阅读说明：本技术 环氧树脂导电复合材料及其制备方法 (Epoxy resin conductive composite material and preparation method thereof ) 是由 刘均 黄进 熊进 张鹏 冯云虎 蔡茂林 于 2021-07-27 设计创作，主要内容包括：本申请公开了一种环氧树脂导电复合材料及其制备方法。该环氧树脂导电复合材料,以重量份计,包括：硅烷偶联剂改性的环氧树脂载体20-30份,导电填料30-70份、金属耐磨粉3-5份、固化剂0.1-1份、溶剂1-10份、催化剂0.1-1份。硅烷偶联剂醇解提高涂料与基材的附着力,醇解缩合产生Si–O–Si网络提高涂层的强度和耐磨性,氨基官能硅烷向环氧体系中引入了Si–O和C–N提高热稳定性及耐高低温性能；另外,利用硅烷偶联剂还可以使涂层的电阻率显著得到降低。(The application discloses an epoxy resin conductive composite material and a preparation method thereof. The epoxy resin conductive composite material comprises the following components in parts by weight: 20-30 parts of silane coupling agent modified epoxy resin carrier, 30-70 parts of conductive filler, 3-5 parts of metal wear-resistant powder, 0.1-1 part of curing agent, 1-10 parts of solvent and 0.1-1 part of catalyst. The adhesion force of the coating and a base material is improved by alcoholysis of the silane coupling agent, a Si-O-Si network generated by alcoholysis condensation improves the strength and wear resistance of the coating, and Si-O and C-N are introduced into an epoxy system by amino functional silane to improve the thermal stability and high and low temperature resistance; in addition, the resistivity of the coating can be obviously reduced by using the silane coupling agent.)

1. The epoxy resin conductive composite material is characterized by comprising the following components in parts by weight: 20-30 parts of silane coupling agent modified epoxy resin carrier, 30-70 parts of conductive filler, 3-5 parts of metal wear-resistant powder, 0.1-1 part of curing agent, 1-10 parts of solvent and 0.1-1 part of catalyst.

2. The epoxy conductive composite of claim 1, wherein the silane coupling agent modified epoxy carrier comprises: 10-40 wt% of epoxy resin soluble in dipropylene glycol methyl ether, and 10-30 wt% of carrier; the content of the silane coupling agent is 1-10 wt%.

3. The epoxy resin conductive composite material according to claim 2, wherein the silane coupling agent is 3-aminopropyltriethoxysilane or propyltrimethoxysilane.

4. The epoxy resin conductive composite according to claim 1, wherein the conductive filler is a plate-like and spherical nano silver powder.

5. The epoxy resin conductive composite material according to claim 4, wherein the spherical nano silver powder has a particle size of 10 to 100 nm; the particle size of the flaky nano silver is 100-200nm, and the height of the flaky nano silver is 1-10 nm.

6. The epoxy resin conductive composite material according to claim 1, wherein the solvent is dipropylene glycol methyl ether.

7. The epoxy resin conductive composite material according to claim 1, wherein the curing agent is diethylenetriamine.

8. The epoxy conductive composite of claim 1, wherein the catalyst is dibutyltin dilaurate.

9. A method for preparing an epoxy resin conductive composite material, which is characterized in that the conductive paste formula based on any one of claims 1 to 8 comprises the following steps:

s1, preparation of a resin carrier: adding a solvent into 1256 epoxy resin, stirring at 80 ℃ to dissolve, filtering by a 200-mesh filter screen after complete dissolution, and cooling for later use;

s2, preparing the conductive composite material: sequentially adding a resin carrier, a silane coupling agent, a curing agent, a solvent, a catalyst, nano silver powder and metal wear-resistant powder into a beaker, uniformly stirring, and then passing through a roller by a three-roller machine;

s3, processing of the coating: and respectively coating strips on the PET film and the PC board by the slurry passing through the roller, and putting the PET film and the PC board into an air drying box for curing.

10. The method for preparing the epoxy resin conductive composite material according to claim 9, wherein the curing condition of the PET film substrate in S3 is 80 ℃ for 2h, and the curing condition of the PC board substrate is 60 ℃ for 2 h.

