conductive adhesive. While improving the flexibility of the thermally cured conductive adhesive, the rheological properties and mechanical properties of the conductive adhesive are guaranteed, and the micron silver powder is used as a conductive filler to ensure the electrical properties of the conductive adhesive.
本申请还提供一种热固化导电胶，该热固化导电胶体积电阻低，粘接强度高，冲击强度高，玻璃化转变温度低，储能模量低。The present application also provides a thermally curable conductive adhesive, which has low volume resistance, high bonding strength, high impact strength, low glass transition temperature and low storage modulus.
本申请还提供一种热固化导电胶，所述热固化导电胶的体积电阻为9-31μΩ·cm，粘接强度为6.8-9.1MPa，冲击强度为2.7-4.0kJ·m -2，玻璃化转变温度为151-161℃，室温时的储能模量为6.1-7.6GPa，175℃时的储能模量为0.7-2.4GPa，240℃时的储能模量为0.5-1.1GPa。 The present application also provides a heat-curable conductive adhesive, the volume resistance of the heat-cured conductive adhesive is 9-31 μΩ·cm, the bonding strength is 6.8-9.1 MPa, the impact strength is 2.7-4.0 kJ·m -2 , the vitrification The transition temperature is 151-161°C, the storage modulus at room temperature is 6.1-7.6GPa, the storage modulus at 175°C is 0.7-2.4GPa, and the storage modulus at 240°C is 0.5-1.1GPa.
在本申请的实施例中，室温是指测量时的室内温度，通常为20-30℃。In the embodiments of the present application, room temperature refers to the indoor temperature during measurement, which is usually 20-30°C.
以下结合实施例对本申请的特征和性能作进一步的详细描述。The features and properties of the present application will be described in further detail below with reference to the embodiments.
实施例1-实施例11采用的微米银粉购于日本福田金属箔粉工业株式会社，AgC-201银粉：敦实密度3.43g·cm -3，比表面积0.72m 2·g -1，平均粒径4.3μm。 The micron silver powder used in Example 1-Example 11 was purchased from Japan Fukuda Metal Foil Powder Industry Co., Ltd., AgC-201 silver powder: solid density 3.43g·cm -3 , specific surface area 0.72m 2 ·g -1 , average particle size 4.3 μm.
实施例1Example 1
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
双酚A环氧树脂(南亚树脂NPEL-128E)14.5份、甲基丙烯酸羟乙酯(麦克林试剂)10份、2-甲基咪唑(麦克林试剂)1份、聚[(4-乙烯基苯酚)-co-(甲基丙烯酸甲酯)](西亚试剂)4.5份、微米银粉(福田金属AgC-201)70份。14.5 parts of bisphenol A epoxy resin (Nanya resin NPEL-128E), 10 parts of hydroxyethyl methacrylate (MacLean's reagent), 1 part of 2-methylimidazole (MacLean's reagent), poly[(4-vinyl) phenol)-co-(methyl methacrylate)] (Xia reagent) 4.5 parts, micron silver powder (Fotian Metal AgC-201) 70 parts.
将上述双酚A环氧树脂、甲基丙烯酸羟乙酯、2-甲基咪唑、聚[(4-乙烯基苯酚)-co-(甲基丙烯酸甲酯)]、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。Fully stirring and dispersing the above-mentioned bisphenol A epoxy resin, hydroxyethyl methacrylate, 2-methylimidazole, poly[(4-vinylphenol)-co-(methyl methacrylate)], and micron silver powder, Then grinding and defoaming, the conductive adhesive raw material is obtained.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为150℃，固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 150° C., and the curing time is 30 minutes.
实施例2Example 2
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
双酚F环氧树脂(南亚树脂NPEF-170)12.7份、甲基丙烯酸羟丙酯(麦克林试剂)8份、2-乙基-4-甲基咪唑(麦克林试剂)0.8份、聚(二甲基硅氧烷-二苯基硅氧烷)(麦克林试剂)3.5份、微米银粉(福田金属AgC-201)75份。12.7 parts of bisphenol F epoxy resin (South Asia resin NPEF-170), 8 parts of hydroxypropyl methacrylate (Mecklin's reagent), 0.8 parts of 2-ethyl-4-methylimidazole (Mecklin's reagent), poly( 3.5 parts of dimethylsiloxane-diphenylsiloxane) (MacLean reagent), 75 parts of micron silver powder (Foton Metal AgC-201).
