WO2022054774A1 - 導電性ペースト及び導電膜 - Google Patents
導電性ペースト及び導電膜 Download PDFInfo
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- WO2022054774A1 WO2022054774A1 PCT/JP2021/032755 JP2021032755W WO2022054774A1 WO 2022054774 A1 WO2022054774 A1 WO 2022054774A1 JP 2021032755 W JP2021032755 W JP 2021032755W WO 2022054774 A1 WO2022054774 A1 WO 2022054774A1
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/205—Compounds containing groups, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L97/00—Compositions of lignin-containing materials
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Definitions
- the present disclosure relates to a conductive paste and a conductive film, and more particularly, to at least one of tannic acid and a tannic acid derivative (A), copper powder (B), a thermosetting resin (C), and a solvent (D).
- the present invention relates to a conductive paste containing the above, and a conductive film containing a cured product of the conductive paste.
- a technique for forming wiring by printing a conductive paste on various substrates is used.
- the conventional conductive paste mainly silver paste and copper paste are known.
- Silver paste has good conductivity, but it is expensive, migration is likely to occur under high humidity, and short circuits caused by it are a problem. Therefore, it is considered to use a copper paste instead of the silver paste, but the copper paste is more easily oxidized than the silver paste, so that the resistivity value tends to increase with time and the conductivity tends to decrease. There was a problem.
- Patent Document 1 by pre-treating metal fine particles with an aqueous surface treatment agent containing an organic acid, an oxide film formed on the surface of easily oxidizable metal particles is effectively removed, and further treated copper powder.
- Patent Document 2 describes the oxidation of copper powder by adding an organic carboxylic acid compound to a conductive copper paste containing copper powder to donate protons to the oxide film on the surface of the copper powder and elution. A method of suppressing the above is disclosed.
- the method of treating the copper powder with an organic acid has been found to have the effect of removing the copper oxide film already existing in the copper powder used as a raw material, and is effective in terms of exhibiting initial conductivity, but it does not oxidize over time. Not enough to suppress. Moreover, the method of adding the organic carboxylic acid compound is not sufficient to suppress the oxidation of the copper powder. Therefore, there is a demand for a material that exhibits more effective reducing power to copper powder, and it is possible to develop the original conductivity of copper at an early stage, and further maintain the conductivity for a long period of time to improve the reliability of the product. It is required to be able to secure it.
- An object of the present disclosure is to provide a conductive paste and a conductive film which are excellent in initial conductivity and can maintain this excellent conductivity for a long period of time.
- the conductive paste according to one aspect of the present disclosure contains at least one (A) of tannic acid and a tannic acid derivative, copper powder (B), a thermosetting resin (C), and a solvent (D). ..
- the conductive film according to one aspect of the present disclosure includes a cured product of the conductive paste.
- the conductive paste of the present embodiment (hereinafter, also referred to as conductive paste (X)) includes at least one (A) of tannic acid and a tannic acid derivative (hereinafter, also referred to as component (A)) and copper powder (B). And a thermosetting resin (C) and a solvent (D).
- the conductive paste (X) can be suitably used for thermosetting to form a conductive film.
- the present inventors have excellent initial conductivity and can maintain excellent conductivity for a long period of time. I found that. That is, the conductive paste (X) can realize an initial low resistivity value and can suppress oxidation over time as evaluated by a wet heat test or the like, and as a result, is conductive over a long period of time. Can be maintained. The reason is not always clear, but for example, tannic acid and tannic acid derivatives can enhance the dispersibility of the copper powder (B) in the conductive paste (X), and due to its reducing property, the copper powder (B).
- the component (A) is considered to exert a high reducing power when the thermosetting resin (C) is heat-cured, and the conductive paste (X) can exhibit a high initial conductivity, in addition. It is considered that the high conductivity of the lever can be maintained for a long period of time due to the reducing power of the component (A). As described above, the conductive paste (X) has excellent initial conductivity, and this excellent conductivity can be maintained for a long period of time.
- the component (A) is at least one of tannic acid and a tannic acid derivative.
- Tannic acid includes both tannic acid in the broad sense and m-galloyl gallic acid, which is the tannic acid in the narrow sense. Tannic acid in a broad sense is a general term for aromatic compounds having a large number of phenolic hydroxyl groups.
- condensed tannin which is a derivative of flavanol, or water obtained by ester-bonding one or more gallic acid and a sugar (usually glucose). Degradable tannins and the like can be mentioned.
- the number of phenolic hydroxyl groups in one molecule of tannic acid is usually 3 or more and 100 or less, preferably 10 or more and 50 or less, and more preferably 20 or more and 30 or less.
- the molecular weight of tannic acid is usually 300 or more and 15,000 or less, preferably 500 or more and 5000 or less, and more preferably 1000 or more and 2500 or less.
