CN120173542B - Conductive adhesive and preparation method thereof - Google Patents
Conductive adhesive and preparation method thereofInfo
- Publication number
- CN120173542B CN120173542B CN202510611957.8A CN202510611957A CN120173542B CN 120173542 B CN120173542 B CN 120173542B CN 202510611957 A CN202510611957 A CN 202510611957A CN 120173542 B CN120173542 B CN 120173542B
- Authority
- CN
- China
- Prior art keywords
- silver powder
- conductive adhesive
- resin
- parts
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a low-temperature conductive adhesive, which comprises, by weight, 70-80 parts of silver powder, 20-30 parts of a resin matrix, 1-10 parts of a curing agent, 0.1-0.5 part of a silane coupling agent, 0.1-0.5 part of a stabilizer and 0.1-0.5 part of a metal salt. The organic metal salt is introduced into the resin matrix, so that the contact resistance of the colloid can be reduced, and the lower contact resistance increasing rate is maintained after the wet heat aging. The invention adopts the combination of the epoxy resin, the acrylic ester and the modified epoxy acrylic resin, and the weight of the epoxy resin and the acrylic ester is less than or equal to the weight of the modified epoxy acrylic resin, so that the low-temperature curing can be realized. The invention can realize curing at 60-80 ℃ for 20-40min, the breaking elongation of the obtained conductive adhesive can reach more than 8%, and the conductive adhesive has relatively stable and relatively small contact resistance before and after humid heat aging, and is particularly suitable for the electronic field with relatively high requirements on the contact resistance.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a low-temperature conductive adhesive and a preparation method thereof.
Background
With the development of science and technology, the application of electronic chips is more and more extensive, the colloid applied to the electronic chips needs to have higher conductivity, and with the wide application of the electronic chips, the use in a high-temperature and high-humidity environment puts higher requirements on the ageing performance and the conductivity of the electronic colloid. The existing conductive adhesive has larger contact resistance and greatly increases the resistivity after being aged by damp and heat, so that development of the conductive adhesive with good conductivity and humidity and heat aging resistance is important.
Chinese patent No. CN104356970a discloses a high-conductivity uv-curable conductive adhesive, which fills the gaps between the flake nano silver powder with a small amount of spherical nano silver powder, so that adjacent flake nano silver powder which is not contacted originally contacts each other, thereby increasing the conductive path, reducing the volume resistivity of the conductive adhesive system, but gaps still exist in the adhesive, and the resistivity is higher. The Chinese patent No. 119505176A discloses a modified epoxy acrylate, a preparation method thereof, a conductive adhesive, a preparation method thereof and application thereof, wherein the adopted modified epoxy acrylate has a long-chain structure, so that the cured modified epoxy acrylate can have excellent flexibility, and the prepared conductive adhesive has excellent properties such as low-temperature curing, flexibility, moist heat resistance, high adhesive force, good conductive performance, low stress and the like, but the temperature and the humidity of the moist heat resistance still cannot meet the requirements.
Disclosure of Invention
In order to develop the conductive adhesive with good conductivity and humidity and heat aging resistance, the first aspect of the invention provides a low-temperature conductive adhesive, which comprises, by weight, 70-80 parts of silver powder, 20-30 parts of a resin matrix, 1-10 parts of a curing agent, 0.1-0.5 part of a silane coupling agent, 0.1-0.5 part of a stabilizer and 0.1-0.5 part of a metal salt, wherein the metal salt is an organic metal salt.
As one embodiment, the resin matrix comprises modified epoxy acrylic resin, acrylic ester and epoxy resin, wherein the weight of the acrylic ester and the epoxy resin is less than or equal to the weight of the modified epoxy acrylic resin.
