CN108531092B - Composite conductive adhesive film and manufacturing method thereof - Google Patents
Composite conductive adhesive film and manufacturing method thereof Download PDFInfo
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- CN108531092B CN108531092B CN201810203552.0A CN201810203552A CN108531092B CN 108531092 B CN108531092 B CN 108531092B CN 201810203552 A CN201810203552 A CN 201810203552A CN 108531092 B CN108531092 B CN 108531092B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
Abstract
The invention discloses a composite conductive adhesive film, which comprises an upper adhesive layer, a reinforcing layer, a conductive adhesive layer and a lower adhesive layer; the conductive adhesive layer comprises conductive particles, the matrix of the conductive adhesive layer is ABS particles, the surface of the ABS particles is coated with an alloy layer, and the alloy layer is further coated with a single metal layer; the particle size of the ABS particles is 10-50 μm; the thickness of the alloy layer is 3-10 μm, the thickness of the single metal layer is 4-8 μm, and the conductive particles are waxberry-like particles with flaky bulges distributed on the surface, waxberry-like particles with needle-shaped bulges distributed on the surface or waxberry-like particles with rod-shaped bulges distributed on the surface; the reinforcing layer is a metal net woven by metal wires with the wire diameter of micron order. The invention has the characteristics of good electrical property, good bonding strength, good soldering tin property, good reliability, good flame resistance and the like; the conductive particles of the present invention can overcome the disadvantages of the conductive particles made of carbon fibers, solder, nickel powder, and the like.
Description
Technical Field
The invention belongs to the technical field of conductive cloth for a printed circuit board, and particularly relates to a composite conductive adhesive film.
Background
With the development of the electronic industry, electronic assemblies are becoming more miniaturized and densified, and many conductive connections are realized by conductive adhesive films without relying on traditional methods such as welding or plugging.
The isotropic conductive adhesive film is a compound formed by dispersing conductive particles in adhesive insulating resin, is used for bonding components and is cured under the conditions of heating and pressurizing, so that the functions of electrifying and bonding are realized. The isotropic conductive adhesive film mainly comprises resin, a curing agent and silver powder, wherein the resin is generally solid resin and liquid resin. The solid resin is mainly used for pre-curing to form a film, and the main body of the liquid resin has the adhesive property and reacts with the curing agent under the action of heat and pressure to play a role in bonding. The solid resin may be either thermoplastic or thermosetting. However, the prior isotropic conductive adhesive film generally has the technical problems of low bonding strength, poor heat resistance and the like after hot-pressing and curing.
Among them, Japanese patent laid-open Nos. S58-223953, H06-339965, H06-349339, and 2001-164232 disclose an anisotropic conductive film (anisotropic sheet) containing conductive particles, which includes insulating organic or inorganic particles and an insulating fibrous filler to prevent aggregation of the conductive particles and thus improve reliability of electrical connection.
However, the above-cited conventional techniques using organic or inorganic particles and insulating fibrous fillers have the following disadvantages: the amount of the conductive particles is limited and it causes many problems during the production of the anisotropic conductive film and may also reduce the long-term reliability of the electrical connection after the connection.
In addition, the conductive particles are subjected to processes such as carbon fibers, solder, nickel powder, composite powder and the like. The carbon fiber has a low conductivity, and in order to obtain a sufficient conductivity, it is necessary to fill 5 to 25% by weight of particles, so that the ACF has a low transparency. Solder particles are liable to form intermetallic compounds (IMC) during soldering, IMC is brittle, and the difference in properties such as thermal expansion coefficient from a base material (electrode, component, substrate, or the like in packaging) is large, and if the IMC is excessively long, cracks are liable to occur, which leads to a problem of reliability. It has been proposed to avoid IMC formation by the instant melting technique, but this process adds a tin-lead coating to the bumps, increasing the complexity of the process. In fine pitch interconnects, the solder particles must be small, but the reliability problem is exacerbated by the shorter time required for small solder particles to diffuse to produce IMC, so in ultra fine pitch ACFs, solder particles are rarely used. The Ni powder is not as easily formed as metal-coated polymer pellets, but can also be used as conductive particles for interconnection of easily oxidizable metal electrodes. Ni powder, especially those with many burrs on the surface, is very suitable for breaking the oxide layer of the interconnection metal electrode. The composite powder mainly refers to polymer pellets coated with metal, and is also the category of the novel composite conductive particles researched by the invention.