将上述双酚F环氧树脂、甲基丙烯酸羟丙酯、2-乙基-4-甲基咪唑、聚(二甲基硅氧烷-二苯基硅氧烷)、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned bisphenol F epoxy resin, hydroxypropyl methacrylate, 2-ethyl-4-methylimidazole, poly(dimethylsiloxane-diphenylsiloxane), and micron silver powder are fully stirred and dispersed. , and then grinding and defoaming to obtain conductive adhesive raw materials.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为150℃，热固化时间为60min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 150° C., and the thermal curing time is 60 min.
实施例3Example 3
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
脂环环氧树脂(CVC树脂Epalloy 5200)10份、1,6-己二醇二丙烯酸酯(麦克林试剂)6.25份、1-氰基-2-乙基-4-甲基咪唑(麦克林试剂)0.75份、聚二甲基硅氧烷二缩水甘油醚(麦克林试剂)3份、微米银粉(福田金属AgC-201)80份。Alicyclic epoxy resin (CVC resin Epalloy 5200) 10 parts, 1,6-hexanediol diacrylate (MacLean reagent) 6.25 parts, 1-cyano-2-ethyl-4-methylimidazole (MacLean reagent) Reagent) 0.75 parts, 3 parts of polydimethylsiloxane diglycidyl ether (MacLean reagent), 80 parts of micron silver powder (Foton Metal AgC-201).
将上述脂环环氧树脂、1,6-己二醇二丙烯酸酯、1-氰基-2-乙基-4-甲基咪唑、聚二甲基硅氧烷二缩水甘油醚、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned alicyclic epoxy resin, 1,6-hexanediol diacrylate, 1-cyano-2-ethyl-4-methylimidazole, polydimethylsiloxane diglycidyl ether, and micron silver powder were sufficiently Stirring, dispersing, then grinding and defoaming, the conductive adhesive raw material is obtained.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为200℃，热固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 200° C., and the thermal curing time is 30 minutes.
实施例4Example 4
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
丙烯酸改性环氧树脂(广树化工GS-5000C)7份、三羟甲基丙烷三丙烯酸酯(麦克林试剂)5.5份、封闭型六氟锑酸盐(麦克林试剂)0.5份、1,3-丙二醇双(4-氨基苯甲酸酯)(麦克林试剂)2份、微米银粉(福田金属AgC-201)85份。7 parts of acrylic modified epoxy resin (Guangshu Chemical GS-5000C), 5.5 parts of trimethylolpropane triacrylate (MacLean's reagent), 0.5 parts of blocked hexafluoroantimonate (MacLean's reagent), 1, 2 parts of 3-propanediol bis(4-aminobenzoate) (MacLean reagent), 85 parts of micron silver powder (Fotian Metal AgC-201).
将上述丙烯酸改性环氧树脂、三羟甲基丙烷三丙烯酸酯、封闭型六氟锑酸盐、1,3-丙二醇双(4-氨基苯甲酸酯)、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above acrylic modified epoxy resin, trimethylolpropane triacrylate, blocked hexafluoroantimonate, 1,3-propanediol bis(4-aminobenzoate), and micron silver powder were fully stirred and dispersed, and then Grinding and defoaming, the conductive adhesive raw material is obtained.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为200℃，热固化时间为60min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 200° C., and the thermal curing time is 60 minutes.
实施例5Example 5
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
聚氨酯改性环氧树脂(南亚树脂NPER-133L)5份、双酚A丙烯酸酯(麦克林试剂)3份、三芳基碘鎓盐(麦克林试剂)0.5份、乙烯基醚(重庆化工研究院)1.5份、微米银粉(福田金属AgC-201)90份。5 parts of polyurethane modified epoxy resin (South Asia resin NPER-133L), 3 parts of bisphenol A acrylate (MacLean reagent), 0.5 part of triaryliodonium salt (MacLean reagent), vinyl ether (Chongqing Chemical Research Institute) ) 1.5 parts, and 90 parts of micron silver powder (Futian Metal AgC-201).
