CN116285233A - Conductive composition, conductive sheet, metal reinforcing plate, wiring board with metal reinforcing plate, and electronic device - Google Patents
Conductive composition, conductive sheet, metal reinforcing plate, wiring board with metal reinforcing plate, and electronic device Download PDFInfo
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- CN116285233A CN116285233A CN202310307224.6A CN202310307224A CN116285233A CN 116285233 A CN116285233 A CN 116285233A CN 202310307224 A CN202310307224 A CN 202310307224A CN 116285233 A CN116285233 A CN 116285233A
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- conductive composition
- resin
- sheet
- conductive
- metal
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides a conductive composition, a conductive sheet, a metal reinforcing plate, a wiring board with the metal reinforcing plate, and an electronic device, wherein the conductive composition has excellent resin flow inhibition, high adhesiveness and conductivity, and can achieve both excellent punching processability and film thickness assurance. The invention is solved by a conductive composition comprising a binder (A), metal particles (B), and resin particles (C), wherein the recovery rate of the resin particles (C) is 5% to 95%. The present invention is also directed to the conductive composition, wherein the binder (a) contains at least one selected from the group consisting of an imide bond, an amide bond, a urethane bond, and a urea bond.
Description
Technical Field
The present invention relates to a conductive composition, a conductive sheet, a metal reinforcing plate, a wiring board with a metal reinforcing plate, and an electronic device.
Background
The wiring board mounted in the electronic device has flexibility, but it is known to arrange a reinforcing plate to suppress deformation in terms of connection between components such as a connector portion. Conventionally, epoxy glass or the like has been used as a reinforcing plate, but a metal plate is used in order to provide an electromagnetic wave noise suppressing function. In connection between the wiring board and the metal plate, a conductive composition containing a resin as a main component is used as an adhesive.
The adhesive may be added with a filler for the purpose of conducting between the metal plate and the wiring board, or for the purpose of controlling the elastic modulus.
For example, patent document 1 discloses that a conductor circuit is connected to a reinforcing plate via an adhesive layer, and describes that a conductive adhesive material containing conductive particles and an adhesive is used as the adhesive layer.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] International publication No. WO2021/167047
Disclosure of Invention
[ problem to be solved by the invention ]
For the purpose of conducting between the metal plate and the wiring board, the adhesive is required to have high conductivity. In recent years, in view of application to in-vehicle parts or mobile phone parts, particularly, it is required to continuously exhibit high conductivity even under severe environments. Patent document 1 discloses a conductive composition that can suppress positional displacement of a conductive filler due to temperature change, vibration, or the like, and exhibits high conductivity (connection stability) by adding inorganic particles having fine pores.
A metal reinforcing plate formed by bonding a metal plate and a bonding agent (conductive composition) is mounted on wiring boards of various shapes, and is thus processed into a shape suitable for each wiring board. The processing mainly uses a method (press processing) of pressing a master plate of a metal reinforcing plate as a base by a press blade, but for example, when the conductive composition contains hard inorganic particles, there are the following problems: the particles are not completely cut and generate cracks or the like, and defects such as cracks are generated in the conductive composition with the cracks as a starting point.
The metal reinforcing plate after press working is joined to the wiring board in the heating and pressing process, but the following problems also occur: the resin of the conductive composition deforms and flows due to the pressure during the heating and pressing, and protrudes from the metal plate to contact an undesired portion of the wiring board, thereby shorting the circuit. (resin flow)
Further, the thickness of the conductive composition is greatly reduced by crushing the composition under pressure during the heat pressing than before the heat pressing, and there is a problem that the total thickness of the completed wiring board with a metal reinforcing plate is greatly deviated from the design value, and a conductive composition having little change in thickness before and after the heat pressing is required. (film thickness Security)
The invention aims to provide a conductive composition, a conductive sheet, a metal reinforcing plate, a wiring board with the metal reinforcing plate and an electronic device, wherein the conductive composition has excellent resin flow inhibition, high adhesiveness and conductivity, and can achieve both excellent punching processing property and film thickness assurance.
[ means of solving the problems ]
The conductive composition of the present invention comprises a binder (A), metal particles (B), and resin particles (C), wherein the recovery rate of the resin particles (C) is 5% to 95%.
[ Effect of the invention ]
The present invention provides a conductive composition and a conductive sheet which are excellent in resin flow inhibition, have high adhesion and conductivity, and can achieve both excellent press workability and film thickness assurance.
The metal reinforcing plate using the conductive composition and the conductive sheet can be processed without generating defects during press processing, so that the production efficiency can be improved. In addition, in the production of the wiring board with a metal reinforcing plate including the metal reinforcing plate of the present invention, the thickness variation at the time of heating and pressing can be suppressed to realize efficient production. Further, a high-quality electronic device in which resin flow is suppressed, short-circuiting due to protrusion of a member is prevented, and malfunction is prevented by high adhesion and conductivity can be provided with good yield.
Drawings
Fig. 1 is a schematic view showing a cross section of a wiring board with a metal reinforcing plate according to the present invention.
[ description of symbols ]
1: conductive composition
2: metal plate
20: wiring board
21: insulating film
22: grounding circuit
23: cover layer
30: an opening part
100: wiring board with metal reinforcing plate
Detailed Description
The conductive composition, the conductive sheet, the metal reinforcing plate, the wiring board with the metal reinforcing plate, and the electronic device of the present invention will be described in order. Unless otherwise specified, the term "to" representing a numerical range includes a lower limit value and an upper limit value. In addition, the drawings are simplified as appropriate for clarity of illustration. In addition, the scale of each structure in the drawings may be greatly different for the sake of explanation.
[ conductive composition ]
The conductive composition of the present invention comprises a binder (A), metal particles (B), and resin particles (C).
[ Adhesives (A) ]
The binder (a) serves as a matrix of the conductive composition, and has a function of dispersing and supporting the metal particles (B) or the resin particles (C). The composition and the like of the binder (a) are not particularly limited as long as the binder (a) has the above-mentioned functions, but preferably contains the resin (a-1). The resin (a-1) in the present invention is usually a solid, semi-solid or solidified body, and is defined as an organic material having a weight average molecular weight (Mw) of 5,000 or more in a softening or melting range.
[ resin (a-1) ]
The resin (a-1) is not particularly limited in composition, molecular structure, and the like other than the weight average molecular weight (Mw), and is preferably a resin having one or more chemical bonds selected from the group consisting of imide bonds, amide bonds, urethane bonds, and urea bonds. Imide bonds, amide bonds, urethane bonds, and urea bonds can achieve strong adhesion by interaction of non-common electron pairs of nitrogen atoms contained in the bonds with an adherend. Examples of the resin having the chemical bond group include: polyurethane resin, polyamide resin, polyimide resin, polyamideimide resin, urea resin, polyurethane urea resin, and the like.