Technical Field

The application relates to the field of conductive composite materials, in particular to an epoxy resin conductive composite material and a preparation method thereof.

Background

The conductive slurry mainly comprises a resin carrier, a conductive filler, a wear-resistant filler, a curing agent, a solvent and other auxiliaries. However, when the conductive paste is applied to a substrate as a coating, the adhesive force, wear resistance and strength are poor, and the thermal stability, high and low temperature resistance are poor, so that the attached silver layer is easy to fall off.

Aiming at the problems that in the related art, when the conductive paste is used as a coating to be coated on a base material, the adhesive force, the wear resistance and the strength are poor, the thermal stability and the high and low temperature resistance are poor, and the attached silver layer is easy to fall off, an effective solution is not provided at present.

Disclosure of Invention

The main purpose of the present application is to provide an epoxy resin conductive composite material and a preparation method thereof, so as to solve the problems that when a conductive paste is coated on a substrate as a coating, the adhesive force is poor, the thermal stability and the high and low temperature resistance are poor, and the attached silver layer is easy to fall off.

In order to achieve the above object, according to one aspect of the present application, there is provided an epoxy conductive composite.

The epoxy resin conductive composite material comprises the following components in parts by weight: 20-30 parts of silane coupling agent modified epoxy resin carrier, 30-70 parts of conductive filler, 3-5 parts of metal wear-resistant powder, 0.1-1 part of curing agent, 1-10 parts of solvent and 0.1-1 part of catalyst.

Further, the silane coupling agent modified epoxy resin carrier includes: 10-40 wt% of epoxy resin soluble in dipropylene glycol methyl ether, and 10-30 wt% of carrier; the content of the silane coupling agent is 1-10 wt%.

Further, the silane coupling agent is 3-aminopropyltriethoxysilane or propyltrimethoxysilane.

Further, the conductive filler is flake and spherical nano silver powder.

Further, the particle size of the spherical nano silver powder is 10-100 nm; the particle size of the flaky nano silver is 100-200nm, and the height of the flaky nano silver is 1-10 nm.

Further, the solvent is dipropylene glycol methyl ether.

Further, the curing agent is diethylenetriamine.

Further, the catalyst is dibutyltin dilaurate.

In order to achieve the above object, according to another aspect of the present application, there is provided a method for preparing an epoxy resin conductive composite.

The preparation method of the epoxy resin conductive composite material comprises the following steps based on any one of the conductive paste formulas: s1, preparation of a resin carrier: adding a solvent into 1256 epoxy resin, stirring at 80 ℃ to dissolve, filtering by a 200-mesh filter screen after complete dissolution, and cooling for later use; s2, sequentially adding a resin carrier, a silane coupling agent, a curing agent, a solvent, a catalyst, nano silver powder and metal wear-resistant powder into a beaker, uniformly stirring, and then rolling by using a three-roll machine; and S3, respectively coating the slurry passing through the rollers on a PET film and a PC board, and placing the PET film and the PC board into an air drying oven for curing.

Further, the curing condition of the PET film substrate in S3 is 80 ℃ curing for 2 hours, and the curing condition of the PC board substrate is 60 ℃ curing for 2 hours.

The alcoholysis of the silane coupling agent improves the adhesive force between the coating and the base material, a S i-O-S i network is generated by alcoholysis condensation to improve the strength and the wear resistance of the coating, and S i-O and C-N are introduced into an epoxy system by amino functional silane to improve the thermal stability and the high and low temperature resistance; in addition, the resistivity of the coating can be obviously reduced by using the silane coupling agent. After the conductive silver paste is solidified on the PET film base material for 2h at 80 ℃, the volume resistivity is 2.54 multiplied by 10 < -7 > omega.m, after the conductive silver paste is solidified on the PC board base material for 2h at 60 ℃, the conductive silver paste is boiled by 30 mn with water at 100 ℃, after being carved with hundreds of grids, the conductive silver paste is stuck by a 3M adhesive tape and vertically torn, the phenomenon that the silver layer falls off does not occur, and the adhesive force reaches the specification of 5B.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this application, serve to provide a further understanding of the application and to enable other features, objects, and advantages of the application to be more apparent. The drawings and their description illustrate the embodiments of the invention and do not limit it. In the drawings:

