CN1788323A - A conductive composition and method of using the same - Google Patents

A conductive composition and method of using the same Download PDF

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Publication number
CN1788323A
CN1788323A CN 03826164 CN03826164A CN1788323A CN 1788323 A CN1788323 A CN 1788323A CN 03826164 CN03826164 CN 03826164 CN 03826164 A CN03826164 A CN 03826164A CN 1788323 A CN1788323 A CN 1788323A
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CN
China
Prior art keywords
electrically conductive
conductive composition
composition
blocking
lubricant
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CN 03826164
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Chinese (zh)
Inventor
H·P·克雷格
D·L·斯蒂尔
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Dow Silicones Corp
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Dow Corning Corp
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Priority to US39242603A priority Critical
Priority to US10/392,425 priority
Priority to US10/392,426 priority
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Publication of CN1788323A publication Critical patent/CN1788323A/en
Pending legal-status Critical Current

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Abstract

A conductive composition includes a conductive metal, a first resin component, and a second resin component, which is an isocyanate component, that is reactive with the first resin component. A metal oxide and a lubricant are present as impurities on a surface of the metal. The second resin component is blocked at a first temperature and unblocked at a second temperature greater than the first temperature to produce fist and second fluxing agents. The first fluxing agent reacts with the lubricant to partially remove the oxide and the lubricant from the surface of the metal. The removal, or cleansing, of the oxide and the lubricant from the metal increases a conductivity of the composition. A method deposits a trace of the composition on a substrate and heats the composition to the second temperature to cause the second resin component to unblock.

Description

The method of electrically conductive composition and use said composition
Technical field
The method of relate generally to electrically conductive composition of the present invention and this electrically conductive composition of use.More particularly, the present invention relates to go up the employed electrically conductive composition of conductive metal deposition trace (trace) at printed circuit board (PCB) (PCB), so that electronics and electric component is connected into circuit and in the preparation of electronics and electric component, matrix is connected on the lead frame.
Background technology
Electrically conductive composition (being also referred to as electrically conductive ink in the art) is known in the art.It also is known in the art using the method for electrically conductive composition.For example, use electrically conductive composition on substrate such as PCB, to form conductive metal trace.In order to conduct electricity, electrically conductive composition comprises the metallic particles of conduction.Typically, these particles are powder or sheet form.An example as conducting metal particles, silver strip is good conductor, for the use in electrically conductive composition, it is preferred, this is because the silver strip per unit weight has bigger surface area, this helps to guarantee that silver strip contacts with each other in specific conductive metal trace, forms continuous conductive silver metal " path ".
Silver strip is to the various factors sensitivity of negative its conductance of infringement.Such factor relates to the production of silver strip.In the presence of lubricant such as stearic acid,, thereby produce silver strip by grinding silver powder.In the production process of silver strip, remove the stearic acid lubricant that silver powder is worn into silver strip within it with solvent.Yet before may removing stearic acid, it and silver strip surface reaction form the salt of lubricant, and specifically silver stearate and solvent can not be removed silver stearate.Silver stearate is to remain in the impurity on the silver strip and the conductance of negative effect silver strip, although this is because the silver stearate conduction, its conductance is well below fine silver, i.e. not oxidation and unlubricated silver.
Another factor of negative effect silver strip conductance is silver strip oxidation in air easily, thereby forms silver oxide on the silver strip surface.Silver oxide is the another kind of impurity that remains on the silver strip.Silver strip in case ground and even after being incorporated into them in the electrically conductive composition, easily oxidation.As silver stearate, although silver oxide conduction, conductance well below fine silver.The conductance of the electrically conductive composition of prior art (it has silver oxide and silver stearate impurity still the is present in lip-deep silver strip) order of magnitude of the resistivity by understanding this electrically conductive composition usually is that 20-50m Ω/sq. understands.
At last, it is also understood that the electrically conductive composition of heating prior art, in heating process or after advantageously do not influence the conductance of electrically conductive composition.In brief, heating does not have influence to the electrically conductive composition of prior art.In addition, the electrically conductive composition of the prior art of requirement curing depends on by conventional smelting furnace or baking oven and heats under very high temperature.These high temperature often damage, i.e. substrate such as PCB that fusing is made by cheap and non-resilient plastic material such as polystyrene usually.
Because the defective of the electrically conductive composition of prior art, comprising above-described those of silver stearate and silver oxide impurity of relating to, be desirable to provide a kind of electrically conductive composition, described electrically conductive composition causes having improved conductance because of the free from admixture state of conducting metal particles.It would also be desirable to provide the method for using this electrically conductive composition.
Summary of the invention
Electrically conductive composition comprises conducting metal, isocyanate component and can with the resin Composition of isocyanate component reaction.In one embodiment, conducting metal exists with the consumption of 40-95 weight portion, isocyanate component exists with the consumption of 2-20 weight portion and resin Composition exists with the consumption of 1-20 weight portion, and wherein all wt part is based on 100 weight portion electrically conductive compositions.
In another embodiment, conducting metal have surface and metal oxide and lubricant be present on this surface and electrically conductive composition comprise first resin Composition and can with second resin Composition of first resin Composition reaction.Second resin Composition is being separated end-blocking by end-blocking with under second temperature higher than first temperature under first temperature.In case separate end-blocking, second resin Composition produces first flux and second flux.First flux and the reactive metal oxide and second flux and lubricant reaction at least at least.Metal oxide and lubricant are removed in these surfaces of reacting to small part from conducting metal, thereby increase the conductance of electrically conductive composition.
