CN111448279B - Conductive adhesive composition - Google Patents
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- CN111448279B CN111448279B CN201980006537.XA CN201980006537A CN111448279B CN 111448279 B CN111448279 B CN 111448279B CN 201980006537 A CN201980006537 A CN 201980006537A CN 111448279 B CN111448279 B CN 111448279B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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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- Spectroscopy & Molecular Physics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
Abstract
Provided is a conductive adhesive composition which can be processed at 120 ℃ or lower and has both isotropic conductivity and excellent adhesion. The conductive adhesive composition contains a resin component and a dendritic conductive filler, wherein the resin component at least contains (A) crystalline thermoplastic resin with a melting point of more than 100 ℃, (B) amorphous thermoplastic resin and (C) carboxyl modified polyester resin, and the dendritic conductive filler accounts for 50-300 parts by mass relative to 100 parts by mass of the resin component.
Description
Technical Field
The present invention relates to a conductive adhesive composition.
Background
As a method for electrically connecting an electronic component and a substrate, a conductive adhesive composition in which a conductive filler is dispersed can be used. As the above-mentioned conductive adhesive composition, for example, patent document 1 describes a thermoplastic resin composition comprising an amorphous thermoplastic resin (component a), a crystalline thermoplastic resin (component B), conductive carbon black (component C), and conductive carbon black or hollow carbon fibers having a larger specific surface area than that of the conductive carbon black of component C, for the purpose of providing a thermoplastic resin composition having excellent mechanical strength and heat resistance and also excellent electrical properties such as conductivity and antistatic property.
However, depending on the application, a conductive adhesive composition capable of obtaining isotropic conductivity may be required, but the thermoplastic resin composition described in patent document 1 has anisotropic conductivity, and when a conductive filler is highly blended to obtain isotropy, the bondability may be impaired.
In recent years, for connection of heat-labile members such as electronic components, for example, conductive adhesive compositions for electrodes of piezoelectric films and the like are required to be processable at low temperatures, particularly at temperatures of 120 ℃. In order to solve the above-described problems, patent document 2 discloses an anisotropic conductive film in which a terminal of a 1 st electronic component and a terminal of a 2 nd electronic component are anisotropically and conductively connected, the anisotropic conductive film including a film-forming resin, a curable resin, a curing agent, and conductive particles, wherein the film-forming resin includes a crystalline resin and an amorphous resin. Patent document 3 discloses an anisotropic conductive film for anisotropically and electrically connecting an end of a 1 st electronic component and an end of a 2 nd electronic component, the anisotropic conductive film comprising: the resin composition contains a crystalline resin, an amorphous resin, and conductive particles, wherein the crystalline resin contains a crystalline resin having a bond imparting a resin characteristic identical to a bond imparting a resin characteristic of the amorphous resin. However, they are all anisotropic conductive films.
However, as described above, it is necessary to highly blend the conductive filler in order to obtain isotropic conductivity, and there is room for further improvement in terms of compatibility between adhesiveness and isotropic conductivity.
Documents of the prior art
Patent document
Disclosure of Invention
Technical problem to be solved by the invention
In view of the above, an object of the present invention is to provide a conductive adhesive composition which can be processed at a low temperature of 120 ℃ or lower and has both isotropic conductivity and excellent bondability.
Means for solving the problems
In order to solve the above-mentioned problems, the conductive adhesive composition of the present invention comprises a resin component and a dendritic conductive filler, wherein the resin component comprises at least (a) a crystalline thermoplastic resin having a melting point of 100 ℃ or higher, (B) an amorphous thermoplastic resin, and (C) a carboxyl-modified polyester resin, and the dendritic conductive filler is contained in an amount of 50 to 300 parts by mass per 100 parts by mass of the resin component.
The crystalline thermoplastic resin (a) is preferably a crystalline polyester, and the amorphous thermoplastic resin (B) is preferably an amorphous polyester.