The inventor finds that the combination of the epoxy resin, the acrylic ester and the modified epoxy acrylic resin is adopted in the experimental process, the weight of the epoxy resin and the acrylic ester is less than or equal to the weight of the modified epoxy acrylic resin, the low-temperature conductive adhesive can be obtained, the low-temperature curing can be realized, the stable and smaller contact resistance exists before and after the wet heat aging, and the possible reasons are that the grafting of the epoxy resin and the acrylic ester can be realized in the preferable weight ratio, the formed colloid crosslinked network has the lower contact resistance, the epoxy resin exceeds the preferable weight ratio, the contact resistance increases and the conductivity decreases after the wet heat aging.
As one embodiment, the silver powder includes plate-like silver powder having a D50 particle diameter of 1 to 10 μm and spherical silver powder having a D50 particle diameter of 500 to 900nm.
As one embodiment, the D50 particle size of the spherical silver powder is 800nm.
As one embodiment, the plate-like silver powder comprises a plate-like silver powder I having a D50 particle diameter of 5 to 10 μm and a plate-like silver powder II having a D50 particle diameter of 1 to 3. Mu.m.
As one embodiment, the silver powder is a combination of plate-like silver powder I having a D50 particle diameter of 5 to 10 μm, plate-like silver powder II having a D50 particle diameter of 1 to 3 μm and spherical silver powder having a D50 particle diameter of 800 nm.
As one embodiment, the weight ratio of the plate-like silver powder I with the D50 particle size of 5-10 μm, the plate-like silver powder II with the D50 particle size of 1-3 μm and the spherical silver powder with the D50 particle size of 800nm is (60-70): (5-15): (1-10).
As one embodiment, the weight ratio of the plate-like silver powder I with the D50 particle size of 5-10 μm, the plate-like silver powder II with the D50 particle size of 1-3 μm and the spherical silver powder with the D50 particle size of 800nm is 65:10:5.
The application adopts the flaky silver powder with the D50 particle size of 5-10 mu m, the silver micro powder with the D50 particle size of 1-3 mu m and the spherical silver powder with the D50 particle size of 800nm, so that the conductivity of the low-temperature conductive adhesive can be further improved, the flaky silver powder is overlapped with the spherical silver powder, the contact resistance of the low-temperature conductive adhesive can be reduced, and the small-particle-size silver micro powder is added, so that the gap between the flaky silver powder and the spherical silver powder can be filled, the resistance increase caused by air pores is reduced, and the conductive effect is further improved.
As one embodiment, the organic metal salt includes at least one of potassium acrylate, zinc acrylate, calcium acrylate, potassium (meth) acrylate, zinc (meth) acrylate, or calcium (meth) acrylate.
As one embodiment, the organometallic salt has a functionality of 2.
The inventor finds that the organic metal salt is introduced into the resin matrix in the experimental process, so that the contact resistance of the colloid can be reduced, and the lower contact resistance increasing rate is maintained after the wet heat aging, probably because the organic metal salt and the resin matrix can generate a coupling effect, and the organic molecular structure can chemically react with the resin matrix, so that the stability of the structure is maintained on the basis of reducing the contact resistance, the contact resistance is not easy to degrade under the wet heat aging condition, and the contact resistance cannot be changed greatly.
As one embodiment, the silane coupling agent is an amine group-containing silane coupling agent including at least one of gamma-glycidoxypropyl trimethoxysilane, a secondary amino silane coupling agent, ureidopropyl trimethoxysilane, bis (gamma-trimethoxysilylpropyl) amine, or N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane.
As one embodiment, the amine group-containing silane coupling agent is gamma-glycidoxypropyl trimethoxysilane.
As one embodiment, the type of the amino-containing silane coupling agent comprises at least one of Michaels Y-9669, A-Link 15, A-1524 CF, A-1120J or A-1170.
As one embodiment, the curing agent includes at least one of a modified amine curing agent, a thiol, or a modified imidazole.
As one embodiment, the curing agent is a modified amine curing agent.
As one embodiment, the modified amine curing agent is a polyester latent curing agent.
