WO2012042780A1 - Electroconductive composition, solar battery cell, and method for producing solar battery cell - Google Patents
Electroconductive composition, solar battery cell, and method for producing solar battery cell Download PDFInfo
- Publication number
- WO2012042780A1 WO2012042780A1 PCT/JP2011/005260 JP2011005260W WO2012042780A1 WO 2012042780 A1 WO2012042780 A1 WO 2012042780A1 JP 2011005260 W JP2011005260 W JP 2011005260W WO 2012042780 A1 WO2012042780 A1 WO 2012042780A1
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- WIPO (PCT)
- Prior art keywords
- epoxy resin
- conductive composition
- curing agent
- composition according
- type epoxy
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 92
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004593 Epoxy Substances 0.000 claims abstract description 35
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 51
- 150000005846 sugar alcohols Polymers 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 21
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 20
- -1 sulfonium cation Chemical class 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
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- 239000000194 fatty acid Substances 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
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- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- BSNFHTQNYVCKGM-UHFFFAOYSA-N OC([Ag])=O Chemical compound OC([Ag])=O BSNFHTQNYVCKGM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 claims description 2
- 239000002003 electrode paste Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
- 239000002245 particle Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
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- 229910000679 solder Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
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- 229910000831 Steel Inorganic materials 0.000 description 3
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- 239000012535 impurity Substances 0.000 description 3
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- 229910001923 silver oxide Inorganic materials 0.000 description 3
- YWZDCTBAHKRVGL-UHFFFAOYSA-M silver;2,2-bis(hydroxymethyl)butanoate Chemical compound [Ag+].CCC(CO)(CO)C([O-])=O YWZDCTBAHKRVGL-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
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- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- SUFQRHZIMVUZOI-UHFFFAOYSA-J [Ag]OC(=O)CC(C(CC(=O)O[Ag])C(=O)O[Ag])C(=O)O[Ag] Chemical compound [Ag]OC(=O)CC(C(CC(=O)O[Ag])C(=O)O[Ag])C(=O)O[Ag] SUFQRHZIMVUZOI-UHFFFAOYSA-J 0.000 description 2
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- SUBDVAVHQMAIST-UHFFFAOYSA-M silver;2-hydroxy-2-methylpropanoate Chemical compound [Ag+].CC(C)(O)C([O-])=O SUBDVAVHQMAIST-UHFFFAOYSA-M 0.000 description 2
- QTPLEVOKSWEYAC-UHFFFAOYSA-N 1,2-diphenyl-9h-fluorene Chemical compound C=1C=CC=CC=1C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 QTPLEVOKSWEYAC-UHFFFAOYSA-N 0.000 description 1
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- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- FGPFIXISGWXSCE-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)propane-1,3-diol Chemical compound C1OC1COCC(CO)(CO)COCC1CO1 FGPFIXISGWXSCE-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- CUGZWHZWSVUSBE-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)ethanol Chemical compound OCCOCC1CO1 CUGZWHZWSVUSBE-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- STHCTMWQPJVCGN-UHFFFAOYSA-N 2-[[2-[1,1,2-tris[2-(oxiran-2-ylmethoxy)phenyl]ethyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1CC(C=1C(=CC=CC=1)OCC1OC1)(C=1C(=CC=CC=1)OCC1OC1)C1=CC=CC=C1OCC1CO1 STHCTMWQPJVCGN-UHFFFAOYSA-N 0.000 description 1
- FPWIFVPKMRUJQJ-UHFFFAOYSA-N 2-[bis(oxiran-2-ylmethoxy)methoxymethyl]oxirane Chemical compound C1OC1COC(OCC1OC1)OCC1CO1 FPWIFVPKMRUJQJ-UHFFFAOYSA-N 0.000 description 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
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- VTPXYFSCMLIIFK-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propan-1-ol Chemical compound C1OC1COCC(COCC1OC1)(CO)COCC1CO1 VTPXYFSCMLIIFK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- C08G59/68—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 catalysts used
- C08G59/687—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 catalysts used containing sulfur
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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, a solar battery cell using the conductive composition, and a method for manufacturing a solar battery.
- conductive particles such as silver particles, a binder made of a thermoplastic resin (eg, acrylic resin, vinyl acetate resin, etc.) or a thermosetting resin (eg, epoxy resin, unsaturated polyester resin, etc.), organic solvent, cured Silver paste (conductive composition) obtained by adding and mixing agents, catalysts, etc., is printed on a synthetic resin substrate (for example, a polyester film) so as to have a predetermined circuit pattern, and these are heated.
- a synthetic resin substrate for example, a polyester film
- Patent Document 1 states that “an epoxy resin having a molecular weight of 900 or more, a silver powder having a weight ratio within a range of 4 to 10 with respect to the epoxy resin, and curing the epoxy resin.
- the conductive paste is characterized in that it contains an imidazole-based curing agent in an amount of addition of at least twice the minimum amount required to make it.
- Patent Document 2 discloses that “(A) an epoxy resin, (B) an oxetane resin, (C) a cationic polymerization curing agent, and (D) a conductive paste characterized by blending conductive powder. Is described.
- thermosetting component is a bisphenol A type epoxy resin having an epoxy equivalent of 2000 to 3500 g / eq; And a polyhydric alcohol-based glycidyl-type epoxy resin having an epoxy equivalent of 1000 g / eq or less and a viscosity of 10 to 100 mPa ⁇ s, and a curing agent, wherein the polyhydric alcohol-based glycidyl-type epoxy resin comprises: An alkyldiol system having the structural formula of Chemical Formula 1 or a polyethylene glycol system having the structural formula of Chemical Formula 2 below, wherein n in the structural formula of Chemical Formula 1 and the structural formula of Chemical Formula 2 is 3 to 9, and the bisphenol A type epoxy The weight mixing ratio of the resin to the polyhydric alcohol-based glycidyl type epoxy resin is 1 to 1 to 1 to 3. Electroconductive paste composition and symptoms. "Is described.
- Patent Documents 4 to 6 describe “a silver paste containing silver powder, an epoxy resin and its curing agent (phenol novolac compound), and a solvent”.
- an object of the present invention is to provide a conductive composition having good solderability to a cured product, a solar battery cell in which an electrode is formed using the conductive composition, and a method for manufacturing a solar battery.
- the present inventor when a sulfonium cation-based curing agent is blended with two specific types of epoxy resins, becomes a conductive composition with good solderability to a cured product. As a result, the present invention has been completed.
- the present invention (1) contains silver powder (A), epoxy resin (B), and curing agent (C),
- the epoxy resin (B) is at least a bisphenol A type epoxy resin (b1) having an epoxy equivalent of 1500 to 4000 g / eq and a polyhydric alcohol-based glycidyl type epoxy resin (b2) having an epoxy equivalent of 1000 g / eq or less
- the present invention also provides: (2) It comprises a surface electrode on the light receiving surface side, a semiconductor substrate and a back electrode, Provided is a solar cell in which the front electrode and / or the back electrode is formed using the conductive composition according to (1) above used for a solar cell electrode paste. Furthermore, the present invention provides (3) a wiring forming step of forming a wiring by applying the conductive composition according to (1) above on a silicon substrate; There is provided a method for manufacturing a solar battery cell, comprising: a heat treatment step of heat-treating the obtained wiring to form a front-surface electrode and / or a back-surface electrode on a light-receiving surface side.
- the present invention it is possible to provide a conductive composition having good solderability to a cured product, a solar battery cell in which an electrode is formed using the conductive composition, and a method for manufacturing a solar battery.
- the conductive composition of the present invention can form an electrode or the like while suppressing the occurrence of disconnection or blurring even when firing at a low temperature (about 150 to 500 ° C.).
- the use of the conductive composition of the present invention is very useful because an electrode or the like can be formed not only on a silicon substrate but also on a substrate having low heat resistance.
- FIG. 1 is a cross-sectional view showing an example of a preferred embodiment of a solar battery cell.
- FIG. 2 is a photograph of silver powder (AgC-103, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) taken with a scanning electron microscope (SEM).
- FIG. 3 is a photograph of silver powder (AgC-2011, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) taken with a scanning electron microscope (SEM).
- the conductive composition of the present invention contains silver powder (A), an epoxy resin (B), and a curing agent (C), and the epoxy resin (B) has at least an epoxy equivalent of 1500 to 4000 g / eq.
- the silver powder (A) used by the electrically conductive composition of this invention is not specifically limited, What is mix
- the silver powder (A) is preferably a spherical silver powder having an average particle diameter of 0.5 to 10 ⁇ m because it has good printability and can form an electrode having a small volume resistivity.
- spherical refers to the shape of a particle having a major axis / minor axis ratio of 2 or less.
- an average particle diameter means the average value of the particle diameter of spherical silver powder, and means the 50% volume cumulative diameter (D50) measured using the laser diffraction type particle size distribution measuring apparatus.
- the particle diameter that is the basis for calculating the average value is the average value obtained by dividing the total value of the major axis and the minor axis by 2, and is a regular circle Refers to its diameter.
- a silver powder (AgC-103, manufactured by Fukuda Metal Foil Powder Co., Ltd.) used in the examples described later corresponds to a spherical silver powder, but silver powder (AgC-2011, Fukuda). What is shown by the photograph (FIG. 3) of a metal foil powder industry company does not correspond to spherical silver powder, but corresponds to flake (scale) -like silver powder.
- the average particle size of the silver powder (A) is preferably 0.7 to 5 ⁇ m for the reason that printability is better, and 1 to 3 ⁇ m for the reason that the sintering speed is appropriate and the workability is excellent. It is more preferable that
- a commercially available product can be used as such silver powder (A).
- Specific examples thereof include AgC-102 (shape: spherical, average particle size: 1.5 ⁇ m, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.).
- AgC-103 (shape: spherical, average particle diameter: 1.5 ⁇ m, manufactured by Fukuda Metal Foil Powder Industries), AG4-8F (shape: spherical, average particle diameter: 2.2 ⁇ m, manufactured by DOWA Electronics), AG2 -1C (shape: spherical, average particle size: 1.0 ⁇ m, manufactured by DOWA Electronics), AG3-11F (shape: spherical, average particle size: 1.4 ⁇ m, manufactured by DOWA Electronics), EHD (shape: spherical, average Particle diameter: 0.5 ⁇ m, manufactured by Mitsui Kinzoku Co., Ltd.), AgC-2011 (shape: flake shape, average particle diameter: 2-10 ⁇ m, manufactured by Fukuda Metal Foil Co., Ltd.), and the like.
- AG4-8F shape: spherical, average particle diameter: 2.2 ⁇ m, manufactured by DOWA Electronics
- AG2 -1C shape:
- the epoxy resin (B) used in the conductive composition of the present invention comprises at least a bisphenol A type epoxy resin (b1) having an epoxy equivalent of 1500 to 4000 g / eq and a polyhydric alcohol glycidyl type having an epoxy equivalent of 1000 g / eq or less. Although it is an epoxy resin (b2), you may use together another epoxy resin (b3) with these epoxy resins.
- the epoxy equivalent of the epoxy resin (B) is the Japanese Industrial Standard JIS. This is a value calculated according to “How to determine epoxy equivalent of epoxy resin” in K-7236: 2001.
- the bisphenol A type epoxy resin (b1) is a bisphenol A type epoxy resin having an epoxy equivalent of 1500 to 4000 g / eq.
- the epoxy equivalent of the bisphenol A-type epoxy resin (b1) is within the above range, the hardness of the conductive composition of the present invention after curing becomes good, and excellent solderability for the cured product can be maintained.
- the epoxy equivalent of the bisphenol A type epoxy resin (b1) has better solderability to the cured product of the conductive composition of the present invention, and the rate of cure shrinkage is small, such as an adherend (for example, a circuit board) ) Is preferably 2000 to 4000 g / eq, more preferably 2000 to 3500 g / eq.
- the polyhydric alcohol glycidyl type epoxy resin (b2) is a polyhydric alcohol glycidyl type epoxy resin having an epoxy equivalent of 1000 g / eq or less.
- the epoxy equivalent of the polyhydric alcohol-based glycidyl type epoxy resin (b2) is preferably 100 to 400 g / eq, and preferably 100 to 300 g / eq, because the viscosity at the time of screen printing becomes appropriate. More preferably.
- the viscosity of the electrically conductive composition of this invention becomes favorable and printability becomes favorable, it is preferable that it is 100 g / eq or more.
- polyhydric alcohol glycidyl type epoxy resin (b2) examples include, for example, ethylene glycol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
- 1,6-hexanediol diglycidyl ether 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polyneopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, propylene glycol diglycidyl ether, tri Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, diethylene Recall diglycidyl ether, polyglycerin polyglycidyl ether, polyoxyethylene glycol diglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polytetramethylene glycol diglycidyl ether, pentaerythritol diglycid
- polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are preferable and more excellent because the hardness after curing of the conductive composition of the present invention becomes good and solderability to the cured product becomes better. It is more preferable to use polyethylene glycol diglycidyl ether because it can provide high conductivity.
- the other epoxy resin (b3) 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.
- Specific examples of the other epoxy resin (b3) include, for example, a bisphenol A type epoxy resin (excluding those corresponding to the bisphenol A type epoxy resin (b1)), a bisphenol F type epoxy resin, and a biphenyl type epoxy. Resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, diphenylfluorene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidylamine type epoxy resin, etc., and these can be used alone. Or two or more of them may be used in combination.
- the content in the case of containing the other epoxy resin (b3) is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the epoxy resin (B).
- the content of the epoxy resin (B) is appropriate for the hardness after curing of the conductive composition of the present invention, so that the adhesion to an adherend (for example, a circuit board) is good, Further, for the reason that the solderability to the cured product becomes better, the amount is preferably 4 to 10 parts by mass, more preferably 4 to 8 parts by mass with respect to 100 parts by mass of the silver powder (A). .
- group glycidyl type epoxy resin (b2) is not specifically limited,
- the hardness after hardening of the electrically conductive composition of this invention Is better, and it is easy to maintain excellent solderability to the cured product, so that the blending amount (mass) of the bisphenol A type epoxy resin (b1) is more than that of the polyhydric alcohol glycidyl type epoxy resin (b2). It is also preferable that there are many.
- the curing agent (C) used in the conductive composition of the present invention is a sulfonium cation curing agent.
- Examples of the curing agent (C) include sulfonium salts represented by the following formula (I).
- R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom
- R 2 is substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms.
- R 3 represents an alkyl group having 1 to 4 carbon atoms
- Q is represented by any of the following formulas (a) to (c):
- X represents SbF 6 , PF 6 , CF 3 SO 3 , (CF 3 SO 2 ) 2 N, BF 4 , B (C 6 F 5 ) 4 or Al (CF 3 SO 3 ) 4 .
- R represents a hydrogen atom, an acetyl group, a methoxycarbonyl group or a benzyloxycarbonyl group.
- X in the above formula (I) is represented by SbF 6 because the solderability to the cured product of the conductive composition of the present invention becomes better.
- a sulfonium salt is preferable, and specific examples thereof include compounds represented by the following formulas (1) and (2).
- cured material of the electrically conductive composition of this invention becomes favorable by using a sulfonium cation type
- curing agent as said hardening
- the degree of polymerization of the epoxy resin (B) is increased by using a sulfonium cationic curing agent that exhibits sufficient curability even at low temperatures (about 150 to 500 ° C.), compared to the case of using an imidazole curing agent, As a result, it is considered that the contact between the silver powders (A) increases.
- the sulfonium cation-based curing agent has hexafluoroantimonate ion (SbF 6 ⁇ ) as an anion, it acts as a metal catalyst, so that solderability is considered to be better.
- curing agent (C) is activated with a heat
- the amount is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight.