将上述聚氨酯改性环氧树脂、双酚A丙烯酸酯、三芳基碘鎓盐、乙烯基醚、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned polyurethane modified epoxy resin, bisphenol A acrylate, triaryliodonium salt, vinyl ether, and micron silver powder are fully stirred and dispersed, and then ground and defoamed to obtain the conductive adhesive raw material.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为175℃，热固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
实施例6Example 6
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
脂环环氧树脂(CVC树脂Epalloy 5200)9.5份、双酚A二甲基丙烯酸酯(麦克林试剂)6份、异丙苯茂铁六氟磷酸盐(麦克林试剂)0.5份、1,3-丙二醇双(4-氨基苯甲酸酯)(麦克林试剂)4份、微米银粉(福田金属AgC-201)80份。Alicyclic epoxy resin (CVC resin Epalloy 5200) 9.5 parts, bisphenol A dimethacrylate (MacLean reagent) 6 parts, cumyl ferrocene hexafluorophosphate (MacLean reagent) 0.5 parts, 1,3 - 4 parts of propylene glycol bis(4-aminobenzoate) (MacLean reagent), 80 parts of micron silver powder (Foton Metal AgC-201).
将上述脂环环氧树脂、双酚A二甲基丙烯酸酯、异丙苯茂铁六氟磷酸盐、1,3-丙二醇双(4-氨基苯甲酸酯)、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。Fully stirring and dispersing the above-mentioned alicyclic epoxy resin, bisphenol A dimethacrylate, cumene ferrocene hexafluorophosphate, 1,3-propylene glycol bis(4-aminobenzoate), and micron silver powder, Then grinding and defoaming, the conductive adhesive raw material is obtained.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为175℃，热固化时间为60min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 60 minutes.
实施例7Example 7
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
聚氨酯改性环氧树脂(南亚树脂NPER-133L)5份、双酚A丙烯酸酯(麦克林试剂)3份、三芳基碘鎓盐(麦克林试剂)0.5份、聚[(4-乙烯基苯酚)-co-(甲基丙烯酸甲酯)](西亚试剂)1.5份、微米银粉(福田金属AgC-201)90份。5 parts of polyurethane modified epoxy resin (South Asia resin NPER-133L), 3 parts of bisphenol A acrylate (MacLean reagent), 0.5 part of triaryliodonium salt (MacLean reagent), poly[(4-vinylphenol) )-co-(methyl methacrylate)] (Xia reagent) 1.5 parts, micron silver powder (Foton Metal AgC-201) 90 parts.
将上述聚氨酯改性环氧树脂、双酚A丙烯酸酯、三芳基碘鎓盐、聚[(4-乙烯基苯酚)-co-(甲基丙烯酸甲酯)]、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned polyurethane-modified epoxy resin, bisphenol A acrylate, triaryliodonium salt, poly[(4-vinylphenol)-co-(methyl methacrylate)], and micron silver powder are fully stirred and dispersed, and then Grinding and defoaming, the conductive adhesive raw material is obtained.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为175℃，热固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
实施例8Example 8
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
聚氨酯改性环氧树脂5份(南亚树脂NPER-133L)、双酚A丙烯酸酯(麦克林试剂)3份、三芳基碘鎓盐(麦克林试剂)0.5份、聚(二甲基硅氧烷-二苯基硅氧烷)(麦克林试剂)1.5份、微米银粉(福田金属AgC-201)90份。5 parts of polyurethane modified epoxy resin (South Asia resin NPER-133L), 3 parts of bisphenol A acrylate (MacLean reagent), 0.5 part of triaryliodonium salt (MacLean reagent), poly(dimethylsiloxane) -Diphenylsiloxane) (MacLean reagent) 1.5 parts, micron silver powder (Foton Metal AgC-201) 90 parts.
将上述聚氨酯改性环氧树脂、双酚A丙烯酸酯、三芳基碘鎓盐、聚(二甲基硅氧烷-二苯基硅氧烷)、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned polyurethane modified epoxy resin, bisphenol A acrylate, triaryliodonium salt, poly(dimethylsiloxane-diphenylsiloxane), and micron silver powder are fully stirred and dispersed, and then ground and defoamed. , that is, the conductive adhesive raw material is obtained.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为175℃，热固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
实施例9Example 9
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
聚氨酯改性环氧树脂(南亚树脂NPER-133L)5份、双酚A丙烯酸酯(麦克林试剂)3份、三芳基碘鎓盐(麦克林试剂)0.5份、聚二甲基硅氧烷二缩水甘油醚(麦克林试剂)1.5份、微米银粉(福田金属AgC-201)90份。5 parts of polyurethane modified epoxy resin (South Asia resin NPER-133L), 3 parts of bisphenol A acrylate (MacLean reagent), 0.5 part of triaryliodonium salt (MacLean reagent), polydimethylsiloxane two 1.5 parts of glycidyl ether (MacLean reagent), 90 parts of micron silver powder (Fotian Metal AgC-201).
