WO2020166180A1 - Composition électroconductrice - Google Patents

Composition électroconductrice Download PDF

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Publication number
WO2020166180A1
WO2020166180A1 PCT/JP2019/047617 JP2019047617W WO2020166180A1 WO 2020166180 A1 WO2020166180 A1 WO 2020166180A1 JP 2019047617 W JP2019047617 W JP 2019047617W WO 2020166180 A1 WO2020166180 A1 WO 2020166180A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
present
curing agent
group
conductive
Prior art date
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PCT/JP2019/047617
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English (en)
Japanese (ja)
Inventor
つばさ 伊藤
一雄 荒川
石川　和憲
Original Assignee
横浜ゴム株式会社
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Application filed by 横浜ゴム株式会社 filed Critical 横浜ゴム株式会社
Priority to CN201980090435.0A priority Critical patent/CN113348194A/zh
Publication of WO2020166180A1 publication Critical patent/WO2020166180A1/fr

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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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • 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
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • 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

Definitions

  • the present invention relates to a conductive composition.
  • Patent Document 1 a conductive composition containing silver particles, an epoxy resin, and a cationic curing agent to form an electrode in a solar cell or the like.
  • an object of the present invention is to provide a conductive composition that exhibits low volume resistivity and low contact resistivity when formed into a conductive film.
  • the present inventors have found that the above problems can be solved by using an ammonium salt as a cationic curing agent, and completed the present invention. That is, the present inventors have found that the above problems can be solved by the following configurations.
  • (1) contains conductive particles, an epoxy resin, and a cationic curing agent, A conductive composition, wherein the cationic curing agent is an ammonium salt.
  • R 1 and R 2 are each independently an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group, and R 3 is The conductive composition according to (2) above, which is a group represented by —L 1 —Ar 1 .
  • L 1 represents a single bond or a divalent unsaturated hydrocarbon group
  • Ar 1 represents an aromatic hydrocarbon group which may have a substituent.
  • the total content of the epoxy resin and the cationic curing agent is 1 to 8 parts by mass with respect to 100 parts by mass of the conductive particles, according to any one of (1) to (3) above.
  • the numerical range represented by "to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
  • each component contained in the conductive composition of the present invention may be used alone or in combination of two or more.
  • the content of the component means the total content unless otherwise specified.
  • the conductive composition of the present invention (hereinafter, also referred to as “the composition of the present invention”) contains conductive particles, an epoxy resin, and a cationic curing agent, and the cationic curing agent is an ammonium salt. , A conductive composition. Since the composition of the present invention has such a constitution, it is considered that the above-mentioned effects can be obtained. Although the reason for this is not clear, it is presumed that the epoxy resin is gently cationically polymerized by the ammonium salt to form a dense conductive film with less distortion.
  • the conductive particles contained in the composition of the present invention are not particularly limited as long as they are granular substances having conductivity.
  • the conductive particles include a metal material having an electric resistivity of 20 ⁇ 10 ⁇ 6 ⁇ cm or less.
  • Specific examples of the metal material include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), and nickel (Ni).
  • the metal material is preferably silver because it has a lower volume resistivity, a lower contact resistivity, and a better resistance to moist heat when formed into a conductive film.
  • “having a lower volume resistivity, a lower contact resistivity, and a better resistance to moist heat” is also referred to as “the effect of the present invention is more excellent”.
  • the conductive particles are at least one selected from the group consisting of silver powder, copper powder, and silver-coated conductive powder having at least a part of the surface coated with silver, for the reason that the effect of the present invention is more excellent. Is preferred.
  • Examples of the core that constitutes the silver-coated conductive powder include particles of the metal material.
  • the average particle diameter of the conductive particles is preferably 0.5 to 10 ⁇ m, more preferably 1 to 5 ⁇ m, for the reason that the effect of the present invention is more excellent.