- the conductive composition of the present invention can form an electrode and the like even when fired at a lower temperature (about 150 to 200 ° C.), and further reduces damage to the silicon substrate due to heat. It preferably contains a salt (D).
- the fatty acid silver salt (D) is not particularly limited as long as it is a silver salt of an organic carboxylic acid.
- a silver salt (D2) Specifically, for example, as the fatty acid silver salt (D1), 2,2-bis (hydroxymethyl) -n-butyric acid silver salt and 2-hydroxyisobutyric acid silver salt can be preferably used.
- the carboxylic acid silver salt (D2) 1,2,3,4-butanetetracarboxylic acid silver salt can be preferably used.
- the content of the fatty acid silver salt (D) is 1 with respect to 100 parts by mass of the silver powder (A) because the printability is good and an electrode having a small volume resistivity can be formed.
- the amount is preferably from 100 to 100 parts by mass, and more preferably from 5 to 80 parts by mass.
- the conductive composition of the present invention preferably further contains a solvent from the viewpoint of workability such as printability.
- the solvent is not particularly limited as long as the conductive composition of the present invention can be applied on a substrate, and specific examples thereof include butyl carbitol, methyl ethyl ketone, isophorone, ⁇ -terpineol, and the like. These may be used alone or in combination of two or more. Further, when the solvent is contained, the content is preferably 2 to 20 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the silver powder (A).
- the electrically conductive composition of this invention may contain additives, such as metal powder other than the silver powder (A) mentioned above, a reducing agent, as needed.
- the metal powder include copper and aluminum. Among them, copper is preferable. Further, a metal powder having a particle diameter of 0.01 to 10 ⁇ m is preferable.
- Specific examples of the reducing agent include ethylene glycols.
- the manufacturing method of the electroconductive composition of this invention is not specifically limited, The said silver powder (A), the said epoxy resin (B), the said hardening
- the solar cell of the present invention comprises a light-receiving surface-side surface electrode, a semiconductor substrate, and a back electrode, and the surface electrode and / or the back electrode is formed using the above-described conductive composition of the present invention. It is a solar battery cell.
- the solar battery cell of the present invention can be applied to the formation of the back electrode of the all back electrode type (so-called back contact type) solar battery because the above-described conductive composition of the present invention can be applied to the all back electrode.
- the present invention can also be applied to a type solar cell. Below, the structure of the photovoltaic cell of this invention is demonstrated using FIG.
- a solar cell 1 of the present invention 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. It is. Further, as shown in FIG. 1, the solar battery cell 1 of the present invention is provided with an antireflection film 3 by, for example, etching the wafer surface to form a pyramidal texture in order to reduce the reflectance. Is preferred.
- the electrode arrangement (pitch), shape, height, The width and the like are not particularly limited.
- the front surface electrode and the back surface electrode usually have a plurality, but in the present invention, for example, only a part of the plurality of front surface electrodes is the conductive composition of the present invention. Or a part of the plurality of front surface electrodes and a part of the plurality of back surface electrodes may be formed of the conductive composition of the present invention.
- the antireflection film that the solar battery cell of the present invention may have 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 film film thickness: about 0.05 to 0.1 ⁇ m
- the silicon substrate included in the solar battery cell of the present invention is not particularly limited, and a known silicon substrate (plate thickness: about 100 to 450 ⁇ m) for forming a solar battery can be used, and a single crystal or polycrystal Any silicon substrate may be used.
- 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 front electrode and / or the back electrode are formed using the conductive composition of the present invention, so that the solderability to each electrode (especially the bus bar portion) is good and modularized. Is easy.
- the manufacturing method of the photovoltaic cell of the present invention is not particularly limited, a wiring forming step of forming the wiring by applying the conductive composition of the present invention on a silicon substrate, and heat treating the obtained wiring to form an electrode (surface A heat treatment step of forming an electrode and / or a back electrode).
- an antireflection film can be formed by well-known methods, such as a plasma CVD method. Below, a wiring formation process and a heat treatment process are explained in full detail.
- the said wiring formation process is a process of apply
- 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 obtaining a conductive wiring (electrode) by heat-treating the wiring obtained in the wiring forming step.
- the heat treatment is not particularly limited, but is preferably a treatment of heating (firing) at a temperature of 150 to 800 ° C. for several seconds to several tens of minutes.
- the temperature and time are within this range, even when an antireflection film is formed on the silicon substrate, the electrode can be easily formed by the fire-through method.
- good heat treatment (firing) can be performed even at a low temperature (about 150 to 500 ° C.).
- the heat treatment step may be performed by irradiation with ultraviolet rays or infrared rays.
- solderability (solder wettability)>
- the prepared conductive composition is applied on a silicon substrate (single crystal silicon wafer, LS-25TVA, 156 mm ⁇ 156 mm ⁇ 200 ⁇ m, manufactured by Shin-Etsu Chemical Co., Ltd.) by screen printing to form a test pattern (2 mm ⁇ 2 mm). did.
- a solder flux was applied on the formed test pattern and then dried on a hot plate at 150 ° C. for 20 seconds. Next, it was dipped in a solder bath at 270 ° C. for 3 seconds and then pulled up, and the solderability was evaluated from the wettability (covering%) of the solder on the test pattern.
- a test pattern having a solder coverage of 100% is evaluated as “A” as having extremely good solderability, and a test pattern solder coverage of 80% or more and less than 100%.
- B was evaluated as having good solderability
- C was evaluated as having poor solderability when solder coverage on the test pattern was less than 80%.
- a wiring was formed by screen printing using the conductive composition prepared in Examples 1 and 10 to 12, and then dried in an oven for 30 minutes under three conditions of 200 ° C., 180 ° C. and 150 ° C. Samples of solar cells on which the wirings (electrodes) were formed were prepared. About the sample of each produced photovoltaic cell, the volume resistivity of the electrode was measured by a 4-terminal 4-probe method using a resistivity meter (Lorestar GP, manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 2 below.
- Silver powder AgC-103 (shape: spherical, average particle size: 1.5 ⁇ m, manufactured by Fukuda Metal Foil Powder Industry)
- ⁇ ⁇ -Terpineol Solvent
- Bisphenol A type epoxy resin YD-019 (epoxy equivalent: 2400-3300 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
- Bisphenol A type epoxy resin YD-020N (epoxy equivalent: 3500 to 4000 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
- Bisphenol A type epoxy resin YD-014 (epoxy equivalent: 900 to 1000 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
- Polyhydric alcohol glycidyl type epoxy resin polyethylene glycol diglycidyl ether (EX-821, epoxy equivalent: 185 g / eq, manufactured by Nagase ChemteX Corporation)
- Polyhydric alcohol glycidyl type epoxy resin diethylene glycol diglycidyl ether (EX-850, epoxy equivalent: 122 g / eq, manufactured by Nagase ChemteX Corporation)
- Polyhydric alcohol glycidyl type epoxy resin ethylene glycol diglycidyl ether (EX-810, epoxy equivalent: 113 g / eq, manufactured by Nagase ChemteX Corporation)
- Polyhydric alcohol glycidyl type epoxy resin 1,6-hexanediol diglycidyl ether (EX-212, epoxy equivalent: 151 g / eq, manufactured by Nagase ChemteX Corporation)
- Curing agent Compound represented by the following formula (1) (Sl-100L, manufactured by Sanshin Chemical Industry Co., Ltd.) Curing agent: Compound represented by the following formula (2) (SI-150, manufactured by Sanshin Chemical Industry Co., Ltd.) Curing agent: Compound represented by the following formula (3) Curing agent: Compound represented by the following formula (4) (Boron trifluoride ethylamine, manufactured by Tokyo Chemical Industry Co., Ltd.)
- R 4 represents a hydroxyl group
- R 5 represents a methyl group
- R 6 represents a methyl group
- Silver salt of 2-hydroxyisobutyrate First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 45 g of 2-hydroxyisobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) are placed in a ball mill and are allowed to stand at room temperature for 24 hours The reaction was allowed to stir. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare white 2-hydroxyisobutyric acid silver salt.
- MEK methyl ethyl ketone
- -1,2,3,4-butanetetracarboxylic acid silver salt First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 1,2,3,4-butanetetracarboxylic acid (manufactured by Shin Nippon Rika Co., Ltd.) 29 g 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 white 1,2,3,4-butanetetracarboxylic acid silver salt.
- MEK methyl ethyl ketone
- the conductive compositions of Comparative Examples 4 and 5 prepared without blending either one of the bisphenol A type epoxy resin and the polyhydric alcohol glycidyl type epoxy resin are inferior in printability and in solderability. I understood.
- the electroconductive composition of the comparative example 6 prepared by using together 2 types of bisphenol A type epoxy resins from which an epoxy equivalent differs is inferior to printability, and solderability.
- the conductive compositions of Examples 1 to 10 prepared using a sulfonium cation curing agent in combination with a bisphenol A type epoxy resin and a polyhydric alcohol glycidyl type epoxy resin having a predetermined epoxy equivalent weight was found to be excellent in printability and solderability.
- the conductive compositions of Examples 1 to 7 and 9 to 12 prepared using a curing agent having hexafluoroantimonate ion (SbF 6 ⁇ ) as an anion may have extremely good solderability. I understood.
- the conductive compositions of Examples 1, 2, 4, 6 to 8, and 10 to 12 in which the blending amount of the bisphenol A type epoxy resin is larger than the blending amount of the polyhydric alcohol glycidyl type epoxy resin, have printability. It turns out that it tends to be very good. Further, from the results shown in Table 2, the conductive compositions of Examples 10 to 12 used in combination with the fatty acid silver salt have a volume resistivity independent of the firing temperature as compared with the conductive composition of Example 1. It turned out to be lower.
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Abstract
The present invention provides an electroconductive composition having excellent solderability to cured products, a solar battery cell having electrodes formed by using said electroconductive composition, and a method for producing a solar battery. The electroconductive composition contains silver powder (A), epoxy resins (B), and a curing agent (C). The epoxy resins (B) are at least a bisphenol-A-type epoxy resin (b1) having an epoxy equivalent of 1500 to 4000 g/eq and a polyol-glycidyl-type epoxy resin (b2) having an epoxy equivalent of 1000 g/eq or less. The curing agent (C) is a sulfonium cationic curing agent.
Description
本発明は、導電性組成物、それを用いて電極を形成した太陽電池セルおよび太陽電池の製造方法に関する。
The present invention relates to a conductive composition, a solar battery cell using the conductive composition, and a method for manufacturing a solar battery.
従来、銀粒子などの導電性粒子に熱可塑性樹脂（例えば、アクリル樹脂、酢酸ビニル樹脂等）や熱硬化性樹脂（例えば、エポキシ樹脂、不飽和ポリエステル樹脂等）などからなるバインダ、有機溶剤、硬化剤、触媒等を添加し混合して得られる銀ペースト（導電性組成物）を、合成樹脂基材上（例えば、ポリエステルフィルム等）に所定の回路パターンとなるように印刷し、これらを加熱して導体回路をなす導電性配線を形成し、回路基板を製造する方法が知られている。
Conventionally, conductive particles such as silver particles, a binder made of a thermoplastic resin (eg, acrylic resin, vinyl acetate resin, etc.) or a thermosetting resin (eg, epoxy resin, unsaturated polyester resin, etc.), organic solvent, cured Silver paste (conductive composition) obtained by adding and mixing agents, catalysts, etc., is printed on a synthetic resin substrate (for example, a polyester film) so as to have a predetermined circuit pattern, and these are heated. There is known a method of manufacturing a circuit board by forming a conductive wiring forming a conductor circuit.
例えば、エポキシ樹脂系のペースト材料として、特許文献１には、「分子量が９００以上のエポキシ樹脂と、前記エポキシ樹脂に対する重量比率が４～１０の範囲内である銀粉末と、前記エポキシ樹脂を硬化させるのに最低限必要な添加量の２倍以上の添加量のイミダゾール系硬化剤とを含むことを特徴とする導電ペースト。」が記載されている。
For example, as an epoxy resin-based paste material, Patent Document 1 states that “an epoxy resin having a molecular weight of 900 or more, a silver powder having a weight ratio within a range of 4 to 10 with respect to the epoxy resin, and curing the epoxy resin. The conductive paste is characterized in that it contains an imidazole-based curing agent in an amount of addition of at least twice the minimum amount required to make it.
また、特許文献２には、「（Ａ）エポキシ樹脂、（Ｂ）オキセタン樹脂、（Ｃ）カチオン重合系硬化剤および（Ｄ）導電性粉末を配合してなることを特長とする導電性ペースト。」が記載されている。
Further, Patent Document 2 discloses that “(A) an epoxy resin, (B) an oxetane resin, (C) a cationic polymerization curing agent, and (D) a conductive paste characterized by blending conductive powder. Is described.
更に、特許文献３には、「銀粉末と加熱硬化性成分と溶剤とを含む導電性ペースト組成物において、前記加熱硬化性成分が、エポキシ当量が２０００ないし３５００ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂と、エポキシ当量が１０００ｇ／ｅｑ以下で粘性率が１０ないし１００ｍＰａ・ｓの多価アルコール系のグリシジル型エポキシ樹脂と、硬化剤とを含有し、前記多価アルコール系のグリシジル型エポキシ樹脂が、以下の化１の構造式を有するアルキルジオール系または以下の化２の構造式を有するポリエチレングリコール系で、化１の構造式と化２の構造式におけるｎが３ないし９であり、前記ビスフェノールＡ型エポキシ樹脂対多価アルコール系のグリシジル型エポキシ樹脂の重量混合比率が、１対１ないし１対３であることを特徴とする導電性ペースト組成物。」が記載されている。
Further, in Patent Document 3, “in a conductive paste composition containing silver powder, a thermosetting component, and a solvent, the thermosetting component is a bisphenol A type epoxy resin having an epoxy equivalent of 2000 to 3500 g / eq; And a polyhydric alcohol-based glycidyl-type epoxy resin having an epoxy equivalent of 1000 g / eq or less and a viscosity of 10 to 100 mPa · s, and a curing agent, wherein the polyhydric alcohol-based glycidyl-type epoxy resin comprises: An alkyldiol system having the structural formula of Chemical Formula 1 or a polyethylene glycol system having the structural formula of Chemical Formula 2 below, wherein n in the structural formula of Chemical Formula 1 and the structural formula of Chemical Formula 2 is 3 to 9, and the bisphenol A type epoxy The weight mixing ratio of the resin to the polyhydric alcohol-based glycidyl type epoxy resin is 1 to 1 to 1 to 3. Electroconductive paste composition and symptoms. "Is described.
更にまた、特許文献４～６には、「銀粉末と、エポキシ樹脂およびその硬化剤（フェノールノボラック化合物）と、溶剤とを含有する銀ペースト」が記載されている。
Furthermore, Patent Documents 4 to 6 describe “a silver paste containing silver powder, an epoxy resin and its curing agent (phenol novolac compound), and a solvent”.
しかしながら、本発明者が、特許文献１～６に記載されたエポキシ樹脂系のペースト材料について検討したところ、スクリーン印刷を用いてペースト材料から形成される配線や電極（以下、「電極等」ともいう。）に対する半田付け性（半田濡れ性）が劣り、例えば、太陽電池セルの集電電極を形成した場合にはモジュール化することが困難であることが明らかとなった。
However, the present inventor examined the epoxy resin-based paste materials described in Patent Documents 1 to 6, and found that wirings and electrodes (hereinafter also referred to as “electrodes”) formed from the paste material using screen printing. )) Is inferior in solderability (solder wettability), and for example, when the collector electrode of a solar battery cell is formed, it has become clear that it is difficult to make a module.