The resin (a-1) more preferably has two or more types selected from the group consisting of imide bonds, amide bonds, urethane bonds, and urea bonds. The adhesive (a) has two or more types selected from the group consisting of an imide bond, an amide bond, a urethane bond, and a urea bond, and thus exhibits a stronger adhesive force by multiplexing the interaction with the adherend. The resin having two or more types selected from the group consisting of imide bonds, amide bonds, urethane bonds, and urea bonds means, for example, a polyamideimide resin, a polyurethane urea resin, and the like.
As described above, the resin (a-1) can be appropriately selected from the viewpoints of composition and molecular structure, but an appropriate resin can also be selected according to the nature of the resin. The resin (a-1) is preferably a thermosetting resin (a-2) or a thermoplastic resin (a-3) in view of exhibiting adhesiveness by applying heat stimulus to the conductive composition.
[ thermosetting resin (a-2) ]
The thermosetting resin (a-2) is a resin having thermosetting properties among the resins (a-1). The term "thermosetting" is defined as "a product which is substantially changeable in insolubility and insolubility when cured by heat, radiation, a catalyst, or the like.
The thermosetting property may be expressed by the reaction of the reactive functional groups with each other when the thermosetting resin (a-2) has the reactive functional groups such as the acidic groups, or by the reaction of the thermosetting resin (a-2) with the reactive functional groups incorporated into the curing agent (D) described later.
The acid value of the thermosetting resin (a-2) is preferably 5mgKOH/g to 40mgKOH/g. When the acid value is within the above range, the density of the crosslinked structure is in an appropriate range, and flexibility and toughness can be both achieved. The acid value is more preferably 10mgKOH/g to 20mgKOH/g.
[ thermoplastic resin (a-3) ]
The thermoplastic resin (a-3) is a resin having thermoplastic properties among the resins (a-1). Thermoplastic is defined as "a state in which softening by heating and hardening by cooling can be repeatedly performed in a temperature range specific to plastics, and in a softened state, the shape can be uniformly formed, extruded, or formed by repeatedly performing flow.
The binder (a) preferably contains at least one functional group selected from the group consisting of epoxy, oxetanyl, alkylthio, and aziridine groups. In the case where the resin (a-1) has a reactive functional group such as an acidic group, the functional group may exhibit high adhesion when the reactive functional group thereof or the functional groups cause a hardening reaction with each other. As a method for making the binder (a) contain the functional group, for example, the following method can be adopted: the resin (a-1) having the functional group is added to the adhesive (a), or a hardener having the functional group among the hardeners (D) described later is added to the adhesive (a).
[ hardener (D) ]
The hardener (D) in the present invention is a substance that promotes or regulates the hardening reaction, and is defined as a substance having a molecular weight or weight average molecular weight (Mw) of less than 5,000. The hardening reaction is defined as "polymerization and/or crosslinking of a prepolymer or a polymerization composition by heating or other means such as radiation, a catalyst, etc., and an irreversible increase in elastic modulus". The adhesive (a) of the present invention preferably contains a hardener (D) in view of the conductive composition exhibiting strong adhesion by polymerization and/or crosslinking of the adhesive (a) by stimulation such as heat.
The curing reaction may be a reaction in which the curing agents (D) react with each other, or may be a reaction with other components in the adhesive (a) such as the resin (a-1). In the case where the resin (a-1) and the curing agent (D) undergo a curing reaction, the resin (a-1) is preferably a thermosetting resin (a-2) from the viewpoint of efficiently undergoing a reaction.
In view of not carrying out a curing reaction during storage and only carrying out a curing reaction during heating, it is preferable to select a combination of the thermosetting resin (a-2) and the curing agent (D) that does not carry out a crosslinking reaction at 50 ℃ and promotes a curing reaction at 150 ℃.
In addition, by appropriately combining two or more types of hardeners having different starting temperatures for the hardening reaction, the crosslinking density of the conductive composition in each temperature zone can be controlled.
The hardener (D) may be exemplified by: epoxy hardeners, oxetane hardeners, episulfide hardeners, aziridine hardeners, amine hardeners, isocyanate hardeners, and imidazole hardeners. Among them, epoxy hardeners, oxetane hardeners, episulfide hardeners, and aziridine hardeners are preferable because they can efficiently undergo a hardening reaction with the thermosetting resin (a-2) and can exhibit high adhesion.
Examples of the epoxy hardener include glycidyl ether type epoxy compounds, glycidyl amine type epoxy compounds, glycidyl ester type epoxy compounds, and cyclic aliphatic (alicyclic) epoxy compounds.
Examples of the glycidyl ether type epoxy compound include: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol AD type epoxy compound, cresol novolak type epoxy compound, phenol novolak type epoxy compound, a-1-naphthol novolak type epoxy compound, bisphenol A type novolak type epoxy compound, dicyclopentadiene type epoxy compound, tetrabromobisphenol A type epoxy compound, brominated phenol novolak type epoxy compound, tris (glycidoxyphenyl) methane, tetrakis (glycidoxyphenyl) ethane, and the like.
Examples of the glycidylamine-type epoxy compound include: tetraglycidyl diaminodiphenylmethane, triglycidyl para-aminophenol, triglycidyl methylaminophenol, tetraglycidyl meta-xylylenediamine, and the like.
Examples of the glycidyl ester type epoxy compound include: diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, and the like.
Examples of the cyclic aliphatic (alicyclic) epoxy compound include epoxycyclohexylmethyl-epoxycyclohexane carboxylate, bis (epoxycyclohexyl) adipate, and the like.
The oxetane hardener may be exemplified by: 1, 4-bis { [ (3-ethyloxetan-3-yl) methoxy ] methyl } benzene, 3-ethyl-3- { [ (3-ethyloxetan-3-yl) methoxy ] methyl } oxetan, 1, 3-bis [ (3-ethyloxetan-3-yl) methoxy ] benzene, 4' -bis [ (3-ethyl-3-oxetan) methoxymethyl ] biphenyl, an esterified product of (2-ethyl-2-oxetan) ethanol and terephthalic acid, an esterified product of (2-ethyl-2-oxetan) ethanol and a phenol novolac resin, an esterified product of (2-ethyl-2-oxetan) ethanol and a polycarboxylic acid compound, and the like.
