WO2002035554A1 - Pate metallique electro-conductrice et procede de production de cette pate - Google Patents
Pate metallique electro-conductrice et procede de production de cette pate Download PDFInfo
- Publication number
- WO2002035554A1 WO2002035554A1 PCT/JP2001/008340 JP0108340W WO0235554A1 WO 2002035554 A1 WO2002035554 A1 WO 2002035554A1 JP 0108340 W JP0108340 W JP 0108340W WO 0235554 A1 WO0235554 A1 WO 0235554A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- ultrafine
- particles
- mass
- compound
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
Definitions
- the present invention relates to a conductive metal paste and a method for producing the same, and more specifically, to digital printing on rigid and flexible printed boards, IC chips, glass substrates, ceramic substrates, and the like by using screen printing, dispensing printing, and the like.
- the present invention relates to a conductive metal paste used for forming a low-impedance and fine circuit corresponding to high-density wiring and forming an interlayer junction, and a method for manufacturing the same. Background technology
- Japanese Patent Application Laid-Open No. H3_34211 discloses that the metal ultrafine particles are prepared by using a gas evaporation method. It discloses a colloidal dispersion of ultrafine metal particles of 10 nm or less and a method for producing the same.
- JP-A-11-319538 discloses that ultrafine metal particles having an average particle diameter of several nm to several tens of nm are dispersed in a colloidal form by using a reduction precipitation method using an amine compound for reduction. And its manufacturing method are disclosed.
- the ultrafine metal particles having an average particle diameter of several nm to several tens of nm disclosed in Japanese Patent Application Laid-Open No. 11-319538 and the like are coated with a polymer resin or the like in order to maintain a colloidal state. It is.
- ultrafine metal particles having an average particle diameter of several nm to several tens of nm are fired at a temperature much lower than the melting point (for example, silver is a fine particle having a clean surface even at 200 ° C or less). It is known to tie. This is because, in ultrafine metal particles, if the particle diameter is sufficiently reduced, the ratio of the high-energy atoms existing on the particle surface to the whole becomes large, and the surface diffusion of metal atoms cannot be ignored. As a result, the interface between particles is not stretched due to this surface diffusion. This is because sintering is performed.
- the processing temperature is such that silver having a low melting point is used as the conductive material. Even when used, the temperature must be at least higher than 300 ° C.
- the ultrafine particles contained in the ultrafine particles form a dense random chain of sintering, and the whole becomes a network, and gradually becomes a network.
- the polymer resin present on the particle surface for maintaining the rolled state is an obstacle. Therefore, when dried and cured at a temperature lower than 300 ° C, the ultra-fine metal particles in the paste are in the form of colloids that are too stabilized. The required random chains cannot be formed, and by practical standards, the resistance is much higher.
- conductive metal bases using ultrafine particles of conventional composition -In a strike the smaller the average particle size, the greater the rate of change in surface area decrease and “volume shrinkage”, and it also induces cracks on the surface of the cured product, or reduces adhesion to the substrate. Interfacial destruction may also be involved.
- a conductive metal paste using ultrafine particles of the conventional composition the film thickness increases and it is difficult to form a uniform film.For example, a thick film having a thickness of several microns or more, particularly, more than ten microns is required. In forming, it is becoming increasingly difficult to bring the conductivity into the desired range.
- general-purpose conductive paste uses metal powder with an average particle size of 0.5 to 20 m, which is produced by a pulverization method, an electrolytic method, a reduction method, etc. As a result, the metal powders are brought into physical contact with each other to establish electrical continuity, so that the resistance in each metal particle is sufficiently small, the contact area is relatively large, and the conductivity is good.
- the ultra-high density which can be applied to ultra-fine circuit printing so that the allowable range of the minimum line width variation in the circuit printing becomes smaller. Or at present, there is no conductive metal paste for printing ultrafine circuits.
- the present invention solves the above problems, and an object of the present invention is to use a metal filler having a larger particle diameter in addition to ultrafine metal particles as a conductive medium constituting a conductive metal paste.
- a metal filler having a larger particle diameter in addition to ultrafine metal particles as a conductive medium constituting a conductive metal paste.
- An object of the present invention is to provide a low-temperature sinterable conductive metal paste for printing and a method for producing the same.
- a metal ultra-fine particle is used as a main component of a conductive medium constituting a conductive metal paste, and is applied on a substrate.
- a low-temperature sintering conductive metal paste for ultra-fine circuit printing which has good adhesion when baked, has an extremely smooth surface shape, and can form low-resistance and ultra-fine circuits, and its manufacture We will provide a method.
- the present inventors have made intensive studies to solve the above-mentioned problems, and as a result, when using ultrafine metal particles as a conductive medium constituting a conductive metal paste, prepare a conductive metal paste itself.
- the stabilized colloidal state is preferable in terms of improving coagulation resistance, but, for example, when heating and curing a thermosetting resin used as an organic binder, it contributes to maintaining the colloidal state. It has been found that if the molecular layer covering the surface of the ultrafine metal particles is left as it is, fusion of the contact interface by sintering at low temperature, which is indispensable for achieving excellent conductivity, will be hindered. .
- the conductive metal base itself was prepared, and the ultrafine metal surface contributed to maintaining a stable colloidal state during storage near room temperature.
- the low-temperature curable organic binder is cured by heating, the molecular layer covering the surface is effectively used. If it is configured to be removable, when applied to thin-film wiring patterns, it will have sufficient adhesion to the substrate by heat treatment at an appropriate temperature, for example, an organic binder that has been cured by heating, and it will be uniformly colloidal
- the conductivity imparted to the formed thin-film wiring pattern is sufficient while maintaining the advantages of smoothness of surface shape and high-density circuit drawing High reproducibility and high reproducibility.
- the ultrafine metal particles constituting the conductive metal paste can form a coordinate bond with the metal element contained in the ultrafine metal particles until the heat treatment (eg, heat curing).
- One or more compounds having a nitrogen, oxygen, or iodo atom as a group and having a group capable of coordinative bonding by a lone pair of electrons of these atoms for example, one kind of an amine compound having one or more terminal amino groups
- one or more compounds having a group containing a nitrogen, oxygen, or iodide atom are contained at a predetermined content ratio with respect to the ultrafine metal particles.
- a compound having a group containing the nitrogen, oxygen, or io atom for example, a terminal amino group of an amine compound
- a composition obtained by adding an organic acid anhydride or a derivative thereof or an organic acid capable of reacting and releasing the compound having a group containing a nitrogen, oxygen, or iodide atom from the surface of the ultrafine metal particles By doing so, it becomes a conductive metal paste that disperses ultra-fine metal particles in a stable colloidal form, while maintaining excellent printability of fine lines and high agglomeration resistance during storage.
- a conductive metal base cured product having a desired conductivity can be obtained by heat treatment, for example, heat curing.
- heat treatment for example, heat curing.
- a metal filler having a particle diameter is also used, the entire film thickness is filled with a sintered structure of ultrafine metal particles while maintaining the overall film thickness by a metal filler, and the surface is flattened.
- the present inventor has found that extremely good conductivity is achieved by the sintered structure of the metal filler and the ultrafine metal particles, and based on such knowledge, completed the present invention. That is, a first embodiment of the present invention is a low-temperature sintered conductive metal paste for high-density circuit printing, and a low-temperature sintered conductive metal paste for high-density circuit printing according to the present invention.
- the conductive metal paste includes a varnish-like resin composition, a metal filler uniformly dispersed therein, and ultrafine metal particles having a fine average particle diameter.
- the average particle diameter is selected in the range of 0.5 to 20 m, and the ultrafine metal particles having the fine average particle diameter are selected in the range of 1 to 100 nm,
- the surface of the ultrafine metal particles contains nitrogen, oxygen, or y-atom as a group capable of coordinating with the metal element contained in the ultrafine metal particles. Coated with at least one compound having a group capable of
- the metal ultrafine particles With respect to 100 parts by mass of the metal ultrafine particles, 0.1 to 60 parts by mass as a total of one or more compounds having a group containing nitrogen, oxygen, or zeo atom,
- varnish-like resin composition When the varnish-like resin composition is heated with respect to a resin component that functions as an organic binder and the compound having a group containing nitrogen, oxygen, or iodine, a group containing the nitrogen, oxygen, or iodine is heated.
- a metal paste For example, when a compound having a group containing a nitrogen, oxygen, or iodine atom is heated, an organic acid is used as a compound component having reactivity with the nitrogen, oxygen, or iodine group.
- ultrafine metal particles having a fine average particle size are composed of silver, gold, copper, platinum, palladium, rhodium, ruthenium, iridium, osmium,
- the resin component functioning as an organic binder contained in the varnish-like resin composition is preferably selected from thermosetting resins.
- one or more amine compounds having one or more terminal amino groups can be selected as the compound having a group containing a nitrogen, oxygen, or iodide atom used for coating the surface of the ultrafine metal particles.
- one or more of the amine compounds having one or more terminal amino groups is an alkylamine.
- the content ratio of the metal filler and the metal ultrafine particles having a fine average particle diameter is 10 parts by mass of the metal ultrafine particles having the fine average particle diameter.
- the metal filler is selected in the range of 0.1 to 100 parts by mass.
- the present invention also provides a method for efficiently producing the above-mentioned conductive metal paste with high reproducibility, that is, the method for producing a conductive metal paste of the present invention is a varnish-like varnish.
- the method for producing a conductive metal paste of the present invention is a varnish-like varnish.
- the metal ultrafine particles having a fine average particle diameter have an average particle diameter of 1 to:
- the surface of the ultrafine metal particles contains nitrogen, oxygen, or y-atom as a group capable of coordinating with the metal element contained in the ultrafine metal particles.
- the dispersion liquid of the metal ultrafine particles may be With respect to 0 parts by mass, the composition containing 0.1 to 60 parts by mass as a total of one or more compounds having a group containing a nitrogen, oxygen, or iodide atom is prepared, For the dispersion,
- a metal filler whose average particle diameter is selected in the range of 0.5 to 20 m is added to the paste-like mixture, and the mixture is uniformly mixed to form a paste.
- the total of ultrafine metal particles having a fine average particle diameter, per 100 parts by mass, is a paste obtained by adjusting the content ratio of the varnish-like resin composition to 5 to 100 parts by mass.
- This is a method for producing a conductive metal paste. For example, when a compound having a group containing a nitrogen, oxygen, or iodo atom is heated, a compound component having reactivity with the group containing a nitrogen, oxygen, or iodo atom becomes an organic acid anhydride.
- a method for producing a conductive metal paste, which is a derivative thereof or an organic acid can be provided.
- the present inventors have also separately completed the invention of a conductive metal paste for printing ultrafine circuits based on the above findings.
- the conductive metal paste itself is prepared and the temperature is reduced to around room temperature.
- a molecular layer is provided to cover the surface of the ultrafine metal particles, which contributes to the maintenance of a stabilized colloidal state.
- the structure that can effectively remove the molecular layer that covers the substrate has a sufficient adhesiveness to the substrate by heat treatment at an appropriate temperature, for example, an organic binder cured by heating.
- Uses ultra-fine particles dispersed in colloidal form to maintain the advantages of smooth surface shape and ultra-fine circuit drawing On the other hand, they have found that the conductivity imparted to the formed thin film wiring pattern is sufficiently high, and that the reproducibility can be kept high.
- the ultrafine metal particles constituting the conductive metal paste have at least one terminal amino group capable of coordinatively bonding with the metal element contained in the ultrafine metal particles before the heat treatment.
- at least one of the amine compounds is contained at a predetermined content ratio with respect to the metal ultrafine particles, and in addition, a varnish in which the colloidal ultrafine metal particles are dispersed.
- an organic acid anhydride or a derivative thereof or an organic acid which reacts with the terminal amino group of the amine compound at the time of heating to enable the amine compound to be released from the surface of the ultrafine metal particles, is used.
- the composition By adding the composition, it becomes a conductive metal paste that disperses ultra-fine metal particles in a stable colloidal form, and has excellent ultra-fine line printability and anti-settling property during storage. Sex remains at a higher, even to perform the heat curing of the organic binder one relatively low temperatures, to be able to a conductive metal paste cured product having a desired conductivity, the present inventors have found.
- the second embodiment of the present invention is a low-temperature sintered conductive metal paste for ultra-fine circuit printing
- the low-temperature sintered conductive metal paste for ultra-fine circuit printing according to the present invention is:
- the conductive metal paste comprises a varnish-like resin composition and metal ultrafine particles having a fine average particle diameter uniformly dispersed therein,
- the ultrafine metal particles having a fine average particle diameter are selected to have an average particle diameter of 1 to 100 nm,
- the surface of the ultrafine metal particles contains nitrogen, oxygen, or y-atom as a group capable of coordinating with the metal element contained in the ultrafine metal particles. Coated with at least one compound having a group capable of
- the compound having a group containing nitrogen, oxygen, or iodide When the varnish-shaped resin composition is heated with respect to the resin component functioning as an organic binder, the compound having a group containing nitrogen, oxygen, or iodide, A compound component having reactivity with the group containing nitrogen, oxygen, or iodide atoms, and at least one or more organic solvents;
- Conductive metal paste 100 to 100 parts by mass of the metal ultrafine particles, 0.1 to 60 parts by mass as a total of one or more compounds having a group containing nitrogen, oxygen, or iodide.
- Conductive metal paste For example, when a compound having a group containing a nitrogen, oxygen, or iodide atom is heated, an organic acid is used as a compound component having reactivity with the nitrogen, oxygen, or a group containing an iodide atom.
- ultrafine metal particles having a fine average particle diameter are selected from silver, gold, copper, platinum, palladium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, zinc, and titanium.
- a conductive metal paste characterized by being ultrafine metal particles formed of at least one kind of metal can be obtained.
- the ultrafine metal particles having a fine average particle diameter have an average particle diameter selected in a range of 2 to 10 nm.
- the resin component contained in the varnish-like resin composition and functioning as an organic binder is selected from a thermosetting resin, or a thermoplastic resin or a thermally decomposable resin. Is preferred.
- the compound having a group containing a nitrogen, oxygen, or zeo atom used for coating the surface of the ultrafine metal particles one or more amine compounds having one or more terminal amino groups can be selected. At that time, for example, it is more preferable that one or more of the amine compounds having one or more terminal amino groups is an alkylamine.
- the present invention also provides a method for efficiently producing the above-described conductive metal paste with high reproducibility, that is, the method for producing a conductive metal paste of the present invention comprises a varnish-like resin. In preparing a conductive metal paste obtained by uniformly dispersing ultrafine metal particles having a fine average particle diameter in the composition,
- the ultrafine metal particles having a fine average particle diameter are selected to have an average particle diameter of 1 to 100 nm,
- the surface of the ultrafine metal particles is coordinated with a metal element contained in the ultrafine metal particles.
- a nitrogen-, oxygen-, or i-atom as a group capable of forming a group, and being covered with at least one compound having a group capable of coordinative bonding by a lone pair of these atoms.
- the dispersion liquid of the metal ultrafine particles is, based on 100 parts by mass of the metal ultrafine particles, a total of one or more compounds having a group containing a nitrogen, oxygen, or iodide atom, 0.1 to 60 parts by mass of the metal ultrafine particles,
- a method for producing a conductive metal paste comprising: For example, when a compound having a group containing a nitrogen, oxygen, or iodo atom is heated, a compound component having reactivity with the group containing a nitrogen, oxygen, or iodo atom becomes an organic acid.
- a method for producing a conductive metal paste which is a hydrate or a derivative thereof or an organic acid, can be provided.
- polyoxyalkyleneamine As the amine compound used in the present invention, besides alkylamine, polyoxyalkyleneamine and the like can also be used.
- This polyoxyalkyleneamine has a polyester skeleton containing a plurality of oxyalkylene units, It means a compound having one or more amino groups at its terminal.
- the conductive metal paste of the present invention is mainly used for forming low-impedance and fine circuits corresponding to digital high-density wiring by using screen printing, dispensing printing, etc., and forming interlayer bonding. For high density printing. in addition, Utilizing the fine printing performance, it can also be used to form conductive films and buried layers that penetrate fine holes. Further, the formed thermosetting film has excellent uniformity of the film thickness, and can be used for forming, for example, a conductive thin film constituting various sensors by utilizing the advantage.
- the low-temperature sintered conductive metal paste for high-density circuit printing of the present invention uses a metal filler and metal ultrafine particles as a conductive medium.
- the metal filler that is, the ultrafine metal particles contained in the conductive metal paste has an average particle diameter of the metal filler of 0 according to the target line width of the printed circuit pattern and the film thickness after heat curing.
- the average particle diameter of the metal ultrafine particles in which the gaps between the metal fillers are densely packed is selected in the range of 1 to 10 O nm.
- the average particle diameter of the ultrafine metal particles is selected in the range of 2 to 10 nm.
- the low-temperature sintering-type conductive metal paste for printing ultrafine circuits of the present invention is used particularly for forming low-impedance and extremely fine circuits corresponding to digital high-density wiring and forming interlayer bonding.
- the metal ultra-fine particles contained as the main conductive medium are averaged according to the target line width of ultra-fine printing and the film thickness after heat treatment (such as thermosetting).
- the particle size is selected in the range from 1 to 100 nm.
- the average particle size is selected in the range of 2 to 10 nm.
- ultrafine metal ultrafine particles in the form of a dry powder
- the metal ultrafine particles adhere to each other to cause agglomeration. It is not suitable for high-density printing as intended by the present invention.
- a coating layer of a low molecule is provided on the surface of the ultrafine metal particles, and the particles dispersed in a liquid are used.
- the contained resin component is subjected to a heat treatment.
- a heat treatment For example, when heated and cured, there is no oxide film on the surface of the ultrafine metal particles so that the ultrafine metal particles contained in the conductive medium will fuse together at the contact interface between them.