FIG. 1 is a schematic flow diagram of a method of making an epoxy conductive composite according to an embodiment of the present application;

FIG. 2 is an AFM topography of a silver flake according to an embodiment of the present application;

FIG. 3 is an AFM topography of a spherical nano silver powder according to an embodiment of the present application;

FIG. 4 is a size distribution of spherical nano silver powder according to an embodiment of the present application;

FIG. 5 is a line graph of the effect of different 3-aminopropyltriethoxysilane levels on coating resistivity in accordance with an embodiment of the present application;

FIG. 6 is a line graph showing the effect of different types of silane coupling agents on the resistivity of a coating according to an embodiment of the present application.

Detailed Description

In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

It should be noted that the terms "first," "second," and the like in the description and claims of this application and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It should be understood that the data so used may be interchanged under appropriate circumstances such that embodiments of the application described herein may be used. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.

In this application, the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings. These terms are used primarily to better describe the invention and its embodiments and are not intended to limit the indicated devices, elements or components to a particular orientation or to be constructed and operated in a particular orientation.

Moreover, some of the above terms may be used to indicate other meanings besides the orientation or positional relationship, for example, the term "on" may also be used to indicate some kind of attachment or connection relationship in some cases. The specific meanings of these terms in the present invention can be understood by those skilled in the art as appropriate.

Furthermore, the terms "mounted," "disposed," "provided," "connected," and "sleeved" are to be construed broadly. For example, it may be a fixed connection, a removable connection, or a unitary construction; can be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements or components. The specific meanings of the above terms in the present invention can be understood by those of ordinary skill in the art according to specific situations.

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.

Example 1

As shown in fig. 1 to 5, the present application relates to an epoxy resin conductive composite material, which comprises the following components in parts by weight: 20 parts of silane coupling agent modified epoxy resin carrier, 30 parts of flaky and spherical nano silver powder, 3 parts of metal wear-resistant powder, 0.1 part of diethylenetriamine, 1 part of dipropylene glycol methyl ether and 0.1 part of dibutyltin dilaurate; the silane coupling agent modified epoxy resin carrier comprises: 10 parts of epoxy resin soluble in dipropylene glycol methyl ether, and 10 parts of carrier; the content of 3-aminopropyltriethoxysilane was 1.25 parts. The particle size of the spherical nano silver powder is 10-100 nm; the particle size of the flaky nano silver is 100-200nm, and the height of the flaky nano silver is 1-10 nm.

A preparation method of an epoxy resin conductive composite material comprises the following steps:

s1: preparation of resin carrier: adding a solvent into 1256 epoxy resin, stirring at 80 ℃ to dissolve, filtering by a 200-mesh filter screen after complete dissolution, and cooling for later use;

s2: sequentially adding the resin carrier prepared in S1, 1.25 parts of 3-aminopropyltriethoxysilane, 0.1 part of diethylenetriamine, 1 part of dipropylene glycol methyl ether, 0.1 part of dibutyltin dilaurate, 30 parts of flaky and spherical nano silver powder and 3 parts of metal wear-resistant powder into a beaker, and uniformly stirring and then rolling by using a three-roll machine;

s3: and respectively coating strips on the PET film and the PC board by the slurry passing through the roller, and putting the PET film and the PC board into an air drying box for curing.

Example 2

As shown in fig. 1 to 5, the present application relates to an epoxy resin conductive composite material, which comprises the following components in parts by weight: 20 parts of silane coupling agent modified epoxy resin carrier, 30 parts of flaky and spherical nano silver powder, 3 parts of metal wear-resistant powder, 0.1 part of diethylenetriamine, 1 part of dipropylene glycol methyl ether and 0.1 part of dibutyltin dilaurate; the silane coupling agent modified epoxy resin carrier comprises: 10 parts of epoxy resin soluble in dipropylene glycol methyl ether, and 10 parts of carrier; the content of 3-aminopropyltriethoxysilane was 2.38 parts. The particle size of the spherical nano silver powder is 10-100 nm; the particle size of the flaky nano silver is 100-200nm, and the height of the flaky nano silver is 1-10 nm.