The following design can be made: the conductive filler is 1 or 2 selected from the group consisting of copper particles, silver particles, gold particles, nickel particles, silver-coated copper alloy particles, and silver-coated nickel particles.
The following design can be made: the glass transition temperature of the carboxyl-modified polyester resin (C) is 10 to 30 ℃.
The following design can be made: the glass transition temperature of the amorphous thermoplastic resin (B) is 50 to 120 ℃.
The following design can be made: the content ratio of the crystalline thermoplastic resin (A) to the amorphous thermoplastic resin (B) is 60/40-90/10 in terms of mass ratio.
The following design can be made: the content of the carboxyl-modified polyester resin (C) is 15 to 35 parts by mass in 100 parts by mass of the resin component.
Effects of the invention
The conductive adhesive composition of the present invention can be processed at a low temperature of 120 ℃ or lower, and can provide isotropic conductivity and excellent adhesion.
Drawings
FIG. 1 is a schematic cross-sectional view of a sample for measurement of creep strength and tensile shear bond strength at 70 ℃;
FIG. 2 is a schematic cross-sectional view of a sample for measurement of 90 DEG peel strength;
[ FIG. 3 ]]For elucidating the determination of the surface resistivity R1A schematic cross-sectional view of the process of (1);
[ FIG. 4 ]]For elucidating the determination of the connection resistivity R2Schematic cross-sectional view of the process of (1).
Detailed Description
Hereinafter, embodiments of the present invention will be specifically described.
The conductive adhesive composition according to the present embodiment contains a resin component and a dendritic conductive filler, wherein the resin component contains at least (A) a crystalline thermoplastic resin having a melting point of 100 ℃ or higher, (B) an amorphous thermoplastic resin, and (C) a carboxyl-modified polyester resin, and the dendritic conductive filler is contained in an amount of 50 to 300 parts by mass per 100 parts by mass of the resin component. The crystalline resin is a polymer substance containing a crystalline portion when solidified, and a Differential Scanning Calorimetry (DSC) curve obtained by such a crystalline resin in a temperature rise process in the DSC (hereinafter also referred to as "DSC") does not generally show a stepwise change in endothermic amount, but shows a clear endothermic peak. The melting point (Tm) of the crystalline resin is a temperature of a peak top among the endothermic peaks. In addition, the amorphous resin refers to a high molecular substance containing no crystalline portion when cured, and a differential scanning calorimetry curve obtained by such an amorphous resin in a temperature rise process by DSC usually does not show a significant endothermic peak. In the present specification, the differential scanning calorimetry is carried out by a differential scanning calorimeter (for example, manufactured by seiko electronic industries, ltd., trade name "DSC 220 type"), and the measurement conditions are as follows: air was introduced at a flow rate of 10 mL/min and kept at 25 ℃ and then the temperature was raised to 200 ℃ at 10 ℃/min. In the present specification, the crystalline thermoplastic resin (a) and the amorphous thermoplastic resin (B) do not contain the carboxyl-modified polyester resin (C).
The crystalline thermoplastic resin (a) is not particularly limited, and examples thereof include Polyester (PEs), Polyethylene (PE), polypropylene (PP), Polyamide (PA), Polyimide (PI), Polycarbonate (PC), Polyacetal (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyphenylene Sulfide (PPs), and the like, and 1 kind thereof may be used alone or 2 or more kinds thereof may be used as a mixture. Among them, polyesters are preferred from the viewpoint of processability at low temperatures of 120 ℃ or lower.
The number average molecular weight of the crystalline thermoplastic resin (A) is not particularly limited, but is preferably 8000 to 30000, more preferably 10000 to 25000. When the viscosity is 8000 or more and 30000 or less, the viscosity is suitable, and a film such as an electrode of a piezoelectric film can be easily formed. In the present specification, the number average molecular weight refers to a value measured by gel permeation chromatography (for example, a measuring apparatus, "liance HPLC System" manufactured by Watts corporation, column, "KF-806L" manufactured by shodex) using tetrahydrofuran as a solvent in terms of standard polystyrene.