As one embodiment, the stabilizer is an acidic stabilizer comprising at least one of salicylic acid, barbituric acid, or boric acid.
As one embodiment, the stabilizer is barbituric acid.
The invention adopts the silane coupling agent containing amino and the polyester latent curing agent, can cure colloid at low temperature, adopts the silane coupling agent containing amino and the polyester latent curing agent to be combined for use, can optimize the reactivity of the curing agent, ensures that metal salts and resin matrixes can react and cure at lower temperature, ensures that the elongation at break of the product can reach more than 8 percent, and has smaller change of mechanical properties after humid heat aging. The invention can be cured at 60-80 ℃ and is applied to electronic products, thereby avoiding the influence of high-temperature curing environment on the internal quality of the electronic products.
As one embodiment, the modified epoxy acrylic resin includes at least one of an aliphatic polyurethane modified epoxy acrylic resin, a polyester modified epoxy acrylic resin, a polybutadiene grafted epoxy acrylic resin, or a silicone modified epoxy acrylic resin.
As one embodiment, the acrylic acid ester includes at least one of isobornyl (meth) acrylate, acryloylmorpholine, 1, 6-hexanediol diacrylate or ethoxylated bisphenol a dimethacrylate.
As one embodiment, the epoxy resin is a polyether modified epoxy resin, and the type of the epoxy resin comprises at least one of Ai Dike EP-4040L, EPR-4030, EP-49-10P2 or Shanghai Hua Yi EBA-30D.
The second aspect of the invention provides a preparation method of a low-temperature conductive adhesive, comprising the following steps:
s1, mixing and stirring a resin matrix and a stabilizer uniformly;
s2, adding a curing agent, mixing and stirring the silane coupling agent and the metal salt uniformly, and grinding;
and S3, adding silver powder after grinding, and uniformly mixing and stirring to obtain the low-temperature conductive adhesive.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the low-temperature conductive adhesive, the organic metal salt is introduced into the resin matrix, so that the contact resistance of the adhesive can be reduced, and a lower contact resistance increasing rate is maintained after the adhesive is subjected to wet heat aging.
(2) The low-temperature conductive adhesive disclosed by the invention adopts the combination of the epoxy resin, the acrylic ester and the modified epoxy acrylic resin, the weight sum of the epoxy resin and the acrylic ester is less than or equal to the weight of the modified epoxy acrylic resin, the low-temperature conductive adhesive can be obtained, the low-temperature curing can be realized, and the low-temperature conductive adhesive has stable and smaller contact resistance before and after humid heat aging.
(3) The low-temperature conductive adhesive adopts the flaky silver powder with the D50 particle size of 5-10 mu m, the silver micro powder with the D50 particle size of 1-3 mu m and the spherical silver powder with the D50 particle size of 800nm, so that the conductivity of the low-temperature conductive adhesive can be further improved.
(4) The low-temperature conductive adhesive adopts the silane coupling agent containing amino groups and the polyester latent curing agent, so that the adhesive can be cured at low temperature, is applied to electronic products, and can avoid the influence of high-temperature curing environment on the internal quality of the electronic products.
(5) The low-temperature conductive adhesive can be cured at 60-80 ℃ for 20-40min, the breaking elongation of the obtained conductive adhesive can reach more than 8%, the conductive adhesive has relatively stable and relatively small contact resistance before and after humid heat aging, and the bonding surface can cover the size of (0.1 multiplied by 0.1 mm) - (20 multiplied by 20 mm), so that the conductive adhesive is particularly suitable for the electronic field with relatively high requirements on the contact resistance.
Detailed Description
The low-temperature conductive adhesive is prepared from silver powder, a resin matrix, a curing agent, a silane coupling agent, a stabilizer and metal salt. The specific amounts added in parts by weight for examples 1-6 are shown in Table 1. The specific amounts of comparative examples 1 to 6 are shown in Table 2.