- tannic acid derivative refers to, for example, a tannic acid in which some or all of the hydrogen atoms in the phenolic hydroxyl group are substituted with a substituent (hereinafter, also referred to as a substituent (S)).
- the tannic acid derivative is a hydrophobic version of tannic acid.
- the component (A) preferably contains a tannic acid derivative.
- a tannic acid derivative obtained by hydrophobizing tannic acid as the component (A), the conductive paste (X) has a greater effect of suppressing oxidation over time, and in particular, a moisture and heat resistivity test (for example, 85 ° C.). , 85% RH, 100 Hr, etc.), the increase in resistivity value can be further suppressed.
- the tannic acid derivative preferably contains a tannic acid derivative in which a urethane bond is formed by reacting a part or all of the phenolic hydroxyl groups of tannic acid with a compound having an isocyanate.
- the tannic acid derivative is one in which a part or all of the phenolic hydroxyl groups of tannic acid form an —Si—O— bond by reaction with a silane coupling agent.
- substituent (S) examples include an alkyl group such as a methyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and a hydrocarbon group such as an aralkyl group such as a benzyl group; the hydrogen atom of this hydrocarbon group.
- R' is carbon.
- Organic group means a group containing at least one carbon atom.
- the substituent (S) preferably contains a group having a polymerizable group.
- the curing shrinkage of the conductive paste (X) at the time of heat curing can be further increased, and as a result, the conductivity can be further improved.
- the polymerizable group include (meth) acryloyl group, vinyl group, epoxy group, glycidyl group, amino group, mercapto group and the like.
- -CONHR as the substituent (S) is formed by reacting tannic acid with a compound having an isocyanate group.
- the organic group represented by R include a monovalent hydrocarbon group such as a substituted or unsubstituted butyl group, a group containing a polymerizable group such as a (meth) acryloyl group, a vinyl group and a glycidyl group, and the like. ..
- R By using R as a group containing a polymerizable group, the curing shrinkage of the conductive paste (X) during thermal curing can be further increased, and the conductivity can be further improved.
- R "as the substituent (S) is formed by reacting tannic acid with a silane coupling agent.
- the hydrocarbon group represented by R' are a methyl group and the like. Examples thereof include an alkyl group such as an ethyl group.
- the organic group represented by R ” include a substituted or unsubstituted monovalent hydrocarbon group, a glycidyl group, an epoxy group, a (meth) acryloyl group and a vinyl group.
- Examples thereof include a group containing a polymerizable group such as an amino group and a mercapto group.
- the substitution rate in the tannic acid derivative (the ratio of the number of substituents (S) in one molecule of the tannic acid derivative to the number of phenolic hydroxyl groups in one molecule of tannic acid before substitution) is preferably 10% or more. In this case, the moisture and heat resistance of the conductive paste (X) can be improved more effectively.
- the substitution rate is more preferably 15% or more, further preferably 20% or more, and particularly preferably 30% or more.
- the substitution rate in the tannic acid derivative is preferably 65% or less. In this case, the oxidation suppressing effect of the conductive paste (X) can be further enhanced.
- the substitution rate is more preferably 60% or less, further preferably 55% or less, and particularly preferably 50% or less.
- the ratio of the component (A) is preferably 0.05 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the copper powder (B). In this case, the conductivity of the conductive paste (X) and its continuity can be further improved.
- the ratio of the component (A) is more preferably 0.1 parts by mass or more and 3.0 parts by mass or less, and 0.4 parts by mass or more and 2.0 parts by mass or less, with respect to 100 parts by mass of the copper powder (B). It is more preferably 0.5 parts by mass or more, and particularly preferably 1.2 parts by mass or less.
- the ratio of the component (A) is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less with respect to the conductive paste (X). , 0.1% by mass or more and 3% by mass or less is more preferable, and 0.4% by mass or more and 1.5% by mass or less is particularly preferable.
- the copper powder (B) is a metal particle containing copper as a main component, and copper is exposed on the surface of the particle.
- Examples of the shape of the copper powder (B) include a spherical shape, a flat shape (scale shape), a dendritic shape, an amorphous shape, and the like.
- the copper powder (B) may be a combination of two or more of these shapes.
- the excellent conductivity and oxidation resistance of the conductive paste (X) are due to the excellent reducing power of the component (A) to copper, and the shape and particle size of the copper powder (B) are not particularly limited.
- the average particle size of the copper powder (B) is preferably 0.1 ⁇ m or more and 30 ⁇ m or less, more preferably 0.5 ⁇ m or more and 20 ⁇ m or less, and 1 ⁇ m or more and 10 ⁇ m or less from the viewpoint of printability. More preferred.
- the average particle size is the median size, and indicates the particle size in the cumulative distribution of 50% by volume by measuring the particle size distribution (volume basis) of the copper powder (B).