将上述聚氨酯改性环氧树脂、双酚A丙烯酸酯、三芳基碘鎓盐、聚二甲基硅氧烷二缩水甘油醚、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned polyurethane modified epoxy resin, bisphenol A acrylate, triaryl iodonium salt, polydimethylsiloxane diglycidyl ether, and micron silver powder are fully stirred and dispersed, and then ground and deaerated to obtain conductive adhesive. raw material.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为175℃，热固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
实施例10Example 10
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
聚氨酯改性环氧树脂5份(南亚树脂NPER-133L)、双酚A丙烯酸酯(麦克林试剂)3份、三芳基碘鎓盐(麦克林试剂)0.5份、1,3-丙二醇双(4-氨基苯甲酸酯)(麦克林试剂)1.5份、微米银粉(福田金属AgC-201)90份。5 parts of polyurethane modified epoxy resin (South Asia resin NPER-133L), 3 parts of bisphenol A acrylate (MacLean reagent), 0.5 part of triaryliodonium salt (MacLean reagent), 1,3-propanediol bis(4 -Aminobenzoate) (MacLean reagent) 1.5 parts, micron silver powder (Fotian Metal AgC-201) 90 parts.
将上述聚氨酯改性环氧树脂、双酚A丙烯酸酯、三芳基碘鎓盐、1,3-丙二醇双(4-氨基苯甲酸酯)、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned polyurethane modified epoxy resin, bisphenol A acrylate, triaryliodonium salt, 1,3-propanediol bis(4-aminobenzoate), and micron silver powder are fully stirred and dispersed, and then ground and defoamed, That is, the conductive adhesive raw material is obtained.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为175℃，热固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
实施例11Example 11
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
聚氨酯改性环氧树脂5份(南亚树脂NPER-133L)、双酚A丙烯酸酯(麦克林试剂)3份、三芳基碘鎓盐(麦克林试剂)0.5份、乙烯-乙酸乙烯共聚物(台湾化学)1.5份、微米银粉(福田金属AgC-201)90份。5 parts of polyurethane modified epoxy resin (South Asia resin NPER-133L), 3 parts of bisphenol A acrylate (MacLean reagent), 0.5 part of triaryliodonium salt (MacLean reagent), ethylene-vinyl acetate copolymer (Taiwan Chemical) 1.5 parts, micron silver powder (Futian Metal AgC-201) 90 parts.
将上述聚氨酯改性环氧树脂、双酚A丙烯酸酯、三芳基碘鎓盐、乙烯-乙酸乙烯共聚物.、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned polyurethane modified epoxy resin, bisphenol A acrylate, triaryliodonium salt, ethylene-vinyl acetate copolymer, and micron silver powder are fully stirred and dispersed, and then ground and defoamed to obtain the conductive adhesive raw material.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为175℃，热固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
对比例1Comparative Example 1
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
聚氨酯改性环氧树脂5份(南亚树脂NPER-133L)、双酚A丙烯酸酯3份(麦克林试剂)、三芳基碘鎓盐0.5份(麦克林试剂)、微米银粉90(福田金属AgC-201)份。5 parts of polyurethane modified epoxy resin (South Asia resin NPER-133L), 3 parts of bisphenol A acrylate (MacLean reagent), 0.5 part of triaryliodonium salt (MacLean reagent), 90 micron silver powder (Futian Metal AgC- 201) copies.
