WO2020020334A1

WO2020020334A1 - Conductive adhesive, raw material composition, electronic element, and preparation method and application

Info

Publication number: WO2020020334A1
Application number: PCT/CN2019/097874
Authority: WO
Inventors: 邓华; 傅强; 孙承啸
Original assignee: 杭州蓉阳电子科技有限公司
Priority date: 2018-07-27
Filing date: 2019-07-26
Publication date: 2020-01-30
Also published as: CN110776847B; CN110776847A; JP2021524881A; JP7196200B2

Abstract

A conductive adhesive, a raw material composition, an electronic element, and a preparation method and application. The raw material composition comprises the following components: a polymer elastomer resin, conductive particles, and hot melt adhesive powder. The mass ratio between the polymer elastomer resin and the hot melt adhesive powder is (4-17):(3-35); the polymer elastomer resin is a polymer elastomer resin that is initiated to be cross-linked by peroxides; and a softening point of hot melt adhesive in the hot melt adhesive powder is higher than 90°C.

Description

Conductive glue, raw material composition, electronic component, preparation method and application

This application claims priority from Chinese patent application 2018108472723 with a filing date of July 27, 2018. This application cites the full text of the aforementioned Chinese patent application.

Technical field

The invention relates to a conductive adhesive, a raw material composition, an electronic component, a preparation method and an application.

Background technique

Conductive adhesive is an adhesive that has a certain electrical conductivity after curing. It usually consists of a polymer matrix resin and conductive particles. Its conductivity is provided by a conductive network in which conductive particles are formed, and its adhesion is provided by a polymer. With the miniaturization of electronic components, the high density and high integration of printed circuit boards, conductive adhesives play an increasingly important role in the preparation and assembly of electronic components, and the requirements for various aspects of conductive adhesives are also increasing. The higher, such as: conductive properties, heat resistance, water resistance, moisture resistance, flexibility, adhesion properties and processability.

Due to the high requirements for conductive properties in various applications, the amount of conductive filler used is very high, and the mass ratio in conductive adhesive is 50-80%. With such a high filler content, due to filler dispersion and other reasons, the overall processability, adhesion, flexibility, etc. of the composite material are usually greatly affected. Therefore, some special methods are usually required for the conductive filler network structure and its structure. The interface force with the polymer matrix is adjusted in order to achieve a good balance between the above properties. At present, many methods used in the literature and patents are: using mixed fillers separately to increase the crosslink density of the polymer matrix and surface modification of the fillers to improve the network bonding ability of the fillers in the polymer matrix in order to achieve the above A balance between performance.

However, with the rapid development of the electronics industry, there are still some problems in the performance of current polymer-based conductive adhesives that are difficult to solve: (1) the current conductive adhesives on the market are based on epoxy, polyurethane or acrylic systems, which are cured It needs to be stored at low temperature before, and the shelf life is usually short; (2) Due to the miniaturization of electronic equipment, the grounding hole tends to be miniaturized and deformed, but the current hole filling performance of conductive glue is poor. Due to these emerging problems and the industry itself has higher requirements for polymer-based conductive adhesives in terms of conductivity, adhesion and weather resistance, it is necessary to develop a kind of small-pores that can be stored at room temperature before use. Or special-shaped hole filling performance and polymer conductive conductive adhesive with excellent comprehensive properties in terms of conductivity, adhesion and weather resistance.

Summary of the Invention

The technical problem to be solved by the present invention is to overcome the defects of harsh storage conditions and poor filling performance of small holes or special-shaped holes in the prior art before using conductive adhesives, and provide a conductive adhesive, raw material composition, electronic component, and preparation method. And application. The polymer-based conductive adhesive prepared by the invention has excellent conductivity, adhesion and weather resistance, and does not need to be stored at low temperature before use, and has better ability to fill small holes or special-shaped holes.

The present invention solves the above technical problems through the following technical solutions.

The present invention provides a raw material composition of a polymer-based conductive adhesive, which includes the following components: a polymer elastomer resin, conductive particles, and a hot-melt adhesive powder, the polymer elastomer resin, and the hot-melt adhesive The mass ratio of the powder is (4-17): (3-35);

The polymer elastomer resin is a polymer elastomer resin crosslinked by a peroxide;

The softening point of the hot-melt adhesive in the hot-melt adhesive powder is ≥90 ° C.

In the present invention, the polymer elastomer resin is preferably a polymer elastomer resin whose monomer includes one or more of ethylene, acrylic acid, and siloxane; more preferably, ethylene acrylic acid block copolymer (EAA), Random copolymer polypropylene resin (CoPP), ethylene n-butyl acrylic copolymer (EBA), ethylene octene copolymer (POE), ethylene methyl acrylate copolymer (EMA), fluorosilicone elastomer resin (FVMQ), and One or more of ethylene hexene copolymers (EH), such as ethylene acrylic block copolymer (EAA), ethylene methyl acrylate copolymer (EMA), ethylene octene copolymer (POE), ethylene hexene copolymer (EH), random copolymer polypropylene resin (CoPP), fluorosilicone elastomer resin (FVMQ), ethylene n-butyl acrylic copolymer (EBA), "ethylene acrylic block copolymer (EAA), and ethylene methacrylate Ester Copolymer (EMA) "," Ethylene Acrylic Block Copolymer (EAA) and Fluorosilicone Elastomer Resin (FVMQ) "," Ethylene Acrylic Block Copolymer (EAA) and Ethylene N-Butyl Acrylic Copolymer (EBA) ) "," Ethylene Acrylic Block Copolymer (EAA) and Ethylene Octene Copolymer (POE) ", Ethylene Acrylic Block Copolymer (EAA) and Ethylene-Butyl Acrylic Copolymer (EBA) "," Ethylene Acrylic Block Copolymer (EAA), Ethylene Methyl Acrylate Copolymer (EMA), and Fluorosilicone Elastomer Resin ( FVMQ) "," Ethylene Acrylic Block Copolymer (EAA) and Random Copolymer Polypropylene Resin (CoPP) "," Ethylene Methyl Acrylate Copolymer (EMA) and Ethylene Hexene Copolymer (EH) "," Ethylene Acrylic Acid Methyl Ester Copolymer (EMA) and Ethylene N-Butyl Acrylic Copolymer (EBA) ", or" Ethylene Acrylic Copolymer (EAA) and Ethylene Methyl Acrylate Copolymer (EMA) ".

The ethylene acrylic block copolymer may be a conventional ethylene acrylic block copolymer in the art, and generally refers to a polymer prepared by copolymerization of ethylene and acrylic acid.

The acid value of the ethylene acrylic acid block copolymer is preferably 37-225 mgKOH / g (test method: 305-OR-1).

The content of acrylic acid in the ethylene acrylic acid block copolymer is preferably 6-15%, for example, 15%. The percentage refers to the weight percentage of acrylic acid in the ethylene acrylic acid block copolymer.

The ethylene acrylic block copolymer is also commercially available, such as Exxon Mobil Escor 5200.

The random copolymerized polypropylene resin may be a conventional random copolymerized polypropylene resin in the art, and generally refers to a polymer obtained by random copolymerization of ethylene and propylene.

The ethylene content in the random copolymerized polypropylene resin may be 9-16% (measured by the EMCC method), for example, 16%, and the percentage refers to the weight percentage of ethylene in the random copolymerized polypropylene resin.

The random copolymer polypropylene resin may also be purchased from a commercially available product such as ExxonMobil Vistamaxx 6102.

The ethylene n-butyl acrylic copolymer may be a conventional ethylene n-butyl acrylic copolymer, and generally refers to an elastomer polymer prepared by copolymerizing ethylene and n-butyl acrylate.

The content of n-butyl acrylic acid in the ethylene n-butyl acrylic copolymer is preferably 30-35%, such as 32.5%. The percentage refers to the weight percentage of n-butyl acrylic acid in the ethylene n-butyl acrylic copolymer.

The ethylene n-butyl acrylic copolymer can also be purchased from a commercially available product, such as ExxonMobil EnBA EN33331.

The ethylene octene copolymer may be the ethylene octene copolymer conventional in the art, and is generally prepared by copolymerizing ethylene and octene.

The melt index of the ethylene octene copolymer is preferably 0.2 to 30 g / 10 min, such as 30 g / 10 min.

The ethylene octene copolymer is also commercially available, such as Dow Chemical Engage 8400.

The ethylene methyl acrylate copolymer may be a conventional ethylene methyl acrylate copolymer in the art, and is generally prepared by random copolymerization of ethylene and methyl acrylate.

The content of methyl acrylate in the ethylene methyl acrylate copolymer is preferably 18-24%, for example, 24%. The percentage refers to the weight percentage of methyl acrylate in the ethylene methyl acrylate copolymer.

The ethylene methyl acrylate copolymer is also available from commercially available products, such as Exxon Mobil Optema TC220 ExCo.

Wherein, the fluorosilicone rubber elastomer resin may be a conventional fluorosilicone rubber elastomer resin in the art, and generally refers to a polysiloxane elastomer resin containing a fluoro group-containing side chain. The type, fluorine-containing group and the proportion of polysiloxane are closely related. For example, γ-trifluoropropylmethylpolysiloxane contains trifluoropropyl side chains, and has the characteristics of silicone rubber and fluorine rubber.

The fluorosilicone elastomer resin can also be purchased from commercially available products, such as Dow Corning XIAMETER LS 4-9060.

The ethylene hexene copolymer may be a conventional ethylene hexene copolymer in the art, and is generally prepared by copolymerizing ethylene and hexene.

The melt index of the ethylene hexene copolymer is preferably 1.1-17 g / 10min (as determined by AMSTD1238), for example, 17g / 10min.

The ethylene hexene copolymer is also commercially available, such as Exxon Mobil Exact 3040.

In the present invention, preferably, the weight percentage of the polymer elastomer resin in the raw material composition of the polymer-based conductive adhesive is 4-17%, for example, 4.47%, 7.00%, 8.00%, 9.00%, 11.47 %, 12.00%, 13.00%, 14.47%, 16.50% or 17.00%.

In the present invention, the polymer elastomer resin is preferably 4.47-17% EAA (for example, 4.47% EAA, 7.00% EAA, 8.00% EAA, 9.00% EAA, 11.47% EAA, 12.00% EAA, 13.00% EAA, 14.47% EAA, 16.50% EAA or 17.00% EAA), 12-13% FVMQ (e.g. 12% FVMQ or 13% FVMQ), 12% POE, 12% EH, 12% CoPP, 12.00% EBA, 12.00% EMA, "6.00% EAA and 6% EMA "," 6.00% EAA and 6% FVMQ "," 9.60% EAA and 2.40% FVMQ "," 6.00% EAA and 6% EBA "," 6.00% EAA and 6% POE "," 9.00% EAA and 3% CoPP "," 6.00% EMA and 6% EH "," 6.00% EMA and 6% EBA "," 6.00% EAA and 6.00% CoPP "," 10.40% EAA and 2.60% EMA "," 2.60% EAA and 10.40% EMA "," 9.10% EAA and 3.90% EMA "," 3.90% EAA and 9.10% EMA ", or" 5.60% EAA, 2.40% FVMQ and 4.00% EMA ", the percentages refer to the polymerization The weight percentage in the raw material composition of the conductive adhesive.

In the present invention, the hot-melt adhesive powder may be a conventional hot-melt adhesive powder, and is generally obtained by grinding the hot-melt adhesive.

The particle size of the hot-melt adhesive powder may be a conventional particle size in the art, and preferably the D _{50 is} less than 30 microns, for example, less than 20 microns, and for example, less than 10 microns. D ₅₀ means that the particle size larger than it accounts for 50% of the volume of particles, and the particle size smaller than it accounts for 50% of the volume of particles. D _{50 is} often used to indicate the average particle size of a powder.

The hot melt adhesive may be a conventional hot melt adhesive in the art, and generally refers to a thermoplastic processable adhesive. In this field, hot-melt adhesives are generally solid, and have the advantages of easy packaging, transportation, storage, no solvents, no pollution, and simple production processes, high added value, and fast speed.

The softening point of the hot melt adhesive is preferably 90-250 ° C, such as 100-250 ° C; more preferably 90-167 ° C, such as 90 ° C, 91 ° C, 94 ° C, 105 ° C, 110 ° C, 130 ° C, 140 ° C. Or 167 ° C.

The hot melt adhesive can also be purchased from commercially available products, such as one or more of Toyobo's VYLON 30P, GM-400, GM460, GM480, GM900, GM990, GK-390, RV-240 and RV-670. ; For example, one or more of PES-3110, PES-3112, PES-3115, PES-3122, PES-3130, PES-3140, and PES-3185 of Shanghai Tianyang Hot Melt Adhesive.

The hot melt adhesive is preferably a polyamide resin, a polyester resin, an ethylene vinyl acetate copolymer (EVA), a styrene-isoprene-styrene block copolymer (SIS), and a styrene-ethylene-butene. -One or more of styrene block copolymer (SEBS), styrene-butadiene block copolymer (SBS), and polyurethane resin, such as polyamide resin, polyester resin, ethylene vinyl acetate copolymer Styrene-isoprene-styrene block copolymer, styrene-ethylene-butene-styrene block copolymer, styrene-butadiene block copolymer or polyurethane resin.