- the ratio of the copper powder (B) is preferably 50% by mass or more and 99% by mass or less, more preferably 60% by mass or more and 98% by mass or less, and 70% by mass with respect to the conductive paste (X). It is more preferably% or more and 95% by mass or less, and particularly preferably 80% by mass or more and 90% by mass or less.
- the conductive paste (X) contains a thermosetting resin (C). Thereby, the conductive paste (X) can be cured by heating to form a conductive film.
- thermosetting resin (C) examples include amino resins, urethane resins, unsaturated polyester resins, epoxy resins, cyanate resins, acrylic resins; phenol resins such as novolak type phenol resins and resol type phenol resins.
- the thermosetting resin (C) does not contain tannic acid and tannic acid derivatives.
- thermosetting resin (C) preferably contains a resin having a phenolic hydroxyl group.
- the curing shrinkage of the thermosetting resin (C) due to heat curing can be further increased, and as a result, the conductivity of the conductive paste (X) can be further improved.
- the thermosetting resin (C) having a phenolic hydroxyl group include a phenol resin and the like.
- the ratio of the thermosetting resin (C) is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 20% by mass or less with respect to the conductive paste (X). It is more preferably 5% by mass or more and 15% by mass or less.
- the conductive paste (X) may contain, for example, a curing agent, a curing accelerator, or the like in order to accelerate the curing of the thermosetting resin (C).
- any material capable of curing the thermosetting resin (C) can be used.
- novolak resin latent amine-based curing such as dicyandiamide, imidazole, BF3 -amine complex, and guanidine derivative.
- Agents such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone; Curing agents containing nitrogen atoms such as cyclophosphazene oligomers; Polyamide resin, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, anhydrous Examples thereof include acid anhydride-based curing agents such as pyromellitic acid.
- the ratio of the curing agent is usually 0.1% by mass or more and 10% by mass or less, and preferably 0.5% by mass or more and 5% by mass or less with respect to the thermosetting resin (C).
- the curing accelerator examples include tertiary amines such as benzyldimethylamine, imidazole, organic acid metal salts, Lewis acid, amine complex salts and the like.
- the ratio of the curing accelerator is usually 0.01% by mass or more and 10% by mass or less, and preferably 0.1% by mass or more and 5% by mass or less with respect to the thermosetting resin (C).
- the conductive paste (X) contains a solvent (D).
- solvent (D) As a result, the viscosity of the conductive paste (X) can be adjusted more appropriately, and it can be suitably used for screen printing and the like.
- Examples of the solvent (D) include diols such as ethylene glycol, propylene glycol and dipropylene glycol, polyhydric alcohols such as triol such as glycerin; sugar alcohols; lower alcohols such as ethanol, methanol, butanol, propanol and isopropanol.
- diols such as ethylene glycol, propylene glycol and dipropylene glycol
- polyhydric alcohols such as triol such as glycerin
- sugar alcohols lower alcohols such as ethanol, methanol, butanol, propanol and isopropanol.
- Ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol mono-iso-propyl ether (iso-propyl cellosolve), ethylene glycol mono-n- Cellosolves such as butyl ether (n-butyl cellosolve), ethylene glycol mono-t-butyl ether (t-butyl cellosolve); diethylene glycol monomethyl ether (methylcarbitol), diethylene glycol monoethyl ether (ethylcarbitol), diethylene glycol mono-n-propyl ether (N-propyl carbitol), diethylene glycol mono-iso-propyl ether (iso-propyl carbitol), ethylene glycol mono-n-butyl ether (n-butyl carbitol), diethylene glycol mono-t-butyl
- the solvent (D) preferably contains a solvent having an alcoholic hydroxyl group.
- the solvent (D) can dissolve the component (A) satisfactorily, and as a result, the oxidation suppressing effect of the component (A) can be further improved. Further, since the solvent (D) having an alcoholic hydroxyl group exhibits reducing property at the time of heat curing, the oxidation suppressing effect of the component (A) can be further improved.
- the solvent (D) preferably contains at least one selected from the group consisting of lower alcohols and glycol ethers from the viewpoint of solubility of tannin acid, printability, etc., and is composed of methanol, ethanol and ethyl carbitol. It is more preferable to include at least one selected from the group.
- the ratio of the solvent (D) is preferably 0.1% by mass or more and 10% by mass or less with respect to the conductive paste (X) from the viewpoint of adjusting the viscosity of the conductive paste (X) more appropriately. It is more preferably 1% by mass or more and 8% by mass or less, and further preferably 3% by mass or more and 7% by mass or less.
- the boric acid includes not only orthoboric acid (H 3 BO 3 ) but also metaboric acid, tetraboric acid and the like which are condensates thereof.
- the conductive paste (X) preferably contains boric acid. This makes it possible to further reduce the specific resistance value of the conductive paste (X). Further, when the thermosetting resin (C) has a hydroxyl group, the hydroxyl group and boric acid form a hydrogen bond, so that further lower resistivity can be realized. Further, since boric acid also forms a hydrogen bond with the phenolic hydroxyl group of the component (A), a network of thermosetting resin (C) -boric acid-tannic acid is formed, so that even better conductivity is obtained. It can be realized.
