CN108531092A - Composite conducting glued membrane and preparation method thereof - Google Patents

Composite conducting glued membrane and preparation method thereof Download PDF

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Publication number
CN108531092A
CN108531092A CN201810203552.0A CN201810203552A CN108531092A CN 108531092 A CN108531092 A CN 108531092A CN 201810203552 A CN201810203552 A CN 201810203552A CN 108531092 A CN108531092 A CN 108531092A
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layer
parts
particle
adhesive layer
particles
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CN108531092B (en
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薛东妹
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Kunshan daikete Electronic Technology Co.,Ltd.
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KUNSHAN HANHUI ELECTRONIC TECHNOLOGY CO LTD
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)

Abstract

The invention discloses a kind of composite conducting glued membranes, including gluing adhesive layer, strengthening course, conductive adhesive layer and lower gluing oxidant layer；Conductive adhesive layer includes conducting particles, and matrix is ABS particles, and the surface of ABS particles coats a laminated layer gold, coats one layer of single metal layer again over the alloyed layer；The grain size of ABS particles is 10 50 μm；The thickness of alloy-layer is 3 10 μm, and the thickness of single metal layer is 48 μm, and conducting particles is that surface is covered with the class strawberry-like particle of sheet protrusion, surface is covered with the class strawberry-like particle of needle-shaped protrusion or surface is covered with the class strawberry-like particle of rod-shaped protrusion；It is metal mesh made of the braiding of micron-sized metal wire that strengthening course, which is by line footpath,.The present invention has the characteristics such as electrical characteristic is good, Bonding strength is good, solderability is good, reliability is good, and flame resistance is good；And the conducting particles in the present invention when can overcome these materials such as carbon fiber, solder, nickel powder as conducting particles the shortcomings that.

Description

Composite conducting glued membrane and preparation method thereof
Technical field
The invention belongs to printed wiring board conductive fabric technical field, more particularly to a kind of composite conducting glued membrane.
Background technology
With the development of electronics industry, Electronic Assemblies are increasingly miniaturized, densification, and many conductive attachments are no longer By traditional approach such as welding or grafting, but realized by conductive adhesive film.
Same sex conductive adhesive film is the compound for forming disperse conductive particles in adhesive insulating resin, uses it for member The bonding of device cures under conditions of heating pressurization, to realize energization and binding function.Same sex conductive adhesive film mainly by Resin, curing agent, silver powder composition, wherein resin is usually hard resin and liquid resin.Hard resin is mainly used for precuring Film forming, its main body cementability of liquid resin have reacted cementation with curing agent under by hot pressing function.Hard resin can be Thermoplastic can also be heat cured.But existing homeotropic orientation conductive adhesive film, after hot-press solidifying, generally existing adhesive strength It is low, the technical problems such as poor heat resistance.
Wherein, Japanese Patent Publication S58-223953, H06-339965, H06-349339 and No. 2001-164232 Disclose a kind of anisotropy conductiving glue piece (adhesivesheet) comprising conductive particle comprising insulation organic or inorganic Particle and insulating fibrous fillers are to prevent the aggregation of conductive particle and therefore improve the reliability of electrical connection.
However, cited above have following lack using the traditional technology of organic or inorganic particle and insulating fibrous fillers Point：The amount of conductive particle is restricted, and it can cause many problems and even during the production of anisotropic conductive film It is also possible to that the long-term reliability of electrical connection can be reduced after connecing.
In addition, conducting particles experienced the processes such as carbon fiber, solder, nickel powder and composite granule.Carbon fiber electrically conductance is not Height, in order to obtain sufficiently large conductance, it is necessary to which the particle of filling weight percentage 5%~25%, such ACF transparencies are very low. Solder grain easily forms intermetallic compound (IMC) in the welding process, and IMC is more crisp, with base material (electrode when encapsulation, zero Component or substrate etc.) between the performance differences such as coefficient of thermal expansion it is larger, if it is long it is too much be easy for generating cracking, bringing can By sex chromosome mosaicism.It has been proposed that the formation of IMC is avoided with moment fusion technology, but the technique increases tin-lead plating on salient point Layer, increases the complexity of technique.In pitch interconnection, the necessary very little of solder grain, but the diffusion of small solder grain generates IMC is required that the time is shorter, and integrity problem is just more serious, so in the ACF of ultra fine pitch, solder grain is rarely employed. Ni powder is easily formed unlike the polymer globules of cladding metal, but can also serve as conductive particle for oxidizable gold Belong to the interconnection of electrode.Ni powder, especially those surfaces are very suitable for destroying the oxygen of interconnection metal electrode there are many particle of burr Change layer.Composite granule refers mainly to the polymer globules for being coated with metal, the NEW TYPE OF COMPOSITE conductive particle that also exactly the present invention is studied Scope belonging to son.
Invention content
The invention mainly solves the technical problem of providing a kind of composite conducting glued membranes, have electrical characteristic good, then strong The characteristics such as good, solderability is good, reliability is good, and flame resistance is good are spent, there is better turn-on effect and connect compared to general conducting resinl Intensity, and production is easily achieved, market application prospect is extensive；Meanwhile the present invention in conducting particles can overcome carbon fiber, The shortcomings that when these materials such as solder, nickel powder are as conducting particles.
In order to solve the above technical problems, one aspect of the present invention is:A kind of composite conducting glued membrane is provided, is wrapped Include gluing adhesive layer, strengthening course, conductive adhesive layer and lower gluing oxidant layer, the strengthening course is located at the gluing adhesive layer and described leads Between electric glue-line, the conductive adhesive layer is located between the strengthening course and the lower gluing oxidant layer；
The thickness of the gluing adhesive layer is 25-35 μm, and the thickness of the lower gluing oxidant layer is 25-35 μm, the conduction Glue-line includes conducting particles, and the matrix of the conducting particles is ABS particles, and the surface of ABS particles coats a laminated layer gold, in institute It states and coats one layer of single metal layer on alloy-layer again, the alloy-layer is albata layer, and the single metal layer is silver layer or layer gold； The grain size of ABS particles is 10-50 μm；The thickness of the alloy-layer is 3-10 μm, and the thickness of the single metal layer is 4-8 μm, institute It is that surface is covered with the class strawberry-like particle of sheet protrusion, surface is covered with the class strawberry-like particle or table of needle-shaped protrusion to state conducting particles Face is covered with the class strawberry-like particle of rod-shaped protrusion；
The conductive adhesive layer further includes adhesive resin, and the ratio of the adhesive resin is 20-50% (weight ratio), institute The ratio for stating conducting particles is 30-80% (weight ratio), and the conducting particles and the adhesive resin ratio are 1:1-2:1 (weight ratio)；
It is metal mesh made of the braiding of micron-sized metal wire that the strengthening course, which is by line footpath, and the metal mesh is uniformly covered with Micropore, the micropore are rectangle or diamond shape, and the area of the micropore is 4-9 μm2。
In order to solve the above technical problems, the further technical solution that the present invention uses is:
The gluing adhesive layer and the lower gluing oxidant layer are all the conductive adhesive layer of epoxy series, and the conductive gluing Layer is made of the raw material of following parts by weight：50-60 parts of metallics, 12-13 parts of solid epoxy solution, 20-30 acetone, 4-8 parts of liquid epoxies, 2-5 parts of organic urine class curing agent, 2-5 parts of modified epoxies and 1-2 parts of three ethoxies of vinyl Base silane.
It further says, the metal wire is copper facing nickel wire, copper facing cobalt line, copper facing solder, copper facing silver wire, plating copper and iron nickel At least one of line, copper facing gold thread and coppered wire.
It further says, the modified epoxy is polyurethane modified epoxy resin or rubber modified epoxy resin, institute The epoxide equivalent for stating modified epoxy is 1000-1200g/eq.
It further says, release film is respectively formed with above the lower section of the lower gluing oxidant layer and the gluing adhesive layer The thickness of layer or carrier layer, the release film layer or carrier layer is 20-80 μm；The release film layer is that the modeling of PET fluorine is release Film layer, PET silicate-containing oils release film layer, PET matts release film layer, PE release film layers or PE lamination paper layers；The release film layer is Two-sided release film layer or single-sided parting film layer.
It further says, the preparation method of the ABS particles is as follows：
In the reactor equipped with mechanical agitation, condenser pipe and import and export of nitrogen, the liquid butadiene of predetermined amount, nothing is added Water-ethanol and deionized water, logical nitrogen are stirred, and are subsequently placed in the water-bath of 70-80 DEG C of temperature for use；Separately claim in beaker Enter the acrylonitrile, cumene hydroperoxide hydrogen and liquid soap of predetermined amount, after oscillation dissolving, be added in flask, be kept stirring and Logical nitrogen state, reaction 10-20h postcoolings terminate, and obtain emulsion product；Then it is dried after separation to particle；
Raw material mass mixture ratio is：100-200 parts of liquid butadiene, 500-800 parts of absolute ethyl alcohol, 40-50 parts of deionized water, 1-1.5 parts of 4-8 parts of acrylonitrile, 0.5-0.6 parts of cumene hydroperoxide hydrogen and liquid soap.
It further says, the method for ABS particle surface chemical alloying layers is as follows：By the matrix ABS particles of conducting particles, warp The pretreatment process such as roughing in surface, sensitization and activation are crossed, finally chemical plating fluid are used to plate last layer corronil on its surface Layer；
Chemical plating fluid quality proportioning and reaction condition are as follows：
Acid chemical plating liquid quality proportioning and reaction condition：14-18 parts of nickel sulfate, 14-20 parts of copper sulphate, sodium hypophosphite 15-16 parts, 11-13 parts of trisodium citrate, 10-15 parts, pH value in reaction 5.0-7.0 of sodium acetate, 35-40 DEG C of reaction temperature, reaction Time 20-35min.
It further says, cupro-nickel coating ABS particle surface chemical silver plating method is as follows：
It is added in plating solution through plating twice, while discontinuously stirring, cupro-nickel coating ABS particle after the plating predetermined time It finishes and isolates particle, and carry out rinsing, drying processing.
The present invention also provides a kind of production methods of the composite conducting glued membrane, include the following steps：
Step 1：The conducting particles prepared is mixed in proportion with adhesive resin, obtains mixture A, makes it fully It is uniformly mixed, it is spare；
Step 2：Braided metal net, it is spare；
Step 3: preparing the raw material of gluing adhesive layer and lower gluing oxidant layer, mixture B is obtained；
Step 4：It is specified from mixture made from shape face application step three up to lower gluing in release film layer or carrier layer Oxidant layer；
Step 5：The mixture made from the topical applying step one of lower gluing oxidant layer forms conductive adhesive layer；
Step 6：The metal mesh made from the other one side pressing step 2 of conductive adhesive layer；
Step 7：Mixture glues adhesive layer to obtain the final product made from the another side coating rapid three of metal net layer；
Step 8：Solidification, winding, slitting are to get finished product.
The beneficial effects of the invention are as follows：The present invention's has at least the following advantages：
One, conductive adhesive layer of the invention includes conducting particles, and wherein conducting particles is that the surface of ABS particles coats one layer Alloy-layer and coat one layer of single metal layer again over the alloyed layer, also conducting particles is the class strawberry-like that surface is covered with sheet protrusion Particle, surface are covered with the class strawberry-like particle of needle-shaped protrusion or surface is covered with the class strawberry-like particle of rod-shaped protrusion, due to conduction The surface bulge of particle, therefore can tend to multi-direction flowing when being generated deformation by hot pressing, conducting particles is being led after making pressing Distribution in electric adhering agent layer has multidirectional and polymolecularity, and then forms turning circuit with the ground hole on soft board, makes Adhesive layer and lower gluing oxidant layer, which must be glued, has good Anisotropically conductive, and electric conductivity is substantially improved, can reduce soft board Impedance ground value；
Two, the invention also includes strengthening courses, and it is metal mesh made of the braiding of micron-sized metal wire, gold that it, which is by line footpath, Belong to net and be uniformly covered with micropore, is realized by micropore therein because its reticular structure is conducive to the conducting particles being added in conductive adhesive layer The connection of upper and lower gluing oxidant layer, while because of its good gas permeability by SMT is not in that plate bursting shows in the processing procedure of the downstreams FPC As can effectively solve the problems, such as the conducting resinl of present market circulation and bury the plate bursting that metal layer conducting resinl can encounter；And it uses Strengthening course, and it is metal mesh made of the braiding of micron-sized metal wire that it, which is by line footpath, first, the electromagnetic screen of enhancing conductive adhesive film Covering property, second is that the mechanical strength of enhancing conductive adhesive film, extends the service life；
Five, the conducting particles in conductive adhesive layer of the invention is that first clad alloy layer coats single metal layer again and surface cloth The class strawberry-like particle of full protrusion, this structure energy band carry out electromagnetic wave screen effect (shielding properties ＞ 85dB)；Due to present IC's The design the more and more light and short, there is electromagnetic wave on many electronic building bricks, the utilization interfering with each other sometimes for influencing performance, And the electromagnetic wave generated on the effective docking point of conductive adhesive film energy of the present invention generates effective shield effectiveness；
Six, when the conducting particles that the conducting particles of the present invention is clad alloy layer, therefore the conducting resinl containing the conducting particles Film has splendid inoxidizability and conductibility, is carried convenient for product storage, and does not interfere with the physical property of product, make product it is stable, Reliability higher.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technical means of the present invention, And can be implemented in accordance with the contents of the specification, below with presently preferred embodiments of the present invention and after coordinating attached drawing to be described in detail such as.
Description of the drawings
Fig. 1 is the structural schematic diagram of the present invention；
Fig. 2 is one of the SEM demonstrative structure shape appearance figures of conducting particles of the present invention (16000 times)；
Fig. 3 is two (16000 times) of the SEM demonstrative structure shape appearance figures of the conducting particles of the present invention；
Fig. 4 is three (20000 times) of the SEM demonstrative structure shape appearance figures of the conducting particles of the present invention；
Reference sign：
Glue adhesive layer 100, strengthening course 200, conductive adhesive layer 300 and lower gluing oxidant layer 400.
Specific implementation mode
Illustrate that the specific implementation mode of the present invention, those skilled in the art can be by these below by way of particular specific embodiment The revealed content of specification understands advantages of the present invention and effect easily.The present invention can also other different modes give Implement, that is, can be in different modification and change under the scope of without departing substantially from disclosed.
Embodiment：A kind of composite conducting glued membrane 100, as shown in fig. 1 to 4, including gluing adhesive layer 100, strengthening course 200, Conductive adhesive layer 300 and lower gluing oxidant layer 400, the strengthening course is between the gluing adhesive layer and the conductive adhesive layer, institute Conductive adhesive layer is stated to be located between the strengthening course and the lower gluing oxidant layer；
The thickness of the gluing adhesive layer is 25-35 μm, and the thickness of the lower gluing oxidant layer is 25-35 μm, the conduction Glue-line includes conducting particles, and the matrix of the conducting particles is ABS particles, and the surface of ABS particles coats a laminated layer gold, in institute It states and coats one layer of single metal layer on alloy-layer again, the alloy-layer is albata layer, and the single metal layer is silver layer or layer gold； The grain size of ABS particles is 10-50 μm；The thickness of the alloy-layer is 3-10 μm, and the thickness of the single metal layer is 4-8 μm, institute It is that surface is covered with the class strawberry-like particle of sheet protrusion, surface is covered with the class strawberry-like particle or table of needle-shaped protrusion to state conducting particles Face is covered with the class strawberry-like particle of rod-shaped protrusion；
The conductive adhesive layer further includes adhesive resin, and the ratio of the adhesive resin is 20-50% (weight ratio), institute The ratio for stating conducting particles is 30-80% (weight ratio), and the conducting particles and the adhesive resin ratio are 1:1-2:1 (weight ratio)；
It is metal mesh made of the braiding of micron-sized metal wire that the strengthening course, which is by line footpath, and the metal mesh is uniformly covered with Micropore, the micropore are rectangle or diamond shape, and the area of the micropore is 4-9 μm2。
In the present embodiment, it is described gluing adhesive layer and the lower gluing oxidant layer be all epoxy series conductive adhesive layer, and The conductive adhesive layer is made of the raw material of following parts by weight：50-60 parts of metallics, 12-13 parts of solid epoxies are molten Liquid, 20-30 acetone, 4-8 parts of liquid epoxies, 2-5 parts of organic urine class curing agent, 2-5 parts of modified epoxies and 1-2 parts Vinyltriethoxysilane.
The metal wire be copper facing nickel wire, copper facing cobalt line, copper facing solder, copper facing silver wire, plating copper and iron nickel wire, copper facing gold thread and At least one of coppered wire, but not limited to this.
The modified epoxy is polyurethane modified epoxy resin or rubber modified epoxy resin, the modified epoxy tree The epoxide equivalent of fat is 1000-1200g/eq.
It is respectively formed with release film layer or carrier film above the lower section of the lower gluing oxidant layer and the gluing adhesive layer The thickness of layer, the release film layer or carrier layer is 20-80 μm；The release film layer is that PET fluorine moulds release film layer, PET contains Silicone oil release film layer, PET matts release film layer, PE release film layers or PE lamination paper layers；The release film layer is two-sided release film Layer or single-sided parting film layer.
The release film layer can two-sided or single side it is release, with it is two-sided it is release be preferred, thickness is preferred with 25-100 μm, too thin Or the too thick following process that is unfavorable for is punched.
The fractal film layer color is pure white, milky or Transparent color, preferentially selects pure white or milky.Numerical control is certainly When dynamicization equipment carves circuit, infrared induction, white areflexia optical issue can be positioned with fast accurate, process operation, and people When work handwork, white has recognition reaction, prevents from artificially leaking and tear.
The preparation method of the ABS particles is as follows：
In the reactor equipped with mechanical agitation, condenser pipe and import and export of nitrogen, the liquid butadiene of predetermined amount, nothing is added Water-ethanol and deionized water, logical nitrogen are stirred, and are subsequently placed in the water-bath of 70-80 DEG C of temperature for use；Separately claim in beaker Enter the acrylonitrile, cumene hydroperoxide hydrogen and liquid soap of predetermined amount, after oscillation dissolving, be added in flask, be kept stirring and Logical nitrogen state, reaction 10-20h postcoolings terminate, and obtain emulsion product；Then it is dried after separation to particle；
Raw material mass mixture ratio is：100-200 parts of liquid butadiene, 500-800 parts of absolute ethyl alcohol, 40-50 parts of deionized water, 1-1.5 parts of 4-8 parts of acrylonitrile, 0.5-0.6 parts of cumene hydroperoxide hydrogen and liquid soap.
The method of ABS particle surface chemical alloying layers is as follows：By the matrix ABS particles of conducting particles, by roughing in surface, The pretreatment process such as sensitization and activation, finally use chemical plating fluid to plate last layer albata layer on its surface；
Chemical plating fluid quality proportioning and reaction condition are as follows：
Acid chemical plating liquid quality proportioning and reaction condition：14-18 parts of nickel sulfate, 14-20 parts of copper sulphate, sodium hypophosphite 15-16 parts, 11-13 parts of trisodium citrate, 10-15 parts, pH value in reaction 5.0-7.0 of sodium acetate, 35-40 DEG C of reaction temperature, reaction Time 20-35min.
Cupro-nickel coating ABS particle surface chemical silver plating method is as follows：
It is added in plating solution through plating twice, while discontinuously stirring, cupro-nickel coating ABS particle after the plating predetermined time It finishes and isolates particle, and carry out rinsing, drying processing.
A kind of production method of the composite conducting glued membrane, it is characterised in that：Include the following steps：
Step 1：The conducting particles prepared is mixed in proportion with adhesive resin (can take ball milling, ball milling when mixing Rotating speed is not easy excessively high, preferentially selects 100-200r/min；Or agitating mode, rotating speed 500-1500r/min, the higher mixing of rotating speed are equal Even property can be preferable), mixture A is obtained, it is made to be sufficiently mixed uniformly, it is spare；
Step 2：Braided metal net, it is spare；
Step 3: preparing the raw material of gluing adhesive layer and lower gluing oxidant layer, mixture B is obtained；
Step 4：It is specified from mixture made from shape face application step three up to lower gluing in release film layer or carrier layer Oxidant layer；
Step 5：The mixture made from the topical applying step one of lower gluing oxidant layer forms conductive adhesive layer；
Step 6：Conductive adhesive layer it is other one side pressing step 2 made from metal mesh (precuring temperature no more than The solidification temperature of adhesive resin itself, in the present invention precuring temperature selection be convenient for subsequent production 80-100 DEG C of centre)；
Step 7：Mixture glues adhesive layer to obtain the final product made from the another side coating rapid three of metal net layer；
Step 8：Solidification, winding, slitting are to get finished product.
Conduction analysis test is carried out to removing the composite conducting glued membrane after release film layer：It is connected with high bridge tester Property analysis test, in gluing adhesive layer and lower adhesive layer side, for false patch nickel plating steel disc with after printed wiring board, pressing is solid respectively Change test sample respectively and cross conduction resistance value data before and after Reflow Soldering, test will be made to the present invention and be used as embodiment, with same Method tests the electric conductivity of common product as comparative example, and the conduction result measured is reported in Table 1 below.
Note：In embodiment 1 and embodiment 2, the microscopic pattern figure of conducting particles is as shown in Figure 2；Embodiment 3 and embodiment 4 In, the microscopic pattern figure of conducting particles is as shown in Figure 3；In embodiment 5, the microscopic pattern figure of conducting particles is as shown in Figure 4.
As seen from the above table, conductive adhesive film of the invention has good conductive effect and weldering really compared to common product Tin heat resistance and have good Bonding strength.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair Equivalent structure made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant technical fields, similarly It is included within the scope of the present invention.

Claims (9)

1. a kind of composite conducting glued membrane, it is characterised in that：Including gluing adhesive layer (100), strengthening course (200), conductive adhesive layer (300) and lower gluing oxidant layer (400), the strengthening course are described to lead between the gluing adhesive layer and the conductive adhesive layer Electric glue-line is located between the strengthening course and the lower gluing oxidant layer；
The thickness of the gluing adhesive layer is 25-35 μm, and the thickness of the lower gluing oxidant layer is 25-35 μm, the conductive adhesive layer Including conducting particles, the matrix of the conducting particles is ABS particles, and the surface of ABS particles coats a laminated layer gold, in the conjunction One layer of single metal layer is coated in layer gold again, the alloy-layer is albata layer, and the single metal layer is silver layer or layer gold；ABS The grain size of particle is 10-50 μm；The thickness of the alloy-layer is 3-10 μm, and the thickness of the single metal layer is 4-8 μm, described to lead Charged particle is that surface is covered with the class strawberry-like particle of sheet protrusion, surface is covered with the class strawberry-like particle or surface cloth of needle-shaped protrusion The class strawberry-like particle of full rod-shaped protrusion；
The conductive adhesive layer further includes adhesive resin, and the ratio of the adhesive resin is 20-50% (weight ratio), described to lead The ratio of charged particle is 30-80% (weight ratio), and the conducting particles and the adhesive resin ratio are 1:1-2:1 (weight Than)；
It is metal mesh made of the braiding of micron-sized metal wire that the strengthening course, which is by line footpath, and the metal mesh is uniformly covered with micro- Hole, the micropore are rectangle or diamond shape, and the area of the micropore is 4-9 μm2。
2. composite conducting glued membrane according to claim 1, it is characterised in that：The gluing adhesive layer and the lower adhesive Layer is all the conductive adhesive layer of epoxy series, and the conductive adhesive layer is made of the raw material of following parts by weight：50-60 parts of gold Belong to particle, 12-13 parts of solid epoxy solution, 20-30 acetone, 4-8 parts of liquid epoxies, 2-5 parts of organic urine class solidifications Agent, 2-5 parts of modified epoxies and 1-2 parts of vinyltriethoxysilane.
3. composite conducting glued membrane according to claim 1, it is characterised in that：The metal wire is copper facing nickel wire, copper facing cobalt At least one of line, copper facing solder, copper facing silver wire, plating copper and iron nickel wire, copper facing gold thread and coppered wire.
4. composite conducting glued membrane according to claim 2, it is characterised in that：The modified epoxy is polyurethane-modified The epoxide equivalent of epoxy resin or rubber modified epoxy resin, the modified epoxy is 1000-1200g/eq.
5. composite conducting glued membrane according to claim 1, it is characterised in that：The lower section of the lower gluing oxidant layer and it is described on It is respectively formed with release film layer or carrier layer above gluing oxidant layer, the thickness of the release film layer or carrier layer is 20- 80μm；The release film layer is that PET fluorine moulds release film layer, PET silicate-containing oils release film layer, PET matts release film layer, PE release films Layer or PE lamination paper layers；The release film layer is two-sided release film layer or single-sided parting film layer.
6. composite conducting glued membrane according to claim 1, it is characterised in that：The preparation method of the ABS particles is as follows：
In the reactor equipped with mechanical agitation, condenser pipe and import and export of nitrogen, the liquid butadiene of predetermined amount, anhydrous second is added Alcohol and deionized water, logical nitrogen are stirred, and are subsequently placed in the water-bath of 70-80 DEG C of temperature for use；It is separately weighed into beaker pre- Quantitative acrylonitrile, cumene hydroperoxide hydrogen and liquid soap is added in flask after oscillation dissolving, is kept stirring and leads to nitrogen Gaseity, reaction 10-20h postcoolings terminate, and obtain emulsion product；Then it is dried after separation to particle；
Raw material mass mixture ratio is：100-200 parts of liquid butadiene, 500-800 parts of absolute ethyl alcohol, 40-50 parts of deionized water, propylene 1-1.5 parts of 4-8 parts of nitrile, 0.5-0.6 parts of cumene hydroperoxide hydrogen and liquid soap.
7. composite conducting glued membrane according to claim 6, it is characterised in that：The method of ABS particle surface chemical alloying layers It is as follows：By the matrix ABS particles of conducting particles, by pretreatment process such as roughing in surface, sensitization and activation, last useization It learns plating solution and plates last layer albata layer on its surface；
Chemical plating fluid quality proportioning and reaction condition are as follows：
Acid chemical plating liquid quality proportioning and reaction condition：14-18 parts of nickel sulfate, 14-20 parts of copper sulphate, sodium hypophosphite 15- 16 parts, 11-13 parts of trisodium citrate, 10-15 parts, pH value in reaction 5.0-7.0 of sodium acetate, 35-40 DEG C of reaction temperature, the reaction time 20-35min。
8. composite conducting glued membrane according to claim 7, it is characterised in that：Cupro-nickel coating ABS particle surface chemical silvering Method is as follows：
By cupro-nickel coating ABS particle, it is added in plating solution through plating twice, while discontinuously stirring, plating finishes after the predetermined time Particle is isolated, and carries out rinsing, drying processing.
9. a kind of production method of composite conducting glued membrane according to claim 8, it is characterised in that：Include the following steps：
Step 1：The conducting particles prepared is mixed in proportion with adhesive resin, mixture A is obtained, it is made to be sufficiently mixed Uniformly, spare；
Step 2：Braided metal net, it is spare；
Step 3: preparing the raw material of gluing adhesive layer and lower gluing oxidant layer, mixture B is obtained；
Step 4：It is specified from mixture made from shape face application step three up to lower adhesive in release film layer or carrier layer Layer；
Step 5：The mixture made from the topical applying step one of lower gluing oxidant layer forms conductive adhesive layer；
Step 6：The metal mesh made from the other one side pressing step 2 of conductive adhesive layer；
Step 7：Mixture glues adhesive layer to obtain the final product made from the another side coating rapid three of metal net layer；
Step 8：Solidification, winding, slitting are to get finished product.
CN201810203552.0A 2018-03-13 2018-03-13 Composite conductive adhesive film and manufacturing method thereof Active CN108531092B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109462937A (en) * 2019-01-08 2019-03-12 昆山域之光电子有限公司 Novel different side's conductive adhesive film and preparation method thereof
CN113845862A (en) * 2020-06-28 2021-12-28 中国科学院理化技术研究所 Conductive and heat-conducting adhesive film and preparation method and application thereof
CN115368849A (en) * 2021-05-20 2022-11-22 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
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
JP2016110995A (en) * 2014-12-08 2016-06-20 日東電工株式会社 Transparent conductive film with pressure-sensitive adhesive layer
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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CN109462937A (en) * 2019-01-08 2019-03-12 昆山域之光电子有限公司 Novel different side's conductive adhesive film and preparation method thereof
CN113845862A (en) * 2020-06-28 2021-12-28 中国科学院理化技术研究所 Conductive and heat-conducting adhesive film and preparation method and application thereof
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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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