The polyester resin may be a conventional polyester resin in the art, and generally refers to a polymer prepared by polycondensation of "diols and dibasic acids" or "polyols and polybasic acids". The softening point of the polyester resin is preferably 130-167 ° C, such as 130 ° C or 167 ° C. The polyester resin can also be purchased from commercially available products, such as POLYESTER (such as SP-176) from Japan Synthetic Chemical Industry, HADDEC from Asahi Kasei Industries, and VYLON resin from Toyobo.

The polyurethane resin may be a conventional polyurethane resin in the art, and generally refers to a polymer containing a urethane group in a main chain of a polymer molecule. The softening point of the polyurethane resin is preferably 100-110 ° C, such as 105 ° C. The polyurethane resin can also be purchased from commercially available products, such as: Macroplast QR5210 and QR4663 of Henkel; Supergrip 2000 of Bostik; JetWeld of 3M; Ever-Lock of Riechhold; ReactTITE and HiPURformer of Franklin; Mor-Melt, etc. of Shanghai Siyuan; Shanghai Yuanzhi Hot Melt Adhesive U1101P and U1105G.

The polyamide resin may be a conventional polyamide resin in the art, and generally refers to a polymer containing an amide group in a repeating unit of a polymer main chain. The polyamide resin can be prepared by ring-opening polymerization of an internal acid amine, or can be prepared by polycondensation of a diamine and a diacid. The softening point of the polyamide resin is preferably 105-115 ° C, for example, 110 ° C. The polyamide resin can also be purchased from commercially available products, such as: GAIBOND S-100, S-160, and S-200, PLATAIDE H105, H005, and H104; Shanghai Yuanzhi Hot Melt Adhesive H1001G; Shanghai Tiantian PA-6120, PA-6200, PA-6300, PA-6106, PA-7200, PA-7300 and PA-9801 of foreign hot melt adhesives; Li Debao PA-120 of Foshan City.

The ethylene vinyl acetate copolymer may be a conventional ethylene vinyl acetate copolymer in the art, and generally refers to a copolymer prepared by copolymerization of ethylene and vinyl acetate. The softening point of the ethylene vinyl acetate copolymer is preferably 90-95 ° C, such as 91 ° C. The ethylene vinyl acetate copolymer (EVA) can also be purchased from commercially available products, such as ExxonMobil Escorene series grades (for example, Escorene Ultra LD 701.1D).

The styrene-butadiene block copolymer may be a conventional styrene-butadiene block copolymer, and generally refers to a block copolymer prepared by copolymerization of styrene and butadiene. And rubber properties. The softening point of the styrene-butadiene block copolymer is preferably 90-91 ° C, such as 90 ° C. The styrene-butadiene block copolymer (SBS) can also be purchased from commercially available products, such as Kraton D-1101, D-4122, Baling Petrochemical YH791, YH792, YH801, YH802, YH795, and YH805.

The styrene-ethylene-butene-styrene block copolymer may be a conventional styrene-ethylene-butene-styrene block copolymer in the art, and generally refers to a copolymerization of styrene, ethylene, and butene. The obtained block copolymer has the characteristics of plastic and rubber. The softening point of the styrene-ethylene-butene-styrene block copolymerization is preferably 135-145 ° C, such as 140 ° C. The styrene-ethylene-butene-styrene block copolymer (SEBS) can also be purchased from commercial products, such as: Baling Petrochemical YH-501 and YH-502, Kraton G series.

The styrene-isoprene-styrene block copolymer may be a conventional styrene-isoprene-styrene block copolymer in the art, and generally refers to a system prepared by copolymerizing styrene and isoprene. The obtained block copolymer has the characteristics of plastic and rubber. The softening point of the styrene-isoprene-styrene block copolymerization is preferably 92-96 ° C, for example, 94 ° C. The styrene-isoprene-styrene block copolymer (SIS) can also be purchased from commercially available products, such as: Baling Petrochemical YH-1105, YH-1209, YH-1106, YH-1124, YH- 1126 and YH-4019; Kraton's D1113, D1161, and D1162.

In the present invention, preferably, the mass ratio of the polymer elastomer resin to the hot-melt adhesive powder is (4.47: 34.88)-(16.5: 3), for example, 17.00: 17.26, 7: 17.26, 8.00: 11.26 , 9.00: 20.26, 12.00: 17.26, 4.47: 34.88, 11.47: 27.79, 14.47: 14.73, 11.47: 7.79, 16.50: 3.00, 13.00: 16.20, 12.00: 17.38 or 12.00: 17.14, but also 7.00: 17.13; more preferably The weight percentage of the hot-melt adhesive powder in the raw material composition of the polymer-based conductive adhesive is 3-35%, such as 3.00%, 7.79%, 11.26%, 14.73%, 16.20%, 17.14%, 17.26 %, 17.38%, 20.26%, 27.79%, or 34.88%, and also 17.13%.

In the present invention, the hot melt adhesive is preferably 3.00-34.88% polyester resin (for example, 3.00%, 7.79%, 11.26%, 14.73%, 16.20%, 17.14%, 17.26%, 17.38%, 27.79%, or 34.88%, It can also be 17.13%), 16.20-20.26% polyurethane resin (e.g. 16.20%, 20.26% or 17.26%), 17.26% polyamide resin, 17.26% ethylene vinyl acetate copolymer, 17.26% styrene-butadiene block Copolymer, 17.26% styrene-ethylene-butene-styrene block copolymer or 17.26% styrene-isoprene-styrene block copolymer.

In the present invention, when the polymer elastomer resin is an ethylene acrylic acid block copolymer (EAA), the hot melt adhesive powder is preferably a polyester resin and / or a polyurethane resin.

In the present invention, when the polymer elastomer resin is a random copolymerized polypropylene resin (CoPP), the hot melt adhesive powder is preferably a polyester resin.

In the present invention, when the polymer elastomer resin is an ethylene n-butyl acrylic copolymer (EBA), the hot melt adhesive powder is preferably a polyester resin and / or an ethylene vinyl acetate copolymer.

In the present invention, when the polymer elastomer resin is an ethylene hexene copolymer (EH), the hot melt adhesive powder is preferably a polyester resin.

In the present invention, when the polymer elastomer resin is an ethylene methyl acrylate copolymer (EMA), the hot melt adhesive powder is preferably a styrene-butadiene block copolymer.

In the present invention, when the polymer elastomer resin is a fluorosilicone elastomer resin (FVMQ), the hot melt adhesive powder is preferably a polyester resin and / or a polyurethane resin.

In the present invention, when the polymer elastomer resin is an ethylene octene copolymer (POE), the hot melt adhesive powder is preferably a polyester resin.

In the present invention, when the polymer elastomer resin is an ethylene acrylic block copolymer (EAA) and a random copolymer polypropylene resin (CoPP), the hot melt adhesive powder is preferably a polyester resin.

In the present invention, when the polymer elastomer resin is ethylene acrylic block copolymer (EAA) and ethylene n-butyl acrylic copolymer (EBA), the hot melt adhesive powder is preferably a polyamide resin and / or benzene Ethylene-isoprene-styrene block copolymer.

In the present invention, when the polymer elastomer resin is ethylene methyl acrylate copolymer (EMA) and ethylene n-butyl acrylic copolymer (EBA), the hot melt adhesive powder is preferably a polyester resin.

In the present invention, when the polymer elastomer resin is an ethylene methyl acrylate copolymer (EMA) and an ethylene hexene copolymer (EH), the hot melt adhesive powder is preferably a polyester resin.

In the present invention, when the polymer elastomer resin is ethylene acrylic acid block copolymer (EAA) and ethylene methyl acrylate copolymer (EMA), the hot melt adhesive powder is preferably a polyurethane resin.

In the present invention, when the polymer elastomer resin is ethylene acrylic block copolymer (EAA) and fluorosilicone rubber elastomer resin (FVMQ), the hot melt adhesive powder is preferably a polyurethane resin, a polyamide resin, and benzene One or more of an ethylene-isoprene-styrene block copolymer, such as a polyurethane resin, a polyamide resin, or a styrene-isoprene-styrene block copolymer.

In the present invention, when the polymer elastomer resin is ethylene acrylic block copolymer (EAA), fluorosilicone rubber elastomer resin (FVMQ) and ethylene methyl acrylate copolymer (EMA), the hot melt adhesive powder A styrene-isoprene-styrene block copolymer is preferred.

In the present invention, when the polymer elastomer resin is ethylene acrylic acid block copolymer (EAA) and ethylene octene copolymer (POE), the hot melt adhesive powder is preferably styrene-ethylene-butene-benzene Ethylene block copolymer.

In the present invention, in the raw material composition of the polymer-based conductive adhesive, the polymer elastomer resin and the hot-melt adhesive powder are preferably: "12.00% EAA and 17.26% polyester resin", "17.00% EAA And 17.26% polyester resin "," 7.00% EAA and 17.26% polyester resin "," 8.00% EAA and 11.26% polyester resin "," 9.00% EAA and 20.26% polyurethane resin "," 6.00% EAA, 6% EMA and 17.26% polyurethane resin "," 6.00% EAA, 6% FVMQ and 17.26% polyurethane resin "," 9.60% EAA, 2.40% FVMQ and 17.26% polyamide resin "," 6.00% EAA, 6% EBA, and 17.26% "Polyamide resin", "6.00% EAA, 6% EBA and 17.26% polyamide resin", "12.00% EVA and 17.26% ethylene vinyl acetate copolymer", "12.00% EBA and 17.26% ethylene vinyl acetate copolymer" , "12.00% EMA and 17.26% styrene-butadiene block copolymer", "6.00% EAA, 6% POE and 17.26% styrene-ethylene-butene-styrene block copolymer", "6.00% EAA, 6% EBA, and 17.26% styrene-isoprene-styrene block copolymer "," 5.60% E AA, 2.40% FVMQ, 4.00% EMA, and 17.26% styrene-isoprene-styrene block copolymer "," 9.60% EAA, 2.40% FVMQ, and 17.26% styrene-isoprene-styrene "Block copolymer", "12% FVMQ and 17.26% polyester resin", "12% POE and 17.26% polyester resin", "12% EH and 17.26% polyester resin", "12% CoPP and 17.26% poly Ester resin "," 6.00% EAA, 6.00% CoPP, and 17.26% polyester resin "," 9.00% EAA, 3% CoPP and 17.14% polyester resin "," 6.00% EMA, 6% EH, and 17.26% polyester Resin "," 6.00% EMA, 6% EH and 17.26% polyester resin "," 12.00% EBA and 17.26% polyester resin "," 6.00% EMA, 6% EBA and 17.26% polyester resin "," 4.47% EAA and 34.88% polyester resin "," 11.47% EAA and 27.79% polyester resin "," 14.47% EAA and 14.73% polyester resin "," 11.47% EAA and 7.79% polyester resin "," 16.50% EAA and 3.00% polyester resin "," 13.00% EAA and 16.20% polyester resin "," 10.40% EAA, 2.60% EMA and 16.20% polyurethane resin "," 2.60% EAA, 10.40% EMA " 16.20% polyurethane resin "," 9.10% EAA, 3.90% EMA and 16.20% polyurethane resin "," 3.90% EAA, 9.10% EMA and 16.20% polyurethane resin "," 13% FVMQ and 16.20% polyurethane resin "," 12.00% EAA and 17.38% polyester resin "," 12.00% EAA and 17.14% polyester resin ", or" 12.00% EAA and 17.38% polyester resin ", and also" 12.00% EAA and 17.13% polyester resin ", The percentage refers to the weight percentage in the raw material composition of the polymer-based conductive adhesive.

In the present invention, the conductive particles may be conventional conductive particles in the art, and may be, for example, one or more of metal particles, non-metal particles, and particles coated with a metal layer on the surface.

The metal particles include, but are not limited to, one or more of gold, silver, copper, aluminum, tin, zinc, titanium, bismuth, tungsten, and lead.

The non-metal particles include, but are not limited to, carbon nanotubes and / or graphene. The carbon nanotubes are also commercially available, such as Nanocyl S.A. (Belgium), NC7000.

Among the particles coated with the metal layer on the surface, the metal used to coat the surface of the particles may be one or more of gold, silver, and nickel. The particles coated with the metal layer are preferably one or more of silver-coated copper particles, silver-coated glass particles, silver-coated polystyrene particles, and nickel-coated copper particles, and preferably silver-coated copper particles. The silver content in the silver-clad copper particles is preferably 10-15 wt.%, For example, 10 wt.% Or 11 wt.%. The wt.% Refers to the weight percentage of the silver content in the surface-coated metal layer particles. The silver-clad copper particles can also be purchased from commercially available products, such as FAC-610 from Ames Goldsmith Corp. or CG-SAB-121 from Dowa Holdings Co., Ltd.