  • the average particle diameter of the conductive particles is obtained by measuring a volume-based particle size distribution using a laser diffraction type particle size distribution measuring device, and a particle diameter at a cumulative 50% (50% cumulative volume diameter). Also referred to as "average particle diameter (D50)".
  • a laser diffraction type particle size distribution measuring device for example, a device according to LA-500 (trade name) manufactured by Horiba, Ltd. can be mentioned.
  • the conductive particles preferably include at least one selected from the group consisting of flaky particles and spherical particles.
  • the term “spherical” means the shape of particles having a ratio of major axis/minor axis of 2 or less.
  • the flake shape means a shape in which the ratio of major axis/minor axis is more than 2.
  • the major axis and the minor axis of the particles forming the conductive particles can be determined based on an image obtained from a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the “major axis” refers to the longest distance among the line segments that pass through substantially the center of gravity of the particle in the particle image obtained by SEM.
  • Short diameter refers to the shortest distance among the line segments passing through the substantial center of gravity of the particle in the particle image obtained by SEM.
  • the flaky particles may be either single crystal or polycrystal.
  • the specific surface area of the flaky particles is preferably 0.2 to 1.0 m 2 /g, more preferably 0.2 to 0.8 m 2 /g for the reason that the effect of the present invention is more excellent.
  • it is more than 1.0 m 2 /g, the viscosity tends to be high and the printability may be deteriorated.
  • it is necessary to add more solvent, which may cause a problem that the aspect ratio of the wiring after printing/curing becomes small because the solid content decreases. ..
  • the specific surface area of the conductive particles means a value obtained from the adsorption isotherm of nitrogen at -196°C based on the BET formula.
  • the average particle size of the flaky particles is preferably 1 to 15 ⁇ m, more preferably 3 to 10 ⁇ m, because the effect of the present invention is more excellent.
  • the thickness is larger than 10 ⁇ m, there is a problem that mesh clogging is likely to occur in a wiring process such as screen printing, and disconnection is likely to occur particularly during fine line patterning. If it is less than 1 ⁇ m, the number of contacts between conductive particles increases, the contact resistance increases, and the resistance of the obtained wiring may increase. Further, the thixotropy of the obtained composition is lowered, which may cause a problem that it is difficult to form a wiring having a high aspect ratio in a wiring process such as screen printing.
  • the specific surface area of spherical particles for reasons that the effect of the present invention is more excellent, preferably 0.5 ⁇ 1.6m 2 / g, more preferably 0.5 ⁇ 1.2m 2 / g. If the amount is more than 1.6 m 2 /g, the viscosity tends to increase and the printability may decrease. In order to obtain a composition in a viscosity range that allows proper printing, it is necessary to add more solvent, which may cause a problem that the aspect ratio of the wiring after printing/curing becomes small because the solid content decreases. .. When it is less than 0.5 m 2 /g, the viscosity tends to be lowered, and the printability may be deteriorated such as the line width being widened.
  • the average particle size of the spherical particles is preferably 0.5 to 3 ⁇ m, and more preferably 0.8 to 2 ⁇ m, from the viewpoint of more excellent printability and conductivity, for the reason that the effect of the present invention is more excellent. If it is larger than 3 ⁇ m, the gap between particles increases, and the density of conductive particles in the composition decreases, so that the resistance of the obtained wiring may increase. When it is smaller than 0.5 ⁇ m, the number of contacts between the conductive particles increases, the contact resistance increases, and the resistance of the obtained wiring may increase.
  • the average specific surface area of the conductive particles is preferably 0.5 to 0.8 m 2 /g for the reason that the effect of the present invention is more excellent. It is more preferably 0.5 to 0.7 m 2 /g.
  • the average specific surface area of the conductive particles can be obtained by dividing the sum of the products of the specific surface area of each conductive particle and its content by the total content of each conductive particle.
  • the mass ratio of the spherical particles to the flake particles is 75/25 because the effect of the present invention is more excellent. It is preferably from 25/75, more preferably from 70/30 to 30/70.
  • the method for producing the conductive particles is not particularly limited.