そこで、本発明は、硬化物に対する半田付け性が良好な導電性組成物、それを用いて電極を形成した太陽電池セルおよび太陽電池の製造方法を提供することを課題とする。
Therefore, an object of the present invention is to provide a conductive composition having good solderability to a cured product, a solar battery cell in which an electrode is formed using the conductive composition, and a method for manufacturing a solar battery.
本発明者は、上記課題を解決するため鋭意検討した結果、特定の２種類のエポキシ樹脂に対してスルホニウムカチオン系硬化剤を配合すると、硬化物に対する半田付け性が良好な導電性組成物になることを見出し、本発明を完成させた。即ち、本発明は、
（１）銀粉（Ａ）と、エポキシ樹脂（Ｂ）と、硬化剤（Ｃ）とを含有し、
上記エポキシ樹脂（Ｂ）が、少なくとも、エポキシ当量が１５００～４０００ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂（ｂ１）およびエポキシ当量が１０００ｇ／ｅｑ以下の多価アルコール系グリシジル型エポキシ樹脂（ｂ２）であり、
上記硬化剤（Ｃ）が、スルホニウムカチオン系硬化剤である導電性組成物、を提供する。 As a result of intensive studies to solve the above problems, the present inventor, when a sulfonium cation-based curing agent is blended with two specific types of epoxy resins, becomes a conductive composition with good solderability to a cured product. As a result, the present invention has been completed. That is, the present invention
(1) contains silver powder (A), epoxy resin (B), and curing agent (C),
The epoxy resin (B) is at least a bisphenol A type epoxy resin (b1) having an epoxy equivalent of 1500 to 4000 g / eq and a polyhydric alcohol-based glycidyl type epoxy resin (b2) having an epoxy equivalent of 1000 g / eq or less,
Provided is a conductive composition in which the curing agent (C) is a sulfonium cationic curing agent.
（１）銀粉（Ａ）と、エポキシ樹脂（Ｂ）と、硬化剤（Ｃ）とを含有し、
上記エポキシ樹脂（Ｂ）が、少なくとも、エポキシ当量が１５００～４０００ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂（ｂ１）およびエポキシ当量が１０００ｇ／ｅｑ以下の多価アルコール系グリシジル型エポキシ樹脂（ｂ２）であり、
上記硬化剤（Ｃ）が、スルホニウムカチオン系硬化剤である導電性組成物、を提供する。 As a result of intensive studies to solve the above problems, the present inventor, when a sulfonium cation-based curing agent is blended with two specific types of epoxy resins, becomes a conductive composition with good solderability to a cured product. As a result, the present invention has been completed. That is, the present invention
(1) contains silver powder (A), epoxy resin (B), and curing agent (C),
The epoxy resin (B) is at least a bisphenol A type epoxy resin (b1) having an epoxy equivalent of 1500 to 4000 g / eq and a polyhydric alcohol-based glycidyl type epoxy resin (b2) having an epoxy equivalent of 1000 g / eq or less,
Provided is a conductive composition in which the curing agent (C) is a sulfonium cationic curing agent.
また、本発明は、
（２）受光面側の表面電極、半導体基板および裏面電極を具備し、
上記表面電極および／または上記裏面電極が、太陽電池電極用ペーストに用いる上記（１）に記載の導電性組成物を用いて形成される太陽電池セル、を提供する。
さらに、本発明は、
（３）上記（１）に記載の導電性組成物をシリコン基板上に塗布して配線を形成する配線形成工程と、
得られた上記配線を熱処理して受光面側の表面電極および／または裏面電極を形成する熱処理工程と、を有する太陽電池セルの製造方法、を提供する。 The present invention also provides:
(2) It comprises a surface electrode on the light receiving surface side, a semiconductor substrate and a back electrode,
Provided is a solar cell in which the front electrode and / or the back electrode is formed using the conductive composition according to (1) above used for a solar cell electrode paste.
Furthermore, the present invention provides
(3) a wiring forming step of forming a wiring by applying the conductive composition according to (1) above on a silicon substrate;
There is provided a method for manufacturing a solar battery cell, comprising: a heat treatment step of heat-treating the obtained wiring to form a front-surface electrode and / or a back-surface electrode on a light-receiving surface side.
（２）受光面側の表面電極、半導体基板および裏面電極を具備し、
上記表面電極および／または上記裏面電極が、太陽電池電極用ペーストに用いる上記（１）に記載の導電性組成物を用いて形成される太陽電池セル、を提供する。
さらに、本発明は、
（３）上記（１）に記載の導電性組成物をシリコン基板上に塗布して配線を形成する配線形成工程と、
得られた上記配線を熱処理して受光面側の表面電極および／または裏面電極を形成する熱処理工程と、を有する太陽電池セルの製造方法、を提供する。 The present invention also provides:
(2) It comprises a surface electrode on the light receiving surface side, a semiconductor substrate and a back electrode,
Provided is a solar cell in which the front electrode and / or the back electrode is formed using the conductive composition according to (1) above used for a solar cell electrode paste.
Furthermore, the present invention provides
(3) a wiring forming step of forming a wiring by applying the conductive composition according to (1) above on a silicon substrate;
There is provided a method for manufacturing a solar battery cell, comprising: a heat treatment step of heat-treating the obtained wiring to form a front-surface electrode and / or a back-surface electrode on a light-receiving surface side.
以下に示すように、本発明によれば、硬化物に対する半田付け性が良好な導電性組成物、それを用いて電極を形成した太陽電池セルおよび太陽電池の製造方法を提供することができる。
また、本発明の導電性組成物は、低温（１５０～５００℃程度）焼成であっても、断線やニジミ等の発生を抑制して電極等を形成することができる。
更に、本発明の導電性組成物を用いれば、シリコン基板のみならず、耐熱性の低い基材上にも電極等を形成することができるため非常に有用である。 As shown below, according to the present invention, it is possible to provide a conductive composition having good solderability to a cured product, a solar battery cell in which an electrode is formed using the conductive composition, and a method for manufacturing a solar battery.
In addition, the conductive composition of the present invention can form an electrode or the like while suppressing the occurrence of disconnection or blurring even when firing at a low temperature (about 150 to 500 ° C.).
Furthermore, the use of the conductive composition of the present invention is very useful because an electrode or the like can be formed not only on a silicon substrate but also on a substrate having low heat resistance.
また、本発明の導電性組成物は、低温（１５０～５００℃程度）焼成であっても、断線やニジミ等の発生を抑制して電極等を形成することができる。
更に、本発明の導電性組成物を用いれば、シリコン基板のみならず、耐熱性の低い基材上にも電極等を形成することができるため非常に有用である。 As shown below, according to the present invention, it is possible to provide a conductive composition having good solderability to a cured product, a solar battery cell in which an electrode is formed using the conductive composition, and a method for manufacturing a solar battery.
In addition, the conductive composition of the present invention can form an electrode or the like while suppressing the occurrence of disconnection or blurring even when firing at a low temperature (about 150 to 500 ° C.).
Furthermore, the use of the conductive composition of the present invention is very useful because an electrode or the like can be formed not only on a silicon substrate but also on a substrate having low heat resistance.
本発明の導電性組成物は、銀粉（Ａ）と、エポキシ樹脂（Ｂ）と、硬化剤（Ｃ）とを含有し、上記エポキシ樹脂（Ｂ）が、少なくとも、エポキシ当量が１５００～４０００ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂（ｂ１）およびエポキシ当量が１０００ｇ／ｅｑ以下の多価アルコール系グリシジル型エポキシ樹脂（ｂ２）であり、上記硬化剤（Ｃ）が、スルホニウムカチオン系硬化剤である導電性組成物である。
以下に、銀粉（Ａ）、エポキシ樹脂（Ｂ）および硬化剤（Ｃ）について詳述する。 The conductive composition of the present invention contains silver powder (A), an epoxy resin (B), and a curing agent (C), and the epoxy resin (B) has at least an epoxy equivalent of 1500 to 4000 g / eq. A bisphenol A type epoxy resin (b1) and a polyhydric alcohol glycidyl type epoxy resin (b2) having an epoxy equivalent of 1000 g / eq or less, and the curing agent (C) is a sulfonium cation type curing agent. It is a thing.
Below, silver powder (A), an epoxy resin (B), and a hardening | curing agent (C) are explained in full detail.
以下に、銀粉（Ａ）、エポキシ樹脂（Ｂ）および硬化剤（Ｃ）について詳述する。 The conductive composition of the present invention contains silver powder (A), an epoxy resin (B), and a curing agent (C), and the epoxy resin (B) has at least an epoxy equivalent of 1500 to 4000 g / eq. A bisphenol A type epoxy resin (b1) and a polyhydric alcohol glycidyl type epoxy resin (b2) having an epoxy equivalent of 1000 g / eq or less, and the curing agent (C) is a sulfonium cation type curing agent. It is a thing.
Below, silver powder (A), an epoxy resin (B), and a hardening | curing agent (C) are explained in full detail.
＜銀粉（Ａ）＞
本発明の導電性組成物で用いる銀粉（Ａ）は特に限定されず、従来公知の導電性ペーストで配合されているものを使用することができる。 <Silver powder (A)>
The silver powder (A) used by the electrically conductive composition of this invention is not specifically limited, What is mix | blended with the conventionally well-known electrically conductive paste can be used.
本発明の導電性組成物で用いる銀粉（Ａ）は特に限定されず、従来公知の導電性ペーストで配合されているものを使用することができる。 <Silver powder (A)>
The silver powder (A) used by the electrically conductive composition of this invention is not specifically limited, What is mix | blended with the conventionally well-known electrically conductive paste can be used.
上記銀粉（Ａ）は、印刷性が良好となり、体積抵抗率の小さい電極等を形成することができる理由から、平均粒子径が０．５～１０μｍの球状の銀粉末であるのが好ましい。
ここで、球状とは、長径／短径の比率が２以下の粒子の形状をいう。
また、平均粒子径とは、球状の銀粉末の粒子径の平均値をいい、レーザー回折式粒度分布測定装置を用いて測定された５０％体積累積径（Ｄ５０）をいう。なお、平均値を算出する基になる粒子径は、球状の銀粉末の断面が楕円形である場合はその長径と短径の合計値を２で割った平均値をいい、正円形である場合はその直径をいう。
例えば、後述する実施例で使用する銀粉（ＡｇＣ－１０３、福田金属箔粉工業社製）の写真（図２）で示されるものは球状の銀粉末に該当するが、銀粉（ＡｇＣ－２０１１、福田金属箔粉工業社製）の写真（図３）で示されるものは球状の銀粉末には該当せず、フレーク（鱗片）状の銀粉末に該当するものである。 The silver powder (A) is preferably a spherical silver powder having an average particle diameter of 0.5 to 10 μm because it has good printability and can form an electrode having a small volume resistivity.
Here, the term “spherical” refers to the shape of a particle having a major axis / minor axis ratio of 2 or less.
Moreover, an average particle diameter means the average value of the particle diameter of spherical silver powder, and means the 50% volume cumulative diameter (D50) measured using the laser diffraction type particle size distribution measuring apparatus. In addition, when the cross section of the spherical silver powder is elliptical, the particle diameter that is the basis for calculating the average value is the average value obtained by dividing the total value of the major axis and the minor axis by 2, and is a regular circle Refers to its diameter.
For example, a silver powder (AgC-103, manufactured by Fukuda Metal Foil Powder Co., Ltd.) used in the examples described later corresponds to a spherical silver powder, but silver powder (AgC-2011, Fukuda). What is shown by the photograph (FIG. 3) of a metal foil powder industry company does not correspond to spherical silver powder, but corresponds to flake (scale) -like silver powder.
ここで、球状とは、長径／短径の比率が２以下の粒子の形状をいう。
また、平均粒子径とは、球状の銀粉末の粒子径の平均値をいい、レーザー回折式粒度分布測定装置を用いて測定された５０％体積累積径（Ｄ５０）をいう。なお、平均値を算出する基になる粒子径は、球状の銀粉末の断面が楕円形である場合はその長径と短径の合計値を２で割った平均値をいい、正円形である場合はその直径をいう。
例えば、後述する実施例で使用する銀粉（ＡｇＣ－１０３、福田金属箔粉工業社製）の写真（図２）で示されるものは球状の銀粉末に該当するが、銀粉（ＡｇＣ－２０１１、福田金属箔粉工業社製）の写真（図３）で示されるものは球状の銀粉末には該当せず、フレーク（鱗片）状の銀粉末に該当するものである。 The silver powder (A) is preferably a spherical silver powder having an average particle diameter of 0.5 to 10 μm because it has good printability and can form an electrode having a small volume resistivity.
Here, the term “spherical” refers to the shape of a particle having a major axis / minor axis ratio of 2 or less.
Moreover, an average particle diameter means the average value of the particle diameter of spherical silver powder, and means the 50% volume cumulative diameter (D50) measured using the laser diffraction type particle size distribution measuring apparatus. In addition, when the cross section of the spherical silver powder is elliptical, the particle diameter that is the basis for calculating the average value is the average value obtained by dividing the total value of the major axis and the minor axis by 2, and is a regular circle Refers to its diameter.
For example, a silver powder (AgC-103, manufactured by Fukuda Metal Foil Powder Co., Ltd.) used in the examples described later corresponds to a spherical silver powder, but silver powder (AgC-2011, Fukuda). What is shown by the photograph (FIG. 3) of a metal foil powder industry company does not correspond to spherical silver powder, but corresponds to flake (scale) -like silver powder.
また、上記銀粉（Ａ）の平均粒子径は、印刷性がより良好となる理由から、０．７～５μｍであるのが好ましく、焼結速度が適当となり作業性に優れる理由から、１～３μｍであるのがより好ましい。
The average particle size of the silver powder (A) is preferably 0.7 to 5 μm for the reason that printability is better, and 1 to 3 μm for the reason that the sintering speed is appropriate and the workability is excellent. It is more preferable that
本発明においては、このような銀粉（Ａ）として市販品を用いることができ、その具体例としては、ＡｇＣ－１０２（形状：球状、平均粒子径：１．５μｍ、福田金属箔粉工業社製）、ＡｇＣ－１０３（形状：球状、平均粒子径：１．５μｍ、福田金属箔粉工業社製）、ＡＧ４－８Ｆ（形状：球状、平均粒子径：２．２μｍ、ＤＯＷＡエレクトロニクス社製）、ＡＧ２－１Ｃ（形状：球状、平均粒子径：１．０μｍ、ＤＯＷＡエレクトロニクス社製）、ＡＧ３－１１Ｆ（形状：球状、平均粒子径：１．４μｍ、ＤＯＷＡエレクトロニクス社製）、ＥＨＤ（形状：球状、平均粒子径：０．５μｍ、三井金属社製）、ＡｇＣ－２０１１（形状：フレーク状、平均粒子径：２～１０μｍ、福田金属箔粉工業社製）等が挙げられる。
In the present invention, a commercially available product can be used as such silver powder (A). Specific examples thereof include AgC-102 (shape: spherical, average particle size: 1.5 μm, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.). ), AgC-103 (shape: spherical, average particle diameter: 1.5 μm, manufactured by Fukuda Metal Foil Powder Industries), AG4-8F (shape: spherical, average particle diameter: 2.2 μm, manufactured by DOWA Electronics), AG2 -1C (shape: spherical, average particle size: 1.0 μm, manufactured by DOWA Electronics), AG3-11F (shape: spherical, average particle size: 1.4 μm, manufactured by DOWA Electronics), EHD (shape: spherical, average Particle diameter: 0.5 μm, manufactured by Mitsui Kinzoku Co., Ltd.), AgC-2011 (shape: flake shape, average particle diameter: 2-10 μm, manufactured by Fukuda Metal Foil Co., Ltd.), and the like.