The melting point of the crystalline thermoplastic resin (A) is not particularly limited as long as it is 100 ℃ or higher, but is preferably 100 to 140 ℃, more preferably 110 to 140 ℃, and still more preferably 110 to 130 ℃. In view of the use of the electronic component and the substrate to be connected by using the conductive adhesive composition according to the present embodiment, it is preferable that the bondability be maintained at 70 ℃ or lower, and if the melting point of the crystalline thermoplastic resin (a) is 100 ℃ or higher, creep deformation at 70 ℃ is less likely to occur, and excellent bondability is easily obtained. When the temperature is 140 ℃ or lower, gelation is difficult even when the resin is dissolved in an organic solvent at room temperature, and excellent processability is easily obtained.
The amorphous thermoplastic resin (B) is not particularly limited, and examples thereof include Polyester (PEs), polyvinyl chloride (PVC), Polystyrene (PS), polymethyl methacrylate (PMMA), acrylonitrile-butadiene-styrene copolymer (ABS), Polycarbonate (PC), Polyether Sulfone (PEs), polyether imide (PEI), and polyamide imide (PAI), and 1 kind or 2 or more kinds thereof may be used alone or as a mixture as described above. Among them, polyesters are preferred from the viewpoint of processability at low temperatures of 120 ℃ or lower.
The number average molecular weight of the amorphous thermoplastic resin (B) is not particularly limited, but is preferably 10000 to 30000, more preferably 12000 to 25000.
The glass transition temperature (Tg) of the amorphous thermoplastic resin (B) is not particularly limited, but is preferably 50 to 120 ℃ and more preferably 60 to 100 ℃. When the temperature is 50 ℃ or higher, excellent adhesiveness, particularly excellent peeling adhesion, can be easily obtained, and when the temperature is 120 ℃ or lower, flexibility is excellent, and the composition is easily applied to applications such as films.
Here, in the present specification, the glass transition temperature refers to a temperature of an inflection point of a differential scanning calorimetry curve obtained by the differential scanning calorimetry.
The carboxyl-modified polyester resin (C) may be crystalline or amorphous, and is preferably amorphous.
The glass transition temperature of the carboxyl-modified polyester resin (C) is not particularly limited, but is preferably 10 to 30 ℃ and more preferably 14 to 30 ℃.
The number average molecular weight of the carboxyl-modified polyester resin (C) is not particularly limited, but is preferably 10000 to 30000, more preferably 14000 to 20000.
The acid value of the carboxyl-modified polyester resin (C) is not particularly limited, but is preferably 10 to 25 mgKOH/g, more preferably 15 to 20 mgKOH/g.
The resin component of the conductive adhesive composition of the present embodiment may contain resins other than the crystalline thermoplastic resin (a), the amorphous thermoplastic resin (B), and the carboxyl-modified polyester resin (C) as described above, within a range not to impair the object of the present invention.
The content ratio ((a)/(B)) of the crystalline thermoplastic resin (a) and the amorphous thermoplastic resin (B) is not particularly limited, and is preferably 60/40 to 90/10, more preferably 70/30 to 90/10 in terms of mass ratio. When the content ratio is within the above range, excellent results are easily obtained in a creep test at 70 ℃ for evaluating the bondability.
The content of the crystalline thermoplastic resin (a) in 100 parts by mass of the resin component is not particularly limited, but is preferably 40 to 70 parts by mass, more preferably 45 to 65 parts by mass, and still more preferably 50 to 60 parts by mass.
The content of the amorphous thermoplastic resin (B) in 100 parts by mass of the resin component is not particularly limited, but is preferably 15 to 35 parts by mass, more preferably 15 to 30 parts by mass, and still more preferably 15 to 25 parts by mass.
The content of the carboxyl-modified polyester resin (C) in 100 parts by mass of the resin component is not particularly limited, but is preferably 15 to 35 parts by mass, more preferably 15 to 30 parts by mass, and still more preferably 20 to 30 parts by mass. When the content ratio is within the above range, excellent results are easily obtained in a 90 ° peel test for evaluating the bondability.