Examples of the episulfide-hardening agent include: bis (1, 2-epithioethyl) sulfide, bis (1, 2-epithioethyl) disulfide, bis (2, 3-epithiopropyl) sulfide, bis (2, 3-epithiopropyl) thiomethane, bis (2, 3-epithiopropyl) dithio-ne, bis (2, 3-epithiopropyl dithio) ethane, bis (6, 7-epithio-3, 4-dithioheptyl) sulfide, bis (6, 7-epithio-3, 4-dithioheptyl) disulfide, 1, 4-dithiane-2, 5-bis (2, 3-epithiopropyl dithiomethyl) benzene, 1, 3-bis (2, 3-epithiopropyl dithiomethyl) -2- (2, 3-epithiopropyl dithioethylthio) -4-thiahexane, 1,2, 3-tris (2, 3-dithiopropyl) propane and the like.
Examples of aziridine hardening agents include: trimethylolpropane-tri-a-2-aziridinyl propionate, tetramethylolmethane-tri-a-2-aziridinylpropionate, N ' -diphenylmethane-4, 4' -bis (1-aziridine carboxamide), N ' -hexamethylene-1, 6-bis (1-aziridine carboxamide), and the like.
Examples of the amine hardener include: diethylenetriamine, triethylenetetramine, methylenebis (2-chloroaniline), methylenebis (2-methyl-6-methylaniline), 1, 5-naphthalene diisocyanate, n-butylbenzyl phthalate, and the like.
Examples of the isocyanate curing agent include: toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, 1, 5-naphthalene diisocyanate, tetramethylxylylene diisocyanate, trimethylhexamethylene diisocyanate, and the like.
Examples of imidazole hardeners include: 2-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and the like.
The hardener (D) may be used singly or in combination of two or more. In terms of adjusting the storage modulus of elasticity or the glass transition temperature of the conductive composition, the hardener (D) is preferably a hardener having a molecular weight or weight average molecular weight of 100 or more.
The curing agent (D) is preferably blended in an amount of 1 to 70 parts by mass, more preferably 3 to 50 parts by mass, per 100 parts by mass of the thermosetting resin (a-2). By setting the amount of the hardener (D) to 1 part by mass or more, the density of the crosslinked structure of the conductive composition can be optimized, the adhesiveness can be improved, and the resin flow can be suppressed or the film thickness assurance can be improved. By setting the addition amount of the hardening agent (D) to 70 parts by mass or less, the conductive composition can be prevented from being excessively hardened, and the adhesiveness and press workability can be improved.
[ Metal particles (B) ]
The metal particles (B) are preferably conductive metals such as gold, platinum, silver, copper, and nickel, and alloys thereof. In addition, in terms of cost reduction, the fine particles of a metal that becomes a core body, not a single composition, are preferably composite fine particles in which a coating layer that covers the surface of the core body is formed from a material that has higher conductivity than the core body.
The core is preferably selected from nickel, silica, copper and alloys thereof. Examples of the coating layer include: gold, platinum, silver, tin, manganese, indium, and the like, and alloys thereof. Among them, silver is preferably used in view of conductivity and material cost.
The metal particles (B) may be used singly or in combination of two or more.
The composite fine particles preferably have a coating layer in a proportion of 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the core body. When the coating is performed in an amount of 1 to 40 parts by mass, the cost can be further reduced while maintaining the conductivity. The composite particles are preferably coated to completely cover the core. However, in practice, a portion of the nucleus may be exposed. Even in this case, if the conductive material covers 70% or more of the surface area of the core body, the conductivity is easily maintained.
The shape of the metal particles (B) is not limited as long as the desired conductivity is obtained. Specifically, examples thereof include: spherical, lamellar, foliate, dendritic, platy, acicular, rod-like, grape-like, amorphous block. In addition, from the viewpoint of improving conductivity, it is more preferably spherical, lamellar, foliated, dendritic, or plate-like.
Regarding the average particle diameter of the metal particles (B), the average particle diameter D 50 Preferably 1 μm to 50 μm, more preferably 3 μm to 30 μm, and still more preferably 5 μm to 20 μm. By mean particle diameter D 50 Within the above range, a suitable conduction path can be formed, and conductivity can be improved. Further, the average particle diameter D 50 The particle size distribution can be determined by a laser diffraction-scattering method particle size distribution measuring device.
Regarding the average particle diameter of the metal particles (B), the average particle diameter D 90 Preferably 1 μm to 120 μm, more preferably 5 μm to 70 μm. By mean particle diameter D 90 Within the above range, adhesion can be suppressed. For example, a conductive sheet having a conductive composition on a releasable film is transported while being wound into a roll. The blocking is a phenomenon in which the conductive composition adheres to the back surface of the releasable film when the conductive sheet is wound out from the rolled conductive sheet.
In the case where the electroconductive composition is in the form of a layer, the electroconductive composition is heated and pressedThe thickness of the conductive composition before being divided by the average particle diameter D of the metal particles (B) 50 The value X obtained is preferably 1 to 35. When X is 35 or less, the conductive path of the metal particle (B) is effectively formed in the conductive composition, and the conductivity is improved. From the viewpoint of improving conductivity, X is more preferably 18 or less. Further, when X is 1 or more, the contact point between the adherend and the metal particles (B) is not excessively increased, and the contact area between the adherend and the adhesive agent (a) is increased, so that the adhesiveness is improved. X is more preferably 5 or more.
The metal particles (B) are preferably contained in an amount of 40 to 90 mass% based on the total solid content of the conductive composition. By setting the content to the above-described level, both conductivity and adhesiveness can be achieved. The content of the metal particles (B) is more preferably 45 to 80 mass%, and still more preferably 50 to 70 mass%.
[ resin particles (C) ]
The resin particles (C) in the present invention are defined as those in which the organic resin is in the form of particles. The resin particles (C) are supported in a state of being dispersed in the binder (A), and are incompatible with the binder (A). The recovery rate of the resin particles (C) is 5% to 95%. When the recovery ratio is within the above range, the shape recovery of the entire conductive composition is performed by the action of recovering the shape of the resin particles (C) after the removal of the charge after the heating and pressing, and the reduction of the thickness can be suppressed. Further, by adding the resin particles (C), excessive flow of the binder (a) when the conductive composition is heated and pressed can be suppressed, and resin flow can be suppressed.