  • conventionally known ones can be mentioned.
  • the method for producing spherical conductive particles (for example, the above-mentioned spherical particles) is not particularly limited, and for example, those produced by a wet reduction method, an electrolytic method, an atomizing method, or the like can be preferably used.
  • the method for producing the flaky conductive particles (for example, the above flake particles) is not particularly limited, and a conventionally known method can be used.
  • the spherical conductive particles produced by the above-mentioned method is used as a base powder, and the base powder is subjected to mechanical treatment by a ball mill, a bead mill, a vibration mill, a stirring type pulverizer, etc., and the base powder is flaked with a physical force. What was manufactured by the method of converting can be used conveniently.
  • the content of the conductive particles in the composition of the present invention is preferably 50 to 99% by mass, more preferably 70 to 97% by mass, and 90 to 95% for the reason that the effect of the present invention is more excellent. More preferably, it is mass %.
  • Epoxy resin The epoxy resin contained in the composition of the present invention is not particularly limited as long as it is a compound having an epoxy group.
  • the epoxy resin is preferably a compound having two or more epoxy groups in one molecule because the effect of the present invention is more excellent.
  • the epoxy equivalent of the epoxy resin is not particularly limited, but it is preferably 90 to 3500 eq/g for the reason that the effect of the present invention is more excellent.
  • a conventionally known epoxy resin can be used as the epoxy resin.
  • an epoxy compound having a bisphenyl group such as bisphenol A type, bisphenol F type, brominated bisphenol A type, bisphenol E type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, and biphenyl type
  • a bifunctional glycidyl ether-based epoxy resin such as a polyalkylene glycol type or alkylene glycol type epoxy compound, an epoxy compound having a naphthalene ring, or an epoxy compound having a fluorene group
  • Multifunctional glycidyl ether epoxy resins such as phenol novolac type, orthocresol novolac type, trishydroxyphenylmethane type, tetraphenylolethane type, etc.
  • Glycidyl ester epoxy resin of synthetic fatty acid such as dimer acid
  • N,N,N′,N′-tetraglycidyldiaminodiphenylmethane TGD
  • An epoxy compound obtainable by a known production method Polyhydric alcohol glycidyl type epoxy resin such as glycidyl ether of poly(oxyalkylene) polyol and glycidyl ether of alkylene polyol; Chelate-modified epoxy resin; Epoxy resin having benzenediol (dihydroxybenzene) skeleton and hydrogenated product thereof; Epoxy resin having phthalic acid skeleton and hydrogenated product thereof; Epoxy resin having benzenedimethanol skeleton; Epoxy resin having cyclohexanedimethanol skeleton; Epoxy resin having a dicyclopentadiene dimethanol skeleton; Alicyclic epoxy resin: Epoxy resin represented by Toray Thiokol Co., Ltd.
  • the epoxy resin is preferably a bisphenol A type epoxy resin or a bisphenol F type epoxy resin because the effect of the present invention is more excellent.
  • the content of the epoxy resin is preferably 0.1 to 20 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the conductive particles described above.
  • the epoxy resin is a liquid epoxy resin that is liquid at 25° C. (hereinafter, also simply referred to as “liquid epoxy resin”) and a solid epoxy resin that is solid at 25° C. (hereinafter, simply “Also referred to as “solid epoxy resin”), and more preferably a liquid epoxy resin that is liquid at 25°C and a solid epoxy resin that is solid at 25°C.
  • the epoxy equivalent of the liquid epoxy resin is preferably less than 500 g/eq, more preferably 100 to 300 g/eq, for the reason that the effect of the present invention is more excellent.
  • the viscosity of the liquid epoxy resin is preferably 15 to 60,000 mPa ⁇ s, and more preferably 50 to 15,000 mPa ⁇ s for the reason that the effect of the present invention is more excellent.
  • the viscosity of the epoxy resin is measured in accordance with JIS Z 8803 under the condition of 25°C.