Use the method for this electrically conductive composition to comprise the steps: trace deposition with electrically conductive composition on substrate, and heat this electrically conductive composition under at least the second temperature, cause that second resin separates end-blocking.In case separate end-blocking, the reaction of first and second resin Compositions is solidified, and produces first and second flux.First and second fluxs are removed metal oxide and lubricant from the surface of conducting metal, thereby increase the conductance of the trace of electrically conductive composition.Heat not damaged substrate of electrically conductive composition of the present invention.
Removing metal oxide and lubricant from the surface of conducting metal with first and second fluxs also can be called as by cleaning or the cleaning conducting metal of fluxing.Clean conducting metal and while conductive composition by fluxing under at least the second temperature, make conducting metal so clean, so that: the supposition conducting metal is the silver of sheet form, silver strip tighter thickly near with contact, by the method that is called as " cold welding of noble metal " that silver strip wherein can weld and link together, silver strip even may combine.Form the trace of conducting metal, with compare (wherein electrically conductive composition comprises that silver oxide and/or lubricant still are present in the silver strip on the silver strip in a large number) with the conductive metal trace that forms by following electrically conductive composition, this conductive metal trace has significantly improved conductance.For example, electrically conductive composition of the present invention has improved conductance, and its conductance is than still having the good 2-10 of the electrically conductive composition that is present in lip-deep silver oxide of silver strip and/or the lubricant in a large number order of magnitude doubly.As the instantiation of this improved conductance, the resistivity of electrically conductive composition of the present invention is generally the order of magnitude of 3-10m Ω/sq..
Heating electrically conductive composition of the present invention advantageously influences the conductance of electrically conductive composition, this is because heating causes under first temperature to be decomposed by second resin Composition of end-blocking, produce first and second fluxs, this flux and aforesaid on electrically-conducting metal surface metal oxide and lubricant reaction or flux.
Therefore, the invention provides a kind of electrically conductive composition, described electrically conductive composition causes having improved conductance because of the free from admixture state of conducting metal particles.Just because of this, the conductance of the trace that is formed by electrically conductive composition of the present invention is improved, this is because these traces have been established conductive path, described conductive path does not make any lubricant such as stearic acid, any oxide such as silver oxide, perhaps any reactive products of lubricant and silver strip is passed as silver stearate.The present invention also provides the method for using this electrically conductive composition.
The accompanying drawing summary
When considered in conjunction with the accompanying drawings, by the following detailed description of reference, other advantage of the present invention will readily appreciate that because can understand these better, wherein these illustrate just to the purpose of setting forth and never limit the scope of the invention, wherein:
Figure 1A is on substrate, the electrically conductive composition of the present invention that specifically deposits on PCB, the cutaway view of formation conductive metal trace;
Figure 1B is the end view of conductive metal trace;
Fig. 2 A is the conductive metal trace and the therefore end view of the electrically conductive composition of sintered form not, so that the conducting metal particles in said composition and trace is discontinuous usually and separate each other;
Fig. 2 B relates to the end view of amplification of Fig. 2 A of conducting metal particles spacing;
Fig. 3 A be explanation after applying carry out microwave radiation heating, the conductive metal trace of Fig. 2 A and the end view of electrically conductive composition, wherein conducting metal particles contacts with each other and fluxes and forms continuous pathways of conductive metal;
Fig. 3 B relates to the connection of conducting metal particles and fluxes, and forms the end view of amplification of Fig. 3 A of continuous pathways of conductive metal;
Fig. 4 illustrates that in the preparation of electronics and electric component electrically conductive composition connects the cutaway view of the preferable use of adhesive as matrix; With
Fig. 5 is the end view that the explanation electrically conductive composition connects another preferable use of electric component matrix to the lead frame.
Detailed Description Of The Invention
Following explanation is to think the best pattern of the present invention of implementing at present.Carry out this explanation, in order that set forth General Principle of the present invention and do not think restriction.By with reference to appended claim, determine scope of the present invention best.
The invention discloses the method for a kind of electrically conductive composition and this electrically conductive composition of use.Especially with reference to Figure 1A and 1B, typically electrically conductive composition is applied to substrate, on preferred nonconducting substrate such as the PCB, to form conductive trace 10.PCB can be especially by the plastics such as the polystyrene manufacturing of low melting glass, in the smelting furnace of routine or the placement in the baking oven, described plastics are not desirable.Be appreciated that conductive trace 10 can be deposited on the various substrates.In other words, substrate can be the substrate of any kind, from PCB in addition another composition such as solder flux or adhesive composition the layer.
In one embodiment, electrically conductive composition comprises conducting metal, isocyanate component and can with the resin Composition of this isocyanate component reaction.Conducting metal (typically being conducting metal particles) is with 40-95, and the consumption of preferred 60-95 weight portion exists.Conductive metal powder, conductive metal sheet etc. intended comprising in term as used herein " particle ".
Preferably, conducting metal is selected from copper, silver, aluminium, gold, platinum, palladium, beryllium, rhodium, nickel, zinc, cobalt, iron, molybdenum, iridium, rhenium, mercury, ruthenium, osmium and combination thereof.More preferably, conducting metal comprises noble metal.In the most preferred embodiment of the present invention, noble metal is a particle, particularly the silver of thin slice 11 forms.A kind of silver strip 11 that is suitable for using in electrically conductive composition of the present invention is Silver Flake 52, and it is commercially available in FerroMet.Just to describing purpose, all the other explanations utilize one or more silver strip 11 as conducting metal.This form of description is for convenience's sake and is not interpreted as restriction.
