WO2024117183A1 - 導電ペースト、rfidインレイ及びrfidインレイの製造方法 - Google Patents
導電ペースト、rfidインレイ及びrfidインレイの製造方法 Download PDFInfo
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- WO2024117183A1 WO2024117183A1 PCT/JP2023/042743 JP2023042743W WO2024117183A1 WO 2024117183 A1 WO2024117183 A1 WO 2024117183A1 JP 2023042743 W JP2023042743 W JP 2023042743W WO 2024117183 A1 WO2024117183 A1 WO 2024117183A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- 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
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- H10W72/071—
Definitions
- the present invention relates to a conductive paste containing a conductive filler.
- the present invention also relates to an RFID inlay using the conductive paste and a method for manufacturing an RFID inlay.
- UHF Ultra High Frequency
- RFID inlays which allow contactless data transmission and reception, are widely used in contactless RFID tags and contactless RFID cards.
- UHF Ultra High Frequency
- RFID inlays have attracted attention due to their long communication distances, and UHF band RFID inlays are used for a variety of items and purposes, such as commuter passes, inventory management, distribution management, and history management.
- a conductive paste containing a conductive filler and binder resin may be used to bond and connect a chip with electrodes on its surface to a substrate with wiring (antenna pattern) on its surface.
- Patent Document 1 discloses an adhesive that can be used for electronic components.
- the adhesive is an acrylic adhesive composition that contains a radical initiator with a 10-hour half-life temperature of 80°C or less, a vinylene-containing oligomer, and at least one diluent.
- the adhesive can snap cure at low temperatures, and the pot life of the adhesive at room temperature is 24 hours or more.
- Patent Document 2 discloses a conductive adhesive that contains a polymerizable acrylic compound, an organic peroxide, and solder particles, and in which the one-minute half-life temperature of the organic peroxide is lower than the solidus temperature of the solder particles.
- the object of the present invention is to provide a conductive paste that can maintain high conductivity reliability even when moisture penetrates into the connection structure.
- the object of the present invention is also to provide an RFID inlay using the conductive paste and a method for manufacturing an RFID inlay.
- This specification discloses the following conductive paste, RFID inlay, and method for manufacturing an RFID inlay.
- a conductive paste comprising a curable compound, a curing agent, and a plurality of conductive fillers, the curable compound comprising a polymerizable monomer having an alicyclic skeleton, and when a test is conducted in which the cured product of the conductive paste is immersed in water for 2 hours under conditions of 121°C, 100% RH, and 2 atm, the water absorption rate of the cured product is 2.0% or less as described below.
- Item 2 The conductive paste according to item 1, wherein the storage modulus of the cured material before the test is 0.8 GPa or more, and the storage modulus of the cured material after the test is 0.5 GPa or more.
- Item 3 The conductive paste according to item 1 or 2, in which the ratio of the storage modulus of the cured product after the test to the storage modulus of the cured product before the test is 0.5 or more.
- Item 4 The conductive paste according to any one of items 1 to 3, wherein the polymerizable monomer having an alicyclic skeleton has a (meth)acryloyl group.
- Item 5 The conductive paste according to any one of items 1 to 4, wherein the polymerizable monomer having an alicyclic skeleton is tricyclodecane dimethanol di(meth)acrylate or isobornyl(meth)acrylate.
- Item 6 The conductive paste according to any one of items 1 to 5, wherein the content of the polymerizable monomer having an alicyclic skeleton is 10% by weight or more and 50% by weight or less in 100% by weight of the curable compound.
- Item 7 The conductive paste according to any one of items 1 to 6, wherein the conductive filler contains nickel.
- Item 8 A conductive paste according to any one of items 1 to 7, used to obtain an RFID inlay.
- An RFID inlay comprising a substrate having wiring on its surface, a chip having electrodes on its surface, and an adhesive portion bonding the substrate and the chip, the adhesive portion being made of the conductive paste described in any one of items 1 to 8, and the wiring and the electrodes being electrically connected by the conductive filler in the adhesive portion.
- a method for manufacturing an RFID inlay comprising: a first arrangement step of arranging the conductive paste according to any one of items 1 to 8 on a surface of a substrate having wiring on its surface; a second arrangement step of arranging a chip having an electrode on its surface on the surface of the conductive paste opposite the substrate; and a bonding step of forming an adhesive part that bonds the substrate and the chip with the conductive paste by heating and pressurizing the conductive paste, and electrically connecting the wiring and the electrodes with the conductive filler in the adhesive part.
- Item 11 The method for manufacturing an RFID inlay according to Item 10, in which the substrate is long and the RFID inlay is manufactured by transporting the long substrate in the first placement process, the second placement process, and the bonding process using a roll-to-roll method.
- the conductive paste according to the present invention is a conductive paste containing a curable compound, a curing agent, and a plurality of conductive fillers.
- the curable compound contains a polymerizable monomer having an alicyclic skeleton.
- the water absorption rate of the cured product is 2.0% or less. Since the conductive paste according to the present invention has the above configuration, it is possible to maintain high conductivity reliability even when moisture penetrates into the connection structure.
- FIG. 1 is a cross-sectional view showing a schematic diagram of an RFID inlay using a conductive paste according to a first embodiment of the present invention.
- the conductive paste according to the present invention is a conductive paste including a curable compound, a curing agent, and a plurality of conductive fillers.
- the curable compound includes a polymerizable monomer having an alicyclic skeleton.
- the water absorption rate of the cured product is 2.0% or less as described below.
- the conductive paste according to the present invention has the above-mentioned configuration, so it can maintain high conductivity reliability even if moisture penetrates into the connection structure (electronic component).
- the water absorption rate of the cured product is preferably 1.8% or less, more preferably 1.7% or less, even more preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0.5% or less. If the water absorption rate of the cured product is equal to or less than the upper limit, high conductivity reliability can be maintained even when moisture penetrates into the connection structure (electronic component). There is no particular limit to the lower limit of the water absorption rate of the cured product.
- the water absorption rate of the cured product may be 0%, 0% or more, or 0.1% or more.
- the water absorption rate of the cured product is measured, for example, as follows.
- the conductive paste is heated at 130°C for 10 minutes to obtain a cured product (cured product before testing).
- a test is performed in which the cured product is immersed in water for 2 hours under conditions of 121°C, 100% RH, and 2 atm to obtain a cured product after testing.
- the weights of the cured product before and after testing are measured, and the water absorption rate of the cured product is calculated as follows.
- the water absorption rate of the cured product can be adjusted by the following methods.
- a method of adjusting the content of a polymerizable monomer having an alicyclic skeleton (particularly, a polymerizable monomer having an alicyclic skeleton and no polar group).
- the storage modulus of the cured material before the test is preferably 0.8 GPa or more, more preferably 1.0 GPa or more, even more preferably 1.2 GPa or more, and is preferably 3.5 GPa or less, more preferably 3.2 GPa or less, even more preferably 3.0 GPa or less. If the storage modulus of the cured material before the test is equal to or more than the lower limit and equal to or less than the upper limit, the adhesiveness and electrical conductivity reliability can be further improved.
- the storage modulus of the cured material after the above test is preferably 0.3 GPa or more, more preferably 0.4 GPa or more, even more preferably 0.5 GPa or more, even more preferably 0.8 GPa or more, particularly preferably 1.0 GPa or more, and is preferably 3.0 GPa or less, more preferably 2.8 GPa or less, and even more preferably 2.5 GPa or less. If the storage modulus of the cured material after the above test is equal to or more than the above lower limit and equal to or less than the above upper limit, the electrical conductivity reliability can be increased, and high adhesion can be maintained even when moisture penetrates the connection structure.
- the ratio of the storage modulus of the cured product after the test to the storage modulus of the cured product before the test is preferably 0.3 or more, more preferably 0.5 or more, even more preferably 0.6 or more, and particularly preferably 0.7 or more.
- the ratio (storage modulus of the cured product after the test/storage modulus of the cured product before the test) is equal to or greater than the lower limit, high electrical conductivity reliability can be maintained even when moisture penetrates into the connection structure (electronic component).