TABLE 1
TABLE 2
The flake silver powder I is purchased from Kunming Norman electronics and has the brand name of APS-05F;
The flake silver powder II is purchased from metalor with the brand of C0083P;
The spherical silver powder is purchased from Kunming Norman electronics and has the brand name of APS-0140H;
the modified epoxy acrylic resins of examples 1-3, comparative examples 1-6 were purchased from satomate under the designation SR2003;
the modified epoxy acrylic resins of examples 4-6 were purchased from Changxing under the designation 6235;
the epoxy resins of examples 1-3, comparative examples 1-6 were purchased from Shanghai Hua Yi under the trade designation EBA-30D;
the epoxy resins of examples 4-6 are available from Ai Dike under the trade designation EP-4040L;
The acrylic ester is purchased from Sadama with the trademark SR238;
the curing agent is purchased from Ai Dike with the trade mark of EH-5057PK;
The silane coupling agents of examples 1-3, comparative examples 1-6 were purchased from Michaels, under the designation Y-9669;
the silane coupling agents of examples 4-6 were purchased from Michaels, under the designation A-Link 15;
The metal salts of examples 1-3, comparative examples 1-6 were purchased from gram Lei Weili under the trade designation Dymalink633;
The metal salts of examples 4-6 were purchased from gram Lei Weili under the trade designation Dymalink 708.
The preparation method of the low-temperature conductive adhesive comprises the following steps:
s1, mixing and stirring a resin matrix and a stabilizer uniformly;
s2, adding a curing agent, mixing and stirring the silane coupling agent and the metal salt uniformly, and grinding to obtain a particle size of less than 5 mu m;
and S3, adding silver powder after grinding, and uniformly mixing and stirring to obtain the low-temperature conductive adhesive.
Performance testing
1. Elongation at break the low temperature conductive adhesives prepared in examples and comparative examples were prepared into 4 dumbbell-shaped samples, which were tested in a 25 ℃ environment using an electronic universal tester, with reference to GBT1040 standard.
2. The contact resistance is that the surface spacing of the ITO conductive glass is 20mm, the glue dripping diameter is 1.5mm, the surface of the ITO conductive glass is an indium tin oxide coating, the thickness of the coating is 50 mu m, the temperature is 60 ℃, the resistance is measured after 40min curing and is marked as R 1, the resistance is measured after 500h, and the resistance is marked as R 2.
Resistance increase rate= (R 2-R1）/R1 ×100%.
The test results are shown in Table 3.
TABLE 3 Table 3
In comparison with comparative examples 4 to 6, comparative examples 4 to 6 of the present invention were larger in contact resistance without adding a metal salt and poor in conductivity.
In the invention, compared with the comparative examples 1-3, the weight sum of the epoxy resin and the acrylic ester in the comparative examples 1-3 is larger than that of the modified epoxy propylene resin, the electric properties before and after the wet heat aging are greatly different, the electric properties rise from 11.3 omega to 13.5 omega, and the elongation at break is reduced from 9.3% to 6.2%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202510611957.8A CN120173542B (en) | 2025-05-13 | 2025-05-13 | Conductive adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202510611957.8A CN120173542B (en) | 2025-05-13 | 2025-05-13 | Conductive adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN120173542A CN120173542A (en) | 2025-06-20 |
| CN120173542B true CN120173542B (en) | 2025-10-03 |
Family
ID=96026307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202510611957.8A Active CN120173542B (en) | 2025-05-13 | 2025-05-13 | Conductive adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN120173542B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023092575A1 (en) * | 2021-11-29 | 2023-06-01 | 广州市白云化工实业有限公司 | Modified epoxy acrylate prepolymer, photo-thermal dual-curing conductive adhesive, and preparation method therefor |
