WO2009116185A1 - Composite silver nanopaste, process for production thereof, method of connection and pattern formation process - Google Patents

Composite silver nanopaste, process for production thereof, method of connection and pattern formation process Download PDF

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Publication number
WO2009116185A1
WO2009116185A1 PCT/JP2008/062238 JP2008062238W WO2009116185A1 WO 2009116185 A1 WO2009116185 A1 WO 2009116185A1 JP 2008062238 W JP2008062238 W JP 2008062238W WO 2009116185 A1 WO2009116185 A1 WO 2009116185A1
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WO
WIPO (PCT)
Prior art keywords
silver
composite
paste
composite silver
resin
Prior art date
Application number
PCT/JP2008/062238
Other languages
French (fr)
Japanese (ja)
Inventor
小松　晃雄
Original Assignee
株式会社応用ナノ粒子研究所
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 株式会社応用ナノ粒子研究所 filed Critical 株式会社応用ナノ粒子研究所
Priority to JP2010503736A priority Critical patent/JP5306322B2/en
Priority to US12/735,435 priority patent/US8348134B2/en
Priority to JP2009549977A priority patent/JP4680313B2/en
Priority to EP08870788.0A priority patent/EP2298471B1/en
Priority to CN2008801281306A priority patent/CN101990474B/en
Priority to KR1020107017975A priority patent/KR101222304B1/en
Priority to PCT/JP2008/073660 priority patent/WO2009090846A1/en
Priority to PCT/JP2008/073751 priority patent/WO2009090849A1/en
Publication of WO2009116185A1 publication Critical patent/WO2009116185A1/en
Priority to US13/707,384 priority patent/US8906317B2/en
Priority to US13/707,298 priority patent/US8459529B2/en

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    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Definitions

  • the present invention relates to a paste composed of composite silver nanoparticles in which an organic coating layer made of an organic substance is formed around a silver nucleus made of a large number of silver atoms. More specifically, the paste is applied and fired.
  • the present invention relates to a composite silver nanopaste in which the organic coating layer and other organic components are diffused to form a silver film, and a semiconductor junction and an electrode pattern are formed from the silver film, a manufacturing method thereof, a bonding method, and a pattern formation method.
  • solder is an alloy of Sn and Pb, and the use of Pb is being prohibited as a recent environmental preservation measure. Therefore, development of a Pb-free alternative solder that replaces the conventional solder is desired.
  • Patent Document 1 Japanese Patent No. 3205793 was published as Patent Document 1.
  • Silver organic compounds (especially silver organic complexes) were selected as starting materials.
  • the silver organic compound is heated at a temperature higher than or equal to the decomposition start temperature and lower than the complete decomposition temperature in an inert gas atmosphere in which air is shut off, and the coating layer of the silver organic compound is formed around the decomposed and reduced silver core.
  • Composite silver nanoparticles were produced.
  • the particle size of silver nuclei is 1 to 100 nm, and is therefore commonly referred to as composite silver nanoparticles. Specifically, when 100 g of silver stearate was heated at 250 ° C. for 4 hours in a flask under a nitrogen stream, composite silver nanoparticles having a silver nucleus with a particle size of 5 nm were generated.
  • Patent Document 2 The inventor is one of the inventors of this international publication. A plurality of inventions are disclosed in this publication, and among them, a method of treating a metal inorganic compound with a surfactant is important. That is, a first step of colloiding a metal inorganic compound with a surfactant in a non-aqueous solvent to form an ultrafine particle precursor, and a reducing agent is added to the colloidal solution to reduce the ultrafine particle precursor. And a second step of generating composite metal nanoparticles in which a surfactant shell is formed as a coating layer on the outer periphery of the metal core.
  • the above-described method has a feature that since the metal inorganic compound is dissolved in a non-aqueous solvent, the produced composite metal nanoparticles are dispersed in the non-aqueous solvent and are not likely to be in a dumpling state.
  • the added surfactant has a large number of carbon atoms, the number of carbon atoms in the surfactant shell, which is an organic coating layer, is naturally large, and the temperature at which the surfactant shell is baked to disperse, that is, the firing temperature is increased. was there.
  • Patent Document 3 it is described that composite silver nanoparticles are made from silver carbonate and myristic acid (C number is 14). Further, it is described that composite silver nanoparticles were produced from silver carbonate and stearyl alcohol (C number is 18). However, since myristic acid (C number is 14) and stearyl alcohol (C number is 18) have a large carbon number, it goes without saying that there is a disadvantage that the firing temperature for silvering becomes high.
  • the present inventors react silver carbonate with C1-C9 or C11 alcohol to produce silver alkoxide-type composite silver nanoparticles consisting of alcohol residues around the silver nucleus. Succeeded.
  • the C1 to C9 or C11 composite silver nanoparticles obtained in this way are naturally lower in silvering temperature than the C14 or C18 composite silver nanoparticles obtained in Patent Document 3.
  • As a result of the decrease in the number of carbon atoms there is an advantage that the silver content increases while the silvering temperature decreases.
  • the present inventors decided to prepare a paste using the composite silver nanoparticles of C1 to C9 or C11.
  • This paste is used to assemble the electronic parts by joining the materials, or to test the formation of the electrode pattern on the substrate to confirm the effectiveness of the paste.
  • the bonding method using paste there are the following two conventional patent publications.
  • Patent Document 4 composite metal ultrafine particles in which the periphery of a core portion substantially composed of a metal component having an average particle diameter of 1 to 10 nm is coated with a coating layer composed of an organic substance having 5 or more carbon atoms are prepared in advance, and the composite Preparing a metal paste by dispersing metal ultrafine particles in a solvent, attaching the metal paste onto a terminal electrode of a circuit board to form a metal paste ball mainly composed of composite metal ultrafine particles, and the metal There are described a step of bonding electrodes of a semiconductor element on a paste ball using a face-down method and a step of electrically connecting the semiconductor element and a circuit board by low-temperature firing.
  • Japanese Patent No. 3638487 is disclosed.
  • composite metal ultrafine particles in which the periphery of a core portion substantially composed of a metal component having an average particle diameter of 1 to 10 nm is coated with a coating layer composed of an organic substance having 5 or more carbon atoms are prepared in advance.
  • a process of forming a solder bump and a process of heat-sealing the solder bump to a terminal electrode of a circuit board are disclosed.
  • Patent Documents 4 and 5 describe that composite metal ultrafine particles are dispersed in a solvent to prepare a metal paste.
  • claim 3 of Patent Document 4 includes a metal having high conductivity in addition to a solvent.
  • a metal paste to which a resin component is added is described.
  • only toluene is exemplified as a solvent, and the roles of Patent Documents 4 and 5 are imparted with a role of reducing the viscosity to make the paste into a solution.
  • the resin component is added to increase the viscosity, and an appropriate amount of solvent and resin component is added to produce a paste having a predetermined viscosity.
  • the present inventor also prepared a paste by dissolving the above-mentioned C1 to C9 or C11 composite silver nanoparticles in toluene.
  • the paste was prepared to have a viscosity that allowed it to flow naturally when tilted at room temperature so that it could be easily applied to a substrate or semiconductor electrode.
  • the paste was stored in a container at room temperature for only 2 weeks. After storage for 2 weeks, a paste film having a thickness of 1 ⁇ m was formed on the circuit board by screen printing, and baked in an electric furnace at 350 ° C. for 20 minutes to form the paste film into a silver film.
  • the surface and cross section of the silver film were observed using an optical microscope and an electron microscope. As a result, some irregularities were found on the surface of the silver film. In the baking at 350 ° C., all organic substances are diffused, but the silver nuclei are not melted, but the surface is melted and the silver nuclei are sintered to form a silver film. Therefore, if the silver nuclei are large, the surface irregularities will be amplified. That is, it was considered that the unevenness on the surface was formed by sintering between large silver nuclei. The reason for the formation of large silver nuclei is considered to be the result of composite silver nanoparticles agglomerating with each other in the paste to form secondary particles during storage for 2 weeks.
  • the composite silver nanoparticles may have aggregated before the addition of the solvent, the composite silver nanoparticles were finely ground in advance in a mortar to be monodispersed, and then the solvent was added to prepare a paste. After leaving this paste for 2 weeks, a paste film was formed on the circuit board and baked at 350 ° C. for 20 minutes. When observed with an electron microscope, the irregularities on the surface of the silver film were somewhat improved, but the irregularities still remained.
  • the composite silver nanoparticles when the composite silver nanoparticles are mixed with a solvent and stored in a fluidized state, the composite silver nanoparticles agglomerate into secondary particles, and the particle size of the secondary particles increases as the storage time increases. The conclusion is reached that increases.
  • the result is that the composite silver nanoparticles are added to a solvent such as toluene having a small viscosity to form a fluid paste having fluidity at room temperature, and the fluid paste is mass-produced and stored for a long period of time. The problem was highlighted.
  • the object of the present invention is to provide a technology for pasting C1-C9 or C11 composite silver nanoparticles in a form that does not aggregate, that is, a non-aggregating paste, and realizing the non-aggregating property with a non-flowable resin. It is to provide a non-flowable paste. Moreover, it is providing the manufacturing method of the non-fluid paste, and also providing the joining method and pattern formation method using a non-fluid paste simultaneously.
  • the present invention has been made in order to solve the above-mentioned problems, and the first embodiment of the present invention has a carbon number of 1 to 9 or around a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms.
  • 11 composed of a metal component containing at least composite silver nanoparticles formed with an organic coating layer composed of at least one alcohol molecule residue, alcohol molecule derivative or alcohol molecule, and the resin is at 10 ° C. or less. It is a composite silver nanopaste that is in a non-flowing state, holds the metal component in a dispersed state, and is fluidized by heating so that it can be applied.
  • the second form of the present invention is a composite silver nanopaste according to the first form, wherein the composite silver nanoparticles are 95 (mass%) or less and the resin is 20 (mass%) or less.
  • a third form of the present invention is a composite silver nanopaste in which silver fine particles having an average particle size of 0.1 to 10 ⁇ m are added as the metal component in the first form.
  • the composite silver nanoparticles are 5 to 85 (mass%), the silver fine particles are 80 to 10 (mass%), and the resin is 20 (mass%).
  • the composite silver nanopaste is as follows.
  • a fifth aspect of the present invention is a composite silver nanopaste according to any one of the first to fourth aspects, wherein a desired amount of a solvent is added to make it flowable even at 10 ° C. or less and can be applied.
  • a resin that is in a non-flowing state at 10 ° C. and fluidized by heating has a carbon number of 1 to 9 or 11 around silver nuclei having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms.
  • a composite silver nanoparticle formed with an organic coating layer composed of one or more of alcohol molecule residues, alcohol molecule derivatives or alcohol molecules, and if necessary, silver fine particles are mixed as a metal component, and the resin is fluidized under heating to make the whole Is cooled to a temperature at which the resin becomes non-flowing after kneading, and the metal component is kept in a dispersed state in the resin.
  • a seventh aspect of the present invention is a method for producing a composite silver nanopaste according to the sixth aspect, wherein the silver nuclei have an average particle diameter of 1 to 20 nm and the silver fine particles have an average particle diameter of 0.1 to 10 ⁇ m.
  • An eighth aspect of the present invention is a method for producing a composite silver nanopaste according to the sixth or seventh aspect, wherein a desired amount of solvent is added to make a paste that can be applied by being fluidized even at 10 ° C. or lower. .
  • a composite silver nanopaste of any one of the first to fifth aspects is prepared, a paste layer is formed by applying the composite silver nanopaste to a lower body, and the paste layer is formed on the paste layer.
  • the upper body is placed, the paste layer is silvered by heating, and the lower body and the upper body are joined.
  • a composite silver nanopaste according to any one of the first to fifth aspects is prepared, and the composite silver nanopaste is applied to a predetermined pattern on a surface of a substrate to form a paste pattern.
  • a pattern forming method in which the paste pattern is silvered by heating to form a silver pattern is provided.
  • an alcohol molecule residue, an alcohol molecule derivative or an alcohol molecule having 1 to 9 or 11 carbon atoms is surrounded by a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms. Since composite silver nanoparticles formed with one or more organic coating layers are used, an inexpensive composite silver nanopaste can be provided. Since the composite silver nanoparticles start from inexpensive C1-C9 or C11 alcohol and a relatively inexpensive silver salt (for example, silver carbonate), inexpensive composite silver nanoparticles can be used.
  • the C1 to C9 alcohols are characterized by a relatively small number of carbon atoms and a relatively high silver content in the composite silver nanoparticles compared to the C10 and C12 alcohols.
  • C11 has a carbon number smaller than C12, silver content rate is higher than C12.
  • C1 is methanol
  • C2 is ethanol
  • C3 is propanol
  • C4 is butanol
  • C5 is pentanol
  • C6 is hexanol
  • C7 is heptanol
  • C8 is octanol
  • C9 is nonanol
  • C11 is unidecanol. That is, the composite silver nanoparticle which has the organic coating layer which consists of many Cn alkoxide groups around the silver nucleus which is an aggregate
  • the alcohol residue is a concept including, for example, an alkoxide group C n H 2n + 1 O when the alcohol is written as C n H 2n + 1 OH.
  • the alcohol derivative is a concept including, for example, C n-1 H 2n-1 CHO, C n-1 H 2n-1 COOH, C n-1 H 2n-1 COO, and the like. Alcohol refers to C n H 2n + 1 OH itself.
  • the characteristic of the composite silver nanopaste according to the present invention is the greatest characteristic in the function of the resin.
  • the resin is in a non-flowing state at 10 ° C. or lower, and has a property of holding the composite silver nanoparticles and the silver fine particles in a dispersed state and fluidizing by heating.
  • the non-flowing state means a solid state or a high-viscosity state, and refers to a property of holding the composite silver nanoparticles and the silver fine particles fixedly in a dispersed state.
  • 10 degrees C or less is a temperature range which carries out low temperature storage in a refrigerator, and the said 10 degrees C or less can be achieved by long-term storage by refrigerator storage.
  • the paste when storing in a refrigerator, the paste is in a non-flowing state, and the composite silver nanoparticles and silver fine particles dispersed therein are fixed in the paste by the resin and cannot be aggregated with each other. Therefore, at 10 ° C. or lower, the particles cannot be aggregated with each other, and the particles are completely prevented from aggregating and forming a dump during storage of the paste.
  • This non-flowable paste can be referred to as a non-cohesive paste.
  • the resin when heated to 40 ° C. or higher, the resin is liquefied or the viscosity is suddenly lowered to be in a fluid state, and can be applied to an object as a paste.
  • the paste of the present invention is produced, it is stored at 10 ° C. or less and non-aggregated (non-fluidized). Just before applying the paste to the object, it is heated and fluidized to make a fluid paste, and if this fluid paste is applied to the object, the metal (silver) is not agglomerated so it is extremely dense. A silver film can be formed. If the remaining fluid paste is immediately cooled to 10 ° C. or less, it can be stored for a long time as a non-aggregating paste.
  • Examples of the resin that changes from a high viscosity to a low viscosity by heating include isobornylcyclohexanol (referred to as rosin) and glycerin (referred to as syrup). Since the melting point of glycerin is 17 ° C., solidification is possible if it is set to 10 ° C. or lower in a dry state.
  • As resins that are solid at 10 ° C. or lower and liquefy when heated alcohols such as myristyl alcohol (C14), palmityl alcohol (C16), stearyl alcohol (C18), and behenyl alcohol (C22), and other substances can be used.
  • the resin of the present invention is not a resin having a normal chemical concept, but is a generic term for substances that exhibit non-fluidity at 10 ° C., and is a substance in which everything is diffused by firing and residues such as carbides do not appear. Means.
  • a dispersant is added to disperse the composite silver nanoparticles, or a surfactant is added.
  • a dispersant is added to disperse the composite silver nanoparticles, or a surfactant is added.
  • these impurity organic substances are added, not only the silver content is lowered, but also when fired, A large amount of gas is generated from the impurity organic substance, and a large amount of voids (bubble voids) are formed in the silver film by this gas.
  • the electrical conductivity is lowered and the bonding force with the substrate is lowered. Bonding performance is reduced.
  • the silver content can be kept high, and at the same time, the amount of generated gas is small, the number of voids is inevitably reduced, the increase in bonding force and electrical conductivity and There is an effect that the thermal conductivity can be increased.
  • a composite silver nanopaste in which the composite silver nanoparticles are 95 (mass%) or less and the resin is 20 (mass%) or less.
  • the simplest paste composition is a mixture of composite silver nanoparticles and resin.
  • the silver component is only composite silver nanoparticles
  • the maximum mass% is 95 mass%
  • the minimum mass% of the resin is 5 mass%. What is necessary is just to increase the mass% of resin according to the fall of the mass% of a composite silver nanoparticle.
  • the silver content in the paste is preferably 80 mass% or more, the mass% of the resin is preferably set to 20 mass% or less.
  • a composite silver nanopaste to which silver fine particles having an average particle size of 0.1 to 10 ⁇ m are added as the metal component.
  • silver fine particles are added as the silver component in addition to the composite silver nanoparticles. Since the silver fine particles are pure silver and do not contain any organic matter, the silver content in the paste can be increased by adding silver fine particles. Since the particle diameter of the silver fine particles is 0.1 to 10 ⁇ m and the silver nucleus particle diameter of the composite silver nanoparticles is 1 to 20 nm, the composite silver nanoparticles are considered to play a role of an adhesive between the silver fine particles. It is done.
  • the composite silver nanoparticles adhere to the surface of the silver fine particles, the organic components are diffused by firing, and the silver fine particles whose surfaces are melted are bonded to each other.
  • the composite silver nanoparticles accumulate in the gaps between the large silver fine particles and the organic matter is diffused by firing, the gaps between the silver fine particles are filled with silver nuclei, and the silver fine particles are Therefore, the silver film itself is densely formed, and a conductor having high strength and high electrical conductivity is provided.
  • the silver nuclei fill the gaps between the silver fine particles, and the gas nuclei are filled back into the voids (voids) after the gas is diffused, and the number of voids is reduced. As a result, it is possible to improve the bonding strength and electrical conductivity with the substrate.
  • the composite silver nanoparticles are 5 to 85 (mass%), the silver fine particles are 80 to 10 (mass%), and the resin is 20 (mass%) or less.
  • a silver nanopaste is provided.
  • the composition of the composite silver nanopaste is composite silver nanoparticles, silver fine particles, and a resin.
  • the composite silver nanoparticles are 5 to 85 (mass%). When the composite silver nanoparticles are less than 5 mass%, the adhesion performance between the silver fine particles is deteriorated.
  • the organic content in the paste becomes excessive. Further, the silver fine particles are 80 to 10 (mass%).
  • the mass is 80 mass% or more, the content of the composite silver nanoparticles is lowered, the adhesion between the silver fine particles is lowered, and when the mass is 10 mass% or less, There is a weak point that the silver content of is reduced. Therefore, within the above range, preparing a composite silver nanopaste having an appropriate silver content, efficiently diffused during firing, and restricting the amount of voids (bubble removal) to an appropriate value Can do.
  • a composite silver nanopaste that can be applied by adding a desired amount of a solvent to make it flowable even at 10 ° C. or lower.
  • a paste to which only a resin is added is provided, and even if the paste is stored at a temperature of 10 ° C. or lower for a long period of time, the paste does not have fluidity. Are immobilized and mutual aggregation does not occur.
  • the solvent of the fifth embodiment can be added and fluidized, and the flowable paste can be applied to the substrate by a dispenser.
