WO2014203897A1 - Composition électroconductrice et cellule solaire - Google Patents

Composition électroconductrice et cellule solaire Download PDF

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Publication number
WO2014203897A1
WO2014203897A1 PCT/JP2014/066041 JP2014066041W WO2014203897A1 WO 2014203897 A1 WO2014203897 A1 WO 2014203897A1 JP 2014066041 W JP2014066041 W JP 2014066041W WO 2014203897 A1 WO2014203897 A1 WO 2014203897A1
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Prior art keywords
silver salt
conductive composition
fatty acid
acid silver
electrode
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PCT/JP2014/066041
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English (en)
Japanese (ja)
Inventor
奈央 佐藤
石川　和憲
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横浜ゴム株式会社
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Priority to KR1020167000003A priority Critical patent/KR20160021178A/ko
Priority to JP2015522935A priority patent/JPWO2014203897A1/ja
Publication of WO2014203897A1 publication Critical patent/WO2014203897A1/fr

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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
    • C08K3/02—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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a conductive composition and a solar battery cell using the same as a collecting electrode.
  • conductive particles such as silver particles, binders made of thermoplastic resin (eg, acrylic resin, vinyl acetate resin, etc.) or thermosetting resin (eg, epoxy resin, unsaturated polyester resin, etc.), organic solvent, curing
  • thermoplastic resin eg, acrylic resin, vinyl acetate resin, etc.
  • thermosetting resin eg, epoxy resin, unsaturated polyester resin, etc.
  • organic solvent curing
  • a substrate for example, a silicon substrate, an epoxy resin substrate, etc.
  • Patent Document 2 “a conductive composition containing silver powder (A), a fatty acid silver salt (B), a resin (C), and a solvent (D),
  • the fatty acid silver salt (B) is a compound having one carboxy silver base (—COOAg) and one or two hydroxyl groups (—OH), and the content of silver oxide is the solvent (D)
  • a conductive composition that is 10 parts by mass or less with respect to 100 parts by mass has been proposed ([Claim 1]).
  • the copper fine particles are employed as the metal fine particles in the metal fine particle ink paste described in Patent Document 1, or when the silver powder of the conductive composition described in Patent Document 2 is changed to copper powder, the copper particles It has been clarified that the volume resistivity of formed electrodes and wirings (hereinafter also referred to as “electrodes”) may be increased depending on the usage environment due to oxidation of at least a part of the surface of the electrode. .
  • an object of the present invention is to provide a conductive composition capable of forming an electrode or the like having a low volume resistivity and a solar battery cell using the same as a collecting electrode.
  • the present inventors have found that in a conductive composition containing copper powder, a fatty acid silver salt and a thermosetting resin, there is a difference between the thermal decomposition peak temperature and the thermal decomposition start temperature.
  • a specific amount of fatty acid silver salt at 40 ° C. or higher, it was found that the volume resistivity of the formed electrode or the like was lowered, and the present invention was completed. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a conductive composition comprising copper powder (A), a fatty acid silver salt (B), and a thermosetting resin (C),
  • the difference between the thermal decomposition peak temperature of the fatty acid silver salt (B) and the thermal decomposition start temperature is 40 ° C. or higher
  • the content of the fatty acid silver salt (B) is 20 to 100 parts by mass with respect to 100 parts by mass of the copper powder (A) in terms of the amount of silver produced from the fatty acid silver salt (B).
  • Conductive composition (2) The conductive composition according to (1), wherein the content of the thermosetting resin (C) is 1 to 50 parts by mass with respect to 100 parts by mass of the copper powder (A).
  • a solar battery cell using the conductive composition according to (1) or (2) above as a collecting electrode is a collecting electrode.
  • the present invention it is possible to provide a conductive composition capable of forming an electrode or the like having a low volume resistivity, and a solar battery cell using the same as a collecting electrode. Further, by using the conductive composition of the present invention, an electrode having a low volume resistivity can be formed even when firing at a low temperature to a medium temperature (less than 450 ° C.), particularly at a low temperature (about 150 to 350 ° C.). Therefore, the solar cell (especially the second preferred embodiment described later) has an effect of reducing damage caused by heat, which is very useful. Furthermore, if the conductive composition of the present invention is used, an electronic circuit, an antenna, etc. not only on a material having high heat resistance such as indium tin oxide (ITO) or silicon but also on a material having low heat resistance such as PET film. This circuit is very useful because it can be manufactured easily and in a short time.