Disclosure of Invention
The invention mainly solves the technical problem of providing a composite conductive adhesive film which has the characteristics of good electrical property, good bonding strength, good soldering tin property, good reliability, good flame resistance and the like, has better conduction effect and bonding strength compared with common conductive adhesives, is easy to produce and has wide market application prospect; meanwhile, the conductive particles in the invention can overcome the defects of the materials such as carbon fiber, solder, nickel powder and the like when the materials are used as the conductive particles.
In order to solve the technical problems, the invention adopts a technical scheme that a composite conductive adhesive film is provided, which comprises an upper adhesive layer, a reinforcing layer, a conductive adhesive layer and a lower adhesive layer, wherein the reinforcing layer is positioned between the upper adhesive layer and the conductive adhesive layer, and the conductive adhesive layer is positioned between the reinforcing layer and the lower adhesive layer;
the thickness of the upper adhesive layer is 25-35 μm, the thickness of the lower adhesive layer is 25-35 μm, the conductive adhesive layer comprises conductive particles, the matrix of the conductive particles is polymer particles, the surface of the polymer particles is coated with an alloy layer, a single metal layer is further coated on the alloy layer, the alloy layer is a copper-nickel alloy layer, and the single metal layer is a silver layer or a gold layer; the particle size of the polymer particles is 10-50 μm; the thickness of the alloy layer is 3-10 μm, the thickness of the single metal layer is 4-8 μm, and the conductive particles are waxberry-like particles with flaky bulges distributed on the surface, waxberry-like particles with needle-shaped bulges distributed on the surface or waxberry-like particles with rod-shaped bulges distributed on the surface;
the conductive adhesive layer also comprises adhesive resin, the proportion of the adhesive resin is 20-50% (weight ratio), the proportion of the conductive particles is 30-80% (weight ratio), and the proportion of the conductive particles to the adhesive resin is 1:1-2:1 (weight ratio);
the reinforcing layer is a metal net woven by metal wires with micron-sized wire diameters, micropores are uniformly distributed in the metal net, the micropores are rectangular or rhombic, and the area of the micropores is 4-9 mu m2。
In order to solve the technical problems, the invention adopts the further technical scheme that:
the upper adhesive layer and the lower adhesive layer are epoxy series conductive adhesive layers, and the conductive adhesive layers are prepared from the following raw materials in parts by weight: 50-60 parts of metal particles, 12-13 parts of solid epoxy resin solution, 20-30 parts of acetone, 4-8 parts of liquid epoxy resin, 2-5 parts of organic urea curing agent, 2-5 parts of modified epoxy resin and 1-2 parts of vinyl triethoxysilane.
Further, the metal wire is at least one of a copper-plated nickel wire, a copper-plated cobalt wire, a copper-plated tin wire, a copper-plated silver wire, a copper-plated iron nickel wire, a copper-plated gold wire and a copper-plated copper wire.
Further, the modified epoxy resin is polyurethane modified epoxy resin or rubber modified epoxy resin, and the epoxy equivalent of the modified epoxy resin is 1000-1200 g/eq.
Further, a release film layer or a carrier film layer is respectively formed below the lower adhesive layer and above the upper adhesive layer, and the thickness of the release film layer or the carrier film layer is 20-80 μm; the release film layer is a PET fluoroplastic release film layer, a PET silicon-oil-containing release film layer, a PET matte release film layer, a PE release film layer or a PE laminating film paper layer; the release film layer is a double-sided release film layer or a single-sided release film layer.