  • the non-fluid paste there are two methods: heating and adding a solvent.
  • a solvent since the organic substance content in the paste increases, there is a weak point in which the amount of gas generated by firing increases and the amount of void generation increases.
  • the solvent has a function of reducing the viscosity of the paste, and general organic solvents that evaporate at a relatively low temperature can be used. For example, C1-C8 alcohol, xylene, toluene, acetone, hexane, and other solvents can be used.
  • a resin that is in a non-flowing state at 10 ° C. and fluidized by heating has a carbon number of 1 to 9 around silver nuclei having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms.
  • the resin is in a non-flowing state at 10 ° C. and has a characteristic of being fluidized by heating.
  • heating is not only heating by a heating means, but also friction during kneading releases frictional heat, so friction is included in one form of heating.
  • friction is included in one form of heating.
  • a two-stage kneading in which a composite silver nanoparticle is added and kneaded after kneading a resin and silver fine particles.
  • silver fine particles are not added, there is only a form of kneading the resin and composite silver nanoparticles.
  • the paste fluidized by heat kneading is cooled to be non-fluidized and stored as a non-fluidized paste. Therefore, in non-fluid storage, composite silver nanoparticles and silver fine particles are not aggregated in the paste.
  • the seventh aspect of the present invention there is provided a method for producing a composite silver nanopaste in which the average particle diameter of the silver nuclei is 1 to 20 nm and the average particle diameter of the silver fine particles is 0.1 to 10 ⁇ m.
  • the silver content in the paste can be increased. Since the particle diameter of the silver fine particles is 0.1 to 10 ⁇ m and the silver core particle diameter of the composite silver nanoparticles is 1 to 20 nm, when the paste is fired, the composite silver nanoparticles are between the silver fine particles. It is thought to play the role of an adhesive.
  • the composite silver nanoparticles adhere to the surface of the silver fine particles, the organic components are diffused by firing, and the silver fine particles whose surfaces are melted are bonded to each other.
  • the composite silver nanoparticles accumulate in the gaps between the large silver fine particles, and when the organic matter is diffused by firing, the gaps between the silver fine particles are filled with silver nuclei, Since the silver fine particles are bonded to each other by the silver nuclei, the silver film itself is densely formed, and a silver conductor having high strength and high electrical conductivity is provided.
  • the silver nuclei fill the gaps between the silver fine particles, and the gas nuclei are filled back into the bubble cavities (voids), and the number of voids is reduced. As a result, it is possible to improve the bonding strength and electrical conductivity with the substrate.
  • a method for producing a composite silver nanopaste that is made into a paste that can be applied by adding a desired amount of solvent to make it flowable even at 10 ° C. or lower.
  • the composite silver nanopaste of the present invention is in a non-flowing state at a low temperature.
  • a method for producing a paste that is in a fluid state even at 10 ° C. is provided by adding a solvent to the production method of the sixth embodiment or the seventh embodiment.
  • the solvent has a function of reducing the viscosity of the paste, and general organic solvents that evaporate at a relatively low temperature can be used.
  • organic solvents that evaporate at a relatively low temperature
  • C1-C8 alcohol, xylene, toluene, acetone, hexane, and other solvents can be used.
  • alcohol is advantageous as a solvent.
  • the composite silver nanopaste of the present invention is prepared, the composite silver nanopaste is applied to the lower body to form a paste layer, and the upper body is disposed on the paste layer,
  • a joining method in which the paste layer is silvered by heating to join the lower body and the upper body.
  • This embodiment is a method for joining two objects using the composite silver nanopaste according to the present invention, in which one object is referred to as a lower body and the other object is referred to as an upper body, and both are bonded via a paste layer and fired.
  • strong bonding can be achieved by silvering the paste layer.
  • the silver film is excellent in electrical conductivity and thermal conductivity and can be fired at a low temperature, it is possible to join low melting point objects.
  • the composite silver nanopaste of the present invention is prepared, the composite silver nanopaste is coated on the surface of the substrate in a predetermined pattern, and the paste pattern is formed by heating.
  • a pattern forming method is provided in which a silver pattern is formed by silveration. For example, when a silver film having a predetermined pattern is formed on a resin substrate having a low melting point, a method for forming a silver film having various patterns on various materials at a low temperature is provided according to the embodiment of the present invention.
  • FIG. 1 is a production process diagram of composite silver nanoparticles CnAgAL.
  • FIG. 2 is a first process diagram of a formation reaction of composite silver nanoparticles.
  • FIG. 3 is a second process diagram of the formation reaction of composite silver nanoparticles.
  • FIG. 4 is a high-resolution transmission electron microscope view of C2AgAL.
  • FIG. 5 is a high-resolution transmission electron microscope view of C4AgAL.
  • FIG. 6 is a thermal analysis diagram of C2AgAL.
  • FIG. 7 is a thermal analysis diagram of C4AgAL.
  • FIG. 8 is a production process diagram of a composite silver nanopaste.
  • FIG. 9 is a characteristic diagram of the viscosity and temperature of IBCH.
  • FIG. 9 is a characteristic diagram of the viscosity and temperature of IBCH.
  • FIG. 10 is a thermal analysis diagram of IBCH with a heating rate of 3 ° C./min.
  • FIG. 11 is a graph showing the relationship between the evaporation temperature of IBCH and the temperature rise rate.
  • FIG. 12 is a characteristic diagram of viscosity and temperature of glycerin.
  • FIG. 13 is a thermal analysis diagram of the composite silver nanopaste (C2AgAL) in the atmosphere.
  • FIG. 14 is a thermal analysis diagram of the composite silver nanopaste (C4AgAL) in the atmosphere.
  • FIG. 15 is a thermal analysis diagram of the composite silver nanopaste (C6AgAL) in the atmosphere.
  • Table 1 is a list of molar ratios of the raw materials for production of the composite silver nanoparticles used in the present invention and the alcohol solution.
  • An inorganic silver salt or an organic silver salt can be used as the silver raw material, and silver carbonate (Ag2CO3) is described as an example of the inorganic silver salt.
  • the number of moles of alcohol in which 100 g (0.363 moles) of silver carbonate fine particles are dispersed ranges from 3.63 moles to 23.2 moles (mole ratio of alcohol / moles of silver carbonate). Number) is in the range of 10-63.9.
  • the composite silver nanoparticles CnAgAL produced by chemical reaction have a very small silver core particle size of 1 to 20 nm, preventing collisions between the composite silver nanoparticles in an alcohol solution, and forming secondary particles by aggregation. It is for suppressing. Ten types of composite silver nanoparticles are produced.
  • Table 2 is a list of molecular weights of raw materials for composite silver nanoparticles and the number of moles of 100 g.
  • Specific names of alcohol (C n H 2n + 1 OH) are methanol (CH 3 OH), ethanol (C 2 H 5 OH), propanol (C 3 H 7 OH), butanol (C 4 H 9 OH), pen ethanol (C 5 H 11 OH), hexanol (C 6 H 13 OH), heptanol (C 7 H 15 OH), octanol (C 8 H 17 OH), nonanol (C 9 H 19 OH), Unidekanoru (C 10 H 21 OH).
  • the boiling point BT (° C.) of the alcohol is also shown.
  • FIG. 1 is a production process diagram of composite silver nanoparticles.
  • a mixed solution of a predetermined amount of silver salt powder and a predetermined amount of alcohol is prepared, and the mixed solution is sealed in a reaction vessel.
  • the mixed solution is heated at a generation temperature PT (° C.) for a predetermined time under an Ar gas flow.
  • PT generation temperature
  • the reaction time is preferably within 1 hour.
  • the composite silver nanoparticles start to aggregate with each other and become secondary particles. Therefore, it is desirable to cool rapidly after the reaction.
  • the composite silver nanoparticles are recovered from the reaction solution as a powder.
  • the composite silver nanoparticle is expressed as CnAgAL, which indicates that it is an alkoxide type composite silver nanoparticle.
  • FIG. 2 is a first process diagram of a formation reaction of composite silver nanoparticles according to the present invention.
  • R n in the formula (3) represents a hydrocarbon group C n H 2n + 1 of the alcohol.
  • the carbon number n is limited to 10 of 1 to 9 or 11.
  • Many silver salt fine particles are insoluble in alcohol, and the hydrophilic group OH of alcohol has a property of easily bonding to the surface of the silver salt fine particles.
  • the hydrophobic group R n of the alcohol has a high affinity with alcohol solvent.
  • Equation (4) silver carbonate (Ag 2 CO 3) is shown as a silver salt.
  • FIG. 3 is a second process diagram of a formation reaction of composite silver nanoparticles according to the present invention.
  • silver carbonate is used as a silver salt.
  • Silver carbonate on the surface of the silver carbonate fine particles reacts with alcohol to form aldehyde R n-1 CHO simultaneously with silveration, as shown in formula (5).
  • aldehyde has a strong reducing action, and as shown in formula (7), silver carbonate is reduced to form carboxylic acid R n-1 COOH simultaneously with silveration.
  • FIG. 4 is a high-resolution transmission electron microscope diagram of C2AgAL.
  • the composite silver nanoparticles C2AgAL were produced in a monodispersed state at a production temperature PT of 65 ° C., and photographed with a high resolution transmission electron microscope.
  • Lattice images consisting of parallel lines were observed in the silver nuclei, confirming that the silver nuclei were single crystals.
  • the lattice spacing of the lattice image is 0.24 nm, which matches the (111) plane spacing of the bulk silver crystal, confirming that the silver nucleus is a silver single crystal.
  • FIG. 5 is a high resolution transmission electron microscope diagram of C4AgAL.
  • the composite silver nanoparticle C4AgAL was produced in a monodispersed state at a production temperature PT of 80 ° C., and was photographed with a high resolution transmission electron microscope.
  • Lattice images consisting of parallel lines were observed in the silver nuclei, confirming that the silver nuclei were single crystals.
  • the lattice spacing of the lattice image was 0.24 nm, which coincided with the (111) plane spacing of the bulk silver crystal, and it was confirmed that the silver nucleus was a silver single crystal.
  • the organic coating layer is strongly decomposed and diffused at the DTA peak temperature T2, and the temperature at which the diffusion is completed corresponds to the metallization temperature T3.
  • TG curve thermogravimetric measurement curve
  • T1 ⁇ T2 ⁇ T3 is generally established, and it has become clear from the numerous experiments conducted by the present inventors that there is a relationship of T2-60 ⁇ T1 ⁇ T2. In other words, it was found that the TG decrease start temperature T1 is within 60 ° C. below the DTA peak temperature T2, and at the same time, is not more than the DTA peak temperature T2.
  • the DTA curve is a differential thermal analysis curve
  • the TG curve is a thermogravimetric curve.
  • TG decrease start temperature T1 103 ° C.
  • DTA peak temperature T2 120 ° C.
  • metallization temperature (silvering temperature) T3 122 ° C. It is also clear that the relationship of T2-60 ⁇ T1 ⁇ T2 is established.
  • the generation temperatures PT of the 10 types of composite silver nanoparticles CnAgAL were all 100 ° C. or lower, and as a result, the DTA peak temperature T2 was also suppressed to 150 ° C. or lower.
  • the metallization temperature T3 is slightly higher than the DTA peak temperature T2, it was shown that the metallization temperature T3 is also 150 ° C. or less.
  • CnAgAL is produced by keeping an alcohol solution at a constant production temperature PT, and since the boiling point of the alcohol is constant in the atmosphere, the production temperature PT can be easily kept at the boiling point BT by reacting the alcohol in a boiling state. . Since the alcohol boiling point of C1 to C3 is 100 ° C. or less, it means that three types of CnAgAL with 1 ⁇ n ⁇ 3 can be produced by alcohol boiling reaction. Of course, other temperature control methods can be used.
  • Table 4 shows the range of the TG decrease start temperature T1 of the composite silver nanoparticles CnAgAL. Table 4 shows the temperatures of T2-60, T1 and T2 with respect to C1 to C9 and C11. As a result, it was found that T2-60 ⁇ T1 ⁇ T2 holds for 10 types of composite silver nanoparticles.
  • FIG. 8 is a production process diagram of composite silver nanopaste.
  • a predetermined weight percent of composite silver nanoparticle CnAgAL powder, a predetermined weight percent of silver fine particle Ag powder, and a predetermined weight percent of resin are prepared, and these three components are put into a mixing container.
  • the resin is fluidized by heating to 40 ° C. in a mixing container, and the paste is uniformly mixed.
  • a rotation-revolution centrifuge that performs rotation at 700 rpm and revolution at 2000 rpm was used. If the heating temperature is about 40 ° C., the temperature is naturally raised by frictional heat, and therefore a forced heating operation is unnecessary. However, when it is 40 ° C. or higher, it can be efficiently fluidized by heating with a heater. Thereafter, the composite silver nanopaste is rapidly cooled, solidified and recovered. By solidification, the uniformly dispersed composite silver nanoparticles and silver fine particles are fixed by the resin and do not aggregate during storage.
  • a method in which the manufacturing process of FIG. 8 is modified is also adopted.
  • a paste intermediate is produced by mixing a predetermined weight% of composite silver nanoparticles CnAgAL powder and a predetermined weight% of resin while heating.
  • a predetermined weight percent of silver fine particle Ag powder is uniformly mixed with this paste intermediate while heating to produce a composite silver nanopaste, which is rapidly cooled to solidify.
  • frictional heat is used, forced heating is not necessary.
  • the composite silver nanoparticles are uniformly dispersed in the resin, and then the silver fine particles are uniformly dispersed. Therefore, the composite silver nanoparticles and the silver fine particles are dispersed independently, and uniform to eliminate the interaction between the two. It is characterized by further increasing dispersibility.
  • a paste intermediate is produced by mixing a predetermined weight% of silver fine particle Ag powder and a predetermined weight% of resin while heating.
  • a predetermined weight percent of composite silver nanoparticle CnAgAL powder is uniformly mixed with this paste intermediate while heating to produce a composite silver nanopaste, which is rapidly cooled to solidify.
  • frictional heat is used, forced heating is not necessary.
  • the silver fine particles are first uniformly dispersed in the resin, and then the composite silver nanoparticles are uniformly dispersed. Therefore, the composite silver nanoparticles and the silver fine particles are independently dispersed to eliminate the interaction between the two. Uniform dispersibility is further increased. Of course, when silver fine particles are not added, it is needless to say that only uniform mixing of CnAgAL and resin is sufficient.
  • IBCH Isobornylcyclohexanol
  • ICBH cyclohexanol
  • Table 5 is an exemplary table of resins used in the present invention.
  • IBCH is a so-called rosin-like, has no fluidity at room temperature, and has a property of fluidizing rapidly by heating.
  • Glycerin has a lower viscosity than ICBH and is in the form of a so-called syrup, but has a melting point of 17 ° C., and thus solidifies at 10 ° C. in an environment without moisture. Therefore, glycerin almost loses its fluidity when cooled to the refrigerator temperature or lower, and fluidizes when heated, so that it can be used as the resin of the present invention in the same manner as IBCH.
  • Both ICBH and glycerin are decomposed and diffused by firing in the air, and no carbides remain.
  • a substance that is solid at room temperature of 10 ° C. or less, has a property of being liquefied when it is 40 ° C. or more, and completely disperses when baked can be used as the resin of the present invention.
  • higher alcohols having 14 or more carbon atoms can be used, and myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol and the like are listed. Their melting points are as shown in Table 3. Needless to say, resins similar to those described above can also be used as the resin of the present invention.
  • Table 6 is a relationship table between viscosity and temperature of IBCH. Since it is 150,000 centipoise (cP) at 30 ° C or lower, naturally it does not have fluidity even at 10 ° C, but when it reaches 40 ° C or higher, especially 50 ° C or higher, fluidity is rapidly developed and is optimal for the present invention Resin.
  • cP centipoise
  • FIG. 9 is a characteristic diagram of viscosity and temperature of IBCH.
  • the relationship between the viscosity and the temperature shown in Table 6 is plotted, and it can be seen that IBCH has a property of changing with temperature so rapidly that the viscosity is displayed on the logarithmic axis. All resins having such properties and having the property of being completely diffused by firing can be used in the present invention.
  • FIG. 10 is a thermal analysis diagram of IBCH with a temperature increase rate of 3 ° C./min. From DTA, the complete evaporation temperature is 205 ° C., and from TG, the weight is found to be 0% at 205 ° C., and it is proved that the entire amount has evaporated and disappeared.
  • Table 7 is a relationship table between the temperature increase rate of IBCH and the evaporation temperature.
  • a temperature increase rate of 3 (° C./min) means a program temperature increase in which the temperature is increased while increasing by 3 ° C. per minute.
  • the evaporation temperature decreases as the temperature increase rate decreases, and the evaporation temperature increases as the temperature increase rate increases. This property can be said to be a property of TG / DTA measurement.
  • FIG. 11 is a graph showing the relationship between the evaporation temperature of IBCH and the temperature rise rate. The relationship between the evaporation temperature shown in Table 7 and the temperature rising rate is plotted. Based on this graph, the evaporation rate can be arbitrarily adjusted by adjusting the temperature increase rate.
  • Table 8 is a relationship table between glycerin viscosity and temperature. At 0 ° C., it is 12100 centipoise (cP). Upon further cooling, the viscosity increases rapidly and becomes non-flowing. On the other hand, when the temperature is set to 10 ° C. or higher, the viscosity becomes 3900 (cP) or lower and exhibits fluidity. At this level of viscosity, the non-flowability may be considered to be small, but these viscosities are open to the atmosphere and absorb moisture. In particular, the melting point of glycerin is 17 ° C., and in an environment without moisture, it becomes solid when it becomes 17 ° C. or lower.
  • non-fluidity at 10 ° C. or lower. While IBCH exhibits a slightly high temperature resin characteristic, glycerin is a resin that exhibits a low temperature resin characteristic, and by appropriately using both, non-fluidity / fluidity change can be realized. As described above, non-fluidity means non-aggregation of composite silver nanoparticles.
  • FIG. 12 is a characteristic diagram of viscosity and temperature of glycerin.
  • the relationship between the viscosity and the temperature shown in Table 8 is plotted, and it can be seen that the glycerin resin also has a property of rapidly changing with respect to temperature as the viscosity is displayed on the logarithmic axis. All resins having such properties and having the property of being completely diffused by firing can be used in the present invention.
  • Table 9 is a list of alcohols used as solvents.
  • the composite silver nanoparticles have the property of dissolving very well in alcohol.
  • the alcohol methanol, ethanol, butanol, hexanol, and octanol can be used.
  • organic solvents such as acetone, ether, benzene, ethyl acetate, terpineol, dihydroterpineol, butyl carbitol, cellosolve and the like can be used.
  • the addition of a solvent reduces the silver content and causes agglomeration of composite silver nanoparticles and silver fine particles when it is made into a fluid paste, so a non-fluid paste without a solvent during storage and storage. It is recommended to add a solvent just before coating. Even when the storage period is very short, there is a possibility of aggregation, and therefore the addition of a solvent immediately before coating is desired. Even when a solvent is added, the amount added is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1 to 2% by mass.
  • Example 11 to 113 Three types of composite silver nanopastes of C1 to C9 and C11]
  • a composite silver nanopaste was prepared using the composite silver nanoparticles.
  • the following three types of pastes were prepared from C1 to C9 and C11 CnAgAL, respectively.
  • One of the three types of CnAgAL was CnAgAL having a metallization temperature T3 shown in Table 3, and the other two were CnAgALs having another slightly different metallization temperature T3.