- the upper limit of the ratio (storage modulus of the cured product after the test/storage modulus of the cured product before the test) is not particularly limited.
- the ratio (storage modulus of the cured product after the test/storage modulus of the cured product before the test) may be 1.0 or less, 0.9 or less, or 0.85 or less.
- the storage modulus of the cured material before the test and the storage modulus of the cured material after the test are measured, for example, as follows. Measurement samples are prepared by cutting the cured material before the test and the cured material after the test into pieces measuring 10 mm in length, 1 to 10 mm in width, and 15 to 50 mm in height. For each measurement sample, the storage modulus of the cured material before the test and the storage modulus of the cured material after the test are measured using a dynamic viscoelasticity measuring device (for example, the "RSA3" manufactured by TA Instruments) under conditions of a frequency of 10 Hz, a strain of 0.1%, a temperature of 20°C to 180°C, and a heating rate of 10°C/min.
- a dynamic viscoelasticity measuring device for example, the "RSA3" manufactured by TA Instruments
- the conductive paste according to the present invention is in a paste form at 25°C.
- the conductive paste is used by discharging it at, for example, 20°C to 50°C. It is preferable that the conductive paste according to the present invention is used by discharging it using a jet dispenser.
- the conductive paste has good adhesive properties.
- the conductive paste is suitable for use as an adhesive.
- the conductive paste is particularly suitable for use in bonding a substrate and a chip.
- the conductive paste is preferably an anisotropic conductive paste.
- the conductive paste is preferably used for electrically connecting electrodes.
- the conductive paste is preferably used for obtaining a connection structure.
- the conductive paste is preferably used for obtaining electronic components.
- the conductive paste is particularly preferably used for obtaining an RFID inlay (use of the conductive paste for obtaining an RFID inlay).
- the conductive paste is preferably used for bonding and connecting a chip having an electrode on its surface to a substrate having wiring (antenna pattern) on its surface (use of the conductive paste for bonding and connecting a chip having an electrode on its surface to a substrate having wiring (antenna pattern) on its surface).
- the conductive paste is preferably used by being applied to a substrate having a surface tension of 30 mN/m or more and 50 mN/m or less (use of the conductive paste on a substrate having a surface tension of 30 mN/m or more and 50 mN/m or less).
- the conductive paste is preferably used to bond a chip having a planar area of 0.50 mm2 or less (use of the conductive paste for bonding a chip having a planar area of 0.50 mm2 or less).
- the conductive paste is preferably thermosetting.
- the conductive paste is preferably a thermosetting conductive paste, and more preferably a thermosetting anisotropic conductive paste.
- (meth)acrylate refers to acrylate and methacrylate.
- (meth)acrylic refers to acrylic and methacrylic.
- (meth)acryloyl refers to acryloyl and methacryloyl.
- the curable compound includes a polymerizable monomer having an alicyclic skeleton. Since the conductive paste has the above-mentioned configuration, the water absorption rate of the cured product can be reduced, and as a result, high electrical conductivity reliability can be maintained even when moisture penetrates into the connection structure (electronic component).
- the polymerizable monomer having an alicyclic skeleton is preferably a (meth)acrylic compound.
- the polymerizable monomer having an alicyclic skeleton is preferably a (meth)acryloyl group.
- the polymerizable monomer having an alicyclic skeleton is preferably a polymerizable monomer having a (meth)acryloyl group.
- the polymerizable functional group in the polymerizable monomer having an alicyclic skeleton is preferably a (meth)acryloyl group.
- the polymerizable monomer having an alicyclic skeleton preferably does not have a polar group.
- the polymerizable monomer having an alicyclic skeleton preferably includes a polymerizable monomer having an alicyclic skeleton and no polar group.
- the polar group include a hydroxyl group, an amino group, and a carboxyl group. In this case, the water absorption rate of the cured product can be reduced, and as a result, high conductivity reliability can be maintained even if moisture penetrates into the connection structure (electronic component).
- the polymerizable monomer having an alicyclic skeleton may be a monofunctional (meth)acrylate or a polyfunctional (meth)acrylate.
- the polymerizable monomer having an alicyclic skeleton may have one (meth)acryloyl group, two, two or more, or ten or less.
- the polymerizable monomer having an alicyclic skeleton is preferably a monofunctional (meth)acrylate and preferably has one (meth)acryloyl group.
- the above-mentioned polymerizable monomers having an alicyclic skeleton include cyclohexyl (meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, isobornyl (meth)acrylate, 4-tert-butylcyclohexanol, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, acrylomorpholine, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
- the above-mentioned polymerizable monomers having an alicyclic skeleton may be used alone or in combination of two or more kinds.
- the polymerizable monomer having the alicyclic skeleton is preferably tricyclodecane dimethanol di(meth)acrylate or isobornyl (meth)acrylate.
- the alicyclic skeleton is preferably a tricyclodecane group or an isobornyl group.
- the molecular weight of the polymerizable monomer having an alicyclic skeleton is preferably 50 or more, more preferably 100 or more, even more preferably 150 or more, particularly preferably 200 or more, and is preferably 1000 or less, more preferably less than 1000, even more preferably 900 or less, particularly preferably 800 or less, and most preferably 700 or less.
- the viscosity of the conductive paste can be adjusted to a suitable range, and the adhesiveness can be further improved, and the conductive reliability can be further improved.
- the molecular weight of the polymerizable monomer having an alicyclic skeleton means a molecular weight that can be calculated from the structural formula of the polymerizable monomer having an alicyclic skeleton, if the structural formula of the polymerizable monomer having an alicyclic skeleton can be specified. If the structural formula of the polymerizable monomer having an alicyclic skeleton cannot be specified, the molecular weight means a weight average molecular weight.
- the weight average molecular weight indicates a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). Since the molecular weight of the polymerizable monomer having an alicyclic skeleton is relatively small, the structural formula can generally be specified.
- the weight average molecular weight can be measured using the following measuring device and under the following measuring conditions.
- Measurement device "Waters GPC System (Waters 2690 + Waters 2414 (RI))" manufactured by Japan Waters Corporation Column: Shodex GPC LF-G x 1, Shodex GPC LF-804 x 2 Mobile phase: THF 1.0 mL/min Sample concentration: 5 mg/mL Detector: Refractive Index Detector (RID) Standard material: polystyrene (manufactured by TOSOH Corporation, weight average molecular weight: 620 to 590,000)
- the curable compound may contain a curable compound other than the polymerizable monomer having an alicyclic skeleton.
- the curable compound other than the polymerizable monomer having an alicyclic skeleton may be a thermosetting compound or a photocurable compound.
- the curable compound other than the polymerizable monomer having an alicyclic skeleton is preferably a thermosetting compound.
- the thermosetting compound is a compound that can be cured by heating. Examples of the thermosetting compound include (meth)acrylic compounds, oxetane compounds, epoxy compounds, episulfide compounds, phenol compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds.
- the curable compound other than the polymerizable monomer having an alicyclic skeleton may be used alone or in combination of two or more.
- the curable compound other than the polymerizable monomer having an alicyclic skeleton preferably contains an epoxy compound or a (meth)acrylic compound, and more preferably contains a (meth)acrylic compound.
- the curable compound other than the polymerizable monomer having an alicyclic skeleton preferably contains a compound having a (meth)acryloyl group ((meth)acrylate).
- the curable compound other than the polymerizable monomer having an alicyclic skeleton preferably has two or more (meth)acryloyl groups.
- the curable compound other than the polymerizable monomer having an alicyclic skeleton is preferably a polyfunctional (meth)acrylate.
- the polyfunctional (meth)acrylate may be a bifunctional (meth)acrylate, a trifunctional (meth)acrylate, or a tetrafunctional or higher (meth)acrylate.
- the curable compound other than the polymerizable monomer having an alicyclic skeleton may have two (meth)acryloyl groups, two or more, three or more, four or more, or ten or less.