The resin flow inhibition effect is an effect that can be exhibited even if the recovery rate of the resin particles (C) is less than 5%, but in the particles having the recovery rate of less than 5%, the space generated by the compression of the resin particles (C) at the time of the heating and pressing is filled with the binder (a), and the thickness of the conductive composition is reduced. When the recovery rate of the resin particles (C) is 5% or more and 95% or less, the effect of suppressing the decrease in thickness (film thickness assurance) of the conductive composition can be obtained by the above-described estimation. The recovery rate of the resin particles (C) is preferably 30% or more and 95% or less, more preferably 40% or more and 95% or less. When the recovery rate falls within the above range, the film thickness assurance is further improved.
The recovery rate of the resin particles (C) can be obtained by a load-unload test using a micro compression tester described later in the examples.
The recovery rate of the resin particles (C) can be controlled by appropriately selecting the type of the organic resin, the type of the raw material (monomer) used, whether or not a crosslinked structure is formed in the particles, the addition of inorganic fine particles, and the like.
The method for producing the resin particles (C) may be, for example, a method of (1) forming particles when synthesizing an organic resin from a monomer as a raw material, or (2) pulverizing a bulk organic resin. Among them, from the viewpoint of precisely controlling the particle size distribution of the resin particles (C), it is preferable that (1) the method of forming particles when synthesizing an organic resin from a monomer as a raw material.
The organic resin constituting the resin particles (C) is not particularly limited as long as it can exhibit a desired recovery rate, and for example, acrylic resin, polyurethane resin, nylon resin, polyimide resin, and styrene resin are preferable in terms of ease of production.
Average particle diameter D of resin particles (C) 50 Preferably 1 μm or more and 15 μm or less. Average particle diameter D by resin particles (C) 50 Within the above range, the shape recovery effect after the heating and pressing can be effectively reflected in the conductive composition, and the film thickness assurance is improved, which is preferable. Further, the average particle diameter D 50 The particle size distribution can be obtained by a laser diffraction/scattering method particle size distribution measuring apparatus similarly to the metal particles (B). Average particle diameter D of resin particles (C) 50 More preferably 1 μm or more and less than 4 μm, still more preferably 2 μm or more and 3 μm or less.
In the case where the electroconductive composition is layered, the thickness of the electroconductive composition before heating and pressing is divided by the average particle diameter D of the resin particles (C) 50 The value Y obtained is preferably 70 or less. When Y is 70 or less, the presence ratio of the resin particles (C) in the thickness direction in the conductive composition increases, and the recovery effect of the resin particles (C) is more effectively exhibited, so that the film thickness assurance is improved. The film thickness assurance is improved In this respect, Y is more preferably 60 or less, and still more preferably 25 or less.
The resin particles (C) are preferably contained in an amount of 0.1 to 35% by mass based on the total solid content of the conductive composition. When the content of the resin particles (C) is 0.1 mass% or more, resin flowability, press workability and film thickness securing property are improved, and when the content of the resin particles (C) is 35 mass% or less, adhesiveness is improved. The content of the resin particles (C) is more preferably 1 to 30% by mass, and still more preferably 2 to 15% by mass.
The resin particles (C) may contain inorganic fine particles such as titanium oxide and iron oxide or pigments for the purpose of adjusting the hardness or coloring, or may be attached to the surface for the purpose of suppressing aggregation and adhesion of the resin particles (C).
The conductive composition of the present embodiment may contain, as other optional components, a heat stabilizer, an inorganic filler, a pigment, a dye, an adhesion-imparting resin, a plasticizer, a silane coupling agent, an ultraviolet absorber, a defoaming agent, a leveling agent, and the like.
Examples of the inorganic filler include: silica, alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, titanium oxide, zinc oxide, antimony trioxide, magnesium oxide, talc, montmorillonite, kaolin, bentonite, and the like. By containing the inorganic filler in the conductive composition, the storage elastic modulus before curing can be controlled to an optimum flow amount.
[ conductive sheet ]
The conductive sheet of the present embodiment is a conductive sheet having a conductive composition on a releasable film. The conductive composition included in the conductive sheet is a solid substance that is not flowable at room temperature and has a layer shape having a certain thickness.
[ Release film ]
The releasable film is not limited as long as it is a film having one or both surfaces subjected to release treatment.
Examples of the releasable film include: polyethylene terephthalate, polyethylene naphthalate, polyvinyl fluoride, polyvinylidene fluoride, rigid polyvinyl chloride, polyvinylidene chloride, nylon, polyimide, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate, polyacrylonitrile, polybutylene, soft polyvinyl chloride, polyethylene, polypropylene, polyurethane, ethylene-vinyl acetate copolymer, plastic sheets such as polyvinyl acetate, and the like, cellophane, fine paper, kraft paper, coated paper and the like, various nonwoven fabrics, synthetic paper, metal foil, composite films formed by combining them, and the like.
The surface of the releasable film may be subjected to matting treatment as needed. The method of matting treatment may be exemplified by: sand matting, etching matting, coating matting, chemical matting, mixing matting, and the like.
The releasable film can be obtained by coating a release agent on a substrate. As the release agent, hydrocarbon resins such as polyethylene and polypropylene, higher fatty acids and metal salts thereof, higher fatty acid soaps, waxes, animal and vegetable oils and fats, mica, talc, silicone surfactants, silicone oils, silicone resins, fluorine-containing surfactants, fluorine resins, fluorine-containing silicone resins, melamine resins, acrylic resins, and the like can be used. The application method of the release agent can be performed by conventionally known methods, such as gravure coating, kiss coating, die coating, lip coating, corner-cut wheel coating, blade coating, roll coating, blade coating, spray coating, bar coating, spin coating, dip coating, and the like.
The thickness of the conductive composition in the conductive sheet is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm, and even more preferably 30 μm to 70 μm, from the viewpoint of both the film property and the conductivity.
[ method for producing conductive sheet ]
The conductive sheet of the present invention can be obtained, for example, by applying the conductive composition to a releasable film, drying the film, and optionally B-stage curing the film. The dried sheet-like conductive composition is also referred to as a conductive resin layer. The coating method may be appropriately selected from known methods in consideration of the film thickness of the adhesive, etc. Specific examples of the coating method include: gravure coating mode, kiss coating mode, die coating mode, lip coating mode, unfilled corner coating mode, blade coating mode, roll coating mode, blade coating mode, spray coating mode, bar coating mode, spin coating mode, dip coating mode, and the like.
The B-stage hardening is a method in which a hardening reaction is partially caused by heating the conductive composition at a predetermined temperature for a predetermined time. By performing the B-stage hardening, strength can be improved while maintaining the adhesive strength of the conductive composition.