- the metal ultrafine particles used as a raw material have, on the surface, a group containing nitrogen, oxygen, or iodine as a group capable of coordinatively bonding with the metal element contained in the metal ultrafine particles. In a state of being coated with one or more compounds.
- the metal surface of the ultrafine metal particles is densely formed by at least one compound having a group containing a nitrogen, oxygen, or iodine atom as a group capable of coordinating with the metal element contained in the ultrafine metal particles.
- a dispersion of ultrafine metal particles dispersed in one or more organic solvents in a state of being coated with one or more amine compounds having one or more terminal amino groups is used. Due to the effect of the coating layer, the metal ultrafine particles are not in direct contact with each other until the heat treatment is performed, the aggregation of the metal ultrafine particles contained in the conductive paste is suppressed, and the The cohesion resistance is kept high.
- the surface of the ultrafine metal particles is already covered with the coating layer, and the metal ultrafine particles are not directly in contact with water molecules or oxygen molecules. Since this does not occur, formation of a natural oxide film on the surface of the ultrafine metal particles due to moisture and oxygen molecules in the atmosphere is also suppressed.
- the compound used for densely coating the surface of the ultrafine metal particles utilizes a group having a lone pair of electrons on nitrogen, oxygen, or iodine when forming a coordinated bond with a metal element.
- an amino group may be mentioned as a group containing a nitrogen atom.
- the group containing a zeo atom include a sulfanyl group (—SH) and a sulfido-type sulfandisyl group (—S—).
- Examples of the group containing an oxygen atom include a hydroxy group and an ether-type oxy group (10-).
- Alkylamines can be mentioned as representatives of compounds having an available amino group.
- the alkylamine does not desorb in a normal storage environment, specifically, in a temperature range of not more than 40 ° C. in a state where a coordination bond is formed with the metal element.
- those having a boiling point of at least 60 ° C, preferably at least 100 ° C are preferred.
- conducting heat treatment (such as heat curing) of the conductive paste Is necessary to be able to be quickly separated from the surface of the ultrafine metal particles, and at least the boiling point does not exceed 300 ° C, usually falls within the range of 250 ° C or less. Are preferred.
- the alkyl group is C 4 to C 20, more preferably C 8 to C 18, and an alkyl group having an amino group at the terminal of the alkyl chain is used.
- the alkylamines in the range of C8 to C18 have thermal stability, their vapor pressure is not so high, and the content is maintained in a desired range when stored at room temperature or the like. ⁇ Suitable for handling due to easy control.
- a primary amine type is preferred because it exhibits a higher binding ability, but a secondary amine type and a tertiary amine type compound are also used. It is possible.
- compounds in which two or more adjacent amino groups participate in binding such as 1,2-diamine type and 1,3-diamine type, can also be used.
- a polyoxyalkylene amine can also be used.
- a hydrophilic terminal group for example, a hydroxylamine-containing hydroxyamine, such as ethanolamine, may be used.
- Alkanethiol can be cited as a typical example of a compound having a usable sulfanyl group (-SH). It is preferable that the alkanol is not desorbed in a normal storage environment, specifically, at a temperature of not more than 40 ° C. in a state where a coordination bond is formed with the metal element. Those having a boiling point of at least 60 ° C., preferably at least 100, are preferred. However, when heating and hardening the conductive paste, it is necessary that the conductive paste can be quickly separated from the surface of the ultrafine metal particles, and at least the boiling point should not exceed 300 ° C. Usually, those having a range of 250 or less are preferable.
- the alkyl group is preferably C 4 to C 20, more preferably C 8 to (: 18), and a sulfanyl group (-SH) at the terminal of the alkyl chain.
- the alkanethiol in the range of C 8 to C 18 has thermal stability, has a not so high vapor pressure, and is difficult to be stored at room temperature or the like. Maintain the content in the desired range 'Easy to control, suitable for handling You can.
- primary thiol-type compounds exhibit higher binding ability and are preferred, but secondary thiol-type and tertiary thiol-type compounds can also be used.
- those in which two or more sulfanyl groups (one SH) are involved in binding such as 1,2-dithiol type, can also be used.
- Alkandiol may be mentioned as a typical example of a compound having an available hydroxy group.
- examples include glycols such as ethylene glycol, diethylene glycol, and polyethylene glycol. It is preferable that the alkanediol does not desorb in a normal storage environment, specifically, at a temperature below 40 ° C in a state where a coordination bond is formed with the metal element. Those having a boiling point in the range of 60 ° C or higher, usually in the range of 100 ° C or lower are preferred. However, when conducting heat treatment (such as heat curing) of the conductive paste, it is necessary that the paste can be quickly separated from the surface of the ultrafine metal particles, and the boiling point must be at least 30%.
- the temperature does not exceed 0 ° C., and usually falls within a range of 250 ° C. or less.
- those in which two or more hydroxy groups are involved in bonding, such as a 1,2-diol type, can be more preferably used.
- a varnish-like tree composition containing a compound component having a reactivity with a group containing a nitrogen, oxygen, or thio atom for example, an organic acid anhydride or an acid anhydride derivative or an organic acid.
- the compound having reactivity with a group containing nitrogen, oxygen, or iodine atom when heated, coats the surface of the above-described ultrafine metal particles, as a group capable of coordinating with a metal element, It is used to remove a coating layer of a compound having a group containing a nitrogen, oxygen, or zeo atom. That is, with heating, at around room temperature, as a result of reacting with a group containing nitrogen, oxygen, or iodide in the coating compound forming the coating layer, the nitrogen, oxygen, or zeoatom is reacted after the reaction. The group containing it becomes difficult to form a coordinate bond with the metal atom on the surface of the ultrafine metal particle surface, and as a result, it is removed.
- the added acid anhydride or acid anhydride derivative upon heating, is a compound having a group containing the nitrogen, oxygen, or iodide atom, for example, an amine compound, a thiol compound, or a diol compound. It is used to form amides, thioesters and esters by reacting with amides.
- the ultrafine metal ultrafine particles are originally uniformly dispersed in the conductive paste, and when applied, for example, fine irregularities on the surface of the substrate to be applied, or are used in combination.
- a dense filling state can be adopted to fill the gap between the metal fillers.
- the surface of the ultrafine metal particles which take a densely packed state, is covered with a coating layer of a compound having a group containing nitrogen, oxygen, or zeo atom, so that the metal surface of the ultrafine metal particles is in direct contact with the metal ultrafine particles.
- the heat treatment proceeds in that state and the coating layer is removed, the metal surface is brought into direct contact with the metal ultrafine particles, even at relatively low temperatures. Wake up.
- the ultrafine metal particles in the coating film maintain a densely filled state so as to fill the fine irregularities on the substrate surface to be coated or the gaps between the metal fillers used together. It becomes a dense sintered body, and good conductivity can be achieved through the dense sintered body as a whole of the thermoset conductive paste.
- the content of the acid anhydride or acid anhydride derivative used for the reaction with the compound having a group containing nitrogen, oxygen, or iodide is determined by the amine compound, thiol compound, It is preferred to add at least an amount equivalent to the total amount of the terminal amino group, sulfanyl group (-SH) and hydroxy group contained in the diol compound and the like.
- the acid anhydride or the acid anhydride derivative when heated, sometimes reacts with a basic metal oxide film present on the surface of the metal filler to form a metal salt of carboxylic acid. In consideration of its reactivity, a slightly excessive amount is appropriately selected.
- organic acid anhydride or derivative thereof or organic acid to be used is not particularly limited as long as it shows the above reactivity.
- available organic acids include C 1 -C 10 linear saturated carboxylic acids, formic acid, acetic acid, propionic acid, butanoic acid, hexanoic acid, octylic acid, stearic acid, isostearic acid, C 1 to C 18 linear or branched saturated or unsaturated carboxylic acids, such as oleic acid, linoleic acid, and acrylic acid, methacrylic acid, crotonic acid, cake acid, benzoic acid, and sorbic acid.
- Acids and polymers such as oleic acid and linoleic acid, such as dimer acid and trimeric acid; and oxalic acid, malonic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, alkylsuccinic acid, and alkenylsuccinic acid
- carboxylic acids such as dibasic acids such as acids, a phosphate group (— 0- P (0) (OH) 2 ) or a sulfo group (- S0 having 3 H)
- phosphoric acid esters such as phosphoric acid esters, sulfonic acid.
- organic acid anhydrides or acid anhydride derivatives examples include anhydrous fluoric acid, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrihydrate).
- Aromatic acid anhydrides such as melitate), dali cerol tris (anhydrotrimellitate), maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, alkylsuccinic anhydride Acid, alkenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrofluoric anhydride, methylcyclyl hexene tetracarboxylic acid anhydrides such as cyclic sulfonic acid anhydride, polyadipic anhydride, polyazerine anhydride, Aliphatic acid anhydrides such as polysebacic anhydride It can be mentioned.
- methyltetrahydrophthalic anhydride, methylhexahydrofluoric anhydride, alkenylsuccinic anhydride, and derivatives thereof can be used, for example, even at a relatively low heat treatment (sintering) temperature aimed at by the present invention. It is suitably used because it has an appropriate reactivity with the terminal amino group of the amine compound.
- This organic acid anhydride or acid anhydride derivative is a compound used as an adhesion layer covering the metal surface of the ultrafine metal particles during heat curing, for example, alkylamine ⁇ It is used to react with an amine compound having a terminal amino group such as polyoxyalkyleneamine to form an amide. Therefore, the content of the acid anhydride or the acid anhydride derivative is determined by the amount of the compound having a group containing nitrogen, oxygen, or iodide contained therein, for example, the alkylamine used as an amine compound having a terminal amino group. (4) It is appropriately selected according to the type of the polyoxyalkyleneamine and its content.
- acid anhydrides or acid anhydride derivatives derived from dibasic acids such as methyltetrahydrophthalic anhydride, methylhexahydrofluoric anhydride, alkenylsuccinic anhydride, and derivatives thereof are used.
- the content (number of moles) is more than 1/2 of the total (number of moles) of the amine compound having a terminal amino group, for example, an alkylamine and a total of amine groups derived from polyoxyalkyleneamine.
- the content of the acid anhydride or acid anhydride derivative derived from a dibasic acid is determined by the sum of the amine compounds having a terminal amino group, for example, the alkylamine and the amine group derived from polyoxyalkyleneamine ( (Molar number) is preferably not more than 1 time.
- the acid anhydride or a derivative of an organic when using an organic acid, and power Rupokishi group, Li phospho groups (one (HP (0) (OH) 2) or a sulfo group (an S0 3 H) may correspond to one molecule of the acid anhydride derived from a dibasic acid, and the amount added may be selected within the above range.
- a low-temperature sintered conductive metal base for high-density circuit printing includes a metal filler and fine metal fine particles having an average particle diameter of lnm to 10 O nm. Is used as a conductive medium.
- metal fillers having a larger average particle diameter are laminated and mainly determine the overall film thickness, the gaps between the laminated metal fillers are densely filled with fine metal fine particles. As a whole, it functions as a good conductive medium.
- the average particle size of the metal fine particles does not need to be extremely small, and the average particle size is desirably selected in the range of 2 to 10 nm.
- thermo-cured products those that mainly govern the overall conductivity (resistance) are those that fill the gaps between the metal fillers and achieve good electrical contact therebetween. This is the resistance at the surface where the metal particles contact each other. The conductivity of each metal particle itself is a secondary factor.
- the metal constituting the ultrafine metal particles is not particularly limited, but in order to achieve the above-mentioned preferable average particle diameter of 10 nm or less, noble metals, copper, tungsten, nickel, tantalum, bismuth, and lead , Indium, tin, zinc, titanium and at least one of the following metals: silver, gold, copper, platinum, palladium, rhodium, osmium, retinium, iridium, tungsten, nickel, tantalum, bismuth, lead, indium It is preferable to select from among tin, zinc, and titanium.
- ultrafine particles of noble metals silver, gold, platinum, palladium, rhodium, osmium, ruthenium, iridium
- silver, gold, and copper have good conductivity and are more preferably used.
- volume shrinkage accompanying the curing of the thermosetting resin composition is used.
- the contact area can be easily enlarged, which is more preferable.
- the conductive metal paste of the present invention preferably uses ultrafine metal particles having an average particle diameter of 10 nm or less in order to fill gaps between metal fillers having a larger particle diameter. Even when ultrafine metal particles of about 100 nm are used, it is possible to achieve a state in which the ultrafine metal particles are uniformly present in the gaps between the metal fillers. Smooth shape, low resistance and fine circuit can be formed. Therefore, even when the film thickness is relatively large with respect to the line width, the film thickness can be uniform and the surface unevenness can be avoided. It becomes a paste.
- the metal filler used in the conventional conductive metal paste as a conductive medium can be a metal particle having an average particle diameter selected from the range of 0.5 to 20 m.
- suitable metal filler materials include gold, silver, palladium, copper, nickel, tin, lead, and even bismuth, indium, and aluminum. Can be mentioned. That is, it is preferable to use the above-described metal particles of silver, gold, copper, etc., which have excellent conductivity of each metal particle itself and high extensibility at the same time. At this time, the same material can be selected for the metal filler and the metal ultrafine particles.
- the metal filler used by being mixed with the metal ultrafine particles has a metal filler content of at least 0.1 to 100 parts by mass per 10 mass parts of the metal ultrafine particles, preferably 10 to 1 part by mass. It is preferable to select the amount within a range of from 0.000 parts by mass, more preferably from 20 to 500 parts by mass.
- the average particle diameter of the metal filler is more preferably at least 10 times or more, preferably more than 50 times, the average particle diameter of the ultrafine metal particles.
- the ultrafine metal particles contained therein have a surface on which nitrogen is formed as a group capable of coordinating with the metal element contained in the ultrafine metal particles. , Oxygen, or y-atoms, and is covered with at least one compound having a group capable of coordinatively bonding with a lone pair of electrons contained in these atoms. It is preferable to be covered with at least one of the above-mentioned amine compounds.
- 100 to 100 parts by mass of the ultrafine metal particles the total amount of one or more of the amine compound, the state containing 0.1 to 60 parts by mass. I do.
- Preferably, with respect to 100 parts by mass of the metal ultrafine particles 0.5 to 30 parts by mass, more preferably 1 to 10 parts by mass, as a total of one or more of the amine compounds.
- the first function of the amine compound contained in the conductive metal paste of the present invention is to form an adhesion layer on the surface of ultrafine metal particles and to prepare a varnish by stirring and mixing in a step of preparing the paste at room temperature. It is an object of the present invention to prevent ultrafine metal particles from coming into direct contact with their clean surfaces in the step of kneading the resin composition in the form of a solid, thereby preventing the metal particles from adhering to each other to form a lump. Therefore, as long as an adhesion layer is formed on the surface of the ultrafine metal particles, there is no particular limitation on the type of the adhesion layer, but it is desirable that the particles do not easily evaporate at room temperature.
- an amine compound having an amino group at the terminal for example, an alkylamine.
- the alkyl group has C4-C20. It is more preferably selected from the range of C8 to C18, and those having an amino group at the terminal end of the alkyl chain are used.
- the alkylamine in the range of C8 to C18 has thermal stability, does not have a very high vapor pressure, and maintains the content in a desired range when stored at room temperature or the like. It is suitable for handling because it is easy to control.
- the content of an amine compound having an amino group at a terminal is determined according to the entire surface of the ultrafine metal particles. It should also be appropriately selected in consideration of the type of metal and the type of the amine compound, for example, alkylamine. Generally, when a C8- (18 alkylamine is used, the specific gravity of the metal itself is about the same as that of silver, gold, and copper, and the average particle diameter of the ultrafine metal particles is not extremely smaller than 10 nm, the colloid is used.
- the amount of alkylamine used in the dispersion contained depends on the type and particle size of the metal, but the content of alkylamine is 0.1 to 60 parts by mass, preferably 100 parts by mass, based on 100 parts by mass of the metal ultrafine particles. It is preferable to select from 0.5 to 30 parts by mass, and more preferably from 1 to 10 parts by mass. On the other hand, it is preferable that the total content of the amine compound is selected within the range of 0.1 to 60 parts by mass, preferably 0.5 to 30 parts by mass, and more preferably 1 to 10 parts by mass.
- the organic solvent contained in the conductive metal paste of the present invention has a function as a solvent when the varnish-like resin composition is prepared by kneading.
- the metal ultrafine particles to be used may be formed in a form having an adhesion layer of an amine compound, for example, an alkylamine on the surface, and may be further modified with an amine compound such as an alkylamine which forms an adhesion layer described later in advance. It is also used as a solvent when adding an amine compound to the adhesion layer on the surface of the ultrafine metal particles, when performing the operation, and as a solvent. Accordingly, the same organic solvent can be used for the two kinds of applications, or different kinds of organic solvents can be used.
- the type is not limited as long as it can be used for the above-mentioned two uses.
- Compounds that form an adhesion layer on the surface of ultrafine metal particles for example, alkyl Amine compounds such as amines or other kinds of amine compounds to be added later have too high a solubility and should be non-polar solvents or low-polar solvents, not solvents with high polarity such that the adhesion layer on the surface of ultrafine metal particles disappears. It is preferable to select.
- the conductive metal paste when actually using the conductive metal paste of the present invention, the conductive metal paste must have thermal stability to the extent that it does not cause thermal decomposition, even at the temperature of heat treatment, for example, heat curing. Is preferred.
- a dispersion in which ultrafine metal particles with an alkylamine as an adhesion layer on the surface thereof are dispersed in a relatively high-boiling non-polar solvent or a low-polar solvent is extremely stable and can be easily handled in handling. Good, but low overall polarity. Therefore, in this state, when mixing with the resin component of the thermosetting resin, an organic acid anhydride or a derivative thereof, or an organic acid to disperse the ultrafine metal particles in the varnish-like resin composition, the resin If the component itself does not have a good affinity for the alkylamine present as an adhesion layer on the surface of the metal ultrafine particles, the metal ultrafine particles coated with alkylamine will gradually separate and agglomerate when left untreated. In addition, even if the mixture in which the ultrafine metal particles are separated and aggregated is printed and applied, and then cured by heating, the surface is not smooth and is not suitable for high-density printing.