将上述聚氨酯改性环氧树脂、双酚A丙烯酸酯、三芳基碘鎓盐、1,3-丙二醇双(4-氨基苯甲酸酯)、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned polyurethane modified epoxy resin, bisphenol A acrylate, triaryliodonium salt, 1,3-propanediol bis(4-aminobenzoate), and micron silver powder are fully stirred and dispersed, and then ground and defoamed, That is, the conductive adhesive raw material is obtained.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为175℃，热固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
对比例2Comparative Example 2
实施例提供一种热固化导电胶，主要通过以下步骤制得：The embodiment provides a thermally cured conductive adhesive, which is mainly prepared by the following steps:
按照以下重量份数备料：Prepare according to the following parts by weight:
聚氨酯改性环氧树脂5份(南亚树脂NPER-133L)、双酚A丙烯酸酯(麦克林试剂)3份、三芳基碘鎓盐(麦克林试剂)0.5份、乙烯基醚(麦克林试剂)0.5份、微米银粉(福田金属AgC-201)90份。5 parts of polyurethane modified epoxy resin (South Asia resin NPER-133L), 3 parts of bisphenol A acrylate (MacLean reagent), 0.5 part of triaryliodonium salt (MacLean reagent), vinyl ether (MacLean reagent) 0.5 part, 90 parts of micron silver powder (Futian Metal AgC-201).
将上述聚氨酯改性环氧树脂、双酚A丙烯酸酯、三芳基碘鎓盐、乙烯基醚、微米银粉充分搅拌、分散，而后研磨、脱泡，即得导电胶原料。The above-mentioned polyurethane modified epoxy resin, bisphenol A acrylate, triaryliodonium salt, vinyl ether, and micron silver powder are fully stirred and dispersed, and then ground and defoamed to obtain the conductive adhesive raw material.
采用烘箱加热方式对上述导电胶原料进行热固化，热固化温度为175℃，热固化时间为30min。The above conductive adhesive raw materials are thermally cured by means of oven heating, the thermal curing temperature is 175° C., and the thermal curing time is 30 minutes.
试验例Test example
对实施例1-11及对比例1至2提供的热固化导电胶以及购于汉高的ABLESTIK 84-1LMISR4导电胶进行如下测试：The heat-curable conductive adhesives provided in Examples 1-11 and Comparative Examples 1 to 2 and the ABLESTIK 84-1LMISR4 conductive adhesives purchased from Henkel were tested as follows:
体积电阻：在玻璃片上印刷实施例1-实施例11的热固化导电胶以及市售产品制得规格为30mm×10mm×0.05mm的导电胶膜，热固化后，采用四点探针法测试电阻，并计算体积电阻。Volume resistance: Print the thermally cured conductive adhesives of Examples 1 to 11 and commercially available products on a glass sheet to obtain a conductive adhesive film with a size of 30mm×10mm×0.05mm. After thermal curing, use the four-point probe method to test the resistance , and calculate the volume resistance.
粘接强度：在玻璃片上印刷实施例1-实施例11的热固化导电胶以及市售产品制得规格为5mm×5mm×0.05mm的导电胶膜，再放置玻璃片(5mm×5mm×1mm)在导电胶膜上，两层玻璃片与一层导电胶膜形成“三明治”结构；热固化后，采用多功能力学测试机测试。Adhesion strength: The thermally cured conductive adhesive of Example 1-Example 11 and commercially available products were printed on the glass sheet to obtain a conductive adhesive film with a size of 5mm×5mm×0.05mm, and then placed on the glass sheet (5mm×5mm×1mm) On the conductive adhesive film, two layers of glass sheets and one layer of conductive adhesive film form a "sandwich" structure; after thermal curing, it is tested by a multifunctional mechanical testing machine.
储能模量：在玻璃片上印刷实施例1-实施例11的热固化导电胶以及市售产品制得规格为50mm×3mm×0.7mm的导电胶膜，热固化后，采用动态力学热分析仪测试导电胶在室温(RT)、175℃、240℃时储能模量。在测试过程中，室温(RT)为26℃。Storage modulus: The thermally cured conductive adhesives of Examples 1 to 11 and commercially available products were printed on glass sheets to obtain a conductive adhesive film with a size of 50 mm × 3 mm × 0.7 mm. After thermal curing, a dynamic mechanical thermal analyzer was used. The storage modulus of the conductive adhesive was tested at room temperature (RT), 175°C, and 240°C. During the test, the room temperature (RT) was 26°C.