- the ratio of boric acid is preferably 1.0% by mass or more and 40% by mass or less with respect to the total of the component (A) and the thermosetting resin (C) (including the curing agent and the curing accelerator). It is more preferably 2% by mass or more and 20% by mass or less.
- the proportion of boric acid is preferably 0.1% by mass or more and 4% by mass or less, and more preferably 0.2% by mass or more and 2% by mass or less with respect to the conductive paste (X).
- the conductive paste (X) contains other components such as a rust inhibitor, an antioxidant, an adhesion-imparting agent, a dispersant, a chelating agent, a leveling agent, a thixo-adjusting agent, and an antifoaming agent. good.
- the ratio of other components is, for example, 2% by mass or less with respect to the conductive paste (X).
- the viscosity of the conductive paste (X) at 25 ° C. is preferably 5.0 Pa ⁇ s or more and 200 Pa ⁇ s or less. In this case, the conductive paste (X) is easy to print, does not impair the workability of screen printing, and easily forms wiring having a good pattern.
- the ticko ratio (Ti value) of the conductive paste (X) is preferably 1.0 or more and 3.0 or less. In this case, the conductive paste (X) does not impair the workability of screen printing, and wiring having a good pattern is likely to be formed.
- the conductive film of the present embodiment includes the cured product of the above-mentioned conductive paste (X). Since the conductive film of the present embodiment is formed from the conductive paste (X), it is excellent in initial conductivity and can maintain excellent conductivity for a long period of time. Further, when the conductive paste (X) contains boric acid and the tannic acid derivative has a urethane bond, the conductive film is also excellent in bending resistance.
- the conductive film of the present embodiment is formed by applying it on a substrate such as a glass plate or a PET film by, for example, a screen printing method, and then heating and curing the conductive film.
- the heating temperature and the heating time are appropriately selected according to the type of the thermosetting resin (C) and the like, but the heating temperature is usually 100 ° C. or higher and 250 ° C. or lower, and 130 ° C. or higher and 200 ° C. or lower. preferable.
- the heating time is usually 1 minute or more and 5 hours or less, and preferably 10 minutes or more and 1 hour or less.
- the shape of the conductive film is not particularly limited, and examples thereof include a plane line-of-sight shape such as a circuit pattern or a band shape, and a plane line-of-sight shape such as a circle or a quadrangle.
- the thickness of the conductive film is, for example, 1 ⁇ m or more and 1 mm or less, preferably 5 ⁇ m or more and 100 ⁇ m or less, and more preferably 10 ⁇ m or more and 50 ⁇ m or less.
- Tannic acid manufactured by Fuji Chemical Industry Co., Ltd., trade name: "tannic acid”
- the total number of hydroxyl groups in one molecule of tannic acid is in a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirrer. 100 g (25 pieces) and 100 g of methyl ethyl ketone were added, mixed and dissolved.
- ethyl isocyanate compound manufactured by Showa Denko KK, trade name "Karenzu AOI" as an isocyanate compound was mixed with the obtained solution, and the mixture was reacted at 60 ° C. for 5 hours. Methyl ethyl ketone was evaporated and dried from the obtained solution to obtain a tannic acid derivative (1).
- 141 g of the isocyanate compound is reacted to obtain the tannic acid derivative (2), 24 g of the isocyanate compound is reacted to obtain the tannic acid derivative (3), and 160 g of the isocyanate compound is reacted to obtain the tannic acid derivative (4).
- the obtained product was reacted with 65 g of butyl isocyanate as an isocyanate compound to obtain a tannic acid derivative (5), which was a silane coupling agent (manufactured by Toray Dow Co., Ltd., trade name "Xiameter OFS-6040 Silane", glycidoxypropyltrimethoxy. 36 g of silane) was reacted to obtain a tannic acid derivative (6).
- the weight average molecular weight of the obtained tannic acid derivative was measured by the GPC measurement method shown below.
- the weight average molecular weight was determined by the GPC method in terms of standard polystyrene. The measurement conditions are shown below.
- Table 1 below also shows the weight average molecular weight of the synthesized tannic acid derivative and tannic acid, and the substitution rate of the hydrogen atom of the phenolic hydroxyl group in the tannic acid derivative.
- Example 1 Contains 0.40 g of tannic acid derivative (1), 4.6 g of epoxy resin (EPICLON EXA4816 manufactured by DIC), 0.02 g of curing accelerator (Curesol 2PHZ-PW manufactured by Shikoku Kasei Co., Ltd.), and 0.5 g of boric acid. Then, it was dissolved in 3.0 g of the solvent ethyl carbitol. 48.0 g of copper particles (manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd., trade name "Cu-HWF-4") were mixed with the obtained resin solution, mixed with a hybrid mixer, and then kneaded with a roll mill to conductivity. Sex paste 1 (DP-1) was obtained.