- the affinity between the resin component itself and the alkylamine present as an adhesion layer on the surface of the ultrafine metal particles is not sufficiently high, the following is intended to supplement the affinity.
- a polyoxyalkyleneamine having a more polar oxy group therein can be further applied to the surface of the ultrafine metal particles as compared with the alkyl group of the alkylamine. That is, the surface of the metal ultrafine particles is compared with the resin component such as thermosetting resin used as the organic binder. It is also preferable to improve the dispersion stability by exchanging the compound for coating with a compound having good affinity.
- the metal ultrafine particles dispersed in the resin composition do not gradually separate and agglomerate during standing, and a uniform dispersion system with more excellent stability can be achieved.
- one monoamine, two diamines, and three triamines are used for the total number of the substituted amino groups at the terminal, and preferably, diamine or triamine, especially when triamine is used, the paste is used. After heat curing, the smoothness becomes better, which is preferable.
- an amine compound having a high affinity for a resin component such as a thermosetting resin is further caused to act on the surface of the ultrafine metal particles and added to the adhesion layer, whereby the above-described thermosetting resin is obtained. It has the effect of improving the affinity with varnish-like resin compositions containing resins and thermoplastic resins.
- the ratio of the alkylamine to the whole of the amine compound is preferably selected within a range of at least 0.1 mol% or more of the total amino groups of the amine compound, at least the amino group derived from the alkylamine.
- the varnish-like resin composition contains a resin component that functions as an organic binder as an essential component.
- the resin component fixes the metal fillers contained therein, contacts the metal ultrafine particles that fill the gap between the metal fillers, and contacts the substrate. It has the function of giving adhesion. Therefore, an organic binder, a thermosetting resin, a thermoplastic resin or a thermally decomposable resin used for a general conductive metal paste can be used.
- one or more resin components that can be sufficiently cured by heat treatment at such a temperature may be selected and used according to a target heating / curing temperature.
- thermosetting resins include phenol resins, epoxy resins, unsaturated polyester resins, vinyl ester resins, diaryl phthalate resins, oligoester acrylate resins, xylene resins, bismaleimidotriazine resins, and furan resins. Resins, urea resins, polyurethane resins, melamine resins, silicone resins, acrylic resins (containing oligomers and exhibiting thermosetting properties), oxetane resins, and oxazine resins.
- thermoplastic resin examples include a polyamide resin, a polyimide resin, an acrylic resin, a ketone resin, and a polystyrene resin.
- the thermoplastic resin is dissolved in an appropriate solvent and is contained in the penic resin composition.
- thermally decomposable resin examples include cellulose resins such as cellulose ester and cellulose ether, and polyacryl nitrile.
- the thermally decomposable resin is also contained in the varnish-like resin composition in a state of being dissolved in an appropriate solvent.
- the conductive paste is printed on a circuit pattern or the like. After application, the solvent is volatilized and removed by heating, followed by cooling and solidification to obtain a cured product in which the thermoplastic resin has become a binder.
- thermoplastic resins polyamide resin, polyimide resin, and acrylic resin show good adhesion even when forming ultra-fine circuits, and their physical properties after solidification are suitable for conductive paste. And can be used suitably.
- the varnish-like resin composition includes a silane coupling agent, a titanium coupling agent, and a silane coupling agent for the purpose of improving adhesion to the surface of an underlying printed circuit board and the like, in addition to a resin component functioning as an organic binder.
- a resin component functioning as an organic binder Components such as glass resin and glass frit can be added in appropriate amounts depending on the target.
- a repelling agent generally used for a conductive paste can be added as needed.
- a varnish-like resin composition to which a diluting solvent has been added in advance can be used in order to obtain a viscosity that is favorable for the coating workability of the obtained conductive paste.
- the content of these resin components contained in the varnish-like resin composition should be appropriately selected according to the total volume of the metal filler and the ultrafine metal particles and the ratio of the voids existing between the particles.
- the total amount of the metal filler and the ultrafine metal particles to be used in combination is preferably 5 to 100 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass.
- a compound component having a reactivity with a group containing a nitrogen, oxygen, or zeo atom, such as an acid anhydride or an acid Includes anhydride derivatives.
- the compound component having a reactivity with a group containing a nitrogen, oxygen, or i-atom for example, an acid anhydride or an acid anhydride derivative mainly includes nitrogen, which coats the surface of the ultrafine metal particles, It is used to remove an adhesion layer made of a compound having a group containing oxygen or an iodine atom, for example, an amine compound.
- a resin component used is an epoxy resin or the like, it may be a curing agent for the resin component.
- the acid anhydride or the acid anhydride derivative reacts with an amine compound, for example, alkylamine during the heat curing, and is used not only to form an amide but also to cure an epoxy resin or the like.
- the terminal amino group of the amine compound since it is also consumed as an agent, it may be added in an amount exceeding the amount determined according to the total of the terminal amino groups contained in the above-mentioned amine compound. Since the terminal amino group of the amine compound also reacts with the epoxy resin or the like, the content of the acid anhydride or the acid anhydride derivative depends on the type of the amine compound such as the alkylamine used and the content thereof. Furthermore, it is appropriately selected in consideration of the type of resin component used and its reactivity.
- a metal filler having a large particle diameter is closely surrounded by a paste-like dispersion in which ultrafine metal particles are sufficiently uniformly dispersed in a varnish-like resin composition. It is preferable to use the mixture as a mixture. Once the above-mentioned paste dispersion is prepared, it is preferable to add a metal filler to finally obtain a conductive metal paste having a desired composition.
- the content of the acid anhydride or the acid anhydride derivative derived from the dibasic acid (molar number) If the total amount (molar number) of the amine groups contained is much less than 1 Z 2, a part of the amine compound such as the alkylamine remains unreacted, and as a result, the electricity of the thermosetting product is reduced. Characteristics may be affected. That is, if the adhesion layer is insufficiently removed by the amine compound covering the surface of the ultrafine metal particles when heated, the fusion between the ultrafine metal particles does not sufficiently proceed and fills the gap between the metal fillers. High conduction properties in the ultrafine metal particle region may hinder achievement.
- the composition (for example, 1 Z 4) of the content (mol number) of the organic acid anhydride or a derivative thereof is significantly smaller than the sum of the amine groups (mol number) of 1 Z 2.
- a conductive metal paste having a lower composition in some cases, the electrical resistance of a thermosetting material cured at a low temperature of 250 ° C or less is not sufficiently low, and its volume resistivity is 1%. there is also to remain in more than 0- 4 ⁇ ⁇ cm.
- the contained organic acid anhydride or a derivative thereof generates an amide by, for example, reaction with an amine compound such as alkylamine, and ring opening of the acid anhydride structure in the molecule occurs.
- the generated hydroxyl group also reacts with alkylamine surrounding the surface of the ultrafine metal particles to form an amide. It also reacts with various organic acids to form amides.
- the amine compound such as alkylamine adhering to the surface of the metal ultrafine particles is detached, the adhesion layer that suppressed the aggregation of the metal ultrafine particles disappears, and the metal ultrafine particles are gradually fused and fused. Agglomeration proceeds, and finally a random chain is formed.
- the ultrafine metal particles filling the gap of the metal filler have clean surfaces in contact with each other, and due to the volume shrinkage of the entire resin composition following the bow, the random chains are in close contact with each other.
- the heat treatment temperature is selected to be 300 ° C. or less, preferably 250 ° C. or less, and usually in the range of 180 ° C. to 230 ° C.
- the heat-treated cured product very low resistance, for example, the specific volume resistivity is as follows 1 0- 5 ⁇ 'cm.
- the metal ultra-fine particles form a surface state without unevenness so that the upper part of the metal fillers is buried flat.
- the metal ultra-fine particle layer covering the upper surface of the filler layer slightly shrinks in volume, the inherent unevenness of the metal filler layer is buried in the metal ultra-fine particle layer covering the upper surface, and the surface is flattened. A kana circuit pattern is obtained.
- the conductive metal paste of the present invention having the above-described structure is formed into a paste in which ultrafine metal particles are once dispersed, then a metal filler is added, and the mixture is further kneaded to form a uniform mixture. If necessary, a thixotropic agent used for the conductive metal paste is appropriately added to adjust the viscosity to be suitable for each paste coating method, and excess organic solvent is removed by evaporation under reduced pressure, or Alternatively, an organic solvent can be added (additional amount).
- the varnish-like resin composition contained in the conductive metal paste may be diluted after the operation of adding the reactive compound and acting on the surface of the ultrafine metal particles is completed. Even if a generally available polar solvent is used, the dispersed state of the ultrafine metal particles contained therein can be kept good.
- a low-temperature sinterable conductive metal base for ultrafine circuit printing among the fine metal particles, metal ultrafine particles having an average particle diameter of 1 nm to 100 nm are used. Used as a conductive medium.
- the heat-treated cured product (thermoset product) formed using the conductive metal paste of the present invention the one that mainly governs the overall conductivity (resistance) is the surface where the fine metal particles contact each other.
- the conductivity of the individual metal microparticles is a secondary factor. Therefore, the metal constituting the ultrafine metal particles is not particularly limited.
- noble metals copper, tungsten, nickel, tantalum, bismuth, lead, and indium
- Tin zinc, titanium, at least one metal such as silver, gold, copper, platinum, palladium, rhodium, osmium, ruthenium, iridium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, It is preferable to select from zinc and titanium. Since high conductivity is required for circuit patterns, more preferably, ultrafine particles of noble metals (silver, gold, platinum, palladium, rhodium, osmium, ruthenium, iridium) or copper are used.
- the conductive metal paste of the present invention preferably uses ultrafine metal particles having an average particle diameter of 10 nm or less, the same applies to the case where ultrafine metal particles having an average particle diameter of about 20 nm are used. With this configuration, when applied and fired on a substrate, it has good adhesion, has a smooth surface shape, and can form a low-resistance and ultra-fine circuit. It becomes a conductive metal paste.
- ultrafine metal particles having an average particle diameter of several nm to several 10 nm are at a temperature much lower than their melting point (for example, in the case of silver, ultrafine particles having a clean surface have a temperature of 200 ° C or less.
- sinter it is also known to sinter. In this low-temperature sintering, if the particle size of the ultrafine metal particles is sufficiently reduced, the ratio of the high-energy atoms existing on the particle surface to the total high-state atoms increases, and the surface diffusion of metal atoms is ignored. As a result, the interface between particles is stretched and sintering is performed due to the surface diffusion.
- this property causes a phenomenon that aggregates are formed when the surfaces of the ultrafine metal particles come into direct contact with each other even near room temperature.
- the effect of improving the uniformity of thickness in the present invention is achieved as a result of forming extremely dense metal fine particles in a densely packed state.
- the formation of aggregates is a factor that impairs the effect of improving the uniformity of thickness.
- the effect of achieving the desired conductivity as a whole by forming a densely filled state, and the high reproducibility of the densely filled state when a structure that partially forms aggregates is mixed in advance Will not be attained.
- the second embodiment of the present invention is the first embodiment of the present invention described above, and the low-temperature sintering for high-density circuit printing.
- the conductive metal paste As in the case of the conductive metal paste, the formation of aggregates of the ultrafine metal particles is suppressed at around room temperature.
- heat treatment such as thermosetting
- low-temperature sintering of the ultrafine metal particles is performed.
- the surface of the metal ultrafine particles contains a nitrogen, oxygen, or iodine atom as a group capable of coordinative bonding with the metal element contained in the metal ultrafine particle
- the varnish-like resin composition is coated with at least one compound having a group capable of coordinative bonding by an electron pair, while the compound having a group containing a nitrogen, oxygen, or iodide atom is contained in a varnish-like resin composition.
- it was heated Employs a configuration adding the compound component having a reactivity with the group containing the nitrogen, oxygen or Iou atom.
- the content of the compound having a group containing a nitrogen, oxygen, or iodide atom and the content of the compound component having a reactivity with the group containing a nitrogen, oxygen, or iodo atom are determined by the metal ultrafine particles used.
- the ratio is essentially the same as that described in the first embodiment of the present invention.
- the surface of the ultrafine metal particles contained therein contains nitrogen, oxygen, or iodine atom as a group capable of coordinating with the metal element contained in the ultrafine metal particles. Containing at least one compound having a group capable of coordinate coordination with a lone electron pair of these atoms.For example, it is coated with at least one amine compound having at least one terminal amino group. It is preferable to be in a state of being bent.
- 0.1 to 60 parts by mass of the amine compound or more is contained with respect to 100 parts by mass of the ultrafine metal particles.
- the first function of the amine compound contained in the conductive metal paste of the present invention is to form an adhesion layer on the surface of ultrafine metal particles and to prepare a varnish by stirring and mixing in a step of preparing the paste at room temperature. It is an object of the present invention to prevent ultrafine metal particles from coming into direct contact with their clean surfaces in the step of kneading the resin composition in the form of a solid, thereby preventing the metal particles from adhering to each other to form a lump. Therefore, as long as an adhesion layer is formed on the surface of the ultrafine metal particles, there is no particular limitation on the type of the adhesion layer, but it is desirable that the particles do not easily evaporate at room temperature.
- an amine compound having an amino group at the terminal for example, an alkylamine.
- the alkyl group is preferably C4 to C20, more preferably selected from the range of C8 to C18, and having an amino group at the terminal end of the alkyl chain.
- the alkylamine in the range of C8 to C18 has thermal stability, does not have a very high vapor pressure, and maintains the content in a desired range when stored at room temperature or the like. It is suitable for handling because it is easy to control.
- the content of an amine compound having an amino group at a terminal depends on the entire surface of the ultrafine metal particles. It should also be appropriately selected in consideration of the type of metal and the type of amine compound, for example, alkylamine. In general, when a C8-C18 alkyl amine is used, and the specific gravity of the metal itself is about the same as silver, gold, and copper, and the average particle diameter of the ultrafine metal particles is not extremely smaller than 10 nm, the colloid is used.
- the amount of the alkylamine used in the dispersion containing the metal depends on the type and particle size of the metal, but the content of the alkylamine is 0.1 to 60 parts by mass, preferably 100 parts by mass, , 0.5 to 30 parts by mass, more preferably 1 to 10 parts by mass.
- the total content of the amine compound is 0.1 to 60 parts by mass, preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the metal ultrafine particles. It is preferable that the amount be selected in the range of parts by mass, more preferably in the range of 1 to 10 parts by mass.
- the organic solvent contained in the conductive metal paste of the present invention has a function as a solvent when the varnish-like resin composition is prepared by kneading.
- the metal ultrafine particles to be used may be formed in a form having an adhesion layer of an amine compound, for example, an alkylamine on the surface, and may be further modified with an amine compound such as an alkylamine which forms an adhesion layer described later in advance. It is also used as a solvent when adding an amine compound to the adhesion layer on the surface of the ultrafine metal particles, when performing the operation, and as a solvent. Accordingly, the same organic solvent can be used as the organic solvent used for these two kinds of applications, or different kinds of organic solvents can be used.
- a compound that forms an adhesion layer on the surface of ultrafine particles of the genus for example, an amine compound such as an alkylamine, or another amine compound to be added later has too high a solubility so that the adhesion layer on the surface of the metal ultrafine particles disappears. It is preferable to select a non-polar solvent or a low-polar solvent instead of a solvent having a high polarity.
- the conductive metal paste of the present invention when the conductive metal paste of the present invention is actually used, the conductive metal paste must have thermal stability at a temperature at which heat treatment (such as heat curing) is performed so that thermal decomposition does not occur. Is preferred.
- a relatively high-boiling nonpolar solvent or a low-polar solvent that does not evaporate such as terbineol, mineral spirit, xylene, toluene, tetradecane, and dodecane, are preferably used.
- a dispersion in which ultrafine metal particles with an alkylamine as an adhesion layer on the surface thereof are dispersed in a relatively high-boiling non-polar solvent or a low-polar solvent is extremely stable and can be easily handled in handling. Good, but low overall polarity. Therefore, in this state, when mixing with the resin component of the thermosetting resin, an organic acid anhydride or a derivative thereof, or an organic acid to disperse the ultrafine metal particles in the varnish-like resin composition, the resin If the component itself does not have a good affinity for the alkylamine present as an adhesion layer on the surface of the metal ultrafine particles, the metal ultrafine particles coated with alkylamine will gradually separate and agglomerate when left untreated. In addition, even if the mixture in which the ultrafine metal particles are separated and aggregated is printed and applied, and then cured by heating, the surface is not smooth and is not suitable for high-density printing.
- the purpose is to supplement the affinity.
- a polyoxyalkylene amine having a more polar oxy group therein can be further allowed to act on the surface of the ultrafine metal particles as compared with the alkyl group of the alkylamine.
- the resin component Before mixing with the alkyl group of the alkylamine, a polyoxyalkyleneamine having a more polar oxy group inside is further applied to the surface of the ultrafine metal particles, so that the thermosetting resin or the heat It is more preferable to improve the affinity for a resin component such as a plastic resin.
- the metal ultrafine particles dispersed in the resin composition do not gradually separate and agglomerate during standing, and a uniform dispersion system with more excellent stability can be achieved. Therefore, the polyoxyalkyleneamine to be used, like the alkylamine, is preferably a compound having an amino group at the terminal and containing a polyester skeleton having a plurality of oxyalkylene units.
- the polyether skeleton preferably has a configuration containing propylene oxide or an oxyalkylene unit derived from ethylene oxide, or a mixture containing the above two types of oxyalkylene units.