Conducting metal has the existence metal oxide thereon and the surface of lubricant.With regard to silver strip 11, each silver strip 11 has the surface and metal oxide typically is silver oxide and lubricant typically is silver stearate.As mentioned above, when in the process of wearing into silver strip 11 by silver powder, using stearic acid, form silver stearate, the surface reaction of silver stearate and silver strip 11.As a result, for the purposes of the present invention, term as used herein " lubricant " typically refers to silver stearate, but also can be any stearic acid residual when silver powder is worn into silver strip 11.
Isocyanate component is with 2-20, and the consumption of preferred 4-12 weight portion exists.Although isocyanate component can comprise the not isocyanate component of end-blocking at first, it preferably includes the isocyanates of end-blocking.Most preferred blocked isocyanate is 1 of an end-blocking, hexamethylene-diisocyanate, but also can use other isocyanates, comprising but be not limited to '-diphenylmethane diisocyanate, toluene di-isocyanate(TDI) etc.Isocyanate component can even comprise isocyanate prepolymer, and described isocyanate prepolymer is the product of isocyanates and polymer such as polyalcohol normally.
The isocyanates of end-blocking end-capping reagent end-blocking.This end-capping reagent is selected from epsilon-caprolactams (ECAP), methyl-ethyl ketoxime (MBKO), diethyl malonate (DEM), dimethyl pyrazole (DMP) and combination thereof.The isocyanates that is fit to be incorporated into the various end-blockings in the electrically conductive composition includes but not limited to Bayhydur BL 116, and (it is commercially available in Pittsburgh, the Bayer Corporation of Pennsylvania) and Trixene  BI 7950, Trixene  BI 7962 and Trixene  BI 7990 (they all are available commercially from the BaxendenChemicals Limited of Britain Lancashire).Trixene  BI 7950 usefulness DMP are as the end-capping reagent end-blocking, Trixene  BI 7962 usefulness DEM as the blend of end-capping reagent end-blocking and Trixene  BI 7990 usefulness DMP and DEM as the end-capping reagent end-blocking.
In general, isocyanate component can with the reaction of metal oxide and lubricant, with from removing metal oxide and lubricant to small part on the surface of conducting metal, thereby increase the conductance of electrically conductive composition.Term as used herein " can with ... reaction " be meant with electrically-conducting metal surface on a certain amount of metal oxide and lubricant reaction or clean simply, clean or otherwise remove them.Isocyanates comprises in the most preferred embodiment of blocked isocyanate therein, and when conductive composition, blocked isocyanate becomes under 80-250 ℃ temperature separates end-blocking, perhaps discharges.Below conductive composition will be described in addition.Accurate temperature when blocked isocyanate is separated end-blocking can change along with selected specific end-capping reagent.
In case separate end-blocking, then form isocyanates and the free end-capping reagent of separating end-blocking.Separate the isocyanates of end-blocking and free end-capping reagent can with metal oxide, particularly with silver oxide and and lubricant, particularly with the reaction of silver stearate and/or stearic acid, thereby, particularly remove metal oxide and lubricant to small part on the surface of silver strip 11 from conducting metal.Removing metal oxide and lubricant from the surface of silver strip 11 increases the conductance of electrically conductive composition, this be because free from admixture promptly not the conductance of oxidation and unlubricated silver greater than the silver strip 11 that carries impurity such as silver oxide and silver stearate.
Can with the resin Composition of isocyanate component reaction with 1-10, the consumption of preferred 2-10 weight portion exists.In one embodiment, resin Composition comprises the resin that forms the hydroxyl-functional of polyurethane when solidified with the isocyanate component reaction.This polyurethane typically is the polyurethane of non-foaming.The resin of most preferred hydroxyl-functional is a phenoxy resin, and it typically is the product of bisphenol-A and chloropropylene oxide.This phenoxy resin can be available commercially from Rock Hill, the InChemCorp. of South Carolina with PKHP-200 Solid GradePhenoxy Resin form.In this embodiment, the ratio of the OH functional group in the NCO functional group in isocyanate component and the hydroxyl functional resin is 1: 1 to 1: 2.In another embodiment, resin Composition comprises the resin that forms the amine official energy of polyureas when solidified with the isocyanate component reaction.
Electrically conductive composition randomly comprises and applies the solvent that electrically conductive composition is used.Just because of this, it is desirable to, the type of solvent and consumption are enough to isocyanate component and resin Composition are dissolved in the solution.If solvent is included in the electrically conductive composition, then solvent is with 5-20, and preferred 6-12 weight portion exists with dissolving isocyanate component and resin Composition.Preferably, the type of solvent is selected from ethylene glycol monobutyl ether.Diethylene glycol monobutyl ether and combination thereof.Ethylene glycol monobutyl ether can butyl cellosolve form be purchased and diethylene glycol monobutyl ether is purchased with the form of butyl carbitol, and the two is all available from Midland, the Dow Chemical of Michigan.Certainly, be appreciated that other solvent can be suitable for being incorporated in the electrically conductive composition.
In embodiment independently, apply for the best of electrically conductive composition, preferably, electrically conductive composition is basically by conducting metal, isocyanate component can be with the resin Composition of isocyanate component reaction and be used to dissolve the embodiment of the solvent composition of isocyanates and resin Composition.In this special embodiment, electrically conductive composition exists with the consumption of 40-95 weight portion, and isocyanate component exists with the consumption of 2-20 weight portion, and resin Composition exists with the consumption of 1-20 weight portion and solvent exists with the consumption of 5-20 weight portion.About embodiment listed above, isocyanate component can with the reaction of the metal oxide that on electrically-conducting metal surface, exists and lubricant so that from removing metal oxide and lubricant to small part on the surface of conducting metal.Just because of this, the conductance of electrically conductive composition increases.