A preparation method of an epoxy resin conductive composite material comprises the following steps:

s1: preparation of resin carrier: adding a solvent into 1256 epoxy resin, stirring at 80 ℃ to dissolve, filtering by a 200-mesh filter screen after complete dissolution, and cooling for later use;

s2: sequentially adding the resin carrier prepared in S1, 2.38 parts of 3-aminopropyltriethoxysilane, 0.1 part of diethylenetriamine, 1 part of dipropylene glycol methyl ether, 0.1 part of dibutyltin dilaurate, 30 parts of dipropylene glycol methyl ether and metal wear-resistant powder into a beaker, and uniformly stirring the mixture to pass through a roller by a three-roller machine;

s3: and respectively coating strips on the PET film and the PC board by the slurry passing through the roller, and putting the PET film and the PC board into an air drying box for curing.

Example 3

As shown in fig. 1 to 4 and 6, the present application relates to an epoxy resin conductive composite material, which comprises the following components in parts by weight: 30 parts of silane coupling agent modified epoxy resin carrier, 70 parts of flaky and spherical nano silver powder, 5 parts of metal wear-resistant powder, 1 part of diethylenetriamine, 10 parts of dipropylene glycol methyl ether and 1 part of dibutyltin dilaurate; the silane coupling agent modified epoxy resin carrier comprises: 40 parts of epoxy resin soluble in dipropylene glycol methyl ether, and 30 parts of carrier; the content of 3-aminopropyltriethoxysilane is 10 parts. The particle size of the spherical nano silver powder is 10-100 nm; the particle size of the flaky nano silver is 100-200nm, and the height of the flaky nano silver is 1-10 nm.

A preparation method of an epoxy resin conductive composite material comprises the following steps:

s1: preparation of resin carrier: adding a solvent into 1256 epoxy resin, stirring at 80 ℃ to dissolve, filtering by a 200-mesh filter screen after complete dissolution, and cooling for later use;

s2: sequentially adding the resin carrier prepared in S1, 10 parts of 3-aminopropyltriethoxysilane, 1 part of diethylenetriamine, 10 parts of dipropylene glycol methyl ether, 1 part of dibutyltin dilaurate, 70 parts of flaky and spherical nano silver powder and metal wear-resistant powder into a beaker, uniformly stirring, and then passing through a roller by a three-roller machine;

s3: and respectively coating strips on the PET film and the PC board by the slurry passing through the roller, and putting the PET film and the PC board into an air drying box for curing.

Example 4

As shown in fig. 1 to 4 and 6, the present application relates to an epoxy resin conductive composite material, which comprises the following components in parts by weight: 30 parts of silane coupling agent modified epoxy resin carrier, 70 parts of flaky and spherical nano silver powder, 5 parts of metal wear-resistant powder, 1 part of diethylenetriamine, 10 parts of dipropylene glycol methyl ether and 1 part of dibutyltin dilaurate; the silane coupling agent modified epoxy resin carrier comprises: 40 parts of epoxy resin soluble in dipropylene glycol methyl ether, and 30 parts of carrier; the propyl trimethoxy silane content is 10 parts. The particle size of the spherical nano silver powder is 10-100 nm; the particle size of the flaky nano silver is 100-200nm, and the height of the flaky nano silver is 1-10 nm.

A preparation method of an epoxy resin conductive composite material comprises the following steps:

s1: preparation of resin carrier: adding a solvent into 1256 epoxy resin, stirring at 80 ℃ to dissolve, filtering by a 200-mesh filter screen after complete dissolution, and cooling for later use;

s2: sequentially adding the resin carrier prepared in S1, 10 parts of propyl trimethoxy silane, 1 part of diethylenetriamine, 10 parts of dipropylene glycol methyl ether, 1 part of dibutyltin dilaurate agent, 70 parts of flaky and spherical nano silver powder and metal wear-resistant powder into a beaker, uniformly stirring, and then passing through a roller by a three-roller machine;

s3: and respectively coating strips on the PET film and the PC board by the slurry passing through the roller, and putting the PET film and the PC board into an air drying box for curing.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.