The content of the conductive filler is 50 to 300 parts by mass, preferably 50 to 280 parts by mass, and more preferably 50 to 250 parts by mass, based on 100 parts by mass of the resin component. When the amount is 50 parts by mass or more, isotropic conductivity is easily obtained, and when the amount is 300 parts by mass or less, both conductivity and adhesiveness are easily achieved.
The conductive filler is not particularly limited as long as it has a dendritic shape, and examples thereof include copper particles, silver particles, gold particles, nickel particles, silver-coated copper alloy particles, and silver-coated nickel particles, and silver-coated copper particles, silver-coated copper alloy particles, and silver-coated nickel particles are preferable from the viewpoint of cost reduction and conductivity reduction. Here, the dendritic shape is a shape containing 1 or more dendritic projections projecting from the particle surface, and the dendritic projections may be only unbranched main branches, or may be a shape in which branched portions branch off from the main branches and grow in a planar or three-dimensional manner.
The silver-coated copper particles may contain copper particles and a silver-containing layer covering the copper particles, the silver-coated copper alloy particles may contain copper alloy particles and a silver-containing layer covering the copper alloy particles, and the silver-coated nickel particles may contain nickel particles and a silver-containing layer covering the nickel particles. The copper alloy particles may contain 0.5 to 20 mass% of nickel and 1 to 20 mass% of zinc. In the above range, nickel and zinc may be contained, the remainder may be made of copper, and the remainder may contain inevitable impurities.
The proportion of the amount of silver coating in the silver-coated copper particles, silver-coated copper alloy particles, or silver-coated nickel particles is preferably 1 to 30 mass%, more preferably 3 to 20 mass%. When the silver coating amount is 1 mass% or more, excellent conductivity is easily obtained, and when the silver coating amount is 30 mass% or less, excellent conductivity can be maintained, and cost can be reduced compared to silver particles.
The average particle diameter of the conductive filler is not particularly limited, but is preferably 1 to 20 μm, more preferably 3 to 15 μm. When the particle diameter is 1 μm or more, excellent dispersibility is easily obtained, and when the particle diameter is 20 μm or less, excellent conductivity is easily obtained. Here, in the present specification, the average particle diameter refers to a particle diameter (primary particle diameter) at an integrated value of 50% in a particle size distribution obtained by a laser diffraction scattering method.
The conductive adhesive composition of the present embodiment can be appropriately blended with silica, polyurethane beads (urethane beads), or the like according to the desired physical and chemical properties to adjust the hardness of the composition. The conductive adhesive composition can be hardened by compounding silica, and the conductive adhesive composition can be softened by compounding urethane beads (urethane beads).
In addition to the above components, the conductive adhesive composition of the present embodiment may further contain an antioxidant, a pigment, a dye, a tackifying resin, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling regulator, a filler, a flame retardant, and the like, within a range not to impair the object of the present invention.
The conductive adhesive composition of the present embodiment can be prepared by mixing and stirring the components in a conventional manner using a Mixer such as a commonly used Banbury Mixer (Banbury Mixer), Kneader (Kneader), or roll (roll).
The conductive adhesive composition of one embodiment can be suitably used as an adhesive for an electrode of a piezoelectric film (piezoelectric film) or a heat-labile electronic component.
The conductive adhesive composition of the present embodiment may be sprayed to a film made of polyethylene terephthalate or the like after release treatment in a desired film thickness to form a film as a conductive bonding film. In addition, a release film may be provided on one surface or both surfaces of the conductive bonding film for the purpose of protecting the conductive bonding film.
Examples
The following are examples of the present invention, but the present invention is not limited to the following examples. Unless otherwise specified, the following compounding ratios and the like are based on mass.