- one monoamine, two diamines, and three triamines are used for the total number of terminal amino groups to be substituted, and preferably, diamine or triamine, particularly when triamine is used, the paste is heat-cured. After that, the smoothness becomes better, which is preferable.
- boroxyalkyleneamine is further applied to the surface of the ultrafine metal particles and added to the adhesion layer, thereby improving the affinity with the thermosetting resin or the thermoplastic resin as described above.
- the polyether skeleton constituting the polyoxyalkyleneamine has, for example, an ether oxygen (oxy group: 1 o-) derived from an oxypropylene unit or an oxethylene unit, and is therefore compared with the alkyl group of the alkylamine.
- the affinity with a thermosetting resin or a thermoplastic resin having a structure having a polarity in the polymerized portion is remarkably superior.
- the property of adhesion to the metal surface is achieved by utilizing the amino group at the terminal, and is in principle the same mechanism as that of alkylamine.
- the content of the polyoxyalkyleneamine should be appropriately selected according to the entire surface of the metal ultrafine particles, and also in consideration of the type of the metal and the type of the polyoxyalkyleneamine, similarly to the alkylamine. It is. In general, a procedure is followed in which a polyoxyalkyleneamine is allowed to act on the surface of the metal ultrafine particles to which the alkylamine has already been adhered, and then adhered, so that the content of polyoxyalkyleneamine relative to the content of alkylamine is taken. To a fixed ratio Is preferred.
- the content of polyoxyalkyleneamine in the range of 15 to 80% by mass, preferably 30 to 60% by mass of the alkylamine content.
- the content of polyoxyalkyleneamine is preferably 0.1 to 48 parts by mass, more preferably 1.5 per 100 parts by mass of the metal ultrafine particles. It is preferable to select from the range of ⁇ 18 parts by mass.
- the varnish-like resin composition contains, as a main component, a resin component that functions as an organic binder.
- Such a resin component has a function of, when the conductive metal paste of the present invention is heated and cured, bringing into contact with the ultrafine metal particles contained therein and imparting adhesiveness to the substrate. Therefore, an organic binder, a thermosetting resin, a thermoplastic resin, or a thermally decomposable resin used for a general conductive metal base can be used.
- an organic binder, a thermosetting resin, a thermoplastic resin, or a thermally decomposable resin used for a general conductive metal base can be used.
- one or more resin components that can be sufficiently cured by heat treatment at such a temperature may be selected and used in accordance with a target heating / hardening temperature. .
- thermosetting resins include phenolic resins, epoxy resins, unsaturated polyester resins, vinyl ester resins, diaryl phthalate resins, oligoester acrylate resins, xylene resins, bismaleimide triazine resins, furan resins, Examples include urea resin, polyurethane resin, melamine resin, silicone resin, acrylic resin (containing an oligomer and exhibiting thermosetting properties), oxetane resin, and oxazine resin. Above all, phenolic resin, epoxy resin, and oxazine resin have good adhesiveness even when forming ultra-fine circuits, and of course, the cured physical properties are also suitable for conductive paste. More preferred.
- thermoplastic resin examples include a polyamide resin, a polyimide resin, an acrylic resin, a ketone resin, and a polystyrene resin.
- the thermoplastic resin is contained in the varnish-like resin composition in a state of being dissolved in an appropriate solvent.
- thermally decomposable resin examples include cellulose ester, cellulose ester, cellulose ester, and polyacrylonitrile.
- heat-decomposable resins are also suitable solvents In the varnish-like resin composition in a dissolved state. After printing and applying a conductive paste on a circuit pattern or the like, the above solvent is volatilized and removed by heating, and then cooled and solidified to form a hard resin having a thermoplastic resin as a binder.
- thermoplastic resins polyamide resin, polyimide resin, and acrylic resin show good adhesion even when forming ultra-fine circuits, and their physical properties after solidification are suitable for conductive paste. And can be used favorably.
- the varnish-like resin composition includes a silane coupling agent, a titanium coupling agent, and a silane coupling agent for the purpose of improving the adhesion to the surface of an underlying printed circuit board or the like, in addition to the resin component functioning as an organic binder. Components such as glass resin and glass frit can be added in appropriate amounts depending on the target.
- a repelling agent generally used for a conductive paste can be added as needed.
- a varnish-like resin composition to which a diluting solvent has been added in advance can be used in order to obtain a viscosity that is advantageous for the coating workability in the obtained conductive paste.
- the content of these resin components contained in the varnish-like resin composition should be appropriately selected according to the total volume of the metal ultrafine particles and the ratio of voids existing between the particles. Usually, it is good to select from 1 to 30 parts by mass, preferably from 3 to 20 parts by mass, per 100 parts by mass of the metal ultrafine particles.
- a varnish-like resin composition in addition to the resin component functioning as the organic binder, when a compound having a group containing nitrogen, oxygen, or iodide described above is heated, when heated, A compound component having reactivity with a group containing nitrogen, oxygen, or iodide, for example, an acid anhydride or an acid anhydride derivative is included.
- the compound component having reactivity with a group containing a nitrogen, oxygen, or i-atom mainly contains nitrogen that coats the surface of the ultrafine metal particles, It is used for removing an adhesion layer formed by a compound having a group containing oxygen or an iodine atom, for example, an amine compound.
- a resin component used is an epoxy resin or the like, it may be a curing agent for the resin component.
- the acid anhydride or the acid anhydride derivative reacts with an amine compound, for example, an alkylamine at the time of heat curing, and is used not only for forming an amide but also for a curing agent for an epoxy resin or the like. Is also consumed as It is advisable to add more than the addition amount determined according to the total of the terminal amino groups contained in the above-mentioned amine compound. Since the terminal amino group of the amine compound also reacts with the epoxy resin or the like, the content of the acid anhydride or acid anhydride derivative depends on the type of the amine compound such as the alkylamine used and the content thereof. Furthermore, it is appropriately selected in consideration of the type of the resin component used and its reactivity.
- an amine compound for example, an alkylamine at the time of heat curing
- the content (number of moles) of acid anhydride or acid anhydride derivative derived from dibasic acid is determined by the total (mol If the number is less than 1 to 2, the alkylamine and a part of the polyoxyalkyleneamine remain unreacted, which may affect the electrical properties of the thermoset.
- the contained organic acid anhydride or a derivative thereof generates an amide by, for example, a reaction with an alkylamine or voroxyalkyleneamine, thereby opening an acid anhydride structure in the molecule. Rings occur. After the ring is opened, the generated lipoxy group also reacts with the alkylamine / polyoxyalkyleneamine surrounding the surface of the ultrafine metal particles to form an amide. Similarly, it reacts with various organic acids to form amides.
- the alkylamine-polyoxyalkyleneamine adhering to the surface of the metal ultrafine particles is separated, the adhesion layer that suppressed the aggregation of the metal ultrafine particles disappears, and the metal ultrafine particles are gradually fused and fused. Agglomeration progresses, and finally a random chain is formed.
- the ultrafine metal particles have clean surfaces in contact with each other, and the random chains achieve close contact with each other due to the subsequent volume shrinkage of the entire resin composition.
- the heat treatment temperature is selected to be 300 ° C. or less, preferably 250 ° C. or less, usually in the range of 180 ° C.
- the obtained heat-treated cured product in the heat cured product
- very low resistance for example, the specific volume resistivity becomes less 1 0- 4 ⁇ ⁇ cm
- also inhomogeneous metal ultrafine A circuit pattern with a smooth surface without irregularities on the surface reflecting the aggregation of the particles can be obtained.
- the conductive metal paste of the present invention having the above-described structure is formed into a paste in which ultrafine metal particles are once dispersed by kneading, and then, if necessary, in order to adjust the viscosity, the conductive metal paste is appropriately added to the conductive metal paste.
- the thixotropic agent to be used can be added, and excess organic solvent can be removed by evaporation under reduced pressure, or an organic solvent can be added (added).
- organic solvent to be added for dilution is already added with polyoxyalkyleneamine and after the operation to act on the surface of the ultrafine metal particles, conductive solvents other than the above non-polar solvents and low-polar solvents are used. Even when a polar solvent generally available for diluting a varnish-like resin composition contained in a metal base is used, the dispersion state of the ultrafine metal particles can be kept good.
- ultrafine particle dispersion of silver (trade name: Independently dispersed ultrafine particle Ag1T Co., Ltd. ULVAC's Corporation Center), specifically, 35 parts by mass of silver ultrafine particle, dodecylamine (alkyl 185.
- a dispersion liquid of ultrafine silver particles having an average particle diameter of 3 nm and containing 1 part by mass of toluene and 58 parts by mass of toluene as an organic solvent was used.
- the conductive metal paste 73 parts by mass of silver particles having an average particle diameter of 10 m per 18 parts by mass of silver fine particles were used together as a metal filler using the dispersion liquid of the ultrafine silver particles.
- As the silver particles having an average particle diameter of 10 m commercially available surface-treated silver powder (trade name: SPN 10 JF Mitsui Kinzoku Co., Ltd.) was used.
- a dispersion liquid of the silver ultrafine particles; 35 wt% AgIT, a liquid amount containing 18 parts by mass of silver ultrafine particles, that is, 18X (100Z35) parts by mass is put into a reaction vessel, NSA (nonenyl succinic anhydride: molecular weight 224)
- NSA nonenyl succinic anhydride: molecular weight 224
- As an additional amine compound 0.9 parts by mass of dicyclohexylamine (molecular weight: 181.3; boiling point: 256 ° C) and pentamethylethylene triamine (molecular weight: 173.3; boiling point: 198) (C) of 1.8 parts by mass, and 0.5 parts by mass of Nopolak type phenolic resin (Regitop PS-2608 manufactured by Gunei Chemical Co., Ltd.) as a thermosetting resin.
- Low boiling components were distilled off with an evaporator while heating to make a total amount of 25.6 parts by mass to prepare a paste in which ultrafine silver
- the conductive metal paste was prepared by stirring and mixing. Using a metal mask, apply the prepared conductive metal paste on a glass substrate to a thickness of 40 rn, 10 x 50 mm in length and width, and check the surface state (agglomerated state). Cured in 60 minutes.
- Table 11-11 also shows the composition of the conductive metal paste, the surface state after application (agglomerated state), and the evaluation results on the volume resistivity of the obtained thermosetting product.
- the ratio of the amide compound; dodecylamine, and anhydride; NSA (nonenyl succinic anhydride) contained in the conductive metal paste described above is a ratio of 1/2 molecule of acid anhydride per amino group. ing.
- the conductive metal paste was prepared by using the dispersion liquid (Ag1T) of ultrafine silver particles described in Example 11-11, and having an average particle diameter of 1 zm per 18 parts by mass of silver particles having an average particle diameter of 3 nm.
- the 73 particles of silver particles were used in combination as a metal filler.
- commercially available surface-treated silver powder (trade name: SPQ03S Mitsui Kinzoku Co., Ltd.) was used.
- a paste containing 18 parts by mass of silver ultrafine particles and a total amount of 25.6 parts by mass, in which silver ultrafine particles are uniformly dispersed. was prepared.
- a pace in which the prepared ultrafine silver particles are uniformly dispersed To 25.6 parts by mass, add 73 parts by mass of surface-treated silver powder having an average particle size of 1: SPQ 03 S (Mitsui Kinzoku Co., Ltd.) and mix them thoroughly.
- a strike was prepared.
- the conductive metal paste prepared here was also coated on a glass substrate with a thickness of 40 m and a size of 10 x 50 mm in length and width using a metal mask, and the surface state (agglomerated state) was checked.
- Table 11-1 also shows the composition of the conductive metal paste, the surface state after application (aggregation state) ', and the evaluation results regarding the volume resistivity of the obtained thermosetting product.
- the ratio of the sum of the amide compounds and ethylene triamine contained in the prepared conductive metal paste and the ratio of acid anhydride; NSA (nonenyl succinic anhydride) was determined per amino group.
- the acid anhydride has the ratio of 1Z2 molecules.
- a conventional conductive metal paste using only silver particles having an average particle diameter of 10 as a conductive medium was prepared.
- Table 11-11 also shows the composition of the conductive metal paste, the surface state after application (agglomerated state), and the evaluation results on the volume resistivity of the obtained thermosetting product.
- Table 1_1 also shows the composition of the conductive metal paste, the surface state after application (agglomerated state), and the evaluation results on the volume resistivity of the obtained thermosetting product.
- a conventional conductive metal paste used for a conductive medium was prepared by using silver particles having an average particle diameter of 1 in addition to silver particles having an average particle diameter of 10 m.
- Table 11-11 also shows the composition of the conductive metal paste, the surface state after application (agglomerated state), and the evaluation results on the volume resistivity of the obtained thermosetting product.
- Table 11-1 summarizes the results of the above-described series of Examples 11-1, 1-2 and Comparative Examples 11-11 to 113. Comparing the results shown in Table 1-1, it can be seen from the results of Examples 1-1, 1-2 and Comparative Examples 1-1-1-3 that silver powder having an average particle diameter of 1 / xm or more and at least average particles When used together with ultra-fine silver particles with a diameter of 10 O nm or less, compared to conductive metal paste using only silver powder with an average particle diameter of 1 / m or more as a conductive medium, it is cured by heating and curing. It can be seen that the volume resistivity of the material was significantly reduced. It should be noted that the volume resistivity of the cured product between Example 1-1 and Example 1-2 was slightly reduced due to the difference in the average particle diameter of the metal filler used, that is, the silver powder. Despite differences, at least average particle size 10
- the contained ultrafine silver particles hold a monomolecular layer of an amine compound such as dodecylamine covering the surface thereof.
- an amine compound such as dodecylamine covering the surface thereof.
- the low-temperature sinterable conductive metal paste for high-density circuit printing of the present invention is, as in the above-mentioned specific example, in a varnish-like resin composition.
- a metal filler having an average particle diameter of 0.5 to 20 xm and ultrafine metal particles having an average particle diameter of 100 nm or less are uniformly dispersed to form a conductive metal paste.
- the varnish-like resin composition includes a resin component that functions as an organic binder, an acid anhydride or a derivative thereof, and at least one or more organic solvents.
- the varnish-like resin composition is contained in an amount of 5 to 100 parts by mass per 100 parts by mass of the ultrafine metal particles having a fine average particle diameter, so that coating and printing can be performed. In this case, the aggregation and fusion of the ultrafine metal particles are suppressed, but thereafter, for example, at 300 ° C.
- the amine compound covering the metal ultrafine particles surface is also removed by utilizing the reaction with an organic acid anhydride and the like, and the resin component is removed.
- the conductive medium (metal particles) components unlike the conventional conductive base that uses metal particles with a relatively large particle size, the physical properties of metal fillers are different.
- the metal ultra-fine particles that fill the gaps also fuse and fuse with each other, and this latter action is the main action, and a dense net-like conductive path of ultra-fine particles is formed. It has the advantage that it is possible to achieve excellent conductivity in the entire conduction path including the metal filler formed.
- an ultrafine circuit can be formed, a low resistance can be achieved even by curing at low temperature, and in addition, a high conduction stability that cannot be obtained by a mere conduction path of contacting particles is not obtained.
- the reproducibility can be ensured, and since it contains a resin that is cured by heating, it has good adhesion to the substrate and becomes a low-temperature sintered conductive metal paste for high-density circuit printing.
- a metal layer having an oxide film on the surface and having a desired average particle diameter for example, a molecular layer in which the surface is previously coated with alkylamine or the like is used.
- the raw material containing as a raw material and mixing with the remaining components of the resin composition, a paste in which the metal ultrafine particles are once dispersed uniformly and stably in the varnish-like resin composition is produced, and further, a larger particle size is obtained.
- a metal filler having the formula (1) and uniformly mixing the low-temperature sintered conductive metal paste for high-density circuit printing of the present invention can be prepared easily and with high reproducibility.
- a commercially available ultrafine particle dispersion of silver (trade name: Independently dispersed ultrafine particle Perfect Silver Vacuum Metallurgy Co., Ltd.), specifically, 100 parts by mass of silver particles, 15 parts by mass of dodecylamine as alkylamine, As an organic solvent, a dispersion liquid of silver fine particles having an average particle diameter of 8 nm and containing 75 parts by mass of terpineol was used.
- Me-HHPA methylhexahydrophthalic anhydride
- a resin-type phenol resin PL-2211 manufactured by Gunei Chemical Co., Ltd.
- the conductive metal paste prepared by stirring was applied on a glass substrate with a metal mask to a film thickness of 50 inches and a size of 10 ⁇ 20 mm in length and width, and the surface state (agglomerated state) was confirmed. After it was confirmed, it was cured at 150 ° for 30 minutes and 210 ° for 60 minutes.
- Table 2-1 shows the composition of the conductive metal paste, the surface state (agglomerated state) after application, the specific resistance of the obtained thermosetting product, and the printability when the viscosity was adjusted to about 8 OPa ⁇ s. The results of the evaluation are also shown.
- the ratio of the amide compound contained in the above-mentioned conductive metal base; dodecylamine, and acid anhydride; Me—HHP A (methylhexahydrohydrofluoric anhydride) is as follows. It is the ratio of anhydride 1Z2 molecules.
- the conductive metal paste was prepared by dissolving 0.45 parts by mass of Me-HHPA (methylhexahydrophthalic anhydride) as an acid anhydride per 100 parts by mass of silver particles in a dispersion of silver particles having the above composition.
- Me-HHPA methylhexahydrophthalic anhydride
- As a curable resin 5 parts by mass of a resole-type phenol resin (PL-2211, manufactured by Gunei Iridaku Co., Ltd.) was added. After mixing these, the conductive metal paste prepared by stirring was applied on a glass substrate with a metal mask to a thickness of 50 nm and a size of 10 x 2 Omm in length and width.