In the present invention, the amount of the conductive particles may be a conventional amount in the art. Preferably, the weight ratio of the polymer elastomer resin and the conductive particles is (4-17): (40-85), for example 12.00: 70.00, 17.00: 65.00, 7.00: 75.00, 8.00: 80.00, 9.00: 70.00, 4.47: 60.00, 11.47: 60.00, 14.47: 70.00, 11.47: 80.00, 16.50: 79.00 or 13.00: 70.00; more preferably, said The weight percentage of the conductive particles in the raw material composition of the polymer-based conductive adhesive is 40-85%, such as 50% -80%, and for example, 60%, 65%, 70%, 75%, 79%, or 80% .

In the present invention, the conductive particles are preferably 65.00-70.00% silver-clad copper particles (e.g. 65.00% or 70.00%) with a silver content of 11 wt.%, And 60.00-80.00% silver-clad copper particles (e.g. 60.00) with a silver content of 10wt.% %, 70.00%, 75.00%, 79.00%, or 80.00%), "35.00% silver-clad copper particles with a silver content of 11 wt.% And 35.00% silver content with a silver-clad copper particles with a content of 10wt.%", 69.50% silver content with a 11wt.% Silver content Silver-coated copper particles and 0.50% carbon nanotubes, or "34.80% silver-coated silver particles 11wt.% Silver-coated copper particles, 34.80% silver-content 10wt.% Silver-coated copper particles and 0.40% carbon nanotubes".

In the present invention, the conductive particles ₅₀ may be conventional in the D field ₅₀ D, preferably 0.1 to 20 microns, more preferably 0.1 to 10 microns.

In the present invention, the raw material composition of the polymer-based conductive adhesive may further include a cross-linking agent and a coupling agent.

The crosslinking agent may be a conventional crosslinking agent in the art, such as dicumyl peroxide (DCP), 2,5-dimethyl-2,5-bis (tert-butylperoxy) ethane. (DBPH), benzoyl peroxide (BPO), di-tert-butyl peroxide (DTBP), dicumyl hydrogen peroxide (DBHP), dilauroyl peroxide (LPO), tert-butyl perbenzoate (TPB), cyclohexanone peroxide (CYHP), diisopropyl peroxydicarbonate (IPP), di (2-ethylhexyl) peroxydicarbonate (EHP), and methyl ethyl ketone peroxide (MEKP). One or more, preferably dicumyl peroxide (DCP), benzoyl peroxide (BPO), dicumyl hydrogen peroxide (DBHP), or "dicumyl peroxide (DCP) And dicumyl hydrogen peroxide (DBHP). "

The dicumyl peroxide (DCP) can also be purchased from a commercially available product, for example, dicumyl peroxide commercially available from Sinopharm (Shanghai) International Medical and Health Co., Ltd. The dicumyl hydrogen peroxide (DBHP) can also be purchased from commercially available products, such as the dicumyl hydrogen peroxide commercially available from Aladdin (China). The benzoyl peroxide (BPO) can also be purchased from commercially available products, such as the benzoyl peroxide commercially available from Aladdin (China).

The commercialized products of the crosslinking agent may further include: AkzoNobel, Perkadox series products, Trigonox series products, or Arkerma company Luperox series products.

The amount of the cross-linking agent may be a conventional amount in the art. Preferably, the weight ratio of the polymer elastomer resin and the cross-linking agent is (4-17): (0.16-1), for example, 4.47: 0.15, 7.00: 0.24, 8.00: 0.24, 9.00: 0.24, 11.47: 0.24, 12.00: 0.24, 13.00: 0.24, 13.00: 0.30, 17.00: 0.24, 16.50: 1.00, 13.00: 0.30, 14.47: 0.30, 12.00: 0.12, 12.00: 0.36 or 13.00: 0.36; more preferably, the weight percentage of the crosslinking agent in the polymer-based conductive adhesive raw material composition is 0.12-1.0%, for example, 0.12%, 0.15%, 0.24%, 0.30% , 0.36% or 1.0%.

The coupling agent may be a conventional coupling agent in the art, such as γ- (2,3-glycidoxy) propyltrimethoxysilane (KH560), γ-aminopropyltriethoxysilane (KH550) and glutaric acid (GA), for example, KH560, KH550 or GA.

The amount of the coupling agent may be a conventional amount in the art. Preferably, the weight ratio of the polymer elastomer resin and the coupling agent is (4-17): (0.16-1), for example, 4.47: 0.50, 7.00: 0.50, 8.00: 0.50, 9.00: 0.50, 11.47: 0.50, 13.00: 0.50, 12.00: 0.50, 14.47: 0.50, 16.50: 0.50 or 17.00: 0.50; more preferably, the coupling agent is in the The weight percentage in the raw material composition of the polymer-based conductive adhesive is 0.50%.

In the present invention, other conventional auxiliaries can be added to the raw material composition of the polymer-based conductive adhesive according to the demand in the actual production process.

Wherein, the other conventional auxiliary agents may be a surfactant, and the surfactant includes, but is not limited to, an antifoaming agent and / or a leveling agent.

The surfactant is preferably a cationic surfactant, such as an amine salt type cationic surfactant and / or a quaternary ammonium salt type cationic surfactant. The lipophilic group of the cationic surfactant may be an alkyl chain having 10 to 18 carbons. The anionic group of the cationic surfactant may be bromine, iodine or chlorine.

The surfactant is preferably a fluorocarbon ion surfactant.

The weight ratio of the polymer elastomer resin and the surfactant is preferably (4-17): (0.01-0.05), such as 7: 0.02; more preferably, the surfactant is in the polymer base The weight percentage in the raw material composition of the conductive adhesive is 0.01-0.05%, such as 0.02%.

In the present invention, the raw material composition of the polymer-based conductive adhesive may further include an inorganic filler and / or an antistatic agent.

The inorganic filler may be a conventional inorganic filler in the art, such as fumed silica. The particle diameter of the fumed silica may be 7-200 nm, for example, 16 nm. The fumed silica can also be purchased from commercially available products such as Evonik, AEROSIL R972.

Wherein, the weight ratio of the polymer elastomer resin and the inorganic filler is preferably (4-17): (0.05-0.15), such as 7: 0.08; more preferably, the inorganic filler is in the polymer base. The weight percentage of the raw material composition of the conductive adhesive is 0.05-0.15%, for example, 0.08%.

The antistatic agent may be a conventional antistatic agent in the art, such as one or more of a cationic antistatic agent, an anionic antistatic agent, and a nonionic antistatic agent. The antistatic agent may also be purchased from a commercially available product, such as JI-WT4 produced by Shandong Juli Antistatic Technology Co., Ltd.

Wherein, the weight ratio of the polymer elastomer resin and the antistatic agent is preferably (4-17): (0.01-0.05), for example, 7: 0.05; more preferably, the inorganic filler is in the polymer The weight percentage in the raw material composition of the conductive adhesive is 0.01-0.05%, for example, 0.03%.

The inorganic filler and / or the antistatic agent can prevent the hot melt adhesive powder from re-aggregating into larger particles during the milling process and prevent the generation of static electricity.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: polymer elastomer resin 4-17%, silver-clad copper powder 50-85%, hot melt The rubber powder is 3 to 35%, the cross-linking agent is 0.16 to 1%, and the coupling agent is 0.3 to 7%. The percentage is the weight percentage in the raw material composition.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 12%, silver-clad copper particles (silver content is 11 wt.%) 70%, polyester Resin is 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 17%, silver-clad copper particles (silver content 11wt.%) 65%, polyester Resin is 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 7%, silver-coated copper particles (silver content 10wt.%) 75%, polyester Resin was 17.26%, DCP crosslinker was 0.24%, and KH560 was 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 8%, silver-clad copper particles (silver content 10wt.%) 80%, polyester Resin 11.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 9%, silver-coated copper particles (silver content 10wt.%) 70%, polyurethane resin 20.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 6%, EMA 6%, silver-clad copper particles (silver content is 11wt.%) 35 %, Silver-coated copper particles (10 wt.% Silver content) 35%, polyurethane resin 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 6%, FVMQ 6%, silver-coated copper particles (silver content is 11wt.%) 35 %, Silver-coated copper particles (10 wt.% Silver content) 35%, polyurethane resin 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 9.6%, FVMQ 2.4%, silver-coated copper particles (silver content is 11 wt.%) 70 %, Polyamide resin 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 6%, EBA 6%, silver-coated copper particles (silver content is 11 wt.%) 70 %, Polyamide resin 17.26%, DCP 0.24%, KH56 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 6%, EBA 6%, silver-coated copper particles (11wt.% Silver content) 69.5 %, Carbon nanotube 0.5%, polyamide resin 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EBA 12%, silver-coated copper particles (silver content 11wt.%) 70%, ethylene acetic acid The vinyl ester copolymer is 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EMA 12%, silver-coated copper particles (silver content 11wt.%) 70%, styrene -Butadiene block copolymer 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EMA 12%, silver-coated copper particles (silver content 11wt.%) 70%, styrene -Butadiene block copolymer 17.26%, DCP 0.12%, DBPH 0.12%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 6%, POE 6%, silver-clad copper particles (silver content is 11 wt.%) 70 %, Styrene-ethylene-butene-styrene block copolymer 17.26%, DCP 0.08%, DBPH 0.16%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 6%, EBA 6%, silver-coated copper particles (silver content 10wt.%) 70 %, Styrene-isoprene-styrene block copolymer 17.26%, DCP 0.16%, DBPH 0.08%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 6%, EBA 6%, silver-coated copper particles (silver content is 11wt.%) 34.8 %, Silver-coated copper particles (silver content of 10 wt.%) 34.8%, carbon nanotubes 0.4%, styrene-isoprene-styrene block copolymer 17.26%, DBPH 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 5.6%, FVMQ 2.4%, EMA 4%, silver-clad copper particles (silver content 10wt (%) 70%, styrene-isoprene-styrene block copolymer 17.26%, DCP 0.24%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 9.6%, FVMQ 2.4%, silver-coated copper particles (silver content 10wt.%) 70 %, Styrene-isoprene-styrene block copolymer 17.26%, DCP 0.24%, GA 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: FVMQ 12%, silver-coated copper particles (silver content 10wt.%) 70%, polyester Resin is 17.26%, DCP 0.24%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: POE 12%, silver-clad copper particles (silver content 10wt.%) 70%, polyester Resin is 17.26%, DCP 0.24%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EH 12%, silver-coated copper particles (silver content 10wt.%) 70%, polyester Resin is 17.26%, DCP 0.24%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: CoPP 12%, silver-clad copper particles (silver content 10wt.%) 70%, polyester Resin is 17.26%, DCP 0.24%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 6%, CoPP 6%, silver-clad copper particles (silver content 10wt.%) 70 %, Polyester resin 17.26%, DBPH 0.24%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 9%, CoPP 3%, silver-coated copper particles (silver content 10wt.%) 70 %, Polyester resin 17.14%, DBPH 0.36%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EMA 6%, EH 6%, silver-coated copper particles (silver content is 10wt.%) 70 %, Polyester resin 17.26%, DCP 0.24%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EMA 6%, EH 6%, silver-coated copper particles (silver content is 10wt.%) 70 %, Polyester resin 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EBA 12%, silver-clad copper particles (silver content 10wt.%) 70%, polyester Resin is 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EMA 6%, EBA 6%, silver-coated copper particles (silver content is 10wt.%) 70 %, Polyester resin 17.26%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 4.47%, silver-clad copper particles (silver content 10wt.%) 60%, polyester Resin was 34.88%, DCP was 0.15%, and KH560 was 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 11.47%, silver-clad copper particles (silver content 10wt.%) 60%, polyester Resin 27.79%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 14.47%, silver-clad copper particles (silver content 10wt.%) 70%, polyester Resin 14.73%, DCP 0.3%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 11.47%, silver-clad copper particles (silver content 10wt.%) 80%, polyester Resin is 7.79%, DCP 0.24%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 16.5%, silver-clad copper particles (silver content 10wt.%) 79%, polyester Resin 3%, DCP 1%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 13%, silver-coated copper particles (silver content 10wt.%) 70%, polyester Resin 16.2%, BPO 0.3%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 10.4%, EMA 2.6%, silver-coated copper particles (silver content 10wt.%) 70 %, Polyurethane resin 16.2%, DBPH 0.3%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 2.6%, EMA 10.4%, silver-coated copper particles (silver content 10wt.%) 70 %, Polyurethane resin 16.2%, DBPH 0.3%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 9.1%, EMA 3.9%, silver-coated copper particles (silver content 10wt.%) 70 %, Polyurethane resin 16.2%, DBPH 0.3%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 3.9%, EMA 9.1%, silver-coated copper particles (silver content 10wt.%) 70 %, Polyurethane resin 16.2%, DBPH 0.3%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: FVMQ 13%, silver-clad copper particles (silver content 10wt.%) 70%, polyurethane resin 16.2%, DBPH 0.15%, DCP 0.15%, KH550 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 12%, silver-clad copper particles (silver content is 11 wt.%) 70%, polyester Resin 17.38%, DCP 0.12%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 12%, silver-clad copper particles (silver content is 11 wt.%) 70%, polyester Resin 17.14%, DCP 0.36%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 12%, silver-clad copper particles (silver content is 11 wt.%) 70%, polyester Resin 17.38%, DBPH 0.12%, KH560 0.5%.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: polymer elastomer resin 4-17%, conductive particles 50-85%, hot melt adhesive powder 3-35%, cross-linking agent 0.16--1%, coupling agent 0.3-7%, surfactant 0.01-0.05%, inorganic filler 0.05-0.15%, antistatic agent 0.01-0.05%, percentages are in the raw materials Weight percent in the composition.