  • ITO indium tin oxide
  • PET film a material having low heat resistance
  • FIG. 1 is a cross-sectional view showing a first preferred embodiment of a solar battery cell.
  • FIG. 2 is a cross-sectional view showing a second preferred embodiment of the solar battery cell.
  • the conductive composition of the present invention is a conductive composition having copper powder (A), a fatty acid silver salt (B), and a thermosetting resin (C).
  • the electrically conductive composition of this invention may contain a hardening
  • the electrically conductive composition of this invention may contain the solvent (E) as needed from viewpoints of printability etc. so that it may mention later.
  • an electrode having a low volume resistivity can be formed.
  • Composition This is not clear in detail, but is estimated to be as follows. That is, by using the fatty acid silver salt (B) having a difference between the thermal decomposition peak temperature and the thermal decomposition starting temperature of 40 ° C. or more, silver is produced from the fatty acid silver salt in a wide temperature range, and the silver is the surface of the copper particles. It is considered that the surface oxidation of the copper particles could be suppressed by efficiently covering the surface.
  • the copper powder (A) used in the conductive composition of the present invention is not particularly limited, and those blended with conventionally known conductive pastes can be used.
  • the copper powder (A) preferably has an average particle diameter of 1.0 to 20 ⁇ m because it has good printability and can form an electrode having a smaller volume resistivity. It is more preferably 0 to 10 ⁇ m.
  • the average particle diameter means an average value of the particle diameters, and is measured by using a laser diffraction / scattering type particle size distribution measuring apparatus, and the 50% volume cumulative diameter (D50) calculated using the particle diameter standard as the number is used.
  • D50 volume cumulative diameter
  • a commercially available product can be used as such copper powder (A).
  • Specific examples thereof include Cu-HWQ (average particle size: 3.0 ⁇ m, manufactured by Fukuda Metal Foil Powder Co., Ltd.), FCC. -TBX (average particle size: 5.05 ⁇ m, manufactured by Fukuda Metal Foil Powder Co., Ltd.)
  • the fatty acid silver salt (B) used in the conductive composition of the present invention is a fatty acid silver salt in which the difference between the thermal decomposition peak temperature and the thermal decomposition start temperature is 40 ° C. or higher.
  • the pyrolysis peak temperature is a value measured in the temperature range from room temperature to 300 ° C. in the air at a temperature rising rate of 5 ° C./min using a differential thermal-thermogravimetric simultaneous measurement device (TG-DTA). The exothermic peak temperature appearing in the DTA curve.
  • the pyrolysis start temperature is measured in the temperature range from room temperature to 300 ° C.
  • the fatty acid silver salt (B) has a difference between the thermal decomposition peak temperature and the thermal decomposition starting temperature of 100 ° C. or more because it can form an electrode having a low volume resistivity after the wet heat test.
  • the temperature is preferably 100 to 130 ° C. This is presumably because the surface of the copper powder (A) could be more efficiently coated with silver derived from the reduction of the fatty acid silver salt (B).
  • the fatty acid silver salt (B) is not particularly limited as long as the difference between the thermal decomposition peak temperature and the thermal decomposition start temperature is 40 ° C. or higher among the silver salts of organic carboxylic acids.
  • JP-A-2008-198595 Fatty acid metal salts (particularly tertiary fatty acid silver salts) described in paragraphs [0063] to [0068] of the gazette fatty acid silver described in paragraph [0030] of Japanese Patent No. 4482930, JP 2010-92684 A Secondary fatty acid silver salts described in the paragraphs [0046] to [0056] of the above can be used.
  • the content of the fatty acid silver salt (B) is 20 to 100 with respect to 100 parts by mass of the copper powder (A) in terms of the amount of silver produced from the fatty acid silver salt (B). Parts by mass, preferably 30 to 100 parts by mass, and more preferably 40 to 100 parts by mass.
  • thermosetting resin (C) used in the conductive composition of the present invention is not particularly limited, and specific examples thereof include an epoxy resin, a polyester resin, a silicone resin, a urethane resin, and the like. You may use, and may use 2 or more types together. Among these, an epoxy resin is preferable because it has a strong adhesion to a silicon substrate and high heat and humidity resistance.
  • the epoxy resin as a suitable example of the thermosetting resin (C) is not particularly limited as long as it is a resin composed of a compound having two or more oxirane rings (epoxy groups) in one molecule.
  • the equivalent is 90-2000.
  • a conventionally well-known epoxy resin can be used as such an epoxy resin.