- polyfunctional (meth)acrylates include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol (meth)acrylate, 1,9-nonanediol di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol (meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, dipropylene glycol di(meth)acrylate, alkoxylated hexanediol di(meth)acrylate, dodecanediol di(meth)acrylate, Examples of such acrylates include polyethylene glycol (600) di(meth)acrylate, 1,
- the curable compound other than the above-mentioned polymerizable monomer having an alicyclic skeleton contains urethane (meth)acrylate.
- the molecular weight of the urethane (meth)acrylate is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, even more preferably 3000 or more, and particularly preferably 5000 or more, and is preferably 30000 or less, more preferably 25000 or less, even more preferably 20000 or less, and particularly preferably 18000 or less.
- the adhesiveness can be further improved and the electrical conductivity reliability can be further improved.
- the molecular weight of the urethane (meth)acrylate refers to the molecular weight that can be calculated from the structural formula of the urethane (meth)acrylate when the structural formula of the urethane (meth)acrylate can be identified.
- the molecular weight refers to the weight average molecular weight.
- the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
- the molecular weight of the urethane (meth)acrylate is preferably the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
- the weight average molecular weight can be measured using the following measuring device and under the following measuring conditions.
- Measurement device "Waters GPC System (Waters 2690 + Waters 2414 (RI))" manufactured by Japan Waters Corporation Column: Shodex GPC LF-G x 1, Shodex GPC LF-804 x 2 Mobile phase: THF 1.0 mL/min Sample concentration: 5 mg/mL Detector: Refractive Index Detector (RID) Standard material: polystyrene (manufactured by TOSOH Corporation, weight average molecular weight: 620 to 590,000)
- the content of the curable compound in the conductive paste (100% by weight) is preferably 30% by weight or more, more preferably 50% by weight or more, and preferably 90% by weight or less, more preferably 85% by weight or less, and even more preferably 80% by weight or less.
- the adhesiveness can be further improved and the electrical conductivity reliability can be further improved.
- the content of the polymerizable monomer having an alicyclic skeleton is preferably 5% by weight or more, more preferably 15% by weight or more, and preferably 50% by weight or less, more preferably 45% by weight or less, even more preferably 40% by weight or less, and particularly preferably 35% by weight or less.
- the content of the polymerizable monomer having an alicyclic skeleton is equal to or more than the lower limit and equal to or less than the upper limit, high conductivity reliability can be maintained even when moisture penetrates into the connection structure (electronic component).
- the content of the polymerizable monomer having an alicyclic skeleton indicates the total content of the polymerizable monomers having an alicyclic skeleton.
- the content of the polymerizable monomer having an alicyclic skeleton is preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 20% by weight or more, and preferably 50% by weight or less, more preferably 40% by weight or less, and even more preferably 30% by weight or less.
- the content of the polymerizable monomer having an alicyclic skeleton is equal to or more than the lower limit and equal to or less than the upper limit, high conductivity reliability can be maintained even when moisture penetrates into the connection structure (electronic component).
- the content of the polymerizable monomer having an alicyclic skeleton indicates the total content of the polymerizable monomers having an alicyclic skeleton.
- the content of the urethane (meth)acrylate in 100% by weight of the curable compound is preferably 15% by weight or more, more preferably 20% by weight or more, and preferably 50% by weight or less, more preferably 45% by weight or less.
- the adhesiveness can be increased and the electrical conductivity reliability can be further improved.
- the total content of the polymerizable monomer having an alicyclic skeleton and the urethane (meth)acrylate is preferably 20% by weight or more, more preferably 40% by weight or more, and preferably 95% by weight or less, more preferably 90% by weight or less.
- the total content of the polymerizable monomer having an alicyclic skeleton and the urethane (meth)acrylate is equal to or more than the lower limit and equal to or less than the upper limit, high conductivity reliability can be maintained even if moisture penetrates into the connection structure (electronic component).
- the content of the polymerizable monomer having an alicyclic skeleton is preferably 15% by weight or more, more preferably 20% by weight or more, and preferably 80% by weight or less, more preferably 70% by weight or less, out of a total of 100% by weight of the polymerizable monomer having an alicyclic skeleton and the urethane (meth)acrylate.
- the content of the polymerizable monomer having an alicyclic skeleton is equal to or more than the lower limit and equal to or less than the upper limit, high conductivity reliability can be maintained even when moisture penetrates into the connection structure (electronic component).
- the content of the polymerizable monomer having an alicyclic skeleton and having no polar group is preferably 50% by weight or less, more preferably 45% by weight or less, and even more preferably 40% by weight or less.
- the content of the polymerizable monomer having an alicyclic skeleton and having no polar group is equal to or less than the upper limit, the water absorption rate of the cured product can be reduced, and as a result, high electrical conductivity reliability can be maintained even when moisture penetrates into the connection structure (electronic component).
- the lower limit of the content of the polymerizable monomer having an alicyclic skeleton and having no polar group is not particularly limited.
- the content of the polymerizable monomer having an alicyclic skeleton and having no polar group may be 5% by weight or more, or may be 10% by weight or more.
- the conductive paste includes a plurality of conductive fillers.
- the conductive fillers are not particularly limited.
- the conductive fillers may be conductive particles or carbon fibers.
- "including a plurality of conductive fillers” means that the conductive paste includes two or more conductive fillers. Only one type of the conductive filler may be used, or two or more types may be used in combination.
- the shape of the conductive filler is not particularly limited.
- the shape of the conductive filler may be spherical, may be a shape other than spherical, or may be flat, etc.
- the conductive filler is preferably a conductive particle.
- the conductive particle may be a solder particle or a metal particle.
- the metal particle may be a metal powder.
- the conductive particle may include a base particle and a conductive portion disposed on the surface of the base particle. From the viewpoint of further increasing the reliability of conduction, the conductive particle preferably includes a base particle and a conductive portion disposed on the surface of the base particle.
- the particle diameter of the conductive particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and even more preferably 3 ⁇ m or more, and is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 10 ⁇ m or less.
- the particle diameter of the conductive particles is equal to or more than the lower limit and equal to or less than the upper limit, the electrical conductivity reliability can be further improved.
- the particle diameter of the conductive particles is preferably an average particle diameter, and more preferably a number average particle diameter.
- the average particle diameter of the conductive particles can be determined, for example, by observing 50 random conductive particles with an electron microscope or optical microscope and calculating the average particle diameter of each conductive particle, or by performing laser diffraction particle size distribution measurement.
- the particle diameter of the conductive particles is measured by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, the measurement can be performed, for example, as follows.
- the conductive particles are added to "Technovit 4000" manufactured by Kulzer so that the content of the conductive particles is 30% by weight, and dispersed to prepare an embedding resin body for conductive particle inspection.
- a cross section of the conductive particle is cut out using an ion milling device ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass through the vicinity of the center of the conductive particles dispersed in the embedding resin body for conductive particle inspection.
- the image magnification is set to 25,000 times, 50 conductive particles are randomly selected, and each conductive particle is observed.
- the circle equivalent diameter of each conductive particle is measured, and the arithmetic average of the measured diameters is determined as the particle diameter of the conductive particle.
- the coefficient of variation (CV value) of the particle diameter of the conductive particles is preferably 10% or less, more preferably 5% or less.
- the coefficient of variation of the particle diameter of the conductive particles is equal to or less than the upper limit, the reliability of electrical conductivity can be further improved.
- the coefficient of variation (CV value) of the particle diameter of the conductive particles may be 0% or more, or 1% or more.
- CV value The above coefficient of variation (CV value) can be measured as follows.
- CV value (%) ( ⁇ /Dn) ⁇ 100 ⁇ : Standard deviation of the particle diameter of the conductive particles Dn: Average particle diameter of the conductive particles
- the conductive filler content in the conductive paste (100% by weight) is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and is preferably 80% by weight or less, more preferably 60% by weight or less, even more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.
- the electrical conductivity reliability can be further improved.