  • the liquid epoxy resin preferably contains the liquid epoxy resin A having a water solubility of 75% or more and the liquid epoxy resin B having a water solubility of less than 75% for the reason that the effect of the present invention is more excellent. It is preferably composed of an epoxy resin B.
  • the water solubility means the solubility when 10 parts by mass of the epoxy resin is dissolved in 90 parts by mass of water at room temperature.
  • the liquid epoxy resin A is a liquid epoxy resin having a water solubility of 75% or more.
  • the liquid epoxy resin A is preferably an epoxy resin having a chain structure because the effect of the present invention is more excellent.
  • Examples of the chain structure include a poly(oxyalkylene) group and an oxyalkylene group.
  • Examples of the epoxy resin having a chain structure include polyglycidyl ethers of poly(oxyalkylene) polyols and polyhydric alcohol glycidyl type epoxy resins such as polyglycidyl ethers of alkylene polyols.
  • the poly(oxyalkylene) polyol or alkylene polyol that can form the polyhydric alcohol glycidyl type epoxy resin is not particularly limited.
  • the alkylene group contained in the poly(oxyalkylene) polyol or the alkylene polyol may be linear or branched.
  • the alkylene group may have 2 to 15 carbon atoms, for example. Examples of the alkylene group include an ethylene group, a propylene group, and a trimethylene group.
  • the number of repeating units of the repeating unit (oxyalkylene group) contained in the above poly(oxyalkylene) polyol is preferably 2 to 15 and more preferably 3 to 10 because the effect of the present invention is more excellent.
  • Examples of the polyglycidyl ether of the alkylene polyol include ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether.
  • Examples of commercial products of the above polyglycidyl ether of alkylene polyol include EX-810 (trade name, manufactured by Nagase Chemtech).
  • Examples of the polyglycidyl ether of the poly(oxyalkylene) polyol include polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.
  • Examples of commercially available polyglycidyl ethers of the above poly(oxyalkylene) polyols include trade names EX-830, EX-841, EX-920, EX-931 (manufactured by Nagase Chemtech).
  • the liquid epoxy resin B is a liquid epoxy resin having a water solubility of less than 75%.
  • the liquid epoxy resin B is preferably an epoxy resin having a cyclic structure because the effect of the present invention is more excellent.
  • the cyclic structure include a cyclic aliphatic hydrocarbon group such as a cyclohexane skeleton; an aromatic hydrocarbon group such as a benzene ring and a hydrogenated product thereof.
  • the epoxy resin having a cyclic structure may further have a urethane bond in addition to the oxirane ring.
  • Examples of the epoxy resin having the above cyclic structure include bisphenol skeletons such as bisphenol A type, bisphenol F type, bisphenol E type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, and bisphenol AF type. And epoxy hydrogenated products thereof; urethane modified products (urethane modified epoxy resins) of the above epoxy resins and hydrogenated products thereof; epoxy resins having one cyclic structure in one molecule and hydrogenated products thereof.
  • the urethane-modified epoxy resin has a plurality of cyclic structures in one molecule.
  • Examples of the above-mentioned epoxy resin having one cyclic structure in one molecule and its hydrogenated product include an epoxy resin having a benzenediol skeleton and its hydrogenated product; an epoxy resin having a phthalic acid skeleton and its hydrogenated product; Examples thereof include an epoxy resin having a benzenedimethanol skeleton; an epoxy resin having a cyclohexanedimethanol skeleton; an epoxy resin having an aniline skeleton; and an epoxy resin having a toluidine skeleton.
  • a urethane-modified epoxy resin, an epoxy resin having one cyclic structure in one molecule is preferable, and a urethane-modified epoxy resin, an epoxy resin having a benzenediol skeleton, and a phthalic acid skeleton are preferable because the effect of the present invention is more excellent.
  • the epoxy resin having the same and the epoxy resin having a cyclohexanedimethanol skeleton are more preferable, and the urethane-modified epoxy resin and the resorcinol diglycidyl ether having a resorcin skeleton are further preferable.