More further in the embodiment, electrically conductive composition comprise conducting metal, first resin Composition and can with second resin Composition of first resin Composition reaction.Conducting metal as mentioned above and have and be present in its lip-deep metal oxide and lubricant.Preferably, conducting metal is a silver strip 11.First resin Composition is equivalent to above-described resin Composition.Just because of this, most preferably first resin Composition comprise the resin of hydroxyl-functional and amine official can resin at least a.
Second resin Composition is separated end-blocking at end-blocking under first temperature with under second temperature higher than first temperature.That is to say that at elevated temperatures, second resin Composition becomes separates end-blocking or release.Preferably, first temperature is 80-250 ℃ less than the scope of 80 ℃ and second temperature.
The separate end-blocking of second resin Composition under second temperature produces first flux and second flux, and first flux can and even can react with lubricant with reactive metal oxide at least.Second flux can with the reaction of lubricant at least and even can with reactive metal oxide.Moreover, be under the situation of silver strip 11 at conducting metal, lubricant can comprise that silver stearate is as stearic acid residual in the processing of silver strip 11.Metal oxide and lubricant are removed in reacting of first and second fluxs to small part from electrically-conducting metal surface, thereby increase the conductance of electrically conductive composition.In case second resin Composition is separated end-blocking, then produce consumption and be enough to effectively clean first and second fluxs that conducting metal is an impurity in the silver strip 11, so that silver strip 11 combines in intimate contact and fusion, the result reduces the resistance at least 50% of electrically conductive composition, and this correspondingly improves conductance.Electrically conductive composition resistance is less than or equal to 10m Ω/sq..Also possible situation is that under the situation that silver strip 11 can weld and link together, silver strip 11 is realized the cold welding of noble metal.
In this specific embodiment, preferred second resin Composition comprises the isocyanates of end-blocking.Yet, be appreciated that second resin Composition can be the chemical agent of other end-blocking of non-isocyanate, as long as it can react with first resin Composition, at end-blocking under first temperature with under second temperature, separate end-blocking, get final product to produce first and second fluxs as mentioned above.If second resin Composition is the isocyanates of end-blocking, then preferably use the end-capping reagent identical to make it end-blocking with the above.That is to say the isocyanates of the preferred end-blocking end-capping reagent end-blocking that is selected from epsilon-caprolactams, methyl-ethyl ketoxime, diethyl malonate, dimethyl pyrazole and the combination thereof.
Second resin Composition is under the situation of blocked isocyanate therein, blocked isocyanate separate end-blocking produce the isocyanates separate end-blocking as first flux and free end-capping reagent as second flux.Under the situation that adopts many end-capping reagents listed above, then the free end-capping reagent that produces when blocked isocyanate is separated end-blocking is the amine that serves as second flux.Just because of this, separate end-blocking isocyanates can with reactive metal oxide at least and may react with lubricant and free end-capping reagent can with lubricant reaction at least and may with reactive metal oxide.The end-capping reagent of separating the isocyanates of end-blocking and dissociating is promptly removed metal oxide and lubricant basically from the surface of silver strip 11 from the surface of conducting metal, the result increases conductance.
The present invention is still further embodied in the method for using electrically conductive composition.This method comprises the step of trace 10 on substrate of depositing electrically conductive composition.As above-mentioned, the trace 10 of electrically conductive composition can be deposited on the various substrates.If substrate is a circuit board, then trace 10 is deposited on the circuit board.Perhaps, the trace 10 of electrically conductive composition can be deposited on the substrate so that electronics and electric component are connected into circuit, perhaps in the preparation of electronics and electric component, can be deposited on the substrate, so that matrix is connected on the lead frame.Yet method of the present invention is not limited to these application.
Method of the present invention comprises that further conductive composition arrives at least the second temperature, promptly is heated to the step under at least 80 ℃, separates end-blocking so that cause second resin Composition.More particularly, preferred conductive composition arrives 80-250 ℃, more preferably 100-200 ℃.Most preferably 180-200 ℃.Conductive composition causes that second resin Composition separates end-blocking or decomposition in these temperature ranges, produces first and second fluxs.Certainly, be appreciated that desirable temperature range can change with the particular type of second resin Composition and consumption and the particular solution end-capping reagent relevant with second resin Composition.
As mentioned above, in case heating, first and second resin Compositions reactions is solidified, and produces first and second flux removing metal oxide and lubricant from the surface of conducting metal, thereby increases the conductance of the trace 10 of electrically conductive composition.In a word, first flux (typically separating the isocyanates of end-blocking) and second flux (typically amine compound) are the very effective fluxs of removing any impurity on the electrically-conducting metal surface (metal oxide and lubricant the two).With reference to figure 2A and 2B, before heating, trace 10 is sintering not at first, separates usually with silver strip 11.On the other hand, with reference to figure 3A and 3B, the heating after, trace 10 be sintered with electrically conductive composition in silver strip 11 become tightr and improved the contact with trace 10.This improved more closely contact improves the conductance of electrically conductive composition and trace 10.
When conductive composition arrives 180-200 ℃ most preferred temperature range, realize two main advantages.The first, electrically conductive composition is handled " snap cure " thereby provide very fast.The second, the conductance of electrically conductive composition significantly improves, thereby compares with the composition that heats under lower temperature range, and the big 2-10 of conductance doubly.First and second resin combinations and first and second flux are that those that describe in more detail with above are identical.