Further, the preparation method of the polymer particles is as follows:
adding predetermined amount of liquid butadiene, absolute ethyl alcohol and deionized water into a reactor equipped with a mechanical stirrer, a condenser pipe and a nitrogen inlet and outlet, introducing nitrogen for stirring, and then placing in a water bath with the temperature of 70-80 ℃ for later use; weighing acrylonitrile, cumene hydroperoxide and soap lye in a beaker according to a preset amount, oscillating and dissolving, adding the mixture into the flask, keeping stirring and introducing nitrogen, reacting for 10-20h, and then cooling and terminating to obtain an emulsion product; then separating and drying to obtain particles;
the raw materials comprise the following components in percentage by mass: 200 portions of liquid butadiene, 800 portions of absolute ethyl alcohol, 40 to 50 portions of deionized water, 4 to 8 portions of acrylonitrile, 0.5 to 0.6 portion of cumene hydroperoxide and 1 to 1.5 portions of soap liquid.
Further, the method for forming the surface chemical alloy layer on the polymer particle is as follows: carrying out surface roughening, sensitizing, activating and other pretreatment procedures on the matrix polymer particles of the conductive particles, and finally plating a copper-nickel alloy layer on the surface of the matrix polymer particles by adopting chemical plating solution;
the mass proportion and the reaction conditions of the chemical plating solution are as follows:
the mass proportion and the reaction conditions of the acidic chemical plating solution are as follows: 14-18 parts of nickel sulfate, 14-20 parts of copper sulfate, 15-16 parts of sodium hypophosphite, 11-13 parts of trisodium citrate and 10-15 parts of sodium acetate, wherein the reaction pH value is 5.0-7.0, the reaction temperature is 35-40 ℃, and the reaction time is 20-35 min.
Further, the chemical silver plating method for the copper-nickel coated polymer particle surface is as follows:
adding the polymer particles coated with copper and nickel into a plating solution, plating for two times, stirring discontinuously, separating the particles after plating for a preset time, and washing and drying the particles.
The invention also provides a manufacturing method of the composite conductive adhesive film, which comprises the following steps:
the method comprises the following steps: mixing the prepared conductive particles and adhesive resin in proportion to obtain a mixture A, and fully and uniformly mixing the mixture A for later use;
step two: weaving a metal net for later use;
step three, preparing raw materials of an upper adhesive layer and a lower adhesive layer to obtain a mixture B;
step four: coating the mixture prepared in the third step on the release coating layer or the carrier film layer designated release coating surface to obtain a lower adhesive layer;
step five: coating the mixture prepared in the first step on the surface of the lower adhesive layer to form a conductive adhesive layer;
step six: pressing the metal mesh prepared in the second step on the other surface of the conductive adhesive layer;
step seven: coating the mixture prepared in the third step on the other surface of the metal mesh layer to obtain an upper adhesive layer;
step eight: curing, rolling and splitting to obtain the finished product.
The invention has the beneficial effects that: the invention has at least the following advantages:
the conductive adhesive layer comprises conductive particles, wherein the surface of each conductive particle is coated with an alloy layer, the alloy layer is further coated with a single metal layer, the surfaces of the conductive particles are provided with flaky raised waxberry-like particles, needle-shaped raised waxberry-like particles or rod-shaped raised waxberry-like particles, and the conductive particles tend to flow in multiple directions when deformed due to hot pressing because of the raised surfaces of the conductive particles, so that the distribution of the conductive particles in the conductive adhesive layer after pressing has multiple directions and high dispersibility, and further forms a conduction circuit with a grounding hole on a soft board, so that the upper adhesive layer and the lower adhesive layer have good anisotropic conductivity, the conductivity is greatly improved, and the grounding impedance value of the soft board can be reduced;
the invention also comprises a reinforcing layer which is a metal net woven by metal wires with the wire diameter of micron order, and the metal net is uniformly distributed with micropores, so that the network structure is favorable for the conduction of conductive particles added in the conductive adhesive layer through the micropores in the conductive adhesive layer, meanwhile, due to good air permeability, the phenomenon of board explosion can not occur in the downstream processing procedure of the FPC through SMT, and the problem of board explosion of the conductive adhesive and the conductive adhesive with a buried metal layer circulating in the current market can be effectively solved; the reinforcing layer is adopted, and the metal mesh is formed by weaving metal wires with the wire diameter of micron order, so that the electromagnetic shielding performance of the conductive adhesive film is enhanced, the mechanical strength of the conductive adhesive film is enhanced, and the service life is prolonged;