  • the epoxy equivalent of the solid epoxy resin is preferably 400 g/eq or more and 5000 g/eq or less, and more preferably 1500 to 3500 g/eq, for the reason that the effect of the present invention is more excellent.
  • the softening point of the solid epoxy resin is preferably 50 to 150° C., and more preferably 100 to 150° C. for the reason that the effect of the present invention is more excellent.
  • the softening point of the epoxy resin is measured according to JIS K-7234.
  • the solid epoxy resin examples include bisphenol skeleton epoxy resins such as bisphenol A type, bisphenol F type, bisphenol E type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, and bisphenol AF type. Is mentioned. Among them, the solid epoxy resin is preferably at least one selected from the group consisting of bisphenol A type and bisphenol F type because the effect of the present invention is more excellent.
  • the ratio of the above-mentioned solid epoxy resin to the total of the above-mentioned solid epoxy resin and the above-mentioned liquid epoxy resin is 10 to 50% by mass because the effect of the present invention is more excellent. preferable.
  • the “ratio of the solid epoxy resin to the total of the solid epoxy resin and the liquid epoxy resin” is also referred to as “solid/(solid+liquid)”.
  • the solid content/(solid content+liquid content) is more preferably 15 to 30 mass% for the reason that the effect of the present invention is more excellent.
  • the ratio of the above-mentioned liquid epoxy resin A to the total of the above-mentioned liquid epoxy resin A and the above-mentioned liquid epoxy resin B is 10 to 90% by mass because the effect of the present invention is more excellent.
  • the “ratio of the liquid epoxy resin A to the total of the liquid epoxy resin A and the liquid epoxy resin B” is also referred to as “A/(A+B)”.
  • A/(A+B) is more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass for the reason that the effect of the present invention is more excellent.
  • the cationic curing agent contained in the present invention is an ammonium salt.
  • the cationic curing agent that is an ammonium salt is also referred to as a "specific curing agent”.
  • the ammonium salt is a salt of a cation that is ammonium and an anion.
  • Ammonium includes pyridinium.
  • the anion is not particularly limited, but is preferably any of the anions represented by the following formulas (i) to (vi) for the reason that the effect of the present invention is more excellent.
  • the specific curing agent is preferably a compound represented by the following formula (1) because the effect of the present invention is more excellent.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or a substituent
  • L 2 represents a single bond or a divalent unsaturated hydrocarbon group
  • Ar 2 represents an aromatic hydrocarbon group which may have a substituent
  • X ⁇ represents an anion
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or a substituent. From the reason that the effect of the present invention is more excellent, R 1 , R 2 and R 3 are each independently preferably a substituent, and more preferably an organic group.
  • the organic group include an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group, a group in which these are combined, and the like.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • aliphatic hydrocarbon group examples include a linear or branched alkyl group (especially 1 to 30 carbon atoms), a linear or branched alkenyl group (especially 2 to 30 carbon atoms), A straight-chain or branched alkynyl group (in particular, having 2 to 30 carbon atoms) and the like can be mentioned.
  • aromatic hydrocarbon group examples include an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
  • R 1 and R 2 in the above formula (1) are each independently an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon, for the reason that the effect of the present invention is more excellent. It is preferably a group. Specific examples and preferable embodiments of the aliphatic hydrocarbon group and the aromatic hydrocarbon group are as described above.
  • R 3 in the above formula (1) is preferably a group represented by —L 1 —Ar 1 because the effect of the present invention is more excellent.
  • L 1 represents a single bond or a divalent unsaturated hydrocarbon group
  • Ar 1 represents an aromatic hydrocarbon group which may have a substituent.
  • L 1 is preferably a single bond because the effect of the present invention is more excellent.
  • the divalent unsaturated hydrocarbon group include a linear or branched alkenyl group (especially 2 to 30 carbon atoms), a linear or branched alkynyl group (especially 2 to 30 carbon atoms). ) And the like. Of these, an alkenyl group is preferable because the effect of the present invention is more excellent.