＜エポキシ樹脂（Ｂ）＞
本発明の導電性組成物で用いるエポキシ樹脂（Ｂ）は、少なくとも、エポキシ当量が１５００～４０００ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂（ｂ１）およびエポキシ当量が１０００ｇ／ｅｑ以下の多価アルコール系グリシジル型エポキシ樹脂（ｂ２）であるが、これらのエポキシ樹脂とともに更に他のエポキシ樹脂（ｂ３）を併用してもよい。
ここで、エポキシ樹脂（Ｂ）のエポキシ当量は、日本工業規格ＪＩＳ
Ｋ－７２３６:2001の「エポキシ樹脂のエポキシ当量の求め方」に従って算出した値をいう。 <Epoxy resin (B)>
The epoxy resin (B) used in the conductive composition of the present invention comprises at least a bisphenol A type epoxy resin (b1) having an epoxy equivalent of 1500 to 4000 g / eq and a polyhydric alcohol glycidyl type having an epoxy equivalent of 1000 g / eq or less. Although it is an epoxy resin (b2), you may use together another epoxy resin (b3) with these epoxy resins.
Here, the epoxy equivalent of the epoxy resin (B) is the Japanese Industrial Standard JIS.
This is a value calculated according to “How to determine epoxy equivalent of epoxy resin” in K-7236: 2001.
本発明の導電性組成物で用いるエポキシ樹脂（Ｂ）は、少なくとも、エポキシ当量が１５００～４０００ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂（ｂ１）およびエポキシ当量が１０００ｇ／ｅｑ以下の多価アルコール系グリシジル型エポキシ樹脂（ｂ２）であるが、これらのエポキシ樹脂とともに更に他のエポキシ樹脂（ｂ３）を併用してもよい。
ここで、エポキシ樹脂（Ｂ）のエポキシ当量は、日本工業規格ＪＩＳ
Ｋ－７２３６:2001の「エポキシ樹脂のエポキシ当量の求め方」に従って算出した値をいう。 <Epoxy resin (B)>
The epoxy resin (B) used in the conductive composition of the present invention comprises at least a bisphenol A type epoxy resin (b1) having an epoxy equivalent of 1500 to 4000 g / eq and a polyhydric alcohol glycidyl type having an epoxy equivalent of 1000 g / eq or less. Although it is an epoxy resin (b2), you may use together another epoxy resin (b3) with these epoxy resins.
Here, the epoxy equivalent of the epoxy resin (B) is the Japanese Industrial Standard JIS.
This is a value calculated according to “How to determine epoxy equivalent of epoxy resin” in K-7236: 2001.
（ビスフェノールＡ型エポキシ樹脂（ｂ１））
上記ビスフェノールＡ型エポキシ樹脂（ｂ１）は、エポキシ当量が１５００～４０００ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂である。
上記ビスフェノールＡ型エポキシ樹脂（ｂ１）のエポキシ当量が上記範囲であると、本発明の導電性組成物の硬化後の硬度が良好となり、硬化物に対する優れた半田付け性を維持することができる。
また、上記ビスフェノールＡ型エポキシ樹脂（ｂ１）のエポキシ当量は、本発明の導電性組成物の硬化物に対する半田付け性がより良好となり、硬化収縮の割合が小さく被着体（例えば、回路基板等）の反りを抑えることができる理由から、２０００～４０００ｇ／ｅｑであるのが好ましく、２０００～３５００ｇ／ｅｑであるのがより好ましい。 (Bisphenol A type epoxy resin (b1))
The bisphenol A type epoxy resin (b1) is a bisphenol A type epoxy resin having an epoxy equivalent of 1500 to 4000 g / eq.
When the epoxy equivalent of the bisphenol A-type epoxy resin (b1) is within the above range, the hardness of the conductive composition of the present invention after curing becomes good, and excellent solderability for the cured product can be maintained.
Further, the epoxy equivalent of the bisphenol A type epoxy resin (b1) has better solderability to the cured product of the conductive composition of the present invention, and the rate of cure shrinkage is small, such as an adherend (for example, a circuit board) ) Is preferably 2000 to 4000 g / eq, more preferably 2000 to 3500 g / eq.
上記ビスフェノールＡ型エポキシ樹脂（ｂ１）は、エポキシ当量が１５００～４０００ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂である。
上記ビスフェノールＡ型エポキシ樹脂（ｂ１）のエポキシ当量が上記範囲であると、本発明の導電性組成物の硬化後の硬度が良好となり、硬化物に対する優れた半田付け性を維持することができる。
また、上記ビスフェノールＡ型エポキシ樹脂（ｂ１）のエポキシ当量は、本発明の導電性組成物の硬化物に対する半田付け性がより良好となり、硬化収縮の割合が小さく被着体（例えば、回路基板等）の反りを抑えることができる理由から、２０００～４０００ｇ／ｅｑであるのが好ましく、２０００～３５００ｇ／ｅｑであるのがより好ましい。 (Bisphenol A type epoxy resin (b1))
The bisphenol A type epoxy resin (b1) is a bisphenol A type epoxy resin having an epoxy equivalent of 1500 to 4000 g / eq.
When the epoxy equivalent of the bisphenol A-type epoxy resin (b1) is within the above range, the hardness of the conductive composition of the present invention after curing becomes good, and excellent solderability for the cured product can be maintained.
Further, the epoxy equivalent of the bisphenol A type epoxy resin (b1) has better solderability to the cured product of the conductive composition of the present invention, and the rate of cure shrinkage is small, such as an adherend (for example, a circuit board) ) Is preferably 2000 to 4000 g / eq, more preferably 2000 to 3500 g / eq.
（多価アルコール系グリシジル型エポキシ樹脂（ｂ２））
上記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）は、エポキシ当量が１０００ｇ／ｅｑ以下の多価アルコール系グリシジル型エポキシ樹脂である。
上記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）のエポキシ当量が上記範囲であると、本発明の導電性組成物の粘度が良好となり、印刷性が良好となる。
また、上記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）のエポキシ当量は、スクリーン印刷をする際の粘度が適当になる理由から、１００～４００ｇ／ｅｑであるのが好ましく、１００～３００ｇ／ｅｑであるのがより好ましい。また、本発明の導電性組成物の粘度が良好となり、印刷性が良好となる理由から、１００ｇ／ｅｑ以上であることが好ましい。 (Polyhydric alcohol glycidyl type epoxy resin (b2))
The polyhydric alcohol glycidyl type epoxy resin (b2) is a polyhydric alcohol glycidyl type epoxy resin having an epoxy equivalent of 1000 g / eq or less.
When the epoxy equivalent of the polyhydric alcohol-based glycidyl type epoxy resin (b2) is within the above range, the viscosity of the conductive composition of the present invention is good, and the printability is good.
The epoxy equivalent of the polyhydric alcohol-based glycidyl type epoxy resin (b2) is preferably 100 to 400 g / eq, and preferably 100 to 300 g / eq, because the viscosity at the time of screen printing becomes appropriate. More preferably. Moreover, since the viscosity of the electrically conductive composition of this invention becomes favorable and printability becomes favorable, it is preferable that it is 100 g / eq or more.
上記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）は、エポキシ当量が１０００ｇ／ｅｑ以下の多価アルコール系グリシジル型エポキシ樹脂である。
上記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）のエポキシ当量が上記範囲であると、本発明の導電性組成物の粘度が良好となり、印刷性が良好となる。
また、上記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）のエポキシ当量は、スクリーン印刷をする際の粘度が適当になる理由から、１００～４００ｇ／ｅｑであるのが好ましく、１００～３００ｇ／ｅｑであるのがより好ましい。また、本発明の導電性組成物の粘度が良好となり、印刷性が良好となる理由から、１００ｇ／ｅｑ以上であることが好ましい。 (Polyhydric alcohol glycidyl type epoxy resin (b2))
The polyhydric alcohol glycidyl type epoxy resin (b2) is a polyhydric alcohol glycidyl type epoxy resin having an epoxy equivalent of 1000 g / eq or less.
When the epoxy equivalent of the polyhydric alcohol-based glycidyl type epoxy resin (b2) is within the above range, the viscosity of the conductive composition of the present invention is good, and the printability is good.
The epoxy equivalent of the polyhydric alcohol-based glycidyl type epoxy resin (b2) is preferably 100 to 400 g / eq, and preferably 100 to 300 g / eq, because the viscosity at the time of screen printing becomes appropriate. More preferably. Moreover, since the viscosity of the electrically conductive composition of this invention becomes favorable and printability becomes favorable, it is preferable that it is 100 g / eq or more.
上記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）としては、具体的には、例えば、エチレングリコールグリシジルエーテル、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ポリネオペンチルグリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリグリセリンポリグリシジルエーテル、ポリオキシエチレングリコールジグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテル、ペンタエリスリトールジグリシジルエーテル、ペンタエリスリトールトリグリシジルエーテル、ポリペンタエリスリトールポリグリシジルエーテル、トリメチルプロパンジグリシジルエーテル、テトラキス（グリシジルオキシフェニル）エタン、トリス（グリシジルオキシ）メタン等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
Specific examples of the polyhydric alcohol glycidyl type epoxy resin (b2) include, for example, ethylene glycol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polyneopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, propylene glycol diglycidyl ether, tri Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, diethylene Recall diglycidyl ether, polyglycerin polyglycidyl ether, polyoxyethylene glycol diglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polytetramethylene glycol diglycidyl ether, pentaerythritol diglycidyl ether, Examples include pentaerythritol triglycidyl ether, polypentaerythritol polyglycidyl ether, trimethylpropanediglycidyl ether, tetrakis (glycidyloxyphenyl) ethane, tris (glycidyloxy) methane, and these may be used alone. More than one species may be used in combination.
これらのうち、本発明の導電性組成物の硬化後の硬度が良好となり、硬化物に対する半田付け性がより良好となる理由から、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテルが好ましく、更に優れた導電性を付与することができる理由から、ポリエチレングリコールジグリシジルエーテルであるのがより好ましい。
Among these, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are preferable and more excellent because the hardness after curing of the conductive composition of the present invention becomes good and solderability to the cured product becomes better. It is more preferable to use polyethylene glycol diglycidyl ether because it can provide high conductivity.
（他のエポキシ樹脂（ｂ３））
上記他のエポキシ樹脂（ｂ３）は、１分子中に２個以上のオキシラン環（エポキシ基）を有する化合物からなる樹脂であれば特に限定されない。
上記他のエポキシ樹脂（ｂ３）としては、具体的には、例えば、ビスフェノールＡ型エポキシ樹脂（上記ビスフェノールＡ型エポキシ樹脂（ｂ１）に該当するものを除く）、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ジフェニルフルオレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
上記他のエポキシ樹脂（ｂ３）を含有する場合の含有量は、エポキシ樹脂（Ｂ）全体の質量に対して、１０質量％以下であるのが好ましく、５質量％以下であるのがより好ましい。 (Other epoxy resin (b3))
The other epoxy resin (b3) 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.
Specific examples of the other epoxy resin (b3) include, for example, a bisphenol A type epoxy resin (excluding those corresponding to the bisphenol A type epoxy resin (b1)), a bisphenol F type epoxy resin, and a biphenyl type epoxy. Resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, diphenylfluorene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidylamine type epoxy resin, etc., and these can be used alone. Or two or more of them may be used in combination.
The content in the case of containing the other epoxy resin (b3) is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the epoxy resin (B).
上記他のエポキシ樹脂（ｂ３）は、１分子中に２個以上のオキシラン環（エポキシ基）を有する化合物からなる樹脂であれば特に限定されない。
上記他のエポキシ樹脂（ｂ３）としては、具体的には、例えば、ビスフェノールＡ型エポキシ樹脂（上記ビスフェノールＡ型エポキシ樹脂（ｂ１）に該当するものを除く）、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ジフェニルフルオレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
上記他のエポキシ樹脂（ｂ３）を含有する場合の含有量は、エポキシ樹脂（Ｂ）全体の質量に対して、１０質量％以下であるのが好ましく、５質量％以下であるのがより好ましい。 (Other epoxy resin (b3))
The other epoxy resin (b3) 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.
Specific examples of the other epoxy resin (b3) include, for example, a bisphenol A type epoxy resin (excluding those corresponding to the bisphenol A type epoxy resin (b1)), a bisphenol F type epoxy resin, and a biphenyl type epoxy. Resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, diphenylfluorene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidylamine type epoxy resin, etc., and these can be used alone. Or two or more of them may be used in combination.
The content in the case of containing the other epoxy resin (b3) is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the epoxy resin (B).
本発明においては、上記エポキシ樹脂（Ｂ）の含有量は、本発明の導電性組成物の硬化後の硬度が適当となるため被着体（例えば、回路基板等）に対する密着性が良好となり、また、硬化物に対する半田付け性がより良好となる理由から、上記銀粉（Ａ）１００質量部に対して、４～１０質量部であるのが好ましく、４～８質量部であるのがより好ましい。
In the present invention, the content of the epoxy resin (B) is appropriate for the hardness after curing of the conductive composition of the present invention, so that the adhesion to an adherend (for example, a circuit board) is good, Further, for the reason that the solderability to the cured product becomes better, the amount is preferably 4 to 10 parts by mass, more preferably 4 to 8 parts by mass with respect to 100 parts by mass of the silver powder (A). .
また、本発明においては、上記ビスフェノールＡ型エポキシ樹脂（ｂ１）と上記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）との割合は特に限定されないが、本発明の導電性組成物の硬化後の硬度がより良好となり、硬化物に対する優れた半田付け性を維持しやすいという理由から、上記ビスフェノールＡ型エポキシ樹脂（ｂ１）の配合量（質量）が上記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）よりも多いのが好ましい。
Moreover, in this invention, although the ratio of the said bisphenol A type epoxy resin (b1) and the said polyhydric alcohol type | system | group glycidyl type epoxy resin (b2) is not specifically limited, The hardness after hardening of the electrically conductive composition of this invention Is better, and it is easy to maintain excellent solderability to the cured product, so that the blending amount (mass) of the bisphenol A type epoxy resin (b1) is more than that of the polyhydric alcohol glycidyl type epoxy resin (b2). It is also preferable that there are many.
＜硬化剤（Ｃ）＞
本発明の導電性組成物で用いる硬化剤（Ｃ）は、スルホニウムカチオン系硬化剤である。
上記硬化剤（Ｃ）としては、例えば、下記式（Ｉ）で表されるスルホニウム塩等が挙げられる。 <Curing agent (C)>
The curing agent (C) used in the conductive composition of the present invention is a sulfonium cation curing agent.
Examples of the curing agent (C) include sulfonium salts represented by the following formula (I).
本発明の導電性組成物で用いる硬化剤（Ｃ）は、スルホニウムカチオン系硬化剤である。
上記硬化剤（Ｃ）としては、例えば、下記式（Ｉ）で表されるスルホニウム塩等が挙げられる。 <Curing agent (C)>
The curing agent (C) used in the conductive composition of the present invention is a sulfonium cation curing agent.
Examples of the curing agent (C) include sulfonium salts represented by the following formula (I).
上記式（Ｉ）で表されるスルホニウム塩のうち、本発明の導電性組成物の硬化物に対する半田付け性がより良好となる理由から、上記式（Ｉ）中のＸがＳｂＦ6で表されるスルホニウム塩であるのが好ましく、その具体例としては、下記式（１）および（２）で表される化合物が挙げられる。
Among the sulfonium salts represented by the above formula (I), X in the above formula (I) is represented by SbF 6 because the solderability to the cured product of the conductive composition of the present invention becomes better. A sulfonium salt is preferable, and specific examples thereof include compounds represented by the following formulas (1) and (2).