fifthly, the conductive particles in the conductive adhesive layer are waxberry-like particles which are coated with the alloy layer and then coated with the single metal layer, and the surfaces of the waxberry-like particles are fully distributed with protrusions, so that the structure can bring electromagnetic wave shielding effect (shielding performance is more than 85 dB); because the design of the existing IC is more and more light, thin, short and small, electromagnetic waves exist on a plurality of electronic components, and sometimes interfere with each other to influence the application of performance, the conductive adhesive film can effectively generate an effective shielding effect on the electromagnetic waves generated on the contact points;
sixth, when the conductive particles of the invention are conductive particles of the clad alloy layer, so the conductive adhesive film containing the conductive particles has excellent oxidation resistance and conductivity, which is convenient for storing and transporting products, and will not affect the physical properties of the products, thus the products are stable and have higher reliability.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is one of SEM exemplary structural topographies (16000 times) of the conductive particles of the present invention;
FIG. 3 is a second (16000 times) SEM exemplary structural topography of the conductive particles of the present invention;
FIG. 4 is a third SEM image (20000 times) of the morphology of an exemplary structure of the conductive particles of the present invention;
description of reference numerals:
an upper adhesive layer 100, a reinforcing layer 200, a conductive adhesive layer 300, and a lower adhesive layer 400.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and the present invention will be described in detail with reference to the accompanying drawings. The invention may be embodied in other different forms, i.e. it is capable of various modifications and changes without departing from the scope of the invention as disclosed.
Example (b): a composite conductive adhesive film 100, as shown in fig. 1 to 4, comprises an upper adhesive layer 100, a reinforcing layer 200, a conductive adhesive layer 300 and a lower adhesive layer 400, wherein the reinforcing layer is located between the upper adhesive layer and the conductive adhesive layer, and the conductive adhesive layer is located between the reinforcing layer and the lower adhesive layer;
the thickness of the upper adhesive layer is 25-35 μm, the thickness of the lower adhesive layer is 25-35 μm, the conductive adhesive layer comprises conductive particles, the matrix of the conductive particles is polymer particles, the surface of the polymer particles is coated with an alloy layer, a single metal layer is further coated on the alloy layer, the alloy layer is a copper-nickel alloy layer, and the single metal layer is a silver layer or a gold layer; the particle size of the polymer particles is 10-50 μm; the thickness of the alloy layer is 3-10 μm, the thickness of the single metal layer is 4-8 μm, and the conductive particles are waxberry-like particles with flaky bulges distributed on the surface, waxberry-like particles with needle-shaped bulges distributed on the surface or waxberry-like particles with rod-shaped bulges distributed on the surface;
the conductive adhesive layer also comprises adhesive resin, the proportion of the adhesive resin is 20-50% (weight ratio), the proportion of the conductive particles is 30-80% (weight ratio), and the proportion of the conductive particles to the adhesive resin is 1:1-2:1 (weight ratio);
the reinforcing layer is a metal net woven by metal wires with micron-sized wire diameters, micropores are uniformly distributed in the metal net, the micropores are rectangular or rhombic, and the area of the micropores is 4-9 mu m2。
In this embodiment, the upper adhesive layer and the lower adhesive layer are epoxy-series conductive adhesive layers, and the conductive adhesive layers are made of the following raw materials in parts by weight: 50-60 parts of metal particles, 12-13 parts of solid epoxy resin solution, 20-30 parts of acetone, 4-8 parts of liquid epoxy resin, 2-5 parts of organic urea curing agent, 2-5 parts of modified epoxy resin and 1-2 parts of vinyl triethoxysilane.
The metal wire is at least one of a copper-plated nickel wire, a copper-plated cobalt wire, a copper-plated tin wire, a copper-plated silver wire, a copper-plated iron-nickel wire, a copper-plated gold wire and a copper-plated copper wire, but is not limited thereto.
The modified epoxy resin is polyurethane modified epoxy resin or rubber modified epoxy resin, and the epoxy equivalent of the modified epoxy resin is 1000-1200 g/eq.