[ Metal reinforcing plate ]
In the metal reinforcing plate of the present invention, the conductive composition is bonded to the metal plate. Examples of the metal plate include conductive metals such as gold, silver, copper, iron, and stainless steel. Among them, stainless steel is preferable in terms of strength, cost and chemical stability as a metal plate. The thickness of the metal plate is generally about 0.04mm to 1 mm. The metal plate is preferably a nickel layer formed on the entire surface of the metal plate. The nickel layer is preferably formed by electrolytic nickel plating. The thickness of the nickel layer is about 0.5 μm to 5 μm, more preferably 1 μm to 4 μm. In addition, the conductive composition included in the metal reinforcing plate is a solid substance that is not flowable at room temperature and has a layer shape with a certain thickness.
[ Wiring Board with Metal reinforcing plate ]
The wiring board with metal reinforcement 100 (see fig. 1) of the present embodiment includes a ground circuit 22 disposed on an insulating film 21, a cover layer 23 covering the ground circuit 22, a wiring board 20 disposed with a part of the ground circuit 22 exposed through an opening 30, and a metal reinforcement disposed on the wiring board 20. The conductive composition 1 of the metal reinforcing plate is layered, and the wiring board 20 is bonded to the metal plate 2. In the printed wiring board of the present embodiment, the ground circuit 22 and the metal plate 2 are electrically connected via the conductive composition 1 by filling a part of the conductive composition 1 into the opening 30. Signal wiring may be further provided on the wiring board 20.
The area of the opening 30 of the wiring board 20 may be, for example, 0.16mm 2 Above and 0.81mm 2 The following is given. By setting the area of the opening 30 to 0.16mm 2 As described above, the filling property of the conductive composition into the opening 30 can be improved. In addition, the area of the opening 30 is set to 0.81mm 2 In the following, the area occupied by the opening 30 in the wiring board 20 can be reduced. The area of the opening 30 is preferably 0.25mm 2 Above and 0.64mm 2 Hereinafter, more preferably 0.36mm 2 Above and 0.49mm 2 The following is given. When the area of the opening 30 is within the above range, the filling property of the conductive composition into the opening 30 can be improved, and the contact resistance between the conductive composition and the ground circuit 22 can be reduced.
The opening 30 may have a rectangular shape or a circular shape in a plan view. When the opening 30 is rectangular, filling the four corners of the rectangular opening with the conductive composition is particularly difficult, and gaps are easily formed at the four corners. However, by using the conductive composition of the present embodiment in which the resin flow is controlled within a suitable range, the conductive composition can be satisfactorily filled into the opening even if the opening is rectangular.
[ electronic device ]
Such a wiring board with a metal reinforcing plate can be mounted on electronic devices such as a mobile phone, a smart phone, a notebook personal computer (personal computer, PC), a digital camera, and a liquid crystal display. The present invention can be suitably mounted on a transportation device such as an automobile, a train, a ship, or an airplane.
Examples (example)
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples. Further, the acid value and weight average molecular weight (Mw) of the resin (a-1), and D of the metal particles (B), the resin particles (C), and the silica particles (Z) for comparative example 50 The average particle diameter was measured by the following method.
[ acid value of resin (a-1) ]
The acid value (mgKOH/g) was obtained by converting the solid content according to the neutralization titration method of Japanese Industrial Standard (Japanese Industrial Standards, JIS) K0070. Approximately 1g of a sample was precisely measured in a co-stopper Erlenmeyer flask, and 100mL of a tetrahydrofuran/ethanol mixture (volume ratio: tetrahydrofuran/ethanol=2/1) was added thereto to dissolve the sample. A phenolphthalein reagent was added thereto as an indicator, titration was performed with a 0.1N alcoholic potassium hydroxide solution, and the time at which the indicator remained pale red for 30 seconds was set as an end point. The acid value (unit: mgKOH/g) was determined from the following formula.
Acid value (mgKOH/g) = (5.611 ×a×f)/S
Wherein, the liquid crystal display device comprises a liquid crystal display device,
s: sample collection amount (g)
a: consumption of 0.1N alcoholic potassium hydroxide solution (mL)
F: titer of 0.1N alcoholic potassium hydroxide solution
[ weight average molecular weight (Mw) of resin (a-1) ]
Mw was measured by gel permeation chromatography (gel permeation chromatograph, GPC) "HPC-8020" (manufactured by Tosoh Co., ltd.). GPC is a liquid chromatograph that separates and quantifies substances dissolved in a solvent (THF) based on differences in molecular size of the substances. The measurement was performed by connecting two "LF-604" in series (manufactured by Showa electric company: GPC column for rapid analysis: 6 mmID. Times.150 mm size) for a column and under conditions of a flow rate of 0.6mL/min and a column temperature of 40 ℃. The Mw is determined by conversion to polystyrene.
[ D of metal particles (B), resin particles (C), and silica particles (Z) for comparative example ] 50 Average particle diameter]
Regarding D 50 The average particle diameter was measured using a laser diffraction/scattering particle size distribution measuring apparatus LS13320 (manufactured by Beckman-coulter). The particle diameter is a value obtained by measuring the conductive filler by the cyclone dry powder sample module, and is 50% of the cumulative value in the cumulative particle diameter distribution. The refractive index was set to 1.6.
[ recovery Rate of resin particles (C) ]
The recovery rate of the resin particles (C) was determined by a load-unload test using a micro compression tester "MCT-211" manufactured by Shimadzu corporation. First, the resin particles (C) were placed on a lower pressing plate (SKS plate), and one individual resin particle (C) was selected by an optical microscope (magnification of 50 times of objective lens) of "MCTM-211". The diameter d of the selected resin particles (C) was measured by using a "MCTM-211" particle diameter measuring cursor. The selected resin particles (C) are determined based on the particle size to be measured.
Next, the test indenter was lowered to the apex of the selected resin particle (C) at the following load speed, and the particle diameter a when the load was applied to the resin particle (C) to the maximum test force of 20mN and the particle diameter B when the load was removed to the minimum test force of 0.3mN were measured. The following formula of recovery rate is used based on the displacement amount (recovery amount) L obtained from the particle diameter A and the particle diameter B and the diameter d measured by the particle diameter measuring cursor
Recovery (%) =recovery amount L (μm)/diameter d (μm) ×100,
the recovery rate of the respective resin particles (C) was obtained. The recovery rate of the three resin particles (C) was measured, and the average value was used as the recovery rate.