- the content of the conductive filler relative to 100 parts by weight of the curable compound in the conductive paste is preferably 2 parts by weight or more, more preferably 3 parts by weight or more, even more preferably 5 parts by weight or more, and particularly preferably 7 parts by weight or more.
- the content of the conductive filler relative to 100 parts by weight of the curable compound in the conductive paste is preferably 35 parts by weight or less, more preferably 30 parts by weight or less, even more preferably 25 parts by weight or less, and particularly preferably 20 parts by weight or less.
- the conductive filler preferably contains a metal.
- the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, ruthenium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, as well as alloys thereof.
- Tin-doped indium oxide (ITO) may also be used as the metal. Only one of the above metals may be used, or two or more of them may be used in combination.
- the conductive filler preferably contains a tin-containing alloy, nickel, palladium, ruthenium, silver, copper or gold, and more preferably contains nickel or palladium. From the viewpoint of increasing the corrosion resistance of the conductive filler and maintaining high electrical conductivity reliability, the conductive filler preferably contains nickel or gold, and more preferably contains nickel. From the viewpoint of increasing the corrosion resistance of the conductive filler and maintaining high electrical conductivity reliability, it is particularly preferable that the conductive filler contains nickel on the outer surface.
- the conductive particles are metal particles
- examples of the metal particles include silver, copper, nickel, silicon, gold, titanium, and alloys such as solder. From the viewpoint of more effectively increasing the reliability of electrical conduction, it is preferable that the material of the metal particles contains nickel or a nickel alloy, and it is more preferable that the material of the metal particles is nickel or a nickel alloy. From the viewpoint of more effectively increasing the reliability of electrical conduction, it is preferable that the outer surface portion of the metal particles contains nickel or a nickel alloy.
- the conductive particle which includes a base particle and a conductive portion disposed on the surface of the base particle.
- the base particles include resin particles, inorganic particles other than metal particles, organic-inorganic hybrid particles, and metal particles.
- the base particles are preferably base particles other than metal particles, and more preferably resin particles, inorganic particles other than metal particles, or organic-inorganic hybrid particles.
- the base particles may be core-shell particles having a core and a shell disposed on the surface of the core.
- the core may be an organic core, and the shell may be an inorganic shell.
- the above-mentioned base particles are more preferably resin particles or organic-inorganic hybrid particles, and may be either resin particles or organic-inorganic hybrid particles. By using these preferred base particles, the effects of the present invention are more effectively exhibited.
- the material for the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polyalkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyether ether ketone, polyether sulfone, divinylbenzene polymer, and polymers obtained by polymerizing one or more of various polymeriz
- the divinylbenzene polymer may be a divinylbenzene copolymer.
- examples of the divinylbenzene copolymer include divinylbenzene-styrene copolymer and divinylbenzene-(meth)acrylic acid ester copolymer.
- the material of the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having multiple ethylenically unsaturated groups.
- examples of the polymerizable monomer having an ethylenically unsaturated group include non-crosslinkable monomers and crosslinkable monomers.
- non-crosslinkable monomers include styrene-based monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride; alkyl (meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; 2-hydroxyethyl Examples of such monomers include oxygen-containing (meth)acrylate compounds such as (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, and
- crosslinkable monomers include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propane tri ...
- suitable (meth)acrylates include polyfunctional (meth)acrylate compounds such as propylene glycol di(meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate; and silane-containing monomers such as triallyl (iso)cyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, ⁇ -(meth)acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, and vinyltrimethoxysilane.
- polyfunctional (meth)acrylate compounds such as propylene glycol di(meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate
- silane-containing monomers such as triallyl (iso)cyanurate, triallyl
- the resin particles can be obtained by polymerizing the polymerizable monomer having the ethylenically unsaturated group by a known method. Examples of such methods include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of using non-crosslinked seed particles to swell and polymerize the monomer together with a radical polymerization initiator.
- the base particles are inorganic particles other than metal particles or organic-inorganic hybrid particles
- examples of the inorganic material of the base particles include silica, alumina, barium titanate, zirconia, and carbon black. It is preferable that the inorganic material is not a metal.
- the particles formed from silica are not particularly limited, but examples include particles obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, and then baking the particles as necessary.
- the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed from a crosslinked alkoxysilyl polymer and an acrylic resin.
- the organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core.
- the core is preferably an organic core.
- the shell is preferably an inorganic shell.
- the base particle is preferably an organic-inorganic hybrid particle having an organic core and an inorganic shell disposed on the surface of the organic core.
- Examples of the organic core material include the resin particle materials mentioned above.
- the material of the inorganic shell may be any of the inorganic substances listed as the material of the base particle described above.
- the material of the inorganic shell is preferably silica.
- the inorganic shell is preferably formed by forming a shell-like material from a metal alkoxide on the surface of the core by a sol-gel method, and then firing the shell-like material.
- the metal alkoxide is preferably a silane alkoxide.
- the inorganic shell is preferably formed from a silane alkoxide.
- the base particles are metal particles
- examples of the metal particles include silver, copper, nickel, silicon, gold, titanium, and alloys such as solder.
- the particle diameter of the base particles is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, even more preferably 0.5 ⁇ m or more, even more preferably 1 ⁇ m or more, and particularly preferably 3 ⁇ m or more, and is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, even more preferably 20 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
- the particle diameter of the base particles is equal to or greater than the lower limit, the electrical conductivity reliability is further increased.
- aggregation is less likely to occur, and aggregated conductive particles are less likely to be formed.
- the conductive particles are easily compressed sufficiently, and the connection resistance between the electrodes connected via the conductive particles can be further effectively reduced.
- the particle diameter of the base particles is preferably an average particle diameter, and more preferably a number average particle diameter.
- the number average particle diameter of the base particles can be measured, for example, as follows.
- the conductive particles are added to "Technovit 4000" manufactured by Kulzer so that the content of the conductive particles is 30% by weight, and dispersed to prepare an embedded resin body for inspecting base particles.
- a cross section of the conductive particles dispersed in the embedded resin body for inspecting base particles is cut out using an ion milling device ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass through the vicinity of the center of the base particle in the conductive particles dispersed in the embedded resin body for inspecting base particles.
- IM4000 manufactured by Hitachi High-Technologies Corporation
- the image magnification is set to 25,000 times, 50 conductive particles are randomly selected, and the base particle of each conductive particle is observed. The particle diameter of the base particle in each conductive particle is measured, and the arithmetic average is taken to determine the average particle diameter of the base particles.
- FE-SEM field emission scanning electron microscope
- the conductive portion preferably contains a metal.
- the metal constituting the conductive portion is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, ruthenium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, as well as alloys thereof.
- tin-doped indium oxide (ITO) may be used as the metal. Only one of the metals may be used, or two or more of them may be used in combination. From the viewpoint of further reducing the connection resistance between the electrodes, an alloy containing tin, nickel, palladium, ruthenium, silver, copper, or gold is preferred, and nickel or palladium is more preferred.
- the conductive portion contains nickel, and it is even more preferable that the outer surface portion of the conductive portion contains nickel.
- the nickel content in 100% by weight of the nickel-containing conductive part is preferably 10% by weight or more, more preferably 50% by weight or more, even more preferably 60% by weight or more, even more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
- the nickel content in 100% by weight of the nickel-containing conductive part may be 99% by weight or less, 90% by weight or less, or 70% by weight or less.
- the conductive portion may be formed of one layer.
- the conductive portion may be formed of multiple layers. That is, the conductive portion may have a laminated structure of two or more layers.
- the metal constituting the outermost layer is preferably an alloy containing gold, silver, nickel, palladium, ruthenium, copper or tin, and is more preferably nickel.
- the connection resistance between the electrodes is further reduced.
- the method for forming the conductive portion on the surface of the base particle is not particularly limited.
- Examples of the method for forming the conductive portion include electroless plating, electroplating, physical collision, mechanochemical reaction, physical vapor deposition or physical adsorption, and coating the surface of the base particle with a metal powder or a paste containing a metal powder and a binder.