A release film layer or a carrier film layer is respectively formed below the lower adhesive layer and above the upper adhesive layer, and the thickness of the release film layer or the carrier film layer is 20-80 μm; the release film layer is a PET fluoroplastic release film layer, a PET silicon-oil-containing release film layer, a PET matte release film layer, a PE release film layer or a PE laminating film paper layer; the release film layer is a double-sided release film layer or a single-sided release film layer.
The release film layer can be released from two sides or one side, preferably from two sides, and preferably has a thickness of 25-100 μm, and is too thin or too thick to facilitate subsequent processing and punching.
The color of the release film layer is pure white, milky white or transparent, and pure white or milky white is preferred. When numerical control automation equipment sculpture circuit, infra red ray induction, white does not have the reverberation problem, can quick accurate location, the processing operation, and during manual work, white has the recognition effect, prevents that the manual work from leaking and tearing etc..
The preparation method of the polymer particles comprises the following steps:
adding predetermined amount of liquid butadiene, absolute ethyl alcohol and deionized water into a reactor equipped with a mechanical stirrer, a condenser pipe and a nitrogen inlet and outlet, introducing nitrogen for stirring, and then placing in a water bath with the temperature of 70-80 ℃ for later use; weighing acrylonitrile, cumene hydroperoxide and soap lye in a beaker according to a preset amount, oscillating and dissolving, adding the mixture into the flask, keeping stirring and introducing nitrogen, reacting for 10-20h, and then cooling and terminating to obtain an emulsion product; then separating and drying to obtain particles;
the raw materials comprise the following components in percentage by mass: 200 portions of liquid butadiene, 800 portions of absolute ethyl alcohol, 40 to 50 portions of deionized water, 4 to 8 portions of acrylonitrile, 0.5 to 0.6 portion of cumene hydroperoxide and 1 to 1.5 portions of soap liquid.
The method for forming the surface chemical alloy layer of the polymer particle is as follows: carrying out surface roughening, sensitizing, activating and other pretreatment procedures on the matrix polymer particles of the conductive particles, and finally plating a copper-nickel alloy layer on the surface of the matrix polymer particles by adopting chemical plating solution;
the mass proportion and the reaction conditions of the chemical plating solution are as follows:
the mass proportion and the reaction conditions of the acidic chemical plating solution are as follows: 14-18 parts of nickel sulfate, 14-20 parts of copper sulfate, 15-16 parts of sodium hypophosphite, 11-13 parts of trisodium citrate and 10-15 parts of sodium acetate, wherein the reaction pH value is 5.0-7.0, the reaction temperature is 35-40 ℃, and the reaction time is 20-35 min.
The chemical silver plating method for the copper-nickel coated polymer particle surface comprises the following steps:
adding the polymer particles coated with copper and nickel into a plating solution, plating for two times, stirring discontinuously, separating the particles after plating for a preset time, and washing and drying the particles.
The manufacturing method of the composite conductive adhesive film is characterized by comprising the following steps of: the method comprises the following steps:
the method comprises the following steps: mixing the prepared conductive particles and the adhesive resin in proportion (ball milling can be adopted during mixing, the rotating speed of the ball milling is not too high, and 100-;
step two: weaving a metal net for later use;
step three, preparing raw materials of an upper adhesive layer and a lower adhesive layer to obtain a mixture B;
step four: coating the mixture prepared in the third step on the release coating layer or the carrier film layer designated release coating surface to obtain a lower adhesive layer;
step five: coating the mixture prepared in the first step on the surface of the lower adhesive layer to form a conductive adhesive layer;
step six: pressing the metal mesh prepared in the second step on the other surface of the conductive adhesive layer (the pre-curing temperature is not higher than the curing temperature of the adhesive resin per se, and the pre-curing temperature is selected to be between 80 and 100 ℃ in the invention, so that the subsequent production is facilitated);
step seven: coating the mixture prepared in the third step on the other surface of the metal mesh layer to obtain an upper adhesive layer;
step eight: curing, rolling and splitting to obtain the finished product.