  • epoxy compounds having a bisphenyl group such as bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type, and polyalkylene Bifunctional glycidyl ether type epoxy resins such as glycol type, alkylene glycol type epoxy compounds, epoxy compounds having a naphthalene ring, and epoxy compounds having a fluorene group; Polyfunctional glycidyl ether type epoxy resins such as phenol novolac type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type; Glycidyl ester epoxy resins of synthetic fatty acids such as dimer acid; N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyldiaminodiphenylsulfone (TGDDM), te
  • epoxy resins may be used alone or in combination of two or more.
  • bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferable from the viewpoints of curability, heat resistance, durability, and cost.
  • the content of the thermosetting resin (C) is 1.0 to 100 parts by mass with respect to 100 parts by mass of the copper powder (A) because the volume resistivity of the formed electrode or the like is lower.
  • the amount is preferably 50 parts by mass, more preferably 2 to 25 parts by mass.
  • the conductive composition of the present invention preferably contains a curing agent (D) composed of a complex of boron trifluoride and an amine compound.
  • a complex of boron trifluoride and an amine compound a complex of boron trifluoride and an aliphatic amine (aliphatic primary amine, aliphatic secondary amine, aliphatic tertiary amine), trifluoride
  • examples thereof include a complex of boron and an alicyclic amine, a complex of boron trifluoride and an aromatic amine, a complex of boron trifluoride and a heterocyclic amine, and the like.
  • the heterocyclic amine may be an alicyclic heterocyclic amine (hereinafter also referred to as an alicyclic heterocyclic amine) or an aromatic heterocyclic amine (hereinafter also referred to as an aromatic heterocyclic amine). Also good.
  • Specific examples of the aliphatic primary amine include methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, n-hexylamine, n-octylamine, 2 -Ethylhexylamine, laurylamine and the like.
  • aliphatic secondary amine examples include dimethylamine, diethylamine, methylethylamine, methylpropylamine, di-iso-propylamine, di-n-propylamine, ethylpropylamine, di-n-butylamine, di- Examples include iso-butylamine, dipropenylamine, chlorobutylpropylamine, di (chlorobutyl) amine, di (bromoethyl) amine and the like.
  • Specific examples of the aliphatic tertiary amine include trimethylamine, triethylamine, tributylamine, triethanolamine and the like.
  • alicyclic amine examples include cyclohexylamine.
  • aromatic amines include benzylamine.
  • alicyclic heterocyclic amine examples include pyrrolidine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, piperazine, and homopiperazine.
  • aromatic heterocyclic amine examples include pyridine, pyrrole, imidazole, pyridazine, pyrimidine, quinoline, triazine, tetrazine, isoquinoline, quinazoline, naphthyridine, pteridine, acridine, phenazine and the like.
  • the curing agent (D) is selected from the group consisting of boron trifluoride piperidine, boron trifluoride ethylamine, and boron trifluoride triethanolamine because the volume resistivity of the formed electrode or the like is lower. A complex is preferred.
  • the content of the curing agent (D) is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the epoxy resin, because the volume resistivity of the formed electrode or the like becomes lower. It is more preferable that it is 10 mass parts.
  • the conductive composition of the present invention preferably contains a solvent (E) from the viewpoint of workability such as printability.
  • the solvent (E) is not particularly limited as long as it can apply the conductive composition of the present invention onto a substrate. Specific examples thereof include butyl carbitol, methyl ethyl ketone, isophorone, ⁇ -terpineol. These may be used, and these may be used alone or in combination of two or more.
  • the electrically conductive composition of this invention may contain additives, such as a reducing agent, as needed.
  • a reducing agent include ethylene glycols.
  • the manufacturing method of the electrically conductive composition of this invention is not specifically limited,
  • (D) the method of mixing the said solvent (E), an additive, etc. with a roll, a kneader, an extruder, a universal stirrer etc. is mentioned.
  • the solar battery cell of the present invention is a solar battery cell using the above-described conductive composition of the present invention as a collecting electrode.
  • a 1st suitable aspect of the photovoltaic cell of this invention comprises the surface electrode by the side of a light-receiving surface, a semiconductor substrate, and a back electrode,
  • the said surface electrode and / or the said back electrode are the electroconductivity of this invention mentioned above.
  • a solar battery cell formed using the composition can be mentioned.
  • the 1st suitable aspect of the photovoltaic cell of this invention is demonstrated using FIG.
  • the solar cell 1 includes a surface electrode 4 on the light receiving surface side, a pn junction silicon substrate 7 in which a p layer 5 and an n layer 2 are joined, and a back electrode 6.