- the composition was cured at 15 O ⁇ X for 30 minutes + 210 ° C for 60 minutes.
- a thixotropic agent or diluent toluene
- the viscosity was adjusted to about 80 Pas
- the line / space 25/25 m was printed on a stainless # 500 mesh screen plate, cured under the above curing conditions, and the printability was evaluated. .
- Table 2-1 shows the composition of the conductive metal paste, the surface state (agglomerated state) after application, the specific resistance of the obtained thermosetting product, and the printability when the viscosity was adjusted to about 8 OPa ⁇ s. The results of the evaluation are also shown.
- the ratio of the amide compound contained in the above conductive metal paste; dodecylamine, and acid anhydride; Me—HHPA (methylhexahydrophthalic anhydride) is as follows. It is a dimer ratio.
- the conductive metal paste prepared by stirring is applied on a glass substrate with a metal mask to a thickness of 50 ⁇ m and a size of 10 x 20 mm in length and width, and the surface state (agglomerated state) After confirming that it was cured at 150 ° ⁇ > ⁇ 30 minutes + 210 in 60 minutes.
- Table 2-1 shows the composition of the conductive metal paste, the surface state (agglomerated state) after application, the specific resistance of the obtained thermosetting product, and the printability when the viscosity was adjusted to about 8 OPa ⁇ s. The results of the evaluation are also shown.
- the ratio of the contained amine compound; dodecylamine and the acid anhydride; Me—HHPA (methylhexahydrophthalic anhydride) is the ratio of acid anhydride 1/2 molecule per amino group.
- a commercially available ultrafine particle dispersion of silver (trade name: Independently dispersed ultrafine particles Perfect Silver Vacuum Metallurgy Co., Ltd.), 0.05 parts by mass of dodecylamine as alkylamine per 100 parts by mass of silver particles contained, organic As a solvent, a dispersion liquid of silver fine particles having an average particle diameter of 8 nm and containing 75 parts by mass of Yuichi Pinole was prepared.
- the conductive metal base contains 0.0225 parts by mass of Me-HHPA (methylhexahydrophthalic anhydride) as an acid anhydride per 100 parts by mass of silver particles in the dispersion of silver particles having the above composition.
- thermosetting resin As a thermosetting resin, 5 parts by mass of a resin-type phenol resin (PL-2211 manufactured by Gunei Chemical Co., Ltd.) was added. After mixing these, the conductive metal base prepared by stirring was applied on a glass substrate with a metal mask to a thickness of 50 urn, 10 x 20 mm in length and width, and the surface state (agglomerated) After confirming the condition), it was cured at 150 ° C for 30 minutes + 210 ° C for 60 minutes.
- a resin-type phenol resin PL-2211 manufactured by Gunei Chemical Co., Ltd.
- Table 2-1 shows the composition of the conductive metal base, the surface state (agglomerated state) after coating, the specific resistance of the obtained thermoset, and the viscosity when the viscosity was adjusted to about 8 OPa ⁇ s.
- the evaluation results regarding printability are also shown.
- the ratio of the amine compound contained in the above-mentioned conductive metal base; dodecylamine, and acid anhydride; Me—HHP A (methylhexahydrophthalic anhydride) is as follows. Dominylamine is a ratio of 1 to 2 molecules, but the amount of the dominylamine is only half the amount required to coat the surface of silver fine particles with a monolayer of dodecylamine.
- silver ultrafine particle dispersion (trade name: Independently dispersed ultrafine particle perfect Alkylamin covering silver fine particles contained by using Silva Vacuum Metallurgy Co., Ltd .; once remove dodecylamine; again contain 75 parts by mass of tapineol as an organic solvent; no dodecylamine coating layer A dispersion liquid of silver fine particles having an average particle diameter of 8 nm was prepared.
- a dispersion of silver fine particles having the above composition was prepared by adding only an acid anhydride, Me-HPA (methylhexahydrofluoric anhydride), per 100 parts by mass of silver fine particles, but merely by thermosetting.
- Me-HPA methylhexahydrofluoric anhydride
- the conductive metal paste prepared by stirring is applied on a glass substrate with a metal mask to a thickness of 50 m and a size of 10 x 0 mm in height and width, and the surface state (agglomerated state) After confirming the curing, the composition was cured at 150 ° C for 30 minutes + 210 ⁇ 60 minutes.
- Table 2-1 shows the composition of the conductive metal paste, the surface state (agglomerated state) after application, the specific resistance of the obtained thermosetting product, and the printability when the viscosity was adjusted to about 8 OPa ⁇ s. The results of the evaluation are also shown.
- polyoxyalkyleneamine average molecular weight: about 440
- silver fine particles corresponding to twice the molar amount of dodecylamine.
- about 100 parts by weight of acetone is added per 1 part by weight of silver fine particles, and washed, and excess is added in the solvent.
- Polyoxyalkyleneamine and free dodecylamine were dissolved. Thereafter, solid-liquid separation between the silver fine particles and the acetone solution was performed by centrifugation to remove the acetone solution part.
- the conductive metal paste As for the conductive metal paste, 4.9 parts by mass of Me-HHPA (methylhexahydrophthalic anhydride) was used as an acid anhydride per 100 parts by mass of silver particles in the dispersion of silver particles subjected to this treatment.
- a thermosetting resin 5 parts by mass of resol type phenol resin (PL-2211 manufactured by Gunei Chemical Co., Ltd.) was added. After mixing these, the conductive metal paste prepared by stirring was applied on a glass substrate with a metal mask to a thickness of 50 wm and a size of 10 x 20 mm in length and width, and the surface state (agglomerated state) ), And cured at 150 ° C for 30 minutes + 210 ° C for 60 minutes.
- Table 2-1 shows the composition of the conductive metal paste, the surface state (agglomerated state) after application, the specific resistance of the obtained thermosetting product, and the printability when the viscosity was adjusted to about 8 OPa ⁇ s. The results of the evaluation are also shown.
- the ratio of the amide compound contained in the above-mentioned conductive metal paste; the sum of the amino groups of dodecylamine and boroxyalkyleneamine to the acid anhydride; Me—HPA (methylhexahydrophthalic anhydride) is as follows. The ratio of acid anhydride 1Z2 molecules per amino group.
- a dispersion liquid of ultrafine silver particles specifically, 100 parts by mass of silver fine particles, and ethanolamine as an amine compound was used.
- a dispersion liquid of silver fine particles having an average particle diameter of 8 nm was prepared, containing 10 parts by mass and 75 parts by mass of terpineol as an organic solvent.
- the conductive metal paste contained 13.8 parts by mass of Me-HHPA (methylhexahydrofluoric anhydride) as an acid anhydride per 100 parts by mass of silver particles in the dispersion of the silver particles.
- Me-HHPA methylhexahydrofluoric anhydride
- As a curable resin 5 parts by mass of a resole type phenol resin (PL-2211 manufactured by Gunei Chemical Co., Ltd.) was added. After mixing these, the conductive metal paste prepared by stirring was mixed with a glass substrate using a metal mask. It was applied on top with a film thickness of 50 / zm, length and width of 10 x 20 mm, and after confirming its surface condition (agglomerated state), it was applied at 150 ° C for 30 minutes + 210 minutes. Cured in minutes.
- a thixotropic agent or a diluting solvent is added to the conductive metal paste to adjust the viscosity to about 80 Pa ⁇ s, and the line Z is made with a stainless # 500 mesh screen plate.
- a space 25/25 m was printed and cured under the above-mentioned conditions, and the printability was evaluated.
- Table 2-1 shows the composition of the conductive metal paste, the surface state after application (agglomeration state), the specific resistance of the resulting thermoset, and the printing when the viscosity was adjusted to about 80 Pa ⁇ s. The results of evaluation on the properties are also shown.
- the ratio of the amine compound contained in the above-mentioned conductive metal base; ethanolamine, and acid anhydride; Me—HHPA (methylhexahydrophthalic anhydride) is calculated as follows. It is the ratio of 12 molecules of acid anhydride.
- Table 2-1 summarizes the results of the above series of Examples 2-1 to 2-5 and Comparative Examples 2-1 and 2-2. Comparing the results shown in Table 1, from the results of Examples 2-1 to 2-3 and Comparative Examples 2-1 and 2-2, the content of dodecylamine per 100 parts by mass of silver fine particles was reduced. As a result, the specific resistance of the cured product obtained by heating and curing the conductive metal paste gradually increases. Also, when the content of dodecylamine per 100 parts by mass of silver fine particles falls below 0.1 part by mass and reaches a range of less than one molecular layer of dodecylamine covering the surface of silver fine particles, the specific resistance is rapidly increased. Is found. At the same time, aggregation of silver fine particles is observed in the applied paste even at room temperature. In addition, the printability is clearly reduced due to the occurrence of such aggregation.
- the remaining Examples 2-1 to 2_3 and Comparative Example 1 each cover the surface of the silver fine particles, except for Comparative Example 2 in which the coating layer of the amine compound was not provided.
- a layer of dodecylamine per 100 parts by mass of silver fine particles, as the content of dodecylamine decreases and the uniform coating layer tends to be deficient, aggregation of the silver fine particles contained at room temperature may occur. And printability is also affected, and it is judged that the printability will decrease.
- the content of the amine compound per 100 parts by mass of the silver fine particles is at least significantly higher than 3 parts by mass. Is not so big. Specifically, comparing the results of Example 2-1 with Examples 2-4 and 2-5, the surface state after application (agglomerated state), the specific resistance of the obtained thermosetting material, and the viscosity The evaluation results on printability when adjusting to about 80 Pa ⁇ s were all good. When Examples 2-1 and Example 2-4 are compared in detail, the results are more preferable, although the sum of the amino groups of the amine compounds is slightly smaller in Example 2-4. Is determined.
- thermosetting product when a portion having a more polar portion is replaced with polyoxyalkyleneamine in addition to the alkylamine, the surface state (agglomeration state) after application is improved, and the aggregation is further suppressed. It is evaluated that the specific resistance of the obtained thermosetting product is further improved.
- Aggregation Completely aggregated X, Partially aggregated ⁇ , Appearance uniform dispersion ⁇ , Uniform dispersion ⁇
- the swell that can be printed is 3 to 4 m.
- Example 2-1 a commercially available ultrafine particle dispersion of silver (trade name: Independently dispersed ultrafine particle Perfect Silver Vacuum Metallurgy Co., Ltd.), specifically, 100 parts by mass of silver fine particles, A dispersion liquid of silver fine particles having an average particle diameter of 8 nm, containing 15 parts by mass of dodecylamine as an alkylamine and 75 parts by mass of turbineol as an organic solvent was used.
- a commercially available ultrafine particle dispersion of silver (trade name: Independently dispersed ultrafine particle Perfect Silver Vacuum Metallurgy Co., Ltd.), specifically, 100 parts by mass of silver fine particles, A dispersion liquid of silver fine particles having an average particle diameter of 8 nm, containing 15 parts by mass of dodecylamine as an alkylamine and 75 parts by mass of turbineol as an organic solvent was used.
- Me-HHPA methylhexahydrofluoric anhydride
- a resole type phenol resin PL-221 1 manufactured by Gunei Chemical Co., Ltd.
- Table 2-2 shows the composition of each conductive metal paste of Examples 21-1 and Reference Examples 2-1 to 2-4, the surface state after application (agglomerated state), and the specific resistance of the obtained thermosetting product. The evaluation results for are also shown. The printability when the viscosity was adjusted to about 8 OPa ⁇ s was good in both Example 2-1 and Reference Examples 2-1 to 2-4, and the evaluation results are omitted. As shown in Table 2_2, the sum of the amino groups of dodecylamine; the range in which the added acid anhydride Me-HHPA is not sufficient with respect to the total amount of amino groups, specifically, silver fine particles.
- thermosetting product When the content of dodecylamine and Me-HHPA is less than 2 parts by mass per 100 parts by mass, the specific resistance of the obtained thermosetting product is significantly increased. The effect has appeared. In particular, in Reference Example 2-11 in which no acid anhydride was added, the specific resistance of the obtained thermosetting product was extremely high. The results of this comparison indicate that the amine compound covering the surface of the silver fine particles prevents aggregation and maintains the uniform dispersion of the silver fine particles in the conductive metal paste, but when heated and treated, Desorption is caused by thermal excitation, but the rate of the thermal desorption process is not sufficient, and rapid desorption is possible by reacting with acid anhydride Me-HHPA. Is determined.
- the amount of acid anhydride added is the sum of the amino groups present in the alkylamine; the amount of addition (moles) of 1Z2 or more of the total amino groups (number of moles). It turns out that it is more preferable to select it. However, it is desirable to avoid adding an unnecessarily high amount. For example, the amount (number of moles) of the acid anhydride to be added does not exceed 1 times the total number of amino groups (number of moles). It turns out that it is more preferable.
- the contained silver fine particles 100 mass Per part, 22 parts by mass of dodecanediol was added as alkanethiol, and the mixture was stirred for 30 minutes or more. After stirring, in order to remove excess dodecanethiol and dodecylamine released by substitution, about 100 parts by mass of acetone is added per 1 part by mass of silver fine particles and washed, and excessive dodecanethiol is released in such a solvent. Dodecylamine was dissolved. Thereafter, solid-liquid separation of the silver fine particles and the acetone solution was performed by centrifugation, and the acetone solution part was removed.
- a dispersion of silver fine particles having the above-mentioned composition was prepared by adding 0.45 parts by mass of Me-HHPA as an acid anhydride, 100 parts by mass of silver particles, and a resin-type phenol as a thermosetting resin. 5 parts by mass of a resin (PL-2211 manufactured by Gunei Chemical Co., Ltd.) was added. After mixing these, the conductive metal base prepared by stirring was applied on a glass substrate with a metal mask to a thickness of 50 m and a size of 10 x 20 mm in length and width, and the surface state (agglomeration). After checking the condition), the composition was cured in 22 OX X 60 minutes.
- a thixotropic agent or a diluting solvent is added to the conductive metal paste to adjust the viscosity to about 8 OPa ⁇ s, and the line / space is 25 on a stainless steel # 500 mesh screen plate. / 25 was printed and cured under the above curing conditions, and its printability was evaluated.
- Table 2-3 shows the composition of the conductive metal paste, the surface state after application (agglomeration state), the specific resistance of the obtained thermosetting paste, and the viscosity adjusted to about 8 OPa ⁇ s.
- the evaluation results on printability of the sample are also shown. Note that the ratio of the iodide-containing compound; dodecanethiol to the acid anhydride; Me-HPA contained in the conductive metal paste is a ratio of 1/2 molecule of the acid anhydride per 1 sulfanyl group. (Example 2-7)
- Liquid polyethylene glycol # 200 represented by (average molecular weight 190-210, measured molecular weight 200) 0.54 parts by mass, as an organic solvent, contains 75 parts by mass of terpineol A dispersion liquid of silver fine particles having an average particle diameter of 8 nm was prepared.
- the ultrafine particle dispersion of silver 100 parts by mass of silver fine particles contained, and 20 parts by mass of the liquid polyethylene glycol # 200 as an oxygen-based ligand were added. Stirred for more than 30 minutes. After stirring, in order to remove excess polyethylene glycol and dodecylamine released by the substitution, about 100 parts by mass of toluene is added per 1 part by mass of the silver fine particles and washed, and excess polyethylene glycol is added to the solvent. And the liberated dodecylamine were dissolved. Thereafter, solid-liquid separation of the silver fine particles and the toluene solution was performed by centrifugal separation, and the toluene solution part was removed.
- the conductive metal paste may be a dispersion of silver fine particles having the above-described composition.
- the conductive metal base prepared by stirring was applied on a glass substrate with a metal mask to a thickness of 50 m and a size of 10 X 2 Omm in length and width, and the surface state (agglomeration). After confirming the state), the composition was cured at 220 ° C for 60 minutes.
- a thixotropic agent or a diluting solvent is added to the conductive metal paste to adjust the viscosity to about 80 Pa ⁇ s, and the line Z space is 25/25 on a stainless steel # 500 mesh screen IS. 25 m was printed and cured under the above curing conditions, and its printability was evaluated.
- Table 2-3 shows the composition of the conductive metal paste, the surface condition (agglomerated state) after application, the specific resistance of the obtained thermosetting product, and the printability when the viscosity was adjusted to about 80 Pa ⁇ s. The results are also shown.
- Coagulation Completely coagulated X, Partially coagulated ⁇ , Uniformly dispersed ⁇
- the swell that can be printed is 3 to 4 m.
- the low-temperature sinterable conductive metal paste for super fine circuit printing of the present invention is a varnish-like
- the varnish-like resin composition functions as an organic binder.
- the resin component, an acid anhydride or a derivative thereof, and at least one or more organic solvents, and the surface of the ultrafine metal particles is capable of coordinating with the metal element contained in the ultrafine metal particles. It is coated with at least one amine compound having at least one terminal amino group, and is based on 100 parts by mass of the ultrafine metal particles having an average particle diameter of 10 O nm or less.
- the coating and printing suppress the aggregation and fusion of the ultrafine metal particles, but thereafter, for example, heat treatment at a relatively low temperature not exceeding 300 ° C. (calcination) Then, the amine compound covering the surface of the metal ultrafine particles is removed by utilizing the reaction with an organic acid anhydride or the like, and the conductive medium (metal fine particles) component is brought into contact with the hardening of the resin component.
- the resin and its reproducibility can be ensured, and because it contains a resin that is cured by heating, it has good adhesion to the substrate and is a low-temperature-curable conductive metal paste for printing ultrafine circuits.
- a metal ultrafine particle having a desired average particle diameter without an oxide film on the surface for example, a molecule of which the surface is previously coated with alkylamine or the like is used.
- the raw material contained as a layer is preferably used, and a polyoxyalkyleneamine is preferably preliminarily acted on the raw material, the surface is partially covered with polyoxyalkyleneamine, and then mixed with the remaining components of the resin composition.