  • CnAgAL having a metallization temperature T3 above 150 ° C. is also used.
  • the solvent was selected from methanol, ethanol, butanol, xylene, and toluene.
  • the resin was selected from IBCH, glycerin, myristyl alcohol (C 14 H 29 OH), palmityl alcohol (C 16 H 33 OH), stearyl alcohol (C 18 H 37 OH).
  • the particle size of the silver particles, the type of solvent, the type of resin, the mass% of each component, and the paste baking temperature in the atmosphere are as described in Tables 10 and 11.
  • the resin is first heated to 50 ° C. and fluidized, CnAgAL powder is mixed and kneaded in this, and cooled to 10 ° C. or lower after kneading.
  • a non-flowable paste was prepared.
  • this non-flowable paste is heated to 50 ° C. to be fluidized and applied to the test surface.
  • the atmospheric paste firing temperature T is set higher than the metallization temperature T3 of CnAgAL. This is because it is necessary not only to metallize CnAgAL but also to evaporate the solvent and evaporate or decompose the resin. In addition, if the CnAgAL paste is baked at a temperature higher than the metallization temperature T3, an excellent metal film can be formed and a silver film having high electrical conductivity can be formed. The excellence of the silver film increases as the firing temperature T in the atmosphere increases. Therefore, as shown in Tables 10 and 11, the atmospheric paste firing temperature T was set higher than the metallization temperature T3.
  • FIG. 13 is a thermal analysis diagram of the C2AgAL paste of Example 23.
  • peaks up to 150 ° C. indicate that IBCH has evaporated.
  • the step up to 175 ° C. shows the decomposition and diffusion of the organic coating layer of C2AgAL. This fact is also understood from the fact that the TG step and the DTA peak coincide.
  • FIG. 14 is a thermal analysis diagram of the C4AgAL paste of Example 43.
  • peaks up to 150 ° C. indicate that IBCH has evaporated.
  • the step up to 175 ° C. shows the decomposition and diffusion of the organic coating layer of C4AgAL. This fact is also understood from the fact that the TG step and the DTA peak coincide.
  • FIG. 15 is a thermal analysis diagram of the C6AgAL paste of Example 63.
  • peaks up to 150 ° C. indicate that IBCH has evaporated.
  • the step up to 195 ° C. shows the decomposition and diffusion of the organic coating layer of C6AgAL. This fact can be understood from the fact that the TG step and the DTA peak coincide.
  • Example 114 Joining of semiconductor electrode and circuit board
  • a bonding test was performed with the semiconductor chip as the upper body and the circuit board as the lower body.
  • the electrode end of the semiconductor chip was inserted into the through hole of the circuit board, and the composite silver nanopaste of Example 11 to Example 113 was applied to the contact part between them to obtain 30 types of paste specimens.
  • the said coating part was heated locally with the paste baking temperature T of Table 10 and Table 11, the said coating part was metalized, and joining was completed. After cooling, when the appearance of the joint was inspected with an optical microscope, there were no problems with 30 types of specimens. An electrical continuity test and an electrical resistance measurement were performed, and it was confirmed that it functions effectively as an alternative solder. From the 30 types of bonding tests, it was found that the composite silver nanopaste according to the present invention can be used industrially as an alternative solder.
  • Example 115 Formation of silver pattern on heat-resistant glass substrate
  • the composite silver nanopastes of Examples 11 to 113 were screen-printed on the base to obtain 30 types of test bodies on which a predetermined paste pattern was formed.
  • the said test body was heated with the atmospheric paste baking temperature T of Table 10 and Table 11 with the electric furnace, and the silver pattern was formed from the said paste pattern.
  • T of Table 10 and Table 11 with the electric furnace
  • the silver pattern was formed from the said paste pattern.
  • After cooling when the surface of the silver pattern was inspected with an optical microscope, there were no problems with 30 types of specimens. From the 30 types of pattern formation tests, it was found that the composite silver nanopaste according to the present invention can be used industrially as a silver pattern forming material.
  • a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms is composed of one or more alcohol molecule residues, alcohol molecule derivatives or alcohol molecules having 1 to 9 or 11 carbon atoms.
  • a metallic component containing at least composite silver nanoparticles having an organic coating layer is mixed with a resin. The resin is in a non-flowing state at 10 ° C. or lower, and the metallic component is held in a dispersed state.
  • a composite silver nanopaste that can be fluidized and applied is provided.
  • a paste that prevents aggregation of composite silver nanoparticles by non-fluidity and develops coating performance by heat fluidity is provided.
  • the composite silver nanopaste of the present invention can be used for electronic materials such as alternative solder, printed wiring, and conductive materials, magnetic materials such as magnetic recording media, electromagnetic wave absorbers, and electromagnetic resonators, far-infrared materials, and composite film forming materials. It can be applied to pastes in various fields such as structural materials, ceramics / metal materials such as sintering aids / coating materials, and medical materials.

Abstract

The invention provides a technique of converting C1-9 or C11 composite silver nanoparticles into a paste by the use of a resin exhibiting non-fluidity at 10°C or below in order to inhibit the nanoparticles from agglomeration in storage, that is, a non-fluid paste of such nanoparticles. A composite silver nanopaste prepared by mixing a metal component containing as the essentials composite silver nanoparticles constituted of both silver cores which are made of silver atom aggregates and have a mean particle diameter of 1 to 20nm and organic coats which cover the cores respectively and are made of at least one member selected from among alcohol residues, alcohol molecule derivatives and alcohol molecules which each contain 1 to 9 or 11 carbon atoms with a resin, characterized in that at 10°C or below, the resin is in a non-fluid state to keep the metal component in a dispersed state, while on heating, it can be fluidized to permit coating.

Description

複合銀ナノペースト、その製法、接合方法及びパターン形成方法Composite silver nanopaste, manufacturing method thereof, bonding method and pattern forming method
　本発明は、多数の銀原子からなる銀核の周囲に有機物からなる有機被覆層を形成した複合銀ナノ粒子を成分とするペーストに関し、更に詳細には、前記ペーストを塗着して焼成することにより前記有機被覆層や他の有機成分を気散させて銀膜を形成し、この銀膜により半導体接合や電極パターンを形成する複合銀ナノペースト、その製法、接合方法及びパターン形成方法に関する。 The present invention relates to a paste composed of composite silver nanoparticles in which an organic coating layer made of an organic substance is formed around a silver nucleus made of a large number of silver atoms. More specifically, the paste is applied and fired. The present invention relates to a composite silver nanopaste in which the organic coating layer and other organic components are diffused to form a silver film, and a semiconductor junction and an electrode pattern are formed from the silver film, a manufacturing method thereof, a bonding method, and a pattern formation method.
　一般に、半導体、電子回路、電子機器などは各種の電子部品を基板に半田で溶融固定して電気的導通性を確保している。しかし、従来の半田はＳｎとＰｂの合金であり、近年の環境保全対策としてＰｂの使用が禁止されつつあるため、前記従来半田に替わるＰｂフリーの代替半田の開発が要望されている。 Generally, in semiconductors, electronic circuits, electronic devices, etc., various electronic components are fused and fixed to a substrate with solder to ensure electrical continuity. However, the conventional solder is an alloy of Sn and Pb, and the use of Pb is being prohibited as a recent environmental preservation measure. Therefore, development of a Pb-free alternative solder that replaces the conventional solder is desired.
　代替半田の特性として、Ｐｂを含有しないことは当然であるが、その他に熱伝導性が高く、融点が低く、電気伝導度が高くしかも安全性が高いことが要望されている。この期待に応える素材として銀が注目され、超微粒子として複合銀ナノ粒子が開発されるに到った。 As a characteristic of the alternative solder, it is natural that Pb is not contained, but there are other demands for high thermal conductivity, low melting point, high electrical conductivity and high safety. Silver has attracted attention as a material that meets this expectation, and composite silver nanoparticles have been developed as ultrafine particles.
　まず、特許文献１として特許第３２０５７９３号公報が公開された。出発物質として銀有機化合物（特に銀有機錯体）が選択された。空気を遮断した不活性ガス雰囲気下で、前記銀有機化合物を分解開始温度以上で、且つ完全分解温度未満の温度で加熱し、分解還元された銀核の周囲に前記銀有機化合物の被覆層を有した複合銀ナノ粒子が製造された。銀核の粒径は１～１００ｎｍであり、そのため通称で複合銀ナノ粒子と称される。具体的には、ステアリン酸銀１００ｇを窒素気流下のフラスコ内で２５０℃で４時間加熱すると、粒径５ｎｍの銀核を有する複合銀ナノ粒子が生成された。 First, Japanese Patent No. 3205793 was published as Patent Document 1. Silver organic compounds (especially silver organic complexes) were selected as starting materials. The silver organic compound is heated at a temperature higher than or equal to the decomposition start temperature and lower than the complete decomposition temperature in an inert gas atmosphere in which air is shut off, and the coating layer of the silver organic compound is formed around the decomposed and reduced silver core. Composite silver nanoparticles were produced. The particle size of silver nuclei is 1 to 100 nm, and is therefore commonly referred to as composite silver nanoparticles. Specifically, when 100 g of silver stearate was heated at 250 ° C. for 4 hours in a flask under a nitrogen stream, composite silver nanoparticles having a silver nucleus with a particle size of 5 nm were generated.
　前記製法では、ステアリン酸銀を溶媒無しの固相法で加熱するため、生成された複合銀ナノ粒子の銀核がたとえ５ｎｍであっても、多数の複合銀ナノ粒子が団子状態に結合して大きな２次粒子になる欠点がある。しかもステアリン酸銀を出発物質とするため、銀核の周囲に炭素数１７のステアリン酸基が有機被覆層となり、銀含有率が小さくなる欠点を有していた。 In the manufacturing method, since silver stearate is heated by a solid phase method without a solvent, even if the silver nuclei of the generated composite silver nanoparticles are 5 nm, a large number of composite silver nanoparticles are bound in a dumpling state. There is a drawback of becoming large secondary particles. In addition, since silver stearate is used as a starting material, a stearic acid group having 17 carbon atoms around the silver core becomes an organic coating layer, which has the disadvantage that the silver content is reduced.
　そこで、特許文献２としてＷＯ００／０７６６９９号公報が公開された。本発明者はこの国際公開公報の発明者の一人である。この公開公報には複数の発明が開示されているが、その中でも金属無機化合物を界面活性剤を用いて処理する方法が重要である。即ち、金属無機化合物を界面活性剤を用いて非水系溶媒中でコロイド化して超微粒子前駆体を形成する第１工程と、このコロイド溶液中に還元剤を添加して前記超微粒子前駆体を還元し、金属核の外周に界面活性剤殻を被覆層として形成した複合金属ナノ粒子を生成する第２工程から構成される。 Therefore, WO 00/076699 was published as Patent Document 2. The inventor is one of the inventors of this international publication. A plurality of inventions are disclosed in this publication, and among them, a method of treating a metal inorganic compound with a surfactant is important. That is, a first step of colloiding a metal inorganic compound with a surfactant in a non-aqueous solvent to form an ultrafine particle precursor, and a reducing agent is added to the colloidal solution to reduce the ultrafine particle precursor. And a second step of generating composite metal nanoparticles in which a surfactant shell is formed as a coating layer on the outer periphery of the metal core.
　前記方法は、非水系溶媒に金属無機化合物を溶解させるから、生成した複合金属ナノ粒子同士が非水系溶媒中に分散し、団子状態になり難い特徴を有している。しかし、添加した界面活性剤は炭素数が大きいため、有機被覆層である界面活性剤殻の炭素数は当然大きく、界面活性剤殻を焼成して気散させる温度、即ち焼成温度が高くなる欠点があった。 The above-described method has a feature that since the metal inorganic compound is dissolved in a non-aqueous solvent, the produced composite metal nanoparticles are dispersed in the non-aqueous solvent and are not likely to be in a dumpling state. However, since the added surfactant has a large number of carbon atoms, the number of carbon atoms in the surfactant shell, which is an organic coating layer, is naturally large, and the temperature at which the surfactant shell is baked to disperse, that is, the firing temperature is increased. was there.
　このような中で、複合銀ナノ粒子の研究が進展し、特許文献３としてＷＯ０１／０７０４３５号公報が公開された。この公開公報中で、炭酸銀とミリスチン酸（Ｃ数は１４）から複合銀ナノ粒子ができたと記載されている。また、炭酸銀とステアリルアルコール（Ｃ数は１８）から複合銀ナノ粒子が生成されたことが記載されている。しかし、ミリスチン酸（Ｃ数は１４）もステアリルアルコール（Ｃ数は１８）も炭素数が大きいため、銀化させるための焼成温度が高くなる欠点があることは云うまでもない。 Under such circumstances, research on composite silver nanoparticles has progressed, and WO 01/070435 has been published as Patent Document 3. In this publication, it is described that composite silver nanoparticles are made from silver carbonate and myristic acid (C number is 14). Further, it is described that composite silver nanoparticles were produced from silver carbonate and stearyl alcohol (C number is 18). However, since myristic acid (C number is 14) and stearyl alcohol (C number is 18) have a large carbon number, it goes without saying that there is a disadvantage that the firing temperature for silvering becomes high.
特許第３２０５７９３号公報Japanese Patent No. 3205793 ＷＯ００／０７６６９９号公報WO00 / 076699 ＷＯ０１／０７０４３５号公報WO01 / 070435 特許第３６３８４８６号公報Japanese Patent No. 3638486 特許第３６３８４８７号公報Japanese Patent No. 3638487
　本発明者等は、銀化温度を低下させるために、炭酸銀とＣ１～Ｃ９又はＣ１１のアルコールを反応させて、銀核の周囲にアルコール残基からなる銀アルコキシド型複合銀ナノ粒子を生成することに成功した。 In order to lower the silvering temperature, the present inventors react silver carbonate with C1-C9 or C11 alcohol to produce silver alkoxide-type composite silver nanoparticles consisting of alcohol residues around the silver nucleus. Succeeded.
　このようにして得られたＣ１～Ｃ９又はＣ１１の複合銀ナノ粒子は、特許文献３で得られたＣ１４又はＣ１８の複合銀ナノ粒子よりも、銀化温度が低くなることは当然である。炭素数が小さくなる結果、銀化温度が低下すると同時に、銀含有率が増大する利点がある。 The C1 to C9 or C11 composite silver nanoparticles obtained in this way are naturally lower in silvering temperature than the C14 or C18 composite silver nanoparticles obtained in Patent Document 3. As a result of the decrease in the number of carbon atoms, there is an advantage that the silver content increases while the silvering temperature decreases.
　そこで、本発明者等は、前記Ｃ１～Ｃ９又はＣ１１の複合銀ナノ粒子を用いてペーストを作製することにした。このペーストを用いて、素材を接合して電子部品を組み立てたり、また基板上に電極パターンを形成する試験を行い、ペーストの有効性を確認する。ペーストを用いた接合方法については、下記の２件の従来特許公報が存在する。 Therefore, the present inventors decided to prepare a paste using the composite silver nanoparticles of C1 to C9 or C11. This paste is used to assemble the electronic parts by joining the materials, or to test the formation of the electrode pattern on the substrate to confirm the effectiveness of the paste. Regarding the bonding method using paste, there are the following two conventional patent publications.
　特許文献４として、特許第３６３８４８６号公報が公開されている。ここには、平均粒径が１～１０ｎｍの実質的に金属成分からなるコア部の周囲を、炭素数が５以上の有機物からなる被覆層で被覆した複合金属超微粒子を予め作製し、該複合金属超微粒子を溶媒に分散させて金属ペーストを調整する工程と、該金属ペーストを回路基板の端子電極上に付着させて主に複合金属超微粒子からなる金属ペーストボールを形成する工程と、該金属ペーストボール上にフェイスダウン法を用いて半導体素子の電極を接合する工程と、低温焼成により半導体素子と回路基板とを電気的に接続する工程が記載されている。 Japanese Patent No. 3638486 is disclosed as Patent Document 4. Here, composite metal ultrafine particles in which the periphery of a core portion substantially composed of a metal component having an average particle diameter of 1 to 10 nm is coated with a coating layer composed of an organic substance having 5 or more carbon atoms are prepared in advance, and the composite Preparing a metal paste by dispersing metal ultrafine particles in a solvent, attaching the metal paste onto a terminal electrode of a circuit board to form a metal paste ball mainly composed of composite metal ultrafine particles, and the metal There are described a step of bonding electrodes of a semiconductor element on a paste ball using a face-down method and a step of electrically connecting the semiconductor element and a circuit board by low-temperature firing.
　また、特許文献５として、特許第３６３８４８７号公報が公開されている。この特許公報には、平均粒径が１～１０ｎｍの実質的に金属成分からなるコア部の周囲を、炭素数が５以上の有機物からなる被覆層で被覆した複合金属超微粒子を予め作製し、該複合金属超微粒子を溶媒に分散させて金属ペーストを調整する工程と、該金属ペーストを半導体素子の電極上に付着させ低温焼成して超微粒子電極を作製する工程と、該超微粒子電極上にはんだバンプを形成する工程と、該はんだバンプを回路基板の端子電極に加熱融着する工程が開示されている。 Also, as patent document 5, Japanese Patent No. 3638487 is disclosed. In this patent publication, composite metal ultrafine particles in which the periphery of a core portion substantially composed of a metal component having an average particle diameter of 1 to 10 nm is coated with a coating layer composed of an organic substance having 5 or more carbon atoms are prepared in advance. A step of preparing a metal paste by dispersing the composite metal ultrafine particles in a solvent, a step of depositing the metal paste on an electrode of a semiconductor element and firing at a low temperature to produce an ultrafine particle electrode, A process of forming a solder bump and a process of heat-sealing the solder bump to a terminal electrode of a circuit board are disclosed.
　前記特許文献４、５には、複合金属超微粒子を溶媒に分散させて金属ペーストを調整することが記載され、特に特許文献４の請求項３には、導電率が高い金属に溶媒に加えて樹脂分が添加される金属ペーストが記載されている。両文献には、溶媒としてトルエンのみが例示されており、特許文献４、５の溶媒とは粘性を低下させてペーストを溶液状にする役割が付与されている。前記樹脂分は粘性を増加させるために添加されるものであり、溶媒と樹脂分を適当量添加して所定粘性のペーストが作製されることになる。 Patent Documents 4 and 5 describe that composite metal ultrafine particles are dispersed in a solvent to prepare a metal paste. In particular, claim 3 of Patent Document 4 includes a metal having high conductivity in addition to a solvent. A metal paste to which a resin component is added is described. In both documents, only toluene is exemplified as a solvent, and the roles of Patent Documents 4 and 5 are imparted with a role of reducing the viscosity to make the paste into a solution. The resin component is added to increase the viscosity, and an appropriate amount of solvent and resin component is added to produce a paste having a predetermined viscosity.
　前記特許文献４及び５に従って、本発明者も、前述したＣ１～Ｃ９又はＣ１１の複合銀ナノ粒子をトルエンに溶解させてペーストを作製した。前記ペーストは、基板や半導体電極に塗着し易いように、室温で傾斜させたときに自然に流下する程度の粘性に調製された。前記ペーストは、２週間だけ室温下で容器内に保管された。２週間の保管後、回路基板に膜厚１μｍのペースト膜をスクリーン印刷法で形成し、電気炉内で３５０℃・２０分間の焼成を行って、ペースト膜から銀膜に成形した。 In accordance with Patent Documents 4 and 5, the present inventor also prepared a paste by dissolving the above-mentioned C1 to C9 or C11 composite silver nanoparticles in toluene. The paste was prepared to have a viscosity that allowed it to flow naturally when tilted at room temperature so that it could be easily applied to a substrate or semiconductor electrode. The paste was stored in a container at room temperature for only 2 weeks. After storage for 2 weeks, a paste film having a thickness of 1 μm was formed on the circuit board by screen printing, and baked in an electric furnace at 350 ° C. for 20 minutes to form the paste film into a silver film.