The conductive adhesive composition was prepared by mixing the components in accordance with the compounding shown in table 1 below. This was applied to a polyethylene terephthalate (PET) film (release film 18) after release treatment to prepare a conductive bonding film having a film thickness of 60 μm. The following are details of the compounds shown in the table, wherein Tm represents a melting point, Tg represents a glass transition temperature, and Mn represents a number average molecular weight.
Seeding crystalline thermoplastic resin 1: crystalline polyester, Tm 120 ℃ and Mn 22000
Seeding crystalline thermoplastic resin 2: crystalline polyester, Tm 95 ℃ and Mn 20000
Seeding amorphous thermoplastic resin: amorphous polyester, Tg 65 deg.C, Mn 16000
Seeded carboxyl-modified polyester resin: tg 15 deg.C, Mn 16000, acid value 18 mgKOH/g
Seed conductive filler 1: dendritic-shaped silver-coated copper particles having an average particle diameter of 5 μm and a silver coating amount of 10% by mass
Seeding conductive filler 2: spherical silver-coated copper particles having an average particle diameter of 5 μm
Seed and seed polyurethane beads (urethane beads): dynamic bead UCN-5050 CLEAR manufactured by Dari refining industry "
Seed and silicon dioxide: SYLOPHOBIC200, FUSHISILICON CHEMICAL.
The adhesion (70 ℃ creep strength, 90 ° peel strength, and tensile shear bond strength), surface resistivity, and connection resistivity of the obtained conductive adhesive composition were measured, and the results are shown in table 1. The following is the measurement method.
Seeding 70 ℃ creep strength: a sample 1 in which a copper foil 12 was laminated on a PET film 10 via a double-sided tape 11 and a sample 2 in which an aluminum deposited film 13 was laminated on the PET film 10 via the double-sided tape 11 with the aluminum deposited surface thereof being a surface were prepared, and the samples were cut so that the sizes of the samples were 50mm × 20mm, respectively. Then, the conductive adhesive film 14 having a thickness of 60 μm and made of the conductive adhesive composition obtained above was cut to a size of 20mm × 5mm, laminated on the copper foil 12 of sample 1, pressure-bonded at a temperature of 100 ℃ and a pressure of 0.5MPa for 30 seconds, and then the release film 18 was peeled off. Then, as shown in FIG. 1, the aluminum deposited surface of the aluminum deposited film 13 of sample 2 and the conductive bonding film 14 were bonded, and they were connected by pressure bonding at 100 ℃ and 0.5MPa for 30 seconds. The end of the sample 1 on the non-bonded side was held and hung in an air oven, and the end of the sample 2 on the non-bonded side was heated at 70 ℃ after applying a weight of 500. + -.2 g, and the time until the separation of the sample 1 and the sample 2 at the bonding site was measured. When the time required for separation is 500 hours or more, the bondability is excellent.
Seed Rate 90 ° Peel Strength (N/5 mm): sample 3 in which copper foil 12 was laminated on glass epoxy substrate 15 via double-sided tape 11 and aluminum deposited film 13 were prepared, and cut so that the dimensions thereof were 5mm × 70mm, respectively. Then, as shown in fig. 2, the conductive bonding film 14 obtained above was cut to a size of 5mm × 50mm, laminated on the copper foil 12 of sample 3, press-bonded at a temperature of 100 ℃ and a pressure of 0.5MPa for 30 seconds, and then the release film 18 was peeled off. Then, the aluminum deposition surface of the aluminum deposition film 13 and the conductive bonding film 14 were bonded, and they were connected by pressure bonding at 100 ℃ and 0.5MPa for 30 seconds. The aluminum deposited film 13 connected to sample 3 was peeled off at a tensile rate of 120 mm/min and a peeling direction of 90 degrees (arrow direction in FIG. 2) by a tensile tester (PT-200N, manufactured by Minebea corporation), and the average value of the load until breakage was determined as a measured value.