玻璃化转变温度：在玻璃片上印刷实施例1-实施例11的热固化导电胶以及市售产品制得规格为50mm×3mm×0.7mm的导电胶膜，热固化后，采用动态力学热分析仪测试。Glass transition temperature: The thermally cured conductive adhesives of Examples 1 to 11 and commercially available products were printed on the glass sheet to obtain a conductive adhesive film with a size of 50 mm × 3 mm × 0.7 mm. After thermal curing, a dynamic mechanical thermal analyzer was used. test.
冲击强度：在玻璃片上印刷实施例1-实施例11的热固化导电胶以及市售产品制得规格为80mm×10mm×4mm的导电胶膜，热固化后，采用摆锤式冲击强度测试仪测试。Impact strength: The thermally cured conductive adhesive of Example 1-Example 11 and commercially available products were printed on the glass sheet to obtain a conductive adhesive film with a size of 80mm×10mm×4mm. After thermal curing, use a pendulum impact strength tester to test .
测试结果如表1所示。The test results are shown in Table 1.
表1Table 1
Figure PCTCN2021139775-appb-000001
Figure PCTCN2021139775-appb-000001
从表1结果可知，经过热固化，本申请提供的热固化导电胶体积电阻低，约为9-31μΩ·cm，粘接强度高，约为6.8-9.1MPa，冲击强度高，约为2.7-4.0kJ·m -2，玻璃化转变温度低，约为151-161℃，储能模量低，RT时约为6.1-7.6GPa，175℃时约为0.7-2.4GPa，240℃时约为0.5-1.1GPa，均优于市售产品。说明本申请实施例提供的热固化导电胶的制备方法得到的热固化导电胶具有体积电阻低，粘接强度高，冲击强度高，玻璃化转变温度低，储能模量低等优点。 It can be seen from the results in Table 1 that after thermal curing, the thermally cured conductive adhesive provided by the application has low volume resistance, about 9-31 μΩ·cm, high bonding strength, about 6.8-9.1 MPa, and high impact strength, about 2.7- 4.0kJ·m -2 , low glass transition temperature, about 151-161℃, low storage modulus, about 6.1-7.6GPa at RT, about 0.7-2.4GPa at 175℃, about 240℃ 0.5-1.1GPa, which are better than commercially available products. It is illustrated that the thermally cured conductive adhesive obtained by the preparation method of the thermally cured conductive adhesive provided in the embodiment of the present application has the advantages of low volume resistance, high bonding strength, high impact strength, low glass transition temperature, and low storage modulus.
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。The above descriptions are only preferred embodiments of the present application, and are not intended to limit the present application. For those skilled in the art, the present application may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of this application shall be included within the protection scope of this application.

Claims (10)

  1. 一种热固化导电胶的制备方法，其特征在于，主要包括以下步骤：A preparation method of thermally cured conductive adhesive, characterized in that it mainly comprises the following steps:
    将原料在150-200℃下热固化30-60min；Heat the raw material at 150-200℃ for 30-60min;
    其中，所述原料包括按重量份数计的以下组分：Wherein, the raw material includes the following components in parts by weight:
    环氧树脂5-14.5份、稀释剂3-10份、固化剂0.5-1份、柔性助剂1.5-4.5份以及微米银粉70-90份。5-14.5 parts of epoxy resin, 3-10 parts of diluent, 0.5-1 part of curing agent, 1.5-4.5 parts of flexibility auxiliary and 70-90 parts of micron silver powder.
  2. 根据权利要求1所述的热固化导电胶的制备方法，其特征在于，所述环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、脂环环氧树脂、丙烯酸改性环氧树脂、聚氨酯改性环氧树脂、有机硅改性环氧树脂、有机钛改性环氧树脂以及有机硼改性环氧树脂中的至少一种。The method for preparing a thermally cured conductive adhesive according to claim 1, wherein the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, and acrylic modified epoxy resin At least one of oxygen resin, polyurethane modified epoxy resin, organosilicon modified epoxy resin, organotitanium modified epoxy resin and organoboron modified epoxy resin.
  3. 根据权利要求1所述的热固化导电胶的制备方法，其特征在于，所述稀释剂选自甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、1,6-己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、苯乙烯、双酚A丙烯酸酯、乙氧基化双酚A二丙烯酸酯以及双酚A二甲基丙烯酸酯中的至少一种。The method for preparing a thermally cured conductive adhesive according to claim 1, wherein the diluent is selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, At least one of trimethylolpropane triacrylate, styrene, bisphenol A acrylate, ethoxylated bisphenol A diacrylate, and bisphenol A dimethacrylate.