　光学顕微鏡と電子顕微鏡を用いて、前記銀膜の表面及び断面が観察された。その結果、銀膜表面に多少の凹凸が発見された。３５０℃の焼成では、有機物は全て気散するが、銀核は溶融せず、表面融解して銀核同士が焼結して銀膜が形成される。従って、銀核が大きければ、表面の凹凸は増幅されることになる。つまり、前記表面の凹凸は、大きな銀核同士の焼結により形成されたものと考えられた。大きな銀核が形成された理由は、２週間の保管中に、ペースト内で複合銀ナノ粒子が相互に凝集して２次粒子化して団子粒子が形成された結果だと考えられる。凝集を防止するために、分散剤や界面活性剤をペーストに添加すると、ペースト中の銀含有率が低下し、また界面活性剤は３５０℃では完全に気散せず、銀膜中に有機物が残留する事態もある。従って、ペーストに余分な有機物を添加することは、低温焼成を視野におく限り、極力避けることが必要である。 The surface and cross section of the silver film were observed using an optical microscope and an electron microscope. As a result, some irregularities were found on the surface of the silver film. In the baking at 350 ° C., all organic substances are diffused, but the silver nuclei are not melted, but the surface is melted and the silver nuclei are sintered to form a silver film. Therefore, if the silver nuclei are large, the surface irregularities will be amplified. That is, it was considered that the unevenness on the surface was formed by sintering between large silver nuclei. The reason for the formation of large silver nuclei is considered to be the result of composite silver nanoparticles agglomerating with each other in the paste to form secondary particles during storage for 2 weeks. When a dispersant or a surfactant is added to the paste to prevent agglomeration, the silver content in the paste decreases, and the surfactant does not completely dissipate at 350 ° C., and organic substances are not present in the silver film. There is also a situation that remains. Therefore, it is necessary to avoid adding extra organic matter to the paste as much as possible as long as low temperature firing is considered.
　複合銀ナノ粒子が溶媒添加前に凝集していた可能性もあるから、複合銀ナノ粒子を事前に乳鉢で微細に磨り潰して単分散化し、その後に溶媒を添加してペーストを作製した。このペーストを２週間置いた後、回路基板上にペースト膜を形成し、３５０℃で２０分間の焼成を行った。電子顕微鏡で観察したところ、銀膜表面の凹凸は多少改善されていたが、まだ凹凸が残留していた。 Since the composite silver nanoparticles may have aggregated before the addition of the solvent, the composite silver nanoparticles were finely ground in advance in a mortar to be monodispersed, and then the solvent was added to prepare a paste. After leaving this paste for 2 weeks, a paste film was formed on the circuit board and baked at 350 ° C. for 20 minutes. When observed with an electron microscope, the irregularities on the surface of the silver film were somewhat improved, but the irregularities still remained.
　以上の結果から、複合銀ナノ粒子を溶媒と混合して流動状態で保管すると、複合銀ナノ粒子同士の凝集が生起して２次粒子化し、保管時間が長くなるに従って、２次粒子の粒径が増加するという結論が得られた。この結果は、複合銀ナノ粒子を粘性の小さなトルエン等の溶媒に添加して、室温で流動性を有した流動性ペーストにし、前記流動性ペーストを量産して長期間に亘って貯蔵することの問題点を浮き彫りにした。 From the above results, when the composite silver nanoparticles are mixed with a solvent and stored in a fluidized state, the composite silver nanoparticles agglomerate into secondary particles, and the particle size of the secondary particles increases as the storage time increases. The conclusion is reached that increases. The result is that the composite silver nanoparticles are added to a solvent such as toluene having a small viscosity to form a fluid paste having fluidity at room temperature, and the fluid paste is mass-produced and stored for a long period of time. The problem was highlighted.
　従って、本発明の目的は、Ｃ１～Ｃ９又はＣ１１の複合銀ナノ粒子を凝集しない形態でペースト化する技術、つまり非凝集性ペーストを提供し、その非凝集性を非流動性の樹脂により実現した非流動性ペーストを提供することである。また、その非流動性ペーストの製造方法を提供し、同時に非流動性ペーストを利用した接合方法及びパターン形成方法を提供することである。 Therefore, the object of the present invention is to provide a technology for pasting C1-C9 or C11 composite silver nanoparticles in a form that does not aggregate, that is, a non-aggregating paste, and realizing the non-aggregating property with a non-flowable resin. It is to provide a non-flowable paste. Moreover, it is providing the manufacturing method of the non-fluid paste, and also providing the joining method and pattern formation method using a non-fluid paste simultaneously.
　本発明は上記課題を解決するためになされたものであり、本発明の第１形態は、銀原子の集合体からなる平均粒径１～２０ｎｍの銀核の周囲に、炭素数１～９又は１１のアルコール分子残基、アルコール分子誘導体又はアルコール分子の一種以上からなる有機被覆層を形成した複合銀ナノ粒子を少なくとも含有する金属成分を樹脂と混合して構成され、前記樹脂は１０℃以下では非流動状態にあって前記金属成分を分散状態に保持し、加熱により流動化して塗着可能になる複合銀ナノペーストである。 The present invention has been made in order to solve the above-mentioned problems, and the first embodiment of the present invention has a carbon number of 1 to 9 or around a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms. 11 composed of a metal component containing at least composite silver nanoparticles formed with an organic coating layer composed of at least one alcohol molecule residue, alcohol molecule derivative or alcohol molecule, and the resin is at 10 ° C. or less. It is a composite silver nanopaste that is in a non-flowing state, holds the metal component in a dispersed state, and is fluidized by heating so that it can be applied.
　本発明の第２形態は、前記第１形態において、前記複合銀ナノ粒子は９５（ｍａｓｓ％）以下であり、前記樹脂は２０（ｍａｓｓ％）以下である複合銀ナノペーストである。 The second form of the present invention is a composite silver nanopaste according to the first form, wherein the composite silver nanoparticles are 95 (mass%) or less and the resin is 20 (mass%) or less.
　本発明の第３形態は、前記第１形態において、前記金属成分として平均粒径０．１～１０μｍの銀微粒子が添加される複合銀ナノペーストである。 A third form of the present invention is a composite silver nanopaste in which silver fine particles having an average particle size of 0.1 to 10 μm are added as the metal component in the first form.
　本発明の第４形態は、前記第３形態において、前記複合銀ナノ粒子は５～８５（ｍａｓｓ％）、前記銀微粒子は８０～１０（ｍａｓｓ％）であり、前記樹脂は２０（ｍａｓｓ％）以下である複合銀ナノペーストである。 According to a fourth aspect of the present invention, in the third aspect, the composite silver nanoparticles are 5 to 85 (mass%), the silver fine particles are 80 to 10 (mass%), and the resin is 20 (mass%). The composite silver nanopaste is as follows.
　本発明の第５形態は、前記第１～第４形態のいずれかにおいて、所望量の溶剤を添加して、１０℃以下でも流動状態化させて塗着可能にする複合銀ナノペーストである。 A fifth aspect of the present invention is a composite silver nanopaste according to any one of the first to fourth aspects, wherein a desired amount of a solvent is added to make it flowable even at 10 ° C. or less and can be applied.
　本発明の第６形態は、１０℃で非流動状態にあり加熱により流動化する樹脂に、銀原子の集合体からなる平均粒径１～２０ｎｍの銀核の周囲に炭素数１～９又は１１のアルコール分子残基、アルコール分子誘導体又はアルコール分子の一種以上からなる有機被覆層を形成した複合銀ナノ粒子及び必要により銀微粒子を金属成分として混合し、加熱下で前記樹脂を流動化させて全体を混練し、混練後に前記樹脂が非流動状態になる温度まで冷却して、前記金属成分を前記樹脂中に分散状態に保持する複合銀ナノペーストの製法である。 In the sixth embodiment of the present invention, a resin that is in a non-flowing state at 10 ° C. and fluidized by heating has a carbon number of 1 to 9 or 11 around silver nuclei having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms. A composite silver nanoparticle formed with an organic coating layer composed of one or more of alcohol molecule residues, alcohol molecule derivatives or alcohol molecules, and if necessary, silver fine particles are mixed as a metal component, and the resin is fluidized under heating to make the whole Is cooled to a temperature at which the resin becomes non-flowing after kneading, and the metal component is kept in a dispersed state in the resin.
　本発明の第７形態は、前記第６形態において、前記銀核の平均粒径が１～２０ｎｍ、前記銀微粒子の平均粒径が０．１～１０μｍである複合銀ナノペーストの製法である。 A seventh aspect of the present invention is a method for producing a composite silver nanopaste according to the sixth aspect, wherein the silver nuclei have an average particle diameter of 1 to 20 nm and the silver fine particles have an average particle diameter of 0.1 to 10 μm.
　本発明の第８形態は、前記第６又は第７形態において、所望量の溶剤を添加して、１０℃以下でも流動状態化させて塗着可能なペーストにする複合銀ナノペーストの製法である。 An eighth aspect of the present invention is a method for producing a composite silver nanopaste according to the sixth or seventh aspect, wherein a desired amount of solvent is added to make a paste that can be applied by being fluidized even at 10 ° C. or lower. .
　本発明の第９形態は、前記第１～第５形態のいずれかの複合銀ナノペーストを用意し、前記複合銀ナノペーストを下体に塗着してペースト層を形成し、前記ペースト層上に上体を配置し、加熱により前記ペースト層を銀化して前記下体と前記上体を接合する接合方法である。 According to a ninth aspect of the present invention, a composite silver nanopaste of any one of the first to fifth aspects is prepared, a paste layer is formed by applying the composite silver nanopaste to a lower body, and the paste layer is formed on the paste layer. In this joining method, the upper body is placed, the paste layer is silvered by heating, and the lower body and the upper body are joined.
　本発明の第１０形態は、前記第１～第５形態のいずれかの複合銀ナノペーストを用意し、前記複合銀ナノペーストを基体の面上に所定パターンに塗着してペーストパターンを形成し、加熱により前記ペーストパターンを銀化して銀パターンを形成するパターン形成方法である。 According to a tenth aspect of the present invention, a composite silver nanopaste according to any one of the first to fifth aspects is prepared, and the composite silver nanopaste is applied to a predetermined pattern on a surface of a substrate to form a paste pattern. And a pattern forming method in which the paste pattern is silvered by heating to form a silver pattern.
　本発明の第１形態によれば、銀原子の集合体からなる平均粒径１～２０ｎｍの銀核の周囲に、炭素数１～９又は１１のアルコール分子残基、アルコール分子誘導体又はアルコール分子の一種以上からなる有機被覆層を形成した複合銀ナノ粒子を用いるから、安価な複合銀ナノペーストを提供できる。前記複合銀ナノ粒子は、安価なＣ１～Ｃ９又はＣ１１のアルコールと、比較的安価な銀塩（例えば、炭酸銀）を出発原料とするから、安価な複合銀ナノ粒子を利用できる。しかも、Ｃ１～Ｃ９のアルコールは、Ｃ１０及びＣ１２のアルコールと比較して、炭素数は比較的小さく、複合銀ナノ粒子における銀含有率が比較的高い特徴がある。また、Ｃ１１はＣ１２よりも炭素数が小さいから、Ｃ１２よりも銀含有率が高い。前記複合銀ナノ粒子は、以下ではＣｎＡｇＡＬ（ｎ＝１～９、１１）と書いたり、Ｃ１ＡｇＡＬ～Ｃ９ＡｇＡＬ、Ｃ１１ＡｇＡＬと書く場合もある。その意味は、炭素数ｎ＝１～９又は１１の銀アルコキシド型の複合銀ナノ粒子である。Ｃ１はメタノール、Ｃ２はエタノール、Ｃ３はプロパノール、Ｃ４はブタノール、Ｃ５はペンタノール、Ｃ６はヘキサノール、Ｃ７はヘプタノール、Ｃ８はオクタノール、Ｃ９はノナノール、Ｃ１１はウニデカノールを意味している。つまり、銀原子の集合体である銀核の周囲に、多数のＣｎアルコキシド基からなる有機被覆層を有する複合銀ナノ粒子をＣｎＡｇＡＬと書く。アルコール残基とは、例えばアルコールをＣｎＨ２ｎ＋１ＯＨと書くと、そのアルコキシド基ＣｎＨ２ｎ＋１Ｏ等を含む概念である。アルコール誘導体とは、例えばＣｎ－１Ｈ２ｎ－１ＣＨＯ、Ｃｎ－１Ｈ２ｎ－１ＣＯＯＨ、Ｃｎ－１Ｈ２ｎ－１ＣＯＯなどを含む概念である。アルコールとはＣｎＨ２ｎ＋１ＯＨ自体を云う。 According to the first aspect of the present invention, an alcohol molecule residue, an alcohol molecule derivative or an alcohol molecule having 1 to 9 or 11 carbon atoms is surrounded by a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms. Since composite silver nanoparticles formed with one or more organic coating layers are used, an inexpensive composite silver nanopaste can be provided. Since the composite silver nanoparticles start from inexpensive C1-C9 or C11 alcohol and a relatively inexpensive silver salt (for example, silver carbonate), inexpensive composite silver nanoparticles can be used. Moreover, the C1 to C9 alcohols are characterized by a relatively small number of carbon atoms and a relatively high silver content in the composite silver nanoparticles compared to the C10 and C12 alcohols. Moreover, since C11 has a carbon number smaller than C12, silver content rate is higher than C12. Hereinafter, the composite silver nanoparticles may be written as CnAgAL (n = 1 to 9, 11), C1AgAL to C9AgAL, or C11AgAL. This means silver alkoxide type composite silver nanoparticles having n = 1-9 or 11 carbon atoms. C1 is methanol, C2 is ethanol, C3 is propanol, C4 is butanol, C5 is pentanol, C6 is hexanol, C7 is heptanol, C8 is octanol, C9 is nonanol, and C11 is unidecanol. That is, the composite silver nanoparticle which has the organic coating layer which consists of many Cn alkoxide groups around the silver nucleus which is an aggregate | assembly of a silver atom is written as CnAgAL. The alcohol residue is a concept including, for example, an alkoxide group C n H 2n + 1 O when the alcohol is written as C n H 2n + 1 OH. The alcohol derivative is a concept including, for example, C n-1 H 2n-1 CHO, C n-1 H 2n-1 COOH, C n-1 H 2n-1 COO, and the like. Alcohol refers to C n H 2n + 1 OH itself.
　本発明に係る複合銀ナノペーストの特徴は、、樹脂の機能に最大の特徴がある。前記樹脂は１０℃以下では非流動状態にあって前記複合銀ナノ粒子と前記銀微粒子を分散状態に保持し、加熱により流動化する性質を有する。前記非流動状態とは、固体状態又は高粘度状態を意味し、前記複合銀ナノ粒子と前記銀微粒子を分散状態に固定的に保持する性質を云う。１０℃以下とは、冷蔵庫内で低温保管する温度領域であり、長期保管では冷蔵庫保管により前記１０℃以下を達成できる。このように冷蔵庫保管する場合には、ペーストは非流動状態にあり、内部に分散した複合銀ナノ粒子や銀微粒子は樹脂によりペースト内で固定され、相互に凝集することはできない。従って、１０℃以下では粒子が相互に凝集することができず、ペースト保存中に粒子相互が凝集して団子化することが完全に防止される。この非流動性ペーストを非凝集性ペーストと称することができる。しかし、例えば４０℃以上に加熱すると、樹脂が液化したり急激に粘性が低下して流動状態になり、ペーストとして対象物に塗着可能になる。従って、本発明のペーストを製造した後は１０℃以下で保存して非凝集化（非流動化）しておく。ペーストを対象物に塗着する直前に加熱して流動化させて流動性ペーストにし、この流動性ペーストを対象物に塗着すれば、金属分（銀分）が凝集していないから極めて緻密な銀膜を形成することが可能になる。余った流動性ペーストは直ちに１０℃以下に冷却すれば、非凝集性ペーストとして長期保存することが出来る。加熱により高粘度から低粘度に変化する樹脂として、例えばイソボルニルシクロヘキサノール（松脂状と称する）やグリセリン（シロップ状と称する）がある。グリセリンの融点は１７℃であるから、乾燥状態で１０℃以下に設定すれば、固化が可能である。１０℃以下で固体であり、加熱すると液化する樹脂として、例えばミリスチルアルコール（Ｃ１４）、パルミチルアルコール（Ｃ１６）、ステアリルアルコール（Ｃ１８）、ベヘニルアルコール（Ｃ２２）といったアルコール類、その他の物質が利用できる。これらの樹脂は、焼成したときに全ての成分が気散するか、又は炭化物などの残留物が極めて少ない性質を有することが必要であり、この性質により焼成により形成される銀膜の電気伝導性や熱伝導性を格段に向上できる。
従って、本発明の樹脂は、通常の化学概念の樹脂ではなく、１０℃で非流動性を発現する物質の総称であり、しかも焼成により全てが気散し、炭化物などの残留物が出現しない物質を意味する。 The characteristic of the composite silver nanopaste according to the present invention is the greatest characteristic in the function of the resin. The resin is in a non-flowing state at 10 ° C. or lower, and has a property of holding the composite silver nanoparticles and the silver fine particles in a dispersed state and fluidizing by heating. The non-flowing state means a solid state or a high-viscosity state, and refers to a property of holding the composite silver nanoparticles and the silver fine particles fixedly in a dispersed state. 10 degrees C or less is a temperature range which carries out low temperature storage in a refrigerator, and the said 10 degrees C or less can be achieved by long-term storage by refrigerator storage. Thus, when storing in a refrigerator, the paste is in a non-flowing state, and the composite silver nanoparticles and silver fine particles dispersed therein are fixed in the paste by the resin and cannot be aggregated with each other. Therefore, at 10 ° C. or lower, the particles cannot be aggregated with each other, and the particles are completely prevented from aggregating and forming a dump during storage of the paste. This non-flowable paste can be referred to as a non-cohesive paste. However, for example, when heated to 40 ° C. or higher, the resin is liquefied or the viscosity is suddenly lowered to be in a fluid state, and can be applied to an object as a paste. Accordingly, after the paste of the present invention is produced, it is stored at 10 ° C. or less and non-aggregated (non-fluidized). Just before applying the paste to the object, it is heated and fluidized to make a fluid paste, and if this fluid paste is applied to the object, the metal (silver) is not agglomerated so it is extremely dense. A silver film can be formed. If the remaining fluid paste is immediately cooled to 10 ° C. or less, it can be stored for a long time as a non-aggregating paste. Examples of the resin that changes from a high viscosity to a low viscosity by heating include isobornylcyclohexanol (referred to as rosin) and glycerin (referred to as syrup). Since the melting point of glycerin is 17 ° C., solidification is possible if it is set to 10 ° C. or lower in a dry state. As resins that are solid at 10 ° C. or lower and liquefy when heated, alcohols such as myristyl alcohol (C14), palmityl alcohol (C16), stearyl alcohol (C18), and behenyl alcohol (C22), and other substances can be used. These resins must have the property that all components are diffused when baked or there are very few residues such as carbides, and due to this property the electrical conductivity of the silver film formed by calcination And thermal conductivity can be greatly improved.