< measurement condition of recovery Rate >)
Test temperature: normal temperature (20 ℃), relative humidity 65%
Upper pressurizing pressure head: plane pressing head (material: diamond) with diameter of 50 mu m
A lower pressing plate: SKS flat plate
Test species: load-load shedding test
Maximum test force: 20mN
Minimum test force: 0.3mN
Load speed: 4.5mN/sec
Load holding time: 3 seconds
Load-removal holding time: 1min
< raw materials >
[ resin (a-1) ]
(a-1) -1: polyester resin: acid value 36mgKOH/g, mw=27,000 (manufactured by TOYO CHEM)
(a-1) -2: polyimide resin: acid value 18mgKOH/g, mw=55,000 (manufactured by TOYO CHEM)
(a-1) -3: polyamide resin: acid value 22mgKOH/g, mw=49,000 (manufactured by TOYO CHEM)
(a-1) -4: polyurethane resin: acid value 16mgKOH/g, mw=98,000 (manufactured by TOYO CHEM)
(a-1) -5: polyurethane urea resin: acid value 15mgKOH/g, mw=100,000 (manufactured by TOYO CHEM)
(a-1) -6: polyacrylic resin: acid value of 55mgKOH/g, mw=120,000 (manufactured by TOYO CHEM)
[ hardener (D) ]
D1: bisphenol a epoxy compound (jER 828, molecular weight=370, mitsubishi chemical manufacturing)
D2: isophthalic acid type oxetane compound (Ai Dana family (ETERNACOLL) OXIPA, manufactured by Yu Zong Co., ltd.) (molecular weight=362)
D3: hydrogenated bisphenol A episulfide Compound (TBIS-AHS, molecular weight=384, manufactured by the chemical industry of Santa Clara)
D4: polyfunctional aziridine compound (chemitet) PZ-33, molecular weight=425, manufactured by japan catalyst)
D5: polycarbodiimide compound (Carbodilite) V-05, molecular weight=1200, manufactured by riqing spinning chemistry
[ Metal particles (B) ]
B1: silver-coated copper powder: d (D) 50 =5.7 μm, dendritic (three well metal mining manufacturing)
B2: silver-coated copper powder: d (D) 50 =31.2 μm, dendritic (three-well metal mining manufacturing)
B3: silver-coated copper powder: d (D) 50 =10.8 μm, spherical (manufactured by Zhaohe electrical material)
B4: silver-coated copper powder: d (D) 50 =7.5 μm, spherical (manufactured by Zhaoya electrical material)
B5: silver-coated copper powder: d (D) 50 11.3 μm, sheet-like (manufactured by DOWA holders)
[ resin particles (C) ]
C1: polyurethane resin particles: d (D) 50 =3μm, recovery 91% (manufactured by TOYO CHEM)
C2: acrylic resin particles: d (D) 50 =3μm, recovery 87% (manufactured by TOYO CHEM)
And C3: acrylic resin particles: d (D) 50 =3μm, recovery 45% (manufactured by TOYO CHEM)
And C4: acrylic resin particles: d (D) 50 =3μm, recovery 38% (manufactured by TOYO CHEM)
C5: acrylic resin particles: d (D) 50 =3μm, recovery 6% (manufactured by TOYO CHEM)
C6: acrylic resin particles: d (D) 50 =3μm, recovery 3% (manufactured by TOYO CHEM)
C7: acrylic resin particles: d (D) 50 =4μm, recovery 83% (manufactured by TOYO CHEM)
And C8: acrylic resin particles: d (D) 50 =16 μm, recovery 76% (manufactured by TOYO CHEM)
C9: acrylic resin particles: d (D) 50 =1.0 μm, recovery 90% (manufactured by TOYO CHEM)
C10: acrylic resin particles: d (D) 50 =1.2 μm, recovery 88% (manufactured by TOYO CHEM)
C11: acrylic resin particles: d (D) 50 =2.7 μm, 86% recovery (manufactured by TOYO CHEM)
And C12: acrylic resin particles: d (D) 50 =3.9 μm, recovery 85% (manufactured by TOYO CHEM)
C13: polyimide resin particles: d (D) 50 =3μm, 75% recovery (manufactured by TOYO CHEM)
Comparative example silica particles (Z)
Z1：D 50 =2.6 μm (manufactured by elegant Dou Ma method (Admafine) SO-6, adema technologies (Admatechs))
Conductive composition and production of conductive sheet
Example 1
100 parts by mass of ((a-1) -5) as the resin (a-1), 212 parts by mass of (B1) as the metal particles (B), and 10.5 parts by mass of (C1) as the resin particles (C) were charged into a container, and methyl ethyl ketone as a solvent was added and mixed so that the nonvolatile content became 40% by mass. Then, 30 parts by mass of (D1) as a hardener (D) was added, and the mixture was stirred for 10 minutes by a stirrer to prepare a conductive composition solution.
Then, the prepared conductive composition solution was applied to one of the surfaces of a releasable film (material of a base material: foamed polyethylene terephthalate, thickness of a base material: 50 μm, and release agent: alkyd-based release agent) by a doctor blade (doctor blade) so that the thickness after drying became 60 μm, and the surface was subjected to release treatment, and dried by an electric oven at 100℃for 2 minutes, whereby a conductive sheet having a conductive composition formed on the releasable film was obtained.
Examples 2 to 55, comparative example 1 and comparative example 3
Conductive sheets of examples 2 to 55 and comparative examples 1 and 3 were obtained in the same manner as in example 1 except that the types and amounts of the components to be blended were as described in tables 1 to 8.
Comparative example 2
A conductive sheet of comparative example 2 was obtained in the same manner as in example 1 except that the resin particles (C) in each of the components to be blended were changed to silica particles (Z1) and the types and blending amounts of the other components were as described in table 8.
< evaluation >
The resin flow, adhesiveness, conductivity, press processability, and film thickness assurance were evaluated for each of the obtained conductive compositions (conductive sheets) in the following manner. The evaluation results are shown in tables 1 to 8. In addition, the value of X: thickness of conductive resin layer before heating and pressing/average particle diameter [ D ] of metal particles (B) 50 ]And Y: thickness of conductive resin layer before heating and pressing/average particle diameter [ D ] of resin-containing particles (C) 50 ]Also shown inIn these tables.
[ resin flow ]
The conductive sheets produced in each of examples and comparative examples were cut into pieces having a width of 40mm and a length of 100mm, and the conductive sheets were stacked on a metal plate having a width of 50mm and a length of 120mm (a metal plate having a nickel layer with a thickness of 2 μm formed on the surface of a commercially available SUS304 plate having a thickness of 0.2 mm) so that the exposed surface of the conductive composition was in contact with the metal plate. Then, a roll laminator was used at 130℃and 3kgf/cm 2 And (3) laminating the conductive sheet and the metal plate under the condition of 0.5m/min, and peeling the peelable film from the conductive composition to obtain the metal plate with the conductive composition.