In a preferred embodiment of the present invention, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: EAA 7%, silver-coated copper particles silver content (11wt.%) 75%, polyester Resin 17.13%, DCP 0.24%, KH560 0.5%, fluorocarbon ion surfactant 0.02%, fumed silica 0.08%, antistatic agent 0.03%.

The invention also provides a method for preparing a polymer-based conductive adhesive by using the aforementioned raw material composition of the polymer-based conductive adhesive. In the presence of a cross-linking agent, the polymer elastomer resin, conductive particles and hot-melt adhesive are prepared. The powder can be ground and blended.

Those skilled in the art know that during the preparation process of the polymer-based conductive adhesive, a cross-linking agent can be added according to the conventional art to cross-link and polymerize each component to prepare a polymer-based conductive adhesive.

The definitions of the polymer elastomer resin, the conductive particles, and the hot-melt adhesive powder are as described above.

The grinding and blending process may be a conventional process in the art. Preferably, the grinding and blending process includes the following steps:

(1) The polymer elastomer resin solution, the conductive particles and the hot-melt adhesive powder are mixed for the first time to obtain mixture A; the polymer elastomer resin solution is obtained by mixing the polymer elastomer resin and the solvent. The definitions of the polymer elastomer resin, conductive particles and hot melt adhesive powder are as described above;

(2) mixing the cross-linking agent and the mixture A described in step (1) a second time to obtain a mixture B, which can be ground;

When the raw material composition further includes a coupling agent and other conventional auxiliary agents, the cross-linking agent, the coupling agent, other conventional auxiliary agents, and the mixture A in step (1) are mixed for a second time to obtain a mixture. C, you can;

When the raw material composition further includes an inorganic filler and / or an antistatic agent, during the preparation of the hot-melt adhesive powder, "the inorganic filler and / or the antistatic agent" and the heat The melt powder is mixed to obtain mixture A ′; and the polymer elastomer resin solution and the conductive particles are mixed to obtain mixture A through the first mixing;

The definitions of the cross-linking agent, the coupling agent, the inorganic filler, the antistatic agent, and the other conventional auxiliaries are as described above.

In the present invention, the terms "first time" and "second time" have no special meaning, and only indicate the order of mixing.

In step (1), the solvent may be a conventional solvent capable of dissolving a polymer elastomer resin, such as diisobutyl ketone (DIBK), methyl isobutyl ketone (MIBK), and cyclohexanone (ANONE ), One or more of isomethylacetone (IPO), ethyl acetate (EAC), and isobutyl acetate (IBAC), such as diisobutyl ketone (DIBK), cyclohexanone (ANONE), Isomethylacetone (IPO), ethyl acetate (EAC), isobutyl acetate (IBAC), or "methyl isobutyl ketone (MIBK) and diisobutyl ketone (DIBK)". In the "methyl isobutyl ketone (MIBK) and diisobutyl ketone (DIBK)", the mass ratio of methyl isobutyl ketone (MIBK) to diisobutyl ketone (DIBK) is preferably 5: 5 .

In step (1), the amount of the solvent may be a conventional amount in the art, for example, the mass ratio of the polymer elastomer resin to the solvent is 1: 2.

In step (1), the temperature at which the polymer elastomer resin and the solvent are mixed may be a temperature conventional in the art, such as a water bath temperature of 40-80 ° C. The mixing time of the polymer elastomer resin and the solvent may be a time conventional in the art, for example, 2 h. Preferably, after the polymer elastomer resin is dissolved in the solvent, stirring is performed at room temperature to obtain a polymer elastomer resin solution, and the stirring time is preferably 3 hours. The room temperature generally refers to 25 ° C.

Step (2), preferably, the "second mixing" may include the steps of pre-mixing, mixing, defoaming, and re-mixing to make the mixture B or C more uniform.

The pre-mixing speed in the "second mixing" is preferably 350-450 rmp, for example, 400 rmp. The pre-mixing time in the "second mixing" is preferably 15-45 seconds, such as 30 seconds.

The rotation speed of the mixing in the “second mixing” is preferably 1800-2200 rmp, for example, 2000 rmp. The mixing time in the "second mixing" is preferably 1-3 minutes, such as 2 minutes or 3 minutes.

The speed of defoaming in the "second mixing" is preferably 2000-2500 rmp, for example, 2200 rmp. The defoaming time in the "second mixing" is preferably 1-3 minutes, such as 2 minutes.

The speed of re-mixing in the "second mixing" is preferably 1800-2200 rmp, for example, 2000 rmp. The time for re-mixing in the "second mixing" is preferably 15-45 seconds, such as 30 seconds.

In step (2), preferably, the mixture B or the mixture C is ground in a grinder. The grinder is preferably a three-roll grinder. The grinding time is preferably 4-6 minutes, such as 5 minutes. Preferably, the solvent in step (1) is added dropwise at the same time as the grinding, and the amount of the dropwise addition may be a conventional amount in the art, and the grinding and lubrication effect may be achieved, for example, 10-100 ml.

The invention also provides a polymer-based conductive adhesive prepared by the aforementioned preparation method.

Wherein, the adhesive strength of the polymer-based conductive adhesive is preferably 8.5-16.2N / cm, such as 8.5N / cm, 9N / cm, 9.1N / cm, 9.2N / cm, 9.5N / cm, 9.6N / cm, 9.7N / cm, 9.8N / cm, 9.9N / cm, 10.1N / cm, 10.5N / cm, 10.9N / cm, 11N / cm, 11.1N / cm, 11.2N / cm, 11.3N / cm , 11.4N / cm, 11.5N / cm, 11.6N / cm, 11.7N / cm, 11.8N / cm, 12N / cm, 12.4N / cm, 14.1N / cm, 15.1N / cm, or 16.2N / cm.

Wherein, the filling resistance (hole diameter 0.5mm) of the polymer-based conductive adhesive is preferably 0.1-0.74Ohm, such as 0.1Ohm, 0.11Ohm, 0.14Ohm, 0.16Ohm, 0.2Ohm, 0.2Ohm, 0.21Ohm, 0.22Ohm , 0.23Ohm, 0.24Ohm, 0.25Ohm, 0.26Ohm, 0.27Ohm, 0.3Ohm, 0.31Ohm, 0.32Ohm, 0.33Ohm, 0.34Ohm, 0.35Ohm, 0.36Ohm, 0.38Ohm, 0.4Ohm, 0.72Ohm or 0.74Ohm.

The invention also provides an application of the aforementioned polymer-based conductive adhesive as an adhesive.

The invention also provides an adhesive, which comprises the aforementioned polymer-based conductive adhesive.

The present invention also provides an electronic component including the aforementioned polymer-based conductive adhesive.

In the present invention, the electronic component may be a conventional component of an electronic product, such as one or more of a CMOS camera module, a fingerprint module, a SIM card holder, a charging connector, and an antenna connector.

In the present invention, the full names corresponding to the abbreviations are as follows:

EAA: ethylene acrylic block copolymer; CoPP: random copolymer polypropylene resin;

EMA: ethylene methyl acrylate copolymer; EBA: ethylene n-butyl acrylic copolymer;

EH: ethylene hexene copolymer; POE: ethylene octene copolymer;

FVMQ: fluorosilicone elastomer resin; EVA: ethylene vinyl acetate copolymer;

SIS: styrene-isoprene-styrene block copolymer;

SEBS: styrene-ethylene-butene-styrene block copolymer;

SBS: styrene-butadiene block copolymer;

DCP: dicumyl peroxide;

DBPH: 2,5-dimethyl-2,5-bis (tert-butylperoxy) ethane;

BPO: benzoyl peroxide;

DTBP: di-tert-butyl peroxide;

DBHP: Dicumyl hydrogen peroxide;

LPO: dilauroyl peroxide;

TPB: tert-butyl perbenzoate;

CYHP: cyclohexanone peroxide;

IPP: diisopropyl peroxide;

EHP: bis (2-ethylhexyl) dicarbonate;

MEKP: methyl ethyl ketone peroxide;

KH560: γ- (2,3-glycidoxy) propyltrimethoxysilane;

KH550: γ-aminopropyltriethoxysilane;

GA: glutaric acid;

DIBK: diisobutyl ketone;

MIBK: methyl isobutyl ketone;

ANONE: cyclohexanone;

IPO: methylacetone;

EAC: ethyl acetate;

IBAC: isobutyl acetate.

On the basis of conforming to common knowledge in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain each preferred embodiment of the present invention.

The reagents and raw materials used in the present invention are all commercially available.

The positive progress effect of the present invention lies in:

(1) The adhesive strength of the polymer-based conductive adhesive prepared by the present invention is 8.5-16.2N / cm, and the bonding performance is good; the filling resistance (hole diameter 0.5mm) is 0.1-0.74 Ohm, the resistance is small, and the conductivity Good; there is no significant change in the filling resistance and bonding properties after reflow soldering, after 100 times of cold and hot shock at -45 ℃ -125 ℃, after 500 hours at 85 ℃ / 85% humidity (hole diameter 0.5 mm) No obvious change, good weather resistance. The polymer-based conductive adhesive prepared by the method has excellent comprehensive performance.

(2) The polymer-based conductive adhesive prepared by the present invention can be filled in pores of different shapes such as circular holes, square holes, rectangular holes, and star holes, and the filling resistance is small, which indicates that the polymer prepared by the invention Small conductive hole or special-shaped hole filling performance is excellent.

(3) The polymer-based conductive adhesive prepared by the present invention is cured and shaped at different temperatures, and its overall viscosity is kept at a low level and its fluidity is good.

(4) The polymer-based conductive adhesive prepared by the present invention can be stored at normal temperature.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing changes in elastic modulus and viscosity of a polymer-based conductive adhesive prepared in Example 1 with time at 70 ° C. FIG.

FIG. 2 is a graph showing changes in elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Example 1 with time at 160 ° C. FIG.

FIG. 3 is a graph showing changes in elastic modulus and viscosity over time after the polymer-based conductive adhesive prepared in Example 1 is cured at 160 ° C. for 3600 s and cooled to 70 ° C.

FIG. 4 is a graph showing changes in elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Examples 1, 40, and 41 over time at 160 ° C.

FIG. 5 is a graph showing changes in elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Examples 1, 40, and 41 after being cured at 160 ° C. to 70 ° C. and time.

FIG. 6 is a graph showing changes in elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Example 42 with time at 70 ° C. FIG.

FIG. 7 is a graph showing changes in elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Example 42 with time at 160 ° C. FIG.

FIG. 8 is a graph showing changes in elastic modulus and viscosity over time after the polymer-based conductive adhesive prepared in Example 42 is cured at 160 ° C. for 3600 s and cooled to 70 ° C. FIG.

FIG. 9 is a graph showing changes in elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Comparative Example 3 with time at 70 ° C. FIG.

FIG. 10 is a graph showing changes in elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Comparative Example 3 over time at 160 ° C.

FIG. 11 is a graph showing changes in elastic modulus and viscosity over time of the polymer-based conductive adhesive prepared in Comparative Example 3 after curing at 160 ° C. for 1800 s and cooling to 70 ° C. FIG.

FIG. 12 is a comparison diagram of changes in elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Example 1, Example 42, and Comparative Example 3 over time at 160 ° C.

detailed description

The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods without specific conditions specified in the following examples were selected according to conventional methods and conditions, or according to product specifications.