- the low-temperature sintering mold for superfine circuit printing of the present invention The conductive metal paste can be easily prepared with high reproducibility. Industrial applicability
- a conductive medium in addition to a metal filler having an average particle diameter of 0.5 to 20 xm, metal ultrafine particles having an average particle diameter of 100 nm or less are used, Its surface contains nitrogen, oxygen, or zeolite atoms as a group capable of coordinating bonds with the metal elements contained in the ultrafine metal particles, which can be coordinated by lone pairs of electrons.
- a resin component that is cured by heating after being coated with at least one compound having at least one terminal group for example, at least one amine compound having at least one terminal amino group, when heated, the nitrogen, oxygen, or
- a compound component having a reactivity with a group containing a zirconium atom for example, an organic acid anhydride or a derivative thereof, an organic acid, and one or more organic solvents;
- Ri when storing at around room temperature, the metal ultrafine particles by nitrogen, the coating layer with a compound containing an oxygen or Iou atom, its aggregation is prevented.
- a coating layer of a compound containing nitrogen, oxygen, or zeo atoms is converted into a compound component having reactivity with the group containing nitrogen, oxygen, or zeo atoms, for example, It is removed by reaction with an organic acid anhydride or a derivative thereof or an organic acid, thereby enabling low-temperature sintering of ultrafine metal particles.
- an organic acid anhydride or a derivative thereof or an organic acid thereby enabling low-temperature sintering of ultrafine metal particles.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB018196713A CN1319075C (zh) | 2000-10-25 | 2001-09-26 | 导电金属膏 |
AT01970208T ATE525730T1 (de) | 2000-10-25 | 2001-09-26 | Elektroleitfähige metallpaste und verfahren zu ihrer herstellung |
US10/415,004 US7081214B2 (en) | 2000-10-25 | 2001-09-26 | Electroconductive metal paste and method for production thereof |
AU2001290266A AU2001290266A1 (en) | 2000-10-25 | 2001-09-26 | Electroconductive metal paste and method for production thereof |
EP01970208A EP1339073B1 (en) | 2000-10-25 | 2001-09-26 | Electroconductive metal paste and method for production thereof |
CA002426861A CA2426861C (en) | 2000-10-25 | 2001-09-26 | Conductive metal paste |
KR1020037005738A KR100647238B1 (ko) | 2000-10-25 | 2001-09-26 | 도전성 금속 페이스트 및 그 제조 방법 |
JP2002538446A JP4155821B2 (ja) | 2000-10-25 | 2001-09-26 | 導電性金属ペースト及びその製造方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000325414 | 2000-10-25 | ||
JP2000-325414 | 2000-10-25 | ||
JP2001-236650 | 2001-08-03 | ||
JP2001236650 | 2001-08-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002035554A1 true WO2002035554A1 (fr) | 2002-05-02 |
WO2002035554A8 WO2002035554A8 (fr) | 2002-07-18 |
Family
ID=26602742
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/008340 WO2002035554A1 (fr) | 2000-10-25 | 2001-09-26 | Pate metallique electro-conductrice et procede de production de cette pate |
Country Status (10)
Country | Link |
---|---|
US (1) | US7081214B2 (ja) |
EP (1) | EP1339073B1 (ja) |
JP (1) | JP4155821B2 (ja) |
KR (1) | KR100647238B1 (ja) |
CN (1) | CN1319075C (ja) |
AT (1) | ATE525730T1 (ja) |
AU (1) | AU2001290266A1 (ja) |
CA (1) | CA2426861C (ja) |
TW (1) | TW591095B (ja) |
WO (1) | WO2002035554A1 (ja) |
Cited By (54)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002334618A (ja) * | 2001-05-07 | 2002-11-22 | Harima Chem Inc | 金属微粒子分散液を用いたメッキ代替導電性金属皮膜の形成方法 |
JP2004111253A (ja) * | 2002-09-19 | 2004-04-08 | Noda Screen:Kk | 電子デバイスの電気的接続用導電性組成物および電子デバイス |
JP2004111254A (ja) * | 2002-09-19 | 2004-04-08 | Asahi Glass Co Ltd | 電子デバイスの電気的接続用金属含有組成物 |
JP2005093826A (ja) * | 2003-09-18 | 2005-04-07 | Ricoh Co Ltd | 導電性接着剤による接続構造体及びその製造方法 |
JP2005129303A (ja) * | 2003-10-22 | 2005-05-19 | Denso Corp | 導体組成物および導体組成物を用いた実装基板ならびに実装構造 |
JP2005174828A (ja) * | 2003-12-12 | 2005-06-30 | Hitachi Ltd | 配線導電体形成用組成物及びそれを用いた配線基板の製造方法、並びに配線基板 |
JP2005183144A (ja) * | 2003-12-18 | 2005-07-07 | Alps Electric Co Ltd | 導電性組成物及びその製造方法 |
JP2005294254A (ja) * | 2004-03-12 | 2005-10-20 | Sumitomo Electric Ind Ltd | 導電性銀ペースト及びそれを用いた電磁波シールド部材 |
JP2006083377A (ja) * | 2004-08-18 | 2006-03-30 | Harima Chem Inc | 導電性接着剤および該導電性接着剤を利用する物品の製造方法 |
JP2006202604A (ja) * | 2005-01-20 | 2006-08-03 | Matsushita Electric Ind Co Ltd | 導電性ペーストならびにこれを用いる配線基板、多層基板および電子部品実装体の製造方法 |
JP2006206730A (ja) * | 2005-01-27 | 2006-08-10 | Sumitomo Bakelite Co Ltd | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
JP2007042301A (ja) * | 2005-07-29 | 2007-02-15 | Toda Kogyo Corp | 導電性組成物、導電性ペースト及び導電性皮膜 |
JP2007083288A (ja) * | 2005-09-22 | 2007-04-05 | Harima Chem Inc | 導電性接合の形成方法 |
JP2007180059A (ja) * | 2005-12-26 | 2007-07-12 | Toshiba Corp | 光半導体装置とその製造方法 |
US7262511B2 (en) | 2004-08-18 | 2007-08-28 | Harima Chemicals, Inc. | Conductive adhesive agent with ultrafine particles |
JP2008063449A (ja) * | 2006-09-07 | 2008-03-21 | Hitachi Ltd | ポリマーナノコンポジット材料、その製造方法電子部品装置およびその製造方法 |
WO2008038534A1 (en) | 2006-09-26 | 2008-04-03 | Dowa Electronics Materials Co., Ltd. | Silver microparticle powder and method for production thereof |
WO2008038535A1 (fr) | 2006-09-27 | 2008-04-03 | Dowa Electronics Materials Co., Ltd. | Poudre composite de particules d'argent et son procédé de production |
JP2008091250A (ja) * | 2006-10-03 | 2008-04-17 | Mitsuboshi Belting Ltd | 低温焼成型銀ペースト |
JP2008166086A (ja) * | 2006-12-28 | 2008-07-17 | Hitachi Ltd | 導電性焼結層形成用組成物、これを用いた導電性被膜形成法および接合法 |
JP2009500802A (ja) * | 2005-07-01 | 2009-01-08 | ナショナル ユニバーシティー オブ シンガポール | 導電性複合材料 |
JP2009037943A (ja) * | 2007-08-03 | 2009-02-19 | Toyo Ink Mfg Co Ltd | 導電性被膜の製造方法 |
WO2009066396A1 (ja) * | 2007-11-22 | 2009-05-28 | Asahi Glass Company, Limited | 導電膜形成用インクおよびプリント配線板の製造方法 |
US20090169730A1 (en) * | 2003-02-20 | 2009-07-02 | The Regents Of The University Of California | Method of forming conductors at low temperatures using metallic nanocrystals and product |
US7556747B2 (en) * | 2003-08-08 | 2009-07-07 | Sumitomo Electric Industries, Ltd. | Electrically conductive pastes |
JP2009177010A (ja) * | 2008-01-25 | 2009-08-06 | Toshiba Corp | フレキシブルプリント配線板および電子機器 |
JP2009275227A (ja) * | 2008-05-16 | 2009-11-26 | Bayer Materialscience Ag | 銀ナノ粒子含有印刷可能組成物、該組成物を用いた導電性被膜の製造方法、および該方法により製造された被膜 |
JP2010108696A (ja) * | 2008-10-29 | 2010-05-13 | Mitsuboshi Belting Ltd | 抵抗体ペースト及び抵抗器 |
JP2011119340A (ja) * | 2009-12-01 | 2011-06-16 | Harima Chemicals Inc | 導電性アルミニウムペースト |
WO2011078140A1 (ja) * | 2009-12-22 | 2011-06-30 | Dic株式会社 | スクリーン印刷用導電性ペースト |
WO2011078141A1 (ja) * | 2009-12-22 | 2011-06-30 | Dic株式会社 | スクリーン印刷用導電性ペースト |
JP2011142259A (ja) * | 2010-01-08 | 2011-07-21 | Ulvac Japan Ltd | 非晶質Si太陽電池基板の製造方法 |
US8021580B2 (en) | 2004-06-23 | 2011-09-20 | Harima Chemicals, Inc. | Conductive metal paste |
WO2011158659A1 (ja) * | 2010-06-16 | 2011-12-22 | 独立行政法人物質・材料研究機構 | 金属ナノ粒子ペースト、並びに金属ナノ粒子ペーストを用いた電子部品接合体、ledモジュール及びプリント配線板の回路形成方法 |
JP2011256382A (ja) * | 2010-06-09 | 2011-12-22 | Xerox Corp | 特定のハンセン溶解度パラメータを有する溶媒を含む銀ナノ粒子組成物 |
JP2013069654A (ja) * | 2011-09-21 | 2013-04-18 | Samsung Electro-Mechanics Co Ltd | 低温焼成用導電性ペースト組成物 |
JP2013143216A (ja) * | 2012-01-10 | 2013-07-22 | Napura:Kk | 機能性材料、電子デバイス、電磁波吸収/遮蔽デバイス及びそれらの製造方法 |
JP2013218829A (ja) * | 2012-04-05 | 2013-10-24 | Ulvac Japan Ltd | 導電性金属ペースト |
JP2013218831A (ja) * | 2012-04-06 | 2013-10-24 | Ulvac Japan Ltd | 導電性金属ペースト |
JP2013218830A (ja) * | 2012-04-05 | 2013-10-24 | Ulvac Japan Ltd | 導電性金属ペースト |
US8643165B2 (en) | 2011-02-23 | 2014-02-04 | Texas Instruments Incorporated | Semiconductor device having agglomerate terminals |
JP2014029845A (ja) * | 2012-06-28 | 2014-02-13 | Nippon Steel & Sumikin Chemical Co Ltd | 導電性ペーストの製造方法 |
JP2014514383A (ja) * | 2011-03-22 | 2014-06-19 | ナノ アンド アドバンスド マテリアルズ インスティトゥート リミテッド | 高輝度led用高性能ダイ取付接着剤(daa)ナノ材料 |
JP2014182913A (ja) * | 2013-03-19 | 2014-09-29 | Fujifilm Corp | 導電膜形成用組成物およびこれを用いる導電膜の製造方法 |
WO2014184641A2 (en) | 2013-05-17 | 2014-11-20 | Toyota Jidosha Kabushiki Kaisha | Metal paste for joining, joining method and joined body |
JP2015049992A (ja) * | 2013-08-30 | 2015-03-16 | 富士フイルム株式会社 | 導電膜形成用組成物およびこれを用いる導電膜の製造方法 |
JP2015082385A (ja) * | 2013-10-22 | 2015-04-27 | 日立化成株式会社 | 銀ペースト及びそれを用いた半導体装置、並びに銀ペーストの製造方法 |
JP2015175001A (ja) * | 2014-03-17 | 2015-10-05 | ゼロックス コーポレイションXerox Corporation | インク組成物およびインク組成物の硬化度を決定する方法 |
WO2016002741A1 (ja) * | 2014-06-30 | 2016-01-07 | 新日鉄住金化学株式会社 | ニッケル粒子組成物、接合材及びそれを用いた接合方法 |
WO2016076306A1 (ja) * | 2014-11-12 | 2016-05-19 | ハリマ化成株式会社 | 導電性ペースト |
US9457406B2 (en) | 2009-09-16 | 2016-10-04 | Hitachi Chemical Company, Ltd. | Copper metal film, method for producing same, copper metal pattern, conductive wiring line using the copper metal pattern, copper metal bump, heat conduction path, bonding material, and liquid composition |
JPWO2015163076A1 (ja) * | 2014-04-25 | 2017-04-13 | 株式会社ダイセル | 銀粒子塗料組成物 |
DE112017004749T5 (de) | 2016-09-21 | 2019-06-27 | Yazaki Corporation | Elektrisch leitfähige Paste und Leiterplatte damit |
JPWO2019065221A1 (ja) * | 2017-09-27 | 2020-12-03 | 京セラ株式会社 | ペースト組成物、半導体装置及び電気・電子部品 |
Families Citing this family (126)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001513697A (ja) * | 1997-02-24 | 2001-09-04 | スーペリア マイクロパウダーズ リミテッド ライアビリティ カンパニー | エアロゾル法及び装置、粒子製品、並びに該粒子製品から製造される電子装置 |
US7045015B2 (en) | 1998-09-30 | 2006-05-16 | Optomec Design Company | Apparatuses and method for maskless mesoscale material deposition |
DE10212945A1 (de) * | 2002-03-22 | 2003-10-02 | Tesa Ag | Polyacrylat-Haftklebemasse, Herstellung und Verwendung |
JP2004006645A (ja) * | 2002-04-19 | 2004-01-08 | Seiko Epson Corp | 圧電体素子の製造方法、圧電体素子並びに液滴吐出式記録ヘッド |
US7601406B2 (en) * | 2002-06-13 | 2009-10-13 | Cima Nanotech Israel Ltd. | Nano-powder-based coating and ink compositions |
US7566360B2 (en) * | 2002-06-13 | 2009-07-28 | Cima Nanotech Israel Ltd. | Nano-powder-based coating and ink compositions |
US7736693B2 (en) * | 2002-06-13 | 2010-06-15 | Cima Nanotech Israel Ltd. | Nano-powder-based coating and ink compositions |
US20040178391A1 (en) * | 2003-01-29 | 2004-09-16 | Conaghan Brian F. | High conductivity inks with low minimum curing temperatures |
US7211205B2 (en) * | 2003-01-29 | 2007-05-01 | Parelec, Inc. | High conductivity inks with improved adhesion |
US7141185B2 (en) * | 2003-01-29 | 2006-11-28 | Parelec, Inc. | High conductivity inks with low minimum curing temperatures |
JP3966294B2 (ja) * | 2003-03-11 | 2007-08-29 | セイコーエプソン株式会社 | パターンの形成方法及びデバイスの製造方法 |
JP2005081501A (ja) * | 2003-09-09 | 2005-03-31 | Ulvac Japan Ltd | 金属ナノ粒子及びその製造方法、金属ナノ粒子分散液及びその製造方法、並びに金属細線及び金属膜及びその形成方法 |
TWI331345B (en) | 2003-09-12 | 2010-10-01 | Nat Inst Of Advanced Ind Scien | A dispersion of nano-size metal particles and a process for forming a layer of an electric conductor with use thereof |
TWI289488B (en) | 2003-10-20 | 2007-11-11 | Harima Chemicals Inc | Fine metal particles, fine metal oxide particles in the form of dried-up powder, and use of the same |
US20050129843A1 (en) * | 2003-12-11 | 2005-06-16 | Xerox Corporation | Nanoparticle deposition process |
JP2005174824A (ja) * | 2003-12-12 | 2005-06-30 | Tanaka Kikinzoku Kogyo Kk | 金属ペースト及び該金属ペーストを用いた膜形成方法 |
CN1930638B (zh) * | 2004-03-10 | 2010-09-22 | 旭硝子株式会社 | 含有金属的微粒、含有金属的微粒分散液及含有导电性金属的材料 |
KR101166001B1 (ko) * | 2004-03-10 | 2012-07-18 | 아사히 가라스 가부시키가이샤 | 금속 함유 미립자, 금속 함유 미립자 분산액 및 도전성금속 함유 재료 |
TWI287477B (en) * | 2004-04-16 | 2007-10-01 | Nat Inst For Materials Science | Colloidal solution of metal micro particles conductive paste material, conductive ink material and method of manufacture |
FR2869444B1 (fr) * | 2004-04-26 | 2006-06-16 | Hologram Ind Sarl | Procede d'inscription de motifs graphiques ou similaires sur la face enregistree d'un support optique d'informations et support optique mettant en oeuvre ce procede |
CN1968773B (zh) * | 2004-06-16 | 2011-08-03 | 东邦钛株式会社 | 镍粉及其制备方法 |
US7695641B2 (en) * | 2004-07-05 | 2010-04-13 | Kri, Inc. | Organic/inorganic composite |
JP2006080013A (ja) * | 2004-09-10 | 2006-03-23 | Mitsui Mining & Smelting Co Ltd | 導電性ペースト及びその導電性ペーストを用いて得られるフレキシブルプリント配線板 |