- the method for forming the conductive portion is preferably electroless plating, electroplating, or physical collision.
- Examples of the physical vapor deposition method include vacuum vapor deposition, ion plating, and ion sputtering.
- a sheeter composer manufactured by Tokuju Kosakusho Co., Ltd. is used.
- the thickness of the conductive portion is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, and is preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.3 ⁇ m or less. If the thickness of the conductive portion is equal to or greater than the lower limit and equal to or less than the upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, allowing the conductive particles to be sufficiently deformed when connected.
- the thickness of the conductive portion of the outermost layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, and preferably 0.5 ⁇ m or less, more preferably 0.1 ⁇ m or less.
- the thickness of the conductive portion of the outermost layer is equal to or greater than the lower limit and equal to or less than the upper limit, the conductive portion of the outermost layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes can be sufficiently low.
- the thickness of the conductive portion can be measured, for example, by observing the cross-section of the conductive particle using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the conductive particles preferably have a plurality of protrusions on the outer surface of the conductive part.
- An oxide film is often formed on the surface of the electrodes connected by the conductive particles.
- the oxide film can be effectively removed by the protrusions by arranging the conductive particles between the electrodes and pressing them together. This allows the electrodes and the conductive part to be in more reliable contact, and the connection resistance between the electrodes is further reduced.
- the protrusions of the conductive particles can effectively remove the filler between the conductive particles and the electrodes. This further increases the reliability of the conduction between the electrodes.
- Methods for forming the above-mentioned protrusions include a method in which a core material is attached to the surface of a base particle and then a conductive portion is formed by electroless plating, and a method in which a conductive portion is formed on the surface of a base particle by electroless plating, then a core material is attached, and then a conductive portion is formed by electroless plating.
- a method may be used in which, without using the above-mentioned core material, a conductive portion is formed on the base particle by electroless plating, plating is deposited in the form of protrusions on the surface of the conductive portion, and then a conductive portion is formed by electroless plating.
- Methods for attaching a core substance to the surface of a base particle include, for example, a method in which a core substance is added to a dispersion liquid of the base particle, and the core substance is accumulated and attached to the surface of the base particle by van der Waals forces, and a method in which a core substance is added to a container containing the base particle, and the core substance is attached to the surface of the base particle by mechanical action such as rotating the container.
- the method for attaching a core substance to the surface of a base particle is preferably a method in which the core substance is accumulated and attached to the surface of the base particle in the dispersion liquid.
- the materials constituting the core material include conductive materials and non-conductive materials.
- the conductive materials include, for example, conductive non-metals such as metals, metal oxides, and graphite, and conductive polymers.
- the conductive polymers include polyacetylene.
- the non-conductive materials include silica, alumina, titanium oxide, tungsten carbide, and zirconia. From the viewpoint of further increasing the reliability of electrical conduction between the electrodes, it is preferable that the core material is a metal.
- the metal is not particularly limited.
- the metal include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, as well as alloys composed of two or more metals, such as tin-lead alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys, and tungsten carbide.
- the metal is preferably nickel, copper, silver, or gold.
- the metal may be the same as or different from the metal constituting the conductive portion.
- the shape of the core material is not particularly limited.
- the core material is preferably in the form of a mass.
- Examples of the core material include particulate masses, agglomerates of multiple microparticles, and amorphous masses.
- the particle diameter (average particle diameter) of the core material is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, and preferably 0.9 ⁇ m or less, more preferably 0.2 ⁇ m or less.
- the particle diameter of the core material is equal to or greater than the lower limit and equal to or less than the upper limit, the connection resistance between the electrodes can be effectively reduced.
- the particle diameter of the core substance is preferably an average particle diameter, and more preferably a number average particle diameter.
- the particle diameter of the core substance can be determined, for example, by observing 50 random core substances with an electron microscope or optical microscope and calculating the average particle diameter of each core substance, or by performing laser diffraction particle size distribution measurement.
- the curing agent is preferably a polymerization initiator.
- the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.
- the polymerization initiator may be used alone or in combination of two or more kinds.
- the polymerization initiator contains a thermal polymerization initiator.
- the thermal polymerization initiator preferably contains a thermal radical polymerization initiator, and is preferably a thermal radical polymerization initiator.
- Examples of the thermal radical polymerization initiator include a peroxide radical polymerization initiator, an azo radical polymerization initiator, and a redox radical polymerization initiator.
- azo radical polymerization initiator examples include azobisisobutyronitrile, azobiscyclohexanecarbonitrile, and azobisdimethylvaleronitrile.
- the above-mentioned peroxide-based radical polymerization initiators include diacyl-based radical polymerization initiators, peroxyester-based radical polymerization initiators, dialkyl-based radical polymerization initiators, percarbonate-based radical polymerization initiators, and ketone peroxide-based radical polymerization initiators.
- the above-mentioned diacyl-based radical polymerization initiators include lauroyl peroxide and benzoyl peroxide.
- the above-mentioned peroxyester-based radical polymerization initiators include t-butyl peroxybenzoate, t-butyl peroxyacetate, t-butyl peroxypivalate, and t-butyl peroxy-2-ethylhexanoate.
- the above-mentioned dialkyl-based radical polymerization initiators include dicumyl peroxide and di-t-butyl peroxide.
- the above-mentioned percarbonate-based radical polymerization initiators include diisopropyl peroxydicarbonate.
- the above-mentioned ketone peroxide-based radical polymerization initiators include methyl ethyl ketone peroxide.
- the redox radical polymerization initiator includes, for example, a peroxide and a reducing agent or a metal-containing compound.
- Specific examples of the redox radical polymerization initiator include a mixture of benzoyl peroxide and organic amines, a mixture of the peroxyester radical polymerization initiator and a reducing agent such as mercaptans, and a mixture of methyl ethyl ketone peroxide and an organic cobalt salt.
- the polymerization initiator contains a peroxide-based radical polymerization initiator.
- the content of the curing agent (polymerization initiator) in 100% by weight of the conductive paste is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, even more preferably 0.5% by weight or more, and is preferably 5% by weight or less, more preferably 4% by weight or less, even more preferably 3% by weight or less.
- the content of the curing agent (polymerization initiator) relative to 100 parts by weight of the curable compound in the conductive paste is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, even more preferably 0.7 parts by weight or more, and is preferably 6 parts by weight or less, more preferably 5 parts by weight or less, and even more preferably 4 parts by weight or less.
- content of the curing agent (polymerization initiator) is equal to or more than the lower limit and equal to or less than the upper limit, reactivity and storage stability can be improved.
- the conductive paste may contain components other than the curable compound, the curing agent, and the plurality of conductive fillers, such as a solvent, an inorganic filler, an organic filler, a colorant, a polymerization inhibitor, a chain transfer agent, an antioxidant, an ultraviolet absorber, a defoaming agent, a leveling agent, a surfactant, a slip agent, an antiblocking agent, a wax, a masking agent, a deodorant, a fragrance, a preservative, an antibacterial agent, an antistatic agent, and an adhesion imparting agent.
- a solvent such as a solvent, an inorganic filler, an organic filler, a colorant, a polymerization inhibitor, a chain transfer agent, an antioxidant, an ultraviolet absorber, a defoaming agent, a leveling agent, a surfactant, a slip agent, an antiblocking agent, a wax, a masking agent, a deodorant, a fragrance, a pre
- the RFID inlay according to the present invention comprises a substrate having wiring on its surface, a chip having electrodes on its surface, and an adhesive portion bonding the substrate and the chip.
- the material of the adhesive portion is the conductive paste described above.
- the wiring and the electrodes are electrically connected by the conductive filler in the adhesive portion.
- FIG. 1 is a cross-sectional view showing a schematic diagram of an RFID inlay using a conductive paste according to a first embodiment of the present invention.
- the RFID inlay 81 shown in FIG. 1 comprises a substrate 82 having wiring on its surface, a chip 83 having electrodes on its surface, and an adhesive portion 84 that bonds the substrate 82 and the chip 83.