Accordingly, the resin of the present invention is not a resin having a normal chemical concept, but is a generic term for substances that exhibit non-fluidity at 10 ° C., and is a substance in which everything is diffused by firing and residues such as carbides do not appear. Means.
　通常のペーストでは、複合銀ナノ粒子を分散させるために分散剤を添加したり、界面活性剤を添加するが、これらの不純物有機物を添加すると、銀含有量が低下するだけでなく、焼成すると前記不純物有機物から大量のガスが発生し、このガスにより銀膜中に大量のボイド（気泡の抜け孔）が形成され、電気伝導度が低下すると同時に、基体との接合力が低下し、銀膜による接合性能が低下する。これに対し、本発明では樹脂以外の有機物を添加しないから、銀含有率を高く保持できると同時に、発生ガス量が少なく、必然的にボイド数が少なくなり、接合力の増大と電気伝導度及び熱伝導度を増大化できる効果がある。 In a normal paste, a dispersant is added to disperse the composite silver nanoparticles, or a surfactant is added. However, when these impurity organic substances are added, not only the silver content is lowered, but also when fired, A large amount of gas is generated from the impurity organic substance, and a large amount of voids (bubble voids) are formed in the silver film by this gas. At the same time, the electrical conductivity is lowered and the bonding force with the substrate is lowered. Bonding performance is reduced. On the other hand, since organic substances other than resin are not added in the present invention, the silver content can be kept high, and at the same time, the amount of generated gas is small, the number of voids is inevitably reduced, the increase in bonding force and electrical conductivity and There is an effect that the thermal conductivity can be increased.
　本発明の第２形態によれば、前記複合銀ナノ粒子は９５（ｍａｓｓ％）以下であり、前記樹脂は２０（ｍａｓｓ％）以下である複合銀ナノペーストが提供される。最も単純なペースト組成は、複合銀ナノ粒子と樹脂の混合物である。この場合には、銀成分は複合銀ナノ粒子だけであり、その最大質量％は９５ｍａｓｓ％で、樹脂の最小質量％は５ｍａｓｓ％である。複合銀ナノ粒子の質量％の低下に応じて樹脂の質量％を増加させれば良い。しかし、ペースト中の銀含有率は８０ｍａｓｓ％以上が好ましいから、樹脂の質量％は２０ｍａｓｓ％以下に設定されることが望ましい。 According to the second embodiment of the present invention, there is provided a composite silver nanopaste in which the composite silver nanoparticles are 95 (mass%) or less and the resin is 20 (mass%) or less. The simplest paste composition is a mixture of composite silver nanoparticles and resin. In this case, the silver component is only composite silver nanoparticles, the maximum mass% is 95 mass%, and the minimum mass% of the resin is 5 mass%. What is necessary is just to increase the mass% of resin according to the fall of the mass% of a composite silver nanoparticle. However, since the silver content in the paste is preferably 80 mass% or more, the mass% of the resin is preferably set to 20 mass% or less.
　本発明の第３形態によれば、前記金属成分として平均粒径０．１～１０μｍの銀微粒子が添加される複合銀ナノペーストである。本形態では、銀成分として、複合銀ナノ粒子に加えて銀微粒子が添加される。銀微粒子は純銀であり、全く有機物を含有しないから、銀微粒子の添加によりペースト中の銀含有率を増加させることができる。銀微粒子の粒径は０．１～１０μｍであり、前記複合銀ナノ粒子の銀核粒径は１～２０ｎｍであるから、前記複合銀ナノ粒子は銀微粒子間の接着剤の役割を奏すると考えられる。銀微粒子の表面に前記複合銀ナノ粒子が付着し、焼成により有機成分が気散して、表面融解した銀核が表面融解した銀微粒子同士を相互に結合させるのである。換言すれば、大きな銀微粒子間の隙間に複合銀ナノ粒子が集積して、焼成して有機物が気散したときに、銀微粒子間の隙間が銀核によって充填され、しかも銀微粒子相互が銀核によって接着されるため、銀膜自体が緻密に形成されて高強度で高電気伝導性を有する導体が提供される。前述した粒径関係にあると、銀核が銀微粒子同士の隙間を充填し、ガスが気散した後の気泡空洞（ボイド）に銀核が埋め戻される形態になり、ボイド発生数が少なくなる結果、基体との接合強度及び電気伝導度の向上を図ることができる。 According to a third embodiment of the present invention, there is provided a composite silver nanopaste to which silver fine particles having an average particle size of 0.1 to 10 μm are added as the metal component. In this embodiment, silver fine particles are added as the silver component in addition to the composite silver nanoparticles. Since the silver fine particles are pure silver and do not contain any organic matter, the silver content in the paste can be increased by adding silver fine particles. Since the particle diameter of the silver fine particles is 0.1 to 10 μm and the silver nucleus particle diameter of the composite silver nanoparticles is 1 to 20 nm, the composite silver nanoparticles are considered to play a role of an adhesive between the silver fine particles. It is done. The composite silver nanoparticles adhere to the surface of the silver fine particles, the organic components are diffused by firing, and the silver fine particles whose surfaces are melted are bonded to each other. In other words, when the composite silver nanoparticles accumulate in the gaps between the large silver fine particles and the organic matter is diffused by firing, the gaps between the silver fine particles are filled with silver nuclei, and the silver fine particles are Therefore, the silver film itself is densely formed, and a conductor having high strength and high electrical conductivity is provided. When the particle size relationship described above is satisfied, the silver nuclei fill the gaps between the silver fine particles, and the gas nuclei are filled back into the voids (voids) after the gas is diffused, and the number of voids is reduced. As a result, it is possible to improve the bonding strength and electrical conductivity with the substrate.
　本発明の第４形態によれば、前記複合銀ナノ粒子は５～８５（ｍａｓｓ％）、前記銀微粒子は８０～１０（ｍａｓｓ％）であり、前記樹脂は２０（ｍａｓｓ％）以下である複合銀ナノペーストが提供される。この場合、複合銀ナノペーストの組成は、複合銀ナノ粒子と銀微粒子と樹脂である。組成比（ｍａｓｓ％）の境界は、複合銀ナノ粒子：銀微粒子：樹脂＝８５：１０：５～５：８０：１５になるが、前記範囲内である種々の組成比の複合銀ナノペーストが構成される。複合銀ナノ粒子は５～８５（ｍａｓｓ％）であり、５ｍａｓｓ％未満になると銀微粒子同士の接着性能が低下し、８５ｍａｓｓ％以上になると、ペースト中の有機分含有率が過大になる。また、銀微粒子は８０～１０（ｍａｓｓ％）であり、８０ｍａｓｓ％以上になると、複合銀ナノ粒子の含有率が低下して銀微粒子同士の接着性が低下し、１０ｍａｓｓ％以下になると、ペースト中の銀含有率が低下する弱点がある。従って、前記範囲内において、適切な銀含有率を有し、焼成時に気散が効率的に為され、しかもボイド（気泡の抜孔）発生量を適正値に制限した複合銀ナノペーストを調製することができる。 According to the fourth aspect of the present invention, the composite silver nanoparticles are 5 to 85 (mass%), the silver fine particles are 80 to 10 (mass%), and the resin is 20 (mass%) or less. A silver nanopaste is provided. In this case, the composition of the composite silver nanopaste is composite silver nanoparticles, silver fine particles, and a resin. The boundary of the composition ratio (mass%) is composite silver nanoparticle: silver fine particle: resin = 85: 10: 5 to 5:80:15, but composite silver nanopastes having various composition ratios within the above range are used. Composed. The composite silver nanoparticles are 5 to 85 (mass%). When the composite silver nanoparticles are less than 5 mass%, the adhesion performance between the silver fine particles is deteriorated. When the composite silver nanoparticles are 85 mass% or more, the organic content in the paste becomes excessive. Further, the silver fine particles are 80 to 10 (mass%). When the mass is 80 mass% or more, the content of the composite silver nanoparticles is lowered, the adhesion between the silver fine particles is lowered, and when the mass is 10 mass% or less, There is a weak point that the silver content of is reduced. Therefore, within the above range, preparing a composite silver nanopaste having an appropriate silver content, efficiently diffused during firing, and restricting the amount of voids (bubble removal) to an appropriate value Can do.
　本発明の第５形態によれば、所望量の溶剤を添加して、１０℃以下でも流動状態化させて塗着可能にする複合銀ナノペーストが提供される。第１形態では、樹脂だけを添加したペーストが提供され、１０℃以下でペーストを長期保存しても、ペーストには流動性が無いから、この非流動性ペースト内で複合銀ナノ粒子や銀微粒子は固定化され、相互の凝集は発生しない。適当期間だけ非流動性ペーストとして保管した後、ペーストを接合する直前に、本第５形態の溶剤を添加して流動化させ、ディスペンサーにより流動性ペーストを基体に塗着させることができる。非流動性ペーストを流動化させるためには、加熱する場合と、溶剤を添加する場合の二つの方法がある。溶剤を添加する本形態では、ペースト内での有機物含有量が増えるから、焼成によるガスが増大し、ボイド発生量が増える弱点がある。しかし、塗着する直前に溶剤を添加すれば、複合銀ナノ粒子が凝集して２次粒子化（即ち、団子化）することを避けることが可能になる。前記溶剤は、ペーストの粘度を低下させる機能を有し、比較的低温で蒸発する有機溶剤一般を使用することが出来る。例えば、Ｃ１～Ｃ８のアルコール、キシレン、トルエン、アセトン、ヘキサン、その他の溶剤が利用できる。 According to the fifth embodiment of the present invention, there is provided a composite silver nanopaste that can be applied by adding a desired amount of a solvent to make it flowable even at 10 ° C. or lower. In the first form, a paste to which only a resin is added is provided, and even if the paste is stored at a temperature of 10 ° C. or lower for a long period of time, the paste does not have fluidity. Are immobilized and mutual aggregation does not occur. After storing as a non-flowable paste for an appropriate period of time, immediately before joining the paste, the solvent of the fifth embodiment can be added and fluidized, and the flowable paste can be applied to the substrate by a dispenser. In order to fluidize the non-fluid paste, there are two methods: heating and adding a solvent. In the present embodiment in which a solvent is added, since the organic substance content in the paste increases, there is a weak point in which the amount of gas generated by firing increases and the amount of void generation increases. However, if a solvent is added immediately before coating, it is possible to avoid the composite silver nanoparticles from agglomerating into secondary particles (ie, dumpling). The solvent has a function of reducing the viscosity of the paste, and general organic solvents that evaporate at a relatively low temperature can be used. For example, C1-C8 alcohol, xylene, toluene, acetone, hexane, and other solvents can be used.
　本発明の第６形態によれば、１０℃で非流動状態にあり加熱により流動化する樹脂に、銀原子の集合体からなる平均粒径１～２０ｎｍの銀核の周囲に炭素数１～９又は１１のアルコール分子残基、アルコール分子誘導体又はアルコール分子の一種以上からなる有機被覆層を形成した複合銀ナノ粒子及び必要により銀微粒子を金属成分として混合し、加熱下で前記樹脂を流動化させて全体を混練し、混練後に前記樹脂が非流動状態になる温度まで冷却して、前記金属成分を前記樹脂中に分散状態に保持する複合銀ナノペーストの製法が提供される。前述した様に、前記樹脂は１０℃で非流動状態にあり加熱により流動化する特性を有している。この中で加熱とは加熱手段による加熱だけでなく、混練時の摩擦も摩擦熱を放出するから、摩擦も加熱の一形態に含まれる。混錬には３方法ある。第１には、樹脂と複合銀ナノ粒子と銀微粒子の同時混連、第２には、樹脂と複合銀ナノ粒子を混練した後、銀微粒子を追加して混練する２段階混練、第３には、樹脂と銀微粒子を混練した後、複合銀ナノ粒子を追加して混練する２段階混練がある。銀微粒子を添加しない場合には、樹脂と複合銀ナノ粒子を混練する形態しか存在しない。いずれにしても、加熱混錬により流動化したペーストを冷却して非流動化し、非流動状態のペーストとして保管する。従って、非流動状態の保管では、ペースト中で複合銀ナノ粒子や銀微粒子が凝集することは無い。 According to the sixth embodiment of the present invention, a resin that is in a non-flowing state at 10 ° C. and fluidized by heating has a carbon number of 1 to 9 around silver nuclei having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms. Or a composite silver nanoparticle formed with an organic coating layer composed of at least one alcohol molecule residue, alcohol molecule derivative or alcohol molecule, and optionally silver fine particles as a metal component, and fluidizing the resin under heating. Thus, there is provided a method for producing a composite silver nanopaste in which the whole is kneaded and cooled to a temperature at which the resin becomes non-flowing after kneading to hold the metal component in a dispersed state in the resin. As described above, the resin is in a non-flowing state at 10 ° C. and has a characteristic of being fluidized by heating. Among them, heating is not only heating by a heating means, but also friction during kneading releases frictional heat, so friction is included in one form of heating. There are three methods for kneading. First, simultaneous mixing of resin, composite silver nanoparticles and silver fine particles, second, two-stage kneading in which resin and composite silver nanoparticles are kneaded and then silver fine particles are added and kneaded; There is a two-stage kneading in which a composite silver nanoparticle is added and kneaded after kneading a resin and silver fine particles. When silver fine particles are not added, there is only a form of kneading the resin and composite silver nanoparticles. In any case, the paste fluidized by heat kneading is cooled to be non-fluidized and stored as a non-fluidized paste. Therefore, in non-fluid storage, composite silver nanoparticles and silver fine particles are not aggregated in the paste.
　本発明の第７形態によれば、前記銀核の平均粒径が１～２０ｎｍ、前記銀微粒子の平均粒径が０．１～１０μｍである複合銀ナノペーストの製法が提供される。銀微粒子の添加によりペースト中の銀含有率を増加させることができる。銀微粒子の粒径は０．１～１０μｍであり、前記複合銀ナノ粒子の銀核粒径は１～２０ｎｍであるから、このペーストを焼成したときに、前記複合銀ナノ粒子は銀微粒子間の接着剤の役割を奏すると考えられる。銀微粒子の表面に前記複合銀ナノ粒子が付着し、焼成により有機成分が気散して、表面融解した銀核が表面融解した銀微粒子同士を相互に結合させるのである。換言すれば、ペーストを塗着したとき、大きな銀微粒子間の隙間に複合銀ナノ粒子が集積し、焼成して有機物が気散したときに、銀微粒子間の隙間が銀核によって充填され、しかも銀微粒子相互が銀核によって接着されるため、銀膜自体が緻密に形成されて高強度で高電気伝導性を有する銀導体が提供される。前述した粒径関係にあると、銀核が銀微粒子同士の隙間を充填し、ガスが気散した後の気泡空洞（ボイド）に銀核が埋め戻される形態になり、ボイド発生数が少なくなる結果、基体との接合強度及び電気伝導度の向上を図ることができる。 According to the seventh aspect of the present invention, there is provided a method for producing a composite silver nanopaste in which the average particle diameter of the silver nuclei is 1 to 20 nm and the average particle diameter of the silver fine particles is 0.1 to 10 μm. By adding silver fine particles, the silver content in the paste can be increased. Since the particle diameter of the silver fine particles is 0.1 to 10 μm and the silver core particle diameter of the composite silver nanoparticles is 1 to 20 nm, when the paste is fired, the composite silver nanoparticles are between the silver fine particles. It is thought to play the role of an adhesive. The composite silver nanoparticles adhere to the surface of the silver fine particles, the organic components are diffused by firing, and the silver fine particles whose surfaces are melted are bonded to each other. In other words, when the paste is applied, the composite silver nanoparticles accumulate in the gaps between the large silver fine particles, and when the organic matter is diffused by firing, the gaps between the silver fine particles are filled with silver nuclei, Since the silver fine particles are bonded to each other by the silver nuclei, the silver film itself is densely formed, and a silver conductor having high strength and high electrical conductivity is provided. When the particle size relationship is as described above, the silver nuclei fill the gaps between the silver fine particles, and the gas nuclei are filled back into the bubble cavities (voids), and the number of voids is reduced. As a result, it is possible to improve the bonding strength and electrical conductivity with the substrate.
　本発明の第８形態によれば、所望量の溶剤を添加して、１０℃以下でも流動状態化させて塗着可能なペーストにする複合銀ナノペーストの製法が提供される。溶剤を添加しない場合には、本発明の複合銀ナノペーストは低温で非流動状態にある。この非流動性ペーストを流動化するには、加熱して温度を上昇させる場合と、溶剤を添加する場合がある。本形態では、第６形態又は第７形態の製法に、溶剤を添加することにより、１０℃でも流動状態にあるペーストの製法を提供する。前記溶剤は、ペーストの粘度を低下させる機能を有し、比較的低温で蒸発する有機溶剤一般を使用することができる。例えば、Ｃ１～Ｃ８のアルコール、キシレン、トルエン、アセトン、ヘキサン、その他の溶剤が利用できる。特に、本発明の複合銀ナノ粒子の有機被覆層はアルコール由来物質であるから、溶剤としてアルコールが有利である。 According to the eighth embodiment of the present invention, there is provided a method for producing a composite silver nanopaste that is made into a paste that can be applied by adding a desired amount of solvent to make it flowable even at 10 ° C. or lower. When no solvent is added, the composite silver nanopaste of the present invention is in a non-flowing state at a low temperature. In order to fluidize this non-flowable paste, there are a case where the temperature is raised by heating and a case where a solvent is added. In this embodiment, a method for producing a paste that is in a fluid state even at 10 ° C. is provided by adding a solvent to the production method of the sixth embodiment or the seventh embodiment. The solvent has a function of reducing the viscosity of the paste, and general organic solvents that evaporate at a relatively low temperature can be used. For example, C1-C8 alcohol, xylene, toluene, acetone, hexane, and other solvents can be used. In particular, since the organic coating layer of the composite silver nanoparticles of the present invention is an alcohol-derived substance, alcohol is advantageous as a solvent.
　本発明の第９形態によれば、本発明の複合銀ナノペーストを用意し、前記複合銀ナノペーストを下体に塗着してペースト層を形成し、前記ペースト層上に上体を配置し、加熱により前記ペースト層を銀化して前記下体と前記上体を接合する接合方法が提供される。本形態は、本発明に係る複合銀ナノペーストを用いた２物体の接合方法であり、一方の物体を下体、他方の物体を上体と称し、両者をペースト層を介して接着させ、焼成してペースト層の銀化により、強固な接合を達成できる。しかも、銀膜は電気伝導性と熱伝導性に優れ、低温焼成が可能であるから、低融点物体同士の接合も可能になる。 According to the ninth aspect of the present invention, the composite silver nanopaste of the present invention is prepared, the composite silver nanopaste is applied to the lower body to form a paste layer, and the upper body is disposed on the paste layer, There is provided a joining method in which the paste layer is silvered by heating to join the lower body and the upper body. This embodiment is a method for joining two objects using the composite silver nanopaste according to the present invention, in which one object is referred to as a lower body and the other object is referred to as an upper body, and both are bonded via a paste layer and fired. Thus, strong bonding can be achieved by silvering the paste layer. Moreover, since the silver film is excellent in electrical conductivity and thermal conductivity and can be fired at a low temperature, it is possible to join low melting point objects.