In the following embodiments:

EAA: ethylene acrylic acid block copolymer, Exxon Mobil Escor 5200, in which the content of acrylic acid is 15wt.%;

CoPP: random copolymer polypropylene resin, ExxonMobil Vistamaxx 6102, in which the ethylene content is 16wt.%;

EMA: ethylene methyl acrylate copolymer, Exxon Mobil Optema TC220 ExCo, in which the content of methyl acrylate is 24wt.%;

EBA: Ethylene n-butyl acrylic copolymer, ExxonMobil EnBA EN33331, in which the content of n-butyl acrylic acid is 32.5wt.%;

EH: Ethylenehexene copolymer, ExxonMobil Exact 3040, Ethylenehexene copolymer has a melt index of 17g / 10min;

POE: ethylene octene copolymer, Dow Chemical Engage 8400, ethylene octene copolymer melt index is 30g / 10min;

FVMQ: fluorosilicone elastomer resin, Dow Corning XIAMETER LS 4-9060;

DCP: Dicumyl peroxide, Sinopharm (Shanghai) International Medical and Health Co., Ltd .;

DBPH: 2,5-dimethyl-2,5-bis (tert-butylperoxy) ethane, Aladdin (China);

BPO: benzoyl peroxide, Aladdin (China);

KH560: γ- (2,3-glycidoxy) propyltrimethoxysilane, Aladdin (China);

KH550: γ-aminopropyltriethoxysilane, Aladdin (China);

GA: glutaric acid, Aladdin (China);

SS: fluorocarbon ion surfactant, Hongshun, 3500;

AS: Fumed Silica, Evonik, AEROSIL R972;

UA: Antistatic agent, Shandong Juli Antistatic Technology Co., Ltd., JI-WT4;

Hot melt adhesive-1: polyester resin, Toyobo, Vylon GA13011 (softening point 167 ° C);

Hot Melt Adhesive-2: Polyester resin, NICHIGO-POLYESTER, SP-176 (softening point: 130 ° C);

Hot melt adhesive-3: Polyurethane resin, Henkel, Macroplast QR5210 (softening point 105 ° C);

Hot melt adhesive-4: polyamide resin, Shanghai Yuanzhi hot melt adhesive, H1001G (softening point 110 ℃);

Hot melt adhesive-5: polyamide resin, Shanghai Tianyang hot melt adhesive, PA-6200 (softening point 110 ℃);

Hot melt adhesive-6: Ethylene vinyl acetate copolymer, Exxon Mobil Escorene Ultra LD 701.1D (softening point 91 ° C);

Hot melt adhesive-7: styrene-butadiene block copolymer, KRATON, D-1101B (softening point 90 ° C);

Hot melt adhesive-8: styrene-ethylene-butene-styrene block copolymer, Baling Petrochemical, YH-501 (softening point 140 ° C);

Hot melt adhesive-9: styrene-isoprene-styrene block copolymer, KRATON, D-1113B (softening point 94 ° C);

Conductive particles-1; silver-clad copper, CG-SAB-121 by Dowa Holdings Co., Ltd. (silver content is 11 wt.%);

Conductive particles-2: silver-clad copper, Ames Goldsmith Corp. FAC-610 (silver content is 10wt.%);

Conductive Particles-3: Carbon Nanotubes, Nanocyl S.A. (Belgium), NC7000.

In the following comparative examples:

FE: Viton, DuPont, Viton GBL600;

FE-1: Viton, Chemical Company, Viton GF 200S;

EAA1: ethylene acrylic acid copolymer, DuPont, Vamac DP;

PE: High-density polyethylene (HDPE), 2911, Fushun Ethylene Chemical Co., Ltd .;

TPSiV: thermoplastic vulcanizate, Dow Corning, TPSiV 3345-65A NAT 25564

PMMA: Semi-crosslinked polymethyl methacrylate particles, Heyo Enterprise (Taiwan Province, China), AC15-F;

Hot melt adhesive 10: ethylene vinyl acetate copolymer, Exxon Mobil, Escorene Ultra AD 2528 (softening point 73 ° C);

Hot Melt Adhesive 11: Copolyetherester Polymer, DuPont China, Hytrel 3078;

Silicon powder-crosslinked silicone rubber powder: Shenzhen Haiyang Powder Technology Co., Ltd., HY-610;

EP: epoxy resin, Jining Huakai resin, Hongchang E-128;

Curing agent: Jining Huakai resin, latent epoxy curing agent;

Accelerator: Jining Huakai resin, 2-ethyl-4-methylimidazole;

Defoaming agent: Jining Huakai resin, tributyl nitrate;

TAIC: crosslinker, triallyl isocyanurate, DuPont Diak 7;

Glymo: cross-linking agent, 3- (2,3-glycidoxy) propyltrimethoxysilane, Sinopharm (Shanghai) International Medicine and Health Co., Ltd .;

Conductive particles-4: silver-clad copper, South Korea Join M, TCSP0415 and TCFL0713 are mixed particles with a mass ratio of 3: 2.

In the following examples and the raw material formulations of the comparative example, the hot melt adhesive exists in the form of hot melt adhesive powder, and the hot melt adhesive is ground to a hot melt adhesive powder having a D _{50 of} less than 20 microns (using a conventional grinding method in the art). 300 mesh filter sieved).

Example 1

A polymer-based conductive adhesive prepared with good conductive properties, adhesive properties, and weather resistance, and which does not require low-temperature storage and has a strong ability to fill small holes or special-shaped holes before use, includes the following weight percentages of raw materials: EAA (12%), conductive particles-1 (70%), hot melt adhesive-1 (17.26%), DCP (0.24%), KH560 (0.5%).

Preparation of samples for performance testing:

(1) Preparation of polymer-based conductive adhesive

1. Add 7.2g of EAA and 14.4g of diisobutyl ketone (DIBK) to a beaker, mechanically stir for 2 hours under a water bath at 70 ° C. After the matrix is dissolved, stir for 3 hours at room temperature to obtain a homogeneous polymer. Solution.

2. Place the polymer solution obtained in step 1 in a plastic beaker, add 42 g of conductive particles-1 and 10.356 g of hot melt adhesive-1, and then add 0.144 g of cross-linking agent DCP and 0.3 g of coupling agent KH560.

3. The raw materials are mixed by a mixer. The mixing process is pre-mixing at 400 rpm for 30 seconds, mixing at 2000 rpm for 3 minutes, defoaming at 2200 rpm for 2 minutes, and mixing at 2000 rpm for 30 seconds. Finally, a uniformly mixed colloid is obtained.

4. Place the colloid in a three-roll mill, grind for 5 minutes, add a small amount of DIBK solvent while grinding, and collect the colloid after grinding to obtain a polymer-based conductive gel.

(2) Molding of polymer-based conductive adhesive

1. Apply the colloid on the release film with the amount of 450g / m ² with a thickness of about 60 μm. The nickel-plated steel sheet was placed on a colloidal film, and cured at 130 ° C and 0.6 MPa for 8 seconds, and the release film was peeled to obtain a sample.

2. Cover the holes with a specific size or shape (without special instructions in all the examples, circular holes with a diameter of 0.5mm in the electrical performance test, and strip-shaped holes with a width of 1cm in the adhesion performance test). The film adheres well to the copper foil.

3. Lay the colloid removed in the first step on the cover film in the second step, and super-cover the nickel-plated steel sheet over the holes, then press at 150 ° C, 4MPa for 5 minutes, and then place it in a 160 ° C oven. Cure for 1 hour.

The preparation of the polymer-based conductive adhesive in Example 2-43 and the molding operation of the polymer-based conductive adhesive are the same as in Example 1.

During the preparation of the polymer-based conductive adhesive, specific solvents or mixed solvents suitable for the polymer need to be selected for different polymer matrices in the embodiments, as shown in Table 1 below.

Table 1

编号Numbering	溶剂Solvent
实施例2Example 2	二异丁基酮(DIBK)Diisobutyl ketone (DIBK)
实施例3Example 3	甲基异丁基酮(MIBK)与二异丁基酮(DIBK)；两者质量比为5:5Methyl isobutyl ketone (MIBK) and diisobutyl ketone (DIBK); their mass ratio is 5: 5
实施例4Example 4	环己酮(ANONE)Cyclohexanone (ANONE)
实施例5Example 5	异甲基丙酮(IPO)Isomethylacetone (IPO)
实施例6Example 6	乙酸乙酯(EAC)Ethyl acetate (EAC)
实施例7Example 7	乙酸异丁酯(IBAC)Isobutyl acetate (IBAC)
实施例8-43Examples 8-43	MIBK与DIBK，两者质量比为5：5MIBK and DIBK with a mass ratio of 5: 5

The specific formulation of each embodiment is as follows.

Example 2

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (17%), conductive particles-1 (65%), hot melt adhesive-1 (17.26%), DCP (0.24%), KH560 (0.5%).

Example 3

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (7%), conductive particles-2 (75%), hot melt adhesive-2 (17.26%), DCP crosslinker (0.24%), KH560 (0.5%).

Example 4

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (8%), conductive particles-2 (80%), hot melt adhesive-2 (11.26%), DCP (0.24%), KH560 (0.5%).

Example 5

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (9%), conductive particles-2 (70%), hot-melt adhesive-3 (20.26%), DCP (0.24%), KH560 (0.5%).

Example 6

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (6%), EMA (6%), conductive particle-1 (35%), conductive particle-2 (35%), hot melt adhesive-3 (17.26%), DCP (0.24%), KH560 (0.5%) .

Example 7

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (6%), FVMQ (6%), conductive particles-1 (35%), conductive particles-2 (35%), hot melt adhesive-3 (17.26%), DCP (0.24%), KH560 (0.5%) .

Example 8

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (9.6%), FVMQ (2.4%), conductive particles-1 (70%), hot melt adhesive-4 (17.26%), DCP (0.24%), KH560 (0.5%).

Example 9

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (6%), EBA (6%), conductive particles-1 (70%), hot melt adhesive-4 (17.26%), DCP (0.24%), KH56 (0.5%).

Example 10

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (6%), EBA (6%), conductive particle-1 (69.5%), conductive particle-3 (0.5%), hot melt adhesive-5 (17.26%), DCP (0.24%), KH560 (0.5%) .

Example 11

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes, which includes the following weight percentages of raw materials: EBA (12%), conductive particles-1 (70%), hot melt adhesive-6 (17.26%), DCP (0.24%), KH560 (0.5%).

Example 12

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not require low-temperature storage and has a strong ability to fill small holes or special holes before use. It includes the following weight percentages of raw materials: EMA (12%), conductive particles-1 (70%), hot melt adhesive-7 (17.26%), DCP (0.24%), KH560 (0.5%).

Example 13

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not require low-temperature storage and has a strong ability to fill small holes or special holes before use. It includes the following weight percentages of raw materials: EMA (12%), conductive particles-1 (70%), hot melt adhesive-7 (17.26%), DCP (0.12%), DBPH (0.12%), KH560 (0.5%).

Example 14

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (6%), POE (6%), conductive particles-1 (70%), hot melt adhesive-8 (17.26%), DCP (0.08%), DBPH (0.16%), KH560 (0.5%).

Example 15

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (6%), EBA (6%), conductive particles-2 (70%), hot melt adhesive-9 (17.26%), DCP (0.16%), DBPH (0.08%), KH560 (0.5%).

Example 16

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (6%), EBA (6%), conductive particle-1 (34.8%), conductive particle-2 (34.8%), conductive particle-3 (0.4%), hot melt adhesive-9 (17.26%), DBPH ( 0.24%), KH560 (0.5%).

Example 17

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (5.6%), FVMQ (2.4%), EMA (4%) conductive particles-2 (70%), hot melt adhesive-9 (17.26%), DCP (0.24%), KH550 (0.5%).

Example 18

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (9.6%), FVMQ (2.4%), conductive particles-2 (70%), hot melt adhesive-9 (17.26%), DCP (0.24%), GA (0.5%).

Example 19

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not need to be stored at low temperature before use and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: FVMQ (12%), conductive particles-2 (70%), hot melt adhesive-1 (17.26%), DCP (0.24%), KH550 (0.5%).

Example 20

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: POE (12%), conductive particles-2 (70%), hot melt adhesive-1 (17.26%), DCP (0.24%), KH550 (0.5%).

Example 21

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not require low-temperature storage and has a strong ability to fill small holes or special holes before use. It includes the following weight percentages of raw materials: EH (12%), conductive particles-2 (70%), hot melt adhesive-1 (17.26%), DCP (0.24%), KH550 (0.5%).

Example 22

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes, which includes the following weight percentages of raw materials: CoPP (12%), conductive particles-2 (70%), hot melt adhesive-2 (17.26%), DCP (0.24%), KH550 (0.5%).

Example 23

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (6%), CoPP (6%), conductive particles-2 (70%), hot melt adhesive-1 (17.26%), DBPH (0.24%), KH550 (0.5%).

Example 24

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (9%), CoPP (3%), conductive particles-2 (70%), hot melt adhesive-1 (17.14%), DBPH (0.36%), KH550 (0.5%).

Example 25

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not require low-temperature storage and has a strong ability to fill small holes or special holes before use. It includes the following weight percentages of raw materials: EMA (6%), EH (6%), conductive particles-2 (70%), hot melt adhesive-2 (17.26%), DCP (0.24%), KH550 (0.5%).

Example 26

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not require low-temperature storage and has a strong ability to fill small holes or special holes before use. It includes the following weight percentages of raw materials: EMA (6%), EH (6%), conductive particles-2 (70%), hot melt adhesive-2 (17.26%), DCP (0.24%), KH560 (0.5%).

Example 27

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes, which includes the following weight percentages of raw materials: EBA (12%), conductive particles-2 (70%), hot melt adhesive-2 (17.26%), DCP (0.24%), KH560 (0.5%).