  • the solar battery cell 1 is preferably provided with an antireflection film 3, for example, by etching the wafer surface to form a pyramidal texture in order to reduce reflectivity.
  • an antireflection film 3 for example, by etching the wafer surface to form a pyramidal texture in order to reduce reflectivity.
  • the arrangement (pitch), shape, height, width and the like of the electrode are not particularly limited.
  • the height of the electrode is usually designed to be several to several tens of ⁇ m, but the ratio of the height and width of the cross section of the electrode formed using the conductive composition of the present invention (height / width) (below) , “Aspect ratio”) can be adjusted to a large value (for example, about 0.4 or more).
  • the front surface electrode and the back surface electrode usually have a plurality, but, for example, only a part of the plurality of surface electrodes is formed of the conductive composition of the present invention.
  • part of the plurality of front surface electrodes and part of the plurality of back surface electrodes may be formed of the conductive composition of the present invention.
  • the antireflection film is a film (film thickness: about 0.05 to 0.1 ⁇ m) formed on a portion of the light receiving surface where the surface electrode is not formed.
  • a silicon oxide film, a silicon nitride film, a titanium oxide It is comprised from a film
  • the silicon substrate has a pn junction, which means that a second conductivity type light-receiving surface impurity diffusion region is formed on the surface side of the first conductivity type semiconductor substrate.
  • the second conductivity type is p-type.
  • the impurity imparting p-type include boron and aluminum
  • examples of the impurity imparting n-type include phosphorus and arsenic.
  • the silicon substrate is not particularly limited, and a known silicon substrate (plate thickness: about 80 to 450 ⁇ m) for forming a solar cell can be used, and either a monocrystalline or polycrystalline silicon substrate can be used. Good.
  • the solar battery cell has a large electrode aspect ratio because the surface electrode and / or the back electrode is formed using the conductive composition of the present invention.
  • the electromotive force generated by light reception can be efficiently taken out as a current.
  • the conductive composition of the present invention described above can also be applied to the formation of the back electrode of an all-back electrode type (so-called back contact type) solar cell, it can also be applied to an all-back electrode type solar cell. Can do.
  • the manufacturing method of a photovoltaic cell (1st suitable aspect) is not specifically limited,
  • the antireflection film can be formed by a known method such as a plasma CVD method.
  • the wiring formation step is a step of forming a wiring by applying the conductive composition of the present invention on a silicon substrate.
  • specific examples of the coating method include inkjet, screen printing, gravure printing, offset printing, letterpress printing, and the like.
  • the heat treatment step is a step of forming a conductive wiring (electrode) by heat-treating the coating film formed in the wiring forming step.
  • a conductive wiring electrode
  • the heat treatment step is a step of forming a conductive wiring (electrode) by heat-treating the coating film formed in the wiring forming step.
  • the heat treatment is not particularly limited, but is preferably a treatment in which heating (firing) is performed at a relatively low temperature of 150 to 350 ° C. for several seconds to several tens of minutes. When the temperature and time are within this range, an electrode can be easily formed even when an antireflection film is formed on a silicon substrate. Further, in the first preferred embodiment of the solar battery cell of the present invention, since the conductive composition of the present invention is used, good heat treatment (firing) can be achieved even at a relatively low temperature of 150 to 350 ° C. ) Can be applied.
  • the heat treatment step may be performed by irradiation with ultraviolet rays or infrared rays.
  • the solar battery cell 100 has an n-type single crystal silicon substrate 11 as a center, i-type amorphous silicon layers 12 a and 12 b, and p-type amorphous silicon layers 13 a and n-type amorphous silicon layers above and below it. 13b, transparent conductive layers 14a and 14b, and current collecting electrodes 15a and 15b formed using the above-described conductive composition of the present invention.
  • the n-type single crystal silicon substrate is a single crystal silicon layer doped with an n-type impurity. Impurities that give n-type are as described above.
  • the i-type amorphous silicon layer is an undoped amorphous silicon layer.
  • the p-type amorphous silicon is an amorphous silicon layer doped with an impurity imparting p-type. Impurities that give p-type are as described above.
  • the n-type amorphous silicon is an amorphous silicon layer doped with an n-type impurity. Impurities that give n-type are as described above.
  • the said collector electrode is a collector electrode formed using the electrically conductive composition of this invention mentioned above. A specific aspect of the current collecting electrode is the same as that of the front surface electrode or the back surface electrode described above.