  • Specific examples of the aromatic hydrocarbon group are as described above.
  • L 2 represents a single bond or a divalent unsaturated hydrocarbon group.
  • L 2 is preferably a single bond because the effect of the present invention is more excellent.
  • Specific examples and preferable embodiments of the divalent unsaturated hydrocarbon group are as described above.
  • L 2 is a single bond, the carbon atom of the methylene group bonded to N + in formula (1) is directly bonded to Ar 2 .
  • Ar 2 represents an aromatic hydrocarbon group which may have a substituent.
  • aromatic hydrocarbon group are as described above.
  • the substituent is not particularly limited, but is preferably an alkoxy group because the effect of the present invention is more excellent.
  • X ⁇ represents an anion.
  • the anion is not particularly limited.
  • the anion is preferably any of the anions represented by the above formulas (i) to (vi) for the reason that the effect of the present invention is more excellent.
  • the content of the specific compound is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the conductive particles described above because the effect of the present invention is more excellent. It is more preferably from 01 to 0.1 parts by mass.
  • the content of the specific compound is preferably 0.5 to 10 mass% with respect to the content of the epoxy resin described above, for the reason that the effect of the present invention is more excellent.
  • the total content of the epoxy resin and the specific curing agent is 1 to 8 parts by mass with respect to 100 parts by mass of the conductive particles described above, for the reason that the effect of the present invention is more excellent.
  • the total content of the epoxy resin and the specific curing agent is 1 to 8 parts by mass with respect to 100 parts by mass of the conductive particles described above, for the reason that the effect of the present invention is more excellent.
  • composition of the present invention may contain components other than the components described above.
  • the composition of the present invention preferably contains a solvent because the effect of the present invention is more excellent.
  • the solvent include butyl carbitol, butyl carbitol acetate, cyclohexanone, methyl ethyl ketone, isophorone, ⁇ -terpineol and the like.
  • a commercial item can be used as a solvent.
  • the content of the solvent in the composition of the present invention is preferably 0.1 to 50% by mass, and more preferably 1 to 10% by mass, for the reason that the effect of the present invention is more excellent.
  • the composition of the present invention may further contain a curing agent other than the specific curing agent, a reducing agent, an additive such as a fatty acid metal salt, if necessary.
  • a curing agent other than the above specific curing agent include boron trifluoride ethylamine, boron trifluoride piperidine, a complex of boron trifluoride and an amine compound, and 2-ethyl-4-methylimidazole.
  • amines include imidazoles, diethylenetriamine, DICY (dicyandiamide), isocyanate compounds, blocked isocyanate compounds, and diaminodiphenylmethane.
  • Specific examples of the reducing agent include ethylene glycols.
  • the fatty acid metal salt is not particularly limited as long as it is a metal salt of an organic carboxylic acid, and for example, at least one selected from the group consisting of silver, magnesium, nickel, copper, zinc, yttrium, zirconium, tin and lead. It is preferable to use a carboxylic acid metal salt of the above metal. Among these, it is preferable to use a silver carboxylic acid metal salt (hereinafter, also referred to as “carboxylic acid silver salt”).
  • the carboxylic acid silver salt is not particularly limited as long as it is a silver salt of an organic carboxylic acid (fatty acid).
  • the fatty acid described in paragraphs [0063] to [0068] of JP-A-2008-198595.
  • Metal salts (particularly, tertiary fatty acid silver salts), fatty acid silver salts described in paragraph [0030] of Japanese Patent No. 4482930, and hydroxyl groups described in paragraphs [0029] to [0045] of JP2010-92684A.
  • the method for producing the composition of the present invention is not particularly limited, and examples thereof include a method of mixing the above-mentioned components with a roll, a kneader, an extruder, a universal stirrer, or the like.
  • the conductive film of the present invention is a conductive film formed using the composition of the present invention.