　本発明の第１０形態によれば、本発明の複合銀ナノペーストを用意し、前記複合銀ナノペーストを基体の面上に所定パターンに塗着してペーストパターンを形成し、加熱により前記ペーストパターンを銀化して銀パターンを形成するパターン形成方法が提供される。例えば、低融点の樹脂基板上に所定パターンの銀膜を形成する場合など、本発明形態により各種素材上に種々パターンの銀膜を低温度で形成する方法が提供される。 According to the tenth aspect of the present invention, the composite silver nanopaste of the present invention is prepared, the composite silver nanopaste is coated on the surface of the substrate in a predetermined pattern, and the paste pattern is formed by heating. A pattern forming method is provided in which a silver pattern is formed by silveration. For example, when a silver film having a predetermined pattern is formed on a resin substrate having a low melting point, a method for forming a silver film having various patterns on various materials at a low temperature is provided according to the embodiment of the present invention.
図１は複合銀ナノ粒子ＣｎＡｇＡＬの製造工程図である。FIG. 1 is a production process diagram of composite silver nanoparticles CnAgAL. 図２は複合銀ナノ粒子の生成反応の第１工程図である。FIG. 2 is a first process diagram of a formation reaction of composite silver nanoparticles. 図３は複合銀ナノ粒子の生成反応の第２工程図である。FIG. 3 is a second process diagram of the formation reaction of composite silver nanoparticles. 図４はＣ２ＡｇＡＬの高分解能透過電子顕微鏡図である。FIG. 4 is a high-resolution transmission electron microscope view of C2AgAL. 図５はＣ４ＡｇＡＬの高分解能透過電子顕微鏡図である。FIG. 5 is a high-resolution transmission electron microscope view of C4AgAL. 図６はＣ２ＡｇＡＬの熱解析図である。FIG. 6 is a thermal analysis diagram of C2AgAL. 図７はＣ４ＡｇＡＬの熱解析図である。FIG. 7 is a thermal analysis diagram of C4AgAL. 図８は複合銀ナノペーストの製造工程図である。FIG. 8 is a production process diagram of a composite silver nanopaste. 図９はＩＢＣＨの粘度と温度の特性図である。FIG. 9 is a characteristic diagram of the viscosity and temperature of IBCH. 図１０は昇温率３℃／ｍｉｎのＩＢＣＨの熱解析図である。FIG. 10 is a thermal analysis diagram of IBCH with a heating rate of 3 ° C./min. 図１１はＩＢＣＨの蒸発温度と昇温率の関係図である。FIG. 11 is a graph showing the relationship between the evaporation temperature of IBCH and the temperature rise rate. 図１２はグリセリンの粘度と温度の特性図である。FIG. 12 is a characteristic diagram of viscosity and temperature of glycerin. 図１３は複合銀ナノペースト（Ｃ２ＡｇＡＬ）の大気中の熱解析図である。FIG. 13 is a thermal analysis diagram of the composite silver nanopaste (C2AgAL) in the atmosphere. 図１４は複合銀ナノペースト（Ｃ４ＡｇＡＬ）の大気中の熱解析図である。FIG. 14 is a thermal analysis diagram of the composite silver nanopaste (C4AgAL) in the atmosphere. 図１５は複合銀ナノペースト（Ｃ６ＡｇＡＬ）の大気中の熱解析図である。FIG. 15 is a thermal analysis diagram of the composite silver nanopaste (C6AgAL) in the atmosphere.
　以下、本発明に係る複合銀ナノペースト、その製法、接合方法及びパターン形成方法の実施形態を図面及び表により詳細に説明する。 Hereinafter, embodiments of a composite silver nanopaste, a manufacturing method, a bonding method, and a pattern forming method according to the present invention will be described in detail with reference to the drawings and tables.
　表１は、本発明に使用される複合銀ナノ粒子の製造原料及びアルコール溶液のモル比の一覧表である。銀原料として無機銀塩や有機銀塩が使用できるが、無機銀塩の一例として炭酸銀（Ａｇ２ＣＯ３）が記載されている。アルコール原料として、ＣｎＨ２ｎ＋１ＯＨ（ｎ＝１～９、１１）が使用される。炭酸銀微粒子１００ｇ（０．３６３モル）を分散させるアルコールのモル数は、表１に示すように、３．６３モル～２３．２モルに亘り、モル比（アルコールのモル数／炭酸銀のモル数）では１０～６３．９の範囲にある。炭酸銀とアルコールの化学量論比よりもアルコールを過剰に投入し、過剰アルコール溶液にして化学反応を行なわせる。その理由は、化学反応により生成される複合銀ナノ粒子ＣｎＡｇＡＬは銀核粒径が１～２０ｎｍと極めて小さく、アルコール溶液中で複合銀ナノ粒子同士の衝突を防止して、凝集による二次粒子化を抑制するためである。生成される複合銀ナノ粒子は１０種類である。 Table 1 is a list of molar ratios of the raw materials for production of the composite silver nanoparticles used in the present invention and the alcohol solution. An inorganic silver salt or an organic silver salt can be used as the silver raw material, and silver carbonate (Ag2CO3) is described as an example of the inorganic silver salt. As the alcohol raw material, C n H 2n + 1 OH (n = 1 to 9, 11) is used. As shown in Table 1, the number of moles of alcohol in which 100 g (0.363 moles) of silver carbonate fine particles are dispersed ranges from 3.63 moles to 23.2 moles (mole ratio of alcohol / moles of silver carbonate). Number) is in the range of 10-63.9. Alcohol is added in excess of the stoichiometric ratio of silver carbonate and alcohol, and an excess alcohol solution is used to cause a chemical reaction. The reason for this is that the composite silver nanoparticles CnAgAL produced by chemical reaction have a very small silver core particle size of 1 to 20 nm, preventing collisions between the composite silver nanoparticles in an alcohol solution, and forming secondary particles by aggregation. It is for suppressing. Ten types of composite silver nanoparticles are produced.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表２は、複合銀ナノ粒子の原料の分子量と１００ｇのモル数の一覧表である。具体的なアルコール（ＣｎＨ２ｎ＋１ＯＨ）の名称は、メタノール（ＣＨ３ＯＨ）、エタノール（Ｃ２Ｈ５ＯＨ）、プロパノール（Ｃ３Ｈ７ＯＨ）、ブタノール（Ｃ４Ｈ９ＯＨ）、ペンタノール（Ｃ５Ｈ１１ＯＨ）、ヘキサノール（Ｃ６Ｈ１３ＯＨ）、ヘプタノール（Ｃ７Ｈ１５ＯＨ）、オクタノール（Ｃ８Ｈ１７ＯＨ）、ノナノール（Ｃ９Ｈ１９ＯＨ）、ウニデカノール（Ｃ１０Ｈ２１ＯＨ）である。アルコールの沸点ＢＴ（℃）も併記されている。 Table 2 is a list of molecular weights of raw materials for composite silver nanoparticles and the number of moles of 100 g. Specific names of alcohol (C n H 2n + 1 OH) are methanol (CH 3 OH), ethanol (C 2 H 5 OH), propanol (C 3 H 7 OH), butanol (C 4 H 9 OH), pen ethanol (C 5 H 11 OH), hexanol (C 6 H 13 OH), heptanol (C 7 H 15 OH), octanol (C 8 H 17 OH), nonanol (C 9 H 19 OH), Unidekanoru (C 10 H 21 OH). The boiling point BT (° C.) of the alcohol is also shown.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　図１は複合銀ナノ粒子の製造工程図である。所定量の銀塩粉体と所定量のアルコールの混合液を調製し、前記混合液を反応容器に封入する。Ａｒガスフロー下で生成温度ＰＴ（℃）にて所定時間だけ前記混合液を加熱する。この加熱過程で銀塩とアルコールが反応して無数の複合銀ナノ粒子が生成される。反応時間は１時間以内がよく、長時間になると複合銀ナノ粒子が相互に凝集を始めて２次粒子化するので、反応後は急速に冷却することが望ましい。最後に、反応液から複合銀ナノ粒子を粉体として回収する。前記複合銀ナノ粒子をＣｎＡｇＡＬと表示し、アルコキシド型複合銀ナノ粒子であることを示す。但し、用いるアルコールは上記１０種であり、ｎ＝１～９又は１１である。 FIG. 1 is a production process diagram of composite silver nanoparticles. A mixed solution of a predetermined amount of silver salt powder and a predetermined amount of alcohol is prepared, and the mixed solution is sealed in a reaction vessel. The mixed solution is heated at a generation temperature PT (° C.) for a predetermined time under an Ar gas flow. During this heating process, the silver salt and alcohol react to produce countless composite silver nanoparticles. The reaction time is preferably within 1 hour. When the reaction time is long, the composite silver nanoparticles start to aggregate with each other and become secondary particles. Therefore, it is desirable to cool rapidly after the reaction. Finally, the composite silver nanoparticles are recovered from the reaction solution as a powder. The composite silver nanoparticle is expressed as CnAgAL, which indicates that it is an alkoxide type composite silver nanoparticle. However, the alcohols used are the above 10 types, and n = 1 to 9 or 11.
　図２は、本発明に係る複合銀ナノ粒子の生成反応の第１工程図である。原料は銀塩（１）と式（２）で示されるアルコールＣｎＨ２ｎ＋１ＯＨ（ｎ＝１～９、１１）である。式（３）のＲｎはアルコールの炭化水素基ＣｎＨ２ｎ＋１を示している。炭素数ｎは１～９又は１１の１０種に限られる。銀塩微粒子はアルコール不溶性のものが多く、アルコールの親水基ＯＨは銀塩微粒子の表面と結合しやすい性質を有する。またアルコールの疎水基Ｒｎはアルコール溶媒と親和性が高い。従って、式（４）に示すように、銀塩微粒子をアルコール溶媒に分散させると、銀塩微粒子表面にアルコールが取巻いた状態になる。銀塩微粒子が超微粒子にまで微細化されると、安定な銀塩微粒子コロイドが形成される。式（４）では、銀塩として炭酸銀（Ａｇ２ＣＯ３）が示される。 FIG. 2 is a first process diagram of a formation reaction of composite silver nanoparticles according to the present invention. The raw materials are silver salt (1) and alcohol C n H 2n + 1 OH (n = 1 to 9, 11) represented by formula (2). R n in the formula (3) represents a hydrocarbon group C n H 2n + 1 of the alcohol. The carbon number n is limited to 10 of 1 to 9 or 11. Many silver salt fine particles are insoluble in alcohol, and the hydrophilic group OH of alcohol has a property of easily bonding to the surface of the silver salt fine particles. The hydrophobic group R n of the alcohol has a high affinity with alcohol solvent. Therefore, as shown in the formula (4), when the silver salt fine particles are dispersed in the alcohol solvent, the alcohol is surrounded on the surface of the silver salt fine particles. When the silver salt fine particles are refined to ultrafine particles, stable silver salt fine particle colloids are formed. In Equation (4), silver carbonate (Ag 2 CO 3) is shown as a silver salt.
　図３は、本発明に係る複合銀ナノ粒子の生成反応の第２工程図である。反応式を明確にするため銀塩として炭酸銀が使用される。炭酸銀微粒子表面の炭酸銀はアルコールと反応して、式（５）に示されるように銀化と同時にアルデヒドＲｎ－１ＣＨＯが生成される。また、式（６）に示されるように、アルデヒドが形成されずに、直ちに銀アルコキシドＡｇＯＲｎが生成される反応経路も存在する。前記アルデヒドは強力な還元作用を有し、式（７）に示されるように、炭酸銀を還元して、銀化と同時にカルボン酸Ｒｎ－１ＣＯＯＨが形成される。中間生成されたＡｇ、ＡｇＯＲｎ、Ｒｎ－１ＣＯＯＨは、式（８）及び式（９）に示される反応により相互に凝集し、複合銀ナノ粒子としてＡｇｋ＋ｍ（ＯＲｎ）ｍ、Ａｇｋ＋ｍ（ＯＲｎ）ｍＲｎ－１ＣＯＯＨが生成される。これらの複合銀ナノ粒子は式（１０）及び式（１１）に図示されている。前記反応は炭酸銀微粒子の表面反応であり、表面から次第に内部に浸透しながら反応が継続し、中心核となる炭酸銀微粒子は銀核へと転化してゆく。最終的に、式（１０）及び式（１１）に示される複合銀ナノ粒子が生成され、本発明では、この複合銀ナノ粒子をＣｎＡｇＡＬと書く。 FIG. 3 is a second process diagram of a formation reaction of composite silver nanoparticles according to the present invention. In order to clarify the reaction formula, silver carbonate is used as a silver salt. Silver carbonate on the surface of the silver carbonate fine particles reacts with alcohol to form aldehyde R n-1 CHO simultaneously with silveration, as shown in formula (5). Moreover, as shown in Formula (6), there is also a reaction route in which silver alkoxide AgOR n is immediately generated without forming an aldehyde. The aldehyde has a strong reducing action, and as shown in formula (7), silver carbonate is reduced to form carboxylic acid R n-1 COOH simultaneously with silveration. The intermediately produced Ag, AgOR n , and R n-1 COOH aggregate with each other by the reactions shown in Formula (8) and Formula (9), and form Ag k + m (OR n ) m , Ag k + m as composite silver nanoparticles. (OR n ) m R n-1 COOH is produced. These composite silver nanoparticles are illustrated in equations (10) and (11). The reaction is a surface reaction of silver carbonate fine particles. The reaction continues while gradually penetrating from the surface into the interior, and the silver carbonate fine particles serving as the central nucleus are converted into silver nuclei. Finally, composite silver nanoparticles represented by formula (10) and formula (11) are produced, and in the present invention, this composite silver nanoparticle is written as CnAgAL.
　図４はＣ２ＡｇＡＬの高分解能透過電子顕微鏡図である。複合銀ナノ粒子Ｃ２ＡｇＡＬは６５℃の生成温度ＰＴにて単分散状態で生成され、高分解能透過型電子顕微鏡により撮影された。銀核には平行線群からなる格子像が観察され、銀核は単結晶であることが確認された。格子像の格子間隔は０．２４ｎｍであり、バルク銀結晶の（１１１）面間隔に一致することから、銀核が銀単結晶であることが確認された。 FIG. 4 is a high-resolution transmission electron microscope diagram of C2AgAL. The composite silver nanoparticles C2AgAL were produced in a monodispersed state at a production temperature PT of 65 ° C., and photographed with a high resolution transmission electron microscope. Lattice images consisting of parallel lines were observed in the silver nuclei, confirming that the silver nuclei were single crystals. The lattice spacing of the lattice image is 0.24 nm, which matches the (111) plane spacing of the bulk silver crystal, confirming that the silver nucleus is a silver single crystal.
　図５はＣ４ＡｇＡＬの高分解能透過電子顕微鏡図である。複合銀ナノ粒子Ｃ４ＡｇＡＬは８０℃の生成温度ＰＴにて単分散状態で生成され、高分解能透過型電子顕微鏡により撮影された。銀核には平行線群からなる格子像が観察され、銀核は単結晶であることが確認された。Ｃ２ＡｇＡＬと同様に、格子像の格子間隔は０．２４ｎｍであり、バルク銀結晶の（１１１）面間隔に一致し、銀核が銀単結晶であることが確認された。 FIG. 5 is a high resolution transmission electron microscope diagram of C4AgAL. The composite silver nanoparticle C4AgAL was produced in a monodispersed state at a production temperature PT of 80 ° C., and was photographed with a high resolution transmission electron microscope. Lattice images consisting of parallel lines were observed in the silver nuclei, confirming that the silver nuclei were single crystals. Similar to C2AgAL, the lattice spacing of the lattice image was 0.24 nm, which coincided with the (111) plane spacing of the bulk silver crystal, and it was confirmed that the silver nucleus was a silver single crystal.
　図６は生成温度ＰＴ＝６５℃で生成された大気中のＣ２ＡｇＡＬの熱解析図である。ＤＴＡ曲線は示差熱分析曲線で、ＤＴＡピーク温度Ｔ２＝１１１℃であり、金属化温度（銀化温度）Ｔ３＝１１５℃である。前記ＤＴＡピーク温度Ｔ２で有機被覆層が強力に分解して気散され、気散が終了した温度が金属化温度Ｔ３に相当する。分解開始温度は図示しない熱重量測定曲線（ＴＧ曲線）で与えられ、ＴＧ減少開始温度Ｔ１＝１０９℃である。以上のように、Ｔ１＜Ｔ２＜Ｔ３が一般的に成立し、本発明者が行なった多数の実験から、Ｔ２－６０≦Ｔ１≦Ｔ２の関係があることが明白になった。換言すると、ＴＧ減少開始温度Ｔ１はＤＴＡピーク温度Ｔ２の下方６０℃以内にあり、同時にＤＴＡピーク温度Ｔ２以下であることが分かった。 FIG. 6 is a thermal analysis diagram of C2AgAL in the atmosphere generated at a generation temperature PT = 65 ° C. The DTA curve is a differential thermal analysis curve with a DTA peak temperature T2 = 111 ° C. and a metallization temperature (silvering temperature) T3 = 115 ° C. The organic coating layer is strongly decomposed and diffused at the DTA peak temperature T2, and the temperature at which the diffusion is completed corresponds to the metallization temperature T3. The decomposition start temperature is given by a thermogravimetric measurement curve (TG curve) not shown, and the TG decrease start temperature T1 = 109 ° C. As described above, T1 <T2 <T3 is generally established, and it has become clear from the numerous experiments conducted by the present inventors that there is a relationship of T2-60 ≦ T1 ≦ T2. In other words, it was found that the TG decrease start temperature T1 is within 60 ° C. below the DTA peak temperature T2, and at the same time, is not more than the DTA peak temperature T2.
　図７は生成温度ＰＴ＝８０℃で生成された大気中のＣ４ＡｇＡＬの熱解析図である。ＤＴＡ曲線は示差熱分析曲線であり、ＴＧ曲線は熱重量測定曲線である。ＴＧ減少開始温度Ｔ１＝１０３℃、ＤＴＡピーク温度Ｔ２＝１２０℃、金属化温度（銀化温度）Ｔ３＝１２２℃である。Ｔ２－６０≦Ｔ１≦Ｔ２の関係が成立することも明らかである。 FIG. 7 is a thermal analysis diagram of C4AgAL in the atmosphere generated at a generation temperature PT = 80 ° C. The DTA curve is a differential thermal analysis curve, and the TG curve is a thermogravimetric curve. TG decrease start temperature T1 = 103 ° C., DTA peak temperature T2 = 120 ° C., metallization temperature (silvering temperature) T3 = 122 ° C. It is also clear that the relationship of T2-60 ≦ T1 ≦ T2 is established.