  • Transparent conductive layer Specific examples of the material for the transparent conductive layer include single metal oxides such as zinc oxide, tin oxide, indium oxide, and titanium oxide, indium tin oxide (ITO), indium zinc oxide, indium titanium oxide, tin cadmium oxide, Various metal oxides such as gallium-doped zinc oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, titanium-doped zinc oxide, titanium-doped indium oxide, zirconium-doped indium oxide, and fluorine-doped tin oxide. Can be mentioned.
  • ITO indium tin oxide
  • ITO indium zinc oxide
  • titanium oxide titanium oxide
  • tin cadmium oxide Various metal oxides such as gallium-doped zinc oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, titanium-doped zinc oxide, titanium-doped indium oxide, zirconium-doped indium oxide, and fluorine-doped
  • the method for producing the solar battery cell is not particularly limited, and can be produced by, for example, the method described in JP 2010-34162 A.
  • the i-type amorphous silicon layer 12a is formed on one main surface of the n-type single crystal silicon substrate 11 by a PECVD (plasma enhanced chemical vapor deposition) method or the like.
  • a p-type amorphous silicon layer 13a is formed on the formed i-type amorphous silicon layer 12a by PECVD or the like.
  • an i-type amorphous silicon layer 12b is formed on the other main surface of the n-type single crystal silicon substrate 11 by PECVD or the like. Further, an n-type amorphous silicon layer 13b is formed on the formed i-type amorphous silicon layer 12b by PECVD or the like.
  • transparent conductive layers 14a and 14b such as ITO are formed on the p-type amorphous silicon layer 13a and the n-type amorphous silicon layer 13b by sputtering or the like.
  • the conductive composition of the present invention is applied on the formed transparent conductive layers 14a and 14b to form wirings, and the formed wirings are heat-treated to form current collecting electrodes 15a and 15b.
  • the method for forming the wiring is the same as the method described in the wiring formation step of the above-described solar battery cell (first preferred embodiment).
  • the method of heat-treating the wiring is the same as the method described in the heat treatment step of the above-described solar battery cell (first preferred embodiment), but the heat treatment temperature (firing temperature) is preferably 150 to 200 ° C.
  • Examples 1 to 17, Comparative Examples 1 to 6 The copper powder etc. which are shown in the following 2nd table
  • ⁇ Adhesion> The evaluation of the adhesion of each formed conductive film to the substrate was performed by a grid peel test. The results are shown in Table 2 below. Specifically, on each of the obtained substrates with conductive coating, 100 1 mm bases (10 ⁇ 10) were made, and cellophane adhesive tape was completely attached on the bases and rubbed 10 times with the belly of the finger. After that, one end of the tape was momentarily pulled apart while keeping one end of the tape at right angles to the conductive film, and the number of base meshes remaining without being completely peeled was examined. It is most preferable that the number of base meshes remaining without being completely peeled is 100, that is, those having not peeled off at all.
  • Copper powder Cu-HWQ (shape: spherical, average particle size: 3.0 ⁇ m, manufactured by Fukuda Metal Foil Powder Industry)
  • Silver salt of 2-methylpropanoate 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 38 g of 2-methylpropanoic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 2-methylpropanoate.
  • MEK methyl ethyl ketone
  • 2-ethylbutyric acid silver salt 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 50.13 g of 2-ethylbutyric acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 2-ethylbutyrate.
  • Neodecanoic acid silver salt 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 74.3 g of neodecanoic acid (manufactured by Toyo Gosei Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Next, MEK was removed by suction filtration, and the obtained powder was dried to prepare a silver neodecanoate.
  • 2-ethylhexanoic acid silver salt 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 49.27 g of 2-ethylhexanoic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 2-ethylhexanoate.
  • -Silver stearate 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 123 g of stearic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare a silver stearate salt.
  • 1,2,3,4-Butanetetracarboxylic acid silver salt First, 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 25.29 g of 1,2,3,4-butanetetracarboxylic acid (manufactured by Shin Nippon Chemical Co., Ltd.) and 300 g of MEK are put into a ball mill and stirred at room temperature for 24 hours. Was reacted. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare 1,2,3,4-butanetetracarboxylic acid silver salt.
  • Glutaric acid silver salt 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 28.5 g of glutaric acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver glutarate.
  • N-butyric acid silver salt 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 38.01 g of n-butyric acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Next, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver n-butyrate.
  • Silver laurate salt 40 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 68 g of lauric acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver laurate.