| KR20240071792A (en) * | 2022-11-16 | 2024-05-23 | 국립금오공과대학교 산학협력단 | Release film for semiconductor package mold including uv-thermal double curable oligomer as a coating layer and manufacturing method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7528189B2 (en) * | 2002-12-04 | 2009-05-05 | Blue Goo, Llc | Metal-acrylate curing agents |
| CN103242775B (en) * | 2013-05-16 | 2015-06-10 | 长春永固科技有限公司 | Acrylic ester modified epoxy resin conductive chip adhesive |
| CN112837844B (en) * | 2021-03-01 | 2022-07-15 | 佛山市瑞纳新材科技有限公司 | HJT low-temperature curing silver paste with dual curing properties and preparation method thereof |
| KR102651592B1 (en) * | 2021-11-17 | 2024-03-27 | 이아이씨티코리아 주식회사 | Dual-curable Electrically Conductive Adhesive Composition Comprising Silver Particles |
| CN118652653A (en) * | 2024-07-10 | 2024-09-17 | 深圳飞世尔新材料股份有限公司 | A low temperature curing epoxy adhesive and preparation method thereof |
-
2025
- 2025-05-13 CN CN202510611957.8A patent/CN120173542B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023092575A1 (en) * | 2021-11-29 | 2023-06-01 | 广州市白云化工实业有限公司 | Modified epoxy acrylate prepolymer, photo-thermal dual-curing conductive adhesive, and preparation method therefor |
| KR20240071792A (en) * | 2022-11-16 | 2024-05-23 | 국립금오공과대학교 산학협력단 | Release film for semiconductor package mold including uv-thermal double curable oligomer as a coating layer and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN120173542A (en) | 2025-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101223218B (en) | Insulated conductive particles and anisotropic conductive adhesive film using the same | |
| CN103178033B (en) | The semiconductor device connected by the anisotropic conductive film comprising conductive micro-balloons | |
| CN110713742B (en) | Preparation and application method of intelligent conductive paint based on liquid metal-polymer | |
| CN111548765A (en) | Organosilicon system conductive adhesive and preparation method thereof | |
| WO2021142752A1 (en) | Organic silicon resin conductive adhesive, and preparation method therefor and application thereof | |
| CN101033379A (en) | Anisotropic conductive adhesive | |
| US20180105724A1 (en) | Sealing agent, liquid crystal panel, liquid crystal display device and fabricating method thereof | |
| CN110343484B (en) | Anisotropic conductive adhesive based on particle matrix coated with liquid metal and preparation method | |
| CN104673111A (en) | Formula and preparation method of epoxy resin based anisotropic conductive adhesive film | |
| CN109852281A (en) | A kind of preparation method of the anisotropy conductiving glue based on liquid metal | |
| CN113372844A (en) | High-temperature-resistant epoxy resin conductive adhesive and preparation method thereof | |
| CN114806432A (en) | A kind of anti-aging and high temperature resistant polyimide tape and preparation method thereof | |
| JP4860587B2 (en) | Method for producing novel conductive fine particles and use of the fine particles | |
| CN120173542B (en) | Conductive adhesive and preparation method thereof | |
| US9758702B2 (en) | Isotropic conductive adhesive | |
| CN111500215A (en) | Pressure-sensitive conductive adhesive and preparation method thereof | |
| CN113412320A (en) | Modified epoxy acrylic resin conductive adhesive and preparation method and application thereof | |
| CN114334220A (en) | Low-temperature curing type three-proofing conductive nickel paste, preparation method and application thereof | |
| CN114283962A (en) | Silver-plated microsphere-based conductive silver paste and preparation method thereof | |
| CN112300726A (en) | Electromagnetic shielding adhesive tape | |
| CN118206941A (en) | Acrylate pressure-sensitive adhesive and preparation method thereof | |
| CN116875252A (en) | Low-temperature curing flip chip filling adhesive and preparation method thereof | |
| CN116496751A (en) | High-temperature-resistant conductive adhesive and preparation method thereof | |
| CN112266742B (en) | Preparation method of conductive adhesive with excellent performance | |
| CN111334044B (en) | Organic silicone gel for precise electronic component encapsulation and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |