CA2120523C - Electrically conductive compositions and methods for the preparation and use thereof - Google Patents
Electrically conductive compositions and methods for the preparation and use thereof Download PDFInfo
- Publication number
- CA2120523C CA2120523C CA002120523A CA2120523A CA2120523C CA 2120523 C CA2120523 C CA 2120523C CA 002120523 A CA002120523 A CA 002120523A CA 2120523 A CA2120523 A CA 2120523A CA 2120523 C CA2120523 C CA 2120523C
- Authority
- CA
- Canada
- Prior art keywords
- solder
- composition
- linking agent
- cross
- volume
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1035—Liquid phase sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
-
- 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
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49827—Via connections through the substrates, e.g. pins going through the substrate, coaxial cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
- H01L23/49883—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials the conductive materials containing organic materials or pastes, e.g. for thick films
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/538—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames the interconnection structure between a plurality of semiconductor chips being formed on, or in, insulating substrates
- H01L23/5384—Conductive vias through the substrate with or without pins, e.g. buried coaxial conductors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
- H01L2224/29299—Base material
- H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01019—Potassium [K]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01068—Erbium [Er]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01079—Gold [Au]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01087—Francium [Fr]
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/18—Printed circuits structurally associated with non-printed electric components
- H05K1/181—Printed circuits structurally associated with non-printed electric components associated with surface mounted components
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0263—Details about a collection of particles
- H05K2201/0272—Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10227—Other objects, e.g. metallic pieces
- H05K2201/10378—Interposers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/04—Soldering or other types of metallurgic bonding
- H05K2203/0425—Solder powder or solder coated metal powder
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1105—Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1216—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by screen printing or stencil printing
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
- H05K3/4053—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques
- H05K3/4069—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques for via connections in organic insulating substrates
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4623—Manufacturing multilayer circuits by laminating two or more circuit boards the circuit boards having internal via connections between two or more circuit layers before lamination, e.g. double-sided circuit boards
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4664—Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders
Abstract
Electrically conductive adhesive compositions and methods for the preparation and use thereof; in which a solder powder, a chemically protected cross-linking agent-with fluxing properties and a reactive monomer or polymer sue the principal components.
Depending upon the intended end use; the compositions comprise three or more of the following: a relatively high melting metal powder; solder powder; the active cross-linking agent which also serves as a fluxing agent; a resin; and a reactive monomer or polymer. The compositions are useful as improved conductive adhesives, such as for attaching electrical components to electrical circuits; the compositions comprising metal powder are ideally suited for creating the conductive paths on printed circuits.
The compositions for forming conductive-paths may first be applied to a substrate in the desired pattern of an electrical circuit, and then heated to cure it. During heating, the action of the cross-linking agent and optional reactive monomer or polymer within the mixture fluxes the metals, enabling sintering to occur between the metal powder and the solder powder.
Depending upon the intended end use; the compositions comprise three or more of the following: a relatively high melting metal powder; solder powder; the active cross-linking agent which also serves as a fluxing agent; a resin; and a reactive monomer or polymer. The compositions are useful as improved conductive adhesives, such as for attaching electrical components to electrical circuits; the compositions comprising metal powder are ideally suited for creating the conductive paths on printed circuits.
The compositions for forming conductive-paths may first be applied to a substrate in the desired pattern of an electrical circuit, and then heated to cure it. During heating, the action of the cross-linking agent and optional reactive monomer or polymer within the mixture fluxes the metals, enabling sintering to occur between the metal powder and the solder powder.
Description
ELECTRICALLY CONDUCTIVE COMPOSTTIONS AND METHODS
FOR THE PREPARATION AND USE THEREOF
Background of the Invention The present invention relates to electrically conductive adhesive compositions suitable for a variety of applications, as well as to methods for the S preparation and use thereof.
In recent years, electronic devices have increasingly employed printed circuits produced using electrically conductive adhesive compositions, commonly known as polymer thick film inks. This method is much more cost-effective and efficient than other known methods of wiring (such as, for example, chemical etching or plating of copper foil). The majority of the electrically conductive adhesive compositions currently in use are in the form of thermosetting or thermoplastic resin pastes with silver or copper powder as the conductor.
Unfortunately, the heretofore known electrically conductive adhesive compositions are not comparable to copper foil wiring in terms of conductivity, adhesion and solderability. The metal-filled pastes also suffer from degradation of electrical conductivity with aging after curing, and they respond poorly to temperature and humidity fluctuations. It is speculated that these problems result in large part from the high silver or copper powder loadings required to achieve acceptable electrical conductivity.
In order to overcome these shortcomings, it has been suggested to disperse within said metal powder-resin formulations a solder powder having a melting point at or below the vitrification temperature of the resin. The purpose of the solder is to sinter the copper or silver particles together before setting the resin, thus creating solid electrically conductive bridges between them. Such formulations have exhibited somewhat improved electrical conductivity and solderability. Nonetheless, the proposed compositions including solder powder also suffer from significant problems which have prevented their commercial use.
One such problem relates to the use of fluxing agents. In general, soldering the metal particles together requires fluxing agents to remove metal CVO 93106943 ~ ~ PC.T/US92/08333 oxides and promote wetting of the metal filler by the molten solder. The meal filler typically consists of many small, irregularly-shaped particles. These compositions have a substantial surface area which must be cleaned of naturally-occurring oxides; in particular, the small particles required for creating fine traces on printed circuits have proportionally large surface areas to be de-oxidized.
The heretofore known compositions usually call for addition to the compositions of substantial quantities of fluxing or activating agents, such as organic and inorganic acids and salts thereof, in order to achieve the required fluxing strength.
Examples of common fluxing agents in general use include abietic acid, stearic acid, hydrochloric acid, amine hydrochlorides and amine resins.
Weak fluxing agents, such as most organic acids, do not clean the large surface areas presented by the metal particles adequately.. Electrically-conductive compositions without strong activating fluxes produce poor conductors, as poor as their polymer thick film ink predecessors. Therefore, strong fluxing agents are required and the strongest acids (such as the amine hydrochlorides) have been shown in the prior art to be the best fluxes. Unfortunately, these strong fluxes are harmful to the compositions after curing, creating problems with adhesion and long term stability. Adding strongly acidic fluxing agents to the compositions increases conductivity markedly, but the acids remain corrosive after the compositions have been cured; the residual corrosive fluxes then degrade the cured compositions on printed circuits. They may also harm other components on a printed circuit board, particularly under conditions of high humidity.
The presence of the strong fluxing agents in the compositions during and after curing also decreases their adhesive strength. Delamination and poor peel strength are characteristics of compositions comprising most acidic fluxing agents.
'These deficiencies arise from the effect of the fluxing agents on the resins employed. One effect is that inorganic acid or salt fluxing agents tend to break up the polymer chains of the resin during cure. Single acid group organic fluxing agents, such as abietic acid (the principal component in rosin flux), tend to reduce cross-linking of the resin by termination of polymeric chains. As a high degree of cross-linking is essential for strong cohesive and adhesive strength of the composition, fluxing agents that tend to terminate polymerization or break up .~.~~3 long polymer chains reduce both adhesion and'~cohesion of the cured composition.
Another technique known in the prior art to reduce the incidence of metal oxide formation has been to pre-coat the metal particles with solder. Pre-coating increases wetting of the metal panicles by the solder when molten. Employing coated particles does not eliminate the need for strong fluxes, however, particularly when compositions include metal particles with diameters below 20 microns. Precoating the metal particles with solder also adds to the expense of the product while producing only inconsistent improvement.
It is an object of the present invention to provide electrically conductive adhesive compositions which overcome the drawbacks of the heretofore known materials.
Summary of the Invention In accordance with the present invention, there are provided electrically conductive adhesive compositions comprising in the most general terms a solder powder, a chemically protected cross-linking agent with fluxing properties and a reactive monomer or polymer. Depending upon the intended end use, the compositions comprise three or more of the following: a relatively high melting metal powder (hereinafter, metal powder); the aforementioned lower melting point metal powder (hereinafter, solder powder); the aforementioned active cross-linking agent which also serves as a fluxing agent; a resin; and a reactive monomer. The compositions may be employed as improved conductive adhesives, such as for attaching electrical components to electrical circuits. The compositions comprising metal powder are ideally suited for creating the conductive paths on printed circuits.
The compositions far forming conductive paths may first be applied to a substrate in the desired pattern of an electrical circuit, then heated to cure it.
During heating, the action of the cross-linking agent and optional reactive monomer or polymer within the mixture fluxes the metals, enabling sintering to occur between the metal powder and the solder powder. For this reason, the composition provides superior electrical conductivity with little opportunity for conductivity deterioration due to oxidation, corrosion or thermal expansion and contraction.
WO 93106943 ~ PCT/US92/08333 Brief Description of the Drawings The invention may be better understood with reference to the accompanying drawings, in which:
Fig. 1 illustrates the effects of varying alloys on conductivity of the S final composition;
Fig. 2 shows the effects of relative concentration changes on resistivities for a preferred sample composition;
Fig. 3 illustrates the effect of adding a third metal or metal alloy powder incorporating high melting point metals which readily dissolve in the molten solder powder;
Fig. 4 is a schematic diagram of a dc-to-do converter circuit; and Fig. 5 is a printed circuit pattern for the converteF circuit illustrated in Fig. 4.
Detailed Description of the Invention The present invention was designed not only to obviate the shortcomings of the heretofore known compositions, but also to provide a conductive adhesive composition with the following advantageous properties:
(a) A bulk electrical conductivity approaching that of solid copper (never achieved with the previous compositions);
(b) Good solderability of the cured compositions without need to piste the resultant cured compositions;
(c) Adhesive strengths comparable to copper clad FR4 epoxy printed circuit board laminates; and (d) Highly corrosion resistant final products with resistance to degradation at high temperatures and relative humidifies.
It had not heretofore been possible to achieve this combination of properties in a single composition.
As a conductive adhesive, the compositions of the present invention offer many desirable characteristics. The electrical conductivity of the inventive compositions are superior to the known conductive polymer thick films. Unlike prior art polymer thick films, moreover, the inventive compositions are generally solderable. The compositions may be screen printed with higher precision than current solder pastes. Unlike current solder pastes, they exhibit less of a tendency towards formation of solder "satellites" and bridging. After curing, no cleaning ory washing for flux removal is required.
The adhesion properties, mechanical integrity, and corrosion resistance of the compositions of the invention are far superior to those of previous compositions, because there is no need to add aggressive fluxing agents. The compositions are fully cross-linked, and all components thereof are chemically immobilised upon curing. Even the reaction by-products of the flux de-oxidation of the metals seem to be chemically bound in the polymer matrix. The presence of the reactive monomer in the composition controls the rate of curing of the resin ensuring strong adhesion of the composition to the circuit board substrate upon curing. With certain formulations, soldering to the cured composition is possible.
In general terms, the electrically conductive adhesive compositions comprise two primary components: a low melting point metal or metal alloy powder and cross-linking agent mixture comprising a protected curing agent, which also acts as a primary fluxing agent. Depending upon the intended end use, the preferred compositions of the invention contain three or more of the following:
( 1 ) Optionally, a high melting point metal or metal alloy powder;
(2) A low melting point metal or metal alloy powder (solder);
(3) Optionally, a resin;
(4) A cross-linking agent mixture comprising a protected curing agent, which also acts as a primary fluxing agent; and - (5) Optionally, a reactive monomer or polymer which can be cross-linked by the curing agent (hereinafter referred to as the "monomer").
The compositions frequently also contain at least one solvent; they may also contain other additives to improve certain properties such as adhesion or solderability. The composition must either contain (3) and/or (S), or alternatively (3) and/or (5) may be combined with (4) into a single species, as in the case of a protected homopolvmerizable resin. Preferably, components (3), (4) and/or (5) 4V~ 93/t16943 are halosenated.
PC,'T/L1S92/08333 In preparing the composition. the proportions of components ( 1}-(5) plus a solvent may be varied aver a considerable range and still yield an electrically conductive material once cured. :vleasurable electrical conductivity can be achieved with component (1) comprising from 0-65% of the volume of the composition (0% being the case of a composition useful as a solder paste).
Similarly, component (2) comprises from 6-b5% by volume of the composition.
Component (3) comprises from 0-45% of the composition by volume {0% being the case of a solder paste which requires no adhesive). Component (4) comprises 0.01-61% of the composition by volume. Component (5) comprises 0-50% of the composition by volume. Some of the compositions within these ranges exhibit some shrinkage and cracking or balling when cured: however, they remain useful as conductive adhesives in applications where these characteristics are harmless.
such as in attaching components to electrical circuits.
Preferably, the composition after curing has a bulk electrical resistivity of less than 10'~ Qhm-cm. This electrical conductivity range can be satisfied by numerous formulations having components {1)-(5) within the following ranges:
Component ( 1 ): 0-38% of the volume of the composition (values near 0% being compositions useful as solder pastes);
Component (2): 6-37% by volume of the composition;
Component (3): 0-42% by volume (values near 0% being campositions useful as solder pastes);
Component (4): 7-60% by volume;
Component (5): 0-47% by volume.
Same of the compositions within these ranges may exhibit shrinkage and cracking or balling when cured, but they remain useful as conductive adhesives in applications where these characteristics are harmless.
Most preferably, the composition has a bulk electrical resistivity of approximately 3 x 10'5 or less. These characteristics can be satisfied by numerous formulations having components ( 1 )-(S) within the following ranges:
Component (1): 13-38% of the volume of the composition (values near 13% being compositions useful as solder pastes);
FOR THE PREPARATION AND USE THEREOF
Background of the Invention The present invention relates to electrically conductive adhesive compositions suitable for a variety of applications, as well as to methods for the S preparation and use thereof.
In recent years, electronic devices have increasingly employed printed circuits produced using electrically conductive adhesive compositions, commonly known as polymer thick film inks. This method is much more cost-effective and efficient than other known methods of wiring (such as, for example, chemical etching or plating of copper foil). The majority of the electrically conductive adhesive compositions currently in use are in the form of thermosetting or thermoplastic resin pastes with silver or copper powder as the conductor.
Unfortunately, the heretofore known electrically conductive adhesive compositions are not comparable to copper foil wiring in terms of conductivity, adhesion and solderability. The metal-filled pastes also suffer from degradation of electrical conductivity with aging after curing, and they respond poorly to temperature and humidity fluctuations. It is speculated that these problems result in large part from the high silver or copper powder loadings required to achieve acceptable electrical conductivity.
In order to overcome these shortcomings, it has been suggested to disperse within said metal powder-resin formulations a solder powder having a melting point at or below the vitrification temperature of the resin. The purpose of the solder is to sinter the copper or silver particles together before setting the resin, thus creating solid electrically conductive bridges between them. Such formulations have exhibited somewhat improved electrical conductivity and solderability. Nonetheless, the proposed compositions including solder powder also suffer from significant problems which have prevented their commercial use.
One such problem relates to the use of fluxing agents. In general, soldering the metal particles together requires fluxing agents to remove metal CVO 93106943 ~ ~ PC.T/US92/08333 oxides and promote wetting of the metal filler by the molten solder. The meal filler typically consists of many small, irregularly-shaped particles. These compositions have a substantial surface area which must be cleaned of naturally-occurring oxides; in particular, the small particles required for creating fine traces on printed circuits have proportionally large surface areas to be de-oxidized.
The heretofore known compositions usually call for addition to the compositions of substantial quantities of fluxing or activating agents, such as organic and inorganic acids and salts thereof, in order to achieve the required fluxing strength.
Examples of common fluxing agents in general use include abietic acid, stearic acid, hydrochloric acid, amine hydrochlorides and amine resins.
Weak fluxing agents, such as most organic acids, do not clean the large surface areas presented by the metal particles adequately.. Electrically-conductive compositions without strong activating fluxes produce poor conductors, as poor as their polymer thick film ink predecessors. Therefore, strong fluxing agents are required and the strongest acids (such as the amine hydrochlorides) have been shown in the prior art to be the best fluxes. Unfortunately, these strong fluxes are harmful to the compositions after curing, creating problems with adhesion and long term stability. Adding strongly acidic fluxing agents to the compositions increases conductivity markedly, but the acids remain corrosive after the compositions have been cured; the residual corrosive fluxes then degrade the cured compositions on printed circuits. They may also harm other components on a printed circuit board, particularly under conditions of high humidity.
The presence of the strong fluxing agents in the compositions during and after curing also decreases their adhesive strength. Delamination and poor peel strength are characteristics of compositions comprising most acidic fluxing agents.
'These deficiencies arise from the effect of the fluxing agents on the resins employed. One effect is that inorganic acid or salt fluxing agents tend to break up the polymer chains of the resin during cure. Single acid group organic fluxing agents, such as abietic acid (the principal component in rosin flux), tend to reduce cross-linking of the resin by termination of polymeric chains. As a high degree of cross-linking is essential for strong cohesive and adhesive strength of the composition, fluxing agents that tend to terminate polymerization or break up .~.~~3 long polymer chains reduce both adhesion and'~cohesion of the cured composition.
Another technique known in the prior art to reduce the incidence of metal oxide formation has been to pre-coat the metal particles with solder. Pre-coating increases wetting of the metal panicles by the solder when molten. Employing coated particles does not eliminate the need for strong fluxes, however, particularly when compositions include metal particles with diameters below 20 microns. Precoating the metal particles with solder also adds to the expense of the product while producing only inconsistent improvement.
It is an object of the present invention to provide electrically conductive adhesive compositions which overcome the drawbacks of the heretofore known materials.
Summary of the Invention In accordance with the present invention, there are provided electrically conductive adhesive compositions comprising in the most general terms a solder powder, a chemically protected cross-linking agent with fluxing properties and a reactive monomer or polymer. Depending upon the intended end use, the compositions comprise three or more of the following: a relatively high melting metal powder (hereinafter, metal powder); the aforementioned lower melting point metal powder (hereinafter, solder powder); the aforementioned active cross-linking agent which also serves as a fluxing agent; a resin; and a reactive monomer. The compositions may be employed as improved conductive adhesives, such as for attaching electrical components to electrical circuits. The compositions comprising metal powder are ideally suited for creating the conductive paths on printed circuits.
The compositions far forming conductive paths may first be applied to a substrate in the desired pattern of an electrical circuit, then heated to cure it.
During heating, the action of the cross-linking agent and optional reactive monomer or polymer within the mixture fluxes the metals, enabling sintering to occur between the metal powder and the solder powder. For this reason, the composition provides superior electrical conductivity with little opportunity for conductivity deterioration due to oxidation, corrosion or thermal expansion and contraction.
WO 93106943 ~ PCT/US92/08333 Brief Description of the Drawings The invention may be better understood with reference to the accompanying drawings, in which:
Fig. 1 illustrates the effects of varying alloys on conductivity of the S final composition;
Fig. 2 shows the effects of relative concentration changes on resistivities for a preferred sample composition;
Fig. 3 illustrates the effect of adding a third metal or metal alloy powder incorporating high melting point metals which readily dissolve in the molten solder powder;
Fig. 4 is a schematic diagram of a dc-to-do converter circuit; and Fig. 5 is a printed circuit pattern for the converteF circuit illustrated in Fig. 4.
Detailed Description of the Invention The present invention was designed not only to obviate the shortcomings of the heretofore known compositions, but also to provide a conductive adhesive composition with the following advantageous properties:
(a) A bulk electrical conductivity approaching that of solid copper (never achieved with the previous compositions);
(b) Good solderability of the cured compositions without need to piste the resultant cured compositions;
(c) Adhesive strengths comparable to copper clad FR4 epoxy printed circuit board laminates; and (d) Highly corrosion resistant final products with resistance to degradation at high temperatures and relative humidifies.
It had not heretofore been possible to achieve this combination of properties in a single composition.
As a conductive adhesive, the compositions of the present invention offer many desirable characteristics. The electrical conductivity of the inventive compositions are superior to the known conductive polymer thick films. Unlike prior art polymer thick films, moreover, the inventive compositions are generally solderable. The compositions may be screen printed with higher precision than current solder pastes. Unlike current solder pastes, they exhibit less of a tendency towards formation of solder "satellites" and bridging. After curing, no cleaning ory washing for flux removal is required.
The adhesion properties, mechanical integrity, and corrosion resistance of the compositions of the invention are far superior to those of previous compositions, because there is no need to add aggressive fluxing agents. The compositions are fully cross-linked, and all components thereof are chemically immobilised upon curing. Even the reaction by-products of the flux de-oxidation of the metals seem to be chemically bound in the polymer matrix. The presence of the reactive monomer in the composition controls the rate of curing of the resin ensuring strong adhesion of the composition to the circuit board substrate upon curing. With certain formulations, soldering to the cured composition is possible.
In general terms, the electrically conductive adhesive compositions comprise two primary components: a low melting point metal or metal alloy powder and cross-linking agent mixture comprising a protected curing agent, which also acts as a primary fluxing agent. Depending upon the intended end use, the preferred compositions of the invention contain three or more of the following:
( 1 ) Optionally, a high melting point metal or metal alloy powder;
(2) A low melting point metal or metal alloy powder (solder);
(3) Optionally, a resin;
(4) A cross-linking agent mixture comprising a protected curing agent, which also acts as a primary fluxing agent; and - (5) Optionally, a reactive monomer or polymer which can be cross-linked by the curing agent (hereinafter referred to as the "monomer").
The compositions frequently also contain at least one solvent; they may also contain other additives to improve certain properties such as adhesion or solderability. The composition must either contain (3) and/or (S), or alternatively (3) and/or (5) may be combined with (4) into a single species, as in the case of a protected homopolvmerizable resin. Preferably, components (3), (4) and/or (5) 4V~ 93/t16943 are halosenated.
PC,'T/L1S92/08333 In preparing the composition. the proportions of components ( 1}-(5) plus a solvent may be varied aver a considerable range and still yield an electrically conductive material once cured. :vleasurable electrical conductivity can be achieved with component (1) comprising from 0-65% of the volume of the composition (0% being the case of a composition useful as a solder paste).
Similarly, component (2) comprises from 6-b5% by volume of the composition.
Component (3) comprises from 0-45% of the composition by volume {0% being the case of a solder paste which requires no adhesive). Component (4) comprises 0.01-61% of the composition by volume. Component (5) comprises 0-50% of the composition by volume. Some of the compositions within these ranges exhibit some shrinkage and cracking or balling when cured: however, they remain useful as conductive adhesives in applications where these characteristics are harmless.
such as in attaching components to electrical circuits.
Preferably, the composition after curing has a bulk electrical resistivity of less than 10'~ Qhm-cm. This electrical conductivity range can be satisfied by numerous formulations having components {1)-(5) within the following ranges:
Component ( 1 ): 0-38% of the volume of the composition (values near 0% being compositions useful as solder pastes);
Component (2): 6-37% by volume of the composition;
Component (3): 0-42% by volume (values near 0% being campositions useful as solder pastes);
Component (4): 7-60% by volume;
Component (5): 0-47% by volume.
Same of the compositions within these ranges may exhibit shrinkage and cracking or balling when cured, but they remain useful as conductive adhesives in applications where these characteristics are harmless.
Most preferably, the composition has a bulk electrical resistivity of approximately 3 x 10'5 or less. These characteristics can be satisfied by numerous formulations having components ( 1 )-(S) within the following ranges:
Component (1): 13-38% of the volume of the composition (values near 13% being compositions useful as solder pastes);
WO 93/t16943 PGT/US92/08333 Component ('): 6-29% by volume or the composition:
Component (3): 0-15% by volume (values near 0% being compositions useful as solder pastes);
Component (4): 30-52% by volume;
Component (5): 0-32% by volume.
While again some of the compositions within these ranges may exhibit shrinkage and cracking or balling when cured, they remain useful as conductive adhesives in applications where these characteristics are harmless.
Typically, the high melting paint metal powder (1) is copper powder, however, other metals such as silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum and high-melting point alloys of these metals, may alternatively be employed. Preferably, the. copper powder is spherical or nearly spherical as produced by gas atomization. Electrohrtic powders or flakes, recommended in the prior art, are not desirable for several reasons. Irregularly-shaped powder particles tend to be sponge-like in morphology, increasing the oxidized surface area substantially as compared to spherical particles. Irregular particles are also more difficult to flux and wet with molten metal. They result in compositions having poorer electrical conductivity.
A spherical powder containing a wide distribution of particle sizes distributed approximately normally about an average particle diameter is preferred over monosized spheres. The wide distribution of sizes increases the density of the packed metal powder as compared to monosized spheres, improving electrical conductivity and mechanical integrity. The powder generally has an average particle diameter of 1 to 50 microns. The preferred powder has a mean particle diameter of 10-30 microns.
Most preferably, the powder is de-oxidized in a hydrogen oven at least at 30f° C for about 10 minutes prior to use. Removal of naturally-existing surface oxides from the copper particles has been shown to have a marked improvement in the resulting resistivity of the final cured composition.
The solder powder may be Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Tl, Sb, Se, Po, or an alloy or other metal having a melting point lower than that of the metal powder in ( 1). Typically, the powder has a mean particle diameter of 1-40 ratcrons: preterabl~~the average particle diameter is ices than or eaual to the .
average diameter of the high melting point metal particles and the ' article size P
dtstnbution is substantially the same as that of the high melting point metal powder. The principal requiremem of the alloy is that it flow in the composition before the vitrification of the polymers in the composition. In order for this t oceur, the sofder alloy mu: ; readily wet copper. For this reason. allays of tin are ideal. Preferably, the solder powder consists of Sn and Pb.
The resin functions principally to adhere the cured composition to the substrata to provide chemical binding sites for the reaction products after curie g, and to increase the cohesive strength of the cured composition. The resin also functions as a medium for delivering flux to the metal powder, as a thickening binder for the composition, and as a medium for increasing the .eau tuition temperature of the cured composition. In order for the composition to achieve the highest electrical conductivities. it must achieve and maintain low viscosity up to the temperature at which the solder powder melts and wets the co er ' PP
powder. If the resin becomes too thick before the solder powder has melted, it will impede the flow of the melt and reduce the degree of metal powder soldering. For this reason. the curing of the resin must occur slowly relative to the time required to reach the melting paint of the solder powder.
0 The resin (3) may be any resin which can be cross-linked by the curie g agent: a metal catalyst, or a hydroxyl group-bearing agent. Resins which meet this requirement include but are not limited to epoxies, phenolics, novolacs (bflth phenolic and cresolic), polwrethanes, polNmides, bismaieimides, maIeimides, cyanate esters, polyvinyl alcohols, polyesters. and potwreas. Other resin systems may be modified to be crass-linkable by the curing a ent, a met g al catalyst, or a hydroxyl group-bearing agent. Examples of such resins are acrylics, rubbers (butyl, nitriIe, etc), polvamides, polyactyiates, polyethers, poivsulfones.
polyethylenes, polypropylenes. polysiloxancs, polyvinyl acetates/polvvin 1 esters Y , polyolefins, cvanoacrylates, and polystyrenes. Typically, any resin would function 30 in this. invention if the resin can be modified to contain at least o ne of the foilowtng functional groups: anhydrides, carboxylic acids, amides. imides, amines.
alcohols/phenols, aldehvdes/ketones, vitro compounds. nitrites. carbamates, WO 93/06943 ~ ~ ~ PGT/US92/08333 isocyanates, amino acidslpeptides. thiols. sulfonamides. setnicarbazones, oximes.
hydrazones, cyanohydrins. ureas, phosphoric esters/acids, thiophosphoric esterslacids, phosphonic esters/acids, phosphites, phosphonamides, sulfonic esters/acids or other functional groups known to one skilled in the an to act as reactive sites for polymerization. For example, a polyolefin would not be suitable as a resin in this invention, as it has no reactive sites for binding and has poor adhesive properties; however, a carboxylated polyolefin functions well when matched with a suitable cross-linking agent. A combination of these and other resins, such as non-cross-linkable thermoplastic resins, may also be used as component (3). Presently preferred is an epoxy resin, such as the -reaction product of epichlorohydrin and bisphenoi A, combined with a phenolic epoxy resin.
The principal feature of the cross-linking agent is that in its unprotected form it acts as an acid or a strong base. Most acids and strong bases function well as fluxing agents, because they can remove oxides from metals. However, if they are left in their reactive form in the composition they would prematurely cross-link the resin or become used up in reactions with the metal powders.
The principal property of a protected curing agent in this invention is that it remain largely unreactive until it is needed to flux the metal powder and cross-link the ?0 resin. Protection may be achieved by chemically binding the agent with a chemically- or thermally-triggered species so that it becomes reactive only at or near the time that the solder powder melts. Protection may also be achieved mechanically, for example by encapsulating the curing agent in a shell of non-reactive material which releases the curing agent only at or near the melting 'S time of the solder powder.
Cross-linking agents (4) known in the art include anhydrides, carboxylic acids, amides, imides, amines, alcohols/phenols, aldehydes/ketones, vitro compounds, nitriles, carbamates, isocyanates, amino acids/peptides, thiols, sulfonamides, semicarbazones, oximes, hydrazones, cyanohydrins, ureas, 30 phosphoric esters/acids, thiophosphoric esters/acids, phosphonic esters/acids, phosphites, phosphonamides, or other agents known to those skilled in the art to cure polymers and to be acidic or strongly basic. Protecting groups are generally WO 93/0693 PC.'T/CJS92/08333 ~.
specific to the curing agent employed and are not generally applicable to ail curing agents. Typical protecting groups include carboxylic acids, amides, alcohols, alkyl halides, acid halides, thiols, areas, alkyl silanes, diazoalkanes, and olefins. In addition, curing agents may be protected by formation of azomethanes, acetals. ketals, transition metal complexes, or other curing agent precursors. There exist many such protecting groups and complexes specific to the curing agents being protected.
A presently preferred cross-linking agent (4) comprises a mixture containing a mono- or polyanhydride. Phthalic anhydrides are preferred. It is of IO particular importance that the majority of the anhydride be protected from reacting with the resin (3) and metal powders (I) and (2) until the flow temperature of (2) is reached. This can be accomplished, for example, by chemically binding a protecting or inhibiting group on the anhydride. The protecting group is preferably selected so that the protected anhydride becomes I5 reactive at elevated temperature. A method of protecting the anhydride is to esterify it with an alcohol or polyol to form the mono-ester acid and its derivatives, as follows:
ff-o-~
otn~
Products o~
O-R
0 or F°ly°I
O
PMhalic Anhydrld, AcidIE~tsr Butyl carbitol, methanol, ethylene glycol, glycerol, meso-erythritol, adonitol, and 20 sorbitol are some examples of esterifying alcohols and polyols which can be employed. In addition, other protecting groups as are well known to those skilled in the art may also be employed.
Glycerol is a preferred esterifving polyol, producing a composition that achieves optimum electrical conductivity at moderate temperatures. The preferred anhydride ester is (2,3-dihydroxvpropyl) hydrogen phthalate, which is suitably prepared by heating phthalic anhydride in glycerol at 180.200°
C in the presence of a trace of acid or water until the concentration of the mono-ester reaches equilibrium. The resulting mixture comprising anhydride, mono ester-mono acid, diacid and other reaction products may be directly employed as the cross-linking agent/flux in preferred compositions.
It is believed that the esterified anhydrides are chemically triggered at elevated temperatures and/or by interaction with the metal oxides. The anhydride and its protecting group are selected to chemically attack the oxides on the surface of the metal particles in an aggressive manner, yet remain non-reactive after curing. The metal oxides are apparently chemically immobilized in the resin system after curing, preventing them from forming caustic salts and acids.
Furthermore. the aggressiveness of the cross-linking agent in attacking the metal oxides can be altered chemically, through selection of the cross-linking agent and its protecting group, and tailored to fit both the melting point of the solder (2) and the type of metal (1) to be fluxed.
The reactive monomer (5) functions to adhere the cured composition to the substrate, to provide chemical binding sites for the reaction products after curing, and to increase the cohesive strength of the cured composition. It also serves to slow the curing of the composition, thus maintaining a low-viscosity background medium during curing. The monomer also may function as a medium for delivering t7ux to the metal powder, as a thickening binder for the composition, and as a medium for decreasing the glass transition temperature of 'S the cured composition if desired. When used with a resin (3), the monomer can slow the vitrification of the resin to allow good wetting of the metal powder (1) by the molten metal (2). It can also lower the glass transition temperature of the cured resin to promote post-cure soldering to the composition.
The monomer may be any species, monomeric or polymeric, which may be 3fl cross-linked by the curing agent, a metal catalyst, or a hydroxyl group-bearing agent. Generally, they are distinguished from resins by having relatively low molecular ~,veights. The preferred reactive monomer (5) contains at least one -4H growp. and preferably two or more -GH ~~'oups. as reactive stte(s) for linking with cross-linking agents and the resin. The _dH-1 groups in the monomer may also serve as antioxidants for the metals during the high temperature curing of the composition. A slightly acidic monomer is preferred. When used with an esterified anhydride curing agent. the acid tends to buffer the decom ition Pas of the esterified anhydride, preserving it in-its protected form until elevated curing temperatures are reached. The acid also acts as a preservative for the metal powders, keeping them from oxidizing through hydrolysis, thus extending the shelf life of the uncured composition. A preferred reactive monomer is bisphenol A.
Component (3): 0-15% by volume (values near 0% being compositions useful as solder pastes);
Component (4): 30-52% by volume;
Component (5): 0-32% by volume.
While again some of the compositions within these ranges may exhibit shrinkage and cracking or balling when cured, they remain useful as conductive adhesives in applications where these characteristics are harmless.
Typically, the high melting paint metal powder (1) is copper powder, however, other metals such as silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum and high-melting point alloys of these metals, may alternatively be employed. Preferably, the. copper powder is spherical or nearly spherical as produced by gas atomization. Electrohrtic powders or flakes, recommended in the prior art, are not desirable for several reasons. Irregularly-shaped powder particles tend to be sponge-like in morphology, increasing the oxidized surface area substantially as compared to spherical particles. Irregular particles are also more difficult to flux and wet with molten metal. They result in compositions having poorer electrical conductivity.
A spherical powder containing a wide distribution of particle sizes distributed approximately normally about an average particle diameter is preferred over monosized spheres. The wide distribution of sizes increases the density of the packed metal powder as compared to monosized spheres, improving electrical conductivity and mechanical integrity. The powder generally has an average particle diameter of 1 to 50 microns. The preferred powder has a mean particle diameter of 10-30 microns.
Most preferably, the powder is de-oxidized in a hydrogen oven at least at 30f° C for about 10 minutes prior to use. Removal of naturally-existing surface oxides from the copper particles has been shown to have a marked improvement in the resulting resistivity of the final cured composition.
The solder powder may be Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Tl, Sb, Se, Po, or an alloy or other metal having a melting point lower than that of the metal powder in ( 1). Typically, the powder has a mean particle diameter of 1-40 ratcrons: preterabl~~the average particle diameter is ices than or eaual to the .
average diameter of the high melting point metal particles and the ' article size P
dtstnbution is substantially the same as that of the high melting point metal powder. The principal requiremem of the alloy is that it flow in the composition before the vitrification of the polymers in the composition. In order for this t oceur, the sofder alloy mu: ; readily wet copper. For this reason. allays of tin are ideal. Preferably, the solder powder consists of Sn and Pb.
The resin functions principally to adhere the cured composition to the substrata to provide chemical binding sites for the reaction products after curie g, and to increase the cohesive strength of the cured composition. The resin also functions as a medium for delivering flux to the metal powder, as a thickening binder for the composition, and as a medium for increasing the .eau tuition temperature of the cured composition. In order for the composition to achieve the highest electrical conductivities. it must achieve and maintain low viscosity up to the temperature at which the solder powder melts and wets the co er ' PP
powder. If the resin becomes too thick before the solder powder has melted, it will impede the flow of the melt and reduce the degree of metal powder soldering. For this reason. the curing of the resin must occur slowly relative to the time required to reach the melting paint of the solder powder.
0 The resin (3) may be any resin which can be cross-linked by the curie g agent: a metal catalyst, or a hydroxyl group-bearing agent. Resins which meet this requirement include but are not limited to epoxies, phenolics, novolacs (bflth phenolic and cresolic), polwrethanes, polNmides, bismaieimides, maIeimides, cyanate esters, polyvinyl alcohols, polyesters. and potwreas. Other resin systems may be modified to be crass-linkable by the curing a ent, a met g al catalyst, or a hydroxyl group-bearing agent. Examples of such resins are acrylics, rubbers (butyl, nitriIe, etc), polvamides, polyactyiates, polyethers, poivsulfones.
polyethylenes, polypropylenes. polysiloxancs, polyvinyl acetates/polvvin 1 esters Y , polyolefins, cvanoacrylates, and polystyrenes. Typically, any resin would function 30 in this. invention if the resin can be modified to contain at least o ne of the foilowtng functional groups: anhydrides, carboxylic acids, amides. imides, amines.
alcohols/phenols, aldehvdes/ketones, vitro compounds. nitrites. carbamates, WO 93/06943 ~ ~ ~ PGT/US92/08333 isocyanates, amino acidslpeptides. thiols. sulfonamides. setnicarbazones, oximes.
hydrazones, cyanohydrins. ureas, phosphoric esters/acids, thiophosphoric esterslacids, phosphonic esters/acids, phosphites, phosphonamides, sulfonic esters/acids or other functional groups known to one skilled in the an to act as reactive sites for polymerization. For example, a polyolefin would not be suitable as a resin in this invention, as it has no reactive sites for binding and has poor adhesive properties; however, a carboxylated polyolefin functions well when matched with a suitable cross-linking agent. A combination of these and other resins, such as non-cross-linkable thermoplastic resins, may also be used as component (3). Presently preferred is an epoxy resin, such as the -reaction product of epichlorohydrin and bisphenoi A, combined with a phenolic epoxy resin.
The principal feature of the cross-linking agent is that in its unprotected form it acts as an acid or a strong base. Most acids and strong bases function well as fluxing agents, because they can remove oxides from metals. However, if they are left in their reactive form in the composition they would prematurely cross-link the resin or become used up in reactions with the metal powders.
The principal property of a protected curing agent in this invention is that it remain largely unreactive until it is needed to flux the metal powder and cross-link the ?0 resin. Protection may be achieved by chemically binding the agent with a chemically- or thermally-triggered species so that it becomes reactive only at or near the time that the solder powder melts. Protection may also be achieved mechanically, for example by encapsulating the curing agent in a shell of non-reactive material which releases the curing agent only at or near the melting 'S time of the solder powder.
Cross-linking agents (4) known in the art include anhydrides, carboxylic acids, amides, imides, amines, alcohols/phenols, aldehydes/ketones, vitro compounds, nitriles, carbamates, isocyanates, amino acids/peptides, thiols, sulfonamides, semicarbazones, oximes, hydrazones, cyanohydrins, ureas, 30 phosphoric esters/acids, thiophosphoric esters/acids, phosphonic esters/acids, phosphites, phosphonamides, or other agents known to those skilled in the art to cure polymers and to be acidic or strongly basic. Protecting groups are generally WO 93/0693 PC.'T/CJS92/08333 ~.
specific to the curing agent employed and are not generally applicable to ail curing agents. Typical protecting groups include carboxylic acids, amides, alcohols, alkyl halides, acid halides, thiols, areas, alkyl silanes, diazoalkanes, and olefins. In addition, curing agents may be protected by formation of azomethanes, acetals. ketals, transition metal complexes, or other curing agent precursors. There exist many such protecting groups and complexes specific to the curing agents being protected.
A presently preferred cross-linking agent (4) comprises a mixture containing a mono- or polyanhydride. Phthalic anhydrides are preferred. It is of IO particular importance that the majority of the anhydride be protected from reacting with the resin (3) and metal powders (I) and (2) until the flow temperature of (2) is reached. This can be accomplished, for example, by chemically binding a protecting or inhibiting group on the anhydride. The protecting group is preferably selected so that the protected anhydride becomes I5 reactive at elevated temperature. A method of protecting the anhydride is to esterify it with an alcohol or polyol to form the mono-ester acid and its derivatives, as follows:
ff-o-~
otn~
Products o~
O-R
0 or F°ly°I
O
PMhalic Anhydrld, AcidIE~tsr Butyl carbitol, methanol, ethylene glycol, glycerol, meso-erythritol, adonitol, and 20 sorbitol are some examples of esterifying alcohols and polyols which can be employed. In addition, other protecting groups as are well known to those skilled in the art may also be employed.
Glycerol is a preferred esterifving polyol, producing a composition that achieves optimum electrical conductivity at moderate temperatures. The preferred anhydride ester is (2,3-dihydroxvpropyl) hydrogen phthalate, which is suitably prepared by heating phthalic anhydride in glycerol at 180.200°
C in the presence of a trace of acid or water until the concentration of the mono-ester reaches equilibrium. The resulting mixture comprising anhydride, mono ester-mono acid, diacid and other reaction products may be directly employed as the cross-linking agent/flux in preferred compositions.
It is believed that the esterified anhydrides are chemically triggered at elevated temperatures and/or by interaction with the metal oxides. The anhydride and its protecting group are selected to chemically attack the oxides on the surface of the metal particles in an aggressive manner, yet remain non-reactive after curing. The metal oxides are apparently chemically immobilized in the resin system after curing, preventing them from forming caustic salts and acids.
Furthermore. the aggressiveness of the cross-linking agent in attacking the metal oxides can be altered chemically, through selection of the cross-linking agent and its protecting group, and tailored to fit both the melting point of the solder (2) and the type of metal (1) to be fluxed.
The reactive monomer (5) functions to adhere the cured composition to the substrate, to provide chemical binding sites for the reaction products after curing, and to increase the cohesive strength of the cured composition. It also serves to slow the curing of the composition, thus maintaining a low-viscosity background medium during curing. The monomer also may function as a medium for delivering t7ux to the metal powder, as a thickening binder for the composition, and as a medium for decreasing the glass transition temperature of 'S the cured composition if desired. When used with a resin (3), the monomer can slow the vitrification of the resin to allow good wetting of the metal powder (1) by the molten metal (2). It can also lower the glass transition temperature of the cured resin to promote post-cure soldering to the composition.
The monomer may be any species, monomeric or polymeric, which may be 3fl cross-linked by the curing agent, a metal catalyst, or a hydroxyl group-bearing agent. Generally, they are distinguished from resins by having relatively low molecular ~,veights. The preferred reactive monomer (5) contains at least one -4H growp. and preferably two or more -GH ~~'oups. as reactive stte(s) for linking with cross-linking agents and the resin. The _dH-1 groups in the monomer may also serve as antioxidants for the metals during the high temperature curing of the composition. A slightly acidic monomer is preferred. When used with an esterified anhydride curing agent. the acid tends to buffer the decom ition Pas of the esterified anhydride, preserving it in-its protected form until elevated curing temperatures are reached. The acid also acts as a preservative for the metal powders, keeping them from oxidizing through hydrolysis, thus extending the shelf life of the uncured composition. A preferred reactive monomer is bisphenol A.
- 10 Halogcnation of cornponen~ (3)~5) is preferred in some c~sa-m order t merease their reaetimnes in the composition. ~, halogenated resin (3) may be produced, for example, by reacting tetrabromobisphenoi A with.epichlorohydrin.
Such resins. an example of which is commercially available from Shell Chemical Company, Anaheim. CA as Shell EPOIvT~'~' 11?3-AgO, have been found to enhance 15 the conductivity of the cured composition. EpoNT"' 1123-A80 is provided in the form of an 80~ 1 % by weight solids solution in acetone having the following properties: a viscosity of 8-18 poise; an epoxide equivalent weight of 420-445; and a bromine content of I8-21% by weight. Additional information concerning the EPONTMseries of resins is available from Shell Chemical Company; additional 20 information concerning the DOW DEN-TMand DER-TMscnes resins is available from Dow Chemical Company, .'viidland, MI. Of course, these commercially-available resins are merely illustrative of epoxy and epoxv_novolac resins which may advantageously be employed in accordance with the presem invention.
Halogenation of the anhydride ester produces a more reactive anhydride --'S and more stable esters. As a preferred embodiment, bromination has been found to enhance the fluxing action of the curing agent. (2,3-dihydroxypropyl) hydrogen tetrabromophthalate. Halogenation of the reactive monomer can also serve to increase its acidity and therefore enhance the properties previously described. A
preferred halogenated monomer (5) is tetrabromobisphenol A. Halogenation of 30 aU constituents. however, may be detrimental to resistivity. The preferred formulation involves halogenation of the resin, and either the monomer or the anhydride ester.
".-.
After curing, soldering electronic components to the composition is observed to be possible with certain formulations. The conducrr,T rf"Pr~~
powders) in the cured composition is covered with a thin layer of cured resin.
It is believed that the ability of molten solder to wet the cured composition depends on the tenacity of the bond between the metal powders and the surrounding cross-linked polymer. Wetting of the conductor by additional molten solder is then possible if the polymer can be displaced from the molten solder during soldering operations.
The ability of molten solder to wet the cured composition is apparently affected by the bond strength between the metal and the cross-linkec~polymcr.
It is believed that the anhydride preferentially attaches itself to the metal surfaces during curing, forming an interfaciaD layer between the metal and the resin.
The strength of bonding between this interfacial layer and the underlying cross-linked polymer may determine how easily molten solder can penetrate to coat the surfaces of the metal conductor in the composition after curing. It is believed that anhydrides which retain free cross-linking sites for the polymer even when attached to the surface of the metal, such as hexafluoroisopropyl-diphthaiiic anhydride, tend to cross-link with the resin. Thus, they form strongly bonded interfacial layers creating very tenacious interfacial films. Such anhydrides have been observed to exhibit poor solder wetting properties when employed in these compositions. Weakly bonded anhydrides, such as phthalic anhydride, probably form weakly bonded interfacial layers. Subsequently, they have exhibited excellent wetting by molten solder.
The electrically conductive adhesive compositions of the present invention '-5 are suitably obtained by first preparing the cross-linking agent.
Typically, the cross-linking agent is prepared by combining a 1:4 molar ratio of the anhydride with glycerol (or other protecting molecule). This mixture is heated while being mechanically stirred to 180°C under nitrogen to effect esterification.
The completeness of this reaction may be followed by using infrared spectroscopy.
A
sharp singlet band at 1800 cm'1 will disappear as the reaction proceeds and be replaced with a broad singlet band at approximately 1740-1750 cm'1. The esterification of tetrabromophthalic anhydride with glycerol is complete in approximately 2-4 xnurs under these conditions. 2' ~ 2 0 5 ~ ~
Finally, a solution of the resin is prepared in the desired solvent. if necde d.
A soluuon of the resin can be made by dissolving it in the desired sohrent and boiling off the original manufacturer's solvent. usually acetone or methyl ethyl ketone (MEK). Ideally, where butyl carbitol is the chosen solvent for EPON' 1123-A-80 resin. the solution at compieti_Qn consists of 80% by weight resin.
Reactive monomer or polymer may also be added, either to this solution or as a separate solution.
The solutions are now intermixed at room temperature to product a thin I0 resinous mixture. Sine the metal powder may cake pan in'the 1 Po yin nzanon reaction with this resin system, and since some of the reactants will be consumed in removing the oxide from the metal powder, it is necessary to determine the ideal stoichiometry for a given set of reactants empirically through measurements of resistivitv, adhesion strength, and solderability of the final cured composition as 15 a function of concentration of each component.
Next, the metal powder and solder powder are mixed in the desired proportions as indicated above. The metal powder mixture is then blended with the resinous mixture to produce a thick composition. Additional solvent may be added to achieve the desired viscosity.
0 To make a printed circuit using this composition. an insulatin s g ubstratc should first be degreased and dried near 100° C for at least 8 hours to expel any absorbed moisture. The composition is applied to the substrate in the desired ' pattern of a punted circuit. In a preferred approach. the composition is screen-primed onto the substrate which is then heated. As noted previously, the _ heating temperature should be selected with consideration for the curio g temperature of the resin and the temperature range within which the solder powder melts. Ideally, the substrate material is compatible with the adhesive in the composition to produce a good strong adhesive bond. In the case of the epoxy resin composition described here, good adhesion can be achieved with such '0 substrates as PEI and epoxy FR4.
Ideally, heating is done in a stepped temperature oven. First, the printed substrate is warmed to a temperature below the cure temperature of the ink to . ., WO 93106943 ~ ~ ~ PGT/U892/08333 evaporate the solvent. When compietelv drv or the solvent. the temperature should be rapidly raised to the melting point of the solder (?). ~t or near this temperature. if the reactants have been properly selected and compounded, the cross-linking agent is activated to react with the metal powder and remove the oxides. Also at this temperature, the reactive monomer reacts with the cross-linking agent and the metal oxide so that the net result is a rapid de-oxidation of the metal particles, a wetting of the oxide free surfaces of the metal particles by the now molten solder, and the beginning of vitrification of the resin surrounding the metal particles. These reactions take only a few seconds.
Subsequently, the oven temperature is maintained at the cure temperature of the epoxy to fully harden the system. The entire reaction can occur in from as little as 10 seconds to as much as several minutes depending on. temperatures and concentrations chosen. Post cure heating below this same temperature for several hours may be necessary to achieve final cure of the composition and optimal adhesion, depending on the resin and curing agent and resin employed.
The printed circuits obtained using this composition as described demonstrate excellent conductivity and adhesion to the substrate. They do not lose conductivity over time, and they can be soldered easily. Nor do they corrode in humid environments. Compositions made using this invention overcome many of the limitations of the prior art and make the technique practical for manufacturing functional printed circuits.
Some solderable compositions prepared as above may have a tendency to delaminate and fall apart upon heating with a soldering iron. To reduce this tendency and improve the soldering reworkability of the cured conductive ink, one '-S may add a third metal or metal alloy powder incorporating high melting point metals which readily dissolve in (2). These additives, typically containing Ni, Ag or other elements to form solid solutions with (2), raise the melting point of the composition subsequent to cure. Upon application of heat during curing, soldering components to the cured ink, or during desoldering or rework of the 30 ink, the additives dissolve into (2) and increase the melting temperature of the metal mixture. The result is that the composition resists melting at common soldering temperatures. This effect is achieved by the dissolving metal raising the melting point of t~ solder. the more the additive dissmves Into the solder, the higher it raises its melting point until the additive is fully dissolved.
'Thus, a liquid phase is produced which resolidifies as the additive dissolves, even at temperatures above the initial melt point of the compositions solder.
When Ni is used as the additive, the preferred concentration of additive is from 1 to 10 weight percent of the total-metal convent of the composition.
Higher concentrations tend to reduce the conductivity of the fine: :ured ink undesirably. Also preferred is a thin coating of Ag over the Ni particles to promote its dissolving in the solder. Typically these metal powder additives havc an average particle diameter below 20 micrometers, Smaller diameter's dissolv c faster by providing more surface area.
Additives to enhance the properties of these compositions to meet specific requirements may also be employed. Adhesion promoting agents. wetting agenu.
and viscosity modifiers are only a few or the additives which may be used at low IS levels to improve properties without significantly altering the conductivity of the material. ~lon-ionic surfactants, such as Surfadone'"' LP Nonionic Surfactants available from GAF Chemicals Corporation, Waync, NJ, have been used at levels between 0.1 weight percent and 1.0 weight percent to increase wetting of the in)t and to increase adhesion. The Surfadone LP-100 and LP-300 surfactants arc N-0 alkyl pvrrolidones in which the N-substituents contain 8 and 12 carbon atoms respectively. These surfactants increased adhesion by as much as 40%. Rubber modified resin systems or other toughening agents may be used to increase the compositions toughness. Products such as DOW's expcumental rubber modified epoxy XU7I790.041 has been shown to increase the film's toughness. A variety of '-S flexibilizing agents may also be added to these formulations to increase the material's flexibility. Flexible resins such as Shell's EPONTM g7Z_X-75 or DOW's DER-736 can be used to increase flexibility of the cured product.
Conductive compositions as described herein are advantageously empioycd in the creation of punted circuits. One method for creating such a circuit '0 comprises .first making a printing screen or stencil containin the g pattern of the desired punted circuit. The processes and apparatus for screen punting and stencil punting are well known to those skilled in the art. The screen is then used ~~' ,_ in a screen printing apparatus to print multiple copies of the printed circuit on the substrates selected. Such substrates may consist of epoxy, polvimide, phenolic or other thermoset laminates. The substrates may be rigid or flexible.
Alternatively, the substrate may be injection molded or extruded sheet of polyetherimide, liquid crystal polymer, or other thermoplastic. Other substrates may be used, including ceramics, insulated metal sheets, or any other material to which the composition can be adhered and which can withstand the curing temperature.
After printing the uncured composition in the pattern of the desired printed circuit on the substrate, the composition is then cured by app~non of heat. A static oven may be employed, but a conveyorized oven with multiple heating stages is preferred. The conveyorized oven's heating method may be infra-red lamps, panel heaters, convection. forced hot air, induction, microwave, or other known heating method. Such ovens are well known to those skilled in the art. The multiple heating stages may then be used to heat, dry, cure, and then cool the composition in a controlled way, minimizing pinholes caused by outgassing, eliminating damage due to severe temperature changes, and achieving complete curing. Holes may be drilled or punched in the printed circuit thus obtained, as in a conventional circuit board. Components may be soldered to the '0 printed circuit with a solder wave. soldering iron, hot air gun, or solder paste reflow, all common techniques well known in the art. Alternatively, components may be adhered to the printed circuit using the composition itself. This is accomplished. for example, by placing the components in the composition prior to curing. This has the advantage of eliminating the soldering operation and 'S subsequent solder flux cleaning operations entirely. Yet another method for adhering components is to first cure the printed circuit, then apply an additional amount of uncured composition as a conductive adhesive for bonding the components.
Multiple-layer printed circuits may be made by starting with a circuit board 30 made as above. Over the cured composition and prior to soldering of the circuit components, a thin layer of a non-conductive insulating thermosetting resin is applies with a screen or stencil printer. The layer applied should be patterned so W~ 93/06943 ~ ~ ~ ~ PCR/LJS92/08333 as to allow vias or passages which remain uncoated with insulating material.
After curing of this layer, a second layer of conductive composition. in the desired printed circuit pattern. may be printed over the insulating layer. The vias or passages would then allow electrical interconnection between the upper and lower layers. In this fashion, a two-layer printed circuit is made. The process may then be repeated multiple times to create a printed circuit containing a plurality of layers. Electronic components may then be attached as described before.
Yet another method for creating a multiple-layered printed circuit is to begin with a series of thin substrates with vias or passages drilled or punched therein. The conductive composition is then screen- or stencil-printed onto each of these substrates in the desired printed circuit pattern, each layer generally being different. The compositions may then be cured, or simply dried and left uncured while the thin substrates are aligned and laminated together under pressure. The laminating pressure will force the conductive layers to interconnect through the vias and passages in the thin substrates, interconnection being made wherever there exists conductive composition directly beneath a via or passage.
Curing of the composition may be done before, during or after this laminating process. The result is a multiply-layered printed circuit.
Conductive compositions as described herein may also be employed to attach electronic components to conventional copper-clad printed circuits. In this application, the compositions make an excellent replacement for heretofore-known solder pastes. The conductive compositions may be stencil- or screen-printed onto the lands of a completed copper-clad printed circuit in a manner known to those skilled in the art. The leads of electrical component are then ?5 placed on the conductive composition and the entire assembly may be cured in an infra-red oven, convection oven, or by vapor reflow, all methods well known to those skilled in the art. The inventive compositions advantageously eliminate the need for cleaning the printed circuit assembly after curing; the generally lower viscosities of the compositions compared to solder pastes make the composition easier to print. Moreover, the formulation of the compositions are such that common problems with solder pastes, such as solder balling, bridging, and componem tombstoning, are eliminated.
ut A
Yet another useful appiicanon for compositions of the present invention is ~n attaching bare microcircuit dies to substrates, as is commonly done in the manufacture of multichip modules. Suitable formulations for this purpose include thermoset adhesives which. once hardened, are difficult to remove without destroying the printed circuit. The compositions described herein may be formulated using resins comprising therrttoplastic and thermosetting blends such that the cured compositions may be melted even after curing by application of moderate heat. In such applications, the conductive composition may be printed onto the substrate of the muItichip module using screen- or stencil-printing as is known to those familiar with the art. The die is then placed on the composition and the assemble is heated in an oven as described previously to achieve curing.
alternatively, heat may be applied to the die from above by a hot platen or hot air blower to achieve curine. The resulting bond between die and substrate may tie easily detached. if necessary, by application or heat to the die by a hot platen, soldering iron. hot air, or any other method known to one skilled in the art.
The die may then be pulled away from the melted composition.
The invention may be better understood by refcrcnce to the following examples which are imended for purposes of illustration and are not to be construed as in any way limiting the scope of the present invention, which is '-0 defined in the claims appended hereto.
Example I
Gas atomized and electrolytic copper powders were compared with respect to the sheet resistiviry of compositions which differed only in the type of powder employed. Compositions were prepared by first combining four molar parts of '-5 glycerol to one pan of tetrabromophthalic anhydride in a glass vessel and heating the mixture to between 180-200° C for approximately four hours. The reaction was monitored by placing samples of the solution in a sodium cell of a Perkin Elmer model 7'_7 infrared spectrophotometer. The 1800'1 cm singlet band was observed to disappear into the baseline and the 1750'' cm singiet band appeared ~0 and reached an eauilibrium before the solution was removed from the heat.
:after cooling, the resulting solution was mixed with the other components of the composition. .-~ solution of Shell EPON''"' 1123-r~-80 in butyl carbitol was prepared A.
~6 ,..,., by dissoivine 8 partsbv weight of the resin solution an 2 parts by weiQllt of butyl carbitol and boiling the resulting mixture at approximately 100°'C
until the manufacturer's solvent was observed to be fully evaporated. The resulting solution was mixed with the other components of the composition after cooling.
A monomer solution of tetrabromobisphenol A was prepared in butyl carbitol, 1:1 by weight, and warmed at approximately-I00° C until fully dissolved.
The resulting solution was mixed with the other components of the composition after cooling. Gas atomized copper powder with average panicle diameter of 15 microns was cleaned by heating in hydrogen gas to 300° C, then cooled in hydrogen and mixed 2:1 by weight with -500 mesh Sn63Pb37 alloy powder to produce the gas atomized composition. Similarly, a 15 micron average particle diameter electrolytic powder was hydrogen cleaned and mixed 2:1 with the same alloy powder to produce the electrolytic composition. The mixtures and solutions were intermixed to produce compositions having the following equivalent IS pre-esterification proportions by volume: Cu - 35.8%; Sn63Pb37 - 19%; Shell EPONTM 1123-A-80 - 8.5%; tetrabromophthalic anhydride - 5%;
tetrabromobisphenol A - 8.6%; butyl carbitol - 13.3%; glycerol - 9.9%. The compositions were screen printed through a 250 mesh screen in a solid rectangular pattern to a thickness of approximately 75 microns on microscope '0 slides. The slides were placed on hot plates at the given temperature for seconds. The resultant cured compositions were tested for conductivity on a Four Dimensions model I01 four point resistivitv probe modified to read on a,scale of 10'3 ohmsisquare. The resulu are reported in Table 1.
?0 A
TAB LE I
Comparison of Gas Atomized and Electroivtic CnnnPr ~.,~.~,...r VIJ
Cu Powder Gas Atomized Electrolytic ~,J
Sheet Resistivity (OhmiSquare)(x i03) COmpOSltlon cured at ~z0 °C
Average 9.71 2~_pp Standard Deviation 0.47 32,00 CompOSltlOn cured at X60 °C
Average 4.30 65.00 Standard Deviation O,gg ~.~
Exam The effects of mean copper powder panicle size on bulk.resistivitv were determined. The comaositions werc prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume:
Cu - 34.9%: Sn63Pb37 - 17.3%; Shell EPON''"' 1123-A-80 - 3.4%a;
tetrabromophthalic anhydride - .~.8%; tetrabromobisphenol A - 13%; butyl carbitol - 17.2%; glycerol - 9.5%. The compositions were screen-printed on a microscope slide and cured on a hot plate at 260° C for 30-45 seconds.
The results are reported in Table II.
TABLE II
Mean Cooper Powder Particle Size and Bulk Resistivitv Mean Particle Size ( um ) 3 fl 15 7 .,5 _ Bulk Resistivitv (Ohm-cm)(x 1051 Average 2.80 ~.~0 4.90 Standard Deviation 0.17 0.I2 0.59 Example 3 The effects of hydrogen cleaning of the copper powder were evaluated.
The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 34.9%;
Sn63Pb37 - 17.3%; Shell EPON'~"' 1123-A-80 - 3.4%; cetrabromophthalic anhydride - 4.8%; tetrabromobisphenol A - 13%; butyl carbitol - 17.?%; glycerol - 9.5%.
The compositions were screen-printed on a microscope slide and cured on a hot ,»~~: k .;":
tt.
2i 20~~~
plate at ~60° C f.or;;p_45 seconas. The results are reported in Table ~.
TABLE iII
Effects of Hvdro en Cleanin on Buik Resistivitv As-delivered HvdroQen-Cleaned Bulk Resistivitv (C~hm-cm tlx t cW
Average .. 5.10 Standard Deviation 1.00 0.17 Examr~le 4 Fig. I indicates the effecu of varying alloys on conductivity of the final COmpOSItlOn. The COmi7oSitinnc m...~ .,._....__~ __ ,.-compositions containing the following pre-esterification proportions by volume:
Cu - 34.9%; alloy - 17.3%; Shell EPON~'~"' 1123-A-80 - 3.4°!0;
tetrabromophthalic anhydride - .~.$%; tetrabromobisphenol A - 13%; butyl carbitol - 17.2%;
glycerol -9.5%. ?he compositions were screen-printed on a microscope slide and cured on a hot plate at the indicated temperature for 30-45 seconds.
Example 5 A variety of resins and resin mixtures were evaluated. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 32.8%; Snb3Pb37 -34.8%; resin - l.?% (for Shell EPON'~ l I23-A-80; the molar concentration for all others was maintained the same); tetrabromophthaiic anhydride - 6%;
tetrabromobisphenol A - ~.8%; butyl carbitol - 7.b%o; glycerol - I 1.8%. 'I'h~
compositions were screen-printed on a microscope slide and cured on a hot plate '-5 at the indicated temperature for 30-45 seconds. PuII test samples were pre ared P
by screen printing 4 x 4 mm squares onto the indicated substrate and curing the coated materials in an infrared belt oven at 220° C for appro~mately 1 minute.
The samples were then dipped in a solder bath for 4-8 seconds in the presence of a type RMA Bux (a mildly activated rosin-based flux) to attach a pull wire.
The 30 pull strengths reported are the ma~dmum force sustained on the ull wire at P
delamination. The results of these evaluations are reported in Table IV.
A
r vd a t 4 TABLE IV
Comparison of Resins and Resin 'Mixtures Sheet Resistivity Ohnvsquare Puil Strength T(g) C of at Cure Temperature !x 103 On Substrate (ko~ 330=ple '_00C ?30C ''60C PEI FR4 EPONT"' 1123_A_80 3.73 3.13 3.25 0.103 0.037 1SS
EPON'''M 1123-A-80/ 3.69 3.26 3.37 0.018 0.06 172 DOW XU7I790.04L
( 1:1) DOW XU71790.04L 3.47 3.39 3.56 0.035 0.069 139 EPON'''"' 2123-A-80/ 3.25 3.06 3.SS 0.203 0.034 120 DOW DEN'~431 ( 1:1 ) DOW DEN'~431 3.46 3.29 3.3I 0.176 0.096 145 EPON~""~ .123-A-801 3.54 3.54 3.4b 0.174 0.129 . 100 1 S DOW DEN''"' 438 ( 1:1 DOW DEN"=.~38 3.5 3.48 3.47 O.1S6 0.09 180 EPON~'~' ~ 123-A-80/ ;.61 3.41 3.29 0.201 0.046 18S
EPON'''~'l~pS164 ( 1:1) EPON~DPS 164 3.73 3.44 3.69 O.1S3 0.044 16S
EPON''"' 1123-A-80l 3.57 3.3 3.34 0.2SS 0.061 145 - I65 EPON~'ppSISS (1:1) EPON1"z DPS 1SS -1.36 3.85 3.75 0.139 0.07 Ig7 Exam~6 Various anhydrides and their derivatives were compared as employed =-.S in conductive compositions. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 3S%; Sn63Pb37 - 37.I%; Shell EPON~"' 1123-A-80 - 3.S%;
anhydride -3.7% (for tetrabromophthalic anhydride; the molar concentration was kept the same for all others. or was zero where no ester is indicated);
tetrabromobisphenol A - S.S%; butyl carbitol - 7.9%; glycerol - 7.3% (far glycerol;
the molar concentration was kept the same for all others, or was zero as indicated).
The compositions were screen-printed on a microscope slide and cured on a hot plate at 260' C far 30-.4S seconds. The results are reported in Table V.
?3 ., TABLE V
Comparison of Curin ~Agents Sheet Resistivitv Curing went (Ohm/Sgl x103 ~ Color Tetrabromophthalic Anhydride > 100 Red Tetrabromophthalic Acid > 100 Red Tetrabromophthalic Anhydride! 4.89 Grey/Silver Butyl Carbitol Ester Tetrachlorophthalic Anhydride 8.83 RedISilver Tetrachlorophthalic Anhydride/ 3.48 Grey/Silver Butyl Carbitol Ester Phthalic Anhydride 5.23 Red/5ilver Phthalic Acid 10.00 Red/Grey Phthalic AnhydrideButyi Carbitol Ester 3.36 GieylSilver 4-Fluorophthalic Anhydride 4.Ob Grey/Silver 4-Fluorophthalic Anhydride/ 3.14 Grey/Silver Butyl Carbitol Ester Oxydiphthalic Anhydride 5.35 Grey/Silver Oxydiphthalic AnhydrideButyi Carbitol 3.40 Grey/Silver Ester Biphenyl Tetracarboxyiic Dianhydride > 100 Red/Grey Biphenyl Tetracarboxylic Dianhydride/ 3.40 Grey/Silver Butyl Carbitol Ester Diphenylsulfone Tetracarboxyiic Dianhydride19.00 Red/Grey Diphenylsulfone Tetracarboxylic Dianhydride/3.41 Grey/Silver '_5 Butyl Carbitol Ester Hexafluoroisopropyl Diphthalic Anhydride> 100 Red Hexafluoroisopropyl Diphthalic Anhydride!4.20 Grey/Silver Butyl Carbitol Ester Benzophenone Tetracarboxylic Dianhydride4.00 Grey/Silver Benzophenone Tetracarboxyiic Dianhydride/3.00 Grey/SiIver Butyl Carbitol Ester Chlorendic Anhydride 6.42 GreylSilver Chlorendic AnhydrideButyl Carbitol Ester3.78 Grey/Silver Epoxy Tetrahydrophthalic Anhydride 4.33 Red/Grey Epoxy Tetrahydrophthalic Anhydride) 3.00 Grey/Silver Butyl Carbitol Ester In all cases. the esterification of the anhydride by the alcohol produced marked improvement in electrical conductivity and in elimination or surface oxidation.
evidenced by consistent greyisilver color of cured compositions.
Exam~Ie 7 A comparison of various esters of tetrabromophthalic anhydride was made.
The compositions were prepared as in Example i with the final compositions containing the following pre-estcrification proportions by volume: Cu - 32%;
Sn63Pb37 - 34%; Shell EPON""' 1123-A-80 - 3.3%; tetrabromophthalic anhydride -5.9%; tetrabromobisphenol A - 5.5% (for tetrabromophthalic anhydride; the molar concentration was the same for all others); butyl carbitol - 7.$%s;
polvol esterifying agem - 11.6% (for glycerol: the molar concentration was the same for ail others). The compositions were screen-printed on a microscope slide and cured on a hot plate at the indicated temperature for 30-45 seconds. Pull test samples were prepared by screen printing 4 x 4 mm squares onto the indicated is substrate and curing in an infrared belt oven at 220° C for approximately 1 minute. The samples were then dipped in a solder bath for 4-8 seconds in the presence of a mildly activated rosin based flux to attach a pull wire. The results are reported in Table VI.
TABLE VI
Comparison of Esters of Tetrabromophthalic Anhydride Estcrincation Agent Sheet Reslstlvlty Pull Strength {Kg) T(g) °C
Ohmlsguare x l~
'~°C ''-''-30°C 260°C PEi FR4 '_'30°C Sample Butyl Carbitol - > 100 9.14 9.43 0.28 0 110 Glycerol 4.7I 4.54 .x.43 0.276 0 115 Adonitol 5.$9 3.57 .x.14 0.223 0 140 Octadecanoi > 100 17 10 * * 80 *Not solderable Example 8 ~0 The utility of various anhydrides as curing agents was evaluated. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 32%;
'A
r,m Sn63Pb37 - 3-1%. Shell EPO'~ 113-~-g0 _ ;.;c~; tetra6romoph .
h , .
t alic anhydride -~.9%; tetrabromobisphenol A
~
3~?' -.
0 (for tetrabromophthalic anhydride: the molar concentrations were the same for ail others ); butyl carbitol .- 7.8%; poiyol esterifyin~ agem - 11.6% (for glycerol; the molar conce ntrations were the samc for all others). Compositions were screen-printed on a i m croscope slide and cured on a hot plate at the indicated temperature for 30-4S
seconds. Pull test samples were prepared as previously indicated. The results are reported in Table VII.
TABLE VII
i0 Comparison of Anhvdrid~c - Anhydride Sheet Resistivity Puli Strength (K
) T
C
g (g) Ohmlsguare x 103 '-~C ''-''-30'C '_'60C PEI FR4 ~30C
Sam~fe 15 Tetrabromophthalic 3.64 3.34 3.56 0 .
.
Anhydride Phthalic Anhydride 5.62 '_.49 0.52 0 .
4-FluorophthaIic 3.28 3.72 4.27 0 .
Anhydride 20 Biphenyl-Tetracarboxyiic 7.97 7.56 9 38 * ' .
Dianhydride Hexafluoroisopropyl 4.75 3 ~5 *
.
.
0.03 1~
Diphthalic Anhydride 'Not solderabie Exam~ole 9 A number of reactive monomers were prepared and evaluated. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume:
Cu - 32.1%;
Sn63Pb37 - 34.1%: Shell EPON'~" 1123 A
--- 3.3%; tetrabromophthalic anhydride -'0 6%; monomer - 5.2% (far tetrabromobisphenol A
th ;
e molar concentration was the same for all others b );
utyl carbitol - 7.5%; glycerol - 11.8%. Compositions were screen-printed on a microscope slide and cured on a hat plate at the indicated temperature for 30-45 seconds. Pull test samples were prepared as previously indicated. The results are repotted in Table VIII.
TABLE viII
COmt7arISOn of Reactive Monomers Reactive 'vtonomers Sheet Resistivity Pull Strength-Ke '(' °C
Ohm~sguare ~ 10' '_'00°C :a0°C ~60°C
Cure Cure Cure PEI FR4 Sample Tetrabromo- _ - -Bisphenol-A 3.5 3.65 3.54 0.059 0.12..5 1~
Bisphenoi-A 3.94 3.58 3.59 0.041 0.089 170 i0 Hexafluoro-Bisphcnol-A 3.93 3.51 3.74 0.05 0.095 93 No monomer 3.74 3.79 3.87 0.05 O.I2 140 - 155°
Example IO
A comparison was made of compositions containing halogenated and non-1 S halogenated reactants. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterirication proportions by volume: Cu - 35.4~Te: Sn63Pb37 - I9.1~''c: resin - 3.5% (for Shell EPON~' 1123-A-80:
the epoxy equivalent concentration was maintained the same for all others);
anhydride - .~.4% (for tetrabromophthalic anhydride; the molar concentration was 20 the same for all others); monomer - 12.5%; butyl carbitoi - 16.6%; glycerol -8.6%. Compositions were screen-printed on a microscope slide and cured on a hot plate at the indicated temperature for 30-45 seconds. The results are reported in Table IX.
?7 TAg~ IX 212n523 .~
Comparison of Haioeenatsd and 'Von-Haio~PnalPr~ Q Aa; talli~
Bulk Resistivity Color Reactants (Ohm-cm ~ x 10°
EPON~'~"' 11~-A-80 Brominated Resin Tetrabromophthalic Anhydride Glycerol Ester w = X6.8 ~ 1.1 Grey Tetrabromobisphenol-A
EPON'~"" 1I?3-A-80 Brominated Resin Phthalic Anhydride Glycerol Ester ~6.6 ~ 2 ~ RedBrown Tetrabromobisphenol-A
Epo.N~ 1123-A-80 Brominated Resin Tetrabromophthalic Anhydride Glycerol Ester ~ ?6.9 ~ 0.8 ~ Grcy Bisphenoi-A
'-fl EpoN'~ 1123-A-80 Brominated Resin Phthaiic Anhydride Glycerol Ester ?9.3 ~ ?.3 Red Bisphenol-A
Example 11 A comparison was made of the solderability of various compositions, depending upon the anhydride employed. The compositions were prepared as in Exampfe 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 32.6%; Sn63Pb37 - 34.6%; Shell EpoN~ 1123-A-80 -4.I%; anhydride - .x.9°!0 (for tetrabromophthalic anhydride; the molar concentration was the same for all others); tetrabromobisphenol A - ~.8%;
butyl 30 carbitol - 8.4%; glycerol - 9.6%. Compositions were screen-printed on a microscope slide- and cured on a hot plate at the indicated temperature for 30-seconds. The results are reported in Table X.
2~2Q523 TABLE X
COmDaTISOn of Soiderabilitv Anhydride Solderabilitv Tetrabromophthalic Anhydride Very Good Phthalic Anhydride Very Good 4-Fluorophthalic Anhydride . Good Biphenyl-Tetracarboxylic Dianhydride None Hexafluoroisopropyi Diphthalic Anhydride None Tetrabromophthalic Anhydride/Biphenyl Tetracarboxylic Dianhydridc (2:1 Mix Ratio) Fair ._ - Tetrabromophthalic AnhydridelHcxafiuoroisopropyi Diphthalic Anhydride (2:1 Mix Ratio) Fir .
ExamDie 1?
The eraphs of Fig. 2 (resistivity response surfaces) show the effects of relative concentration changes on resistivity for a preferred sample composition.
In Fig. ?. isoquants of least squares response surfaces of resistivity as a function of concentration of components were generated using experimental design and analysis computer software (Echip Inc., Hockessin, DE). Starting solutions were prepared as in Example 1. The experimental design portion of the program was used to specify a series of varying composition formulations. by weight, of each of the starting solutions and metal powders. The formulations specified by the program were prepared and resistivity measurement slides were created and tested. The bulk resistivity of the samples was used to normalize out thickness variations. The resulting data was installed into the computer program which '-S generated the triangle graphs shown. The compositions were cured on a hot plate at 200° C for 30-45 seconds. The experimental resin consisted of EPON
1123-A-80 in glycerol (4:1 by weight). The anhydride was esterified in glycerot (1:2 molar proportion) as before. The bisphenol A was dissolved in butyl carbitoi (1:1 by weight). The numbers shown arc for weight fractions of these starting ~0 solutions. Compositions were screen-printed on a microscope slide and cured on a hot plate at 200° C for 30-45 seconds.
r -1y~ -~r.,t~..
~.
~:.~r..
Exam~ie i3 Fig. ~ graphically demonstrates the effect of adding a third metal or metal alloy powder incorporating high melting point metals which readily dissolve in the solder powder. In the experiments depicted in Fig. ~. the compositions were prepared as in Example 1 with the final compositions containing the following pre-esterincation proportions by voiume~Cu - 33.2%: Sn63Pb37 - 16.7%;
Shell EPON'"" 1123-A-80 - 3.4%; tetrabromophthalic anhydride - 4.8%;
tetrabromobisphenol A - 13%; butyl carbitol - 17.2%; glycerol -9.5%; Ag-coated Ni - 2.3%. The composition was placed in a Perkin Elmer Model 4 differential scanning calorimeter and cured with a temperature ramp of 20 C under nitrogen to 500 C. The top curve displays the various endotherms encountered during this cure cycle. The melt endotherm of the alloy was at 183 C. After cooling the sample back to room temperature, the temperature was romped up again and the lower curve was obtained. The melting point of the composition shifted up over 1~ 100 degrees.
Example 14 A comparison of protected vs. unprotected anhydrides was made. The tetrabromophthalic anhydride glycerol ester composition in Table XI was prepared as in Example 1. The compositions in the bottom half of the table we re '0 mixed from the starting materials listed without heating as in Example 1. The final compositions contained the following pre-esterification proportions by volume: Cu - 35.7%; Sn63Pb37 - 18.3%; Shell EPONT"' 1123-A-80 -3.9%:
anhydride - -~.3% (for tetrabromophthalic anhydride; the molar concentration was the same for all others, or was zero if so indicated); tetrabromobisphenoi A -'-5 i2.2%; butyl carbitol - 16.3%; additional solvent or ester as listed - 8.5% (for glycerol; the molar concentration was the same for all others);
Ag-coated Ni -0.9%. The compositions were screened onto a microscope slide and cured on a hot plate at the indicated temperature for 30-45 seconds. The resuiu are reported in Table XI. The data suggest that it is the mono-ester, mono-acid 30 derivative of the anhydride which serves to produce the best electrical conductivity. Comparison of the data in Table XI with that in Table V illustrates the effects of esterifying halogenated versus non-haloeenated anhydrides.
.m.
1.:~~.
r ,, ~212~523 TABLE ~I
Comparison of Protected Anhydrides vs inn Prnr....va ~...av.u Anhydrides Anhydride or Derivative Sheet Resistivitv ' OhmlSquai--~00C '30C 260C
Tetrabromophthalic Anhydride/
Glycerol Esterified 4.08 3 .
4.05 Tetrabromophthalic Anhydride/
tetrahydrofuran (additional solvent) 6.64 4 .
4.20 Tetrabromophthalic Acid/
tctrahydrofuran (additional solvent) 8.56 5 .
4.52 Dimethyl Phthalate;
dimcthyl sulfoxide > 100 > I00 > lOp Methyl Hydrogen Phthalate!
dimethyl sulfoxide .x.84 -i 2'~
.
Phthaiic Acid/
dimethyl sulfoxide 4.01 3 .
4.68 Phthalic Anhydride!
dimethyl sulfoxide 4 .
4.63 4.76 Example 15 -'S A comparison of a printed circuit made with a conductive com sition on Po a polyetherimide substrate versus a circuit made from etched copper clad epoxy laminate was made. The circuit chosen for comparison w d as a c-to-de converter.
The schematic diagram of the- circuit is shown in Fig. 4; this schematic was taken from EDN, January 5, 1976. Resistor R~ was selected to be I80 Oh ms. A
30 printed circuit pattern for this circuit was designed; the pattern is shown in Fig. 5.
This pattern was etched imp the copper clad epoxy laminate using conventional methods known in the art. Holes were drilled and components w ld ere so ered with a soldering iron.
A composition was prepared consisting of the following pre-esterification proportions by volume: Cu - 26.8%; Sn63Pb37 - 28.4%; Shell EPO~~ 11?3-A-80 resin - '.6%; tetrabromophthaIic anhydride - 0.1%; tetrabromobisphenol A -IiVO 93106943 ~ PGT/US92/08333 2~.2fl~~~
0.1%a; butyl carbitol - .~2%. The anhydride was esterified as in Example 1 wnh butyl carbitol. A 250 mesh stainless steel screen of the same printed circuit pattern was made. The screen was mounted on an SMT model SP1414PD screen printing press. The pattern of the printed circuit was then screen-printed onto a bare .060 in thick poiyetherimide substrate using the conductive composition.
The .
substrate and composition thereon were flash exposed for 15 seconds to high intensity tungsten filament infra-red lamps in an RTC model LSOOTF infra red oven to achieve cure. Upon completion, holes were drilled in the printed circuit and the components were inserted and soldered with a solder iron set at 255° C
using Sn63 rosin core solder wire. Voltage signals were observed on-a~
oscilloscope at the test points labeled A-I in the schematic diagram. The resultant voltages and duty cycles observed were recorded. in Table XII for the two circuits thus obtained under a 220 Ohm load with 15 volts in, unless indicated otherwise. The comparison indicated nearly identical electrical performance for both printed circuits.
TABLE XII
Copper Clad Printed Circuit Composition Circuit Volts-pp Duty Cycle% Volts-pp Duty Cycle%
Test Point LOAD Output Voltage Output Voltage t lOK Ohm 10 Volts 10 Volts 220 Ohm 10 Volts 10 Volts 100 Ohm 7 Volts 7 Volts ,.-Gxarnoie i 6 A comparison was made of the electrical resistivities of a composition formulated as taught herein and a conductive composition formulated in accordance with the prior art. The first composition was prepared as in Example 1 containing the following pre-esterification proportions by volume: Cu -34.1%;
Sn63Pb37 - I7.4%; Shell EPON'''M 1123-A-$0 . 3.6%; tetrabromophthalic anhydride 5.7%; tetrabromobisphenol A - lL6%; butyl carbitol - 15.4%; glyccroi - 11.3%;
Ag coated Ni - 0.9%. The resulting paste was screen-printed onto a glass microscope slide. The composition was cured at 230° C far i minute. The I0 r~ststivity was measured as before.
' The prior art composition was prepared by dissolving 2.5 grams of Shell EPONT'" 82g resin, ?.5 grams oleic acid. 1.0 gram phthalic acid in .1 grate ethylene glycol acetate without heating. ,~ mixture of 31.7 grams electrolytic copper powder (Metz Metallurgical #11. S. Plaintieid. N1) was mixed with 3.2 grams of 1S Sn50Pb50 allay powder and 3.2 grams of Bi58Sn42 alloy powder. The two were intermixed and the resulting paste was screen-printed as before. The composition was cured for 10 minutes at a temperature of 230'° C on a hot plate.
The sample was then treated as above. Table XIII records the results of these measurements.
TABLE XIII
20 Comparison of Resistivities of Inventive Composition v Pr;or Art Resistivi tv Ohtn/square Composition r 103 Invention 4.35 Ptiar Art From the foregoing description, one skilled in the art can readily ascertain the essential characteristics of, the invention and, without departing from the spirit and scope thereof, can adapt the invention to various usages and conditions.
Changes in form and substitution of equivalents are contemplated as 30 circumstances may suggest or render expedient, and although specific terms have been employed herein, they are intended in a descriptive sense and not for purposes of limitation.
.A'
Such resins. an example of which is commercially available from Shell Chemical Company, Anaheim. CA as Shell EPOIvT~'~' 11?3-AgO, have been found to enhance 15 the conductivity of the cured composition. EpoNT"' 1123-A80 is provided in the form of an 80~ 1 % by weight solids solution in acetone having the following properties: a viscosity of 8-18 poise; an epoxide equivalent weight of 420-445; and a bromine content of I8-21% by weight. Additional information concerning the EPONTMseries of resins is available from Shell Chemical Company; additional 20 information concerning the DOW DEN-TMand DER-TMscnes resins is available from Dow Chemical Company, .'viidland, MI. Of course, these commercially-available resins are merely illustrative of epoxy and epoxv_novolac resins which may advantageously be employed in accordance with the presem invention.
Halogenation of the anhydride ester produces a more reactive anhydride --'S and more stable esters. As a preferred embodiment, bromination has been found to enhance the fluxing action of the curing agent. (2,3-dihydroxypropyl) hydrogen tetrabromophthalate. Halogenation of the reactive monomer can also serve to increase its acidity and therefore enhance the properties previously described. A
preferred halogenated monomer (5) is tetrabromobisphenol A. Halogenation of 30 aU constituents. however, may be detrimental to resistivity. The preferred formulation involves halogenation of the resin, and either the monomer or the anhydride ester.
".-.
After curing, soldering electronic components to the composition is observed to be possible with certain formulations. The conducrr,T rf"Pr~~
powders) in the cured composition is covered with a thin layer of cured resin.
It is believed that the ability of molten solder to wet the cured composition depends on the tenacity of the bond between the metal powders and the surrounding cross-linked polymer. Wetting of the conductor by additional molten solder is then possible if the polymer can be displaced from the molten solder during soldering operations.
The ability of molten solder to wet the cured composition is apparently affected by the bond strength between the metal and the cross-linkec~polymcr.
It is believed that the anhydride preferentially attaches itself to the metal surfaces during curing, forming an interfaciaD layer between the metal and the resin.
The strength of bonding between this interfacial layer and the underlying cross-linked polymer may determine how easily molten solder can penetrate to coat the surfaces of the metal conductor in the composition after curing. It is believed that anhydrides which retain free cross-linking sites for the polymer even when attached to the surface of the metal, such as hexafluoroisopropyl-diphthaiiic anhydride, tend to cross-link with the resin. Thus, they form strongly bonded interfacial layers creating very tenacious interfacial films. Such anhydrides have been observed to exhibit poor solder wetting properties when employed in these compositions. Weakly bonded anhydrides, such as phthalic anhydride, probably form weakly bonded interfacial layers. Subsequently, they have exhibited excellent wetting by molten solder.
The electrically conductive adhesive compositions of the present invention '-5 are suitably obtained by first preparing the cross-linking agent.
Typically, the cross-linking agent is prepared by combining a 1:4 molar ratio of the anhydride with glycerol (or other protecting molecule). This mixture is heated while being mechanically stirred to 180°C under nitrogen to effect esterification.
The completeness of this reaction may be followed by using infrared spectroscopy.
A
sharp singlet band at 1800 cm'1 will disappear as the reaction proceeds and be replaced with a broad singlet band at approximately 1740-1750 cm'1. The esterification of tetrabromophthalic anhydride with glycerol is complete in approximately 2-4 xnurs under these conditions. 2' ~ 2 0 5 ~ ~
Finally, a solution of the resin is prepared in the desired solvent. if necde d.
A soluuon of the resin can be made by dissolving it in the desired sohrent and boiling off the original manufacturer's solvent. usually acetone or methyl ethyl ketone (MEK). Ideally, where butyl carbitol is the chosen solvent for EPON' 1123-A-80 resin. the solution at compieti_Qn consists of 80% by weight resin.
Reactive monomer or polymer may also be added, either to this solution or as a separate solution.
The solutions are now intermixed at room temperature to product a thin I0 resinous mixture. Sine the metal powder may cake pan in'the 1 Po yin nzanon reaction with this resin system, and since some of the reactants will be consumed in removing the oxide from the metal powder, it is necessary to determine the ideal stoichiometry for a given set of reactants empirically through measurements of resistivitv, adhesion strength, and solderability of the final cured composition as 15 a function of concentration of each component.
Next, the metal powder and solder powder are mixed in the desired proportions as indicated above. The metal powder mixture is then blended with the resinous mixture to produce a thick composition. Additional solvent may be added to achieve the desired viscosity.
0 To make a printed circuit using this composition. an insulatin s g ubstratc should first be degreased and dried near 100° C for at least 8 hours to expel any absorbed moisture. The composition is applied to the substrate in the desired ' pattern of a punted circuit. In a preferred approach. the composition is screen-primed onto the substrate which is then heated. As noted previously, the _ heating temperature should be selected with consideration for the curio g temperature of the resin and the temperature range within which the solder powder melts. Ideally, the substrate material is compatible with the adhesive in the composition to produce a good strong adhesive bond. In the case of the epoxy resin composition described here, good adhesion can be achieved with such '0 substrates as PEI and epoxy FR4.
Ideally, heating is done in a stepped temperature oven. First, the printed substrate is warmed to a temperature below the cure temperature of the ink to . ., WO 93106943 ~ ~ ~ PGT/U892/08333 evaporate the solvent. When compietelv drv or the solvent. the temperature should be rapidly raised to the melting point of the solder (?). ~t or near this temperature. if the reactants have been properly selected and compounded, the cross-linking agent is activated to react with the metal powder and remove the oxides. Also at this temperature, the reactive monomer reacts with the cross-linking agent and the metal oxide so that the net result is a rapid de-oxidation of the metal particles, a wetting of the oxide free surfaces of the metal particles by the now molten solder, and the beginning of vitrification of the resin surrounding the metal particles. These reactions take only a few seconds.
Subsequently, the oven temperature is maintained at the cure temperature of the epoxy to fully harden the system. The entire reaction can occur in from as little as 10 seconds to as much as several minutes depending on. temperatures and concentrations chosen. Post cure heating below this same temperature for several hours may be necessary to achieve final cure of the composition and optimal adhesion, depending on the resin and curing agent and resin employed.
The printed circuits obtained using this composition as described demonstrate excellent conductivity and adhesion to the substrate. They do not lose conductivity over time, and they can be soldered easily. Nor do they corrode in humid environments. Compositions made using this invention overcome many of the limitations of the prior art and make the technique practical for manufacturing functional printed circuits.
Some solderable compositions prepared as above may have a tendency to delaminate and fall apart upon heating with a soldering iron. To reduce this tendency and improve the soldering reworkability of the cured conductive ink, one '-S may add a third metal or metal alloy powder incorporating high melting point metals which readily dissolve in (2). These additives, typically containing Ni, Ag or other elements to form solid solutions with (2), raise the melting point of the composition subsequent to cure. Upon application of heat during curing, soldering components to the cured ink, or during desoldering or rework of the 30 ink, the additives dissolve into (2) and increase the melting temperature of the metal mixture. The result is that the composition resists melting at common soldering temperatures. This effect is achieved by the dissolving metal raising the melting point of t~ solder. the more the additive dissmves Into the solder, the higher it raises its melting point until the additive is fully dissolved.
'Thus, a liquid phase is produced which resolidifies as the additive dissolves, even at temperatures above the initial melt point of the compositions solder.
When Ni is used as the additive, the preferred concentration of additive is from 1 to 10 weight percent of the total-metal convent of the composition.
Higher concentrations tend to reduce the conductivity of the fine: :ured ink undesirably. Also preferred is a thin coating of Ag over the Ni particles to promote its dissolving in the solder. Typically these metal powder additives havc an average particle diameter below 20 micrometers, Smaller diameter's dissolv c faster by providing more surface area.
Additives to enhance the properties of these compositions to meet specific requirements may also be employed. Adhesion promoting agents. wetting agenu.
and viscosity modifiers are only a few or the additives which may be used at low IS levels to improve properties without significantly altering the conductivity of the material. ~lon-ionic surfactants, such as Surfadone'"' LP Nonionic Surfactants available from GAF Chemicals Corporation, Waync, NJ, have been used at levels between 0.1 weight percent and 1.0 weight percent to increase wetting of the in)t and to increase adhesion. The Surfadone LP-100 and LP-300 surfactants arc N-0 alkyl pvrrolidones in which the N-substituents contain 8 and 12 carbon atoms respectively. These surfactants increased adhesion by as much as 40%. Rubber modified resin systems or other toughening agents may be used to increase the compositions toughness. Products such as DOW's expcumental rubber modified epoxy XU7I790.041 has been shown to increase the film's toughness. A variety of '-S flexibilizing agents may also be added to these formulations to increase the material's flexibility. Flexible resins such as Shell's EPONTM g7Z_X-75 or DOW's DER-736 can be used to increase flexibility of the cured product.
Conductive compositions as described herein are advantageously empioycd in the creation of punted circuits. One method for creating such a circuit '0 comprises .first making a printing screen or stencil containin the g pattern of the desired punted circuit. The processes and apparatus for screen punting and stencil punting are well known to those skilled in the art. The screen is then used ~~' ,_ in a screen printing apparatus to print multiple copies of the printed circuit on the substrates selected. Such substrates may consist of epoxy, polvimide, phenolic or other thermoset laminates. The substrates may be rigid or flexible.
Alternatively, the substrate may be injection molded or extruded sheet of polyetherimide, liquid crystal polymer, or other thermoplastic. Other substrates may be used, including ceramics, insulated metal sheets, or any other material to which the composition can be adhered and which can withstand the curing temperature.
After printing the uncured composition in the pattern of the desired printed circuit on the substrate, the composition is then cured by app~non of heat. A static oven may be employed, but a conveyorized oven with multiple heating stages is preferred. The conveyorized oven's heating method may be infra-red lamps, panel heaters, convection. forced hot air, induction, microwave, or other known heating method. Such ovens are well known to those skilled in the art. The multiple heating stages may then be used to heat, dry, cure, and then cool the composition in a controlled way, minimizing pinholes caused by outgassing, eliminating damage due to severe temperature changes, and achieving complete curing. Holes may be drilled or punched in the printed circuit thus obtained, as in a conventional circuit board. Components may be soldered to the '0 printed circuit with a solder wave. soldering iron, hot air gun, or solder paste reflow, all common techniques well known in the art. Alternatively, components may be adhered to the printed circuit using the composition itself. This is accomplished. for example, by placing the components in the composition prior to curing. This has the advantage of eliminating the soldering operation and 'S subsequent solder flux cleaning operations entirely. Yet another method for adhering components is to first cure the printed circuit, then apply an additional amount of uncured composition as a conductive adhesive for bonding the components.
Multiple-layer printed circuits may be made by starting with a circuit board 30 made as above. Over the cured composition and prior to soldering of the circuit components, a thin layer of a non-conductive insulating thermosetting resin is applies with a screen or stencil printer. The layer applied should be patterned so W~ 93/06943 ~ ~ ~ ~ PCR/LJS92/08333 as to allow vias or passages which remain uncoated with insulating material.
After curing of this layer, a second layer of conductive composition. in the desired printed circuit pattern. may be printed over the insulating layer. The vias or passages would then allow electrical interconnection between the upper and lower layers. In this fashion, a two-layer printed circuit is made. The process may then be repeated multiple times to create a printed circuit containing a plurality of layers. Electronic components may then be attached as described before.
Yet another method for creating a multiple-layered printed circuit is to begin with a series of thin substrates with vias or passages drilled or punched therein. The conductive composition is then screen- or stencil-printed onto each of these substrates in the desired printed circuit pattern, each layer generally being different. The compositions may then be cured, or simply dried and left uncured while the thin substrates are aligned and laminated together under pressure. The laminating pressure will force the conductive layers to interconnect through the vias and passages in the thin substrates, interconnection being made wherever there exists conductive composition directly beneath a via or passage.
Curing of the composition may be done before, during or after this laminating process. The result is a multiply-layered printed circuit.
Conductive compositions as described herein may also be employed to attach electronic components to conventional copper-clad printed circuits. In this application, the compositions make an excellent replacement for heretofore-known solder pastes. The conductive compositions may be stencil- or screen-printed onto the lands of a completed copper-clad printed circuit in a manner known to those skilled in the art. The leads of electrical component are then ?5 placed on the conductive composition and the entire assembly may be cured in an infra-red oven, convection oven, or by vapor reflow, all methods well known to those skilled in the art. The inventive compositions advantageously eliminate the need for cleaning the printed circuit assembly after curing; the generally lower viscosities of the compositions compared to solder pastes make the composition easier to print. Moreover, the formulation of the compositions are such that common problems with solder pastes, such as solder balling, bridging, and componem tombstoning, are eliminated.
ut A
Yet another useful appiicanon for compositions of the present invention is ~n attaching bare microcircuit dies to substrates, as is commonly done in the manufacture of multichip modules. Suitable formulations for this purpose include thermoset adhesives which. once hardened, are difficult to remove without destroying the printed circuit. The compositions described herein may be formulated using resins comprising therrttoplastic and thermosetting blends such that the cured compositions may be melted even after curing by application of moderate heat. In such applications, the conductive composition may be printed onto the substrate of the muItichip module using screen- or stencil-printing as is known to those familiar with the art. The die is then placed on the composition and the assemble is heated in an oven as described previously to achieve curing.
alternatively, heat may be applied to the die from above by a hot platen or hot air blower to achieve curine. The resulting bond between die and substrate may tie easily detached. if necessary, by application or heat to the die by a hot platen, soldering iron. hot air, or any other method known to one skilled in the art.
The die may then be pulled away from the melted composition.
The invention may be better understood by refcrcnce to the following examples which are imended for purposes of illustration and are not to be construed as in any way limiting the scope of the present invention, which is '-0 defined in the claims appended hereto.
Example I
Gas atomized and electrolytic copper powders were compared with respect to the sheet resistiviry of compositions which differed only in the type of powder employed. Compositions were prepared by first combining four molar parts of '-5 glycerol to one pan of tetrabromophthalic anhydride in a glass vessel and heating the mixture to between 180-200° C for approximately four hours. The reaction was monitored by placing samples of the solution in a sodium cell of a Perkin Elmer model 7'_7 infrared spectrophotometer. The 1800'1 cm singlet band was observed to disappear into the baseline and the 1750'' cm singiet band appeared ~0 and reached an eauilibrium before the solution was removed from the heat.
:after cooling, the resulting solution was mixed with the other components of the composition. .-~ solution of Shell EPON''"' 1123-r~-80 in butyl carbitol was prepared A.
~6 ,..,., by dissoivine 8 partsbv weight of the resin solution an 2 parts by weiQllt of butyl carbitol and boiling the resulting mixture at approximately 100°'C
until the manufacturer's solvent was observed to be fully evaporated. The resulting solution was mixed with the other components of the composition after cooling.
A monomer solution of tetrabromobisphenol A was prepared in butyl carbitol, 1:1 by weight, and warmed at approximately-I00° C until fully dissolved.
The resulting solution was mixed with the other components of the composition after cooling. Gas atomized copper powder with average panicle diameter of 15 microns was cleaned by heating in hydrogen gas to 300° C, then cooled in hydrogen and mixed 2:1 by weight with -500 mesh Sn63Pb37 alloy powder to produce the gas atomized composition. Similarly, a 15 micron average particle diameter electrolytic powder was hydrogen cleaned and mixed 2:1 with the same alloy powder to produce the electrolytic composition. The mixtures and solutions were intermixed to produce compositions having the following equivalent IS pre-esterification proportions by volume: Cu - 35.8%; Sn63Pb37 - 19%; Shell EPONTM 1123-A-80 - 8.5%; tetrabromophthalic anhydride - 5%;
tetrabromobisphenol A - 8.6%; butyl carbitol - 13.3%; glycerol - 9.9%. The compositions were screen printed through a 250 mesh screen in a solid rectangular pattern to a thickness of approximately 75 microns on microscope '0 slides. The slides were placed on hot plates at the given temperature for seconds. The resultant cured compositions were tested for conductivity on a Four Dimensions model I01 four point resistivitv probe modified to read on a,scale of 10'3 ohmsisquare. The resulu are reported in Table 1.
?0 A
TAB LE I
Comparison of Gas Atomized and Electroivtic CnnnPr ~.,~.~,...r VIJ
Cu Powder Gas Atomized Electrolytic ~,J
Sheet Resistivity (OhmiSquare)(x i03) COmpOSltlon cured at ~z0 °C
Average 9.71 2~_pp Standard Deviation 0.47 32,00 CompOSltlOn cured at X60 °C
Average 4.30 65.00 Standard Deviation O,gg ~.~
Exam The effects of mean copper powder panicle size on bulk.resistivitv were determined. The comaositions werc prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume:
Cu - 34.9%: Sn63Pb37 - 17.3%; Shell EPON''"' 1123-A-80 - 3.4%a;
tetrabromophthalic anhydride - .~.8%; tetrabromobisphenol A - 13%; butyl carbitol - 17.2%; glycerol - 9.5%. The compositions were screen-printed on a microscope slide and cured on a hot plate at 260° C for 30-45 seconds.
The results are reported in Table II.
TABLE II
Mean Cooper Powder Particle Size and Bulk Resistivitv Mean Particle Size ( um ) 3 fl 15 7 .,5 _ Bulk Resistivitv (Ohm-cm)(x 1051 Average 2.80 ~.~0 4.90 Standard Deviation 0.17 0.I2 0.59 Example 3 The effects of hydrogen cleaning of the copper powder were evaluated.
The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 34.9%;
Sn63Pb37 - 17.3%; Shell EPON'~"' 1123-A-80 - 3.4%; cetrabromophthalic anhydride - 4.8%; tetrabromobisphenol A - 13%; butyl carbitol - 17.?%; glycerol - 9.5%.
The compositions were screen-printed on a microscope slide and cured on a hot ,»~~: k .;":
tt.
2i 20~~~
plate at ~60° C f.or;;p_45 seconas. The results are reported in Table ~.
TABLE iII
Effects of Hvdro en Cleanin on Buik Resistivitv As-delivered HvdroQen-Cleaned Bulk Resistivitv (C~hm-cm tlx t cW
Average .. 5.10 Standard Deviation 1.00 0.17 Examr~le 4 Fig. I indicates the effecu of varying alloys on conductivity of the final COmpOSItlOn. The COmi7oSitinnc m...~ .,._....__~ __ ,.-compositions containing the following pre-esterification proportions by volume:
Cu - 34.9%; alloy - 17.3%; Shell EPON~'~"' 1123-A-80 - 3.4°!0;
tetrabromophthalic anhydride - .~.$%; tetrabromobisphenol A - 13%; butyl carbitol - 17.2%;
glycerol -9.5%. ?he compositions were screen-printed on a microscope slide and cured on a hot plate at the indicated temperature for 30-45 seconds.
Example 5 A variety of resins and resin mixtures were evaluated. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 32.8%; Snb3Pb37 -34.8%; resin - l.?% (for Shell EPON'~ l I23-A-80; the molar concentration for all others was maintained the same); tetrabromophthaiic anhydride - 6%;
tetrabromobisphenol A - ~.8%; butyl carbitol - 7.b%o; glycerol - I 1.8%. 'I'h~
compositions were screen-printed on a microscope slide and cured on a hot plate '-5 at the indicated temperature for 30-45 seconds. PuII test samples were pre ared P
by screen printing 4 x 4 mm squares onto the indicated substrate and curing the coated materials in an infrared belt oven at 220° C for appro~mately 1 minute.
The samples were then dipped in a solder bath for 4-8 seconds in the presence of a type RMA Bux (a mildly activated rosin-based flux) to attach a pull wire.
The 30 pull strengths reported are the ma~dmum force sustained on the ull wire at P
delamination. The results of these evaluations are reported in Table IV.
A
r vd a t 4 TABLE IV
Comparison of Resins and Resin 'Mixtures Sheet Resistivity Ohnvsquare Puil Strength T(g) C of at Cure Temperature !x 103 On Substrate (ko~ 330=ple '_00C ?30C ''60C PEI FR4 EPONT"' 1123_A_80 3.73 3.13 3.25 0.103 0.037 1SS
EPON'''M 1123-A-80/ 3.69 3.26 3.37 0.018 0.06 172 DOW XU7I790.04L
( 1:1) DOW XU71790.04L 3.47 3.39 3.56 0.035 0.069 139 EPON'''"' 2123-A-80/ 3.25 3.06 3.SS 0.203 0.034 120 DOW DEN'~431 ( 1:1 ) DOW DEN'~431 3.46 3.29 3.3I 0.176 0.096 145 EPON~""~ .123-A-801 3.54 3.54 3.4b 0.174 0.129 . 100 1 S DOW DEN''"' 438 ( 1:1 DOW DEN"=.~38 3.5 3.48 3.47 O.1S6 0.09 180 EPON~'~' ~ 123-A-80/ ;.61 3.41 3.29 0.201 0.046 18S
EPON'''~'l~pS164 ( 1:1) EPON~DPS 164 3.73 3.44 3.69 O.1S3 0.044 16S
EPON''"' 1123-A-80l 3.57 3.3 3.34 0.2SS 0.061 145 - I65 EPON~'ppSISS (1:1) EPON1"z DPS 1SS -1.36 3.85 3.75 0.139 0.07 Ig7 Exam~6 Various anhydrides and their derivatives were compared as employed =-.S in conductive compositions. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 3S%; Sn63Pb37 - 37.I%; Shell EPON~"' 1123-A-80 - 3.S%;
anhydride -3.7% (for tetrabromophthalic anhydride; the molar concentration was kept the same for all others. or was zero where no ester is indicated);
tetrabromobisphenol A - S.S%; butyl carbitol - 7.9%; glycerol - 7.3% (far glycerol;
the molar concentration was kept the same for all others, or was zero as indicated).
The compositions were screen-printed on a microscope slide and cured on a hot plate at 260' C far 30-.4S seconds. The results are reported in Table V.
?3 ., TABLE V
Comparison of Curin ~Agents Sheet Resistivitv Curing went (Ohm/Sgl x103 ~ Color Tetrabromophthalic Anhydride > 100 Red Tetrabromophthalic Acid > 100 Red Tetrabromophthalic Anhydride! 4.89 Grey/Silver Butyl Carbitol Ester Tetrachlorophthalic Anhydride 8.83 RedISilver Tetrachlorophthalic Anhydride/ 3.48 Grey/Silver Butyl Carbitol Ester Phthalic Anhydride 5.23 Red/5ilver Phthalic Acid 10.00 Red/Grey Phthalic AnhydrideButyi Carbitol Ester 3.36 GieylSilver 4-Fluorophthalic Anhydride 4.Ob Grey/Silver 4-Fluorophthalic Anhydride/ 3.14 Grey/Silver Butyl Carbitol Ester Oxydiphthalic Anhydride 5.35 Grey/Silver Oxydiphthalic AnhydrideButyi Carbitol 3.40 Grey/Silver Ester Biphenyl Tetracarboxyiic Dianhydride > 100 Red/Grey Biphenyl Tetracarboxylic Dianhydride/ 3.40 Grey/Silver Butyl Carbitol Ester Diphenylsulfone Tetracarboxyiic Dianhydride19.00 Red/Grey Diphenylsulfone Tetracarboxylic Dianhydride/3.41 Grey/Silver '_5 Butyl Carbitol Ester Hexafluoroisopropyl Diphthalic Anhydride> 100 Red Hexafluoroisopropyl Diphthalic Anhydride!4.20 Grey/Silver Butyl Carbitol Ester Benzophenone Tetracarboxylic Dianhydride4.00 Grey/Silver Benzophenone Tetracarboxyiic Dianhydride/3.00 Grey/SiIver Butyl Carbitol Ester Chlorendic Anhydride 6.42 GreylSilver Chlorendic AnhydrideButyl Carbitol Ester3.78 Grey/Silver Epoxy Tetrahydrophthalic Anhydride 4.33 Red/Grey Epoxy Tetrahydrophthalic Anhydride) 3.00 Grey/Silver Butyl Carbitol Ester In all cases. the esterification of the anhydride by the alcohol produced marked improvement in electrical conductivity and in elimination or surface oxidation.
evidenced by consistent greyisilver color of cured compositions.
Exam~Ie 7 A comparison of various esters of tetrabromophthalic anhydride was made.
The compositions were prepared as in Example i with the final compositions containing the following pre-estcrification proportions by volume: Cu - 32%;
Sn63Pb37 - 34%; Shell EPON""' 1123-A-80 - 3.3%; tetrabromophthalic anhydride -5.9%; tetrabromobisphenol A - 5.5% (for tetrabromophthalic anhydride; the molar concentration was the same for all others); butyl carbitol - 7.$%s;
polvol esterifying agem - 11.6% (for glycerol: the molar concentration was the same for ail others). The compositions were screen-printed on a microscope slide and cured on a hot plate at the indicated temperature for 30-45 seconds. Pull test samples were prepared by screen printing 4 x 4 mm squares onto the indicated is substrate and curing in an infrared belt oven at 220° C for approximately 1 minute. The samples were then dipped in a solder bath for 4-8 seconds in the presence of a mildly activated rosin based flux to attach a pull wire. The results are reported in Table VI.
TABLE VI
Comparison of Esters of Tetrabromophthalic Anhydride Estcrincation Agent Sheet Reslstlvlty Pull Strength {Kg) T(g) °C
Ohmlsguare x l~
'~°C ''-''-30°C 260°C PEi FR4 '_'30°C Sample Butyl Carbitol - > 100 9.14 9.43 0.28 0 110 Glycerol 4.7I 4.54 .x.43 0.276 0 115 Adonitol 5.$9 3.57 .x.14 0.223 0 140 Octadecanoi > 100 17 10 * * 80 *Not solderable Example 8 ~0 The utility of various anhydrides as curing agents was evaluated. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 32%;
'A
r,m Sn63Pb37 - 3-1%. Shell EPO'~ 113-~-g0 _ ;.;c~; tetra6romoph .
h , .
t alic anhydride -~.9%; tetrabromobisphenol A
~
3~?' -.
0 (for tetrabromophthalic anhydride: the molar concentrations were the same for ail others ); butyl carbitol .- 7.8%; poiyol esterifyin~ agem - 11.6% (for glycerol; the molar conce ntrations were the samc for all others). Compositions were screen-printed on a i m croscope slide and cured on a hot plate at the indicated temperature for 30-4S
seconds. Pull test samples were prepared as previously indicated. The results are reported in Table VII.
TABLE VII
i0 Comparison of Anhvdrid~c - Anhydride Sheet Resistivity Puli Strength (K
) T
C
g (g) Ohmlsguare x 103 '-~C ''-''-30'C '_'60C PEI FR4 ~30C
Sam~fe 15 Tetrabromophthalic 3.64 3.34 3.56 0 .
.
Anhydride Phthalic Anhydride 5.62 '_.49 0.52 0 .
4-FluorophthaIic 3.28 3.72 4.27 0 .
Anhydride 20 Biphenyl-Tetracarboxyiic 7.97 7.56 9 38 * ' .
Dianhydride Hexafluoroisopropyl 4.75 3 ~5 *
.
.
0.03 1~
Diphthalic Anhydride 'Not solderabie Exam~ole 9 A number of reactive monomers were prepared and evaluated. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterification proportions by volume:
Cu - 32.1%;
Sn63Pb37 - 34.1%: Shell EPON'~" 1123 A
--- 3.3%; tetrabromophthalic anhydride -'0 6%; monomer - 5.2% (far tetrabromobisphenol A
th ;
e molar concentration was the same for all others b );
utyl carbitol - 7.5%; glycerol - 11.8%. Compositions were screen-printed on a microscope slide and cured on a hat plate at the indicated temperature for 30-45 seconds. Pull test samples were prepared as previously indicated. The results are repotted in Table VIII.
TABLE viII
COmt7arISOn of Reactive Monomers Reactive 'vtonomers Sheet Resistivity Pull Strength-Ke '(' °C
Ohm~sguare ~ 10' '_'00°C :a0°C ~60°C
Cure Cure Cure PEI FR4 Sample Tetrabromo- _ - -Bisphenol-A 3.5 3.65 3.54 0.059 0.12..5 1~
Bisphenoi-A 3.94 3.58 3.59 0.041 0.089 170 i0 Hexafluoro-Bisphcnol-A 3.93 3.51 3.74 0.05 0.095 93 No monomer 3.74 3.79 3.87 0.05 O.I2 140 - 155°
Example IO
A comparison was made of compositions containing halogenated and non-1 S halogenated reactants. The compositions were prepared as in Example 1 with the final compositions containing the following pre-esterirication proportions by volume: Cu - 35.4~Te: Sn63Pb37 - I9.1~''c: resin - 3.5% (for Shell EPON~' 1123-A-80:
the epoxy equivalent concentration was maintained the same for all others);
anhydride - .~.4% (for tetrabromophthalic anhydride; the molar concentration was 20 the same for all others); monomer - 12.5%; butyl carbitoi - 16.6%; glycerol -8.6%. Compositions were screen-printed on a microscope slide and cured on a hot plate at the indicated temperature for 30-45 seconds. The results are reported in Table IX.
?7 TAg~ IX 212n523 .~
Comparison of Haioeenatsd and 'Von-Haio~PnalPr~ Q Aa; talli~
Bulk Resistivity Color Reactants (Ohm-cm ~ x 10°
EPON~'~"' 11~-A-80 Brominated Resin Tetrabromophthalic Anhydride Glycerol Ester w = X6.8 ~ 1.1 Grey Tetrabromobisphenol-A
EPON'~"" 1I?3-A-80 Brominated Resin Phthalic Anhydride Glycerol Ester ~6.6 ~ 2 ~ RedBrown Tetrabromobisphenol-A
Epo.N~ 1123-A-80 Brominated Resin Tetrabromophthalic Anhydride Glycerol Ester ~ ?6.9 ~ 0.8 ~ Grcy Bisphenoi-A
'-fl EpoN'~ 1123-A-80 Brominated Resin Phthaiic Anhydride Glycerol Ester ?9.3 ~ ?.3 Red Bisphenol-A
Example 11 A comparison was made of the solderability of various compositions, depending upon the anhydride employed. The compositions were prepared as in Exampfe 1 with the final compositions containing the following pre-esterification proportions by volume: Cu - 32.6%; Sn63Pb37 - 34.6%; Shell EpoN~ 1123-A-80 -4.I%; anhydride - .x.9°!0 (for tetrabromophthalic anhydride; the molar concentration was the same for all others); tetrabromobisphenol A - ~.8%;
butyl 30 carbitol - 8.4%; glycerol - 9.6%. Compositions were screen-printed on a microscope slide- and cured on a hot plate at the indicated temperature for 30-seconds. The results are reported in Table X.
2~2Q523 TABLE X
COmDaTISOn of Soiderabilitv Anhydride Solderabilitv Tetrabromophthalic Anhydride Very Good Phthalic Anhydride Very Good 4-Fluorophthalic Anhydride . Good Biphenyl-Tetracarboxylic Dianhydride None Hexafluoroisopropyi Diphthalic Anhydride None Tetrabromophthalic Anhydride/Biphenyl Tetracarboxylic Dianhydridc (2:1 Mix Ratio) Fair ._ - Tetrabromophthalic AnhydridelHcxafiuoroisopropyi Diphthalic Anhydride (2:1 Mix Ratio) Fir .
ExamDie 1?
The eraphs of Fig. 2 (resistivity response surfaces) show the effects of relative concentration changes on resistivity for a preferred sample composition.
In Fig. ?. isoquants of least squares response surfaces of resistivity as a function of concentration of components were generated using experimental design and analysis computer software (Echip Inc., Hockessin, DE). Starting solutions were prepared as in Example 1. The experimental design portion of the program was used to specify a series of varying composition formulations. by weight, of each of the starting solutions and metal powders. The formulations specified by the program were prepared and resistivity measurement slides were created and tested. The bulk resistivity of the samples was used to normalize out thickness variations. The resulting data was installed into the computer program which '-S generated the triangle graphs shown. The compositions were cured on a hot plate at 200° C for 30-45 seconds. The experimental resin consisted of EPON
1123-A-80 in glycerol (4:1 by weight). The anhydride was esterified in glycerot (1:2 molar proportion) as before. The bisphenol A was dissolved in butyl carbitoi (1:1 by weight). The numbers shown arc for weight fractions of these starting ~0 solutions. Compositions were screen-printed on a microscope slide and cured on a hot plate at 200° C for 30-45 seconds.
r -1y~ -~r.,t~..
~.
~:.~r..
Exam~ie i3 Fig. ~ graphically demonstrates the effect of adding a third metal or metal alloy powder incorporating high melting point metals which readily dissolve in the solder powder. In the experiments depicted in Fig. ~. the compositions were prepared as in Example 1 with the final compositions containing the following pre-esterincation proportions by voiume~Cu - 33.2%: Sn63Pb37 - 16.7%;
Shell EPON'"" 1123-A-80 - 3.4%; tetrabromophthalic anhydride - 4.8%;
tetrabromobisphenol A - 13%; butyl carbitol - 17.2%; glycerol -9.5%; Ag-coated Ni - 2.3%. The composition was placed in a Perkin Elmer Model 4 differential scanning calorimeter and cured with a temperature ramp of 20 C under nitrogen to 500 C. The top curve displays the various endotherms encountered during this cure cycle. The melt endotherm of the alloy was at 183 C. After cooling the sample back to room temperature, the temperature was romped up again and the lower curve was obtained. The melting point of the composition shifted up over 1~ 100 degrees.
Example 14 A comparison of protected vs. unprotected anhydrides was made. The tetrabromophthalic anhydride glycerol ester composition in Table XI was prepared as in Example 1. The compositions in the bottom half of the table we re '0 mixed from the starting materials listed without heating as in Example 1. The final compositions contained the following pre-esterification proportions by volume: Cu - 35.7%; Sn63Pb37 - 18.3%; Shell EPONT"' 1123-A-80 -3.9%:
anhydride - -~.3% (for tetrabromophthalic anhydride; the molar concentration was the same for all others, or was zero if so indicated); tetrabromobisphenoi A -'-5 i2.2%; butyl carbitol - 16.3%; additional solvent or ester as listed - 8.5% (for glycerol; the molar concentration was the same for all others);
Ag-coated Ni -0.9%. The compositions were screened onto a microscope slide and cured on a hot plate at the indicated temperature for 30-45 seconds. The resuiu are reported in Table XI. The data suggest that it is the mono-ester, mono-acid 30 derivative of the anhydride which serves to produce the best electrical conductivity. Comparison of the data in Table XI with that in Table V illustrates the effects of esterifying halogenated versus non-haloeenated anhydrides.
.m.
1.:~~.
r ,, ~212~523 TABLE ~I
Comparison of Protected Anhydrides vs inn Prnr....va ~...av.u Anhydrides Anhydride or Derivative Sheet Resistivitv ' OhmlSquai--~00C '30C 260C
Tetrabromophthalic Anhydride/
Glycerol Esterified 4.08 3 .
4.05 Tetrabromophthalic Anhydride/
tetrahydrofuran (additional solvent) 6.64 4 .
4.20 Tetrabromophthalic Acid/
tctrahydrofuran (additional solvent) 8.56 5 .
4.52 Dimethyl Phthalate;
dimcthyl sulfoxide > 100 > I00 > lOp Methyl Hydrogen Phthalate!
dimethyl sulfoxide .x.84 -i 2'~
.
Phthaiic Acid/
dimethyl sulfoxide 4.01 3 .
4.68 Phthalic Anhydride!
dimethyl sulfoxide 4 .
4.63 4.76 Example 15 -'S A comparison of a printed circuit made with a conductive com sition on Po a polyetherimide substrate versus a circuit made from etched copper clad epoxy laminate was made. The circuit chosen for comparison w d as a c-to-de converter.
The schematic diagram of the- circuit is shown in Fig. 4; this schematic was taken from EDN, January 5, 1976. Resistor R~ was selected to be I80 Oh ms. A
30 printed circuit pattern for this circuit was designed; the pattern is shown in Fig. 5.
This pattern was etched imp the copper clad epoxy laminate using conventional methods known in the art. Holes were drilled and components w ld ere so ered with a soldering iron.
A composition was prepared consisting of the following pre-esterification proportions by volume: Cu - 26.8%; Sn63Pb37 - 28.4%; Shell EPO~~ 11?3-A-80 resin - '.6%; tetrabromophthaIic anhydride - 0.1%; tetrabromobisphenol A -IiVO 93106943 ~ PGT/US92/08333 2~.2fl~~~
0.1%a; butyl carbitol - .~2%. The anhydride was esterified as in Example 1 wnh butyl carbitol. A 250 mesh stainless steel screen of the same printed circuit pattern was made. The screen was mounted on an SMT model SP1414PD screen printing press. The pattern of the printed circuit was then screen-printed onto a bare .060 in thick poiyetherimide substrate using the conductive composition.
The .
substrate and composition thereon were flash exposed for 15 seconds to high intensity tungsten filament infra-red lamps in an RTC model LSOOTF infra red oven to achieve cure. Upon completion, holes were drilled in the printed circuit and the components were inserted and soldered with a solder iron set at 255° C
using Sn63 rosin core solder wire. Voltage signals were observed on-a~
oscilloscope at the test points labeled A-I in the schematic diagram. The resultant voltages and duty cycles observed were recorded. in Table XII for the two circuits thus obtained under a 220 Ohm load with 15 volts in, unless indicated otherwise. The comparison indicated nearly identical electrical performance for both printed circuits.
TABLE XII
Copper Clad Printed Circuit Composition Circuit Volts-pp Duty Cycle% Volts-pp Duty Cycle%
Test Point LOAD Output Voltage Output Voltage t lOK Ohm 10 Volts 10 Volts 220 Ohm 10 Volts 10 Volts 100 Ohm 7 Volts 7 Volts ,.-Gxarnoie i 6 A comparison was made of the electrical resistivities of a composition formulated as taught herein and a conductive composition formulated in accordance with the prior art. The first composition was prepared as in Example 1 containing the following pre-esterification proportions by volume: Cu -34.1%;
Sn63Pb37 - I7.4%; Shell EPON'''M 1123-A-$0 . 3.6%; tetrabromophthalic anhydride 5.7%; tetrabromobisphenol A - lL6%; butyl carbitol - 15.4%; glyccroi - 11.3%;
Ag coated Ni - 0.9%. The resulting paste was screen-printed onto a glass microscope slide. The composition was cured at 230° C far i minute. The I0 r~ststivity was measured as before.
' The prior art composition was prepared by dissolving 2.5 grams of Shell EPONT'" 82g resin, ?.5 grams oleic acid. 1.0 gram phthalic acid in .1 grate ethylene glycol acetate without heating. ,~ mixture of 31.7 grams electrolytic copper powder (Metz Metallurgical #11. S. Plaintieid. N1) was mixed with 3.2 grams of 1S Sn50Pb50 allay powder and 3.2 grams of Bi58Sn42 alloy powder. The two were intermixed and the resulting paste was screen-printed as before. The composition was cured for 10 minutes at a temperature of 230'° C on a hot plate.
The sample was then treated as above. Table XIII records the results of these measurements.
TABLE XIII
20 Comparison of Resistivities of Inventive Composition v Pr;or Art Resistivi tv Ohtn/square Composition r 103 Invention 4.35 Ptiar Art From the foregoing description, one skilled in the art can readily ascertain the essential characteristics of, the invention and, without departing from the spirit and scope thereof, can adapt the invention to various usages and conditions.
Changes in form and substitution of equivalents are contemplated as 30 circumstances may suggest or render expedient, and although specific terms have been employed herein, they are intended in a descriptive sense and not for purposes of limitation.
.A'
Claims (31)
1. A conductive adhesive composition of matter comprising:
6-65% of a solder, wherein said solder has a melting temperature and is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Ti, Sb, Se, and alloys thereof;
greater than 0 up to 65% of a high melting point metal, wherein the high melting point metal is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof;
0.01-61% of a chemically or mechanically protected cross-linking agent with fluxing properties which is reactive only at or near a time at which the solder is melted, wherein said chemically protected cross-linking agent is an acid or a strong base, wherein said acid or strong base is selected from the group consisting of anhydrides, carboxylic acids, amides, imides, amines, alcohols, phenols, aldehydes, ketones, nitro compounds, nitriles, carbamates, isocyanates, amino acids, peptides, thiols, sulfonamides, semicarbazones, oximes, hydrazones, cyanohydrins, areas, phosphoric acids, phosphoric esters, thiophosphoric acids, thiophosphoric esters, phosphonic acids, phosphonic esters, phosphites, phosphonamides, sulfonic acids and sulfonic esters, and wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, amides, alcohols, glycols, polyols, alkyl halides, acid halides, thiols, areas, alkyl silanes, diazoalkanes, azomethanes, acetals, ketals and transition metal complexes;
0-50% of a reactive monomer or polymer; and, 0-45% of a resin;
wherein all percentages referred to herein are based on volume.
6-65% of a solder, wherein said solder has a melting temperature and is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Ti, Sb, Se, and alloys thereof;
greater than 0 up to 65% of a high melting point metal, wherein the high melting point metal is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof;
0.01-61% of a chemically or mechanically protected cross-linking agent with fluxing properties which is reactive only at or near a time at which the solder is melted, wherein said chemically protected cross-linking agent is an acid or a strong base, wherein said acid or strong base is selected from the group consisting of anhydrides, carboxylic acids, amides, imides, amines, alcohols, phenols, aldehydes, ketones, nitro compounds, nitriles, carbamates, isocyanates, amino acids, peptides, thiols, sulfonamides, semicarbazones, oximes, hydrazones, cyanohydrins, areas, phosphoric acids, phosphoric esters, thiophosphoric acids, thiophosphoric esters, phosphonic acids, phosphonic esters, phosphites, phosphonamides, sulfonic acids and sulfonic esters, and wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, amides, alcohols, glycols, polyols, alkyl halides, acid halides, thiols, areas, alkyl silanes, diazoalkanes, azomethanes, acetals, ketals and transition metal complexes;
0-50% of a reactive monomer or polymer; and, 0-45% of a resin;
wherein all percentages referred to herein are based on volume.
2. A composition according to claim 1, comprising:
6-37% by volume of said solder, up to about 38 % by volume of said high melting point metal, 11-60% by volume of said cross-linking agent, up to 42% by volume of said resin, when present, and up to 47% by volume of said reactive monomer or polymer, when present.
6-37% by volume of said solder, up to about 38 % by volume of said high melting point metal, 11-60% by volume of said cross-linking agent, up to 42% by volume of said resin, when present, and up to 47% by volume of said reactive monomer or polymer, when present.
3. A composition according to claim 1, wherein the high melting point metal constitutes 13-65% by volume of said composition.
4. A composition according to claim 3, wherein:
the solder constitutes 6-29% by volume of said composition, the resin constitutes 0-15% by volume of said composition, the cross-linking agent constitutes 7-60% by volume of said composition, and the reactive monomer or polymer comprises 0-32% by volume of said composition.
the solder constitutes 6-29% by volume of said composition, the resin constitutes 0-15% by volume of said composition, the cross-linking agent constitutes 7-60% by volume of said composition, and the reactive monomer or polymer comprises 0-32% by volume of said composition.
5. A composition according to any one of claims 1 to 4, wherein said acid or strong base is selected from the group consisting of anhydrides, carboxylic acids, amines and phenols.
6. A composition according to claim 5, wherein said acid or strong base is an anhydride.
7. A composition according to any one of claims 1 to 6, wherein said acid or strong base is protected by encapsulating the cross-linking agent in a shell of non-reactive material which releases the cross-linking agent only at or near the time the solder is melted.
8. A composition according to any one of claims 1 to 6, wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, alcohols, polyols and phenols.
9. A composition according to claim 8, wherein said protecting group is an alcohol or polyol.
10. A composition according to claim 9, wherein said alcohol or polyol is selected from the group consisting of butyl carbitol, methanol, ethylene glycol, glycerol, mesoerythritol, adonitol and sorbitol.
11. A composition according to any one of claims 1 to 10, wherein said solder is a metal mixture that includes a metal additive that alters the melting temperature of the solder, said metal additive being selected from the group consisting of nickel and silver and wherein said metal additive constitutes 1 to 10 weight percent of a total metal content of the composition.
12. A composition according to claim 11, wherein the additive is silver.
13. A composition according to any one of claims 1 to 10, further comprising a metal additive that comprises a second high melting point metal which readily dissolves in said solder to form a solid solution, wherein said metal additive constitutes 1 to 10 weight percent of a total metal content of the composition.
14. A composition according to any one of claims 1 to 13, wherein said solder is an alloy having the chemical formula Sn63Pb37.
15. A composition according to any one of claims 1 to 14, wherein the reactive monomer or polymer, when present, contains at least one -OH group as a reactive site for linking with said cross-linking agent.
16. A composition according to any one of claims 1 to 15, wherein the high melting point metal comprises spherical particles having an average particle diameter of 1-50 microns.
17. A composition according to claim 16, wherein the high melting point metal is copper.
18. An electrically conductive ink composition comprising:
0.0001-38% by volume of a high melting point metal powder selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof, 6-37% by volume of a solder powder selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Ti, Sb, Se, Po, alloys thereof and other metals having a melting point lower than that of the high melting point metal powder, 11-60% by volume of a cross-linking agent mixture comprising a chemically- or mechanically-protected cross-linking agent, and at least one of a) up to 42% by volume of a resin, and b) up to 47 % by volume of a reactive monomer or polymer, wherein said protected cross-linking agent is an acid or a strong base protected by a protecting group or by encapsulation so as to become reactive sufficiently near a temperature at which the solder powder is melted in order to flux the solder prior to vitrification of the reactive monomer, polymer or resin.
0.0001-38% by volume of a high melting point metal powder selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof, 6-37% by volume of a solder powder selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Ti, Sb, Se, Po, alloys thereof and other metals having a melting point lower than that of the high melting point metal powder, 11-60% by volume of a cross-linking agent mixture comprising a chemically- or mechanically-protected cross-linking agent, and at least one of a) up to 42% by volume of a resin, and b) up to 47 % by volume of a reactive monomer or polymer, wherein said protected cross-linking agent is an acid or a strong base protected by a protecting group or by encapsulation so as to become reactive sufficiently near a temperature at which the solder powder is melted in order to flux the solder prior to vitrification of the reactive monomer, polymer or resin.
19. A conductive ink formed by a process comprising the steps of:
providing a composition comprising:
greater than 0 up to 65% of a high melting point metal, wherein the high melting point metal is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof;
6-65% of a solder, wherein said solder is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Ti, Sb, Se, and alloys thereof;
0-45% of a resin;
0.01-61% of a chemically protected cross-linking agent with fluxing properties which is reactive only at or near a time at which the solder is melted, wherein said chemically protected cross-linking agent is an acid or a strong base, wherein said add or strong base is selected from the group consisting of anhydrides, carboxylic acids, amides, amines and phenols, and wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, alcohols, glycols and polyols;
and 0-50% of a reactive monomer or polymer, wherein all percentages referred to herein are based on volume; and heating the composition to a temperature sufficient to melt the solder and to activate the chemically protected cross-linking agent.
providing a composition comprising:
greater than 0 up to 65% of a high melting point metal, wherein the high melting point metal is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof;
6-65% of a solder, wherein said solder is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Ti, Sb, Se, and alloys thereof;
0-45% of a resin;
0.01-61% of a chemically protected cross-linking agent with fluxing properties which is reactive only at or near a time at which the solder is melted, wherein said chemically protected cross-linking agent is an acid or a strong base, wherein said add or strong base is selected from the group consisting of anhydrides, carboxylic acids, amides, amines and phenols, and wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, alcohols, glycols and polyols;
and 0-50% of a reactive monomer or polymer, wherein all percentages referred to herein are based on volume; and heating the composition to a temperature sufficient to melt the solder and to activate the chemically protected cross-linking agent.
20. A conductive ink according to one of claims 18 and 19, wherein the conductive ink has a bulk electrical resistivity of less than 10 -4 Ohms-cm.
21. A conductive ink according to any one of claims 18 to 20, wherein the high melting point metal comprises spherical particles having an average particle diameter of 1-50 microns.
22. A conductive ink according to claim 21, wherein the high melting point metal is copper.
23. A conductive ink according to any one of claims 18 to 22, wherein the chemically protected cross-linking agent is a chemically protected anhydride.
24. A method for preparing a printed circuit, said method comprising:
applying a conductive ink composition according to any one of claims 1 to 23 onto a substrate in a predetermined pattern to provide a patterned substrate;
heating the patterned substrate to a temperature at or near the melting temperature of the solder powder for a period of time sufficient to both activate the chemically- or mechanically-protected cross-linking agent, whereby the chemically- or mechanically-protected cross-linking agent reacts with the high melting point metal powder, and to cure the conductive ink composition.
applying a conductive ink composition according to any one of claims 1 to 23 onto a substrate in a predetermined pattern to provide a patterned substrate;
heating the patterned substrate to a temperature at or near the melting temperature of the solder powder for a period of time sufficient to both activate the chemically- or mechanically-protected cross-linking agent, whereby the chemically- or mechanically-protected cross-linking agent reacts with the high melting point metal powder, and to cure the conductive ink composition.
25. A method for preparing a printed circuit, said method comprising:
applying a composition onto a substrate in a predetermined pattern to provide a patterned substrate; and heating the patterned substrate to cure the composition, wherein said composition comprises:
6-65% of a solder, wherein said solder is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Ti, Sb, Se, and alloys thereof;
greater than 0 up to 65% of a high melting point metal, wherein the high melting point metal is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof;
0.01-61% of a chemically or mechanically protected cross-linking agent with fluxing properties which is reactive only at or near a time at which the solder is melted, wherein said chemically protected cross-linking agent is an acid or a strong base, wherein said acid or strong base is selected from the group consisting of anhydrides, carboxylic acids, amides, imides, amines, alcohols, phenols, aldehydes, ketones, nitro compounds, nitriles, carbamates, isocyanates, amino acids, peptides, thiols, sulfonamides, semicarbazones, oximes, hydrazones, cyanohydrins, areas, phosphoric acids, phosphoric esters, thiophosphoric acids, thiophosphoric esters, phosphonic acids, phosphonic esters, phosphites, phosphonamides, sulfonic acids and sulfonic esters, and wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, amides, alcohols, glycols, polyols, alkyl halides, acid halides, thiols, areas, alkyl silanes, diazoalkanes, azomethanes, acetals, ketals and transition metal complexes;
0-50% of a reactive monomer or polymer, and 0-45% of a resin;
wherein all percentages referred to herein are based on volume.
applying a composition onto a substrate in a predetermined pattern to provide a patterned substrate; and heating the patterned substrate to cure the composition, wherein said composition comprises:
6-65% of a solder, wherein said solder is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Te, Hg, Ti, Sb, Se, and alloys thereof;
greater than 0 up to 65% of a high melting point metal, wherein the high melting point metal is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, and alloys thereof;
0.01-61% of a chemically or mechanically protected cross-linking agent with fluxing properties which is reactive only at or near a time at which the solder is melted, wherein said chemically protected cross-linking agent is an acid or a strong base, wherein said acid or strong base is selected from the group consisting of anhydrides, carboxylic acids, amides, imides, amines, alcohols, phenols, aldehydes, ketones, nitro compounds, nitriles, carbamates, isocyanates, amino acids, peptides, thiols, sulfonamides, semicarbazones, oximes, hydrazones, cyanohydrins, areas, phosphoric acids, phosphoric esters, thiophosphoric acids, thiophosphoric esters, phosphonic acids, phosphonic esters, phosphites, phosphonamides, sulfonic acids and sulfonic esters, and wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, amides, alcohols, glycols, polyols, alkyl halides, acid halides, thiols, areas, alkyl silanes, diazoalkanes, azomethanes, acetals, ketals and transition metal complexes;
0-50% of a reactive monomer or polymer, and 0-45% of a resin;
wherein all percentages referred to herein are based on volume.
26. A method for preparing a printed circuit, comprising:
applying a conductive ink composition comprising a solder powder, a high melting metal powder, and a cross-linking agent mixture comprising a chemically protected cross-linking agent with fluxing properties onto a substrate in a desired pattern to provide a patterned substrate;
rapidly heating the patterned substrate to a temperature at or near a melting temperature of the solder powder for a period of time sufficient to activate the chemically protected cross-linking agent, whereby the chemically-protected cross-linking agent reacts with the high melting metal powder; and heating the patterned substrate to a temperature and for a period of time sufficient to cure the composition, wherein the high melting metal powder is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum and alloys thereof, the solder powder is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ca, In, Te, Hg, Ti, Sb, Se, Po, alloys thereof and other metals having a melting point lower than that of the high melting metal powder, and the composition comprises 6-29% by volume of the solder powder, 13-38% by volume of the high melting metal powder, 0-15% by volume of the resin, 30-52% by volume of the cross-linking agent mixture and 0-32%
by volume of the reactive monomer or polymer.
applying a conductive ink composition comprising a solder powder, a high melting metal powder, and a cross-linking agent mixture comprising a chemically protected cross-linking agent with fluxing properties onto a substrate in a desired pattern to provide a patterned substrate;
rapidly heating the patterned substrate to a temperature at or near a melting temperature of the solder powder for a period of time sufficient to activate the chemically protected cross-linking agent, whereby the chemically-protected cross-linking agent reacts with the high melting metal powder; and heating the patterned substrate to a temperature and for a period of time sufficient to cure the composition, wherein the high melting metal powder is selected from the group consisting of copper, silver, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum and alloys thereof, the solder powder is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ca, In, Te, Hg, Ti, Sb, Se, Po, alloys thereof and other metals having a melting point lower than that of the high melting metal powder, and the composition comprises 6-29% by volume of the solder powder, 13-38% by volume of the high melting metal powder, 0-15% by volume of the resin, 30-52% by volume of the cross-linking agent mixture and 0-32%
by volume of the reactive monomer or polymer.
27. A method according to any one of claims 25 or 26, wherein said acid or strong base is selected from the group consisting of anhydrides, carboxylic acids, amides, imides, amines, alcohols, phenols, aldehydes, ketones, nitro compounds, nitriles, carbamates, isocyanates, amino acids, peptides, thiols, sulfonamides, semicarbazones, oximes, hydrazones, cyanohydrins, ureas, phosphoric acids, phosphoric esters, thiophosphoric acids, thiophosphoric esters, phosphoric acids, phosphoric esters, phosphites, phosphonamides, sulfonic acids and sulfonic esters.
28. A method according to any one of claims 25 or 26, wherein said chemically protected cross-linking agent with fluxing properties is an acid or a strong base which is protected so as to become reactive only at or near a time at which the solder powder is melted.
29. A method according to any one of claims 25 to 28, wherein said acid or strong base is protected by a protecting group selected from the group consisting of carboxylic acids, amides, alcohols, alkyl halides, acid halides, thiols, ureas, alkyl silanes, diazoatkanes, azomethanes, acetals, ketals and transition metal complexes.
30. A method according to any one of claims 25 to 29, wherein said acid or strong base is protected by encapsulating the cross-linking agent in a shell of non-reactive material which releases the cross-linking agent only at or near the time the solder is melted.
31. A method according to any one of claims 24 to 30, wherein the pattern is screen-printed onto the substrate.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/769,892 US5376403A (en) | 1990-02-09 | 1991-10-01 | Electrically conductive compositions and methods for the preparation and use thereof |
US07/769,892 | 1991-10-01 | ||
PCT/US1992/008333 WO1993006943A1 (en) | 1991-10-01 | 1992-10-01 | Electrically conductive compositions and methods for the preparation and use thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2120523A1 CA2120523A1 (en) | 1993-04-15 |
CA2120523C true CA2120523C (en) | 2004-09-14 |
Family
ID=25086815
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002120523A Expired - Lifetime CA2120523C (en) | 1991-10-01 | 1992-10-01 | Electrically conductive compositions and methods for the preparation and use thereof |
Country Status (10)
Country | Link |
---|---|
US (2) | US5376403A (en) |
EP (1) | EP0646048B1 (en) |
JP (1) | JP2972338B2 (en) |
KR (1) | KR970010170B1 (en) |
AT (1) | ATE315963T1 (en) |
AU (1) | AU663342B2 (en) |
CA (1) | CA2120523C (en) |
DE (1) | DE69233595T2 (en) |
MX (1) | MX9205644A (en) |
WO (1) | WO1993006943A1 (en) |
Families Citing this family (178)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5502889A (en) * | 1988-06-10 | 1996-04-02 | Sheldahl, Inc. | Method for electrically and mechanically connecting at least two conductive layers |
US5948533A (en) * | 1990-02-09 | 1999-09-07 | Ormet Corporation | Vertically interconnected electronic assemblies and compositions useful therefor |
US5853622A (en) * | 1990-02-09 | 1998-12-29 | Ormet Corporation | Transient liquid phase sintering conductive adhesives |
US5716663A (en) * | 1990-02-09 | 1998-02-10 | Toranaga Technologies | Multilayer printed circuit |
US6476487B2 (en) * | 1992-10-30 | 2002-11-05 | Showa Denko K.K. | Solder circuit |
US5428190A (en) * | 1993-07-02 | 1995-06-27 | Sheldahl, Inc. | Rigid-flex board with anisotropic interconnect and method of manufacture |
JP2677161B2 (en) * | 1993-07-08 | 1997-11-17 | 双葉電子工業株式会社 | Fluorescent display tube |
EP0651602B1 (en) | 1993-10-29 | 1999-04-07 | Matsushita Electric Industrial Co., Ltd. | Conductive paste compound for via hole filling, printed circuit board which uses the conductive paste, and method of manufacturing the same |
KR100339767B1 (en) * | 1993-12-09 | 2002-11-30 | 메소드 일렉트로닉스 인코포레이티드 | Electrical connector for electric signal transmission and its manufacturing method |
DE4406418C1 (en) * | 1994-02-28 | 1995-07-13 | Bosch Gmbh Robert | Anisotropically conductive adhesive |
FR2726001B1 (en) * | 1994-10-19 | 1996-11-29 | Solaic Sa | CONDUCTIVE INK COMPRISING METALLIC GRAINS HAVING DIFFERENT MELTING POINTS |
TW340132B (en) * | 1994-10-20 | 1998-09-11 | Ibm | Structure for use as an electrical interconnection means and process for preparing the same |
TW301843B (en) * | 1994-11-15 | 1997-04-01 | Ibm | Electrically conductive paste and composite and their use as an electrically conductive connector |
US5736624A (en) * | 1994-12-02 | 1998-04-07 | Abbott Laboratories | Phosphatase activated crosslinking, conjugating and reducing agents; methods of using such agents; and reagents comprising phosphatase activated crosslinking and conjugating agents |
EP0804865A1 (en) * | 1995-01-18 | 1997-11-05 | Coates Brothers PLC | Production of electrical circuit boards |
DE19511553C2 (en) * | 1995-03-29 | 1997-02-20 | Litton Precision Prod Int | Method for producing electrically conductive structures, an electrically conductive structure obtained according to the method and combination for producing electrically conductive structures |
JP3498427B2 (en) * | 1995-06-19 | 2004-02-16 | ソニー株式会社 | Flux for molding solder |
JP2001517153A (en) * | 1995-08-11 | 2001-10-02 | カーストン・ケネス・ジェイ | Solder paste mainly composed of epoxy resin |
US7041771B1 (en) * | 1995-08-11 | 2006-05-09 | Kac Holdings, Inc. | Encapsulant with fluxing properties and method of use in flip-chip surface mount reflow soldering |
KR0155877B1 (en) * | 1995-09-12 | 1998-12-15 | 이대원 | Multi layer circuit board and manufacturing method of the same |
US5699613A (en) * | 1995-09-25 | 1997-12-23 | International Business Machines Corporation | Fine dimension stacked vias for a multiple layer circuit board structure |
JP3689159B2 (en) * | 1995-12-01 | 2005-08-31 | ナミックス株式会社 | Conductive adhesive and circuit using the same |
US5839188A (en) | 1996-01-05 | 1998-11-24 | Alliedsignal Inc. | Method of manufacturing a printed circuit assembly |
US6147870A (en) * | 1996-01-05 | 2000-11-14 | Honeywell International Inc. | Printed circuit assembly having locally enhanced wiring density |
CA2196024A1 (en) * | 1996-02-28 | 1997-08-28 | Craig N. Ernsberger | Multilayer electronic assembly utilizing a sinterable composition and related method of forming |
US5851311A (en) * | 1996-03-29 | 1998-12-22 | Sophia Systems Co., Ltd. | Polymerizable flux composition for encapsulating the solder in situ |
EP0933010B1 (en) * | 1996-08-16 | 2002-01-23 | Hugh P. Craig | Printable compositions, and their application to dielectric surfaces used in the manufacture of printed circuit boards |
US7022266B1 (en) | 1996-08-16 | 2006-04-04 | Dow Corning Corporation | Printable compositions, and their application to dielectric surfaces used in the manufacture of printed circuit boards |
US5759737A (en) * | 1996-09-06 | 1998-06-02 | International Business Machines Corporation | Method of making a component carrier |
US6074728A (en) * | 1996-09-11 | 2000-06-13 | Samsung Aerospace Industries, Ltd. | Multi-layered circuit substrate |
US5985043A (en) * | 1997-07-21 | 1999-11-16 | Miguel Albert Capote | Polymerizable fluxing agents and fluxing adhesive compositions therefrom |
DE19835613C2 (en) * | 1997-01-13 | 2002-12-12 | Aisin Seiki | Electrically conductive resin composition and its use for the production of molded resin parts |
US6180696B1 (en) | 1997-02-19 | 2001-01-30 | Georgia Tech Research Corporation | No-flow underfill of epoxy resin, anhydride, fluxing agent and surfactant |
JPH1145616A (en) * | 1997-05-28 | 1999-02-16 | Yazaki Corp | Forming method of conductive filler, conductive paste and circuit body |
US5846459A (en) * | 1997-06-26 | 1998-12-08 | Ucar Carbon Technology Corporation | Method of forming a flexible graphite sheet with decreased anisotropy |
US6734368B1 (en) | 1997-07-09 | 2004-05-11 | International Business Machines Corporation | Metal backed printed circuit board assemblies |
US5985456A (en) * | 1997-07-21 | 1999-11-16 | Miguel Albert Capote | Carboxyl-containing polyunsaturated fluxing adhesive for attaching integrated circuits |
US6335571B1 (en) | 1997-07-21 | 2002-01-01 | Miguel Albert Capote | Semiconductor flip-chip package and method for the fabrication thereof |
US6017634A (en) * | 1997-07-21 | 2000-01-25 | Miguel Albert Capote | Carboxyl-containing polyunsaturated fluxing agent and carboxyl-reactive neutralizing agent as adhesive |
US6367150B1 (en) | 1997-09-05 | 2002-04-09 | Northrop Grumman Corporation | Solder flux compatible with flip-chip underfill material |
US5980785A (en) * | 1997-10-02 | 1999-11-09 | Ormet Corporation | Metal-containing compositions and uses thereof, including preparation of resistor and thermistor elements |
US6160714A (en) | 1997-12-31 | 2000-12-12 | Elpac (Usa), Inc. | Molded electronic package and method of preparation |
JP2004506309A (en) | 1997-12-31 | 2004-02-26 | エルパック(ユーエスエー)、インコーポレイテッド | Molded electronic package, manufacturing method and shielding method |
US6165309A (en) * | 1998-02-04 | 2000-12-26 | General Electric Co. | Method for improving the adhesion of metal films to polyphenylene ether resins |
AU3617999A (en) * | 1998-04-22 | 1999-11-08 | Hugh Patrick Craig | Adhesive and encapsulating material with fluxing properties |
US6399426B1 (en) | 1998-07-21 | 2002-06-04 | Miguel Albert Capote | Semiconductor flip-chip package and method for the fabrication thereof |
US6274070B1 (en) | 1998-08-07 | 2001-08-14 | Aisin Seiki Kabushiki Kaisha | Methods of producing resin moldings |
US6116494A (en) * | 1998-09-01 | 2000-09-12 | Hewlett-Packard Company | Method for re-attachment of a SMT component using a heated air jet |
KR100629923B1 (en) * | 1998-09-30 | 2006-09-29 | 돗빤호무즈가부시기가이샤 | Conductive paste, curing method therof, method for fabricating antenna for contactless data transmitter-receiver, and contactless data transmitter-receiver |
US6054761A (en) * | 1998-12-01 | 2000-04-25 | Fujitsu Limited | Multi-layer circuit substrates and electrical assemblies having conductive composition connectors |
US6592943B2 (en) | 1998-12-01 | 2003-07-15 | Fujitsu Limited | Stencil and method for depositing solder |
US6344157B1 (en) | 1999-02-12 | 2002-02-05 | National Starch And Chemical Investment Holding Corporation | Conductive and resistive materials with electrical stability for use in electronics devices |
US6326555B1 (en) | 1999-02-26 | 2001-12-04 | Fujitsu Limited | Method and structure of z-connected laminated substrate for high density electronic packaging |
FR2793949B1 (en) * | 1999-05-21 | 2001-08-10 | Thomson Plasma | MIXTURE FOR PRODUCING ELECTRODES AND METHOD FOR FORMING ELECTRODES |
US6352881B1 (en) | 1999-07-22 | 2002-03-05 | National Semiconductor Corporation | Method and apparatus for forming an underfill adhesive layer |
US6475555B2 (en) | 1999-10-29 | 2002-11-05 | International Business Machines Corporation | Process for screening features on an electronic substrate with a low viscosity paste |
AU1467501A (en) | 1999-11-03 | 2001-05-14 | Nexicor Llc | Hand held induction tool |
US6402013B2 (en) * | 1999-12-03 | 2002-06-11 | Senju Metal Industry Co., Ltd | Thermosetting soldering flux and soldering process |
US6528169B2 (en) | 2000-07-06 | 2003-03-04 | 3M Innovative Properties Company | No-flow flux adhesive compositions |
GB2365816B (en) * | 2000-08-09 | 2002-11-13 | Murata Manufacturing Co | Method of bonding conductive adhesive and electrode,and bonded structure |
US6524721B2 (en) * | 2000-08-31 | 2003-02-25 | Matsushita Electric Industrial Co., Ltd. | Conductive adhesive and packaging structure using the same |
DE60142119D1 (en) * | 2000-10-02 | 2010-06-24 | Asahi Kasei Emd Corp | PARTICLES OF A FUNCTIONAL METAL ALLOY. |
US6800169B2 (en) * | 2001-01-08 | 2004-10-05 | Fujitsu Limited | Method for joining conductive structures and an electrical conductive article |
US6884313B2 (en) * | 2001-01-08 | 2005-04-26 | Fujitsu Limited | Method and system for joining and an ultra-high density interconnect |
US6866741B2 (en) * | 2001-01-08 | 2005-03-15 | Fujitsu Limited | Method for joining large substrates |
US6534179B2 (en) | 2001-03-27 | 2003-03-18 | International Business Machines Corporation | Halogen free triazines, bismaleimide/epoxy polymers, prepregs made therefrom for circuit boards and resin coated articles, and use |
US6583201B2 (en) | 2001-04-25 | 2003-06-24 | National Starch And Chemical Investment Holding Corporation | Conductive materials with electrical stability for use in electronics devices |
US20030111519A1 (en) * | 2001-09-04 | 2003-06-19 | 3M Innovative Properties Company | Fluxing compositions |
US6802446B2 (en) * | 2002-02-01 | 2004-10-12 | Delphi Technologies, Inc. | Conductive adhesive material with metallurgically-bonded conductive particles |
JP2003275895A (en) * | 2002-03-22 | 2003-09-30 | Toyo Aluminium Kk | Pasty composition for brazing and brazing method using the same |
US6791839B2 (en) * | 2002-06-25 | 2004-09-14 | Dow Corning Corporation | Thermal interface materials and methods for their preparation and use |
US7423337B1 (en) | 2002-08-19 | 2008-09-09 | National Semiconductor Corporation | Integrated circuit device package having a support coating for improved reliability during temperature cycling |
US7751174B2 (en) * | 2002-12-09 | 2010-07-06 | Matsushita Electric Industrial Co., Ltd. | Electronic part with external electrode |
US7211205B2 (en) * | 2003-01-29 | 2007-05-01 | Parelec, Inc. | High conductivity inks with improved adhesion |
US20040178391A1 (en) * | 2003-01-29 | 2004-09-16 | Conaghan Brian F. | High conductivity inks with low minimum curing temperatures |
US7141185B2 (en) * | 2003-01-29 | 2006-11-28 | Parelec, Inc. | High conductivity inks with low minimum curing temperatures |
US7301222B1 (en) | 2003-02-12 | 2007-11-27 | National Semiconductor Corporation | Apparatus for forming a pre-applied underfill adhesive layer for semiconductor wafer level chip-scale packages |
US6821878B2 (en) * | 2003-02-27 | 2004-11-23 | Freescale Semiconductor, Inc. | Area-array device assembly with pre-applied underfill layers on printed wiring board |
KR20050109977A (en) * | 2003-03-18 | 2005-11-22 | 다우 코닝 코포레이션 | A conductive adhesive composition |
US20060289842A1 (en) * | 2003-03-18 | 2006-12-28 | Craig Hugh P | Conductive composition and method of using the same |
CN100404597C (en) * | 2003-04-01 | 2008-07-23 | 天鹰技术公司 | Thermally conductive adhesive composition and process for device attachment |
DE10319888A1 (en) | 2003-04-25 | 2004-11-25 | Siemens Ag | Solder material based on SnAgCu |
US7166491B2 (en) * | 2003-06-11 | 2007-01-23 | Fry's Metals, Inc. | Thermoplastic fluxing underfill composition and method |
TWI329534B (en) * | 2003-07-09 | 2010-09-01 | Fry Metals Inc | Coating metal particles |
TWI395256B (en) * | 2003-07-09 | 2013-05-01 | Fry Metals Inc | Deposition and patterning process |
US20050056365A1 (en) * | 2003-09-15 | 2005-03-17 | Albert Chan | Thermal interface adhesive |
US7282375B1 (en) | 2004-04-14 | 2007-10-16 | National Semiconductor Corporation | Wafer level package design that facilitates trimming and testing |
US7247683B2 (en) * | 2004-08-05 | 2007-07-24 | Fry's Metals, Inc. | Low voiding no flow fluxing underfill for electronic devices |
TW200615074A (en) * | 2004-08-25 | 2006-05-16 | Matsushita Electric Ind Co Ltd | Solder composition, connecting process with soldering, and connection structure with soldering |
CN101005917A (en) * | 2004-08-25 | 2007-07-25 | 松下电器产业株式会社 | Solder composition, connection method and structure utilizing welding |
WO2006052616A1 (en) | 2004-11-03 | 2006-05-18 | Tessera, Inc. | Stacked packaging improvements |
WO2006064849A1 (en) * | 2004-12-15 | 2006-06-22 | Tamurakaken Corporation | Conductive adhesive, and utilizing the same, conductive section and electronic part module |
US7452568B2 (en) * | 2005-02-04 | 2008-11-18 | International Business Machines Corporation | Centrifugal method for filing high aspect ratio blind micro vias with powdered materials for circuit formation |
US7413805B2 (en) * | 2005-02-25 | 2008-08-19 | Fry's Metals, Inc. | Preparation of metallic particles for electrokinetic or electrostatic deposition |
US7446136B2 (en) * | 2005-04-05 | 2008-11-04 | Momentive Performance Materials Inc. | Method for producing cure system, adhesive system, and electronic device |
US7405246B2 (en) * | 2005-04-05 | 2008-07-29 | Momentive Performance Materials Inc. | Cure system, adhesive system, electronic device |
US8058101B2 (en) | 2005-12-23 | 2011-11-15 | Tessera, Inc. | Microelectronic packages and methods therefor |
DE102006048513A1 (en) * | 2006-04-29 | 2007-11-08 | Michael Metzke | Heat conducting layer and method for its production |
US20100044088A1 (en) * | 2006-07-05 | 2010-02-25 | Ablestik (Japan) Co. Ltd. | Conductive adhesive |
US7780801B2 (en) * | 2006-07-26 | 2010-08-24 | International Business Machines Corporation | Flux composition and process for use thereof |
WO2008026517A1 (en) | 2006-08-28 | 2008-03-06 | Murata Manufacturing Co., Ltd. | Conductive bonding material and electronic device |
JP4432949B2 (en) * | 2006-09-15 | 2010-03-17 | パナソニック株式会社 | Electrical component connection method |
US7758916B2 (en) * | 2006-11-13 | 2010-07-20 | Sulzer Metco (Us), Inc. | Material and method of manufacture of a solder joint with high thermal conductivity and high electrical conductivity |
US20080217589A1 (en) * | 2007-03-08 | 2008-09-11 | Tsung-Chih Tsai | Terminal composition for an electrical component |
EP2139629B1 (en) * | 2007-03-26 | 2018-09-05 | LORD Corporation | Method for producing heterogeneous composites |
JP5277564B2 (en) * | 2007-05-29 | 2013-08-28 | 住友ベークライト株式会社 | Semiconductor wafer bonding method and semiconductor device manufacturing method |
US20090226701A1 (en) * | 2007-08-24 | 2009-09-10 | Mark Charles Carbone | Boiling Enhancement Coating Produced Using Viscous Bulking Agent to Create Voids |
EP2188834A4 (en) * | 2007-09-11 | 2014-03-19 | Dow Corning | Composite, thermal interface material containing the composite, and methods for their preparation and use |
DE102008023882A1 (en) * | 2008-05-16 | 2009-11-19 | Bayer Materialscience Ag | Printable composition based on silver particles for the production of electrically conductive coatings |
EP2334728B1 (en) | 2008-09-26 | 2018-03-21 | Alpha Assembly Solutions Inc. | Lead-free conductive compositions and methods of using them |
KR100929136B1 (en) * | 2009-02-16 | 2009-12-01 | (주)덕산테코피아 | Conductive paste and the manufacturing method thereof and the electric device comprising thereof |
KR100977163B1 (en) * | 2009-03-23 | 2010-08-20 | 덕산하이메탈(주) | Solder adhesive and the manufacturing method thereof and the electric device comprising thereof |
US8221518B2 (en) * | 2009-04-02 | 2012-07-17 | Ormet Circuits, Inc. | Conductive compositions containing blended alloy fillers |
BR112012000203B1 (en) * | 2009-06-12 | 2020-01-28 | Lord Corp | method for protecting a substrate against lightning |
TWI481728B (en) * | 2009-11-05 | 2015-04-21 | Ormet Circuits Inc | Preparation of metallurgic network compositions and methods of use thereof |
KR101225497B1 (en) * | 2009-11-05 | 2013-01-23 | (주)덕산테코피아 | Conductive paste and the manufacturing method thereof and the electric device comprising thereof |
CN101781541B (en) * | 2010-02-02 | 2012-12-05 | 华南理工大学 | In situ preparation method of nano silver/epoxy conductive adhesive |
KR101061048B1 (en) * | 2010-02-17 | 2011-09-01 | (주)덕산테코피아 | Solder Ink and Electronic Device Package Using the Same |
US9748043B2 (en) | 2010-05-26 | 2017-08-29 | Kemet Electronics Corporation | Method of improving electromechanical integrity of cathode coating to cathode termination interfaces in solid electrolytic capacitors |
US8896986B2 (en) * | 2010-05-26 | 2014-11-25 | Kemet Electronics Corporation | Method of improving electromechanical integrity of cathode coating to cathode termination interfaces in solid electrolytic capacitors |
US8482111B2 (en) | 2010-07-19 | 2013-07-09 | Tessera, Inc. | Stackable molded microelectronic packages |
US9682447B2 (en) | 2010-08-20 | 2017-06-20 | Henkel IP & Holding GmbH | Organic acid- or latent organic acid-functionalized polymer-coated metal powders for solder pastes |
TW201210733A (en) | 2010-08-26 | 2012-03-16 | Dynajoin Corp | Variable melting point solders |
JP5886300B2 (en) * | 2010-10-05 | 2016-03-16 | ヘレウス プレシャス メタルズ ノース アメリカ コンショホーケン エルエルシー | One-part low temperature curable polymer composition and related methods |
JP4795488B1 (en) * | 2011-01-18 | 2011-10-19 | パナソニック株式会社 | WIRING BOARD, WIRING BOARD MANUFACTURING METHOD, AND VIA PASTE |
US9579738B2 (en) | 2011-02-25 | 2017-02-28 | International Business Machines Corporation | Flux composition and techniques for use thereof |
US9815149B2 (en) | 2011-02-25 | 2017-11-14 | International Business Machines Corporation | Flux composition and techniques for use thereof |
KR101128063B1 (en) | 2011-05-03 | 2012-04-23 | 테세라, 인코포레이티드 | Package-on-package assembly with wire bonds to encapsulation surface |
US20120286218A1 (en) * | 2011-05-11 | 2012-11-15 | Nanosolar, Inc. | Low cost alternatives to conductive silver-based inks |
US9117811B2 (en) | 2011-06-13 | 2015-08-25 | Tessera, Inc. | Flip chip assembly and process with sintering material on metal bumps |
US8404520B1 (en) | 2011-10-17 | 2013-03-26 | Invensas Corporation | Package-on-package assembly with wire bond vias |
US20140332072A1 (en) * | 2011-12-13 | 2014-11-13 | Dow Corning Corporation | Photovoltaic Cell And Method Of Forming The Same |
KR20130066929A (en) * | 2011-12-13 | 2013-06-21 | 한국전자통신연구원 | Pattern forming composition and pattern forming method using the same |
CN103170757A (en) * | 2011-12-23 | 2013-06-26 | 富泰华工业(深圳)有限公司 | Solder paste and preparation method thereof |
US8946757B2 (en) | 2012-02-17 | 2015-02-03 | Invensas Corporation | Heat spreading substrate with embedded interconnects |
US8372741B1 (en) | 2012-02-24 | 2013-02-12 | Invensas Corporation | Method for package-on-package assembly with wire bonds to encapsulation surface |
US9056438B2 (en) | 2012-05-02 | 2015-06-16 | 3M Innovative Properties Company | Curable composition, articles comprising the curable composition, and method of making the same |
US8835228B2 (en) | 2012-05-22 | 2014-09-16 | Invensas Corporation | Substrate-less stackable package with wire-bond interconnect |
US9583453B2 (en) | 2012-05-30 | 2017-02-28 | Ormet Circuits, Inc. | Semiconductor packaging containing sintering die-attach material |
US9391008B2 (en) | 2012-07-31 | 2016-07-12 | Invensas Corporation | Reconstituted wafer-level package DRAM |
US9502390B2 (en) | 2012-08-03 | 2016-11-22 | Invensas Corporation | BVA interposer |
US9005330B2 (en) | 2012-08-09 | 2015-04-14 | Ormet Circuits, Inc. | Electrically conductive compositions comprising non-eutectic solder alloys |
US11440142B2 (en) | 2012-11-16 | 2022-09-13 | Ormet Circuits, Inc. | Alternative compositions for high temperature soldering applications |
US8878353B2 (en) | 2012-12-20 | 2014-11-04 | Invensas Corporation | Structure for microelectronic packaging with bond elements to encapsulation surface |
US9136254B2 (en) | 2013-02-01 | 2015-09-15 | Invensas Corporation | Microelectronic package having wire bond vias and stiffening layer |
DE102013102725A1 (en) * | 2013-03-18 | 2014-09-18 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Reactive resin system |
US9167710B2 (en) | 2013-08-07 | 2015-10-20 | Invensas Corporation | Embedded packaging with preformed vias |
US9685365B2 (en) | 2013-08-08 | 2017-06-20 | Invensas Corporation | Method of forming a wire bond having a free end |
US20150076714A1 (en) | 2013-09-16 | 2015-03-19 | Invensas Corporation | Microelectronic element with bond elements to encapsulation surface |
US9583456B2 (en) | 2013-11-22 | 2017-02-28 | Invensas Corporation | Multiple bond via arrays of different wire heights on a same substrate |
US9263394B2 (en) | 2013-11-22 | 2016-02-16 | Invensas Corporation | Multiple bond via arrays of different wire heights on a same substrate |
US9379074B2 (en) | 2013-11-22 | 2016-06-28 | Invensas Corporation | Die stacks with one or more bond via arrays of wire bond wires and with one or more arrays of bump interconnects |
US9583411B2 (en) | 2014-01-17 | 2017-02-28 | Invensas Corporation | Fine pitch BVA using reconstituted wafer with area array accessible for testing |
US10381326B2 (en) | 2014-05-28 | 2019-08-13 | Invensas Corporation | Structure and method for integrated circuits packaging with increased density |
US10161835B1 (en) | 2014-11-20 | 2018-12-25 | National Technology & Engineering Solutions Of Sandia, Llc | Microsampler and method of making the same |
US9735084B2 (en) | 2014-12-11 | 2017-08-15 | Invensas Corporation | Bond via array for thermal conductivity |
JP5944979B1 (en) * | 2014-12-26 | 2016-07-05 | 千住金属工業株式会社 | Solder transfer sheet, solder bump, and solder pre-coating method using solder transfer sheet |
US9888579B2 (en) | 2015-03-05 | 2018-02-06 | Invensas Corporation | Pressing of wire bond wire tips to provide bent-over tips |
US9502372B1 (en) | 2015-04-30 | 2016-11-22 | Invensas Corporation | Wafer-level packaging using wire bond wires in place of a redistribution layer |
US9761554B2 (en) | 2015-05-07 | 2017-09-12 | Invensas Corporation | Ball bonding metal wire bond wires to metal pads |
US9490222B1 (en) | 2015-10-12 | 2016-11-08 | Invensas Corporation | Wire bond wires for interference shielding |
US10490528B2 (en) | 2015-10-12 | 2019-11-26 | Invensas Corporation | Embedded wire bond wires |
US9515044B1 (en) * | 2015-10-14 | 2016-12-06 | Napra Co., Ltd. | Electronic device, method of manufacturing the same, metal particle, and electroconductive paste |
US10332854B2 (en) | 2015-10-23 | 2019-06-25 | Invensas Corporation | Anchoring structure of fine pitch bva |
US10181457B2 (en) | 2015-10-26 | 2019-01-15 | Invensas Corporation | Microelectronic package for wafer-level chip scale packaging with fan-out |
US10043779B2 (en) | 2015-11-17 | 2018-08-07 | Invensas Corporation | Packaged microelectronic device for a package-on-package device |
US9659848B1 (en) | 2015-11-18 | 2017-05-23 | Invensas Corporation | Stiffened wires for offset BVA |
US9984992B2 (en) | 2015-12-30 | 2018-05-29 | Invensas Corporation | Embedded wire bond wires for vertical integration with separate surface mount and wire bond mounting surfaces |
US9935075B2 (en) | 2016-07-29 | 2018-04-03 | Invensas Corporation | Wire bonding method and apparatus for electromagnetic interference shielding |
JP6346389B1 (en) * | 2016-08-03 | 2018-06-20 | 古河電気工業株式会社 | Metal particle-containing composition |
US10299368B2 (en) | 2016-12-21 | 2019-05-21 | Invensas Corporation | Surface integrated waveguides and circuit structures therefor |
JP7189209B2 (en) | 2017-06-12 | 2022-12-13 | オルメット・サーキッツ・インコーポレイテッド | Metallic adhesive composition with good pot life and thermal conductivity, its production method and use |
KR20200131264A (en) | 2018-03-15 | 2020-11-23 | 프린트씨비 리미티드 | 2-component printable conductive composition |
WO2020240894A1 (en) * | 2019-05-27 | 2020-12-03 | 千住金属工業株式会社 | Flux |
JP6617847B1 (en) * | 2019-05-27 | 2019-12-11 | 千住金属工業株式会社 | flux |
JP6617848B1 (en) * | 2019-05-27 | 2019-12-11 | 千住金属工業株式会社 | flux |
CN115151414A (en) * | 2020-02-26 | 2022-10-04 | 提克纳有限责任公司 | Polymer composition for electronic devices |
CN111548194A (en) * | 2020-05-29 | 2020-08-18 | 南京凯泰化学科技有限公司 | Preparation method of printed circuit board |
Family Cites Families (104)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE237840C (en) * | ||||
US2993815A (en) * | 1959-05-25 | 1961-07-25 | Bell Telephone Labor Inc | Metallizing refractory substrates |
SU134737A1 (en) | 1960-03-24 | 1960-11-30 | Л.И. Бродолин | Conductor conductive paste |
US3256109A (en) * | 1962-12-20 | 1966-06-14 | Berger Carl | Metal formation within a substrate |
US3324081A (en) * | 1963-12-31 | 1967-06-06 | Gulf Research Development Co | Polyepoxy resin-biaryl anhydride composition |
US3410714A (en) * | 1965-10-18 | 1968-11-12 | Gen Electric | Metallizing and bonding non-metallic bodies |
US3681135A (en) * | 1970-06-24 | 1972-08-01 | Lucas Industries Ltd | Printed circuits and method of making same |
US3714709A (en) * | 1970-07-06 | 1973-02-06 | Rca Corp | Method of manufacturing thick-film hybrid integrated circuits |
US3801364A (en) * | 1971-02-03 | 1974-04-02 | Matsushita Electric Ind Co Ltd | Method for making printed circuits which include printed resistors |
US3679439A (en) * | 1971-03-23 | 1972-07-25 | Du Pont | Lead-containing metallizations |
GB1378520A (en) * | 1971-05-10 | 1974-12-27 | Atomic Energy Authority Uk | Metallising pastes |
US3791027A (en) * | 1971-06-30 | 1974-02-12 | Ibm | Soldering method |
GB1387267A (en) * | 1971-07-27 | 1975-03-12 | Lucas Industries Ltd | Thick film circuits |
US3800020A (en) * | 1972-03-23 | 1974-03-26 | Cramer P Co | Method of making a circuit board |
US3904555A (en) * | 1972-10-05 | 1975-09-09 | Nippon Steel Corp | Weldable paint composition |
JPS4997846A (en) * | 1972-12-29 | 1974-09-17 | ||
JPS49112196A (en) | 1973-02-12 | 1974-10-25 | ||
JPS50100596A (en) * | 1974-01-09 | 1975-08-09 | ||
US3983075A (en) * | 1974-06-21 | 1976-09-28 | Kennecott Copper Corporation | Copper filled conductive epoxy |
US4000016A (en) * | 1974-11-29 | 1976-12-28 | International Business Machines Corporation | Water soluble fluxes |
US4001146A (en) * | 1975-02-26 | 1977-01-04 | E. I. Du Pont De Nemours And Company | Novel silver compositions |
US3960777A (en) * | 1975-06-23 | 1976-06-01 | E. I. Du Pont De Nemours And Company | Gold compositions |
CA1097495A (en) * | 1976-05-24 | 1981-03-17 | James H. Aumiller | Electrically conductive adhesive |
JPS5933924B2 (en) * | 1976-09-09 | 1984-08-18 | ジェイエスアール株式会社 | pressure sensitive resistor |
US4147669A (en) * | 1977-03-28 | 1979-04-03 | Rockwell International Corporation | Conductive adhesive for providing electrical and thermal conductivity |
JPS53133799A (en) * | 1977-04-27 | 1978-11-21 | Idearisaachi Yuugen | Electroconductive paint |
JPS6034615B2 (en) * | 1977-07-27 | 1985-08-09 | 日立電線株式会社 | Copper alloy for leads of semiconductor equipment |
US4293451A (en) * | 1978-06-08 | 1981-10-06 | Bernd Ross | Screenable contact structure and method for semiconductor devices |
US4327124A (en) * | 1978-07-28 | 1982-04-27 | Desmarais Jr Raymond C | Method for manufacturing printed circuits comprising printing conductive ink on dielectric surface |
US4186036A (en) * | 1978-08-25 | 1980-01-29 | The Dow Chemical Company | Weldable coating compositions |
US4233103A (en) * | 1978-12-20 | 1980-11-11 | The United States Of America As Represented By The Secretary Of The Air Force | High temperature-resistant conductive adhesive and method employing same |
JPS55160072A (en) * | 1979-05-31 | 1980-12-12 | Matsushita Electric Ind Co Ltd | Electrically conductive adhesive |
US4273593A (en) * | 1979-06-25 | 1981-06-16 | Scm Corporation | Metal-joining paste and vehicle therefor |
JPS565840A (en) | 1979-06-28 | 1981-01-21 | Shin Etsu Polymer Co Ltd | Anisotropic pressure electrically-conductive elastomer molded article |
JPS5632605A (en) * | 1979-08-28 | 1981-04-02 | Kogyo Gijutsuin | Group iiivi metal compound semiconductor electrode material in periodic table |
US4278702A (en) * | 1979-09-25 | 1981-07-14 | Anthony J. Casella | Method of making printed circuit board by induction heating of the conductive metal particles on a plastic substrate |
US4457861A (en) * | 1979-12-13 | 1984-07-03 | Additive Technology Corporation | Method, materials and apparatus for manufacturing printed circuits |
US4429657A (en) * | 1979-12-13 | 1984-02-07 | Additive Technology Corporation | Method, materials and apparatus for manufacturing printed circuits |
JPS56103260A (en) * | 1980-01-22 | 1981-08-18 | Asahi Kagaku Kenkyusho:Kk | Conductive paint containing copper powder |
US4352899A (en) * | 1980-04-05 | 1982-10-05 | Sakai Chemical Industry Co., Ltd. | Coating composition for metal-substrate |
US4368281A (en) * | 1980-09-15 | 1983-01-11 | Amp Incorporated | Printed circuits |
US4496475A (en) * | 1980-09-15 | 1985-01-29 | Potters Industries, Inc. | Conductive paste, electroconductive body and fabrication of same |
JPS57111034A (en) * | 1980-12-10 | 1982-07-10 | Hitachi Ltd | Semiconductor device and its manufacture |
JPS57113505A (en) * | 1981-01-07 | 1982-07-15 | Matsushita Electric Ind Co Ltd | Conductive composition |
JPS57185316A (en) * | 1981-05-11 | 1982-11-15 | Sumitomo Metal Mining Co Ltd | Electrically conductive resin paste |
CA1190736A (en) * | 1981-06-03 | 1985-07-23 | Robert J. Moneta | Copper conductor composition for porcelain enamel steel substrates |
GB2102026B (en) * | 1981-06-05 | 1985-07-10 | Matsushita Electric Ind Co Ltd | Conductive pastes |
NL8102809A (en) * | 1981-06-11 | 1983-01-03 | Philips Nv | RESISTANCE PASTE FOR A RESISTANCE BODY. |
JPS57208002A (en) * | 1981-06-18 | 1982-12-21 | Shinetsu Polymer Co | Thermal pressure conductive composition |
JPS5842651A (en) * | 1981-09-07 | 1983-03-12 | Toshiba Corp | Electrically conductive paste |
JPS5861144A (en) * | 1981-10-06 | 1983-04-12 | Matsushita Electric Ind Co Ltd | Electrical conductive composition |
US4396666A (en) * | 1981-11-02 | 1983-08-02 | Cts Corporation | Solderable conductive employing an organic binder |
FR2516739A1 (en) * | 1981-11-17 | 1983-05-20 | Rhone Poulenc Spec Chim | METHOD FOR MANUFACTURING HYBRID-LIKE ELECTRONIC CIRCUITS WITH THICK-COATED LAYERS, MEANS FOR CARRYING OUT SAID METHOD AND CIRCUITS OBTAINED BY SAID METHOD |
JPS58104969A (en) * | 1981-12-17 | 1983-06-22 | Matsushita Electric Ind Co Ltd | Electrically conductive paint |
JPS58127742A (en) * | 1982-01-26 | 1983-07-29 | Sanko Kagaku Kk | Electrically conductive resin blend composition |
US4459166A (en) * | 1982-03-08 | 1984-07-10 | Johnson Matthey Inc. | Method of bonding an electronic device to a ceramic substrate |
JPS5949272A (en) * | 1982-09-14 | 1984-03-21 | Toshiba Corp | Electrically-conductive coating compound |
JPS59100176A (en) * | 1982-11-30 | 1984-06-09 | Nec Corp | Adhesive |
US4503090A (en) * | 1983-02-23 | 1985-03-05 | At&T Bell Laboratories | Thick film resistor circuits |
JPS59210966A (en) * | 1983-05-16 | 1984-11-29 | Daicel Chem Ind Ltd | Highly conductive styrene resin composition |
US4533685A (en) * | 1983-07-26 | 1985-08-06 | Hudgin Donald E | Polymer-metal blend |
US4564563A (en) * | 1983-09-30 | 1986-01-14 | Electro Materials Corp. Of America | Solderable conductor |
US4535012A (en) * | 1983-09-30 | 1985-08-13 | Electro Materials Corp. Of America | Fast curing solderable conductor |
DE3443789A1 (en) * | 1983-12-02 | 1985-06-27 | Osaka Soda Co. Ltd., Osaka | ELECTRICAL CONDUCTIVE ADHESIVE |
US4557857A (en) * | 1984-05-30 | 1985-12-10 | Allied Corporation | High conducting polymer-metal alloy blends |
US4592861A (en) * | 1984-06-08 | 1986-06-03 | Uniroyal Chemical Company, Inc. | Antistatic thermoplastic composition comprising a graft polymer, halogenated thermoplastic polymer and conductive carbon black |
US4575432A (en) * | 1984-07-09 | 1986-03-11 | W. R. Grace & Co. | Conductive thermosetting compositions and process for using same |
US4639396A (en) * | 1984-07-19 | 1987-01-27 | Princeton Polymer Laboratories | Thermoplastics-metal fiber threads |
EP0170063B1 (en) * | 1984-07-31 | 1988-08-24 | Mitsubishi Petrochemical Co., Ltd. | Copper-type conductive coating composition |
JPS6167702A (en) * | 1984-09-07 | 1986-04-07 | Mitsui Mining & Smelting Co Ltd | Electrically conductive powder and electrically conductive composition using said powder |
US4581158A (en) * | 1984-09-26 | 1986-04-08 | W. R. Grace & Co. | Conductive thermosetting compositions and process for using same |
JPS61123665A (en) * | 1984-11-19 | 1986-06-11 | Matsushita Electric Ind Co Ltd | Production of electrically conductive resin composition |
US4680141A (en) * | 1984-11-29 | 1987-07-14 | Mcdonnell Douglas Corporation | Solder composition |
JPS61159793A (en) * | 1984-12-31 | 1986-07-19 | 株式会社 アサヒ化学研究所 | Formation of conductive circuit on substrate |
US4578425A (en) * | 1985-02-13 | 1986-03-25 | Schenectady Chemicals, Inc. | Phenolic resins, carboxylic resins and the elastomers containing adhesive |
US4786437A (en) * | 1985-03-27 | 1988-11-22 | Ercon, Inc. | One-component, particle-filled compositions |
US4716081A (en) * | 1985-07-19 | 1987-12-29 | Ercon, Inc. | Conductive compositions and conductive powders for use therein |
US4652398A (en) * | 1985-09-12 | 1987-03-24 | Stauffer Chemical Company | Rapid curing, thermally stable adhesive composition comprising epoxy resin, polyimide, reactive solvent, and crosslinker |
US4673532A (en) * | 1986-01-22 | 1987-06-16 | Mcdonnell Douglas Corporation | Rosin-free solder composition |
JPS62179889A (en) * | 1986-01-31 | 1987-08-07 | Senjiyu Kinzoku Kogyo Kk | Creamy solder |
US4732702A (en) * | 1986-02-13 | 1988-03-22 | Hitachi Chemical Company, Ltd. | Electroconductive resin paste |
US4859268A (en) * | 1986-02-24 | 1989-08-22 | International Business Machines Corporation | Method of using electrically conductive composition |
US4780371A (en) * | 1986-02-24 | 1988-10-25 | International Business Machines Corporation | Electrically conductive composition and use thereof |
US4880570A (en) * | 1986-03-31 | 1989-11-14 | Harris Corporation | Electroconductive adhesive |
EP0239901B1 (en) * | 1986-03-31 | 1992-11-11 | Tatsuta Electric Wire & Cable Co., Ltd | Conductive copper paste composition |
JPS6355807A (en) * | 1986-08-27 | 1988-03-10 | 古河電気工業株式会社 | Conducting paste |
US4765929A (en) * | 1986-08-29 | 1988-08-23 | Gte Products Corporation | Silk-screenable circuit paste |
US4733018A (en) * | 1986-10-02 | 1988-03-22 | Rca Corporation | Thick film copper conductor inks |
FR2606784B1 (en) * | 1986-11-14 | 1989-03-03 | Rhone Poulenc Multi Tech | ELECTRICALLY CONDUCTIVE POTENTIALLY ADHESIVE COMPOSITION |
JPS63165457A (en) * | 1986-12-27 | 1988-07-08 | Lion Corp | Electrically conductive resin composition |
US4816184A (en) * | 1987-02-20 | 1989-03-28 | General Electric Company | Electrically conductive material for molding |
KR880011821A (en) * | 1987-03-09 | 1988-10-31 | 오오자와 히데오 | Conductive resin composition and molded article thereof |
US4731130A (en) * | 1987-05-27 | 1988-03-15 | Gte Government Systems Corporation | Soldering composition |
CA1249064A (en) * | 1987-07-06 | 1989-01-17 | Reginald B.P. Bennett | Process for application of overlay conductors to surface of printed circuit board assemblies |
JPH0749560B2 (en) * | 1987-08-07 | 1995-05-31 | ポリプラスチックス株式会社 | Conductive primer or conductive paint for painting plastics |
JPS6481866A (en) * | 1987-09-22 | 1989-03-28 | Sumitomo Metal Mining Co | Composition for forming electrically conductive coating film |
JPH0759660B2 (en) * | 1987-09-25 | 1995-06-28 | アルプス電気株式会社 | Conductive composition |
US4874548A (en) * | 1988-03-14 | 1989-10-17 | Ameron, Inc. | Conductive adhesive |
US4872928A (en) * | 1988-06-07 | 1989-10-10 | Johnson Matthey Inc. | Solder paste |
US5045141A (en) * | 1988-07-01 | 1991-09-03 | Amoco Corporation | Method of making solderable printed circuits formed without plating |
US4940498A (en) * | 1989-08-14 | 1990-07-10 | Multicore Solders Limited | Flux composition |
US5064481A (en) * | 1990-05-17 | 1991-11-12 | Motorola, Inc. | Use or organic acids in low residue solder pastes |
US5128746A (en) * | 1990-09-27 | 1992-07-07 | Motorola, Inc. | Adhesive and encapsulant material with fluxing properties |
US5116433A (en) * | 1990-10-31 | 1992-05-26 | Motorola, Inc. | Solder paste having solder alloy/formate complexes as oxide scavengers, and method for preparing same |
-
1991
- 1991-10-01 US US07/769,892 patent/US5376403A/en not_active Expired - Lifetime
-
1992
- 1992-10-01 AU AU27678/92A patent/AU663342B2/en not_active Expired
- 1992-10-01 CA CA002120523A patent/CA2120523C/en not_active Expired - Lifetime
- 1992-10-01 JP JP5507034A patent/JP2972338B2/en not_active Expired - Lifetime
- 1992-10-01 AT AT92921540T patent/ATE315963T1/en not_active IP Right Cessation
- 1992-10-01 DE DE69233595T patent/DE69233595T2/en not_active Expired - Lifetime
- 1992-10-01 MX MX9205644A patent/MX9205644A/en active IP Right Grant
- 1992-10-01 EP EP92921540A patent/EP0646048B1/en not_active Expired - Lifetime
- 1992-10-01 WO PCT/US1992/008333 patent/WO1993006943A1/en active IP Right Grant
-
1994
- 1994-03-29 KR KR94701007A patent/KR970010170B1/en active
- 1994-10-17 US US08/324,060 patent/US5830389A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
WO1993006943A1 (en) | 1993-04-15 |
KR970010170B1 (en) | 1997-06-21 |
ATE315963T1 (en) | 2006-02-15 |
JPH07502369A (en) | 1995-03-09 |
EP0646048A1 (en) | 1995-04-05 |
AU663342B2 (en) | 1995-10-05 |
DE69233595D1 (en) | 2006-04-06 |
MX9205644A (en) | 1994-08-31 |
EP0646048B1 (en) | 2006-01-18 |
AU2767892A (en) | 1993-05-03 |
EP0646048A4 (en) | 1994-08-10 |
US5376403A (en) | 1994-12-27 |
US5830389A (en) | 1998-11-03 |
CA2120523A1 (en) | 1993-04-15 |
DE69233595T2 (en) | 2006-09-14 |
JP2972338B2 (en) | 1999-11-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2120523C (en) | Electrically conductive compositions and methods for the preparation and use thereof | |
US5538789A (en) | Composite substrates for preparation of printed circuits | |
US5853622A (en) | Transient liquid phase sintering conductive adhesives | |
US5716663A (en) | Multilayer printed circuit | |
US7022266B1 (en) | Printable compositions, and their application to dielectric surfaces used in the manufacture of printed circuit boards | |
JP4368946B2 (en) | Printable composition and its application to dielectric surfaces used in the manufacture of printed circuit boards | |
US4595606A (en) | Solderable conductive compositions having high adhesive strength | |
KR930000776B1 (en) | Conductive compositions and preparation thereof | |
EP0239901B1 (en) | Conductive copper paste composition | |
US5922397A (en) | Metal-plating of cured and sintered transient liquid phase sintering pastes | |
KR970001560B1 (en) | Tacking agents | |
US4548879A (en) | Solderable polymer thick films | |
KR101293914B1 (en) | Conductive ink and device using the same | |
JPH05506876A (en) | Highly conductive polymeric thick film composition | |
WO1995011129A1 (en) | Composite substrates for preparation of printed circuits | |
JP2006035259A (en) | Solder paste | |
JP6737873B2 (en) | Photo-sintering of polymer thick film copper conductor composition | |
JPH0248184B2 (en) | ||
JPH07252460A (en) | Adhesive | |
JP2018529001A (en) | Photosintering of solderable polymer thick film copper conductor composition | |
JPS5933923B2 (en) | Conductor composition for resistance wiring board | |
JPH06100804A (en) | Conductive paste composition | |
JPH0248187B2 (en) | ||
JPH0248186B2 (en) | ||
JPH0248183B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKEX | Expiry |