本発明においては、上記硬化剤（Ｃ）としてスルホニウムカチオン系硬化剤を用いることにより、本発明の導電性組成物の硬化物に対する半田付け性が良好となる。
これは、低温（１５０～５００℃程度）でも十分な硬化性を示すスルホニウムカチオン系硬化剤を使用することにより、イミダゾール系硬化剤を使用した場合よりもエポキシ樹脂（Ｂ）の重合度が上がり、その結果、銀粉（Ａ）同士の接触が多くなるためであると考えられる。特に、スルホニウムカチオン系硬化剤がアニオンとして六フッ化アンチモン酸イオン（ＳｂＦ6 －）を有すると、これが金属触媒としても作用するため半田付け性がより良好になると考えられる。 In this invention, the solderability with respect to the hardened | cured material of the electrically conductive composition of this invention becomes favorable by using a sulfonium cation type | system | group hardening | curing agent as said hardening | curing agent (C).
This is because the degree of polymerization of the epoxy resin (B) is increased by using a sulfonium cationic curing agent that exhibits sufficient curability even at low temperatures (about 150 to 500 ° C.), compared to the case of using an imidazole curing agent, As a result, it is considered that the contact between the silver powders (A) increases. In particular, when the sulfonium cation-based curing agent has hexafluoroantimonate ion (SbF 6 − ) as an anion, it acts as a metal catalyst, so that solderability is considered to be better.
これは、低温（１５０～５００℃程度）でも十分な硬化性を示すスルホニウムカチオン系硬化剤を使用することにより、イミダゾール系硬化剤を使用した場合よりもエポキシ樹脂（Ｂ）の重合度が上がり、その結果、銀粉（Ａ）同士の接触が多くなるためであると考えられる。特に、スルホニウムカチオン系硬化剤がアニオンとして六フッ化アンチモン酸イオン（ＳｂＦ6 －）を有すると、これが金属触媒としても作用するため半田付け性がより良好になると考えられる。 In this invention, the solderability with respect to the hardened | cured material of the electrically conductive composition of this invention becomes favorable by using a sulfonium cation type | system | group hardening | curing agent as said hardening | curing agent (C).
This is because the degree of polymerization of the epoxy resin (B) is increased by using a sulfonium cationic curing agent that exhibits sufficient curability even at low temperatures (about 150 to 500 ° C.), compared to the case of using an imidazole curing agent, As a result, it is considered that the contact between the silver powders (A) increases. In particular, when the sulfonium cation-based curing agent has hexafluoroantimonate ion (SbF 6 − ) as an anion, it acts as a metal catalyst, so that solderability is considered to be better.
また、本発明においては、上記硬化剤（Ｃ）の含有量は、熱により活性化してエポキシ基の開環反応を十分に進行させることができるという理由から、上記エポキシ樹脂（Ｂ）１００質量部に対して１～１０質量部であるのが好ましく、１～５質量部であるのがより好ましい。
Moreover, in this invention, content of the said hardening | curing agent (C) is activated with a heat | fever, and since the ring-opening reaction of an epoxy group can fully advance, 100 mass parts of said epoxy resins (B) The amount is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight.
＜脂肪酸銀塩（Ｄ）＞
本発明の導電性組成物は、より低温（１５０～２００℃程度）の焼成であっても電極等を形成することができ、シリコン基板への熱によるダメージをより軽減できる理由から、更に脂肪酸銀塩（Ｄ）を含有するのが好ましい。 <Fatty acid silver salt (D)>
The conductive composition of the present invention can form an electrode and the like even when fired at a lower temperature (about 150 to 200 ° C.), and further reduces damage to the silicon substrate due to heat. It preferably contains a salt (D).
本発明の導電性組成物は、より低温（１５０～２００℃程度）の焼成であっても電極等を形成することができ、シリコン基板への熱によるダメージをより軽減できる理由から、更に脂肪酸銀塩（Ｄ）を含有するのが好ましい。 <Fatty acid silver salt (D)>
The conductive composition of the present invention can form an electrode and the like even when fired at a lower temperature (about 150 to 200 ° C.), and further reduces damage to the silicon substrate due to heat. It preferably contains a salt (D).
上記脂肪酸銀塩（Ｄ）は、有機カルボン酸の銀塩であれば特に限定されず、例えば、日本公開特許公報第２００８－１９８５９５号の段落［００６３］～［００６８］に記載された脂肪酸金属塩（特に３級脂肪酸銀塩）、日本特許公報第４４８２９３０号の段落［００３０］に記載された脂肪酸銀、日本公開特許公報第２０１０－９２６８４号の段落［００２９］～［００４５］に記載された水酸基を１個以上有する脂肪酸銀塩、同公報の段落［００４６］～［００５６］に記載された２級脂肪酸銀塩等を用いることができる。
これらのうち、カルボキシ銀塩基（－ＣＯＯＡｇ）と水酸基（－ＯＨ）とをそれぞれ１個以上有する脂肪酸銀塩（Ｄ１）、および／または、カルボキシ銀塩基（－ＣＯＯＡｇ）を３個以上有するポリカルボン酸銀塩（Ｄ２）を用いるのが好ましい。
具体的には、例えば、上記脂肪酸銀塩（Ｄ１）としては、２，２－ビス（ヒドロキシメチル）－ｎ－酪酸銀塩、２－ヒドロキシイソ酪酸銀塩を好適に用いることができ、上記ポリカルボン酸銀塩（Ｄ２）としては、１，２，３，４－ブタンテトラカルボン酸銀塩を好適に用いることができる。 The fatty acid silver salt (D) is not particularly limited as long as it is a silver salt of an organic carboxylic acid. For example, the fatty acid metal salt described in paragraphs [0063] to [0068] of Japanese Patent Application Publication No. 2008-198595. (Particularly tertiary fatty acid silver salt), fatty acid silver described in paragraph [0030] of Japanese Patent Publication No. 4482930, and hydroxyl groups described in paragraphs [0029] to [0045] of Japanese Published Patent Publication No. 2010-92684 Or a fatty acid silver salt described in paragraphs [0046] to [0056] of the same publication.
Among these, a fatty acid silver salt (D1) having at least one carboxy silver base (—COOAg) and a hydroxyl group (—OH) and / or a polycarboxylic acid having at least three carboxy silver bases (—COOAg) It is preferable to use a silver salt (D2).
Specifically, for example, as the fatty acid silver salt (D1), 2,2-bis (hydroxymethyl) -n-butyric acid silver salt and 2-hydroxyisobutyric acid silver salt can be preferably used. As the carboxylic acid silver salt (D2), 1,2,3,4-butanetetracarboxylic acid silver salt can be preferably used.
これらのうち、カルボキシ銀塩基（－ＣＯＯＡｇ）と水酸基（－ＯＨ）とをそれぞれ１個以上有する脂肪酸銀塩（Ｄ１）、および／または、カルボキシ銀塩基（－ＣＯＯＡｇ）を３個以上有するポリカルボン酸銀塩（Ｄ２）を用いるのが好ましい。
具体的には、例えば、上記脂肪酸銀塩（Ｄ１）としては、２，２－ビス（ヒドロキシメチル）－ｎ－酪酸銀塩、２－ヒドロキシイソ酪酸銀塩を好適に用いることができ、上記ポリカルボン酸銀塩（Ｄ２）としては、１，２，３，４－ブタンテトラカルボン酸銀塩を好適に用いることができる。 The fatty acid silver salt (D) is not particularly limited as long as it is a silver salt of an organic carboxylic acid. For example, the fatty acid metal salt described in paragraphs [0063] to [0068] of Japanese Patent Application Publication No. 2008-198595. (Particularly tertiary fatty acid silver salt), fatty acid silver described in paragraph [0030] of Japanese Patent Publication No. 4482930, and hydroxyl groups described in paragraphs [0029] to [0045] of Japanese Published Patent Publication No. 2010-92684 Or a fatty acid silver salt described in paragraphs [0046] to [0056] of the same publication.
Among these, a fatty acid silver salt (D1) having at least one carboxy silver base (—COOAg) and a hydroxyl group (—OH) and / or a polycarboxylic acid having at least three carboxy silver bases (—COOAg) It is preferable to use a silver salt (D2).
Specifically, for example, as the fatty acid silver salt (D1), 2,2-bis (hydroxymethyl) -n-butyric acid silver salt and 2-hydroxyisobutyric acid silver salt can be preferably used. As the carboxylic acid silver salt (D2), 1,2,3,4-butanetetracarboxylic acid silver salt can be preferably used.
本発明においては、上記脂肪酸銀塩（Ｄ）の含有量は、印刷性が良好となり、体積抵抗率が小さい電極を形成することができる理由から、上記銀粉（Ａ）１００質量部に対して１～１００質量部であるのが好ましく、５～８０質量部であるのがより好ましい。
In the present invention, the content of the fatty acid silver salt (D) is 1 with respect to 100 parts by mass of the silver powder (A) because the printability is good and an electrode having a small volume resistivity can be formed. The amount is preferably from 100 to 100 parts by mass, and more preferably from 5 to 80 parts by mass.
＜溶媒＞
本発明の導電性組成物は、印刷性等の作業性の観点から、更に溶媒を含有するのが好ましい。
上記溶媒は、本発明の導電性組成物を基材上に塗布することができるものであれば特に限定されず、その具体例としては、ブチルカルビトール、メチルエチルケトン、イソホロン、α－テルピネオール等が挙げられ、これらを１種単独で用いても２種以上を併用してもよい。
また、上記溶媒を含有する場合の含有量は、上記銀粉（Ａ）１００質量部に対して、２～２０質量部であるのが好ましく、５～１５質量部であるのがより好ましい。 <Solvent>
The conductive composition of the present invention preferably further contains a solvent from the viewpoint of workability such as printability.
The solvent is not particularly limited as long as the conductive composition of the present invention can be applied on a substrate, and specific examples thereof include butyl carbitol, methyl ethyl ketone, isophorone, α-terpineol, and the like. These may be used alone or in combination of two or more.
Further, when the solvent is contained, the content is preferably 2 to 20 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the silver powder (A).
本発明の導電性組成物は、印刷性等の作業性の観点から、更に溶媒を含有するのが好ましい。
上記溶媒は、本発明の導電性組成物を基材上に塗布することができるものであれば特に限定されず、その具体例としては、ブチルカルビトール、メチルエチルケトン、イソホロン、α－テルピネオール等が挙げられ、これらを１種単独で用いても２種以上を併用してもよい。
また、上記溶媒を含有する場合の含有量は、上記銀粉（Ａ）１００質量部に対して、２～２０質量部であるのが好ましく、５～１５質量部であるのがより好ましい。 <Solvent>
The conductive composition of the present invention preferably further contains a solvent from the viewpoint of workability such as printability.
The solvent is not particularly limited as long as the conductive composition of the present invention can be applied on a substrate, and specific examples thereof include butyl carbitol, methyl ethyl ketone, isophorone, α-terpineol, and the like. These may be used alone or in combination of two or more.
Further, when the solvent is contained, the content is preferably 2 to 20 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the silver powder (A).
＜添加剤＞
本発明の導電性組成物は、必要に応じて、上述した銀粉（Ａ）以外の金属粉、還元剤等の添加剤を含有していてもよい。
上記金属粉としては、具体的には、例えば、銅、アルミニウム等が挙げられ、中でも、銅であるのが好ましい。また、０．０１～１０μｍの粒径の金属粉であるのが好ましい。
上記還元剤としては、具体的には、例えば、エチレングリコール類等が挙げられる。 <Additives>
The electrically conductive composition of this invention may contain additives, such as metal powder other than the silver powder (A) mentioned above, a reducing agent, as needed.
Specific examples of the metal powder include copper and aluminum. Among them, copper is preferable. Further, a metal powder having a particle diameter of 0.01 to 10 μm is preferable.
Specific examples of the reducing agent include ethylene glycols.
本発明の導電性組成物は、必要に応じて、上述した銀粉（Ａ）以外の金属粉、還元剤等の添加剤を含有していてもよい。
上記金属粉としては、具体的には、例えば、銅、アルミニウム等が挙げられ、中でも、銅であるのが好ましい。また、０．０１～１０μｍの粒径の金属粉であるのが好ましい。
上記還元剤としては、具体的には、例えば、エチレングリコール類等が挙げられる。 <Additives>
The electrically conductive composition of this invention may contain additives, such as metal powder other than the silver powder (A) mentioned above, a reducing agent, as needed.
Specific examples of the metal powder include copper and aluminum. Among them, copper is preferable. Further, a metal powder having a particle diameter of 0.01 to 10 μm is preferable.
Specific examples of the reducing agent include ethylene glycols.
本発明の導電性組成物の製造方法は特に限定されず、上記銀粉（Ａ）、上記エポキシ樹脂（Ｂ）および上記硬化剤（Ｃ）ならびに所望により含有してもよい上記脂肪酸銀塩（Ｄ）、上記溶媒および添加剤を、ロール、ニーダー、押出し機、万能かくはん機等により混合する方法が挙げられる。
The manufacturing method of the electroconductive composition of this invention is not specifically limited, The said silver powder (A), the said epoxy resin (B), the said hardening | curing agent (C), and the said fatty acid silver salt (D) which may be contained depending on necessity. And a method of mixing the solvent and additives with a roll, a kneader, an extruder, a universal agitator or the like.
本発明の太陽電池セルは、受光面側の表面電極、半導体基板および裏面電極を具備し、上記表面電極および／または上記裏面電極が、上述した本発明の導電性組成物を用いて形成される太陽電池セルである。
ここで、本発明の太陽電池セルは、上述した本発明の導電性組成物が全裏面電極型（いわゆるバックコンタクト型）太陽電池の裏面電極の形成にも適用することができるため、全裏面電極型の太陽電池にも適用することができる。
以下に、本発明の太陽電池セルの構成について図１を用いて説明する。 The solar cell of the present invention comprises a light-receiving surface-side surface electrode, a semiconductor substrate, and a back electrode, and the surface electrode and / or the back electrode is formed using the above-described conductive composition of the present invention. It is a solar battery cell.
Here, the solar battery cell of the present invention can be applied to the formation of the back electrode of the all back electrode type (so-called back contact type) solar battery because the above-described conductive composition of the present invention can be applied to the all back electrode. The present invention can also be applied to a type solar cell.
Below, the structure of the photovoltaic cell of this invention is demonstrated using FIG.
ここで、本発明の太陽電池セルは、上述した本発明の導電性組成物が全裏面電極型（いわゆるバックコンタクト型）太陽電池の裏面電極の形成にも適用することができるため、全裏面電極型の太陽電池にも適用することができる。
以下に、本発明の太陽電池セルの構成について図１を用いて説明する。 The solar cell of the present invention comprises a light-receiving surface-side surface electrode, a semiconductor substrate, and a back electrode, and the surface electrode and / or the back electrode is formed using the above-described conductive composition of the present invention. It is a solar battery cell.
Here, the solar battery cell of the present invention can be applied to the formation of the back electrode of the all back electrode type (so-called back contact type) solar battery because the above-described conductive composition of the present invention can be applied to the all back electrode. The present invention can also be applied to a type solar cell.
Below, the structure of the photovoltaic cell of this invention is demonstrated using FIG.
図１に示すように、本発明の太陽電池セル１は、受光面側の表面電極４と、ｐ層５およびｎ層２が接合したｐｎ接合シリコン基板７と、裏面電極６とを具備するものである。
また、図１に示すように、本発明の太陽電池セル１は、反射率低減のため、例えば、ウェハー表面にエッチングを施して、ピラミッド状のテクスチャを形成し、反射防止膜３を具備するのが好ましい。 As shown in FIG. 1, a solar cell 1 of the present invention includes a surface electrode 4 on the light-receiving surface side, a pnjunction silicon substrate 7 in which a p layer 5 and an n layer 2 are joined, and a back electrode 6. It is.