Although do not require, preferably by adopting suitable microwave oven to make electrically conductive composition accept microwave radiation, thereby conductive composition is at least the second temperature.In the most preferred embodiment of the present invention, accept variable frequency microwave radiation by making electrically conductive composition, conductive composition is at least the second temperature.From the energy waves conductive composition of variable frequency microwave radiation to second temperature.If use the variable frequency microwave radiation conductive composition, then typically electrically conductive composition is carried out radiation 3-20 minute time period of this form.
Heating electrically conductive composition of the present invention advantageously influences the conductance of the trace 10 of electrically conductive composition and electrically conductive composition, this is to decompose because heating causes second resin Composition of end-blocking under first temperature, thereby produce first and second fluxs, as mentioned above, metal oxide on described flux and the electrically-conducting metal surface and lubricant reaction are perhaps fluxed them.
In addition, under temperature listed above and according to preferred variable frequency microwave radiation conductive composition, there is not the negative effect substrate.First and second resin components cure, silver strip 11 fusions and/or the closely contact that becomes each other, thus improve conductance, and non-conductive substrate demonstrates slight influence to any heating, this is because can heated substrates by variable frequency microwave radiation.
Refer now to Figure 4 and 5, show some application of electrically conductive composition.With reference to figure 4, use electrically conductive composition to connect adhesive as matrix.Component 21 is adhered on the substrate 22 by the lead 23 that is connected on the pad 24.Pad 24 is made by electrically conductive composition, and according to the present invention, described electrically conductive composition also serves as adhesive.With reference to figure 5, use electrically conductive composition that the electric component matrix is connected on the lead frame.By the operation of electrically conductive composition, with electric component 31 physically and be electrically connected on the lead frame 32, according to the present invention, described electrically conductive composition also serves as adhesive 33.
The following embodiment of the method for the elaboration electrically conductive composition of herein listing and this electrically conductive composition of use intends setting forth rather than restriction the present invention.The benchmark of all wt part is based on 100 weight portion electrically conductive compositions in the application.
With reference to following table, in weight portion (pbw), also react by adding following substances, thus the preparation electrically conductive composition.The pbw of the pbw of each component of herein listing, particularly conducting metal, isocyanate component and resin Composition solidifies and lower resistivity the reaction of the best, and promptly the conductance of Ti Gaoing is important.
Component Embodiment 1 g Embodiment 1 pbw/100 Embodiment 2 g Embodiment 2 pbw/100 Embodiment 3 g Embodiment 3 pbw/100 Embodiment 4 g Embodiment 4 pbw/100
First resin Composition ?7.50 ??2.08 ?0.34 ??2.86 ?0.49 ??3.33 ?0.43 ??3.21
The second resin Composition #1 ?30.00 ??8.33 ?- ??- ?- ??- ?- ??-
The second resin Composition #2 ?- ??- ?1.00 ??8.40 ?- ??- ?- ??-
The second resin Composition #3 ?- ??- ?- ??- ?1.00 ??6.80 ?- ??-
The second resin Composition #4 ?- ??- ?- ??- ?- ??- ?1.00 ??7.46
Conducting metal ?300.00 ??83.33 ?9.52 ??80.00 ?11.76 ??80.00 ?10.70 ??79.85
Solvent ?22.50 ??6.26 ?1.04 ??8.74 ?1.45 ??9.87 ?1.27 ??9.48
In last table:
First resin Composition is PKHP-200 Solid Grade Phenoxy Resin (InChemCorp.);
The second resin Composition #1 is Bayhydur BL 116 (Bayer Corporation);
The second resin Composition #2 is Trixene  BI 7950 (Baxenden);
The second resin Composition #3 is Trixene  BI 7962 (Baxenden);
The second resin Composition #4 is Trixene  BI 7990 (Baxenden);
Conducting metal is Silver Flake 52 (FerroMet); With
Solvent is butyl cellosolve (Dow Chemical).
On glass substrate the electrically conductive composition of blade coating embodiment 2-4 and at first 80 ℃ down dry 5 minutes as prebake conditions, to flash away solvent.Next, down solidified these embodiment 5 minutes, and film with scraping of the reference examples of not mixing blocked isocyanate and to compare at 180 ℃.At first dry reference examples, was solidified 5 minutes down at 180 ℃ to flash away solvent as prebake conditions in 1 minute then under 80 ℃.Estimate the resistance of electrically conductive composition and the thickness of film, in order that the resistivity between effective comparing embodiment 2-4 and the reference examples.Following table has been summarized the result.
Embodiment Drying condition Heating and condition of cure Resistivity (Ω) Thickness (μ m) Normalize to the resistivity (m Ω) of 25 μ Normalize to the resistivity (m Ω) of 40 μ
??2 80 ℃ 5 minutes 180 ℃ 5 minutes ??0.071 ??30 ??8.5 ??5.3
??3 80 ℃ 5 minutes 180 ℃ 5 minutes ??0.069 ??30 ??8.3 ??5.2
??4 80 ℃ 5 minutes 180 ℃ 5 minutes ??0.074 ??30 ??8.9 ??5.6
Reference examples 80 ℃ 1 minute 180 ℃ 5 minutes ??0.148 ??30 ??17.8 ??11.1
The data that comprise in last table show that the order of magnitude of the resistivity of electrically conductive composition of the present invention is generally the normalized resistance rate of the electrically conductive composition of 3-10m Ω/sq. and embodiment 2-4 and hangs down at least 50% than the normalized resistance rate of reference examples.Certainly, also realized corresponding effect on conductivity.