  • 4-cyclohexene-1,2-dicarboxylic acid silver salt 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 36.67 g of 4-cyclohexene-1,2-dicarboxylic acid (manufactured by Shin Nippon Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. . Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 4-cyclohexene-1,2-dicarboxylate.
  • Azelaic acid silver salt 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 40.60 g of azelaic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were put into a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare azelaic acid silver salt.
  • 2,2-bis (hydroxymethyl) -n-butyric acid silver salt 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 64 g of 2,2-bis (hydroxymethyl) -n-butyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. . Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare 2,2-bis (hydroxymethyl) -n-butyric acid silver salt.
  • 2-hydroxyisobutyric acid silver salt 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 45 g of 2-hydroxyisobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver 2-hydroxyisobutyrate.
  • Silver glycolate 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 16.40 g of glycolic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Next, MEK was removed by suction filtration, and the resulting powder was dried to prepare silver glycolate.
  • Hydroxypivalic acid silver salt 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 25.48 g of hydroxypivalic acid (manufactured by Kanto Chemical Co., Ltd.) and 300 g of MEK were placed in a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the resulting powder was dried to prepare a hydroxypivalic acid silver salt.
  • Malonic acid silver salt 50 g of silver oxide (manufactured by Toyo Kagaku Kogyo Co., Ltd.), 11 g of malonic acid and 300 g of MEK were put into a ball mill and reacted by stirring at room temperature for 24 hours. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare silver malonate.
  • Thermosetting resin bisphenol A type epoxy resin (EP-4100E, manufactured by ADEKA)
  • Thermosetting resin bisphenol F type epoxy resin (EP-4901E, manufactured by ADEKA)
  • -Thermosetting resin Urethane-modified epoxy resin (EPU-1395, manufactured by ADEKA)
  • Curing agent Boron trifluoride ethylamine (manufactured by Stella Chemifa)
  • Solvent Terpinel
  • the comparison between Examples 1 to 13 reveals that the volume resistivity after the wet heat resistance test can be further reduced when the difference between the thermal decomposition peak temperature and the thermal decomposition start temperature is 100 ° C. or more. Further, from the comparison with Examples 8, 14 and 15, when the content of the thermosetting resin (C) is 1.0 to 50 parts by mass with respect to 100 parts by mass of the copper powder (A), the formed electrode It has been found that the volume resistivity of etc. becomes lower.

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Abstract

La présente invention vise à mettre au point : une composition électroconductrice apte à former une électrode ou similaire ayant une faible résistivité volumique, ainsi qu'une cellule solaire qui l'utilise dans une électrode collectrice. La composition électroconductrice présente une poudre de cuivre (A), un sel d'argent d'acide gras (B) et une résine thermodurcissable (C), la différence entre la température de début de pyrolyse et la température de crête de pyrolyse du sel d'argent d'acide gras (B) est d'au moins 40 °C, et la teneur en sel d'argent d'acide gras (B) est de 20 à 100 parties en masse pour 100 parties en masse de la poudre de cuivre (A) lorsque la conversion s'effectue à partir du sel d'argent d'acide gras (B) pour obtenir la quantité d'argent générée.
PCT/JP2014/066041 2013-06-19 2014-06-17 Composition électroconductrice et cellule solaire WO2014203897A1 (fr)

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JP6357599B1 (ja) * 2017-02-24 2018-07-11 Ｄｏｗａエレクトロニクス株式会社 導電性ペースト

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JP6709943B2 (ja) * 2017-12-13 2020-06-17 ナミックス株式会社 導電性ペースト

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JP2013045742A (ja) * 2011-08-26 2013-03-04 Yokohama Rubber Co Ltd:The 導電性組成物、太陽電池セルおよび太陽電池モジュール

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JP2012022798A (ja) * 2010-07-12 2012-02-02 Yokohama Rubber Co Ltd:The 導電性組成物および太陽電池セル
JP2012023096A (ja) * 2010-07-12 2012-02-02 Yokohama Rubber Co Ltd:The 導電性組成物および太陽電池セル
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JP2012038846A (ja) * 2010-08-05 2012-02-23 Yokohama Rubber Co Ltd:The 太陽電池電極用ペーストおよび太陽電池セル
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6357599B1 (ja) * 2017-02-24 2018-07-11 Ｄｏｗａエレクトロニクス株式会社 導電性ペースト
WO2018155393A1 (fr) * 2017-02-24 2018-08-30 Ｄｏｗａエレクトロニクス株式会社 Pâte électroconductrice

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