Next, the metal plate (metal reinforcing plate) with the conductive composition was cut into a size of 5mm×12mm using a press working machine, and then the exposed surface of the conductive composition was thermally laminated on a polyimide film (manufactured by Toray-Dupont, kapton (Kapton) 500H) having a thickness of 125 μm at 100 ℃ to obtain a laminate. Then, heat-resistant release films (manufactured by ompartent) CR1012MT4150 μm and samsung chemical torpedo (Mitsui Chemicals Tohcello) were placed one on each of the upper and lower sides of the metal plates of the laminate, and the laminate was subjected to thermocompression bonding at 170 ℃, 2.0MPa for 5 minutes, to thereby obtain samples for evaluation ("laminate of polyimide film/conductive composition/metal plate").
Next, the evaluation sample was observed with a magnifying glass having a magnification of 200 to 1000 times, and the flow amount of the conductive composition extending from the end portion of the metal plate (the maximum movement distance of the edge portion of the conductive composition, the maximum length of the end portion of the metal plate and the end portion of the extending conductive composition) was measured, and the appearance was evaluated based on the following evaluation standard using the measured value as an index.
And (3) the following materials: is very excellent (flow of 100 μm or less)
O: excellent (flow amount of more than 100 μm and less than 200 μm)
Delta: can be practically used (the flow rate exceeds 200 μm and is 300 μm or less)
X: not practical (flow over 300 μm)
[ adhesion ]
The conductive sheets produced in each of examples and comparative examples were cut into pieces having a width of 25mm and a length of 100mm, and the conductive sheets were stacked on a metal plate having a width of 30mm and a length of 150mm (a metal plate having a nickel layer with a thickness of 2 μm formed on the surface of a commercially available SUS304 plate having a thickness of 0.2 mm) so that the exposed surface of the conductive composition was in contact with the metal plate. Then, a roll laminator was used at 130℃and 3kgf/cm 2 After roll-laminating the conductive sheet and the metal plate under conditions of 0.5m/min, the releasable film was peeled off from the conductive composition, and a copper foil (thickness: 25 μm) was laminated on the exposed surface of the conductive composition, and the laminate was laminated at 130℃and 3kgf/cm using a roll laminator 2 The conductive composition and the copper foil were roll laminated at 0.5m/min to obtain a sample for evaluation.
Then, using a tensile tester (manufactured by small bench TEST machine EZ-TEST, shimadzu corporation), the adhesion was evaluated according to the following evaluation criteria under the condition of a tensile speed of 50mm/min, using the adhesion strength of the conductive composition in the 90 DEG peel (peel) TEST to the metal plate of the sample for evaluation as an index.
And (3) the following materials: is very excellent (adhesive strength is more than 3N/cm)
O: excellent (adhesive strength of 2N/cm or more and less than 3N/cm)
Delta: can be practically used (the bonding strength is more than 1N/cm and less than 2N/cm)
X: is not practical (adhesive strength less than 1N/cm)
[ conductivity ]
The conductive sheets (20 mm in width and 20mm in length) produced in each of examples and comparative examples were stacked on a metal plate (a metal plate having a nickel layer with a thickness of 2 μm formed on the surface of a commercially available SUS304 plate with a thickness of 0.1 mm) with a surface exposed from the conductive composition in contact with the metal plate having a width of 20mm and a length of 20 mm. Then, a roll laminator was used at 90℃and 3kgf/cm 2 Under the condition of 1m/min, the conductive sheet and the conductive sheet are subjected to the following conditionsThe metal plate is roll laminated to obtain a metal plate with a conductive sheet.
Next, the peelable film of the conductive sheet in the conductive sheet-attached metal plate was peeled off and removed, and then, a square having one side of 10mm was punched out by a press working machine, thereby obtaining a conductive composition-attached metal plate (hereinafter, referred to as "conductive composition-attached metal plate"). Then, using a separately produced flexible printed wiring board, the exposed surface of the conductive composition (the surface of the conductive composition opposite to the metal plate) of the metal plate with the conductive composition was superimposed on the wiring board, and the laminate was laminated at 130℃with a roll laminator at 3kgf/cm 2 And adhering the metal plate with the conductive composition to the wiring board under the condition of 1 m/min. Then, after they were thermally press-bonded at 170℃and 2MPa for 5 minutes, they were heated at 160℃for 60 minutes using an electric furnace, whereby samples for evaluation were obtained. Further, the wiring board has copper foil circuits each having a thickness of 32 μm formed on both sides of a polyimide film having a thickness of 75 μm, and a square having one side of 0.7mm and an opening area of 0.49mm is laminated on the copper foil circuits 2 An insulating cover film (cover layer) with adhesive having a thickness of 37.5 μm is formed in the through hole (opening). Further, an insulating cover film with an adhesive thickness of 37.5 μm, which does not have a through hole, was laminated on the other copper foil circuit (the copper foil circuit and the cover film were arranged symmetrically with respect to the polyimide film so as not to warp the flexible printed wiring board).
Next, the resistance (connection resistance value) between the copper foil circuit and the metal plate of the sample for evaluation was measured using a resistance value measuring instrument and a BSP probe (model: MCP-TP05P, manufactured by mitsubishi chemical analysis technique (Mitsubishi Chemical Analytech)), and the conductivity was evaluated based on the measurement value as an index.
And (3) the following materials: good (connection resistance value is less than 20mΩ)
O: can be practically used (the connection resistance value is more than 20mΩ and less than 100mΩ)
Delta: can be practically used (the connection resistance value is more than 100mΩ and less than 500mΩ)
X: is not practical (connection resistance is more than 500mΩ)
[ stamping processability ]
The conductive sheets produced in each of examples and comparative examples were stacked on a metal plate (a metal plate having a nickel layer with a thickness of 2 μm formed on the surface of a commercially available SUS304 plate with a thickness of 0.1 mm) such that the exposed surface of the conductive composition was in contact with the metal plate. Then, a roll laminator (small-sized bench test laminator "SA-1010", manufactured by the test machine industry, the same applies hereinafter) was used at 130℃and 3kgf/cm 2 And (3) laminating the conductive sheet and the metal plate by a roller under the condition of 1m/min to obtain the metal plate with the conductive sheet.
Then, using a press working machine (model: hand press QCD, manufactured by protocol printing technology, the same applies hereinafter), the metal plate with conductive sheet was released into 50 pieces (pieces) in a size of 5mm×12mm with a gap of 2.5 μm, thereby obtaining a sample for evaluation.