In embodiment independently, the electrically conductive composition of embodiment 1 is deposited on high impact polystyrene (HIP) substrate and Kapton  (DuPont) the polyimide film substrate with the trace form.Next, by carrying out variable frequency microwave (VFM) radiation heating electrically conductive composition and each substrate, produce various straight lines and crooked trace.Following table has been summarized this result of experiment.
Type of substrate The trace type Heating and condition of cure Resistivity (Ω)
??HIP Straight line/narrow VFM85 ℃ 5 minutes 5.5
??HIP Straight line/medium VFM85 ℃ 5 minutes 3.2
??HIP Straight line/wide VFM85 ℃ 5 minutes 1.4
??HIP Crooked/wide VFM85 ℃ 5 minutes 1.9
??HIP Straight line/narrow VFM90 ℃ 10 minutes 5.0
??HIP Straight line/medium VFM90 ℃ 10 minutes 3.1
??HIP Straight line/narrow VFM90 ℃ 10 minutes 1.4
??HIP Crooked/narrow VFM90 ℃ 10 minutes 4.7
??HIP Crooked/wide VFM90 ℃ 10 minutes 2.3
??HIP Straight line/narrow VFM90 ℃ 15 minutes 4.5
??HIP Straight line/medium VFM90 ℃ 15 minutes 2.8
??HIP Straight line/narrow VFM90 ℃ 15 minutes 1.2
??HIP Crooked/narrow VFM90 ℃ 15 minutes 4.6
??HIP Crooked/wide VFM90 ℃ 15 minutes 2.2
Type of substrate The trace type Heating and condition of cure Resistivity (Ω)
??Kapton Straight line/narrow VFM70 ℃ 15 minutes 4.2
??Kapton Straight line/medium VFM70 ℃ 15 minutes 2.9
??Kapton Straight line/wide VFM70 ℃ 15 minutes 1.4
??Kapton Crooked/narrow VFM70 ℃ 15 minutes 5.0
??Kapton Crooked/wide VFM70 ℃ 15 minutes 1.9
??Kapton Straight line/narrow VFM90 ℃ 10 minutes 4.4
??Kapton Straight line/medium VFM90 ℃ 10 minutes 2.7
??Kapton Straight line/wide VFM90 ℃ 10 minutes 1.3
??Kapton Crooked/narrow VFM90 ℃ 10 minutes 5.4
??Kapton Crooked/wide VFM90 ℃ 10 minutes 2.2
??Kapton Straight line/narrow VFM130 ℃ 10 minutes 2.9
??Kapton Straight line/medium VFM130 ℃ 10 minutes 2.1
??Kapton Straight line/wide VFM130 ℃ 10 minutes 1.1
??Kapton Crooked/narrow VFM130 ℃ 10 minutes 3.7
??Kapton Crooked/wide VFM130 ℃ 10 minutes 1.6
In a further embodiment, the electrically conductive composition of embodiment 1 is deposited on the exposed FR4 as substrate, realizes required heating and the condition of cure of electrically conductive composition full solidification to estimate.For evaluate cure, observe three kinds of physical properties:
(1) specific insulation and surface resistivity.Use is connected to Keithley 2400 universal instruments of the correction on 4 utmost point probes, measurement volumes resistance.With 0.1 " the 3M Scotch#600 adhesive tape thickness of wide * 1 (about 0.0013 ") apply electrically conductive composition.The reading of 1 " * 0.1 " that obtains by Keithley universal instrument (10sq.) is determined surface resistivity.
(2) adhesion/tape pull.Use 3M Scotch Tape #810 and in the electrically conductive composition that solidifies, write " X ", go up adhesive tape at " X " that write, tractive adhesive tape then, and observe the quantity of material of taking out of with adhesive tape objectively.
(3) solvent resistance.Use acetone.The fritter garrha is immersed in the acetone.The electrically conductive composition that solidifies with the scraping of this piece garrha then.Calculate the scraping number, up to remove this material from substrate.If the scraping number reaches 100 times, then stop this physical property test.
Following table has been summarized this experimental result.
Heating and condition of cure Specific insulation (Ω-cm) Sheet resistance (m Ω/sq) Adhesion/tape pull Solvent resistance Remarks
100 ℃ 10 minutes ??3.72E-05 ??11.0 Difference ?3 With hot plate heating/curing
130 ℃ 10 minutes ??1.96E-05 ??6.3 Difference ?25 With hot plate heating/curing
130 ℃ 20 minutes ??2.55E-05 ??7.2 Difference ?25 With baking oven heating/curing
130 ℃ 30 minutes ??2.16E-05 ??6.0 Difference ?90 With baking oven heating/curing
130 ℃ 60 minutes ??2.05E-05 ??6.6 Good ?>100 With baking oven heating/curing
150 ℃ 10 minutes ??1.95E-05 ??6.5 Medium ?>100 With baking oven heating/curing
150 ℃ 20 minutes ??2.04E-05 ??6.3 Good ?>100 With baking oven heating/curing
180 ℃ 5 minutes ??1.67E-05 ??5.2 Good ?>100 With baking oven heating/curing
As previously mentioned, the electrically conductive composition of embodiment 1 mixes Bayhydur BL116 blocked isocyanate as second resin Composition, and described blocked isocyanate is just separated end-blocking up to about 130-140 ℃.Therefore, as above shown in the data in the table, do not solidify at 100 ℃ of electrically conductive compositions that heated down 10 minutes, as a result the surface resistivity height of this sample.