- Example 2 Conductive paste 2 (DP-2) was obtained in the same manner as in Example 1 except that boric acid was not added.
- Example 3 A conductive paste 3 (DP-3) was obtained in the same manner as in Example 1 except that tannic acid was used instead of the tannic acid derivative (1).
- Example 4 A conductive paste 4 (DP-4) was obtained in the same manner as in Example 1 except that the tannic acid derivative (6) was used.
- Example 5 Example 2 except that a resole-type phenol resin (manufactured by Meiwa Kasei Co., Ltd., trade name: "MWF-2620", solid content 70% by mass) was used as the thermosetting resin instead of the epoxy resin and the curing accelerator.
- the conductive paste 5 (DP-5) was obtained in the same manner as above.
- Example 6 A conductive paste 6 (DP-6) was obtained in the same manner as in Example 1 except that the tannic acid derivative (2) was used.
- Example 7 A conductive paste 7 (DP-7) was obtained in the same manner as in Example 1 except that the solvent was replaced with ethyl carbitol acetate.
- Example 8 A conductive paste 8 (DP-8) was obtained in the same manner as in Example 1 except that the tannic acid derivative (3) was used.
- Example 9 A conductive paste 9 (DP-9) was obtained in the same manner as in Example 1 except that the tannic acid derivative (4) was used.
- Example 10 A conductive paste 10 (DP-10) was obtained in the same manner as in Example 1 except that the tannic acid derivative (5) was used.
- the dispersibility of the copper powder was evaluated according to the following criteria.
- Table 2 below also shows the measured values and Ti values of the paste viscosity (Pa ⁇ s) (5 rpm, 0.5 rpm) and the evaluation results of the dispersibility of the copper powder.
- conductive pastes 1 to 11 (DP-1 to DP-11) were each applied on a PET film by a screen printing method in a strip-shaped wiring shape having a width of 1 mm, a length of 50 mm, and a thickness of 20 ⁇ m. Then, it was heated at 150 ° C. for 30 minutes and cured to obtain substrates 1 to 11 with a conductive film having conductive films 1 to 11 (DM-1 to 11).
- Durability test Durability tests were conducted on the conductive films 1 to 11 in a high temperature and high humidity environment. That is, the substrate with the conductive films 1 to 11 (DM-1 to DM-11) was held in a bath at 85 ° C. and 85% RH at a high temperature and high humidity for 100 hours, and then the conductive films 1 to 11 (DM- The resistivity values of 1 to DM-11) were measured, and the resistivity values were calculated after the durability test.
- Bending resistance evaluation The obtained conductive films 1 to 11 (DM-1 to DM-11) were wound around a 2 mm ⁇ iron core using a bending tester, bent, and then unbent, and then the specific resistance value was measured. Bending resistance was evaluated according to the following criteria. S: The rate of increase in the resistivity value before and after bending is 20% or less. A: The rate of increase in resistivity before and after bending is more than 20% and 40% or less. B: The rate of increase in the resistivity value before and after bending is more than 40% and 100% or less. C: The rate of increase in the specific resistance value before and after bending is more than 100%.
- Table 3 shows the resistance value ( ⁇ ) of the conductive film, the film thickness ( ⁇ m) of the conductive film, the specific resistance value (volume resistivity) ( ⁇ ⁇ cm) calculated from the resistance value and the film thickness, and after the durability test.
- the formed conductive film has excellent initial conductivity and can maintain excellent conductivity for a long period of time.
- the conductive pastes of Examples 1 to 5 have excellent dispersibility of copper powder, and in Examples 1, 3, 4 and 5, they have a low resistivity value of about 100 ⁇ ⁇ cm and are particularly excellent.
- a conductive film can be obtained.
- Examples 1, 2, 4, 5, 6, 7, 8 and 10 using the tannic acid derivative having a substitution rate of 10 to 65% a conductive film having excellent durability can be obtained.
- the conductive paste of Comparative Example 1 has poor dispersibility of copper powder, has a high resistivity value of the conductive film from the beginning, is considered to be oxidized in the process of preparing the conductive paste, and also has a resistivity value in a moisture resistance test. Is rising.
- the conductive films of Examples 1, 6, 7, 9 and 10 formed from the conductive paste in which the tannic acid derivative having a urethane bond and boric acid are combined are bending resistant. Good sex.
- the conductive paste of Example 9 using a tannic acid derivative in which the substitution rate of hydrogen atoms of the phenolic hydroxyl group exceeds a certain value the initial resistivity value increases, the dispersibility of the copper powder decreases, and after the durability test. Since the rate of increase in the resistivity value of tannic acid is high, it is considered that the effect of the tannic acid derivative is reduced. Since the conductive paste of Example 7 does not use a solvent having a hydroxyl group, it is considered that the rust preventive effect of the tannic acid derivative at the time of preparing the paste is reduced.