JP4148213B2 (ja) * | 2004-10-21 | 2008-09-10 | セイコーエプソン株式会社 | パターン形成方法および機能性膜 |
WO2006057348A1 (ja) | 2004-11-29 | 2006-06-01 | Dainippon Ink And Chemicals, Inc. | 表面処理された銀含有粉末の製造方法、及び表面処理された銀含有粉末を用いた銀ペースト |
US7674671B2 (en) | 2004-12-13 | 2010-03-09 | Optomec Design Company | Aerodynamic jetting of aerosolized fluids for fabrication of passive structures |
US7938341B2 (en) * | 2004-12-13 | 2011-05-10 | Optomec Design Company | Miniature aerosol jet and aerosol jet array |
US7533361B2 (en) * | 2005-01-14 | 2009-05-12 | Cabot Corporation | System and process for manufacturing custom electronics by combining traditional electronics with printable electronics |
WO2006076606A2 (en) * | 2005-01-14 | 2006-07-20 | Cabot Corporation | Optimized multi-layer printing of electronics and displays |
WO2006076610A2 (en) * | 2005-01-14 | 2006-07-20 | Cabot Corporation | Controlling ink migration during the formation of printable electronic features |
US20060190917A1 (en) * | 2005-01-14 | 2006-08-24 | Cabot Corporation | System and process for manufacturing application specific printable circuits (ASPC'S) and other custom electronic devices |
US20060163744A1 (en) * | 2005-01-14 | 2006-07-27 | Cabot Corporation | Printable electrical conductors |
WO2006076612A2 (en) | 2005-01-14 | 2006-07-20 | Cabot Corporation | A process for manufacturing application specific printable circuits (aspc’s) and other custom electronic devices |
US7824466B2 (en) | 2005-01-14 | 2010-11-02 | Cabot Corporation | Production of metal nanoparticles |
US8383014B2 (en) | 2010-06-15 | 2013-02-26 | Cabot Corporation | Metal nanoparticle compositions |
US8167393B2 (en) * | 2005-01-14 | 2012-05-01 | Cabot Corporation | Printable electronic features on non-uniform substrate and processes for making same |
US20090032293A1 (en) * | 2005-03-23 | 2009-02-05 | Hidenori Miyakawa | Electroconductive Bonding Material and Electric/Electronic Device Using the Same |
US20090123732A1 (en) * | 2005-04-12 | 2009-05-14 | Sumitomo Metal Mining Co., Ltd. | Electroconductive Metal Film and Production Method Thereof |
CN101522947A (zh) * | 2005-06-10 | 2009-09-02 | 西玛耐诺技术以色列有限公司 | 增强的透明导电涂料及其制备方法 |
US20090029065A1 (en) * | 2005-06-25 | 2009-01-29 | Nobuto Terada | Conductive circuit manufacturing method |
TWI297513B (en) * | 2005-10-06 | 2008-06-01 | Ind Tech Res Inst | Electrode and method for forming the same |
US20070154634A1 (en) * | 2005-12-15 | 2007-07-05 | Optomec Design Company | Method and Apparatus for Low-Temperature Plasma Sintering |
US20070144305A1 (en) * | 2005-12-20 | 2007-06-28 | Jablonski Gregory A | Synthesis of Metallic Nanoparticle Dispersions |
US8721931B2 (en) * | 2005-12-21 | 2014-05-13 | E I Du Pont De Nemours And Company | Paste for solar cell electrode, solar cell electrode manufacturing method, and solar cell |
JP4821396B2 (ja) * | 2006-03-27 | 2011-11-24 | 住友金属鉱山株式会社 | 導電性組成物及び導電膜形成方法 |
US8344523B2 (en) * | 2006-05-08 | 2013-01-01 | Diemat, Inc. | Conductive composition |
KR101009564B1 (ko) * | 2006-06-30 | 2011-01-18 | 아사히 가세이 일렉트로닉스 가부시끼가이샤 | 도전성 충전재 |
JP4355010B2 (ja) * | 2006-10-04 | 2009-10-28 | 昭栄化学工業株式会社 | 積層電子部品用導体ペースト |
US7919015B2 (en) * | 2006-10-05 | 2011-04-05 | Xerox Corporation | Silver-containing nanoparticles with replacement stabilizer |
CN101234455B (zh) * | 2007-01-30 | 2012-03-28 | 播磨化成株式会社 | 焊锡膏组合物及焊锡预涂法 |
KR100851982B1 (ko) * | 2007-02-23 | 2008-08-12 | 삼성전자주식회사 | 강유전체 나노도트를 포함하는 강유전체 정보저장매체 및그 제조방법 |
CA2680201A1 (en) * | 2007-03-01 | 2008-09-25 | Pchem Associates, Inc. | Shielding based on metallic nanoparticle compositions and devices and methods thereof |
US20100310630A1 (en) * | 2007-04-27 | 2010-12-09 | Technische Universitat Braunschweig | Coated surface for cell culture |
US8128794B2 (en) * | 2007-05-16 | 2012-03-06 | Korea Atomic Energy Research Institute | Water pollution sensor for detecting heavy metal and method of manufacturing the same |
US20080311738A1 (en) * | 2007-06-18 | 2008-12-18 | Lakshmi Supriya | Method of forming an interconnect joint |
TWI482662B (zh) | 2007-08-30 | 2015-05-01 | Optomec Inc | 機械上一體式及緊密式耦合之列印頭以及噴霧源 |
US8048488B2 (en) * | 2008-01-14 | 2011-11-01 | Xerox Corporation | Methods for removing a stabilizer from a metal nanoparticle using a destabilizer |
CN101911219B (zh) | 2008-01-17 | 2015-12-16 | 日亚化学工业株式会社 | 导电性材料及其制造方法、电子设备、发光装置及其制造方法 |
US8253233B2 (en) | 2008-02-14 | 2012-08-28 | Infineon Technologies Ag | Module including a sintered joint bonding a semiconductor chip to a copper surface |
US20100015462A1 (en) * | 2008-02-29 | 2010-01-21 | Gregory Jablonski | Metallic nanoparticle shielding structure and methods thereof |
EP2291471A1 (en) * | 2008-06-12 | 2011-03-09 | NanoMas Technologies, Inc. | Conductive inks and pastes |
JP2010044967A (ja) * | 2008-08-13 | 2010-02-25 | Sumitomo Electric Ind Ltd | 導電性接着剤およびそれを用いたled基板 |
KR100999506B1 (ko) * | 2008-09-09 | 2010-12-09 | 삼성전기주식회사 | 인쇄회로기판 및 그 제조 방법 |
KR20100033143A (ko) * | 2008-09-19 | 2010-03-29 | 삼성전자주식회사 | 유기금속 전구체 및 이를 이용한 금속 필름 또는 패턴 |
CN102264491B (zh) * | 2008-11-21 | 2014-11-26 | 汉高公司 | 可热分解聚合物涂布的金属粉末 |
US20100233361A1 (en) * | 2009-03-12 | 2010-09-16 | Xerox Corporation | Metal nanoparticle composition with improved adhesion |
US9011570B2 (en) * | 2009-07-30 | 2015-04-21 | Lockheed Martin Corporation | Articles containing copper nanoparticles and methods for production and use thereof |
US9072185B2 (en) | 2009-07-30 | 2015-06-30 | Lockheed Martin Corporation | Copper nanoparticle application processes for low temperature printable, flexible/conformal electronics and antennas |
JP5246096B2 (ja) * | 2009-08-10 | 2013-07-24 | 日立電線株式会社 | 複合金属微粒子材料、金属膜及び金属膜の製造方法、並びにプリント配線板及び電線ケーブル |
US9137902B2 (en) | 2009-08-14 | 2015-09-15 | Xerox Corporation | Process to form highly conductive feature from silver nanoparticles with reduced processing temperature |
KR101206250B1 (ko) * | 2009-10-13 | 2012-11-28 | 주식회사 엘지화학 | 식각 마스크 패턴 형성용 페이스트 및 이의 스크린 인쇄법을 이용한 실리콘 태양전지의 제조방법 |
TW201114876A (en) * | 2009-10-29 | 2011-05-01 | Giga Solar Materials Corp | Conductive paste with surfactants |
US8587460B2 (en) * | 2009-12-11 | 2013-11-19 | Nec Corporation | A/D conversion device and compensation control method for A/D conversion device |
TWI494389B (zh) * | 2010-01-08 | 2015-08-01 | Toyo Boseki | 導電性糊及金屬薄膜 |
JP5707726B2 (ja) * | 2010-04-09 | 2015-04-30 | 日立金属株式会社 | 導電性金属ペースト用金属微粒子および導電性金属ペーストならびに金属膜 |
US8911823B2 (en) * | 2010-05-03 | 2014-12-16 | Pen Inc. | Mechanical sintering of nanoparticle inks and powders |
JP5464046B2 (ja) * | 2010-05-21 | 2014-04-09 | 日立金属株式会社 | 金属微粒子、導電性金属ペースト、および金属膜 |
US8685284B2 (en) * | 2010-09-17 | 2014-04-01 | Endicott Interconnect Technologies, Inc. | Conducting paste for device level interconnects |
DE102010042721A1 (de) * | 2010-10-20 | 2012-04-26 | Robert Bosch Gmbh | Ausgangswerkstoff einer Sinterverbindung und Verfahren zur Herstellung der Sinterverbindung |
DE102010042702A1 (de) * | 2010-10-20 | 2012-04-26 | Robert Bosch Gmbh | Ausgangswerkstoff einer Sinterverbindung und Verfahren zur Herstellung der Sinterverbindung |
KR101428131B1 (ko) * | 2010-10-28 | 2014-08-07 | 엘지이노텍 주식회사 | 전도성 페이스트 조성물 |
JP5830237B2 (ja) * | 2010-11-10 | 2015-12-09 | Dowaエレクトロニクス株式会社 | 銀粒子含有組成物、分散液ならびにペーストの製造方法 |
US8419981B2 (en) | 2010-11-15 | 2013-04-16 | Cheil Industries, Inc. | Conductive paste composition and electrode prepared using the same |
KR20120066944A (ko) * | 2010-12-15 | 2012-06-25 | 삼성전기주식회사 | 내부전극용 도전성 페이스트 조성물, 이를 이용한 적층 세라믹 전자부품 및 그 제조방법 |
JP5741809B2 (ja) * | 2011-02-22 | 2015-07-01 | 三菱マテリアル株式会社 | 接合用ペースト、および半導体素子と基板の接合方法 |
JP2012182111A (ja) * | 2011-02-28 | 2012-09-20 | Samsung Electro-Mechanics Co Ltd | 導電性金属ペースト組成物及びその製造方法 |
KR20120119167A (ko) * | 2011-04-20 | 2012-10-30 | 삼성전기주식회사 | 관성센서의 제조방법 |
TWI608062B (zh) * | 2011-05-31 | 2017-12-11 | 住友電木股份有限公司 | 樹脂組成物、使用它之半導體裝置及半導體裝置之製造方法 |
WO2013036523A1 (en) * | 2011-09-06 | 2013-03-14 | Henkel Corporation | Conductive material and process |
CN104024351B (zh) | 2011-09-06 | 2016-11-16 | 汉高知识产权控股有限责任公司 | 导电金属和方法 |
EP2753442B1 (en) | 2011-09-06 | 2019-10-30 | Henkel IP & Holding GmbH | Di-or poly-functional electron deficient olefins coated metal powders for solder pastes |
JP6037494B2 (ja) * | 2012-01-11 | 2016-12-07 | 国立大学法人山形大学 | 銀ナノ粒子の製造方法及び銀ナノ粒子、並びに銀塗料組成物 |
KR101999795B1 (ko) * | 2012-06-27 | 2019-07-12 | 삼성전자주식회사 | 도전성 페이스트, 상기 도전성 페이스트를 사용하여 형성된 전극을 포함하는 전자 소자 및 태양 전지 |
JP6457390B2 (ja) * | 2012-08-31 | 2019-01-23 | ヘレウス プレシャス メタルズ ゲーエムベーハー ウント コンパニー カーゲー | 電極の製造における銀ナノ粒子及び球形の銀ミクロ粒子を含む導電性ペースト |
TWI666656B (zh) * | 2012-10-29 | 2019-07-21 | 阿爾發裝配解決方案公司 | 燒結粉末 |
EP2763141B1 (en) | 2013-02-01 | 2016-02-03 | Heraeus Precious Metals North America Conshohocken LLC | Low fire silver paste |
US20140287158A1 (en) * | 2013-03-21 | 2014-09-25 | Intrinsiq Materials, Inc. | Performance of conductive copper paste using copper flake |
JP6184731B2 (ja) * | 2013-04-25 | 2017-08-23 | Dowaエレクトロニクス株式会社 | 銀−ビスマス粉末、導電性ペースト及び導電膜 |
US20160121432A1 (en) * | 2013-05-16 | 2016-05-05 | Bando Chemical Industries, Ltd. | Composition for metal bonding |
US20140357910A1 (en) * | 2013-05-30 | 2014-12-04 | Elena Shevchenko | Surface modification of catalystic surface by organic molecules and metal cations for selective catalysis |
JP6118192B2 (ja) * | 2013-06-21 | 2017-04-19 | Dowaエレクトロニクス株式会社 | 接合材およびそれを用いた接合方法 |
KR102172950B1 (ko) | 2013-08-16 | 2020-11-03 | 헨켈 아이피 앤드 홀딩 게엠베하 | 서브마이크론 은 입자 잉크 조성물, 방법 및 응용 |
TW201611198A (zh) * | 2014-04-11 | 2016-03-16 | 阿爾發金屬公司 | 低壓燒結粉末 |
US10894302B2 (en) * | 2014-06-23 | 2021-01-19 | Alpha Assembly Solutions Inc. | Multilayered metal nano and micron particles |
WO2016130709A1 (en) | 2015-02-10 | 2016-08-18 | Optomec, Inc. | Fabrication of three-dimensional structures by in-flight curing of aerosols |
JP6220966B2 (ja) * | 2015-04-17 | 2017-10-25 | バンドー化学株式会社 | 銀微粒子組成物 |
FR3041968B1 (fr) * | 2015-10-01 | 2019-11-01 | Genes'ink Sa | Encre a base de nanoparticules d'argent |
FR3036402B1 (fr) * | 2015-05-20 | 2017-05-19 | Genes'ink Sa | Encre a base de nanoparticules d'argent |
EP3299099A4 (en) * | 2015-05-20 | 2019-01-16 | National University Corporation Yamagata University | METHOD FOR PRODUCING A SILVER NANOPARTICLE DISPERSION AND METHOD FOR PRODUCING A SILVER NANOPARTICLE INK |
ES2900477T3 (es) | 2015-05-20 | 2022-03-17 | Genesink Sa | Tinta a base de nanopartículas de plata |
US10696932B2 (en) | 2015-08-03 | 2020-06-30 | Fujifilm Electronic Materials U.S.A., Inc. | Cleaning composition |
EP3337861B1 (en) | 2015-08-17 | 2020-12-02 | Henkel IP & Holding GmbH | Ink compositions with improved conductivity |
JP6594156B2 (ja) * | 2015-10-14 | 2019-10-23 | 株式会社ノリタケカンパニーリミテド | 加熱硬化型導電性ペースト |
US20170271294A1 (en) * | 2016-03-15 | 2017-09-21 | Indium Corporation | Spacer particles for bond line thickness control in sintering pastes |
KR102305794B1 (ko) * | 2016-05-26 | 2021-09-28 | 가부시키가이샤 오사카소다 | 도전성 접착체 |
JP7007140B2 (ja) | 2016-09-30 | 2022-01-24 | Dowaエレクトロニクス株式会社 | 接合材およびそれを用いた接合方法 |
WO2018062220A1 (ja) * | 2016-09-30 | 2018-04-05 | Dowaエレクトロニクス株式会社 | 接合材およびそれを用いた接合方法 |
EP3583151B1 (en) * | 2017-02-15 | 2021-06-09 | 3M Innovative Properties Company | Epoxy stabilization using metal nanoparticles and nitrogen-containing catalysts, and methods |
KR20200087196A (ko) | 2017-11-13 | 2020-07-20 | 옵토멕 인코포레이티드 | 에어로졸 스트림의 셔터링 |
JP7032126B2 (ja) * | 2017-12-25 | 2022-03-08 | 住友電気工業株式会社 | プリント配線板用基材及びプリント配線板 |
KR102465591B1 (ko) * | 2018-01-16 | 2022-11-09 | 한국전기연구원 | 계층구조를 갖는 금속/이차원 나노소재 하이브리드 잉크, 하이브리드 잉크 제조방법 및 하이브리드 잉크를 통해 형성된 전도막 |
CN108753197B (zh) * | 2018-04-04 | 2021-01-05 | 佛山市瑞福物联科技有限公司 | 一种热固性导电胶及其制备方法 |
JP2020004524A (ja) * | 2018-06-26 | 2020-01-09 | ナミックス株式会社 | 真空印刷用導電性ペースト |
JP6609073B1 (ja) | 2019-01-15 | 2019-11-20 | 株式会社日本マイクロニクス | プローブ基板及び電気的接続装置 |
CN114437506B (zh) * | 2022-02-17 | 2023-06-27 | 深圳市普颂电子有限公司 | 一种无磁传感器检测构件的制作方法 |
CN115231829B (zh) * | 2022-08-26 | 2024-01-05 | 四川英诺维新材料科技有限公司 | 一种真空玻璃用封接材料及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10312712A (ja) * | 1997-05-14 | 1998-11-24 | Asahi Chem Ind Co Ltd | はんだ付け可能な導電性ペースト |
US5922403A (en) * | 1996-03-12 | 1999-07-13 | Tecle; Berhan | Method for isolating ultrafine and fine particles |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57185316A (en) * | 1981-05-11 | 1982-11-15 | Sumitomo Metal Mining Co Ltd | Electrically conductive resin paste |