Certainly, be appreciated that the temperature when then blocked isocyanate is separated end-blocking can change if select other isocyanates as second resin Composition.For example, according to estimates, know with the Trixene  BI 7950 of DMP end-blocking and separating end-blocking under about 120 ℃ and under about 80 ℃, separating end-blocking with the Trixene  BI7962 of DEM end-blocking.Therefore, if select Trixene  BI 7962, then 100 ℃ heating-up temperature * 10 minute can be enough to full solidification and improve conductance.
Obviously, in view of above-mentioned instruction, many modifications of the present invention and change are possible.Can beyond claims are described particularly, put into practice the present invention.

Claims (39)

1. electrically conductive composition, it comprises:
The conducting metal that exists with the consumption of 40-95 weight portion;
The isocyanate component that exists with the consumption of 2-20 weight portion; With
Can with reaction of described isocyanate component and the resin Composition that exists with the consumption of 1-20 weight portion,
Wherein all wt part is based on the described electrically conductive composition of 100 weight portions.
2. the electrically conductive composition of claim 1, wherein said conducting metal is selected from copper, silver, aluminium, gold, platinum, palladium, beryllium, rhodium, nickel, zinc, cobalt, iron, molybdenum, iridium, rhenium, mercury, ruthenium, osmium and combination thereof.
3. the electrically conductive composition of claim 1, wherein said conducting metal comprises noble metal.
4. the electrically conductive composition of claim 3, wherein said noble metal comprises the silver of particle form.
5. the electrically conductive composition of claim 1, wherein said isocyanate component comprises the isocyanates of end-blocking.
6. the electrically conductive composition of claim 5, the isocyanate component of wherein said end-blocking comprises 1 of end-blocking, hexamethylene-diisocyanate.
7. the electrically conductive composition of claim 5, the isocyanates of wherein said end-blocking is with the end-capping reagent end-blocking that is selected from epsilon-caprolactams, methyl-ethyl ketoxime, diethyl malonate, dimethyl pyrazole and combination thereof.
8. the electrically conductive composition of claim 7, the isocyanates of wherein said end-blocking is separated end-blocking under 80-250 ℃ temperature, thereby forms isocyanates and the free end-capping reagent of separating end-blocking.
9. the electrically conductive composition of claim 8, wherein metal oxide and lubricant are present on the surface of described conducting metal, can react with described metal oxide and described lubricant with described isocyanates and the described free end-capping reagent of separating end-blocking, with from removing described metal oxide and described lubricant to small part on the described surface of described conducting metal, thereby increase the conductance of described electrically conductive composition.
10. the electrically conductive composition of claim 1, wherein metal oxide and lubricant are present on the surface of described conducting metal, can react with described metal oxide and described lubricant with described isocyanate component, with from removing described metal oxide and described lubricant to small part on the described surface of be confused conducting metal, thereby increase the conductance of described electrically conductive composition.
11. the electrically conductive composition of claim 1, wherein said resin Composition comprise the resin that forms the hydroxyl-functional of polyurethane when solidified with described isocyanate component reaction.
12. the electrically conductive composition of claim 11, the resin of wherein said hydroxyl-functional is a phenoxy resin.
13. the electrically conductive composition of claim 11, wherein the ratio of the OH functional group in the resin of the NCO functional group in described isocyanate component and described hydroxyl-functional is 1: 1 to 1: 2.
14. the electrically conductive composition of claim 1, wherein said resin Composition comprise the resin that forms the amine official energy of polyureas when solidified with described isocyanate component reaction.
15. the electrically conductive composition of claim 1 comprises that further solvent that the consumption with the 5-20 weight portion exists is to dissolve described isocyanate component and described resin Composition.
16. the electrically conductive composition of claim 15, wherein said solvent is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and combination thereof.
17. the electrically conductive composition of claim 1, wherein said conducting metal exists with the consumption of 65-90 weight portion.
18. the electrically conductive composition of claim 1, wherein said isocyanate component exists with the consumption of 4-12 weight portion.
19. the electrically conductive composition of claim 1, wherein said resin Composition exists with the consumption of 2-10 weight portion.
20. the electrically conductive composition of claim 15, wherein said solvent exists with the consumption of 6-12 weight portion.
21. the electrically conductive composition of claim 1, its resistance is less than or equal to 10m Ω/sq..
22. a substrate, it has the conductive trace that the described electrically conductive composition by claim 1 forms.
23. an electrically conductive composition, it is made up of following substances basically:
The conducting metal that exists with the consumption of 40-95 weight portion;
The isocyanate component that exists with the consumption of 2-20 weight portion;
Can with reaction of described isocyanate component and the resin Composition that exists with the consumption of 1-20 weight portion; With
The solvent that exists with the consumption of 5-20 weight portion, dissolving described isocyanate component and described resin Composition,
Wherein all wt part is based on the described electrically conductive composition of 100 weight portions.
24. the electrically conductive composition of claim 23, wherein metal oxide and lubricant are present on the surface of described conducting metal, can react with described metal oxide and described lubricant with described isocyanate component, with from removing described metal oxide and described lubricant to small part on the described surface of described conducting metal, thereby increase the conductance of described electrically conductive composition.
25. an electrically conductive composition, it comprises:
Conducting metal with metal oxide and lubricant existence surface thereon; With
First resin Composition;
Described electrically conductive composition is characterised in that and second resin Composition of described first resin Composition reaction that wherein said second resin Composition is separated end-blocking at end-blocking under first temperature with under than the second high temperature of described first temperature, thereby produces
First flux and
Second flux
Wherein said first flux and described at least reactive metal oxide, with described second flux and described at least lubricant reaction, with from removing described metal oxide and described lubricant to small part on the described surface of described conducting metal, thereby increase the conductance of described electrically conductive composition.