Further, as shown in FIG. 1, the solar battery cell 1 of the present invention is provided with anantireflection film 3 by, for example, etching the wafer surface to form a pyramidal texture in order to reduce the reflectance. Is preferred.
また、図１に示すように、本発明の太陽電池セル１は、反射率低減のため、例えば、ウェハー表面にエッチングを施して、ピラミッド状のテクスチャを形成し、反射防止膜３を具備するのが好ましい。 As shown in FIG. 1, a solar cell 1 of the present invention includes a surface electrode 4 on the light-receiving surface side, a pn
Further, as shown in FIG. 1, the solar battery cell 1 of the present invention is provided with an
＜表面電極／裏面電極＞
本発明の太陽電池セルが具備する表面電極および裏面電極は、いずれか一方または両方が本発明の導電性組成物を用いて形成されていれば、電極の配置（ピッチ）、形状、高さ、幅等は特に限定されない。
ここで、表面電極および裏面電極は、図１に示すように、通常、複数個有するものであるが、本発明においては、例えば、複数の表面電極の一部のみが本発明の導電性組成物で形成されたものであってもよく、複数の表面電極の一部と複数の裏面電極の一部が本発明の導電性組成物で形成されたものであってもよい。 <Front electrode / Back electrode>
If either one or both of the front electrode and the back electrode included in the solar battery cell of the present invention are formed using the conductive composition of the present invention, the electrode arrangement (pitch), shape, height, The width and the like are not particularly limited.
Here, as shown in FIG. 1, the front surface electrode and the back surface electrode usually have a plurality, but in the present invention, for example, only a part of the plurality of front surface electrodes is the conductive composition of the present invention. Or a part of the plurality of front surface electrodes and a part of the plurality of back surface electrodes may be formed of the conductive composition of the present invention.
本発明の太陽電池セルが具備する表面電極および裏面電極は、いずれか一方または両方が本発明の導電性組成物を用いて形成されていれば、電極の配置（ピッチ）、形状、高さ、幅等は特に限定されない。
ここで、表面電極および裏面電極は、図１に示すように、通常、複数個有するものであるが、本発明においては、例えば、複数の表面電極の一部のみが本発明の導電性組成物で形成されたものであってもよく、複数の表面電極の一部と複数の裏面電極の一部が本発明の導電性組成物で形成されたものであってもよい。 <Front electrode / Back electrode>
If either one or both of the front electrode and the back electrode included in the solar battery cell of the present invention are formed using the conductive composition of the present invention, the electrode arrangement (pitch), shape, height, The width and the like are not particularly limited.
Here, as shown in FIG. 1, the front surface electrode and the back surface electrode usually have a plurality, but in the present invention, for example, only a part of the plurality of front surface electrodes is the conductive composition of the present invention. Or a part of the plurality of front surface electrodes and a part of the plurality of back surface electrodes may be formed of the conductive composition of the present invention.
＜反射防止膜＞
本発明の太陽電池セルが具備していてもよい反射防止膜は、受光面の表面電極が形成されていない部分に形成される膜（膜厚：０．０５～０．１μｍ程度）であって、例えば、シリコン酸化膜、シリコン窒化膜、酸化チタン膜、これらの積層膜等から構成されるものである。 <Antireflection film>
The antireflection film that the solar battery cell of the present invention may have is a film (film thickness: about 0.05 to 0.1 μm) formed on a portion of the light receiving surface where the surface electrode is not formed. For example, a silicon oxide film, a silicon nitride film, a titanium oxide film, or a laminated film thereof.
本発明の太陽電池セルが具備していてもよい反射防止膜は、受光面の表面電極が形成されていない部分に形成される膜（膜厚：０．０５～０．１μｍ程度）であって、例えば、シリコン酸化膜、シリコン窒化膜、酸化チタン膜、これらの積層膜等から構成されるものである。 <Antireflection film>
The antireflection film that the solar battery cell of the present invention may have is a film (film thickness: about 0.05 to 0.1 μm) formed on a portion of the light receiving surface where the surface electrode is not formed. For example, a silicon oxide film, a silicon nitride film, a titanium oxide film, or a laminated film thereof.
＜シリコン基板＞
本発明の太陽電池セルが具備するシリコン基板は特に限定されず、太陽電池を形成するための公知のシリコン基板（板厚：１００～４５０μｍ程度）を用いることができ、また、単結晶または多結晶のいずれのシリコン基板であってもよい。 <Silicon substrate>
The silicon substrate included in the solar battery cell of the present invention is not particularly limited, and a known silicon substrate (plate thickness: about 100 to 450 μm) for forming a solar battery can be used, and a single crystal or polycrystal Any silicon substrate may be used.
本発明の太陽電池セルが具備するシリコン基板は特に限定されず、太陽電池を形成するための公知のシリコン基板（板厚：１００～４５０μｍ程度）を用いることができ、また、単結晶または多結晶のいずれのシリコン基板であってもよい。 <Silicon substrate>
The silicon substrate included in the solar battery cell of the present invention is not particularly limited, and a known silicon substrate (plate thickness: about 100 to 450 μm) for forming a solar battery can be used, and a single crystal or polycrystal Any silicon substrate may be used.
また、上記シリコン基板はｐｎ接合を有するが、これは、第１導電型の半導体基板の表面側に第２導電型の受光面不純物拡散領域が形成されていることを意味する。なお、第１導電型がｎ型の場合には、第２導電型はｐ型であり、第１導電型がｐ型の場合には、第２導電型はｎ型である。
ここで、ｐ型を与える不純物としては、ホウ素、アルミニウム等が挙げられ、ｎ型を与える不純物としては、リン、砒素などが挙げられる。 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. When the first conductivity type is n-type, the second conductivity type is p-type. When the first conductivity type is p-type, the second conductivity type is n-type.
Here, examples of the impurity imparting p-type include boron and aluminum, and examples of the impurity imparting n-type include phosphorus and arsenic.
ここで、ｐ型を与える不純物としては、ホウ素、アルミニウム等が挙げられ、ｎ型を与える不純物としては、リン、砒素などが挙げられる。 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. When the first conductivity type is n-type, the second conductivity type is p-type. When the first conductivity type is p-type, the second conductivity type is n-type.
Here, examples of the impurity imparting p-type include boron and aluminum, and examples of the impurity imparting n-type include phosphorus and arsenic.
本発明の太陽電池セルは、表面電極および／または裏面電極が本発明の導電性組成物を用いて形成されているため、各電極（特にバスバー部）に対する半田付け性が良好となり、モジュール化することが容易である。
In the solar battery cell of the present invention, the front electrode and / or the back electrode are formed using the conductive composition of the present invention, so that the solderability to each electrode (especially the bus bar portion) is good and modularized. Is easy.
本発明の太陽電池セルの製造方法は特に限定されないが、本発明の導電性組成物をシリコン基板上に塗布して配線を形成する配線形成工程と、得られた配線を熱処理して電極（表面電極および／または裏面電極）を形成する熱処理工程とを有する方法が挙げられる。
なお、本発明の太陽電池セルが反射防止層を具備する場合、反射防止膜は、プラズマＣＶＤ法等の公知の方法により形成することができる。
以下に、配線形成工程、熱処理工程について詳述する。 Although the manufacturing method of the photovoltaic cell of the present invention is not particularly limited, a wiring forming step of forming the wiring by applying the conductive composition of the present invention on a silicon substrate, and heat treating the obtained wiring to form an electrode (surface A heat treatment step of forming an electrode and / or a back electrode).
In addition, when the photovoltaic cell of this invention comprises an antireflection layer, an antireflection film can be formed by well-known methods, such as a plasma CVD method.
Below, a wiring formation process and a heat treatment process are explained in full detail.
なお、本発明の太陽電池セルが反射防止層を具備する場合、反射防止膜は、プラズマＣＶＤ法等の公知の方法により形成することができる。
以下に、配線形成工程、熱処理工程について詳述する。 Although the manufacturing method of the photovoltaic cell of the present invention is not particularly limited, a wiring forming step of forming the wiring by applying the conductive composition of the present invention on a silicon substrate, and heat treating the obtained wiring to form an electrode (surface A heat treatment step of forming an electrode and / or a back electrode).
In addition, when the photovoltaic cell of this invention comprises an antireflection layer, an antireflection film can be formed by well-known methods, such as a plasma CVD method.
Below, a wiring formation process and a heat treatment process are explained in full detail.
＜配線形成工程＞
上記配線形成工程は、本発明の導電性組成物をシリコン基材上に塗布して配線を形成する工程である。
ここで、塗布方法としては、具体的には、例えば、インクジェット、スクリーン印刷、グラビア印刷、オフセット印刷、凸版印刷等が挙げられる。 <Wiring formation process>
The said wiring formation process is a process of apply | coating the electrically conductive composition of this invention on a silicon base material, and forming wiring.
Here, specific examples of the coating method include inkjet, screen printing, gravure printing, offset printing, letterpress printing, and the like.
上記配線形成工程は、本発明の導電性組成物をシリコン基材上に塗布して配線を形成する工程である。
ここで、塗布方法としては、具体的には、例えば、インクジェット、スクリーン印刷、グラビア印刷、オフセット印刷、凸版印刷等が挙げられる。 <Wiring formation process>
The said wiring formation process is a process of apply | coating the electrically conductive composition of this invention on a silicon base material, and forming wiring.
Here, specific examples of the coating method include inkjet, screen printing, gravure printing, offset printing, letterpress printing, and the like.
＜熱処理工程＞
上記熱処理工程は、上記配線形成工程で得られた配線を熱処理して導電性の配線（電極）を得る工程である。
ここで、上記熱処理は特に限定されないが、１５０～８００℃の温度で、数秒～数十分間、加熱（焼成）する処理であるのが好ましい。温度および時間がこの範囲であると、シリコン基板上に反射防止膜を形成した場合であっても、ファイヤースルー法により容易に電極を形成することができる。
本発明においては、本発明の導電性組成物を用いているため、低温（１５０～５００℃程度）であっても、良好な熱処理（焼成）を施すことができる。 <Heat treatment process>
The heat treatment step is a step of obtaining a conductive wiring (electrode) by heat-treating the wiring obtained in the wiring forming step.
Here, the heat treatment is not particularly limited, but is preferably a treatment of heating (firing) at a temperature of 150 to 800 ° C. for several seconds to several tens of minutes. When the temperature and time are within this range, even when an antireflection film is formed on the silicon substrate, the electrode can be easily formed by the fire-through method.
In the present invention, since the conductive composition of the present invention is used, good heat treatment (firing) can be performed even at a low temperature (about 150 to 500 ° C.).
上記熱処理工程は、上記配線形成工程で得られた配線を熱処理して導電性の配線（電極）を得る工程である。
ここで、上記熱処理は特に限定されないが、１５０～８００℃の温度で、数秒～数十分間、加熱（焼成）する処理であるのが好ましい。温度および時間がこの範囲であると、シリコン基板上に反射防止膜を形成した場合であっても、ファイヤースルー法により容易に電極を形成することができる。
本発明においては、本発明の導電性組成物を用いているため、低温（１５０～５００℃程度）であっても、良好な熱処理（焼成）を施すことができる。 <Heat treatment process>
The heat treatment step is a step of obtaining a conductive wiring (electrode) by heat-treating the wiring obtained in the wiring forming step.
Here, the heat treatment is not particularly limited, but is preferably a treatment of heating (firing) at a temperature of 150 to 800 ° C. for several seconds to several tens of minutes. When the temperature and time are within this range, even when an antireflection film is formed on the silicon substrate, the electrode can be easily formed by the fire-through method.
In the present invention, since the conductive composition of the present invention is used, good heat treatment (firing) can be performed even at a low temperature (about 150 to 500 ° C.).
なお、本発明においては、上記配線形成工程で得られた配線は、紫外線または赤外線の照射でも電極を形成することができるため、上記熱処理工程は、紫外線または赤外線の照射によるものであってもよい。
In the present invention, since the wiring obtained in the wiring formation step can form electrodes even by irradiation with ultraviolet rays or infrared rays, the heat treatment step may be performed by irradiation with ultraviolet rays or infrared rays. .
以下、実施例を用いて、本発明の導電性組成物について詳細に説明する。ただし、本発明はこれに限定されるものではない。
Hereinafter, the conductive composition of the present invention will be described in detail using examples. However, the present invention is not limited to this.
（実施例１～１２、比較例１～６）
ボールミルに、下記第１表に示す銀粉等を下記第１表中に示す組成比となるように添加し、これらを混合することにより導電性組成物を調製した。 (Examples 1 to 12, Comparative Examples 1 to 6)
To the ball mill, silver powder and the like shown in Table 1 below were added so as to have the composition ratio shown in Table 1 below, and these were mixed to prepare a conductive composition.
ボールミルに、下記第１表に示す銀粉等を下記第１表中に示す組成比となるように添加し、これらを混合することにより導電性組成物を調製した。 (Examples 1 to 12, Comparative Examples 1 to 6)
To the ball mill, silver powder and the like shown in Table 1 below were added so as to have the composition ratio shown in Table 1 below, and these were mixed to prepare a conductive composition.
＜スクリーン印刷性＞
調製した導電性組成物を、シリコン基板（単結晶シリコンウェハー、ＬＳ－２５ＴＶＡ、１５６ｍｍ×１５６ｍｍ×２００μｍ、信越化学工業社製）上に、スクリーン印刷で塗布して配線（線幅：７０μｍ、長さ：５ｃｍ）を形成した。
スクリーン印刷で形成した乾燥（焼成）前の配線を光学顕微鏡で観察した。
その結果、断線、蛇行、ニジミおよびメッシュ跡のいずれも確認されない場合を印刷性が極めて良好なものとして「Ａ」と評価し、断線は確認されないが、蛇行、ニジミおよびメッシュ跡のいずれか１つが確認された場合を印刷性が良好なものとして「Ｂ」と評価し、断線は確認されないが、蛇行、ニジミおよびメッシュ跡のいずれか２つ以上が確認された場合を印刷性が劣るものとして「Ｃ」と評価し、断線が確認された場合を印刷性が極めて劣るものとして「Ｄ」と評価した。これらの結果を下記第１表に示す。 <Screen printability>
The prepared conductive composition was applied on a silicon substrate (single crystal silicon wafer, LS-25TVA, 156 mm × 156 mm × 200 μm, manufactured by Shin-Etsu Chemical Co., Ltd.) by screen printing and wiring (line width: 70 μm, length) : 5 cm).
Wiring before drying (firing) formed by screen printing was observed with an optical microscope.
As a result, the case where none of the disconnection, meandering, bleeding and mesh marks is confirmed is evaluated as “A” as the printability is extremely good. When confirmed, the printability is evaluated as “B”, and disconnection is not confirmed. However, when any two or more of meandering, bleeding and mesh marks are confirmed, the printability is inferior. The case where the disconnection was confirmed was evaluated as “D” because the printability was extremely inferior. These results are shown in Table 1 below.
調製した導電性組成物を、シリコン基板（単結晶シリコンウェハー、ＬＳ－２５ＴＶＡ、１５６ｍｍ×１５６ｍｍ×２００μｍ、信越化学工業社製）上に、スクリーン印刷で塗布して配線（線幅：７０μｍ、長さ：５ｃｍ）を形成した。
スクリーン印刷で形成した乾燥（焼成）前の配線を光学顕微鏡で観察した。
その結果、断線、蛇行、ニジミおよびメッシュ跡のいずれも確認されない場合を印刷性が極めて良好なものとして「Ａ」と評価し、断線は確認されないが、蛇行、ニジミおよびメッシュ跡のいずれか１つが確認された場合を印刷性が良好なものとして「Ｂ」と評価し、断線は確認されないが、蛇行、ニジミおよびメッシュ跡のいずれか２つ以上が確認された場合を印刷性が劣るものとして「Ｃ」と評価し、断線が確認された場合を印刷性が極めて劣るものとして「Ｄ」と評価した。これらの結果を下記第１表に示す。 <Screen printability>
The prepared conductive composition was applied on a silicon substrate (single crystal silicon wafer, LS-25TVA, 156 mm × 156 mm × 200 μm, manufactured by Shin-Etsu Chemical Co., Ltd.) by screen printing and wiring (line width: 70 μm, length) : 5 cm).