　本発明は１０種の複合銀ナノ粒子ＣｎＡｇＡＬ（ｎ＝１～９、１１）に関係し、これらの生成温度ＰＴ、ＴＧ減少開始温度Ｔ１、ＤＴＡピーク温度Ｔ２、金属化温度Ｔ３及びアルコール沸点ＢＴが表３に示されている。 The present invention relates to 10 types of composite silver nanoparticles CnAgAL (n = 1 to 9, 11), and the generation temperature PT, TG decrease start temperature T1, DTA peak temperature T2, metalization temperature T3, and alcohol boiling point BT are It is shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　１０種の複合銀ナノ粒子ＣｎＡｇＡＬ（ｎ＝１～９、１１）の生成温度ＰＴは全て１００℃以下であり、その結果、ＤＴＡピーク温度Ｔ２も１５０℃以下に低く抑えられることが分かった。しかも、金属化温度Ｔ３はＤＴＡピーク温度Ｔ２より僅かに高い目になるが、金属化温度Ｔ３も１５０℃以下であることが示された。ＣｎＡｇＡＬは、アルコール溶液を一定の生成温度ＰＴに保持して生成され、大気中ではアルコールの沸点は一定であるから、アルコールを沸騰状態で反応させると容易に生成温度ＰＴをその沸点ＢＴに保持できる。Ｃ１～Ｃ３のアルコール沸点は１００℃以下であるから、１≦ｎ≦３の３種のＣｎＡｇＡＬはアルコール沸騰反応で生成できることを意味する。勿論、他の温度制御方法を行なうことも可能である。 It was found that the generation temperatures PT of the 10 types of composite silver nanoparticles CnAgAL (n = 1 to 9, 11) were all 100 ° C. or lower, and as a result, the DTA peak temperature T2 was also suppressed to 150 ° C. or lower. Moreover, although the metallization temperature T3 is slightly higher than the DTA peak temperature T2, it was shown that the metallization temperature T3 is also 150 ° C. or less. CnAgAL is produced by keeping an alcohol solution at a constant production temperature PT, and since the boiling point of the alcohol is constant in the atmosphere, the production temperature PT can be easily kept at the boiling point BT by reacting the alcohol in a boiling state. . Since the alcohol boiling point of C1 to C3 is 100 ° C. or less, it means that three types of CnAgAL with 1 ≦ n ≦ 3 can be produced by alcohol boiling reaction. Of course, other temperature control methods can be used.
　表４は、複合銀ナノ粒子ＣｎＡｇＡＬのＴＧ減少開始温度Ｔ１の範囲を示すものである。表４には、Ｔ２－６０、Ｔ１及びＴ２の各温度がＣ１～Ｃ９及びＣ１１に関して示されている。その結果、Ｔ２－６０≦Ｔ１≦Ｔ２が１０種の複合銀ナノ粒子について成立することが分かった。 Table 4 shows the range of the TG decrease start temperature T1 of the composite silver nanoparticles CnAgAL. Table 4 shows the temperatures of T2-60, T1 and T2 with respect to C1 to C9 and C11. As a result, it was found that T2-60 ≦ T1 ≦ T2 holds for 10 types of composite silver nanoparticles.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　図８は複合銀ナノペーストの製造工程図である。所定重量％の複合銀ナノ粒子ＣｎＡｇＡＬ粉体と、所定重量％の銀微粒子Ａｇ粉体と、所定重量％の樹脂を用意し、これら３成分を混合容器に投入する。混合容器内で例えば４０℃に加熱して樹脂を流動化させ、ペーストを均一混合する。このとき、７００ｒｐｍの自転と２０００ｒｐｍの公転を行う自転公転型の遠心器を利用した。４０℃位の加熱温度であれば、摩擦熱により自然に昇温するから、強制加熱操作は不要である。しかし、４０℃以上になるとヒーター加熱すると効率的に流動化できる。その後、複合銀ナノペーストを急速に冷却し、固形化して回収する。固形化により、均一に分散した複合銀ナノ粒子と銀微粒子が樹脂により固定化され、保管中に凝集することは無い。 FIG. 8 is a production process diagram of composite silver nanopaste. A predetermined weight percent of composite silver nanoparticle CnAgAL powder, a predetermined weight percent of silver fine particle Ag powder, and a predetermined weight percent of resin are prepared, and these three components are put into a mixing container. For example, the resin is fluidized by heating to 40 ° C. in a mixing container, and the paste is uniformly mixed. At this time, a rotation-revolution centrifuge that performs rotation at 700 rpm and revolution at 2000 rpm was used. If the heating temperature is about 40 ° C., the temperature is naturally raised by frictional heat, and therefore a forced heating operation is unnecessary. However, when it is 40 ° C. or higher, it can be efficiently fluidized by heating with a heater. Thereafter, the composite silver nanopaste is rapidly cooled, solidified and recovered. By solidification, the uniformly dispersed composite silver nanoparticles and silver fine particles are fixed by the resin and do not aggregate during storage.
　図８の製造工程を変形した方法も採用される。まず、所定重量％の複合銀ナノ粒子ＣｎＡｇＡＬ粉体と所定重量％の樹脂を加熱しながら混合してペースト中間体を製造する。このペースト中間体に所定重量％の銀微粒子Ａｇ粉体を加熱しながら均一混合して複合銀ナノペーストを製造し、急速冷却して固形化する。摩擦熱を利用する場合には、強制加熱は不要である。この製造法では、まず樹脂中に複合銀ナノ粒子を均一分散させ、その次に銀微粒子を均一分散させるから、複合銀ナノ粒子と銀微粒子が独立に分散され、両者の相互作用を無くすため均一分散性が一層に増大する特徴がある。
　また、他の変形例として、まず所定重量％の銀微粒子Ａｇ粉体と所定重量％の樹脂を加熱しながら混合してペースト中間体を製造する。このペースト中間体に所定重量％の複合銀ナノ粒子ＣｎＡｇＡＬ粉体を加熱しながら均一混合して複合銀ナノペーストを製造し、急速冷却して固形化する。摩擦熱を利用する場合には、強制加熱は不要である。この変形製造法では、まず樹脂中に銀微粒子を均一分散させ、その次に複合銀ナノ粒子を均一分散させるから、複合銀ナノ粒子と銀微粒子が独立に分散され、両者の相互作用を無くすため均一分散性が一層に増大する。
勿論、銀微粒子を添加しない場合には、ＣｎＡｇＡＬと樹脂の均一混合だけで済むことは云うまでも無い。 A method in which the manufacturing process of FIG. 8 is modified is also adopted. First, a paste intermediate is produced by mixing a predetermined weight% of composite silver nanoparticles CnAgAL powder and a predetermined weight% of resin while heating. A predetermined weight percent of silver fine particle Ag powder is uniformly mixed with this paste intermediate while heating to produce a composite silver nanopaste, which is rapidly cooled to solidify. When frictional heat is used, forced heating is not necessary. In this manufacturing method, the composite silver nanoparticles are uniformly dispersed in the resin, and then the silver fine particles are uniformly dispersed. Therefore, the composite silver nanoparticles and the silver fine particles are dispersed independently, and uniform to eliminate the interaction between the two. It is characterized by further increasing dispersibility.
As another modification, first, a paste intermediate is produced by mixing a predetermined weight% of silver fine particle Ag powder and a predetermined weight% of resin while heating. A predetermined weight percent of composite silver nanoparticle CnAgAL powder is uniformly mixed with this paste intermediate while heating to produce a composite silver nanopaste, which is rapidly cooled to solidify. When frictional heat is used, forced heating is not necessary. In this modified manufacturing method, the silver fine particles are first uniformly dispersed in the resin, and then the composite silver nanoparticles are uniformly dispersed. Therefore, the composite silver nanoparticles and the silver fine particles are independently dispersed to eliminate the interaction between the two. Uniform dispersibility is further increased.
Of course, when silver fine particles are not added, it is needless to say that only uniform mixing of CnAgAL and resin is sufficient.
　表５は本発明に使用される樹脂の例示表である。イソボルニルシクロヘキサノール（ＩＢＣＨ）は、いわゆる松脂状であり、室温では流動性が無く、加熱により急速に流動化する性質を有する。グリセリンはＩＣＢＨよりも粘性が小さく、いわゆるシロップ状であるが、１７℃の融点を有しているから、１０℃では水分の無い環境下では固形化する。従って、グリセリンは冷蔵庫温度以下まで冷却すれば殆んど流動性を消失し、加熱すると流動化するから、前記ＩＢＣＨと同様に本発明の樹脂として使用できる。ＩＣＢＨもグリセリンも、大気中焼成により全て分解気散し、炭化物などは一切残留しない。その他、１０℃以下の室温で固体状であり、例えば４０℃以上になると液化する性質を有し、焼成すると完全に気散する物質も本発明の樹脂として使用できる。例えば、Ｃ数が１４以上の高級アルコールが利用でき、ミリスチルアルコール、パルミチルアルコール、ステアリルアルコール、ベヘニルアルコールなどが列挙される。それらの融点は表３に示す通りである。上記と同様な樹脂も本発明の樹脂として利用できることは云うまでもない。 Table 5 is an exemplary table of resins used in the present invention. Isobornylcyclohexanol (IBCH) is a so-called rosin-like, has no fluidity at room temperature, and has a property of fluidizing rapidly by heating. Glycerin has a lower viscosity than ICBH and is in the form of a so-called syrup, but has a melting point of 17 ° C., and thus solidifies at 10 ° C. in an environment without moisture. Therefore, glycerin almost loses its fluidity when cooled to the refrigerator temperature or lower, and fluidizes when heated, so that it can be used as the resin of the present invention in the same manner as IBCH. Both ICBH and glycerin are decomposed and diffused by firing in the air, and no carbides remain. In addition, a substance that is solid at room temperature of 10 ° C. or less, has a property of being liquefied when it is 40 ° C. or more, and completely disperses when baked can be used as the resin of the present invention. For example, higher alcohols having 14 or more carbon atoms can be used, and myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol and the like are listed. Their melting points are as shown in Table 3. Needless to say, resins similar to those described above can also be used as the resin of the present invention.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表６はＩＢＣＨの粘度と温度の関係表である。３０℃以下では１５万センチポイズ（ｃＰ）であるから、当然に１０℃でも流動性は無いが、４０℃以上、特に５０℃以上になると急速に流動性を発現するようになり、本発明に最適の樹脂である。 Table 6 is a relationship table between viscosity and temperature of IBCH. Since it is 150,000 centipoise (cP) at 30 ° C or lower, naturally it does not have fluidity even at 10 ° C, but when it reaches 40 ° C or higher, especially 50 ° C or higher, fluidity is rapidly developed and is optimal for the present invention Resin.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　図９は、ＩＢＣＨの粘度と温度の特性図である。表６に示された粘度の温度に対する関係をプロットしたもので、ＩＢＣＨは粘度が対数軸で表示されるほど急激に温度に関して変化する性質を有していることが分かる。このような性質を有し、且つ焼成により全てが気散する性質を有する全ての樹脂が本発明に利用できる。 FIG. 9 is a characteristic diagram of viscosity and temperature of IBCH. The relationship between the viscosity and the temperature shown in Table 6 is plotted, and it can be seen that IBCH has a property of changing with temperature so rapidly that the viscosity is displayed on the logarithmic axis. All resins having such properties and having the property of being completely diffused by firing can be used in the present invention.
　図１０は、昇温率３℃／ｍｉｎのＩＢＣＨの熱解析図である。ＤＴＡから完全蒸発温度は２０５℃であり、ＴＧから２０５℃で重量がゼロ％になっていることが分かり、全量が蒸発して消失したことが証明されている。 FIG. 10 is a thermal analysis diagram of IBCH with a temperature increase rate of 3 ° C./min. From DTA, the complete evaporation temperature is 205 ° C., and from TG, the weight is found to be 0% at 205 ° C., and it is proved that the entire amount has evaporated and disappeared.
　表７はＩＢＣＨの昇温率と蒸発温度の関係表である。昇温率３（℃／ｍｉｎ）とは１分間に３℃上昇させながら昇温させてゆくプログラム昇温を意味する。昇温率が小さいほど蒸発温度は低くなり、昇温率が大きくなると蒸発温度が高くなる性質がある。この性質はＴＧ・ＤＴＡ測定の性質と言って良い。本発明の複合銀ナノペーストを焼成する場合、まず樹脂を先に気散させる場合には、昇温率を小さく設定し、樹脂が完全に蒸発した後にアルコキシド基を気散させることになる。逆に、まずアルコキシド基を先に気散させる場合には、昇温率を大きく設定すればよく、その後に樹脂が完全蒸発することになる。通常は樹脂を完全蒸発させた後に、アルコキシド基を気散させる方法が採用される。 Table 7 is a relationship table between the temperature increase rate of IBCH and the evaporation temperature. A temperature increase rate of 3 (° C./min) means a program temperature increase in which the temperature is increased while increasing by 3 ° C. per minute. The evaporation temperature decreases as the temperature increase rate decreases, and the evaporation temperature increases as the temperature increase rate increases. This property can be said to be a property of TG / DTA measurement. When the composite silver nanopaste of the present invention is baked, when the resin is first diffused, the rate of temperature increase is set small, and the alkoxide group is diffused after the resin is completely evaporated. On the other hand, when the alkoxide group is first diffused, the temperature increase rate should be set large, and then the resin will be completely evaporated. Usually, after the resin is completely evaporated, a method in which alkoxide groups are diffused is employed.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　図１１は、ＩＢＣＨの蒸発温度と昇温率の関係図である。表７に示された蒸発温度と昇温率の関係をプロットしたものである。このグラフに基づいて、昇温率を調整して蒸発温度を任意に調節することができる。 FIG. 11 is a graph showing the relationship between the evaporation temperature of IBCH and the temperature rise rate. The relationship between the evaporation temperature shown in Table 7 and the temperature rising rate is plotted. Based on this graph, the evaporation rate can be arbitrarily adjusted by adjusting the temperature increase rate.
　表８はグリセリンの粘度と温度の関係表である。０℃では１２１００センチポイズ（ｃＰ）であり、更に冷却すると粘度は急速に増加し非流動状態になる。他方、温度を１０℃以上にすると粘度は３９００（ｃＰ）以下になり、流動性を示すようになる。この程度の粘度では非流動性は小さいと考えるであろうが、これらの粘度は大気に開放され、水分を吸収する環境下での話である。特に、グリセリンの融点は１７℃であり、水分の無い環境下では、１７℃以下になると固形化する。従って、１０℃以下では非流動性を有すると言うことができる。ＩＢＣＨがやや高い温度の樹脂特性を示すのに対し、グリセリンは低い温度での樹脂特性を示す樹脂であり、両者を適当に使い分けることにより、非流動性・流動性変化を実現できる。前述したように、非流動性とは複合銀ナノ粒子の非凝集性を意味する。 Table 8 is a relationship table between glycerin viscosity and temperature. At 0 ° C., it is 12100 centipoise (cP). Upon further cooling, the viscosity increases rapidly and becomes non-flowing. On the other hand, when the temperature is set to 10 ° C. or higher, the viscosity becomes 3900 (cP) or lower and exhibits fluidity. At this level of viscosity, the non-flowability may be considered to be small, but these viscosities are open to the atmosphere and absorb moisture. In particular, the melting point of glycerin is 17 ° C., and in an environment without moisture, it becomes solid when it becomes 17 ° C. or lower. Therefore, it can be said that it has non-fluidity at 10 ° C. or lower. While IBCH exhibits a slightly high temperature resin characteristic, glycerin is a resin that exhibits a low temperature resin characteristic, and by appropriately using both, non-fluidity / fluidity change can be realized. As described above, non-fluidity means non-aggregation of composite silver nanoparticles.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　図１２は、グリセリンの粘度と温度の特性図である。表８に示された粘度の温度に対する関係をプロットしたもので、グリセリン樹脂も粘度が対数軸で表示されるほど急激に温度に関して変化する性質を有していることが分かる。このような性質を有し、且つ焼成により全てが気散する性質を有する全ての樹脂が本発明に利用できる。 FIG. 12 is a characteristic diagram of viscosity and temperature of glycerin. The relationship between the viscosity and the temperature shown in Table 8 is plotted, and it can be seen that the glycerin resin also has a property of rapidly changing with respect to temperature as the viscosity is displayed on the logarithmic axis. All resins having such properties and having the property of being completely diffused by firing can be used in the present invention.
　表９は、溶剤として使用されるアルコールの一覧表である。本発明に使用する複合銀ナノ粒子はＣｎＡｇＡＬ（ｎ＝１～９、１１）のアルコキシド型複合銀ナノ粒子であり、銀核を取巻く有機被覆層はアルコキシド基であり、溶剤としてアルコールを使用した場合には、複合銀ナノ粒子はアルコールに極めて良く溶解する性質を有する。アルコールとしては、メタノール、エタノール、ブタノール、ヘキサノール、オクタノールが使用できる。アルコール以外にも、例えば、アセトン、エーテル、ベンゼン、酢酸エチル、テルピネオール、ジヒドロテルピネオール、ブチルカルビトール、セロソルブ等の有機溶媒が利用できる。 Table 9 is a list of alcohols used as solvents. The composite silver nanoparticles used in the present invention are CnAgAL (n = 1 to 9, 11) alkoxide type composite silver nanoparticles, the organic coating layer surrounding the silver core is an alkoxide group, and alcohol is used as a solvent. In addition, the composite silver nanoparticles have the property of dissolving very well in alcohol. As the alcohol, methanol, ethanol, butanol, hexanol, and octanol can be used. In addition to alcohol, organic solvents such as acetone, ether, benzene, ethyl acetate, terpineol, dihydroterpineol, butyl carbitol, cellosolve and the like can be used.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　前述したように、溶剤の添加は、銀含有率を低下させ、流動性ペースト化した場合には複合銀ナノ粒子や銀微粒子の凝集が生起するから、保管貯蔵中は溶剤の無い非流動性ペーストとし、塗着する直前に溶剤を添加することが推奨される。保存期間が極めて短期間の場合でも、凝集の可能性があるから、塗着直前の溶剤添加が望まれる。また、溶剤を添加する場合でも、添加量は全量の１０ｍａｓｓ％以下が好ましく、５ｍａｓｓ％以下でもよく、特に１～２ｍａｓｓ％が望ましい。 As described above, the addition of a solvent reduces the silver content and causes agglomeration of composite silver nanoparticles and silver fine particles when it is made into a fluid paste, so a non-fluid paste without a solvent during storage and storage. It is recommended to add a solvent just before coating. Even when the storage period is very short, there is a possibility of aggregation, and therefore the addition of a solvent immediately before coating is desired. Even when a solvent is added, the amount added is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1 to 2% by mass.
[実施例１１～１１３：Ｃ１～Ｃ９、Ｃ１１の３種の複合銀ナノペースト]
　次に、前記複合銀ナノ粒子を用いて複合銀ナノペーストを作成した。Ｃ１～Ｃ９及びＣ１１のＣｎＡｇＡＬの夫々から次の３種類のペーストを作成した。（１）ＣｎＡｇＡＬ＋樹脂、（２）ＣｎＡｇＡＬ＋溶剤＋樹脂、（３）ＣｎＡｇＡＬ＋銀粒子＋溶剤＋粘性付与剤。前記３種類のＣｎＡｇＡＬの一つは表３に示される金属化温度Ｔ３を有したＣｎＡｇＡＬが使用され、残り２種は別のやや異なる金属化温度Ｔ３を有するＣｎＡｇＡＬが使用された。１５０℃を超える金属化温度Ｔ３を有するＣｎＡｇＡＬも使用されている。銀粒子の粒径は０．４μｍと１．０μｍの２種類が使用された。溶剤は、メタノール、エタノール、ブタノール、キシレン、トルエンから選択された。樹脂は、ＩＢＣＨ、グリセリン、ミリスチルアルコール（Ｃ１４Ｈ２９ＯＨ）、パルミチルアルコール（Ｃ１６Ｈ３３ＯＨ）、ステアリルアルコール（Ｃ１８Ｈ３７ＯＨ）から選択された。 [Examples 11 to 113: Three types of composite silver nanopastes of C1 to C9 and C11]
Next, a composite silver nanopaste was prepared using the composite silver nanoparticles. The following three types of pastes were prepared from C1 to C9 and C11 CnAgAL, respectively. (1) CnAgAL + resin, (2) CnAgAL + solvent + resin, (3) CnAgAL + silver particles + solvent + viscosity imparting agent. One of the three types of CnAgAL was CnAgAL having a metallization temperature T3 shown in Table 3, and the other two were CnAgALs having another slightly different metallization temperature T3. CnAgAL having a metallization temperature T3 above 150 ° C. is also used. Two types of silver particles having a particle size of 0.4 μm and 1.0 μm were used. The solvent was selected from methanol, ethanol, butanol, xylene, and toluene. The resin was selected from IBCH, glycerin, myristyl alcohol (C 14 H 29 OH), palmityl alcohol (C 16 H 33 OH), stearyl alcohol (C 18 H 37 OH).