- the conductive paste of the first aspect according to the present disclosure comprises at least one of tannic acid and a tannic acid derivative (A), copper powder (B), and a thermosetting resin (C). , And the solvent (D).
- the conductive paste has excellent initial conductivity, and this excellent conductivity can be maintained for a long period of time.
- the component (A) contains a tannin acid derivative
- the tannin acid derivative is a substituent in which a hydrogen atom in a part of the phenolic hydroxyl group of tannin acid is a substituent. It is substituted, and the substitution rate is 10% or more and 65% or less.
- the effect of suppressing oxidation of the conductive paste over time can be further enhanced, and in particular, in the moisture resistance test, the increase in resistivity can be further suppressed, and the moisture resistance can be improved. It can be improved more effectively.
- the conductive paste of the third aspect is a compound in which the component (A) contains a tannic acid derivative, and the tannic acid derivative has a part or all of the phenolic hydroxyl group of tannic acid having an isocyanate group. A urethane bond was formed by the reaction with.
- the effect of suppressing oxidation with time becomes greater, and in particular, in a moisture resistance test, an increase in resistivity can be further suppressed, and a urethane bond is formed on the tannic acid derivative.
- the flexibility of the conductive film formed from the conductive paste becomes higher, so that it is expected to be applied to a flexible base material such as a film base material.
- the conductive paste of the fourth aspect further contains boric acid in any one of the first to third aspects.
- thermosetting resin (C) has a hydroxyl group
- the hydroxyl group and boric acid form a hydrogen bond, so that further lower resistivity can be realized.
- boric acid also forms a hydrogen bond with the phenolic hydroxyl group of the component (A)
- a network of thermosetting resin (C) -boric acid-tannic acid is formed, so that even better conductivity is obtained. It can be realized.
- the solvent (D) has an alcoholic hydroxyl group in any one of the first to the fourth aspects.
- the solvent (D) can satisfactorily dissolve the component (A), the oxidation inhibitory effect of the component (A) can be further improved. Further, since the solvent (D) having an alcoholic hydroxyl group exhibits reducing property at the time of heat curing, the oxidation suppressing effect of the component (A) can be further improved.
- thermosetting resin (C) has a phenolic hydroxyl group in any one of the first to fifth aspects.
- the curing shrinkage of the thermosetting resin (C) due to heat curing can be further increased, and as a result, the conductivity of the conductive paste can be further improved.