- the material of the adhesive portion 84 is a conductive paste containing conductive filler 1.
- the adhesive portion 84 is formed from a conductive paste containing conductive filler 1. It is preferable that the adhesive portion 84 is formed by hardening the conductive paste containing conductive filler 1.
- the substrate 82 has wiring 82a on its surface (upper surface).
- the chip 83 has an electrode 83a on its surface (lower surface).
- the wiring 82a and the electrode 83a are electrically connected by the conductive filler 1 in the adhesive portion 84.
- the manufacturing method of the RFID inlay according to the present invention comprises the following steps (1) to (3): (1) A first arrangement step of arranging the above-mentioned conductive paste on the surface of a substrate having wiring on its surface. (2) A second arrangement step of arranging a chip having an electrode on its surface on the surface of the conductive paste opposite the substrate. (3) A bonding step of forming an adhesive part that bonds the substrate and the chip with the conductive paste by heating and pressurizing the conductive paste, and electrically connecting the wiring and the electrodes with the conductive filler in the adhesive part.
- the RFID inlay and manufacturing method for the RFID inlay according to the present invention use a specific conductive paste, which improves adhesion between the substrate and the chip and increases the reliability of electrical continuity.
- the substrate is long and that the RFID inlay is manufactured by transporting the long substrate using a roll-to-roll method in the first arrangement step, the second arrangement step, and the bonding step.
- multiple RFID inlays can be manufactured continuously, and the manufacturing efficiency of the RFID inlay can be further improved.
- the conductive paste can be applied by, for example, applying it with a dispenser, screen printing, or ejecting it with an inkjet device.
- the heating temperature in the bonding process is preferably 100°C or higher, more preferably 150°C or higher, and is preferably 400°C or lower, more preferably 300°C or lower, and even more preferably 250°C or lower. If the heating temperature in the bonding process is equal to or higher than the lower limit and equal to or lower than the upper limit, good electrical connection between the chip and the wiring (antenna pattern) can be achieved.
- the applied pressure in the bonding process is preferably 0.5 N or more, more preferably 1 N or more, and is preferably 3.5 N or less, more preferably 3 N or less, and even more preferably 2.5 N or less.
- the applied pressure in the bonding process is equal to or more than the lower limit and equal to or less than the upper limit, the adhesion between the substrate and the chip can be improved, and the electrical conductivity reliability can be improved.
- the heating and pressurizing time in the bonding process is not particularly limited.
- the heating and pressurizing time in the bonding process may be 2 seconds or more, 15 seconds or less, or 10 seconds or less.
- the RFID inlay may be cut to a predetermined size as necessary, or may be cut before use. It is preferable that a plurality of the chips are adhered to a long substrate by a plurality of the adhesive parts. A plurality of laminates of the chips and the adhesive parts may be arranged on the long substrate. In the first arrangement step, it is preferable that the conductive paste is arranged at a plurality of locations on the surface of the long substrate. In the second arrangement step, it is preferable that the chips are arranged using a plurality of chips on the surface opposite the substrate side of each of the conductive pastes arranged at a plurality of locations. After the chips are adhered to the long substrate by the adhesive parts, the long substrate may be cut.
- the substrate is not particularly limited.
- the substrate is preferably a circuit board.
- the circuit board include a resin film, a flexible printed circuit board, a rigid-flexible board, a glass board, and a paper board.
- the substrate may be a resin board, a glass board, or a paper board.
- the substrate has wiring (antenna pattern) on its surface.
- the substrate has wiring (antenna pattern) formed on its surface.
- the substrate preferably has a base material and wiring (antenna pattern) disposed on the surface of the base material.
- the substrate may be made of resin, glass, paper, or the like.
- the resin may be made of PET (polyethylene terephthalate), PP (polypropylene), PVC (polyvinyl chloride), or the like.
- the paper may be impregnated with epoxy resin or phenolic resin.
- the substrate is preferably made of resin or paper, and more preferably made of PET (polyethylene terephthalate) or paper.
- the substrate may be made of resin, glass, or paper.
- the above wiring may be gold wiring, nickel wiring, tin wiring, aluminum wiring, silver wiring, SUS wiring, copper wiring, molybdenum wiring, tungsten wiring, etc. From the viewpoint of improving the operating sensitivity in the UHF band (860 MHz to 920 MHz), the above wiring is preferably aluminum wiring.
- the thickness of the substrate is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, and is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less.
- the shapes of the substrate and the base material are not particularly limited. From the viewpoint of manufacturing RFID inlays by a roll-to-roll method, it is preferable that the substrate and the base material are long.
- the length of the substrate and the base material is not particularly limited. The length of the substrate and the base material may be 1 m or more, 10 m or more, 5000 m or less, or 1000 m or less.
- the surface tension of the substrate (base material) is preferably 30 mN/m or more, more preferably 32 mN/m or more, even more preferably 34 mN/m or more, and is preferably 50 mN/m or less, more preferably 48 mN/m or less, even more preferably 45 mN/m or less. If the surface tension of the substrate (base material) is equal to or more than the lower limit and equal to or less than the upper limit, the adhesiveness can be further improved.
- the conductive paste of the present invention can be suitably used for application to a substrate (base material) having a surface tension equal to or more than the lower limit and equal to or less than the upper limit.
- the surface tension of the above substrate (base material) can be measured in accordance with JIS K6768 using the following method. A cotton swab is dipped in the JIS-specified liquid and applied to the substrate (base material). The surface tension is determined from the shape of the coating two seconds after application.
- the above chips include semiconductor chips (IC chips), etc.
- the chip has an electrode on its surface.
- the electrode include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, silver electrodes, SUS electrodes, copper electrodes, molybdenum electrodes, and tungsten electrodes. From the viewpoint of further improving the reliability of electrical conduction, the electrode is preferably a copper electrode or a gold electrode, and more preferably a copper electrode.
- the number of electrodes per chip is not particularly limited.
- the number of electrodes per chip may be 1 or more, 4 or more, 20 or less, or 10 or less.
- the shape of the tip is not particularly limited.
- the tip may be rectangular, triangular, or circular.
- the plane area of the chip is preferably 0.04 mm2 or more, more preferably 0.09 mm2 or more, even more preferably 0.16 mm2 or more, and is preferably 0.50 mm2 or less, more preferably 0.40 mm2 or less, even more preferably 0.30 mm2 or less.
- the conductive paste can be arranged on the fine wiring with high precision.
- the conductive reliability can be maintained even when the RFID inlay is left in a high-temperature and high-humidity environment for a long period of time.
- the conductive paste according to the present invention can be suitably used for bonding relatively small chips.
- Conductive filler "NIELB-005-S” manufactured by Sekisui Chemical Co., Ltd. (conductive particles having a base particle and a conductive portion on the surface of the base particle, nickel content in 100% by weight of the conductive portion: 52% by weight, average particle size: 5 ⁇ m) Nikko Jamaica Corporation "4SP-10” (metal particles (nickel), average particle size: 6.5 ⁇ m) "1300Y” manufactured by Mitsui Mining & Smelting Co., Ltd. (metal particles (copper), average particle size: 3.5 ⁇ m)
- Perbutyl PV peroxyester radical polymerization initiator (t-butyl peroxybutyrate)
- Inorganic filler Silica (Tokuyama Corporation “SSP-04M")
- Tips IC chip (copper electrode, NXP "UCODE7", surface area: 0.22 mm 2 )
- PET film long, resin film with aluminum wiring and operating frequency in the UHF band (860 MHz to 920 MHz), surface tension: 43 mN/m
- Example 1 (1) Preparation of Conductive Paste The materials shown in Table 1 below were mixed in the amounts shown in Table 1 below and stirred using a planetary mixer (Thinky Corporation's "Awatori Rentaro") to obtain a conductive paste (anisotropic conductive paste).