EP0239901B1 (en) * | 1986-03-31 | 1992-11-11 | Tatsuta Electric Wire & Cable Co., Ltd | Conductive copper paste composition |
JPH033421A (ja) | 1989-05-31 | 1991-01-09 | Hitachi Ltd | 半導体集積回路装置 |
JPH0412595A (ja) * | 1990-05-02 | 1992-01-17 | Mitsubishi Petrochem Co Ltd | 導電性ペースト組成物 |
JPH04146976A (ja) * | 1990-10-08 | 1992-05-20 | Asahi Chem Res Lab Ltd | 導電性ペースト組成物 |
JP3222950B2 (ja) * | 1992-10-26 | 2001-10-29 | 旭化成株式会社 | 強固なはんだ付け可能な導電性ペースト |
DE69417684T2 (de) * | 1993-10-29 | 1999-09-09 | Dai-Ichi Kogyo Seiyaku Co. | Leitfähige Pastenzusammensetzung zum Füllen von Kontaktlöchern, Leiterplatte unter Anwendung dieser leifähigen Paste und Verfahren zur Herstellung |
JPH11319538A (ja) | 1998-05-20 | 1999-11-24 | Nippon Paint Co Ltd | 貴金属又は銅のコロイドの製造方法 |
-
2001
- 2001-09-26 CA CA002426861A patent/CA2426861C/en not_active Expired - Lifetime
- 2001-09-26 TW TW090123742A patent/TW591095B/zh not_active IP Right Cessation
- 2001-09-26 EP EP01970208A patent/EP1339073B1/en not_active Expired - Lifetime
- 2001-09-26 AU AU2001290266A patent/AU2001290266A1/en not_active Abandoned
- 2001-09-26 JP JP2002538446A patent/JP4155821B2/ja not_active Expired - Lifetime
- 2001-09-26 KR KR1020037005738A patent/KR100647238B1/ko active IP Right Grant
- 2001-09-26 US US10/415,004 patent/US7081214B2/en not_active Expired - Lifetime
- 2001-09-26 WO PCT/JP2001/008340 patent/WO2002035554A1/ja active Application Filing
- 2001-09-26 AT AT01970208T patent/ATE525730T1/de not_active IP Right Cessation
- 2001-09-26 CN CNB018196713A patent/CN1319075C/zh not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5922403A (en) * | 1996-03-12 | 1999-07-13 | Tecle; Berhan | Method for isolating ultrafine and fine particles |
JPH10312712A (ja) * | 1997-05-14 | 1998-11-24 | Asahi Chem Ind Co Ltd | はんだ付け可能な導電性ペースト |
Cited By (71)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002334618A (ja) * | 2001-05-07 | 2002-11-22 | Harima Chem Inc | 金属微粒子分散液を用いたメッキ代替導電性金属皮膜の形成方法 |
JP2004111253A (ja) * | 2002-09-19 | 2004-04-08 | Noda Screen:Kk | 電子デバイスの電気的接続用導電性組成物および電子デバイス |
JP2004111254A (ja) * | 2002-09-19 | 2004-04-08 | Asahi Glass Co Ltd | 電子デバイスの電気的接続用金属含有組成物 |
US20090169730A1 (en) * | 2003-02-20 | 2009-07-02 | The Regents Of The University Of California | Method of forming conductors at low temperatures using metallic nanocrystals and product |
US7556747B2 (en) * | 2003-08-08 | 2009-07-07 | Sumitomo Electric Industries, Ltd. | Electrically conductive pastes |
JP2005093826A (ja) * | 2003-09-18 | 2005-04-07 | Ricoh Co Ltd | 導電性接着剤による接続構造体及びその製造方法 |
JP2005129303A (ja) * | 2003-10-22 | 2005-05-19 | Denso Corp | 導体組成物および導体組成物を用いた実装基板ならびに実装構造 |
US7807073B2 (en) | 2003-10-22 | 2010-10-05 | Denso Corporation | Conductor composition, a mounting substrate and a mounting structure utilizing the composition |
US7459201B2 (en) | 2003-12-12 | 2008-12-02 | Hitachi Cable, Ltd. | Compound for forming wiring conductor, fabrication method of circuit board using the same and circuit board |
JP2005174828A (ja) * | 2003-12-12 | 2005-06-30 | Hitachi Ltd | 配線導電体形成用組成物及びそれを用いた配線基板の製造方法、並びに配線基板 |
JP2005183144A (ja) * | 2003-12-18 | 2005-07-07 | Alps Electric Co Ltd | 導電性組成物及びその製造方法 |
JP2005294254A (ja) * | 2004-03-12 | 2005-10-20 | Sumitomo Electric Ind Ltd | 導電性銀ペースト及びそれを用いた電磁波シールド部材 |
US8021580B2 (en) | 2004-06-23 | 2011-09-20 | Harima Chemicals, Inc. | Conductive metal paste |
US7262511B2 (en) | 2004-08-18 | 2007-08-28 | Harima Chemicals, Inc. | Conductive adhesive agent with ultrafine particles |
JP2006083377A (ja) * | 2004-08-18 | 2006-03-30 | Harima Chem Inc | 導電性接着剤および該導電性接着剤を利用する物品の製造方法 |
JP2006202604A (ja) * | 2005-01-20 | 2006-08-03 | Matsushita Electric Ind Co Ltd | 導電性ペーストならびにこれを用いる配線基板、多層基板および電子部品実装体の製造方法 |
JP4510649B2 (ja) * | 2005-01-20 | 2010-07-28 | パナソニック株式会社 | 配線基板、多層基板および電子部品実装体の製造方法 |
JP2006206730A (ja) * | 2005-01-27 | 2006-08-10 | Sumitomo Bakelite Co Ltd | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
JP4665532B2 (ja) * | 2005-01-27 | 2011-04-06 | 住友ベークライト株式会社 | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
JP2009500802A (ja) * | 2005-07-01 | 2009-01-08 | ナショナル ユニバーシティー オブ シンガポール | 導電性複合材料 |
JP2015122310A (ja) * | 2005-07-01 | 2015-07-02 | ナショナル ユニヴァーシティー オブ シンガポール | 導電性複合材料の調製方法、前記材料及び前記材料を含む装置 |
JP2007042301A (ja) * | 2005-07-29 | 2007-02-15 | Toda Kogyo Corp | 導電性組成物、導電性ペースト及び導電性皮膜 |
JP2007083288A (ja) * | 2005-09-22 | 2007-04-05 | Harima Chem Inc | 導電性接合の形成方法 |
JP2007180059A (ja) * | 2005-12-26 | 2007-07-12 | Toshiba Corp | 光半導体装置とその製造方法 |
JP2008063449A (ja) * | 2006-09-07 | 2008-03-21 | Hitachi Ltd | ポリマーナノコンポジット材料、その製造方法電子部品装置およびその製造方法 |
WO2008038534A1 (en) | 2006-09-26 | 2008-04-03 | Dowa Electronics Materials Co., Ltd. | Silver microparticle powder and method for production thereof |
WO2008038535A1 (fr) | 2006-09-27 | 2008-04-03 | Dowa Electronics Materials Co., Ltd. | Poudre composite de particules d'argent et son procédé de production |
JP2008091250A (ja) * | 2006-10-03 | 2008-04-17 | Mitsuboshi Belting Ltd | 低温焼成型銀ペースト |
JP2008166086A (ja) * | 2006-12-28 | 2008-07-17 | Hitachi Ltd | 導電性焼結層形成用組成物、これを用いた導電性被膜形成法および接合法 |
JP2009037943A (ja) * | 2007-08-03 | 2009-02-19 | Toyo Ink Mfg Co Ltd | 導電性被膜の製造方法 |
WO2009066396A1 (ja) * | 2007-11-22 | 2009-05-28 | Asahi Glass Company, Limited | 導電膜形成用インクおよびプリント配線板の製造方法 |
JP2009177010A (ja) * | 2008-01-25 | 2009-08-06 | Toshiba Corp | フレキシブルプリント配線板および電子機器 |
JP2009275227A (ja) * | 2008-05-16 | 2009-11-26 | Bayer Materialscience Ag | 銀ナノ粒子含有印刷可能組成物、該組成物を用いた導電性被膜の製造方法、および該方法により製造された被膜 |
JP2010108696A (ja) * | 2008-10-29 | 2010-05-13 | Mitsuboshi Belting Ltd | 抵抗体ペースト及び抵抗器 |
US9457406B2 (en) | 2009-09-16 | 2016-10-04 | Hitachi Chemical Company, Ltd. | Copper metal film, method for producing same, copper metal pattern, conductive wiring line using the copper metal pattern, copper metal bump, heat conduction path, bonding material, and liquid composition |
JP2011119340A (ja) * | 2009-12-01 | 2011-06-16 | Harima Chemicals Inc | 導電性アルミニウムペースト |
WO2011078141A1 (ja) * | 2009-12-22 | 2011-06-30 | Dic株式会社 | スクリーン印刷用導電性ペースト |
WO2011078140A1 (ja) * | 2009-12-22 | 2011-06-30 | Dic株式会社 | スクリーン印刷用導電性ペースト |
JP4835810B2 (ja) * | 2009-12-22 | 2011-12-14 | Dic株式会社 | スクリーン印刷用導電性ペースト |
DE112010004960T5 (de) | 2009-12-22 | 2012-12-06 | Dic Corporation | Leitpaste für Siebdruckverfahren |
DE112010004973T5 (de) | 2009-12-22 | 2013-02-28 | Dic Corp. | Leitpaste für Siebdruckverfahren |
JP4835809B2 (ja) * | 2009-12-22 | 2011-12-14 | Dic株式会社 | スクリーン印刷用導電性ペースト |
US9390830B2 (en) | 2009-12-22 | 2016-07-12 | Dic Corporation | Conductive paste for screen printing |
US9039941B2 (en) | 2009-12-22 | 2015-05-26 | Dic Corporation | Conductive paste for screen printing |
JP2011142259A (ja) * | 2010-01-08 | 2011-07-21 | Ulvac Japan Ltd | 非晶質Si太陽電池基板の製造方法 |
JP2011256382A (ja) * | 2010-06-09 | 2011-12-22 | Xerox Corp | 特定のハンセン溶解度パラメータを有する溶媒を含む銀ナノ粒子組成物 |
WO2011158659A1 (ja) * | 2010-06-16 | 2011-12-22 | 独立行政法人物質・材料研究機構 | 金属ナノ粒子ペースト、並びに金属ナノ粒子ペーストを用いた電子部品接合体、ledモジュール及びプリント配線板の回路形成方法 |
JP2012023014A (ja) * | 2010-06-16 | 2012-02-02 | National Institute For Materials Science | 金属ナノ粒子ペースト、並びに金属ナノ粒子ペーストを用いた電子部品接合体、ledモジュール及びプリント配線板の回路形成方法 |
US8643165B2 (en) | 2011-02-23 | 2014-02-04 | Texas Instruments Incorporated | Semiconductor device having agglomerate terminals |
JP2014514383A (ja) * | 2011-03-22 | 2014-06-19 | ナノ アンド アドバンスド マテリアルズ インスティトゥート リミテッド | 高輝度led用高性能ダイ取付接着剤(daa)ナノ材料 |
JP2013069654A (ja) * | 2011-09-21 | 2013-04-18 | Samsung Electro-Mechanics Co Ltd | 低温焼成用導電性ペースト組成物 |
JP2013143216A (ja) * | 2012-01-10 | 2013-07-22 | Napura:Kk | 機能性材料、電子デバイス、電磁波吸収/遮蔽デバイス及びそれらの製造方法 |
JP2013218830A (ja) * | 2012-04-05 | 2013-10-24 | Ulvac Japan Ltd | 導電性金属ペースト |
JP2013218829A (ja) * | 2012-04-05 | 2013-10-24 | Ulvac Japan Ltd | 導電性金属ペースト |
JP2013218831A (ja) * | 2012-04-06 | 2013-10-24 | Ulvac Japan Ltd | 導電性金属ペースト |
JP2014029845A (ja) * | 2012-06-28 | 2014-02-13 | Nippon Steel & Sumikin Chemical Co Ltd | 導電性ペーストの製造方法 |
JP2014182913A (ja) * | 2013-03-19 | 2014-09-29 | Fujifilm Corp | 導電膜形成用組成物およびこれを用いる導電膜の製造方法 |
WO2014184641A2 (en) | 2013-05-17 | 2014-11-20 | Toyota Jidosha Kabushiki Kaisha | Metal paste for joining, joining method and joined body |
JP2015049992A (ja) * | 2013-08-30 | 2015-03-16 | 富士フイルム株式会社 | 導電膜形成用組成物およびこれを用いる導電膜の製造方法 |
WO2015060245A1 (ja) * | 2013-10-22 | 2015-04-30 | 日立化成株式会社 | 銀ペースト及びそれを用いた半導体装置、並びに銀ペーストの製造方法 |
JP2015082385A (ja) * | 2013-10-22 | 2015-04-27 | 日立化成株式会社 | 銀ペースト及びそれを用いた半導体装置、並びに銀ペーストの製造方法 |
JP2015175001A (ja) * | 2014-03-17 | 2015-10-05 | ゼロックス コーポレイションXerox Corporation | インク組成物およびインク組成物の硬化度を決定する方法 |
JPWO2015163076A1 (ja) * | 2014-04-25 | 2017-04-13 | 株式会社ダイセル | 銀粒子塗料組成物 |
US10207373B2 (en) | 2014-06-30 | 2019-02-19 | Nippon Steel Chemical & Material Co., Ltd. | Nickel particle composition, bonding material, and bonding method in which said material is used |
JPWO2016002741A1 (ja) * | 2014-06-30 | 2017-04-27 | 新日鉄住金化学株式会社 | ニッケル粒子組成物、接合材及びそれを用いた接合方法 |
WO2016002741A1 (ja) * | 2014-06-30 | 2016-01-07 | 新日鉄住金化学株式会社 | ニッケル粒子組成物、接合材及びそれを用いた接合方法 |
WO2016076306A1 (ja) * | 2014-11-12 | 2016-05-19 | ハリマ化成株式会社 | 導電性ペースト |
JPWO2016076306A1 (ja) * | 2014-11-12 | 2017-08-24 | ハリマ化成株式会社 | 導電性ペースト |
DE112017004749T5 (de) | 2016-09-21 | 2019-06-27 | Yazaki Corporation | Elektrisch leitfähige Paste und Leiterplatte damit |
JPWO2019065221A1 (ja) * | 2017-09-27 | 2020-12-03 | 京セラ株式会社 | ペースト組成物、半導体装置及び電気・電子部品 |
JP7100651B2 (ja) | 2017-09-27 | 2022-07-13 | 京セラ株式会社 | ペースト組成物、半導体装置及び電気・電子部品 |
Also Published As
Publication number | Publication date |
---|---|
US20040004209A1 (en) | 2004-01-08 |
CN1478285A (zh) | 2004-02-25 |
EP1339073A4 (en) | 2004-12-15 |
US7081214B2 (en) | 2006-07-25 |
ATE525730T1 (de) | 2011-10-15 |
WO2002035554A8 (fr) | 2002-07-18 |
AU2001290266A1 (en) | 2002-05-06 |
CN1319075C (zh) | 2007-05-30 |
KR20040030441A (ko) | 2004-04-09 |
EP1339073A1 (en) | 2003-08-27 |
CA2426861A1 (en) | 2003-04-24 |
JP4155821B2 (ja) | 2008-09-24 |
EP1339073B1 (en) | 2011-09-21 |
TW591095B (en) | 2004-06-11 |
CA2426861C (en) | 2008-10-28 |
JPWO2002035554A1 (ja) | 2004-03-04 |
KR100647238B1 (ko) | 2006-11-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2002035554A1 (fr) | Pate metallique electro-conductrice et procede de production de cette pate | |
TWI516556B (zh) | Metal nano-particle paste, and the use of metal nano-particles paste electronic parts assembly, LED module and printed circuit board circuit formation method | |
JP4928639B2 (ja) | 接合材およびそれを用いた接合方法 | |
JP4414145B2 (ja) | 導電性ナノ粒子ペースト | |
KR100771393B1 (ko) | 건조 분말상의 금속 미립자 및 금속 산화물 미립자와 그용도 | |
JP6380792B2 (ja) | 銀ペースト及びそれを用いた半導体装置、並びに銀ペーストの製造方法 | |
JP6303392B2 (ja) | 銀ペースト及びそれを用いた半導体装置、並びに銀ペーストの製造方法 | |
US20080272344A1 (en) | Conductive polymer composites | |
WO2018043681A1 (ja) | 銀被覆合金粉末、導電性ペースト、電子部品及び電気装置 | |
JP2011526054A (ja) | 導電性インクおよびペースト | |
EP2990142A1 (en) | Metal nanoparticle dispersion, process for producing metal nanoparticle dispersion, and bonding method | |
TWI729373B (zh) | 導電性膠及燒結體 | |
WO2016002741A1 (ja) | ニッケル粒子組成物、接合材及びそれを用いた接合方法 | |
JP5750259B2 (ja) | 導電性金属ペースト | |
JP4235888B2 (ja) | 導電ペースト | |
JP6562196B2 (ja) | 銅微粒子焼結体と導電性基板の製造方法 | |
TWI690946B (zh) | 導電性糊劑 | |
JP2011119340A (ja) | 導電性アルミニウムペースト | |
JP3879749B2 (ja) | 導電粉及びその製造方法 | |
JP6303022B2 (ja) | 銅粉 | |
JP2019031735A (ja) | 表面処理銀被覆合金粉末、該粉末の製造方法、導電性ペースト、電子部品及び電気装置 | |
JP2009097070A (ja) | ニッケル粒子もしくはニッケル合金粒子の処理方法、防錆剤で被覆されたニッケル粒子もしくはニッケル合金粒子の製造方法、導電性接着剤および電子機器 | |
WO2022185571A1 (ja) | 接合用導電性組成物及びこれを用いた接合構造及びその製造方法 | |
JP2017130393A (ja) | 導電性ペーストおよび銀膜の形成方法 | |
JP6603989B2 (ja) | 複合粒子及びその製造方法、導電性ペースト、焼結体、並びに半導体装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: C1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: C1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2002538446 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10415004 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2426861 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020037005738 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2001970208 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 018196713 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 2001970208 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1020037005738 Country of ref document: KR |