Wiring before drying (firing) formed by screen printing was observed with an optical microscope.
As a result, the case where none of the disconnection, meandering, bleeding and mesh marks is confirmed is evaluated as “A” as the printability is extremely good. When confirmed, the printability is evaluated as “B”, and disconnection is not confirmed. However, when any two or more of meandering, bleeding and mesh marks are confirmed, the printability is inferior. The case where the disconnection was confirmed was evaluated as “D” because the printability was extremely inferior. These results are shown in Table 1 below.
＜半田付け性（半田濡れ性）＞
調製した導電性組成物を、シリコン基板（単結晶シリコンウェハー、ＬＳ－２５ＴＶＡ、１５６ｍｍ×１５６ｍｍ×２００μｍ、信越化学工業社製）上に、スクリーン印刷で塗布してテストパターン（２ｍｍ×２ｍｍ）を形成した。
形成したテストパターン上に半田フラックスを塗布した後、１５０℃のホットプレート上で２０秒間乾燥させた。
次いで、２７０℃の半田槽中に３秒間浸漬させ後に引き上げ、テストパターン上の半田の濡れ性（被覆％）から半田付け性を評価した。
テストパターン上の半田の被覆面積が１００％であるものを半田付け性が極めて良好なものとして「Ａ」と評価し、テストパターン上の半田の被覆面積が８０％以上１００％未満であるものを半田付け性が良好なものとして「Ｂ」と評価し、テストパターン上の半田の被覆面積が８０％未満であるものを半田付け性が劣るものとして「Ｃ」と評価した。これらの結果を下記第１表に示す。 <Solderability (solder wettability)>
The prepared conductive composition is applied on a silicon substrate (single crystal silicon wafer, LS-25TVA, 156 mm × 156 mm × 200 μm, manufactured by Shin-Etsu Chemical Co., Ltd.) by screen printing to form a test pattern (2 mm × 2 mm). did.
A solder flux was applied on the formed test pattern and then dried on a hot plate at 150 ° C. for 20 seconds.
Next, it was dipped in a solder bath at 270 ° C. for 3 seconds and then pulled up, and the solderability was evaluated from the wettability (covering%) of the solder on the test pattern.
A test pattern having a solder coverage of 100% is evaluated as “A” as having extremely good solderability, and a test pattern solder coverage of 80% or more and less than 100%. “B” was evaluated as having good solderability, and “C” was evaluated as having poor solderability when solder coverage on the test pattern was less than 80%. These results are shown in Table 1 below.
調製した導電性組成物を、シリコン基板（単結晶シリコンウェハー、ＬＳ－２５ＴＶＡ、１５６ｍｍ×１５６ｍｍ×２００μｍ、信越化学工業社製）上に、スクリーン印刷で塗布してテストパターン（２ｍｍ×２ｍｍ）を形成した。
形成したテストパターン上に半田フラックスを塗布した後、１５０℃のホットプレート上で２０秒間乾燥させた。
次いで、２７０℃の半田槽中に３秒間浸漬させ後に引き上げ、テストパターン上の半田の濡れ性（被覆％）から半田付け性を評価した。
テストパターン上の半田の被覆面積が１００％であるものを半田付け性が極めて良好なものとして「Ａ」と評価し、テストパターン上の半田の被覆面積が８０％以上１００％未満であるものを半田付け性が良好なものとして「Ｂ」と評価し、テストパターン上の半田の被覆面積が８０％未満であるものを半田付け性が劣るものとして「Ｃ」と評価した。これらの結果を下記第１表に示す。 <Solderability (solder wettability)>
The prepared conductive composition is applied on a silicon substrate (single crystal silicon wafer, LS-25TVA, 156 mm × 156 mm × 200 μm, manufactured by Shin-Etsu Chemical Co., Ltd.) by screen printing to form a test pattern (2 mm × 2 mm). did.
A solder flux was applied on the formed test pattern and then dried on a hot plate at 150 ° C. for 20 seconds.
Next, it was dipped in a solder bath at 270 ° C. for 3 seconds and then pulled up, and the solderability was evaluated from the wettability (covering%) of the solder on the test pattern.
A test pattern having a solder coverage of 100% is evaluated as “A” as having extremely good solderability, and a test pattern solder coverage of 80% or more and less than 100%. “B” was evaluated as having good solderability, and “C” was evaluated as having poor solderability when solder coverage on the test pattern was less than 80%. These results are shown in Table 1 below.
＜体積抵抗率（比抵抗）＞
実施例１および１０～１２で調製した導電性組成物を用いて、スクリーン印刷で配線を形成した後、オーブンにて２００℃、１８０℃および１５０℃の３つの条件で３０分間乾燥し、導電性の配線（電極）を形成させた太陽電池セルのサンプルを作製した。
作製した各太陽電池セルのサンプルについて、電極の体積抵抗率を抵抗率計（ロレスターＧＰ、三菱化学社製）を用いた４端子４探針法により測定した。この結果を下記第２表に示す。 <Volume resistivity (specific resistance)>
A wiring was formed by screen printing using the conductive composition prepared in Examples 1 and 10 to 12, and then dried in an oven for 30 minutes under three conditions of 200 ° C., 180 ° C. and 150 ° C. Samples of solar cells on which the wirings (electrodes) were formed were prepared.
About the sample of each produced photovoltaic cell, the volume resistivity of the electrode was measured by a 4-terminal 4-probe method using a resistivity meter (Lorestar GP, manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 2 below.
実施例１および１０～１２で調製した導電性組成物を用いて、スクリーン印刷で配線を形成した後、オーブンにて２００℃、１８０℃および１５０℃の３つの条件で３０分間乾燥し、導電性の配線（電極）を形成させた太陽電池セルのサンプルを作製した。
作製した各太陽電池セルのサンプルについて、電極の体積抵抗率を抵抗率計（ロレスターＧＰ、三菱化学社製）を用いた４端子４探針法により測定した。この結果を下記第２表に示す。 <Volume resistivity (specific resistance)>
A wiring was formed by screen printing using the conductive composition prepared in Examples 1 and 10 to 12, and then dried in an oven for 30 minutes under three conditions of 200 ° C., 180 ° C. and 150 ° C. Samples of solar cells on which the wirings (electrodes) were formed were prepared.
About the sample of each produced photovoltaic cell, the volume resistivity of the electrode was measured by a 4-terminal 4-probe method using a resistivity meter (Lorestar GP, manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 2 below.
第１表および第２表中の各成分は、以下のものを使用した。
・銀粉：ＡｇＣ－１０３（形状：球状、平均粒子径：１．５μｍ、福田金属箔粉工業社製）
・α－テルピネオール：溶媒 The following were used for each component in Table 1 and Table 2.
Silver powder: AgC-103 (shape: spherical, average particle size: 1.5 μm, manufactured by Fukuda Metal Foil Powder Industry)
・ Α-Terpineol: Solvent
・銀粉：ＡｇＣ－１０３（形状：球状、平均粒子径：１．５μｍ、福田金属箔粉工業社製）
・α－テルピネオール：溶媒 The following were used for each component in Table 1 and Table 2.
Silver powder: AgC-103 (shape: spherical, average particle size: 1.5 μm, manufactured by Fukuda Metal Foil Powder Industry)
・ Α-Terpineol: Solvent
・ビスフェノールＡ型エポキシ樹脂：ＹＤ－０１９（エポキシ当量：２４００～３３００ｇ／ｅｑ、新日鐵化学社製）
・ビスフェノールＡ型エポキシ樹脂：ＹＤ－０２０Ｎ（エポキシ当量：３５００～４０００ｇ／ｅｑ、新日鐵化学社製）
・ビスフェノールＡ型エポキシ樹脂：ＹＤ－０１４（エポキシ当量：９００～１０００ｇ／ｅｑ、新日鐵化学社製）
・ビスフェノールＡ型エポキシ樹脂：ＥＰ－４１００Ｅ（エポキシ当量：１９０ｇ／ｅｑ、ＡＤＥＫＡ社製） Bisphenol A type epoxy resin: YD-019 (epoxy equivalent: 2400-3300 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
Bisphenol A type epoxy resin: YD-020N (epoxy equivalent: 3500 to 4000 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
Bisphenol A type epoxy resin: YD-014 (epoxy equivalent: 900 to 1000 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
Bisphenol A type epoxy resin: EP-4100E (epoxy equivalent: 190 g / eq, manufactured by ADEKA)
・ビスフェノールＡ型エポキシ樹脂：ＹＤ－０２０Ｎ（エポキシ当量：３５００～４０００ｇ／ｅｑ、新日鐵化学社製）
・ビスフェノールＡ型エポキシ樹脂：ＹＤ－０１４（エポキシ当量：９００～１０００ｇ／ｅｑ、新日鐵化学社製）
・ビスフェノールＡ型エポキシ樹脂：ＥＰ－４１００Ｅ（エポキシ当量：１９０ｇ／ｅｑ、ＡＤＥＫＡ社製） Bisphenol A type epoxy resin: YD-019 (epoxy equivalent: 2400-3300 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
Bisphenol A type epoxy resin: YD-020N (epoxy equivalent: 3500 to 4000 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
Bisphenol A type epoxy resin: YD-014 (epoxy equivalent: 900 to 1000 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.)
Bisphenol A type epoxy resin: EP-4100E (epoxy equivalent: 190 g / eq, manufactured by ADEKA)
・多価アルコール系グリシジル型エポキシ樹脂：ポリエチレングリコールジグリシジルエーテル（ＥＸ－８２１、エポキシ当量：１８５ｇ／ｅｑ、ナガセケムテックス社製）
・多価アルコール系グリシジル型エポキシ樹脂：ジエチレングリコールジグリシジルエーテル（ＥＸ－８５０、エポキシ当量：１２２ｇ／ｅｑ、ナガセケムテックス社製）
・多価アルコール系グリシジル型エポキシ樹脂：エチレングリコールジグリシジルエーテル（ＥＸ－８１０、エポキシ当量：１１３ｇ／ｅｑ、ナガセケムテックス社製）
・多価アルコール系グリシジル型エポキシ樹脂：１，６－ヘキサンジオールジグリシジルエーテル（ＥＸ－２１２、エポキシ当量：１５１ｇ／ｅｑ、ナガセケムテックス社製） Polyhydric alcohol glycidyl type epoxy resin: polyethylene glycol diglycidyl ether (EX-821, epoxy equivalent: 185 g / eq, manufactured by Nagase ChemteX Corporation)
Polyhydric alcohol glycidyl type epoxy resin: diethylene glycol diglycidyl ether (EX-850, epoxy equivalent: 122 g / eq, manufactured by Nagase ChemteX Corporation)
Polyhydric alcohol glycidyl type epoxy resin: ethylene glycol diglycidyl ether (EX-810, epoxy equivalent: 113 g / eq, manufactured by Nagase ChemteX Corporation)
Polyhydric alcohol glycidyl type epoxy resin: 1,6-hexanediol diglycidyl ether (EX-212, epoxy equivalent: 151 g / eq, manufactured by Nagase ChemteX Corporation)
・多価アルコール系グリシジル型エポキシ樹脂：ジエチレングリコールジグリシジルエーテル（ＥＸ－８５０、エポキシ当量：１２２ｇ／ｅｑ、ナガセケムテックス社製）
・多価アルコール系グリシジル型エポキシ樹脂：エチレングリコールジグリシジルエーテル（ＥＸ－８１０、エポキシ当量：１１３ｇ／ｅｑ、ナガセケムテックス社製）
・多価アルコール系グリシジル型エポキシ樹脂：１，６－ヘキサンジオールジグリシジルエーテル（ＥＸ－２１２、エポキシ当量：１５１ｇ／ｅｑ、ナガセケムテックス社製） Polyhydric alcohol glycidyl type epoxy resin: polyethylene glycol diglycidyl ether (EX-821, epoxy equivalent: 185 g / eq, manufactured by Nagase ChemteX Corporation)
Polyhydric alcohol glycidyl type epoxy resin: diethylene glycol diglycidyl ether (EX-850, epoxy equivalent: 122 g / eq, manufactured by Nagase ChemteX Corporation)
Polyhydric alcohol glycidyl type epoxy resin: ethylene glycol diglycidyl ether (EX-810, epoxy equivalent: 113 g / eq, manufactured by Nagase ChemteX Corporation)
Polyhydric alcohol glycidyl type epoxy resin: 1,6-hexanediol diglycidyl ether (EX-212, epoxy equivalent: 151 g / eq, manufactured by Nagase ChemteX Corporation)
・硬化剤：下記式（１）で表される化合物（Ｓｌ－１００Ｌ、三新化学工業社製）
・硬化剤：下記式（２）で表される化合物（ＳＩ－１５０、三新化学工業社製）
・硬化剤：下記式（３）で表される化合物
・硬化剤：下記式（４）で表される化合物（三フッ化ホウ素エチルアミン、東京化成社製） Curing agent: Compound represented by the following formula (1) (Sl-100L, manufactured by Sanshin Chemical Industry Co., Ltd.)
Curing agent: Compound represented by the following formula (2) (SI-150, manufactured by Sanshin Chemical Industry Co., Ltd.)
Curing agent: Compound represented by the following formula (3) Curing agent: Compound represented by the following formula (4) (Boron trifluoride ethylamine, manufactured by Tokyo Chemical Industry Co., Ltd.)
・硬化剤：下記式（２）で表される化合物（ＳＩ－１５０、三新化学工業社製）
・硬化剤：下記式（３）で表される化合物
・硬化剤：下記式（４）で表される化合物（三フッ化ホウ素エチルアミン、東京化成社製） Curing agent: Compound represented by the following formula (1) (Sl-100L, manufactured by Sanshin Chemical Industry Co., Ltd.)
Curing agent: Compound represented by the following formula (2) (SI-150, manufactured by Sanshin Chemical Industry Co., Ltd.)
Curing agent: Compound represented by the following formula (3) Curing agent: Compound represented by the following formula (4) (Boron trifluoride ethylamine, manufactured by Tokyo Chemical Industry Co., Ltd.)
・２，２－ビス（ヒドロキシメチル）－ｎ－酪酸銀塩：まず、酸化銀（東洋化学工業社製）５０ｇ、２，２－ビス（ヒドロキシメチル）－ｎ－酪酸（東京化成社製）６４ｇおよびメチルエチルケトン（ＭＥＫ）３００ｇをボールミルに投入し、室温で２４時間撹拌させることにより反応させた。次いで、吸引ろ過によりＭＥＫを取り除き、得られた粉末を乾燥させることにより、白色の２，２－ビス（ヒドロキシメチル）－ｎ－酪酸銀塩を調製した。
・ 2,2-bis (hydroxymethyl) -n-butyric acid silver salt: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 64 g of 2,2-bis (hydroxymethyl) -n-butyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, 300 g of methyl ethyl ketone (MEK) was put into 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 white 2,2-bis (hydroxymethyl) -n-butyric acid silver salt.