- a planetary mixer Thinky Corporation's "Awatori Rentaro”
- connection step the wiring on the surface of the PET film and the electrodes on the surface of the chip were electrically connected by the conductive filler (conductive particles) in the adhesive part to obtain a connection structure (adhesion step).
- the first arrangement step, the second arrangement step, and the adhesion step were performed using a "DDA40000" (roll-to-roll method) manufactured by Muhlbauer.
- the resulting connection structure was cut to a size of 5 cm x 1.5 cm using a "DCL30000” manufactured by Muhlbauer, to obtain 50 RFID inlays.
- Examples 2 to 10 and Comparative Examples 1 to 3 A conductive paste and an RFID inlay were obtained in the same manner as in Example 1, except that the ingredients and amounts of the conductive paste were changed as shown in Tables 1, 3, and 5.
- ⁇ The absolute value of the difference in peak sensitivity of all RFID inlays is less than 2 dBm. ⁇ : Does not fall under either ⁇ or ⁇ . ⁇ : The absolute value of the difference in initial peak sensitivity of at least one RFID inlay is 3 dBm or more.
- REFERENCE SIGNS LIST 1 conductive filler 81
- RFID inlay 82 ...substrate having wiring on its surface 82a
- wiring 83 ...chip having electrode on its surface 83a
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Abstract
Description
本発明に係る導電ペーストは、硬化性化合物と、硬化剤と、複数の導電性フィラーとを含む導電ペーストである。本発明に係る導電ペーストでは、上記硬化性化合物が、脂環式骨格を有する重合性単量体を含む。本発明に係る導電ペーストでは、上記導電ペーストの硬化物を121℃、100%RH、及び2atmの条件で2時間水に浸漬させる試験を行ったときに、下記の硬化物の吸水率が、2.0%以下である。
上記硬化性化合物は、脂環式骨格を有する重合性単量体を含む。上記導電ペーストでは、上記の構成が備えられているので、上記硬化物の吸水率を低くすることができ、結果として、接続構造体(電子部品)に水分が浸入した場合にも、高い導通信頼性を維持することができる。
カラム:Shodex GPC LF-G×1本、Shodex GPC LF-804×2本
移動相:THF 1.0mL/分
サンプル濃度:5mg/mL
検出器:示差屈折率検出器(RID)
標準物質:ポリスチレン(TOSOH社製、重量平均分子量:620~590000)
カラム:Shodex GPC LF-G×1本、Shodex GPC LF-804×2本
移動相:THF 1.0mL/分
サンプル濃度:5mg/mL
検出器:示差屈折率検出器(RID)
標準物質:ポリスチレン(TOSOH社製、重量平均分子量:620~590000)
上記導電ペーストは、複数の導電性フィラーを含む。上記導電性フィラーは、特に限定されない。上記導電性フィラーは、導電性粒子であってもよく、カーボンファイバーであってもよい。なお、本明細書において、「複数の導電性フィラーを含む」とは、導電ペーストが2個以上の導電性フィラーを含むことを意味する。上記導電性フィラーは、1種のみが用いられてもよく、2種以上が併用されてもよい。
ρ:導電性粒子の粒子径の標準偏差
Dn:導電性粒子の粒子径の平均値
上記基材粒子としては、樹脂粒子、金属粒子を除く無機粒子、有機無機ハイブリッド粒子及び金属粒子等が挙げられる。上記基材粒子は、金属粒子を除く基材粒子であることが好ましく、樹脂粒子、金属粒子を除く無機粒子又は有機無機ハイブリッド粒子であることがより好ましい。上記基材粒子は、コアと、該コアの表面上に配置されたシェルとを備えるコアシェル粒子であってもよい。上記コアが有機コアであってもよく、上記シェルが無機シェルであってもよい。
上記導電部は、金属を含むことが好ましい。上記導電部を構成する金属は、特に限定されない。上記金属としては、例えば、金、銀、銅、白金、パラジウム、亜鉛、鉛、アルミニウム、コバルト、インジウム、ルテニウム、ニッケル、クロム、チタン、アンチモン、ビスマス、ゲルマニウム及びカドミウム、並びにこれらの合金等が挙げられる。また、上記金属として、錫ドープ酸化インジウム(ITO)を用いてもよい。上記金属は1種のみが用いられてもよく、2種以上が併用されてもよい。電極間の接続抵抗をより一層低くする観点からは、錫を含む合金、ニッケル、パラジウム、ルテニウム、銀、銅又は金が好ましく、ニッケル又はパラジウムがより好ましい。
上記導電性粒子は、上記導電部の外表面に複数の突起を有することが好ましい。導電性粒子により接続される電極の表面には、酸化被膜が形成されていることが多い。導電部の表面に突起を有する導電性粒子を用いた場合には、電極間に導電性粒子を配置して圧着させることにより、突起により上記酸化被膜を効果的に排除できる。このため、電極と導電部とがより一層確実に接触し、電極間の接続抵抗がより一層低くなる。さらに、電極間の接続時に、導電性粒子の突起によって、導電性粒子と電極との間のフィラーを効果的に排除できる。このため、電極間の導通信頼性がより一層高くなる。
上記脂環式骨格を有する重合性単量体を含む硬化性化合物を硬化させる観点からは、上記硬化剤は、重合開始剤であることが好ましい。上記重合開始剤としては、光重合開始剤、及び熱重合開始剤等が挙げられる。上記重合開始剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記導電ペーストは、上記硬化性化合物、上記硬化剤、及び複数の上記導電性フィラー以外の成分を含んでいてもよい。上記導電ペーストは、他の成分として、溶剤、無機フィラー、有機フィラー、着色剤、重合禁止剤、連鎖移動剤、酸化防止剤、紫外線吸収剤、消泡剤、レベリング剤、界面活性剤、スリップ剤、アンチブロッキング剤、ワックス、マスキング剤、消臭剤、芳香剤、防腐剤、抗菌剤、帯電防止剤、及び密着性付与剤等を含んでいてもよい。
本発明に係るRFIDインレイは、配線を表面に有する基板と、電極を表面に有するチップと、上記基板と上記チップとを接着している接着部とを備える。本発明に係るRFIDインレイでは、上記接着部の材料が、上述した導電ペーストである。本発明に係るRFIDインレイでは、上記配線と上記電極とが、上記接着部中の上記導電性フィラーにより電気的に接続されている。
脂環式骨格を有する重合性単量体:
イソボルニルアクリレート(共栄社化学社製「IBXA」、分子量:208)
トリシクロデカンジメタノールジアクリレート(ダイセルオルネクス社製「IRR-214」、分子量:304)
1,4-シクロヘキサンジメタノールモノアクリレート(三菱ケミカル社製「CHDMMA」、分子量:198)
脂環式骨格を有さない重合性単量体:
ポリエステルウレタンアクリレート(根上工業社製「UN-353」、分子量(重量平均分子量):5000)
ポリエータルウレタンアクリレート(根上工業社製「UN-6306」、分子量(重量平均分子量):6600)
トリメチロールプロパントリアクリレート(新中村化学工業社製「A-TMPT」、分子量:296)
ヒドロキシエチルメタクリレート(富士フイルム和光純薬社製、分子量:130)
2-フェノキシエチルアクリレート(ダイセルオルネクス社製「EBCRYL114」、分子量:192)