　銀粒子の粒径、溶剤の種類、樹脂の種類、各成分のｍａｓｓ％及び大気中ペースト焼成温度は表１０及び表１１に記載された通りである。ＣｎＡｇＡＬと樹脂の２成分でペーストを作成する場合には、まず樹脂を５０℃に加熱して流動化させておき、この中にＣｎＡｇＡＬ粉体を混合して混練し、混練後に１０℃以下に冷却して非流動性ペーストを作成した。塗着する直前に、この非流動性ペーストを５０℃まで昇温して流動化させ、試験面に塗着する。溶剤を添加する場合には、樹脂と溶剤を混合して樹脂を流動化させ、この中にＣｎＡｇＡＬ粉体と銀粒子を添加して混練した。そして、この流動性ペーストを試験面に塗着した。
　Ｃ１～Ｃ９及びＣ１１のＣｎＡｇＡＬの金属化温度Ｔ３(℃)と実際の大気中ペースト焼成温度Ｔ（℃）が表１０及び表１１に記載されている。 The particle size of the silver particles, the type of solvent, the type of resin, the mass% of each component, and the paste baking temperature in the atmosphere are as described in Tables 10 and 11. When preparing a paste with two components of CnAgAL and resin, the resin is first heated to 50 ° C. and fluidized, CnAgAL powder is mixed and kneaded in this, and cooled to 10 ° C. or lower after kneading. Thus, a non-flowable paste was prepared. Immediately before application, this non-flowable paste is heated to 50 ° C. to be fluidized and applied to the test surface. In the case of adding a solvent, the resin and the solvent were mixed to fluidize the resin, and CnAgAL powder and silver particles were added and kneaded therein. And this fluid paste was applied to the test surface.
Tables 10 and 11 show the metallization temperature T3 (° C.) of CnAgAL of C1 to C9 and C11 and the actual paste firing temperature T (° C.) in the air.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　大気中ペースト焼成温度ＴはＣｎＡｇＡＬの金属化温度Ｔ３よりも高く設定されている。その理由は、ＣｎＡｇＡＬを金属化させるだけでなく、溶剤を蒸発させたり、樹脂を蒸発又は分解気散させる必要があるからである。また、金属化温度Ｔ３よりも高い温度でＣｎＡｇＡＬペーストを焼成すると、秀麗な金属膜が形成でき、しかも電気伝導度の高い銀膜を形成できるからでもある。前記大気中焼成温度Ｔが高いほど銀膜の秀麗性は増大する。従って、表１０及び表１１に示されるように、大気中ペースト焼成温度Ｔは前記金属化温度Ｔ３よりも高く設定された。 The atmospheric paste firing temperature T is set higher than the metallization temperature T3 of CnAgAL. This is because it is necessary not only to metallize CnAgAL but also to evaporate the solvent and evaporate or decompose the resin. In addition, if the CnAgAL paste is baked at a temperature higher than the metallization temperature T3, an excellent metal film can be formed and a silver film having high electrical conductivity can be formed. The excellence of the silver film increases as the firing temperature T in the atmosphere increases. Therefore, as shown in Tables 10 and 11, the atmospheric paste firing temperature T was set higher than the metallization temperature T3.
　実施例１１～実施例１１３に示される３０種類のペーストを耐熱ガラス基板に塗着し、表１０及び表１１の大気中ペースト焼成温度で焼成したところ、ガラス基板には秀麗な銀膜が形成された。形成された銀膜表面を光学顕微鏡で観察し、比抵抗を測定したところ、実用に耐える銀膜であることが確認され、本発明の複合銀ナノペーストが有効であることが結論された。 When 30 types of pastes shown in Examples 11 to 113 were applied to a heat-resistant glass substrate and baked at the atmospheric paste baking temperature in Tables 10 and 11, an excellent silver film was formed on the glass substrate. It was. When the surface of the formed silver film was observed with an optical microscope and the specific resistance was measured, it was confirmed that the film was a practical silver film, and it was concluded that the composite silver nanopaste of the present invention was effective.
　次に、実施例２３、実施例４３及び実施例６３のペーストを熱解析した。図１３は実施例２３のＣ２ＡｇＡＬペーストの熱解析図である。ＴＧ曲線で、１５０℃までの山はＩＢＣＨが蒸発していることを示す。更に、１７５℃までの段部は、Ｃ２ＡｇＡＬの有機被覆層の分解気散を示している。このＴＧ段部とＤＴＡピークが一致していることからもその事実が理解される。 Next, the pastes of Example 23, Example 43, and Example 63 were subjected to thermal analysis. FIG. 13 is a thermal analysis diagram of the C2AgAL paste of Example 23. In the TG curve, peaks up to 150 ° C. indicate that IBCH has evaporated. Further, the step up to 175 ° C. shows the decomposition and diffusion of the organic coating layer of C2AgAL. This fact is also understood from the fact that the TG step and the DTA peak coincide.
　図１４は実施例４３のＣ４ＡｇＡＬペーストの熱解析図である。ＴＧ曲線で、１５０℃までの山はＩＢＣＨが蒸発していることを示す。更に、１７５℃までの段部は、Ｃ４ＡｇＡＬの有機被覆層の分解気散を示している。このＴＧ段部とＤＴＡピークが一致していることからもその事実が理解される。 FIG. 14 is a thermal analysis diagram of the C4AgAL paste of Example 43. In the TG curve, peaks up to 150 ° C. indicate that IBCH has evaporated. Furthermore, the step up to 175 ° C. shows the decomposition and diffusion of the organic coating layer of C4AgAL. This fact is also understood from the fact that the TG step and the DTA peak coincide.
　図１５は実施例６３のＣ６ＡｇＡＬペーストの熱解析図である。ＴＧ曲線で、１５０℃までの山はＩＢＣＨが蒸発していることを示す。更に、１９５℃までの段部は、Ｃ６ＡｇＡＬの有機被覆層の分解気散を示している。このＴＧ段部とＤＴＡピークが一致していることから、その事実が理解できる。 FIG. 15 is a thermal analysis diagram of the C6AgAL paste of Example 63. In the TG curve, peaks up to 150 ° C. indicate that IBCH has evaporated. Furthermore, the step up to 195 ° C. shows the decomposition and diffusion of the organic coating layer of C6AgAL. This fact can be understood from the fact that the TG step and the DTA peak coincide.
[実施例１１４：半導体電極と回路基板との接合]
　半導体チップを上体とし、回路基板を下体として接合試験を行った。半導体チップの電極端を回路基板のスルーホールに挿入し、両者間の接触部に実施例１１～実施例１１３の複合銀ナノペーストを塗着して、３０種のペースト試験体を得た。その後、前記塗着部を表１０及び表１１に記載のペースト焼成温度Ｔで局所的に加熱して、前記塗着部を金属化させ、接合を完了した。冷却した後、光学顕微鏡により、前記接合部の外観を検査したところ、３０種の試験体で問題はなかった。電気導通試験と電気抵抗測定を行なったが、代替半田として有効に機能していることが確認された。前記３０種類の接合試験から、本発明に係る複合銀ナノペーストは代替半田として工業的に利用できることが分かった。 [Example 114: Joining of semiconductor electrode and circuit board]
A bonding test was performed with the semiconductor chip as the upper body and the circuit board as the lower body. The electrode end of the semiconductor chip was inserted into the through hole of the circuit board, and the composite silver nanopaste of Example 11 to Example 113 was applied to the contact part between them to obtain 30 types of paste specimens. Then, the said coating part was heated locally with the paste baking temperature T of Table 10 and Table 11, the said coating part was metalized, and joining was completed. After cooling, when the appearance of the joint was inspected with an optical microscope, there were no problems with 30 types of specimens. An electrical continuity test and an electrical resistance measurement were performed, and it was confirmed that it functions effectively as an alternative solder. From the 30 types of bonding tests, it was found that the composite silver nanopaste according to the present invention can be used industrially as an alternative solder.
[実施例１１５：耐熱ガラス基板上への銀パターンの形成]
　耐熱ガラス基板を基体とし、この基体上に実施例１１～実施例１１３の複合銀ナノペーストをスクリーン印刷して、所定パターンのペーストパターンを形成した３０種類の試験体を得た。その後、前記試験体を電気炉により表１０及び表１１に記載の大気中ペースト焼成温度Ｔで加熱して、前記ペーストパターンから銀パターンを形成した。冷却した後、光学顕微鏡により、前記銀パターンの表面を検査したところ、３０種の試験体で問題はなかった。前記３０種類のパターン形成試験から、本発明に係る複合銀ナノペーストは銀パターン形成用材料として工業的に利用できることが分かった。 [Example 115: Formation of silver pattern on heat-resistant glass substrate]
Using the heat-resistant glass substrate as a base, the composite silver nanopastes of Examples 11 to 113 were screen-printed on the base to obtain 30 types of test bodies on which a predetermined paste pattern was formed. Then, the said test body was heated with the atmospheric paste baking temperature T of Table 10 and Table 11 with the electric furnace, and the silver pattern was formed from the said paste pattern. After cooling, when the surface of the silver pattern was inspected with an optical microscope, there were no problems with 30 types of specimens. From the 30 types of pattern formation tests, it was found that the composite silver nanopaste according to the present invention can be used industrially as a silver pattern forming material.
　本発明は、上記実施形態や変形例に限定されるものではなく、本発明の技術的思想を逸脱しない範囲における種々変形例、設計変更などをその技術的範囲内に包含するものであることは云うまでもない。 The present invention is not limited to the above-described embodiments and modifications, and includes various modifications and design changes within the technical scope without departing from the technical idea of the present invention. Needless to say.
　本発明によれば、銀原子の集合体からなる平均粒径１～２０ｎｍの銀核の周囲に、炭素数１～９又は１１のアルコール分子残基、アルコール分子誘導体又はアルコール分子の一種以上からなる有機被覆層を形成した複合銀ナノ粒子を少なくとも含有する金属成分を樹脂と混合して構成され、前記樹脂は１０℃以下では非流動状態にあって前記金属成分を分散状態に保持し、加熱により流動化して塗着可能になる複合銀ナノペーストが提供される。非流動性により複合銀ナノ粒子の凝集を防止し、加熱流動性により塗着性能を発現するペーストが提供される。従って、本発明の複合銀ナノペーストは、代替半田・プリント配線・導電性材料などの電子材料、磁気記録媒体・電磁波吸収体・電磁波共鳴器などの磁性材料、遠赤外材料・複合皮膜形成材などの構造材料、焼結助剤・コーティング材料などのセラミックス・金属材料、医療材料などの各種分野のペーストに適用できる。 According to the present invention, a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms is composed of one or more alcohol molecule residues, alcohol molecule derivatives or alcohol molecules having 1 to 9 or 11 carbon atoms. A metallic component containing at least composite silver nanoparticles having an organic coating layer is mixed with a resin. The resin is in a non-flowing state at 10 ° C. or lower, and the metallic component is held in a dispersed state. A composite silver nanopaste that can be fluidized and applied is provided. A paste that prevents aggregation of composite silver nanoparticles by non-fluidity and develops coating performance by heat fluidity is provided. Therefore, the composite silver nanopaste of the present invention can be used for electronic materials such as alternative solder, printed wiring, and conductive materials, magnetic materials such as magnetic recording media, electromagnetic wave absorbers, and electromagnetic resonators, far-infrared materials, and composite film forming materials. It can be applied to pastes in various fields such as structural materials, ceramics / metal materials such as sintering aids / coating materials, and medical materials.

Claims (10)

  1. 銀原子の集合体からなる平均粒径１～２０ｎｍの銀核の周囲に、炭素数１～９又は１１のアルコール分子残基、アルコール分子誘導体又はアルコール分子の一種以上からなる有機被覆層を形成した複合銀ナノ粒子を少なくとも含有する金属成分を樹脂と混合して構成され、前記樹脂は１０℃以下では非流動状態にあって前記金属成分を分散状態に保持し、加熱により流動化して塗着可能になることを特徴とする複合銀ナノペースト。 An organic coating layer composed of one or more alcohol molecule residues, alcohol molecule derivatives or alcohol molecules having 1 to 9 or 11 carbon atoms was formed around silver nuclei having an average particle diameter of 1 to 20 nm made of an aggregate of silver atoms. It is composed by mixing a metal component containing at least composite silver nanoparticles with a resin, and the resin is in a non-flowing state at 10 ° C. or lower, holding the metal component in a dispersed state, and fluidized by heating and can be applied. A composite silver nano paste characterized by
  2. 前記複合銀ナノ粒子は９５（ｍａｓｓ％）以下であり、前記樹脂は２０（ｍａｓｓ％）以下である請求項１に記載の複合銀ナノペースト。 The composite silver nanopaste according to claim 1, wherein the composite silver nanoparticles are 95 (mass%) or less, and the resin is 20 (mass%) or less.
  3. 前記金属成分として平均粒径０．１～１０μｍの銀微粒子が添加される請求項１に記載の複合銀ナノペースト。 The composite silver nanopaste according to claim 1, wherein silver fine particles having an average particle diameter of 0.1 to 10 µm are added as the metal component.
  4. 前記複合銀ナノ粒子は５～８５（ｍａｓｓ％）、前記銀微粒子は８０～１０（ｍａｓｓ％）であり、前記樹脂は２０（ｍａｓｓ％）以下である請求項３に記載の複合銀ナノペースト。 The composite silver nanopaste according to claim 3, wherein the composite silver nanoparticles are 5 to 85 (mass%), the silver fine particles are 80 to 10 (mass%), and the resin is 20 (mass%) or less.
  5. 所望量の溶剤を添加して、１０℃以下でも流動状態化させて塗着可能にする請求項１～４のいずれかに記載の複合銀ナノペースト。 The composite silver nanopaste according to any one of claims 1 to 4, wherein a desired amount of a solvent is added so that the fluidized state can be applied even at 10 ° C or lower to enable coating.
  6. 　１０℃で非流動状態にあり加熱により流動化する樹脂に、銀原子の集合体からなる平均粒径１～２０ｎｍの銀核の周囲に炭素数１～９又は１１のアルコール分子残基、アルコール分子誘導体又はアルコール分子の一種以上からなる有機被覆層を形成した複合銀ナノ粒子及び必要により銀微粒子を金属成分として混合し、加熱下で前記樹脂を流動化させて全体を混練し、混練後に前記樹脂が非流動状態になる温度まで冷却して、前記金属成分を前記樹脂中に分散状態に保持することを特徴とする複合銀ナノペーストの製法。 A resin that is non-flowable at 10 ° C. and fluidized by heating, an alcohol molecule residue having 1 to 9 or 11 carbon atoms and an alcohol molecule around a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms Composite silver nanoparticles formed with an organic coating layer composed of one or more of derivatives or alcohol molecules and, if necessary, silver fine particles are mixed as metal components, the resin is fluidized under heating to knead the whole, and after the kneading, the resin A method for producing a composite silver nanopaste, wherein the metal component is cooled in a non-flowing state to keep the metal component in a dispersed state in the resin.
  7. 前記銀核の平均粒径は１～２０ｎｍ、前記銀微粒子の平均粒径は０．１～１０μｍである請求項６に記載の複合銀ナノペーストの製法。 The method for producing a composite silver nanopaste according to claim 6, wherein the average particle diameter of the silver nuclei is 1 to 20 nm, and the average particle diameter of the silver fine particles is 0.1 to 10 µm.
  8. 所望量の溶剤を添加して、１０℃以下でも流動状態化させて塗着可能なペーストにする請求項６又は７に記載の複合銀ナノペーストの製法。 The method for producing a composite silver nanopaste according to claim 6 or 7, wherein a desired amount of a solvent is added to make a paste that can be applied by being fluidized even at 10 ° C or lower.
  9. 請求項１～５のいずれかに記載の複合銀ナノペーストを用意し、前記複合銀ナノペーストを下体に塗着してペースト層を形成し、前記ペースト層上に上体を配置し、加熱により前記ペースト層を銀化して前記下体と前記上体を接合することを特徴とする接合方法。 A composite silver nanopaste according to any one of claims 1 to 5 is prepared, the composite silver nanopaste is applied to a lower body to form a paste layer, the upper body is disposed on the paste layer, and heated. A joining method, wherein the paste layer is silvered to join the lower body and the upper body.
  10. 請求項１～５のいずれかに記載の複合銀ナノペーストを用意し、前記複合銀ナノペーストを基体の面上に所定パターンに塗着してペーストパターンを形成し、加熱により前記ペーストパターンを銀化して銀パターンを形成することを特徴とするパターン形成方法。 A composite silver nanopaste according to any one of claims 1 to 5 is prepared, the composite silver nanopaste is coated on a surface of a substrate in a predetermined pattern to form a paste pattern, and the paste pattern is silvered by heating. Forming a silver pattern by patterning.
PCT/JP2008/062238 2008-01-17 2008-07-04 Composite silver nanopaste, process for production thereof, method of connection and pattern formation process WO2009116185A1 (en)

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JP2010503736A JP5306322B2 (en) 2008-03-18 2008-07-04 Composite silver nanopaste, manufacturing method thereof, bonding method and pattern forming method
US12/735,435 US8348134B2 (en) 2008-01-17 2008-12-25 Composite silver nanoparticle, composite silver nanopaste, bonding method and patterning method
JP2009549977A JP4680313B2 (en) 2008-01-17 2008-12-25 COMPOSITE SILVER NANOPARTICLES, COMPOSITE SILVER NANOPASTE, PROCESS FOR PRODUCING THE SAME, MANUFACTURING APPARATUS, JOINING METHOD, AND PATTERN FORMING METHOD
EP08870788.0A EP2298471B1 (en) 2008-01-17 2008-12-25 Composite silver nanoparticles, composite silver nanopaste, and production methodof the same
CN2008801281306A CN101990474B (en) 2008-01-17 2008-12-25 Composite silver nanoparticles, composite silver nanopaste, and production method, production apparatus, conjugation method and patterning method of the same
KR1020107017975A KR101222304B1 (en) 2008-01-17 2008-12-25 Composite silver nanoparticles, composite silver nanopaste, and production method, production apparatus, conjugation method and patterning method of the same
PCT/JP2008/073660 WO2009090846A1 (en) 2008-01-17 2008-12-25 Composite silver nanoparticles, composite silver nanopaste, and production method, production apparatus, conjugation method and patterning method of the same
PCT/JP2008/073751 WO2009090849A1 (en) 2008-01-17 2008-12-26 Method of wire bonding and structure including mounted electronic part
US13/707,384 US8906317B2 (en) 2008-01-17 2012-12-06 Production apparatus of composite silver nanoparticle
US13/707,298 US8459529B2 (en) 2008-01-17 2012-12-06 Production method of composite silver nanoparticle

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