・２－ヒドロキシイソ酪酸銀塩：まず、酸化銀（東洋化学工業社製）５０ｇ、２－ヒドロキシイソ酪酸（東京化成社製）４５ｇおよびメチルエチルケトン（ＭＥＫ）３００ｇをボールミルに投入し、室温で２４時間撹拌させることにより反応させた。次いで、吸引ろ過によりＭＥＫを取り除き、得られた粉末を乾燥させることにより、白色の２－ヒドロキシイソ酪酸銀塩を調製した。
Silver salt of 2-hydroxyisobutyrate: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 45 g of 2-hydroxyisobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 g of methyl ethyl ketone (MEK) are placed in a ball mill and are allowed to stand at room temperature for 24 hours The reaction was allowed to stir. Subsequently, MEK was removed by suction filtration, and the obtained powder was dried to prepare white 2-hydroxyisobutyric acid silver salt.
・１，２，３，４－ブタンテトラカルボン酸銀塩：まず、酸化銀（東洋化学工業社製）５０ｇ、１，２，３，４－ブタンテトラカルボン酸（新日本理化社製）２５．２９ｇおよびメチルエチルケトン（ＭＥＫ）３００ｇをボールミルに投入し、室温で２４時間撹拌させることにより反応させた。次いで、吸引ろ過によりＭＥＫを取り除き、得られた粉末を乾燥させることによって、白色の１，２，３，４－ブタンテトラカルボン酸銀塩を調製した。
-1,2,3,4-butanetetracarboxylic acid silver salt: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 1,2,3,4-butanetetracarboxylic acid (manufactured by Shin Nippon Rika Co., Ltd.) 29 g 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 white 1,2,3,4-butanetetracarboxylic acid silver salt.
第１表に示す結果から、エポキシ当量が１５００未満のビスフェノールＡ型エポキシ樹脂を用いて調製した比較例１の導電性組成物は、半田付け性は良好であるものの印刷性が劣ることが分かった。
また、エポキシ当量が低い汎用のビスフェノールＡ型エポキシ樹脂を用いて調製した比較例２の導電性組成物は、印刷性は極めて良好だが、半田付け性が劣ることが分かった。
また、スルホニウムカチオン系ではない硬化剤を用いて調製した比較例３の導電性組成物は、印刷性は極めて良好だが、半田付け性が劣ることが分かった。
また、ビスフェノールＡ型エポキシ樹脂および多価アルコール系グリシジル型エポキシ樹脂のいずれか一方を配合せずに調製した比較例４および５の導電性組成物は、印刷性に劣り、半田付け性も劣ることが分かった。
また、エポキシ当量の異なる２種のビスフェノールＡ型エポキシ樹脂を併用して調製した比較例６の導電性組成物は、印刷性に劣り、半田付け性も劣ることが分かった。 From the results shown in Table 1, it was found that the conductive composition of Comparative Example 1 prepared using a bisphenol A type epoxy resin having an epoxy equivalent of less than 1500 had poor solderability but good printability. .
Moreover, it turned out that the electroconductive composition of the comparative example 2 prepared using the general purpose bisphenol A type epoxy resin with a low epoxy equivalent has very good printability, but is inferior in solderability.
Moreover, it turned out that the electroconductive composition of the comparative example 3 prepared using the hardening | curing agent which is not a sulfonium cation type | system | group is very good in printability, but inferior in solderability.
In addition, the conductive compositions of Comparative Examples 4 and 5 prepared without blending either one of the bisphenol A type epoxy resin and the polyhydric alcohol glycidyl type epoxy resin are inferior in printability and in solderability. I understood.
Moreover, it turned out that the electroconductive composition of the comparative example 6 prepared by using together 2 types of bisphenol A type epoxy resins from which an epoxy equivalent differs is inferior to printability, and solderability.
また、エポキシ当量が低い汎用のビスフェノールＡ型エポキシ樹脂を用いて調製した比較例２の導電性組成物は、印刷性は極めて良好だが、半田付け性が劣ることが分かった。
また、スルホニウムカチオン系ではない硬化剤を用いて調製した比較例３の導電性組成物は、印刷性は極めて良好だが、半田付け性が劣ることが分かった。
また、ビスフェノールＡ型エポキシ樹脂および多価アルコール系グリシジル型エポキシ樹脂のいずれか一方を配合せずに調製した比較例４および５の導電性組成物は、印刷性に劣り、半田付け性も劣ることが分かった。
また、エポキシ当量の異なる２種のビスフェノールＡ型エポキシ樹脂を併用して調製した比較例６の導電性組成物は、印刷性に劣り、半田付け性も劣ることが分かった。 From the results shown in Table 1, it was found that the conductive composition of Comparative Example 1 prepared using a bisphenol A type epoxy resin having an epoxy equivalent of less than 1500 had poor solderability but good printability. .
Moreover, it turned out that the electroconductive composition of the comparative example 2 prepared using the general purpose bisphenol A type epoxy resin with a low epoxy equivalent has very good printability, but is inferior in solderability.
Moreover, it turned out that the electroconductive composition of the comparative example 3 prepared using the hardening | curing agent which is not a sulfonium cation type | system | group is very good in printability, but inferior in solderability.
In addition, the conductive compositions of Comparative Examples 4 and 5 prepared without blending either one of the bisphenol A type epoxy resin and the polyhydric alcohol glycidyl type epoxy resin are inferior in printability and in solderability. I understood.
Moreover, it turned out that the electroconductive composition of the comparative example 6 prepared by using together 2 types of bisphenol A type epoxy resins from which an epoxy equivalent differs is inferior to printability, and solderability.
これに対し、所定のエポキシ当量のビスフェノールＡ型エポキシ樹脂および多価アルコール系グリシジル型エポキシ樹脂を併用し、スルホニウムカチオン系硬化剤を用いて調製した実施例１～１０の導電性組成物は、いずれも印刷性に優れ、半田付け性も良好となることが分かった。
特に、六フッ化アンチモン酸イオン（ＳｂＦ6 -）をアニオンとして有する硬化剤を用いて調製した実施例１～７、９～１２の導電性組成物は、半田付け性も極めて良好となることが分かった。
また、ビスフェノールＡ型エポキシ樹脂の配合量が多価アルコール系グリシジル型エポキシ樹脂の配合量よりも多い実施例１，２，４，６～８および１０～１２の導電性組成物は、印刷性が極めて良好となる傾向があることが分かった。
また、第２表に示す結果から、脂肪酸銀塩を併用した実施例１０～１２の導電性組成物は、実施例１の導電性組成物と比較して、焼成温度に依らず体積抵抗率が低くなることが分かった。 On the other hand, the conductive compositions of Examples 1 to 10 prepared using a sulfonium cation curing agent in combination with a bisphenol A type epoxy resin and a polyhydric alcohol glycidyl type epoxy resin having a predetermined epoxy equivalent weight Was found to be excellent in printability and solderability.
In particular, the conductive compositions of Examples 1 to 7 and 9 to 12 prepared using a curing agent having hexafluoroantimonate ion (SbF 6 − ) as an anion may have extremely good solderability. I understood.
In addition, the conductive compositions of Examples 1, 2, 4, 6 to 8, and 10 to 12, in which the blending amount of the bisphenol A type epoxy resin is larger than the blending amount of the polyhydric alcohol glycidyl type epoxy resin, have printability. It turns out that it tends to be very good.
Further, from the results shown in Table 2, the conductive compositions of Examples 10 to 12 used in combination with the fatty acid silver salt have a volume resistivity independent of the firing temperature as compared with the conductive composition of Example 1. It turned out to be lower.
特に、六フッ化アンチモン酸イオン（ＳｂＦ6 -）をアニオンとして有する硬化剤を用いて調製した実施例１～７、９～１２の導電性組成物は、半田付け性も極めて良好となることが分かった。
また、ビスフェノールＡ型エポキシ樹脂の配合量が多価アルコール系グリシジル型エポキシ樹脂の配合量よりも多い実施例１，２，４，６～８および１０～１２の導電性組成物は、印刷性が極めて良好となる傾向があることが分かった。
また、第２表に示す結果から、脂肪酸銀塩を併用した実施例１０～１２の導電性組成物は、実施例１の導電性組成物と比較して、焼成温度に依らず体積抵抗率が低くなることが分かった。 On the other hand, the conductive compositions of Examples 1 to 10 prepared using a sulfonium cation curing agent in combination with a bisphenol A type epoxy resin and a polyhydric alcohol glycidyl type epoxy resin having a predetermined epoxy equivalent weight Was found to be excellent in printability and solderability.
In particular, the conductive compositions of Examples 1 to 7 and 9 to 12 prepared using a curing agent having hexafluoroantimonate ion (SbF 6 − ) as an anion may have extremely good solderability. I understood.
In addition, the conductive compositions of Examples 1, 2, 4, 6 to 8, and 10 to 12, in which the blending amount of the bisphenol A type epoxy resin is larger than the blending amount of the polyhydric alcohol glycidyl type epoxy resin, have printability. It turns out that it tends to be very good.
Further, from the results shown in Table 2, the conductive compositions of Examples 10 to 12 used in combination with the fatty acid silver salt have a volume resistivity independent of the firing temperature as compared with the conductive composition of Example 1. It turned out to be lower.
１ 太陽電池セル
２ ｎ層
３ 反射防止膜
４ 表面電極
５ ｐ層
６ 裏面電極
７ シリコン基板 DESCRIPTION OF SYMBOLS 1 Solar cell 2N layer 3 Antireflection film 4 Surface electrode 5 P layer 6 Back electrode 7 Silicon substrate
２ ｎ層
３ 反射防止膜
４ 表面電極
５ ｐ層
６ 裏面電極
７ シリコン基板 DESCRIPTION OF SYMBOLS 1 Solar cell 2
Claims (12)
- 銀粉（Ａ）と、エポキシ樹脂（Ｂ）と、硬化剤（Ｃ）とを含有し、
前記エポキシ樹脂（Ｂ）が、少なくとも、エポキシ当量が１５００～４０００ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂（ｂ１）およびエポキシ当量が１０００ｇ／ｅｑ以下の多価アルコール系グリシジル型エポキシ樹脂（ｂ２）であり、
前記硬化剤（Ｃ）が、スルホニウムカチオン系硬化剤である導電性組成物。 Contains silver powder (A), epoxy resin (B), and curing agent (C),
The epoxy resin (B) is at least a bisphenol A type epoxy resin (b1) having an epoxy equivalent of 1500 to 4000 g / eq and a polyhydric alcohol glycidyl type epoxy resin (b2) having an epoxy equivalent of 1000 g / eq or less,
The electrically conductive composition whose said hardening | curing agent (C) is a sulfonium cation type hardening | curing agent. - 前記硬化剤（Ｃ）が、下記式（Ｉ）で表されるスルホニウム塩である請求項１に記載の導電性組成物。
- 前記硬化剤（Ｃ）が、前記式（Ｉ）中のＸがＳｂＦ6で表される請求項２に記載の導電性組成物。 The conductive composition according to claim 2, wherein the curing agent (C) is such that X in the formula (I) is represented by SbF 6 .
- 前記硬化剤（Ｃ）の含有量が、前記エポキシ樹脂（Ｂ）１００質量部に対して１～１０質量部である請求項１～３のいずれかに記載の導電性組成物。 The conductive composition according to any one of claims 1 to 3, wherein the content of the curing agent (C) is 1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (B).
- 前記ビスフェノールＡ型エポキシ樹脂（ｂ１）は、エポキシ当量が２０００～３５００ｇ／ｅｑである請求項１～４のいずれかに記載の導電性組成物。 The conductive composition according to any one of claims 1 to 4, wherein the bisphenol A type epoxy resin (b1) has an epoxy equivalent of 2000 to 3500 g / eq.
- 前記多価アルコール系グリシジル型エポキシ樹脂（ｂ２）が、ポリエチレングリコールジグリシジルエーテルである請求項１～５のいずれかに記載の導電性組成物。 The conductive composition according to any one of claims 1 to 5, wherein the polyhydric alcohol glycidyl type epoxy resin (b2) is polyethylene glycol diglycidyl ether.
- 前記エポキシ樹脂（Ｂ）の含有量が、前記銀粉（Ａ）１００質量部に対して４～１０質量部である請求項１～６のいずれかに記載の導電性組成物。 The conductive composition according to any one of claims 1 to 6, wherein the content of the epoxy resin (B) is 4 to 10 parts by mass with respect to 100 parts by mass of the silver powder (A).
- 更に、脂肪酸銀塩（Ｄ）を含有し、
前記脂肪酸銀塩（Ｄ）が、カルボキシ銀塩基（－ＣＯＯＡｇ）と水酸基（－ＯＨ）とをそれぞれ１個以上有する脂肪酸銀塩（Ｄ１）、および／または、カルボキシ銀塩基（－ＣＯＯＡｇ）を３個以上有するポリカルボン酸銀塩（Ｄ２）である請求項１～７のいずれかに記載の導電性組成物。 Furthermore, it contains a fatty acid silver salt (D),
The fatty acid silver salt (D) includes three fatty acid silver salts (D1) having at least one carboxy silver base (—COOAg) and one hydroxyl group (—OH) and / or three carboxy silver bases (—COOAg). The conductive composition according to any one of claims 1 to 7, which is a polycarboxylic acid silver salt (D2) having the above. - 前記脂肪酸銀塩（Ｄ）の含有量が、前記銀粉（Ａ）１００質量部に対して１～１００質量部である請求項８に記載の導電性組成物。 The conductive composition according to claim 8, wherein the content of the fatty acid silver salt (D) is 1 to 100 parts by mass with respect to 100 parts by mass of the silver powder (A).
- 太陽電池電極用ペーストに用いる請求項１～９のいずれかに記載の導電性組成物。 10. The conductive composition according to claim 1, which is used for a solar cell electrode paste.
- 受光面側の表面電極、半導体基板および裏面電極を具備し、
前記表面電極および／または前記裏面電極が、請求項１０に記載の導電性組成物を用いて形成される太陽電池セル。 It comprises a surface electrode on the light receiving surface side, a semiconductor substrate and a back electrode,
The photovoltaic cell in which the said surface electrode and / or the said back surface electrode are formed using the electrically conductive composition of Claim 10. - 請求項１～１０のいずれかに記載の導電性組成物をシリコン基板上に塗布して配線を形成する配線形成工程と、
得られた前記配線を熱処理して受光面側の表面電極および／または裏面電極を形成する熱処理工程と、を備える太陽電池セルの製造方法。 A wiring forming step of forming a wiring by applying the conductive composition according to any one of claims 1 to 10 on a silicon substrate;
A heat treatment step of heat-treating the obtained wiring to form a front-surface electrode and / or a back-surface electrode on the light-receiving surface side.
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| WO2023048098A1 (en) * | 2021-09-24 | 2023-03-30 | 住友ベークライト株式会社 | Conductive paste, cured product, sintering accelerator and method for accelerating sintering |
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| JP5877133B2 (en) * | 2012-07-09 | 2016-03-02 | デクセリアルズ株式会社 | Conductive adhesive for solar cell, solar cell module, and manufacturing method thereof |
| JP5304932B1 (en) * | 2012-07-18 | 2013-10-02 | 横浜ゴム株式会社 | Conductive composition and solar battery cell |
| KR101956734B1 (en) * | 2012-09-19 | 2019-03-11 | 엘지전자 주식회사 | Solar cell and manufacturing method thereof |
| JP6620744B2 (en) * | 2014-07-11 | 2019-12-18 | 横浜ゴム株式会社 | Conductive composition for forming solar battery collecting electrode, solar battery cell and solar battery module |
| JPWO2018020941A1 (en) * | 2016-07-29 | 2019-05-16 | 名古屋ファインケミカル株式会社 | Epoxy composition, curing method thereof and storage method thereof |
| CN110249001A (en) * | 2017-01-26 | 2019-09-17 | 横滨橡胶株式会社 | Conductive composition |
| JP6361843B1 (en) * | 2017-01-26 | 2018-07-25 | 横浜ゴム株式会社 | Conductive composition |
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