積水化学工業社製「NIELB-005-S」(基材粒子と基材粒子の表面上に導電部とを備える導電性粒子、導電部100重量%中のニッケルの含有量:52重量%、平均粒子径:5μm)
日興リカ社製「4SP-10」(金属粒子(ニッケル)、平均粒子径:6.5μm)
三井金属鉱業社製「1300Y」(金属粒子(銅)、平均粒子径:3.5μm)
日油社製「パーブチルPV」(パーオキシエステル系ラジカル重合開始剤(t-ブチルパーオキシブチレート))
シリカ(トクヤマ社製「SSP-04M」)
ICチップ(銅電極、NXP社製「UCODE7」、平面積:0.22mm2)
PETフィルム(長尺状、動作周波数がUHF帯(860MHz~920MHz)であるアルミニウム配線を有する樹脂フィルム、表面張力:43mN/m)
(1)導電ペーストの作製
下記の表1に示す材料を、下記の表1に示す配合量で配合して、遊星式撹拌装置(シンキー社製「あわとり練太郎」)を用いて撹拌することで、導電ペースト(異方性導電ペースト)を得た。
PETフィルム上に、得られた導電ペーストをジェットディスペンス法で塗工し、導電ペースト層(接着部層)を形成した(第1の配置工程)。次に、導電ペースト層(接着部層)の基材側とは反対の表面上に、ICチップを、PETフィルム表面の配線とチップ表面の電極とが対向するように積層した(第2の配置工程)。その後、上部ヒートツール180℃、下部ヒートツール175℃、圧力2N、圧着時間7秒の条件で熱圧着し、導電ペースト層(接着部層)を硬化させ、接着部を形成した。また、PETフィルムの表面の配線とチップの表面の電極とを、接着部中の導電性フィラー(導電性粒子)により電気的に接続して、接続構造体を得た(接着工程)。なお、上記第1の配置工程、上記第2の配置工程、及び上記接着工程は、Muhlbauer社製「DDA40000」(ロールツーロール方式)を用いて行った。得られた接続構造体を、Muhlbauer社製「DCL30000」を用いて5cm×1.5cmの大きさにカットして、RFIDインレイを50台得た。
導電ペーストの配合成分及び配合量を表1,3,5のように変更したこと以外は、実施例1と同様にして、導電ペースト及びRFIDインレイを得た。
(1)硬化物の吸水率
得られた導電ペーストを130℃で10分間加熱して硬化物(試験前の硬化物)を得た。上記硬化物を121℃、100%RH、及び2atmの条件で2時間水に浸漬させる試験を行い、試験後の硬化物を得た。試験前の硬化物の重量と、試験後の硬化物の重量とを測定し、下記の硬化物の吸水率を計算した。
硬化物の吸水率(%)=(試験後の硬化物の重量-試験前の硬化物の重量)×100/試験前の硬化物の重量
(1)で得られた試験前の硬化物及び試験後の硬化物を縦10mm、横1mm~10mm、高さ15mm~50mmの大きさに切り出して、測定サンプルを作製した。各測定サンプルについて、動的粘弾性測定装置(TA Instruments社製「RSA3」)を用いて、周波数10Hz、ひずみ0.1%、温度20℃~180℃、及び昇温速度10℃/分の条件で、上記試験前の上記硬化物の貯蔵弾性率、及び上記試験後の上記硬化物の貯蔵弾性率を測定した。また、比(試験後の硬化物の貯蔵弾性率/試験前の硬化物の貯蔵弾性率)を計算した。
得られたRFIDインレイ50台を、外部電波を遮断する暗箱内に入れ、周波数読み取り機(Voyantic社製「Tagformance Pro」)を用いて、UHF帯(860MHz~920MHz)での25℃でのピーク感度を測定して、初期のピーク感度とした。また、得られたRFIDインレイを30分間水に浸漬させた後に乾燥させた。浸漬後のRFIDインレイについて、UHF帯での25℃でのピーク感度を同様に測定し、初期のピーク感度との差の絶対値を求めた。初期、浸漬後の導通信頼性を、下記の基準で判定した。
○○:全てのRFIDインレイの初期のピーク感度が、-18dBm未満
○:○○及び×のいずれにも該当しない
×:少なくとも1台のRFIDインレイの初期のピーク感度が、-17dBm以上
○○:すべてのRFIDインレイのピーク感度の差の絶対値が、2dBm未満
○:○○及び×のいずれにも該当しない
×:少なくとも1台のRFIDインレイの初期のピーク感度の差の絶対値が、3dBm以上
81…RFIDインレイ
82…配線を表面に有する基板
82a…配線
83…電極を表面に有するチップ
83a…電極
84…接着部
Claims (11)
- 硬化性化合物と、硬化剤と、複数の導電性フィラーとを含む導電ペーストであり、
前記硬化性化合物が、脂環式骨格を有する重合性単量体を含み、
前記導電ペーストの硬化物を121℃、100%RH、及び2atmの条件で2時間水に浸漬させる試験を行ったときに、下記の硬化物の吸水率が、2.0%以下である、導電ペースト。
硬化物の吸水率(%)=(試験後の硬化物の重量-試験前の硬化物の重量)×100/試験前の硬化物の重量 - 前記試験前の前記硬化物の貯蔵弾性率が、0.8GPa以上であり、
前記試験後の前記硬化物の貯蔵弾性率が、0.5GPa以上である、請求項1に記載の導電ペースト。 - 前記試験後の前記硬化物の貯蔵弾性率の、前記試験前の前記硬化物の貯蔵弾性率に対する比が、0.5以上である、請求項1又は2に記載の導電ペースト。
- 前記脂環式骨格を有する重合性単量体が、(メタ)アクリロイル基を有する、請求項1~3のいずれか1項に記載の導電ペースト。
- 前記脂環式骨格を有する重合性単量体が、トリシクロデカンジメタノールジ(メタ)アクリレート、又はイソボルニル(メタ)アクリレートである、請求項1~4のいずれか1項に記載の導電ペースト。
- 前記硬化性化合物100重量%中、前記脂環式骨格を有する重合性単量体の含有量が、10重量%以上50重量%以下である、請求項1~5のいずれか1項に記載の導電ペースト。
- 前記導電性フィラーが、ニッケルを含む、請求項1~6のいずれか1項に記載の導電ペースト。
- RFIDインレイを得るために用いられる、請求項1~7のいずれか1項に記載の導電ペースト。
- 配線を表面に有する基板と、電極を表面に有するチップと、前記基板と前記チップとを接着している接着部とを備え、
前記接着部の材料が、請求項1~8のいずれか1項に記載の導電ペーストであり、
前記配線と前記電極とが、前記接着部中の前記導電性フィラーにより電気的に接続されている、RFIDインレイ。 - 配線を表面に有する基板の表面上に、請求項1~8のいずれか1項に記載の導電ペーストを配置する第1の配置工程と、
前記導電ペーストの前記基板側とは反対の表面上に、電極を表面に有するチップを配置する第2の配置工程と、
前記導電ペーストを加熱及び加圧することで、前記基板と前記チップとを接着している接着部を、前記導電ペーストにより形成し、かつ、前記配線と前記電極とを、前記接着部中の前記導電性フィラーにより電気的に接続する接着工程とを備える、RFIDインレイの製造方法。 - 前記基板が長尺状であり、
前記第1の配置工程、前記第2の配置工程、及び前記接着工程において、ロールツーロール方式により、長尺状の前記基板を搬送させてRFIDインレイを製造する、請求項10に記載のRFIDインレイの製造方法。
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| WO2018181694A1 (ja) * | 2017-03-30 | 2018-10-04 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
| WO2018230470A1 (ja) * | 2017-06-12 | 2018-12-20 | 積水化学工業株式会社 | 樹脂粒子、導電性粒子、導電材料、接着剤、接続構造体及び液晶表示素子 |
| WO2020054288A1 (ja) * | 2018-09-14 | 2020-03-19 | 積水化学工業株式会社 | 導電材料及び接続構造体 |
| WO2020230842A1 (ja) * | 2019-05-14 | 2020-11-19 | 積水化学工業株式会社 | 樹脂粒子、導電性粒子、導電材料及び接続構造体 |
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| WO2018230470A1 (ja) * | 2017-06-12 | 2018-12-20 | 積水化学工業株式会社 | 樹脂粒子、導電性粒子、導電材料、接着剤、接続構造体及び液晶表示素子 |
| WO2020054288A1 (ja) * | 2018-09-14 | 2020-03-19 | 積水化学工業株式会社 | 導電材料及び接続構造体 |
| WO2020230842A1 (ja) * | 2019-05-14 | 2020-11-19 | 積水化学工業株式会社 | 樹脂粒子、導電性粒子、導電材料及び接続構造体 |
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