26. the electrically conductive composition of claim 25, wherein said second resin Composition comprises the isocyanates of end-blocking.
27. the electrically conductive composition of claim 26, the isocyanates of the wherein said end-blocking end-capping reagent end-blocking that is selected from epsilon-caprolactams, methyl-ethyl ketoxime, diethyl malonate, dimethyl pyrazole and combination thereof.
28. the electrically conductive composition of claim 26, produce in case the isocyanates of wherein said end-blocking is separated end-blocking the isocyanates of separating end-blocking as described first flux and free end-capping reagent as described second flux.
29. the electrically conductive composition of claim 26, wherein first resin Composition comprise the resin of hydroxyl-functional and amine official can resin at least a.
30. the electrically conductive composition of claim 25, wherein said first temperature is 80-250 ℃ less than the scope of 80 ℃ and described second temperature.
31. the electrically conductive composition of claim 25, its resistance is less than or equal to 10m Ω/sq..
32. a method of using electrically conductive composition, described method comprises the steps:
The trace of depositing electrically conductive composition on substrate, wherein this electrically conductive composition comprises:
1) has the conducting metal that there are surface thereon in metal oxide and lubricant;
2) first resin Composition; With
3) can with second resin Composition of first resin Composition reaction, wherein second resin Composition is separated end-blocking at end-blocking under first temperature with under second temperature higher than first temperature, to produce
3a) first flux and
3b) second flux
Wherein first flux and reactive metal oxide at least and second flux and lubricant reaction at least are with from removing metal oxide and lubricant to small part on the surface of conducting metal; With
Heat this electrically conductive composition under at least the second temperature, separate end-blocking so that cause second resin Composition, make the reaction of first and second resin Compositions solidify, and produce first and second flux, with from removing metal oxide and lubricant to small part on the surface of conducting metal, thereby increase the conductance of electrically conductive composition trace.
33. the method for claim 32, wherein conductive composition is further defined as to the described step under at least the second temperature and makes electrically conductive composition accept microwave radiation, arrives at least the second temperature with conductive composition.
34. the method for claim 33, the described step that wherein makes electrically conductive composition accept microwave radiation is further defined as and makes electrically conductive composition accept variable frequency microwave radiation.
35. being further defined as, the method for claim 34, the step that wherein makes electrically conductive composition accept variable frequency microwave radiation make electrically conductive composition accept variable frequency microwave radiation 3-20 minute time period.
36. the method for claim 32, wherein to be lower than 80 ℃ and second temperature range be 80-250 ℃ to first temperature, so that conductive composition is further defined as conductive composition at least 80 ℃ to the described step under at least the second temperature.
37. the method for claim 32, wherein substrate is the trace that the described step of circuit board and described trace at depositing electrically conductive composition on the substrate is further defined as depositing electrically conductive composition on circuit board.
38. the method for claim 32, wherein the described step at the trace of depositing electrically conductive composition on the substrate is further defined as the trace of depositing electrically conductive composition on substrate so that electronics and electric component connect into circuit.
39. the method for claim 32 wherein is further defined as in the preparation of electronics and electric component trace at depositing electrically conductive composition on the substrate so that matrix is connected on the lead frame in the described step of the trace of depositing electrically conductive composition on the substrate.
CN 03826164 2003-03-18 2003-09-18 A conductive composition and method of using the same Pending CN1788323A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102056973A (en) * 2008-07-22 2011-05-11 E.I.内穆尔杜邦公司 Polymer thick film silver electrode composition for use in thin-film photovoltaic cells
CN102160124B (en) * 2008-08-29 2013-03-06 Sscp株式会社 Conductive paste composition
CN103646686A (en) * 2007-09-13 2014-03-19 汉高股份两合公司 Conductive composition
CN104603914A (en) * 2012-09-07 2015-05-06 应用材料公司 Integrated processing of porous dielectric, polymer-coated substrates and epoxy within a multi-chamber vacuum system confirmation
CN107682946A (en) * 2016-08-02 2018-02-09 通用汽车环球科技运作有限责任公司 For improving the treated heated windows grid of durability in the presence of a harsh environment
US10388423B2 (en) 2007-09-13 2019-08-20 Henkel Ag & Co. Kgaa Electrically conductive composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10388423B2 (en) 2007-09-13 2019-08-20 Henkel Ag & Co. Kgaa Electrically conductive composition
CN103646686A (en) * 2007-09-13 2014-03-19 汉高股份两合公司 Conductive composition
CN102056973B (en) * 2008-07-22 2014-02-12 E.I.内穆尔杜邦公司 Polymer thick film silver electrode composition for use in thin-film photovoltaic cells
CN102056973A (en) * 2008-07-22 2011-05-11 E.I.内穆尔杜邦公司 Polymer thick film silver electrode composition for use in thin-film photovoltaic cells
CN102160124B (en) * 2008-08-29 2013-03-06 Sscp株式会社 Conductive paste composition
CN104603914A (en) * 2012-09-07 2015-05-06 应用材料公司 Integrated processing of porous dielectric, polymer-coated substrates and epoxy within a multi-chamber vacuum system confirmation
CN107682946A (en) * 2016-08-02 2018-02-09 通用汽车环球科技运作有限责任公司 For improving the treated heated windows grid of durability in the presence of a harsh environment

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