Seeding tensile shear joint strength (N/20 mm): sample 1 and sample 2 were joined by bonding with the conductive joining film 14 in the same manner as the creep strength at 70 ℃, and a tensile test was carried out at a tensile speed of 200 mm/min using a tensile tester "AGS-X50S" manufactured by shimadzu corporation (ltd.) in accordance with JIS K6850, and the maximum load at break was measured. The adhesiveness is excellent when 60N/20 mm or more.
Seed surface resistivity (Ω/□): as shown in FIG. 3As shown, a cubic electrode A, B (electrode area: 1 cm) was placed on the conductive bonding film 14 prepared above2(each side is 1 cm); electrode surface: gold plating treatment). The electrodes A, B are now spaced 10mm apart. A load of 4.9N was applied to each electrode in the vertical direction, and the resistance value between the electrodes A and B was measured by the 2-terminal method, and the value after 1 minute from the start of the measurement was taken as the surface resistivity R1。
Seeding junction resistivity: the electrical resistivity of the connection to the aluminum deposition surface and the electrical resistivity of the connection to the copper foil surface were measured. Specifically, as shown in fig. 4, an aluminum deposited film 17 having an aluminum deposited layer 16 formed on a PET film 10 was prepared, and the conductive adhesive film 14 having a film thickness of 60 μm and made of the conductive adhesive composition obtained above was pressed against the aluminum deposited film 17 at a temperature of 100 ℃ and a pressure of 0.5MPa for 30 seconds, and transferred to the aluminum deposited film 17, and the release film 18 was peeled off. Then, a cubic-shaped electrode C, D (electrode area: 1 cm)2(each side is 1 cm); electrode surface: gold plating treatment) is placed on the conductive bonding film 14, and the electrode D is placed on the aluminum deposited film 17. In addition, the connection resistivity R between C-D electrodes is the same as the surface resistivity2The measurement was carried out. The measurement of the connection resistivity to the copper foil surface was performed in the same manner as described above except that the electrode D was placed on the copper foil using the copper foil instead of the aluminum deposited film 17.
The average values of the measured atmosphere temperatures at room temperature (18 to 28 ℃) and the test number n of 5 are shown in table 1. When the resistivity is 10. omega./□ or less, the conductivity can be judged to be excellent. At this time, whether the electrical connection is anisotropic or isotropic was also evaluated, and the surface resistivity R is anisotropic1Is evaluated as blank (-).
[ Table 1]
As shown in Table 1, examples 1 to 5 were excellent in all of the adhesiveness (creep strength at 70 ℃, 90 ℃ peel strength, tensile shear bond strength), surface resistivity and connection resistivity.
Comparative example 1 is an example containing no carboxyl group-modified polyester resin (C), and the 90 ℃ peel strength is poor.
Comparative example 2 is an example using only the carboxyl-modified polyester resin (C), and the creep strength at 70 ℃ is poor.
Comparative example 3 is an example using a spherical conductive filler, and isotropic conductivity was not obtained. In addition, the connection resistivity of the aluminum vapor plating surface and the copper foil surface is poor.
In comparative example 4, the crystalline thermoplastic resin had a melting point outside a certain range and had poor creep strength at 70 ℃.
Reference numerals
Seeds, trees and seeds
2, seeds and seeds
3, seeds and seeds
Seed, seed and PET film
Seed, seed and double-sided adhesive
12 seed, seed and copper foil
Evaporated film of 13 seed, seed and aluminium
Seeds, trees, or seeds and conductive junction film
15 seed, seed and glass epoxy resin substrate
16 seed, seed and aluminium evaporation layer
Evaporated film of 17 seed, seed and aluminium
18 seed, seed and release film
A, B, C, D, seeds and seeds electrodes
Claims (6)
1. An electrically conductive adhesive composition characterized by:
the conductive adhesive composition contains a resin component and a dendritic conductive filler, wherein the resin component at least contains (A) crystalline thermoplastic resin with a melting point of more than 100 ℃, (B) non-crystalline thermoplastic resin, (C) carboxyl modified polyester resin, and the dendritic conductive filler accounts for 50-300 parts by mass relative to 100 parts by mass of the resin component,
the content ratio of the crystalline thermoplastic resin (A) to the amorphous thermoplastic resin (B) is 60/40-90/10 in terms of mass ratio;
the crystalline thermoplastic resin (A) and the amorphous thermoplastic resin (B) do not contain a carboxyl-modified polyester resin (C).