- the conductive film of the seventh aspect includes a cured product of the conductive paste of any one of the first to sixth aspects.
- the conductive film has excellent initial conductivity and can maintain excellent conductivity for a long period of time.
- the initial conductivity is excellent, the moisture resistance is excellent, and a long period of time is obtained by thermal curing without the need to use special equipment that requires an inert gas or the like. It is possible to form a conductive film that can maintain this excellent conductivity.
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Abstract
Description
本実施形態の導電性ペースト(以下、導電性ペースト(X)ともいう)は、タンニン酸及びタンニン酸誘導体の少なくとも一方(A)(以下、成分(A)ともいう)と、銅粉(B)と、熱硬化性樹脂(C)と、溶剤(D)とを含有する。導電性ペースト(X)は、熱硬化して導電膜を形成するために好適に用いることができる。
成分(A)は、タンニン酸及びタンニン酸誘導体の少なくとも一方である。「タンニン酸」とは、広義のタンニン酸と、狭義のタンニン酸であるm-ガロイル没食子酸の両方を含む。広義のタンニン酸とは、多数のフェノール性水酸基を有する芳香族化合物の総称であり、例えばフラバノールの誘導体である縮合型タンニンや、1個以上の没食子酸と糖(通常グルコース)がエステル結合した加水分解型タンニンなどが挙げられる。タンニン酸1分子中のフェノール性水酸基の数は、通常3以上100以下であり、10以上50以下であることが好ましく、20以上30以下であることがより好ましい。タンニン酸の分子量は、通常300以上15000以下であり、500以上5000以下であることが好ましく、1000以上2500以下であることがより好ましい。
銅粉(B)は、銅を主成分とする金属粒子であり、粒子表面に銅が露出しているものである。
導電性ペースト(X)は、熱硬化性樹脂(C)を含有する。これにより、加熱により、導電性ペースト(X)を硬化させ、導電膜を形成することができる。
導電性ペースト(X)は、溶剤(D)を含有する。これにより、導電性ペースト(X)は、粘度をより適度に調整することができ、スクリーン印刷等に好適に用いることができる。
ホウ酸としては、オルトホウ酸(H3BO3)以外にも、この縮合物であるメタホウ酸、四ホウ酸等も含まれる。導電性ペースト(X)は、ホウ酸を含有することが好ましい。これにより、導電性ペースト(X)のさらなる低比抵抗値化を実現できる。また、熱硬化性樹脂(C)が水酸基を有する場合、その水酸基とホウ酸とが水素結合を形成することにより、さらなる低比抵抗値化を実現することができる。また、ホウ酸は、成分(A)のフェノール性水酸基とも水素結合を形成するため、熱硬化性樹脂(C)-ホウ酸-タンニン酸のネットワークが形成されることにより、さらに良好な導電性を実現することができる。
導電性ペースト(X)は、その他の成分として、例えば防錆剤、酸化防止剤、密着性付与剤、分散剤、キレート剤、レベリング剤、チクソ調整剤、消泡剤などを含有していてもよい。その他の成分の割合は、導電性ペースト(X)に対して、例えば2質量%以下である。
導電性ペースト(X)の25℃における粘度は、5.0Pa・s以上200Pa・s以下であることが好ましい。この場合、導電性ペースト(X)は、印刷しやすく、スクリーン印刷の作業性を損なうことがなく、また、良好なパターンを有する配線が形成されやすい。導電性ペースト(X)のチクソ比(Ti値)は、1.0以上3.0以下であることが好ましい。この場合、導電性ペースト(X)は、スクリーン印刷の作業性を損なうことがなく、また、良好なパターンを有する配線が形成されやすい。チクソ比は、25℃、0.5rpmでの粘度と、25℃、5rpmでの粘度との比率で表される(チクソ比=(25℃、0.5rpmでの粘度)/(25℃、5rpmでの粘度))。
本実施形態の導電膜は、前述の導電性ペースト(X)の硬化物を含む。本実施形態の導電膜は、導電性ペースト(X)から形成されるので、初期の導電性に優れ、かつ優れた導電性を長期にわたって維持することができる。また、導電性ペースト(X)がホウ酸を含有し、かつタンニン酸誘導体がウレタン結合を有する場合、導電膜は、耐折り曲げ性にも優れている。
還流冷却器、温度計、窒素導入管、及び撹拌機を取り付けた四ツ口フラスコに、タンニン酸(富士化学工業社製、商品名:「タンニン酸」、タンニン酸1分子中の水酸基の総数は25個である)100g、及びメチルエチルケトン100gを入れて混合し溶解させた。得られた溶液にイソシアネート化合物としてのアクリル酸イソシアネートエチル(昭和電工社製、商品名「カレンズAOI」)82gを混合し、60℃で5時間反応させた。得られた溶液からメチルエチルケトンを蒸発、乾燥させ、タンニン酸誘導体(1)を得た。
重量平均分子量は、GPC法により標準ポリスチレン換算で求めた。測定条件を以下に示す。
・装置:島津製作所社製、「Prominence LC-20AD」
・カラム:昭和電工社製、「GPC KF-801,GPC KF-803,GPC KF-805」計3本
・ガードカラム:昭和電工社製、「GPC-KF-G 4A」
・サンプル濃度:タンニン酸又はタンニン酸誘導体の濃度が0.5質量%になるようにテトラヒドロフランで希釈した。
・移動相溶媒:テトラヒドロフラン
・流量:1.0mL/分
・カラム温度:40℃
(実施例1)