Next, using a magnifying glass having a magnification of 200 to 1000 times, the press workability was evaluated based on the following evaluation criteria, using the defective rate (mixing rate of defective products) of the evaluation sample as an index. The defective product means a defective product which is processed into a mold-released shape, and has at least one of a state where a part of the metal plate is not peeled off from the conductive composition, and a state where an end portion of the conductive composition after pressing is deformed.
And (3) the following materials: is very excellent (reject ratio is less than 10%)
O: excellent (reject ratio is 10% or more and less than 15%)
Delta: can be practically used (the reject ratio is more than 15% and less than 25%)
X: is not practical (reject ratio is more than 25 percent)
[ film thickness Security ]
The conductive sheet produced in each of examples and comparative examples was cut into a sheet having a width of 40mm and a length of 100mm, and the conductive sheet was brought into contact with a metal plate having a width of 50mm and a length of 120mm (a metal plate having a nickel layer with a thickness of 2 μm formed on the surface of a commercially available SUS304 plate having a thickness of 0.2 mm) so that the surface exposed by the conductive composition was in contact with the metal plate The electrical sheet is overlapped on the metal plate. Then, a roll laminator was used at 130℃and 3kgf/cm 2 After roll-laminating the conductive sheet and the metal plate under the condition of 0.5m/min, the releasable film was peeled off from the conductive composition to obtain a metal plate (metal reinforcing plate) with the conductive composition.
Next, the metal plate (metal reinforcing plate) with the conductive composition was cut into a size of 5mm×12mm using a press working machine, and then the exposed surface of the conductive composition was thermally laminated on a polyimide film (manufactured by Toray-Dupont, kapton (Kapton) 500H) having a thickness of 125 μm at 100 ℃ to obtain a laminate. Then, heat-resistant release films (manufactured by ompartent) CR1012MT4150 μm and samsung chemical torpedo (Mitsui Chemicals Tohcello) were placed one on each of the upper and lower sides of the metal plates of the laminate, and the laminate was subjected to thermocompression bonding at 170 ℃, 2.0MPa for 5 minutes, to thereby obtain samples for evaluation ("laminate of polyimide film/conductive composition/metal plate").
Next, the sample for evaluation was cut near the center of the long side, the vicinity of the cross section was cut by a cross section polisher (cross section polisher), and the cross section after the processing was observed by a scanning electron microscope (Scanning Electron Microscope, SEM), and the thickness (H1) of the conductive composition was measured. The thickness of the conductive composition in the conductive sheet before the metal plate was H2, and Δh=h1/H2 was obtained for each of the examples and comparative examples, and was evaluated according to the following evaluation criteria.
And (3) the following materials: is very excellent (delta H is more than 0.6)
O: excellent (delta H is more than 0.5 and less than 0.6)
Delta: can be practically used (delta H is more than 0.4 and less than 0.5)
X: not practical (DeltaH less than 0.4)
TABLE 1
TABLE 8
Claims (15)
1. A sheet-like conductive composition comprising: binder (A), metal particles (B), and resin particles (C),
the recovery rate of the resin particles (C) is 5% to 95%,
comprising 40 to 90 mass% of the metal particles (B).
2. The sheet-like conductive composition according to claim 1, wherein the binder (a) contains at least one selected from the group consisting of an imide bond, an amide bond, a urethane bond, and a urea bond.
3. The sheet-like conductive composition according to claim 1 or 2, wherein the binder (a) contains at least one selected from the group consisting of an epoxy group, an oxetanyl group, an alkylthio group, and an aziridine group.
4. The sheet-like conductive composition according to any one of claims 1 to 3, comprising 0.1 to 35 mass% of the resin particles (C).
5. The sheet-like conductive composition according to any one of claims 1 to 4, wherein the resin particles (C) have an average particle diameter D 50 Is 1-15 μm.
6. The sheet-like conductive composition according to any one of claims 1 to 5, wherein the thickness is 5 μm to 200 μm.
7. The sheet-like conductive composition according to any one of claims 1 to 6, wherein the recovery rate of the resin particles (C) is 30% or more and 95% or less.
8. The sheet-like conductive composition according to any one of claims 1 to 7, wherein the resin particles (C) have an average particle diameter D 50 Is 1 μm or more and less than 4 μm.
9. The sheet-like conductive composition according to any one of claims 1 to 8, wherein a thickness of the sheet-like conductive composition is divided by an average particle diameter D of the metal particles (B) 50 The value X obtained is 1 to 35.
10. The sheet-like conductive composition according to any one of claims 1 to 9, wherein a thickness of the sheet-like conductive composition is divided by an average particle diameter D of the resin particles (C) 50 The value Y obtained is 70 or less.
11. The sheet-like conductive composition according to any one of claims 1 to 10, wherein the binder (a) contains 1 to 70 parts by mass of the hardener (D) per 100 parts by mass of the thermosetting resin (a-2).
12. A conductive sheet comprising the sheet-like conductive composition according to any one of claims 1 to 11, and a releasable film.
13. A metal reinforcing plate comprising the sheet-like conductive composition according to any one of claims 1 to 11, and a metal plate.
14. A wiring board with a metal reinforcing plate comprising the metal reinforcing plate according to claim 13.
15. An electronic device comprising the wiring board with metal reinforcing plate according to claim 14.
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| JP2022053710A JP7226621B1 (en) | 2022-03-29 | 2022-03-29 | Conductive composition, conductive sheet, metal reinforcing plate, wiring board with metal reinforcing plate, and electronic device |
| JP2022-053710 | 2022-03-29 |
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| CN116285233A true CN116285233A (en) | 2023-06-23 |
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| JP (2) | JP7226621B1 (en) |
| KR (1) | KR102611197B1 (en) |
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| CN108281761B (en) * | 2018-01-08 | 2021-06-18 | 国御望泓(山东)科技有限公司 | Carbon/metal conductive composite material and application thereof |
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- 2023-01-17 JP JP2023004881A patent/JP2023147186A/en active Pending
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| TWI827494B (en) | 2023-12-21 |
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Country or region after: Japan Address after: Japan Tokyo central Beijing two chome 2 No. 1 Applicant after: Aitiansi Co.,Ltd. Applicant after: TOYOCHEM Co.,Ltd. Address before: Japan Tokyo central Beijing two chome 2 No. 1 Applicant before: TOYO INK SC HOLDINGS Co.,Ltd. Country or region before: Japan Applicant before: TOYOCHEM Co.,Ltd. |