  • Examples of the method for forming the conductive film of the present invention include a method of applying the composition of the present invention to a substrate and heating the composition at 180 to 230° C. to cure the composition.
  • the base material is not particularly limited.
  • a silicon substrate, glass, metal, a resin substrate, a film, etc. can be mentioned.
  • the substrate may be treated with a TCO film (transparent oxide conductive film) such as an ITO film (indium tin oxide film).
  • the conductive film of the present invention can be used, for example, as an electrode (collection electrode) of a solar battery cell, an electrode of a touch panel, or a die bond of an LED.
  • a solar cell module can be manufactured using the solar cell having the conductive film of the present invention.
  • Each conductive composition was prepared by mixing the components shown in Table 1 below in the proportions (parts by mass) shown in the same table.
  • ⁇ Volume resistivity> The obtained conductive composition was applied onto a glass substrate by screen printing to form a solid test pattern of 2 cm ⁇ 2 cm. Then, it dried and hardened
  • the volume resistivity of each produced conductive film was evaluated by a 4-terminal 4-probe method using a resistivity meter (Lorestar GP, manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 1. Practically, the volume resistivity is preferably less than 7.5 ⁇ cm, and more preferably less than 7.0 ⁇ cm.
  • ⁇ Contact resistivity> An ITO film was formed as a transparent conductive film on a soda lime glass substrate to prepare a glass substrate for evaluation.
  • the obtained conductive composition was applied onto the glass substrate for evaluation by screen printing to form a test pattern having a width of 300 ⁇ m and a length of 2.5 cm. After that, it was dried in an oven at 200° C. for 30 minutes to produce a thin wire-shaped conductive film (thin wire electrode). The distance between the electrodes was 2 mm. Then, the resistance value between the fine line electrodes was measured using a digital multimeter (HIKKI:3541 RESISTANCE HiTESTER). Then, the contact resistivity was obtained. The results are shown in Table 1 (before the wet heat test).
  • the contact resistivity is preferably 2.0 m ⁇ cm 2 or less. Further, the obtained thin wire electrode was held in an oven at 80° C. and 95% relative humidity for 24 hours, and the contact resistivity was similarly determined. The results are shown in Table 1 (after the wet heat test). Further, Table 1 shows the contact resistance after the wet heat test (contact resistance after the wet heat test/contact resistance before the wet heat test) with respect to the contact resistance before the wet heat test (after test/before test). From the viewpoint of moisture resistance, it is preferable that “contact resistance after wet heat test/contact resistance before wet heat test” is small.
  • the specific curing agents 1 to 10 and the comparative curing agent 1 are salts composed of the cation site (cation) shown in Table 2 and the anion site (anion) shown in Table 2. Since the specific curing agents 1 to 10 are ammonium salts, they correspond to the specific curing agents described above. On the other hand, the comparative curing agents 1 and 2 are not ammonium salts and therefore do not correspond to the above-mentioned specific curing agents.
  • the cation site and anion site of the cationic curing agent are as follows.
  • Me represents a methyl group.
  • epoxy resin+curing agent represents the total mass part of the epoxy resin and the cationic curing agent.
  • solid/(solid+liquid) means the above-mentioned “solid/(solid+liquid)”.
  • A/(A+B) represents the above-mentioned “A/(A+B)”.
  • Examples 1 to 21 containing the specific curing agent had lower volume resistivity and lower contact resistivity than Comparative Examples 1 to 8 not containing the specific curing agent. ..
  • Examples 1 to 10 compare between modes in which only the type of the specific curing agent is different
  • Examples 1 to 9 in which the specific curing agent is the compound represented by the above formula (1) have lower volumes. It exhibited a resistivity, lower contact resistivity, and better resistance to moist heat.
  • Examples 1 to 4 (comparison between modes in which the specific curing agent is the compound represented by the above formula (1) and only the kind of the cation of the specific curing agent is different)
  • L 2 is a single bond. Examples 1-3 showed better moist heat resistance.
  • Examples 1 and 2 in which Ar 2 is a phenyl group which may have a substituent showed further excellent heat and humidity resistance.