2. The conductive adhesive composition according to claim 1, wherein:
the crystalline thermoplastic resin (a) is a crystalline polyester, and the amorphous thermoplastic resin (B) is an amorphous polyester.
3. The conductive adhesive composition according to claim 1, wherein:
the conductive filler is 1 or 2 or more selected from the group consisting of copper particles, silver particles, gold particles, nickel particles, silver-coated copper alloy particles, and silver-coated nickel particles.
4. The conductive adhesive composition according to claim 1, wherein:
the glass transition temperature of the carboxyl modified polyester resin (C) is 10-30 ℃.
5. The conductive adhesive composition according to claim 1, wherein:
the glass transition temperature of the amorphous thermoplastic resin (B) is 50-120 ℃.
6. A conductive adhesive composition according to any one of claims 1 to 5, wherein:
the content of the carboxyl-modified polyester resin (C) is 15 to 35 parts by mass per 100 parts by mass of the resin component.
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| JP2018-014062 | 2018-01-30 | ||
| JP2018014062 | 2018-01-30 | ||
| PCT/JP2019/002763 WO2019151188A1 (en) | 2018-01-30 | 2019-01-28 | Conductive adhesive composition |
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| CN111448279A CN111448279A (en) | 2020-07-24 |
| CN111448279B true CN111448279B (en) | 2021-08-10 |
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| JP (1) | JP7225505B2 (en) |
| KR (1) | KR102580259B1 (en) |
| CN (1) | CN111448279B (en) |
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| CN104604035A (en) * | 2012-09-18 | 2015-05-06 | 迪睿合电子材料有限公司 | Anisotropic conductive film, connection method, and assembly |
| CN106104929A (en) * | 2014-03-11 | 2016-11-09 | 迪睿合株式会社 | Anisotropic conductive film and method of attachment and conjugant |
| JP2017117794A (en) * | 2017-01-11 | 2017-06-29 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method, and assembly |
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| JPH03131679A (en) * | 1989-10-17 | 1991-06-05 | Fujikura Ltd | Conductive adhesive |
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2019
- 2019-01-28 CN CN201980006537.XA patent/CN111448279B/en active Active
- 2019-01-28 JP JP2019569097A patent/JP7225505B2/en active Active
- 2019-01-28 KR KR1020207010207A patent/KR102580259B1/en active IP Right Grant
- 2019-01-28 WO PCT/JP2019/002763 patent/WO2019151188A1/en active Application Filing
- 2019-01-29 TW TW108103297A patent/TWI784126B/en active
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| JP2006152233A (en) * | 2004-11-01 | 2006-06-15 | Tatsuta System Electronics Kk | Anisotropic electroconductive adhesive and electronic equipment formed by using the same |
| CN104604035A (en) * | 2012-09-18 | 2015-05-06 | 迪睿合电子材料有限公司 | Anisotropic conductive film, connection method, and assembly |
| CN106104929A (en) * | 2014-03-11 | 2016-11-09 | 迪睿合株式会社 | Anisotropic conductive film and method of attachment and conjugant |
| JP2017117794A (en) * | 2017-01-11 | 2017-06-29 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method, and assembly |
Also Published As
| Publication number | Publication date |
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| JP7225505B2 (en) | 2023-02-21 |
| KR102580259B1 (en) | 2023-09-19 |
| JPWO2019151188A1 (en) | 2021-02-12 |
| CN111448279A (en) | 2020-07-24 |
| KR20200111667A (en) | 2020-09-29 |
| TW201936845A (en) | 2019-09-16 |
| TWI784126B (en) | 2022-11-21 |
| WO2019151188A1 (en) | 2019-08-08 |
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