Example 28

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not require low-temperature storage and has a strong ability to fill small holes or special holes before use. It includes the following weight percentages of raw materials: EMA (6%), EBA (6%), conductive particles-2 (70%), hot melt adhesive-2 (17.26%), DCP (0.24%), KH560 (0.5%).

Example 29

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (4.47%), conductive particles-2 (60%), hot melt adhesive-2 (34.88%), DCP (0.15%), KH560 (0.5%).

Example 30

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (11.47%), conductive particles-2 (60%), hot melt adhesive-2 (27.79%), DCP (0.24%), KH560 (0.5%).

Example 31

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (14.47%), conductive particles-2 (70%), hot melt adhesive-2 (14.73%), DCP (0.3%), KH560 (0.5%).

Example 32

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (11.47%), conductive particles-2 (80%), hot melt adhesive-2 (7.79%), DCP (0.24%), KH560 (0.5%).

Example 33

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (16.5%), conductive particles-2 (79%), hot melt adhesive-2 (3%), DCP (1%), KH560 (0.5%).

Example 34

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (13%), conductive particles-2 (70%), hot melt adhesive-2 (16.2%), BPO (0.3%), KH550 (0.5%).

Example 35

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (10.4%), EMA (2.6%), conductive particles-2 (70%), hot melt adhesive-3 (16.2%), DBPH (0.3%), KH550 (0.5%).

Example 36

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (2.6%), EMA (10.4%), conductive particles-2 (70%), hot melt adhesive-3 (16.2%), DBPH (0.3%), KH550 (0.5%).

Example 37

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (9.1%), EMA (3.9%), conductive particles-2 (70%), hot melt adhesive-3 (16.2%), DBPH (0.3%), KH550 (0.5%).

Example 38

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (3.9%), EMA (9.1%), conductive particles-2 (70%), hot melt adhesive-3 (16.2%), DBPH (0.3%), KH550 (0.5%).

Example 39

A polymer-based conductive adhesive that has good conductivity, adhesion and weather resistance, and does not need to be stored at low temperature before use and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: FVMQ (13%), conductive particles-2 (70%), hot melt adhesive-3 (16.2%), DBPH (0.15%), DCP (0.15%), KH550 (0.5%).

Example 40

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (12%), conductive particles-1 (70%), hot melt adhesive-1 (17.38%), DCP (0.12%), KH560 (0.5%).

Example 41

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (12%), conductive particles-1 (70%), hot melt adhesive-1 (17.14%), DCP (0.36%), KH560 (0.5%).

Example 42

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (12%), conductive particles-1 (70%), hot melt adhesive-1 (17.38%), DBPH (0.12%), KH560 (0.5%).

Example 43

A polymer-based conductive adhesive that has good electrical conductivity, adhesive properties and weather resistance, and does not need to be stored at low temperature before use, and has a strong ability to fill small holes or special holes. It includes the following weight percentages of raw materials: EAA (7%), conductive particle-2 (75%), hot melt adhesive-2 (17.13%), DCP crosslinker (0.24%), KH560 (0.5%), SS (0.02%), AS (0.08%) , UA (0.03%).

Example 43 The preparation process of the polymer-based conductive adhesive is as follows:

(1) Mix AS, UA and Hot Melt Adhesive-2. Under this condition, grind the hot melt adhesive to a hot melt adhesive powder with a D _{50 of} less than 20 microns (obtained by sieving with a 300 mesh filter);

(2) The preparation of the polymer elastomer resin solution is the same as in Example 1;

(3) Place the polymer solution obtained in step (2) in a plastic beaker, add conductive particles-1 and the hot-melt adhesive powder obtained in step (1), and then add the cross-linking agent DCP and the coupling agent in this order. KH 560 and surfactant SS. The rest is the same as in Example 1.

The preparation and molding methods of the polymer-based conductive adhesive in the following Comparative Examples 1-2 and 5-11 are the same as in Example 1.

During the preparation of the polymer-based conductive adhesive, a specific solvent or a mixed solvent suitable for the polymer needs to be selected for different polymer matrices in each comparative example, as shown in Table 2 below.

Table 2

编号Numbering	溶剂Solvent
对比例1Comparative Example 1	二异丁基酮(DIBK)Diisobutyl ketone (DIBK)
对比例2Comparative Example 2	二异丁基酮(DIBK)Diisobutyl ketone (DIBK)
对比例5-7Comparative Examples 5-7	二异丁基酮(DIBK)Diisobutyl ketone (DIBK)
对比例8Comparative Example 8	二甲苯Xylene

Comparative Examples 7-11

Diisobutyl ketone (DIBK)

Preparation method of epoxy system conductive adhesive in Comparative Example 3:

1. Mix all the raw materials, including EP, conductive particles-2, KH550, curing agent, accelerator and defoaming agent through a blender. The mixing process is 400rpm pre-mixing for 30 seconds, 2000rpm mixing for 3 minutes, and 2200rpm defoaming for 2 minutes. Mix at 2000 rpm for 30 seconds. Finally, a uniformly mixed colloid is obtained.

2. Put the colloid in a three-roll mill and grind for 5 min. Collect the colloid after grinding to obtain the epoxy system conductive adhesive.

The method for preparing the conductive adhesive is the same as in Example 1.

The method for forming the conductive tape in Comparative Example 3 is the same as in Example 1.

The conductive tape in Comparative Example 4 is a commercially available product, and the performance test can be performed directly after processing according to the molding method in Example 1.

The specific formulation of each comparative example is as follows.

Comparative Example 1

In terms of weight percentage, the raw materials include: FE (4%), EAA (6%), conductive particles-4 (60%), hot melt adhesive-11 (14.82%), PMMA (14.82%), DBPH (0.08%) , DCP (0.12%), TAIC (0.15%), Glymo (0.01%).

Comparative Example 2

In terms of weight percentage, the raw materials include: FE (8%), EAA (2%), conductive particles-4 (60%), hot melt adhesive-11 (14.82%), PMMA (14.82%), DBPH (0.16%) , DCP (0.04%), TAIC (0.15%), Glymo (0.01%).

Comparative Example 3 (epoxy system)

In terms of weight percentage, the raw materials include: EP (20%), conductive particles-2 (70%), KH550 (0.5%), curing agent (9.26%), accelerator (0.2%), defoamer (0.04%) .

Comparative Example 4

Conductive tape, TATSUTA, CBF300 (Alibaba).

Comparative Example 5

In terms of weight percentage, the raw materials include: EAA (4%), conductive particles-2 (55%), hot melt adhesive-1 (40.2%), DBPH (0.15%), DCP (0.15%), KH550 (0.5%) .

Comparative Example 6

In terms of weight percentage, the raw materials include: EAA (28%), conductive particles-2 (60%), hot melt adhesive-1 (11.2%), DBPH (0.15%), DCP (0.15%), KH550 (0.5%) .

Comparative Example 7

In terms of weight percentage, the raw materials include: EAA (9.1%), EMA (3.9%), conductive particles-2 (70%), hot melt adhesive -10 (16.2%), DBPH (0.3%), KH550 (0.5%) .

Comparative Example 8

In terms of weight percentage, the raw materials include: PE (13%), conductive particles-2 (70%), hot melt adhesive-1 (16.2%), DBPH (0.3%), KH550 (0.5%).

Comparative Example 9

In terms of weight percentage, the raw materials include: TPSiV (13%), conductive particles-2 (70%), hot-melt adhesive-1 (16.2%), DBPH (0.3%), KH550 (0.5%).

Comparative Example 10

In terms of weight percent, the raw materials include: FE (14.45%), EAA (14.45%), conductive particles-2 (70%), DBPH (0.3%), DCP (0.3%), KH550 (0.5%).

Comparative Example 11

In terms of weight percentage, the raw materials include: FE (4%), EAA (6%), conductive particles-4 (60%), hot melt adhesive -11 (14.82%), silicon powder (14.82%), DBPH (0.08% ), DCP (0.12%), TAIC (0.15%), Glymo (0.01%).

Comparative Example 12

In terms of weight percentage, the raw materials include: FE (4%), EAA1 (6%), conductive particles-4 (60%), hot melt adhesive-11 (14.82%), PMMA (14.82%), DBPH (0.08%) , DCP (0.12%), TAIC (0.15%), Glymo (0.01%).

Comparative Example 13

In terms of weight percentage, the raw materials include: FE (8%), EAA1 (2%), conductive particles-4 (60%), hot melt adhesive-11 (14.82%), PMMA (14.82%), DBPH (0.16%) , DCP (0.04%), TAIC (0.15%), Glymo (0.01%).

Comparative Example 14

In terms of weight percentage, the raw materials include: FE (14.45%), EAA1 (14.45%), conductive particles-2 (70%), DBPH (0.3%), DCP (0.3%), KH550 (0.5%).

Comparative Example 15

In terms of weight percentage, the raw materials include: FE (4%), EAA1 (6%), conductive particles-4 (60%), hot melt adhesive-11 (14.82%), silicon powder (14.82%), DBPH (0.08% ), DCP (0.12%), TAIC (0.15%), Glymo (0.01%).

Comparative Example 16

In terms of weight percentage, the raw materials include: FE-1 (4%), EAA1 (6%), conductive particles-4 (60%), hot melt adhesive-11 (14.82%), PMMA (14.82%), DBPH (0.08 %), DCP (0.12%), TAIC (0.15%), Glymo (0.01%).

Effect Example 1

Take the formed polymer-based conductive adhesive prepared in Examples 1 to 43, and measure its bonding performance, hole resistance, hole resistance and reflow resistance after reflow, and hole resistance after 100 times of cold and heat shock. And the perforation resistance after 500 hours at 85 ° C / 85% humidity, and at the same time visually observe whether it has bubbles and delamination.

The specific test methods are as follows:

Adhesion performance test: The conductive adhesive prepared in each example was bonded between a nickel-plated steel sheet and a cover film, and the sample width was 1 cm. The cover film was peeled at a 90-degree angle with a stretcher. Stretching speed is 50mm / min. Stretching equipment: Instron 5567;

Filling resistance: after the gel formation and filling of the conductive paste prepared in each embodiment are completed, the filling resistance is measured at room temperature by using a two-point method, and the test instrument is Keithley 6487;

Cold and hot shock: tested according to JEDEC standard JESD22-A106B, from -45 ° C to 125 ° C, temperature conversion time 15 seconds, high and low temperature retention time 5 minutes each, 100 cycles. Test equipment: Dongguan Ruikai Environmental Testing Instrument Co., Ltd., R-TS-49 (A-D);

Damp heat aging test: aging for 500 hours at 85 ° C and 85% humidity, testing equipment: Dongguan Ruikai Environmental Testing Instrument Co., Ltd., R-PTH-100S;

Reflow soldering: 265 ° C, 10 seconds (3 times); 288 ° C, 10 seconds (3 times); Test equipment: Tin melting furnace, Baihe TXD-S060.

Specific data can be found in Table 3 below.

table 3

Effect Example 2

Take the molded polymer-based conductive adhesive prepared in Comparative Examples 1-3 and 5-16, and the molded polymer-based conductive adhesive prepared in the commercially available conductive tape in Comparative Example 4, and measure its adhesive properties. And filling resistance, filling resistance after reflow soldering and adhesive performance, filling resistance after 100 times of hot and cold shock, and filling resistance after 500 hours at 85 ° C / 85% humidity.

The test method is the same as effect Example 1.

Specific data can be found in Table 4 below.

Table 4

Effect Example 3

The polymer-based conductive adhesive prepared in Examples 1 and 18 and the commercially available conductive tape in Comparative Example 4 were taken. According to the molding method of Example 1, the filling holes of the conductive adhesives under different filling hole sizes and shapes were measured. resistance.

The test method is the same as effect Example 1.

Specific data can be found in Table 5 below.

table 5

Effect Example 4 Rheological Performance Detection

The conditions of the rheological test (including the test of elastic modulus and viscosity) in the embodiment of the effect are as follows:

Instrument: Malvern Rotary Rheometer (Gemini 200HR, Bohlin Instrument, UK)

Test temperature: 70 ℃, 160 ℃

Shearing frequency: 1Hz

Shear strain: 0.5%

The polymer-based conductive adhesives used for the rheological test in this example of effect are all polymer-based conductive adhesives that have not been processed.

(1) Rheological test of polymer-based conductive adhesive prepared in Example 1

The polymer-based conductive adhesive prepared in Example 1 was cured at 70 ° C, 160 ° C, and 160 ° C for 3600s and cooled down to 70 ° C to test the changes in elastic modulus and viscosity over time. See Figure 1-3. .

As can be seen from FIG. 1, the polymer-based conductive adhesive prepared in Example 1 had an initial viscosity of about 1.5 × 10 ⁴ Pa · s at 70 ° C., and the viscosity and elastic modulus of the system increased with the evaporation of the solvent. the trend of.

It can be seen from FIG. 2 that due to the increase in temperature, the initial viscosity of the polymer-based conductive adhesive is reduced to about 5 × 10 ² Pa · s compared to the condition of 70 ° C., which has better fluidity. And within 600s, the viscosity of the system remained low (less than 3 × 10 ³ Pa · s).