  • Example 2 in which Ar 2 was a phenyl group having an alkoxy group showed particularly excellent wet heat resistance.
  • the anion of the specific curing agent is represented by the above formulas (i) to (ii), or Examples 2, 5 and 7 to 9 which are the anions represented by the above formulas (iv) to (vi) showed more excellent resistance to moist heat.
  • Examples 2 and 5 in which the anion of the specific curing agent is the anion represented by the above formulas (i) to (ii) showed further excellent heat and moisture resistance.
  • the content of the epoxy resin is 2 to 6 parts by mass with respect to 100 parts by mass of the conductive particles.
  • Examples 2, 11-17 and 20-21 showed better resistance to moist heat.
  • Examples 2 and 11 to 15 in which solid/(solid+liquid) is 10 to 50 mass% and A/(A+B) is 10 to 90 mass% show lower volume resistivity. It was Among them, Example 2 in which A/(A+B) was more than 40% by mass and 80% by mass or less showed more excellent wet heat resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

Le but de la présente invention est de fournir une composition électroconductrice qui donne des films électroconducteurs ayant une faible résistivité volumique et une faible résistivité de contact. La composition électroconductrice de la présente invention comprend des particules électroconductrices, une résine époxy et un durcisseur cationique, le durcisseur cationique étant un sel d'ammonium.
PCT/JP2019/047617 2019-02-13 2019-12-05 Composition électroconductrice WO2020166180A1 (fr)

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JP2014089818A (ja) * 2012-10-29 2014-05-15 Namics Corp 熱硬化型導電性ペースト
JP2014135207A (ja) * 2013-01-10 2014-07-24 Sekisui Chem Co Ltd 導電材料、接続構造体及び接続構造体の製造方法
US20170162531A1 (en) * 2015-12-07 2017-06-08 Samsung Sdi Co., Ltd. Composition for anisotropic conductive film, anisotropic conductive film, and connection structure using the same
JP2017152354A (ja) * 2016-02-22 2017-08-31 デクセリアルズ株式会社 異方性導電フィルム
JP2017214472A (ja) * 2016-05-31 2017-12-07 日立化成株式会社 接着剤組成物及びフィルム状接着剤組成物
JP2019106305A (ja) * 2017-12-13 2019-06-27 ナミックス株式会社 導電性ペースト

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JP2013095820A (ja) * 2011-10-31 2013-05-20 Fujifilm Corp 導電性組成物、並びにこれを用いた導電性膜及び導電性積層体
US20190359842A1 (en) * 2017-01-26 2019-11-28 The Yokohama Rubber Co., Ltd. Electrically Conductive Composition
JP6894290B2 (ja) * 2017-05-17 2021-06-30 東京応化工業株式会社 硬化性組成物、硬化膜、表示パネル、及び硬化物の製造方法

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JP2011071057A (ja) * 2009-09-28 2011-04-07 Kyoto Elex Kk 加熱硬化型導電性ペースト組成物およびその導電性ペースト組成物を用いた電極並びに配線パターンの形成方法
JP2014089818A (ja) * 2012-10-29 2014-05-15 Namics Corp 熱硬化型導電性ペースト
JP2014135207A (ja) * 2013-01-10 2014-07-24 Sekisui Chem Co Ltd 導電材料、接続構造体及び接続構造体の製造方法
US20170162531A1 (en) * 2015-12-07 2017-06-08 Samsung Sdi Co., Ltd. Composition for anisotropic conductive film, anisotropic conductive film, and connection structure using the same
JP2017152354A (ja) * 2016-02-22 2017-08-31 デクセリアルズ株式会社 異方性導電フィルム
JP2017214472A (ja) * 2016-05-31 2017-12-07 日立化成株式会社 接着剤組成物及びフィルム状接着剤組成物
JP2019106305A (ja) * 2017-12-13 2019-06-27 ナミックス株式会社 導電性ペースト

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