Conducting conductivity analysis and test on the composite conductive adhesive film after the release film layer is torn off: a high-bridge tester is used for conducting conductivity analysis and test, after a nickel-plated steel sheet and a printed circuit board are respectively and temporarily attached to the surfaces of an upper adhesive layer and a lower adhesive layer, pressing and curing are respectively carried out to test conductivity resistance data of a sample piece before and after reflow soldering, the test of the invention is taken as an example, the conductivity of a common product is tested by the same method as a comparative example, and the measured conductivity result is recorded in a table 1.
Note: in examples 1 and 2, the microscopic morphology of the conductive particles is shown in fig. 2; in examples 3 and 4, the microscopic morphology of the conductive particles is shown in fig. 3; in example 5, a microscopic morphology of the conductive particles is shown in fig. 4.
As can be seen from the above table, the conductive adhesive film of the present invention has better conductive effect, solder heat resistance and adhesion strength compared to the general products.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures made by using the contents of the specification and the drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (7)
1. A composite conductive adhesive film is characterized in that: the adhesive comprises an upper adhesive layer (100), a reinforcing layer (200), a conductive adhesive layer (300) and a lower adhesive layer (400), wherein the reinforcing layer is positioned between the upper adhesive layer and the conductive adhesive layer, and the conductive adhesive layer is positioned between the reinforcing layer and the lower adhesive layer;
the thickness of the upper adhesive layer is 25-35 μm, the thickness of the lower adhesive layer is 25-35 μm, the conductive adhesive layer comprises conductive particles, the matrix of the conductive particles is polymer particles, the surface of the polymer particles is coated with an alloy layer, a single metal layer is further coated on the alloy layer, the alloy layer is a copper-nickel alloy layer, and the single metal layer is a silver layer or a gold layer; the particle size of the polymer particles is 10-50 μm; the thickness of the alloy layer is 3-10 μm, the thickness of the single metal layer is 4-8 μm, and the conductive particles are waxberry-like particles with flaky bulges distributed on the surface, waxberry-like particles with needle-shaped bulges distributed on the surface or waxberry-like particles with rod-shaped bulges distributed on the surface;
the conductive adhesive layer also comprises adhesive resin, wherein the weight ratio of the adhesive resin is 20-50%, the weight ratio of the conductive particles is 30-80%, and the weight ratio of the conductive particles to the adhesive resin is 1:1-2: 1;
the reinforcing layer is a metal net woven by metal wires with micron-sized wire diameters, micropores are uniformly distributed in the metal net, the micropores are rectangular or rhombic, and the area of the micropores is 4-9 mu m2；
The metal wire is at least one of a copper-plated nickel wire, a copper-plated cobalt wire, a copper-plated tin wire, a copper-plated silver wire, a copper-plated iron-nickel wire and a copper-plated gold wire;
the electromagnetic wave shielding performance of the conductive adhesive film is more than 85 dB;
the upper adhesive layer and the lower adhesive layer are epoxy series conductive adhesive layers;
the preparation method of the polymer particles comprises the following steps:
adding predetermined amount of liquid butadiene, absolute ethyl alcohol and deionized water into a reactor equipped with a mechanical stirrer, a condenser pipe and a nitrogen inlet and outlet, introducing nitrogen for stirring, and then placing in a water bath with the temperature of 70-80 ℃ for later use; weighing acrylonitrile, cumene hydroperoxide and soap lye in a beaker according to a preset amount, oscillating and dissolving, adding the mixture into the flask, keeping stirring and introducing nitrogen, reacting for 10-20h, and then cooling and terminating to obtain an emulsion product; then separating and drying to obtain particles;
the raw materials comprise the following components in percentage by mass: 200 portions of liquid butadiene, 800 portions of absolute ethyl alcohol, 40 to 50 portions of deionized water, 4 to 8 portions of acrylonitrile, 0.5 to 0.6 portion of cumene hydroperoxide and 1 to 1.5 portions of soap liquid.
2. The composite conductive adhesive film according to claim 1, wherein: the conductive adhesive layer is prepared from the following raw materials in parts by weight: 50-60 parts of metal particles, 12-13 parts of solid epoxy resin solution, 20-30 parts of acetone, 4-8 parts of liquid epoxy resin, 2-5 parts of organic urea curing agent, 2-5 parts of modified epoxy resin and 1-2 parts of vinyl triethoxysilane.