It can be seen from FIG. 2 and FIG. 3 that after the polymer-based conductive adhesive is cured for 3600 s, the viscosity of the system rises to about 8 × 10 ³ Pa · s. After cooling to 70 ° C, the colloid viscosity is about 8.5 × 10 ⁴ Pa · s, and the elastic modulus is about 5.3 × 10 ⁵ Pa.

(2) Rheological property test of polymer-based conductive adhesive prepared in Examples 1, 40, and 41

The polymer-based conductive adhesives prepared in Examples 1, 40, and 41 were respectively cured at 160 ° C and 160 ° C for 3600s and cooled to 70 ° C to test the changes in elastic modulus and viscosity over time. See Figure 4- 5.

FIG. 4 shows the polymer bases prepared by using DCP cross-linking agents in the weight percentage of the raw material composition of 0.12 wt% (Example 40), 0.24 wt% (Example 1), and 0.36 wt% (Example 41). The curing curve of the conductive adhesive at 160 ° C. According to Figure 4, it can be seen that the DCP crosslinker has little effect on the initial viscosity of the polymer-based conductive adhesive. The increase in the viscosity and elastic modulus of the polymer-based conductive adhesive prepared in Example 41 is particularly obvious. At 600s, the viscosity is about 4.4 × 10 ³ Pa · s (Example 40) and 3 × 10 ³ Pa · s. (Example 1) and 1.7 × 10 ⁴ Pa · s (Example 41).

FIG. 5 is a graph showing changes in elastic modulus and viscosity with time of the samples of the above embodiments after curing at 160 ° C for 3600s and cooling to 70 ° C. It can be seen from FIG. 5 that after curing for 3600 s, the viscosity of the system of Example 40 and Example 1 remained below 10 ⁵ Pa · s, while the viscosity of Example 41 increased to 1 × 10 ⁵ Pa · s. Three groups of conductive adhesives were cured at 160 ° C for 3600s and then cooled to 70 ° C. After 400-500s, the system viscosity was about 3.2 × 10 ⁴ Pa · s (Example 40) and 8.5 × 10 ⁴ Pa · s (Example 1). ) And 1.4 × 10 ⁵ Pa · s (Example 41), the elastic moduli were 1.4 × 10 ⁵ Pa, 5.3 × 10 ⁵ Pa, and 8.7 × 10 ⁵ Pa, respectively.

From the above discussion, it can be known that the DCP content has a great influence on the viscosity change of the conductive adhesive during and after curing, and it is more suitable when the DCP content is 0.24 wt%. If the content is too low, the elastic modulus of the colloid is low after curing, which may result in insufficient strength. If the content is too high, the viscosity of the colloid increases too much during the curing process, which may cause molding difficulties.

(3) Rheological property test of polymer-based conductive adhesive prepared in Example 42

The polymer-based conductive adhesive prepared in Example 42 was cured at 70 ° C, 160 ° C, and 160 ° C for 3600s and cooled down to 70 ° C to test the changes in elastic modulus and viscosity over time. See Figure 6-8 .

The curing agent used in Example 42 is DBPH. As can be seen from FIG. 6, the polymer-based conductive adhesive prepared in Example 42 has an initial viscosity of about 8.7 × 10 ³ Pa · s at 70 ° C. The volatilization, the viscosity and the elastic modulus of the system show an upward trend. The performance is similar to that of the conductive adhesive prepared in Example 1.

As can be seen from FIG. 7, due to the increase in temperature, the initial viscosity of the polymer-based conductive adhesive is lower than that at 70 ° C., which is about 4 × 10 ² Pa · s, and the viscosity of the system is maintained at 600 s. 3 × 10 ³ Pa · s or less, with good moldability. The performance is similar to that of the conductive adhesive prepared in Example 1.

As can be seen from FIG. 7 and FIG. 8, after the polymer-based conductive adhesive is cured for 3600 s, the viscosity of the system rises to 7.3 × 10 ³ Pa · s. When the temperature dropped to 70 ° C, the final colloid viscosity was 9 × 10 ⁴ Pa · s and the elastic modulus was 5.6 × 10 ⁵ Pa · s.

(4) Rheological test of polymer-based conductive adhesive prepared in Comparative Example 3

The polymer-based conductive adhesive prepared in Comparative Example 3 was cured at 70 ° C, 160 ° C, and 160 ° C for 1800s and cooled down to 70 ° C to test the changes in elastic modulus and viscosity over time. See Figure 9-11. .

Figure 9 shows the curve of the elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Comparative Example 3 over time at 70 ° C. Since there is no solvent in the system, the viscosity and There was almost no significant change in the elastic modulus, and the viscosity was maintained at about 10 ³ Pa · s. After lasting 10,000s, the viscosity and elastic modulus of the system began to increase significantly, indicating that the system would undergo a crosslinking reaction at 70 ° C.

FIG. 10 shows the curve of the elastic modulus and viscosity of the polymer-based conductive adhesive prepared in Comparative Example 3 over time at 160 ° C. As can be seen from FIG. 10, the polymer-based conductive adhesive prepared in Comparative Example 3 had almost no change in the colloid viscosity within 300 s, and remained at about 10 ² Pa · s. After 300 s, the cross-linking reaction occurred in the colloid, and the viscosity of the system increased sharply. At 600 s, the viscosity exceeded 3 × 10 ⁴ Pa · s, and at 1800 s, the viscosity reached 3.2 × 10 ⁵ Pa · s and there was still an upward trend.

FIG. 11 shows the curve of the elastic modulus and viscosity with time of the polymer-based conductive adhesive prepared in Comparative Example 3 which was cured at 160 ° C. for 1800 s and then cooled to 70 ° C. As shown in FIG. 11, after the temperature was lowered to 70 ° C. for 400 s, the viscosity and the elastic modulus were 6.2 × 10 ⁵ Pa · s and 3.9 × 10 ⁶ Pa, respectively.

(5) Comparison of the rheological properties of the polymer-based conductive adhesive prepared in Example 1, Example 42 and Comparative Example 3

Take the polymer-based conductive adhesives prepared in Example 1, Example 42, and Comparative Example 3 at 70 ° C and 160 ° C, respectively, to check the changes in the elastic modulus and viscosity with time. The curing tendency chart at 160 ° C can be seen in Figure 12 For specific data, see Table 6.

Table 6

It can be known from Figures 7 and 6 that the curing curves of Example 1 and Example 42 have the same trend and similar values. The elastic modulus and viscosity increase quickly and then flatten, and the overall viscosity remains at a low level within 600s The viscosity was maintained at 3 × 10 ³ Pa · s. In the curing process of Comparative Example 3, due to the high temperature, the initial viscosity of the conductive colloid is extremely low, which is not good for fixed molding; after about 300s, it rises sharply, and within 600s the viscosity rises to 3 × 10 ⁴ Pa · s, and the fluidity changes. Poor; the final viscosity is 1-2 orders of magnitude higher than the conductive adhesives of Examples 1, 42. It is generally believed that when the viscosity is higher than 9.5 × 10 ³ Pa · s, the flow of the conductive adhesive will be very slow, which is not conducive to the filling of small holes or special-shaped holes.

Although the specific embodiments of the present invention are described above, those skilled in the art should understand that these are merely examples, and that various changes or modifications may be made to these embodiments without departing from the principle and essence of the present invention. modify. Therefore, the protection scope of the present invention is defined by the appended claims.

Claims

A raw material composition for a polymer-based conductive adhesive, characterized in that it includes the following components: a polymer elastomer resin, conductive particles, and a hot-melt adhesive powder, the polymer elastomer resin and the hot-melt adhesive The mass ratio of the powder is (4-17): (3-35);

The polymer elastomer resin is a polymer elastomer resin crosslinked by a peroxide;

The softening point of the hot-melt adhesive in the hot-melt adhesive powder is ≥90 ° C.
The raw material composition for a polymer-based conductive adhesive according to claim 1, wherein the polymer elastomer resin is a polymer elastomer whose monomers include one or more of ethylene, acrylic acid, and siloxane. Resin; preferably ethylene acrylic block copolymer, random copolymer polypropylene resin, ethylene n-butyl acrylic copolymer, ethylene octene copolymer, ethylene methyl acrylate copolymer, fluorosilicone elastomer resin and ethylene hexene copolymer One or more of them; more preferably ethylene acrylic block copolymer, ethylene methyl acrylate copolymer, ethylene octene copolymer, ethylene hexene copolymer, random copolymer polypropylene resin, fluorosilicone rubber elastomer Resin, ethylene n-butyl acrylic copolymer, "ethylene acrylic block copolymer and ethylene methyl acrylate copolymer", "ethylene acrylic block copolymer and fluorosilicone elastomer resin", "ethylene acrylic block copolymer and "Ethylene n-butyl acrylic copolymer", "Ethylene acrylic block copolymer and ethylene octene copolymer", "Ethylene acrylic block copolymer and ethylene n-butyl copolymer" "Acrylic copolymer", "ethylene acrylic block copolymer, ethylene methyl acrylate copolymer and fluorosilicone elastomer resin", "ethylene acrylic block copolymer and random copolymer polypropylene resin", "ethylene methyl acrylate copolymer Polymer and ethylene hexene copolymer "," ethylene methyl acrylate copolymer and ethylene n-butyl acrylic copolymer ", or" ethylene acrylic block copolymer and ethylene methyl acrylate copolymer "; said ethylene acrylic block The acid value of the copolymer is preferably 37-225 mgKOH / g; the content of acrylic acid in the ethylene acrylic block copolymer is preferably 6-15%, more preferably 15%, and the percentage refers to acrylic acid in the ethylene acrylic block The weight percentage in the copolymer; the ethylene content in the random copolymerized polypropylene resin is preferably 9-16%, more preferably 16%, and the percentage refers to the weight percentage of ethylene in the random copolymerized polypropylene resin; The content of n-butyl acrylic acid in the ethylene n-butyl acrylic copolymer is preferably 30-35%, and more preferably 32.5%. The percentage means that n-butyl acrylic acid is in the ethylene n-butyl acrylic acid copolymer. Weight percentage in acrylic copolymer; the melt index of the ethylene octene copolymer is preferably 0.2-30g / 10min, more preferably 30g / 10min; the content of methyl acrylate in the ethylene methyl acrylate copolymer is preferably 18-24%, more preferably 24%, the percentage refers to the weight percentage of methyl acrylate in the ethylene methyl acrylate copolymer; the fluorosilicone rubber elastomer resin is preferably γ-trifluoropropylmethyl poly Siloxane; the melt index of the ethylene hexene copolymer is preferably 1.1-17g / 10min, more preferably 17g / 10min;

And / or, the weight percentage of the polymer elastomer resin in the raw material composition of the polymer-based conductive adhesive is 4-17%, preferably 4.47%, 7.00%, 8.00%, 9.00%, 11.47%, 12.00%, 13.00%, 14.47%, 16.50% or 17.00%.
The raw material composition for a polymer-based conductive adhesive according to claim 1 or 2, wherein the softening point of the hot-melt adhesive is 90-250 ° C, and more preferably a polyamide resin, a polyester resin, and ethylene acetic acid. Among vinyl ester copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butene-styrene block copolymers, styrene-butadiene block copolymers, and polyurethane resins One or more, most preferably polyamide resin, polyester resin, ethylene vinyl acetate copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butene-styrene copolymer Block copolymer, styrene-butadiene block copolymer or polyurethane resin;

And / or, the hot-melt adhesive powder is a powder with a D 50 of less than 30 microns, preferably a powder with a D 50 of less than 20 microns, and more preferably a powder with a D 50 of less than 10 microns;

And / or, the mass ratio of the polymer elastomer resin to the hot-melt adhesive powder is (4.47: 34.88)-(16.5: 3); preferably, the hot-melt adhesive powder is conductive on the polymer base The weight percentage in the raw material composition of the gum is 3 to 35%, and further preferably 3.00%, 7.79%, 11.26%, 14.73%, 16.20%, 17.13%, 17.14%, 17.26%, 17.38%, 20.26%, 27.79% Or 34.88%;

And / or, the conductive particles are one or more of metal particles, non-metal particles and particles coated with a metal layer on the surface; the metal particles are preferably gold, silver, copper, aluminum, tin, zinc, titanium One or more of bismuth, bismuth, tungsten, and lead; the non-metal particles are preferably carbon nanotubes and / or graphene; among the particles coated with a metal layer on the surface, The metal is preferably one or more of gold, silver, and nickel; the surface-coated metal layer particles are preferably silver-coated copper particles, silver-coated glass particles, silver-coated polystyrene particles, and nickel-coated copper particles. One or more, more preferably silver-clad copper particles; the silver content in the silver-coated copper particles is preferably 10-15 wt.%, Where wt.% Refers to the weight percentage of the silver content in the particles of the surface-coated metal layer;