タンニン酸誘導体(1)0.40g、エポキシ樹脂(DIC社製、EPICLON EXA4816)4.6g、硬化促進剤(四国化成社製、キュアゾール2PHZ-PW)0.02g、及びホウ酸0.5gを配合して、溶剤エチルカルビトール3.0gに溶解させた。得られた樹脂溶液に、銅粒子(福田金属箔粉工業社製、商品名「Cu-HWF-4」)48.0gを配合し、ハイブリッドミキサーで混合した後、ロールミルにより混錬を行い、導電性ペースト1(DP-1)を得た。
ホウ酸を配合しないこと以外は、実施例1と同様にして導電性ペースト2(DP-2)を得た。
タンニン酸誘導体(1)の代わりに、タンニン酸を用いた以外は、実施例1と同様にして導電性ペースト3(DP-3)を得た。
タンニン酸誘導体(6)を用いた以外は、実施例1と同様にして導電性ペースト4(DP-4)を得た。
熱硬化性樹脂として、エポキシ樹脂及び硬化促進剤に代えて、レゾール型フェノール樹脂(明和化成社製、商品名:「MWF-2620」、固形分70質量%)を用いた以外は、実施例2と同様にして導電性ペースト5(DP-5)を得た。
タンニン酸誘導体(2)を用いた以外は、実施例1と同様にして導電性ペースト6(DP-6)を得た。
溶剤をエチルカルビトールアセテートに代えた以外は、実施例1と同様にして導電性ペースト7(DP-7)を得た。
タンニン酸誘導体(3)を用いた以外は、実施例1と同様にして導電性ペースト8(DP-8)を得た。
タンニン酸誘導体(4)を用いた以外は、実施例1と同様にして導電性ペースト9(DP-9)を得た。
タンニン酸誘導体(5)を用いた以外は、実施例1と同様にして導電性ペースト10(DP-10)を得た。
タンニン酸及びタンニン酸誘導体を添加しなかった以外は、実施例1と同様にして導電性ペースト11(DP-11)を得た。
(粘度、Ti値の測定)
実施例1~9及び比較例1で得られた各導電性ペーストの25℃における粘度(5rpm及び0.5rpm)をコーンプレート型粘度計(東機産業社製)にて測定した。また、これらの測定値から、Ti値(=0.5rpmでの粘度/5rpmでの粘度)を求めた。
得られた導電性ペースト中の銅粉の分散性を評価するため、グラインドゲージ(太佑機材社製、「GM-7470」、0~25μm)を用いて、JIS K5600-2-5(分散度)を参照して、粗粒の確認を行った。
A:グラインドゲージ判定結果が7.5μm以下であった。
B:グラインドゲージ判定結果が10.0μmであった。
C:グラインドゲージ判定結果が12.5μm以上であった。
前記得られた導電性ペースト1~11(DP-1~DP-11)をそれぞれ、スクリーン印刷法により、PETフィルム上に、幅1mm、長さ50mm、厚さ20μmの帯状の配線形状に塗布した後、150℃で30分間加熱して硬化させ、導電膜1~11(DM-1~11)を有する導電膜付き基材1~11を得た。
(導電膜の抵抗値の測定)
得られた導電膜1~11(DM-1~DM-11)の抵抗値(Ω)を、四探針抵抗測定値計(日置社製、RESISTANCE METER RM3544-01)を用いて測定した。
導電膜付き基材1~11について、高温高湿の環境下での耐久性試験を行った。すなわち、導電膜1~11(DM-1~DM-11)付き基材を、85℃、85%RHの高温高湿とした槽内で100時間保持した後、導電膜1~11(DM-1~DM-11)の抵抗値を測定し、耐久性試験後比抵抗値を算出した。
得られた導電膜1~11(DM-1~DM-11)を、折り曲げ試験機を用い、2mmΦの鉄芯に巻き付けて折り曲げ、折り曲げを戻した後に、比抵抗値を測定した。耐折り曲げ性を、以下の基準により評価した。
S:折り曲げ前後の比抵抗値の上昇率が20%以下である。
A:折り曲げ前後の比抵抗値の上昇率が20%超40%以下である。
B:折り曲げ前後の比抵抗値の上昇率が40%超100%以下である。
C:折り曲げ前後の比抵抗値の上昇率が100%超である。
以上から明らかなように、本開示に係る第一の態様の導電性ペーストは、タンニン酸及びタンニン酸誘導体の少なくとも一方(A)と、銅粉(B)と、熱硬化性樹脂(C)と、溶剤(D)とを含有する。
Claims (7)
- タンニン酸及びタンニン酸誘導体の少なくとも一方(A)と、銅粉(B)と、熱硬化性樹脂(C)と、溶剤(D)とを含有する導電性ペースト。
- 前記(A)成分がタンニン酸誘導体を含み、前記タンニン酸誘導体がタンニン酸の一部のフェノール性水酸基中の水素原子が置換基で置換されたものであり、その置換率が10%以上65%以下である請求項1に記載の導電性ペースト。
- 前記(A)成分がタンニン酸誘導体を含み、前記タンニン酸誘導体がタンニン酸の一部又は全部のフェノール性水酸基がイソシアネート基を有する化合物との反応によりウレタン結合を形成したものである請求項1に記載の導電性ペースト。
- ホウ酸をさらに含有する請求項1乃至3のいずれか一項に記載の導電性ペースト。
- 前記溶剤(D)がアルコール性水酸基を有する請求項1乃至4のいずれか一項に記載の導電性ペースト。
- 前記熱硬化性樹脂(C)がフェノール性水酸基を有する請求項1乃至5のいずれか一項に記載の導電性ペースト。
- 請求項1乃至6のいずれか一項に記載の導電性ペーストの硬化物を含む導電膜。
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US7390564B2 (en) * | 2002-05-14 | 2008-06-24 | Nippon Steel Corporation | Coated metal material capable of being welded which is excellent in corrosion resistance of worked zone |
KR100727434B1 (ko) * | 2005-03-04 | 2007-06-13 | 주식회사 잉크테크 | 투명 은 잉크 조성물 및 이를 이용한 박막 형성방법 |
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JP6089175B2 (ja) | 2012-06-29 | 2017-03-08 | 荒川化学工業株式会社 | 導電性ペーストの製造方法 |
CN104123974B (zh) * | 2014-01-21 | 2015-11-04 | 深圳唯一科技股份有限公司 | 一种手机触摸屏用导电浆料及其制备方法 |
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