3. The composite conductive adhesive film according to claim 2, wherein: the modified epoxy resin is polyurethane modified epoxy resin or rubber modified epoxy resin, and the epoxy equivalent of the modified epoxy resin is 1000-1200 g/eq.
4. The composite conductive adhesive film according to claim 1, wherein: a release film layer or a carrier film layer is respectively formed below the lower adhesive layer and above the upper adhesive layer, and the thickness of the release film layer or the carrier film layer is 20-80 μm; the release film layer is a PET fluoroplastic release film layer, a PET silicon-oil-containing release film layer, a PET matte release film layer, a PE release film layer or a PE laminating film paper layer; the release film layer is a double-sided release film layer or a single-sided release film layer.
5. The composite conductive adhesive film according to claim 4, wherein: the method for forming the surface chemical alloy layer of the polymer particle is as follows: carrying out surface roughening, sensitizing and activating pretreatment on the matrix polymer particles of the conductive particles, and plating a copper-nickel alloy layer on the surface of the matrix polymer particles by adopting chemical plating solution;
the mass proportion and the reaction conditions of the chemical plating solution are as follows:
the mass proportion and the reaction conditions of the acidic chemical plating solution are as follows: 14-18 parts of nickel sulfate, 14-20 parts of copper sulfate, 15-16 parts of sodium hypophosphite, 11-13 parts of trisodium citrate and 10-15 parts of sodium acetate, wherein the reaction pH value is 5.0-7.0, the reaction temperature is 35-40 ℃, and the reaction time is 20-35 min.
6. The composite conductive adhesive film according to claim 5, wherein: the chemical silver plating method for the copper-nickel coated polymer particle surface comprises the following steps:
adding the polymer particles coated with copper and nickel into a plating solution, plating for two times, stirring discontinuously, separating the particles after plating for a preset time, and washing and drying the particles.
7. The method for manufacturing the composite conductive adhesive film according to claim 6, wherein: the method comprises the following steps:
the method comprises the following steps: mixing the prepared conductive particles and adhesive resin in proportion to obtain a mixture A, and fully and uniformly mixing the mixture A for later use;
step two: weaving a metal net for later use;
step three, preparing raw materials of an upper adhesive layer and a lower adhesive layer to obtain a mixture B;
step four: coating the mixture prepared in the third step on the release coating layer or the carrier film layer designated release coating surface to obtain a lower adhesive layer;
step five: coating the mixture prepared in the first step on the surface of the lower adhesive layer to form a conductive adhesive layer;
step six: pressing the metal mesh prepared in the second step on the other surface of the conductive adhesive layer;
step seven: coating the mixture prepared in the third step on the other surface of the metal mesh layer to obtain an upper adhesive layer;
step eight: curing, rolling and splitting to obtain the finished product.
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| CN113845862B (en) * | 2020-06-28 | 2023-01-24 | 中国科学院理化技术研究所 | Conductive and heat-conducting adhesive film and preparation method and application thereof |
| CN115368849B (en) * | 2021-05-20 | 2023-10-03 | 中国科学院福建物质结构研究所 | Anisotropic conductive adhesive film and preparation method and application thereof |
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| CN102176337A (en) * | 2011-01-06 | 2011-09-07 | 天津大学 | Composite conductive particles for anisotropic conductive film and preparation method |
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| CN202054778U (en) * | 2011-05-06 | 2011-11-30 | 广州方邦电子有限公司 | Conductive adhesive film |
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| CN206077830U (en) * | 2016-10-10 | 2017-04-05 | 昆山雅森电子材料科技有限公司 | A kind of novel multi-layer Anisotropically conductive glued membrane |
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| CN102176337A (en) * | 2011-01-06 | 2011-09-07 | 天津大学 | Composite conductive particles for anisotropic conductive film and preparation method |
| CN202030694U (en) * | 2011-05-06 | 2011-11-09 | 广州方邦电子有限公司 | High peel strength conductive glue film with through holes |
| CN202054778U (en) * | 2011-05-06 | 2011-11-30 | 广州方邦电子有限公司 | Conductive adhesive film |
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