  4. 根据权利要求1所述的热固化导电胶的制备方法，其特征在于，所述固化剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、1-氰基-2-乙基-4-甲基咪唑、封闭型六氟锑酸盐、三芳基碘鎓盐、烷基碘鎓盐以及异丙苯茂铁六氟磷酸盐中的至少一种。The method for preparing a thermally cured conductive adhesive according to claim 1, wherein the curing agent is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyano-2-ethyl At least one of base-4-methylimidazole, blocked hexafluoroantimonate, triaryliodonium salt, alkyl iodonium salt and cumene ferrocene hexafluorophosphate.
  5. 根据权利要求1所述的热固化导电胶的制备方法，其特征在于，所述柔性助剂选自聚[(4-乙烯基苯酚)-co-(甲基丙烯酸甲酯)]、聚(二甲基硅氧烷-二苯基硅氧烷)、聚二甲基硅氧烷二缩水甘油醚、1,3-丙二醇双(4-氨基苯甲酸酯)以及乙烯基醚中的至少一种。The method for preparing a thermally cured conductive adhesive according to claim 1, wherein the flexibility assistant is selected from the group consisting of poly[(4-vinylphenol)-co-(methyl methacrylate)], poly(dimethacrylate) At least one of methylsiloxane-diphenylsiloxane), polydimethylsiloxane diglycidyl ether, 1,3-propanediol bis(4-aminobenzoate) and vinyl ether .
  6. 根据权利要求1所述的热固化导电胶的制备方法，其特征在于，所述微米银粉D50的粒径为3-5μm，敦实密度为3-5g·cm -3，比表面积为0.5-1m 2·g -1。 The method for preparing a thermally cured conductive adhesive according to claim 1, wherein the micron silver powder D50 has a particle size of 3-5 μm, a solid density of 3-5 g·cm -3 , and a specific surface area of 0.5-1 m 2 ·g -1 .
  7. 根据权利要求1-6任一项所述的热固化导电胶的制备方法，其特征在于，将原料在150-200℃下热固化30-60min之前还包括：The method for preparing a thermally cured conductive adhesive according to any one of claims 1-6, characterized in that before thermally curing the raw materials at 150-200° C. for 30-60 min, the method further comprises:
    将所述环氧树脂、所述稀释剂、所述固化剂、所述柔性助剂以及所述微米银粉混合后研磨、脱泡制备所述原料。The raw material is prepared by mixing the epoxy resin, the diluent, the curing agent, the flexibility assistant and the micron silver powder, and then grinding and defoaming.
  8. 根据权利要求1-6任一项所述的热固化导电胶的制备方法，其特征在于，所述原料的热固化温度为150-175℃。The method for preparing a thermally cured conductive adhesive according to any one of claims 1-6, wherein the thermal curing temperature of the raw material is 150-175°C.
  9. 一种热固化导电胶，其特征在于，所述热固化导电胶通过权利要求1-8任一项所述的热固化导电胶的制备方法制得。A heat-curing conductive adhesive, characterized in that the heat-curing conductive adhesive is prepared by the method for preparing a heat-curing conductive adhesive according to any one of claims 1-8.
  10. 一种热固化导电胶，其特征在于，所述热固化导电胶的体积电阻为9-31μΩ·cm，粘接强度为6.8-9.1MPa，冲击强度为2.7-4.0kJ·m -2，玻璃化转变温度为151-161℃，室温时的储能模量为6.1-7.6GPa，175℃时的储能模量为0.7-2.4GPa，240℃时的储能模量为0.5-1.1GPa。 A thermally cured conductive adhesive, characterized in that the thermally cured conductive adhesive has a volume resistance of 9-31 μΩ·cm, a bonding strength of 6.8-9.1 MPa, an impact strength of 2.7-4.0 kJ·m -2 , and a vitrification of 6.8-9.1 MPa. The transition temperature is 151-161°C, the storage modulus at room temperature is 6.1-7.6GPa, the storage modulus at 175°C is 0.7-2.4GPa, and the storage modulus at 240°C is 0.5-1.1GPa.
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