And / or, the weight ratio of the polymer elastomer resin to the conductive particles is (4-17): (40-85), preferably 12.00: 70.00, 17.00: 65.00, 7.00: 75.00, 8.00: 80.00, 9.00: 70.00, 4.47: 60.00, 11.47: 60.00, 14.47: 70.00, 11.47: 80.00, 16.50: 79.00, or 13.00: 70.00; more preferably, the conductive particles in the raw material composition of the polymer-based conductive adhesive The weight percentage is 40-85%, more preferably 50% -80%, and most preferably 60%, 65%, 70%, 75%, 79%, or 80%.
The raw material composition for a polymer-based conductive adhesive according to at least one of claims 1-3, wherein the raw material composition for the polymer-based conductive adhesive further comprises a cross-linking agent, a coupling agent, and a surface One or more of an active agent, an inorganic filler, and an antistatic agent;

The cross-linking agent is preferably dicumyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) ethane, benzoyl peroxide, di-tert-butyl peroxide , Dicumyl hydrogen peroxide, dilauroyl peroxide, tert-butyl perbenzoate, cyclohexanone peroxide, diisopropyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate And one or more of methyl ethyl ketone peroxide, more preferably dicumyl peroxide, benzoyl peroxide, dicumyl peroxide, or "dicumyl peroxide and hydrogen peroxide di Cumene ";

Preferably, the weight ratio of the polymer elastomer resin and the crosslinking agent is (4-17): (0.16-1), more preferably 4.47: 0.15, 7.00: 0.24, 8.00: 0.24, 9.00: 0.24 11.47: 0.24, 12.00: 0.24, 13.00: 0.24, 13.00: 0.30, 17.00: 0.24, 16.50: 1.00, 13.00: 0.30, 14.47: 0.30, 12.00: 0.12, 12.00: 0.36, or 13.00: 0.36; further preferably, all The weight percentage of the crosslinking agent in the polymer-based conductive adhesive raw material composition is 0.12-1.0%, and most preferably 0.12%, 0.15%, 0.24%, 0.30%, 0.36%, or 1.0%;

The coupling agent is preferably one or more of γ- (2,3-glycidoxy) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, and glutaric acid, and more preferably KH560, KH550 or GA;

Preferably, the weight ratio of the polymer elastomer resin and the coupling agent is (4-17): (0.16-1), more preferably 4.47: 0.50, 7.00: 0.50, 8.00: 0.50, 9.00: 0.50 11.47: 0.50, 13.00: 0.50, 12.00: 0.50, 14.47: 0.50, 16.50: 0.50, or 17.00: 0.50; further preferably, the weight percentage of the coupling agent in the raw material composition of the polymer-based conductive adhesive 0.50%;

The surfactant is preferably a cationic surfactant, more preferably an amine salt type cationic surfactant and / or a quaternary ammonium salt type cationic surfactant; the lipophilic group of the cationic surfactant is preferably 10 to 10 carbons. An alkyl chain of carbon 18; the anionic group of the cationic surfactant is preferably bromine, iodine or chlorine; the surfactant is preferably a fluorocarbon surfactant;

Preferably, the weight ratio of the polymer elastomer resin and the surfactant is (4-17): (0.01-0.05); more preferably, the surfactant is in the polymer-based conductive adhesive. The weight percentage in the raw material composition is 0.01-0.05%;

The inorganic filler is preferably fumed silica, and the particle diameter of the fumed silica is preferably 7-200 nm;

Preferably, the weight ratio of the polymer elastomer resin and the inorganic filler is (4-17): (0.05-0.15); more preferably, the inorganic filler is in a raw material combination of the polymer-based conductive adhesive. The weight percentage in the content is 0.05-0.15%;

The antistatic agent is preferably a cationic antistatic agent, an anionic antistatic agent, and a nonionic antistatic agent;

Preferably, the weight ratio of the polymer elastomer resin and the antistatic agent is (4-17): (0.01-0.05), and more preferably, the inorganic filler is a raw material of the polymer-based conductive adhesive. The weight percentage in the composition is 0.01-0.05%.
The raw material composition of a polymer-based conductive adhesive according to claim 1, wherein the polymer elastomer resin is 4.47-17% EAA, 12-13% FVMQ, 12% POE , 12% EH, 12% CoPP, 12.00% EBA, 12.00% EMA, "6.00% EAA and 6% EMA", "6.00% EAA and 6% FVMQ", "9.60% EAA and 2.40% FVMQ", "6.00% EAA and 6% EBA "," 6.00% EAA and 6% POE "," 9.00% EAA and 3% CoPP "," 6.00% EMA and 6% EH "," 6.00% EMA and 6% EBA "," 6.00% EAA and 6.00% CoPP "," 10.40% EAA and 2.60% EMA "," 2.60% EAA and 10.40% EMA "," 9.10% EAA and 3.90% EMA "," 3.90% EAA and 9.10% EMA ", or," 5.60% EAA, 2.40% FVMQ and 4.00% EMA ", the percentage refers to the weight percentage in the raw material composition of the polymer-based conductive adhesive;

And / or, the hot melt adhesive is 3.00-34.88% polyester resin, 16.20-20.26% polyurethane resin, 17.26% polyamide resin, 17.26% ethylene vinyl acetate copolymer, 17.26% styrene-butadiene block Copolymer, 17.26% styrene-ethylene-butene-styrene block copolymer or 17.26% styrene-isoprene-styrene block copolymer;

And / or, the conductive particles are 65.00-70.00% silver-clad copper particles with a silver content of 11wt.%, 60.00-80.00% silver content 10wt.% Silver-clad copper particles, and "35.00% silver content 11wt.% Silver-clad Copper particles and silver-clad copper particles with 35.00% silver content of 10 wt.% ", Silver-clad copper particles with 69.50% silver content of 11 wt.% And 0.50% carbon nanotubes, or silver-clad copper with 34.80% silver content of 11 wt.% Particles, 34.80% silver-coated copper particles with 10wt.% Silver content and 0.40% carbon nanotubes. "
The raw material composition of a polymer-based conductive adhesive according to claim 1, wherein the polymer elastomer resin and the hot-melt adhesive powder are: “12.00% EAA and 17.26% Polyester resin "," 17.00% EAA and 17.26% polyester resin "," 7.00% EAA and 17.26% polyester resin "," 8.00% EAA and 11.26% polyester resin "," 9.00% EAA and 20.26% polyurethane resin " "," 6.00% EAA, 6% EMA, and 17.26% polyurethane resin "," 6.00% EAA, 6% FVMQ, and 17.26% polyurethane resin "," 9.60% EAA, 2.40% FVMQ, and 17.26% polyamide resin "," 6.00 % EAA, 6% EBA and 17.26% polyamide resin "," 6.00% EAA, 6% EBA and 17.26% polyamide resin "," 12.00% EVA and 17.26% ethylene vinyl acetate copolymer "," 12.00% EBA and 17.26% ethylene vinyl acetate copolymer "," 12.00% EMA and 17.26% styrene-butadiene block copolymer "," 6.00% EAA, 6% POE, and 17.26% styrene-ethylene-butene-styrene Block copolymer "," 6.00% EAA, 6% EBA, and 17.26% styrene-isoprene-styrene Segment copolymer "," 5.60% EAA, 2.40% FVMQ, 4.00% EMA, and 17.26% styrene-isoprene-styrene block copolymer "," 9.60% EAA, 2.40% FVMQ, and 17.26% styrene -Isoprene-styrene block copolymer "," 12% FVMQ and 17.26% polyester resin "," 12% POE and 17.26% polyester resin "," 12% EH and 17.26% polyester resin ", "12% CoPP and 17.26% polyester resin", "6.00% EAA, 6.00% CoPP, and 17.26% polyester resin", "9.00% EAA, 3% CoPP and 17.14% polyester resin", "6.00% EMA, 6% EH and 17.26% polyester resin "," 6.00% EMA, 6% EH and 17.26% polyester resin "," 12.00% EBA and 17.26% polyester resin "," 6.00% EMA, 6% EBA and 17.26% "Polyester resin", "4.47% EAA and 34.88% polyester resin", "11.47% EAA and 27.79% polyester resin", "14.47% EAA and 14.73% polyester resin", "11.47% EAA and 7.79% polyester Resin "," 16.50% EAA and 3.00% polyester resin "," 13.00% EAA and 16.20% polyester resin "," 10.40% EAA, 2.60% EMA, and 16.20% polyurethane resin " "2.60% EAA, 10.40% EMA, and 16.20% polyurethane resin", "9.10% EAA, 3.90% EMA, and 16.20% polyurethane resin", "3.90% EAA, 9.10% EMA, and 16.20% polyurethane resin", "13% FVMQ and 16.20% polyurethane resin "," 12.00% EAA and 17.38% polyester resin "," 12.00% EAA and 17.14% polyester resin "," 12.00% EAA and 17.38% polyester resin ", or" 12.00% EAA and 17.13 " "% Polyester resin", the percentage means the weight percentage in the raw material composition of the polymer-based conductive adhesive;

And / or, when the raw material composition of the polymer-based conductive adhesive includes a cross-linking agent and a coupling agent, the raw material composition of the polymer-based conductive adhesive includes the following weight percentage components: polymer elastomer Resin 4-17%, silver-clad copper powder 50-85%, hot-melt adhesive powder 3-35%, cross-linking agent 0.16--1%, coupling agent 0.3-7%, the percentage is in the raw material composition Weight percentage

And / or, when the raw material composition of the polymer-based conductive adhesive includes a cross-linking agent, a coupling agent, a surfactant, an inorganic filler, and an antistatic agent, the raw material composition of the polymer-based conductive adhesive includes the following The weight percentage of the components: polymer elastomer resin 4-17%, conductive particles 50-85%, hot melt adhesive powder 3-35%, cross-linking agent 0.16--1%, coupling agent 0.3-7%, surface The active agent is 0.01-0.05%, the inorganic filler is 0.05-0.15%, and the antistatic agent is 0.01-0.05%. The percentage is the weight percentage in the raw material composition.
A method for preparing a polymer-based conductive adhesive by using the raw material composition of a polymer-based conductive adhesive according to any one of claims 1-6, characterized in that, in the presence of the crosslinking agent, The polymer elastomer resin, the conductive particles, and the hot-melt adhesive powder can be ground and blended.

Preferably, the grinding and blending process includes the following steps:

(1) A polymer elastomer resin solution, conductive particles and hot melt adhesive powder are mixed for the first time to obtain mixture A; the polymer elastomer resin solution is obtained by mixing a polymer elastomer resin and a solvent;

(2) mixing the cross-linking agent and the mixture A described in step (1) a second time to obtain a mixture B, which can be ground;

When a coupling agent is further included in the raw material composition, the cross-linking agent, the coupling agent, and the mixture A in step (1) are mixed for a second time to obtain a mixture C;

When the raw material composition further includes an inorganic filler and / or an antistatic agent, during the preparation of the hot-melt adhesive powder, "the inorganic filler and / or the antistatic agent" and the heat The melt powder is mixed to obtain mixture A ′; and the polymer elastomer resin solution and the conductive particles are mixed to obtain mixture A through the first mixing;

In step (1), the solvent is preferably one or more of diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, isomethylacetone, ethyl acetate, and isobutyl acetate, and more Preferably it is diisobutyl ketone, cyclohexanone, isomethylacetone, ethyl acetate, isobutyl acetate, or "methyl isobutyl ketone and diisobutyl ketone"; said "methyl isobutyl ketone" "Base ketone and diisobutyl ketone", the mass ratio of methyl isobutyl ketone to diisobutyl ketone is preferably 5: 5; the mass ratio of the polymer elastomer resin to the solvent is preferably 1: 2;

In step (1), the temperature at which the polymer elastomer resin and the solvent are mixed is preferably 40-80 ° C, the temperature of the water bath; the time at which the polymer elastomer resin and the solvent are mixed is preferably 2 h; preferably, in the polymerization After the physical elastomer resin is dissolved in the solvent, it is stirred at room temperature to obtain a polymer elastomer resin solution, and the stirring time is preferably 3 hours;

Step (2), preferably, the "second mixing" may include steps of pre-mixing, mixing, defoaming, and re-mixing; the rotation speed of the pre-mixing in the "second mixing" is preferably 350-450 rmp ; The pre-mixing time in the "second mixing" is preferably 15-45 seconds; the rotation speed of the mixing in the "second mixing" is preferably 1800-2200 rmp; in the "second mixing" The mixing time is preferably 1-3 minutes; the speed of defoaming in the "second mixing" is preferably 2000-2500rmp; the time of defoaming in the "second mixing" is preferably 1-3 Minutes; the re-mixing speed in the "second mixing" is preferably 1800-2200 rmp; the re-mixing time in the "second mixing" is preferably 15-45 seconds; in step (2), it is preferably Ground, the mixture B or the mixture C is ground in a grinder; the grinder is preferably a three-roll grinder; the grinding time is preferably 4-6 minutes.
A polymer-based conductive adhesive prepared by the preparation method of claim 7.
The use of a polymer-based conductive adhesive according to claim 8 as an adhesive.
An electronic component comprising the polymer-based conductive paste according to claim 8.