WO2012102076A1 - 導電性接着剤組成物、導電性接着剤付金属導線、接続体及び太陽電池モジュール - Google Patents
導電性接着剤組成物、導電性接着剤付金属導線、接続体及び太陽電池モジュール Download PDFInfo
- Publication number
- WO2012102076A1 WO2012102076A1 PCT/JP2012/050361 JP2012050361W WO2012102076A1 WO 2012102076 A1 WO2012102076 A1 WO 2012102076A1 JP 2012050361 W JP2012050361 W JP 2012050361W WO 2012102076 A1 WO2012102076 A1 WO 2012102076A1
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- WO
- WIPO (PCT)
- Prior art keywords
- conductive adhesive
- metal
- adhesive composition
- resin
- conductive
- Prior art date
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- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
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- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
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- 229920013716 polyethylene resin Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000000790 scattering method Methods 0.000 description 1
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 239000005341 toughened glass Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- H01L31/02002—Arrangements for conducting electric current to or from the device in operations
- H01L31/02005—Arrangements for conducting electric current to or from the device in operations for device characterised by at least one potential jump barrier or surface barrier
- H01L31/02008—Arrangements for conducting electric current to or from the device in operations for device characterised by at least one potential jump barrier or surface barrier for solar cells or solar cell modules
- H01L31/02013—Arrangements for conducting electric current to or from the device in operations for device characterised by at least one potential jump barrier or surface barrier for solar cells or solar cell modules comprising output lead wires elements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
- H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
- H01L31/0512—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module made of a particular material or composition of materials
-
- 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 adhesive composition and a metal conductor with a conductive adhesive that are suitably used for electrical joining of a plurality of solar cells, and a connection body and a solar battery module using these.
- Sn-Ag-Cu solder not containing Pb is coated on a copper wire, which is a metal conductor, and heated to a temperature higher than the melting temperature of the solder, so that the electrode of the solar battery cell and the metal conductor Is known (Patent Documents 1 and 2).
- This conductive adhesive composition is a composition in which metal particles typified by silver particles are mixed and dispersed in a thermosetting resin, and the metal particles are mainly physically combined with the electrodes and metal conductors of the solar battery cells. Electrical connection is expressed by contact.
- thermosetting resin and metal particles and flux that melts at low temperatures, such as lead-free solder, and has a low melting temperature, good wettability, and high adhesive strength Has been proposed (Patent Document 4).
- the present invention has an object to provide a conductive adhesive composition that is not tacky at room temperature and can be electrically joined at a low temperature, and a metal wire with a conductive adhesive using the composition. And Moreover, it aims at providing the connection body and solar cell module using these electrically conductive adhesive compositions or the metal conducting wire with an electrically conductive adhesive.
- “no tackiness” means that no tackiness is found as a result of the predetermined test described in the examples.
- conductive particles containing a metal having a melting point of 210 ° C. or lower (hereinafter also simply referred to as “(A) conductive particles”), (B) the softening point of the metal in the conductive particles
- a conductive adhesive composition containing a resin having a melting point or lower and a solid at room temperature (hereinafter also simply referred to as “(B) resin”), (C) a flux activator, and (D) a solvent.
- the “melting point” means, for example, a value measured by differential scanning calorimetry (DSC), and the “softening point” can change the measured temperature, for example. What is measured with a rheometer.
- the metal in the conductive particles preferably contains at least one component selected from bismuth, indium, tin and zinc. Thereby, melting
- the resin preferably contains a thermosetting resin, particularly preferably an epoxy resin, from the viewpoint of excellent connection stability.
- the above-mentioned conductive adhesive composition contains a thermosetting resin, it is preferable to further contain a curing agent or a curing accelerator.
- the flux activator preferably contains a compound having a hydroxyl group and a carboxyl group.
- the boiling point of the solvent is preferably 20 ° C or higher and 300 ° C or lower. Thereby, it becomes easy to remove the solvent, and the conductive adhesive composition can be uniformly applied to the electrode surface of the solar battery cell.
- the above-mentioned conductive adhesive composition can be suitably used for electrically connecting the electrode of the solar battery cell and the metal conductor.
- the present invention is also a connection body in which a plurality of solar cells are connected via a metal conductor, and the electrode of the solar cell and the metal conductor are connected via the above-described conductive adhesive composition. Provide a connected body.
- the present invention is also a metal conductor with a conductive adhesive comprising a metal conductor and an adhesive layer covering the metal conductor, and the adhesive layer uses the above-mentioned conductive adhesive composition.
- a metal wire with a conductive adhesive made of an adhesive is also a metal conductor with a conductive adhesive comprising a metal conductor and an adhesive layer covering the metal conductor, and the adhesive layer uses the above-mentioned conductive adhesive composition.
- a metal wire with a conductive adhesive made of an adhesive.
- the present invention also provides a connection body comprising a plurality of solar cells and a metal wire with a conductive adhesive disposed on the electrode surface of the solar cells and electrically connecting the plurality of solar cells.
- a connection body is provided in which the metal wire with conductive adhesive is the metal wire with conductive adhesive described above.
- the present invention also includes a step of laminating a sealing material on both surfaces of the connection body, a glass on the light-receiving surface side sealing material of the solar battery cell, and a protective film on the sealing material on the back surface of the solar battery cell.
- a method of manufacturing a solar cell module comprising: a step of laminating; and a step of sealing the solar cell while electrically connecting and bonding the solar cell and the metal conductor by heating the obtained laminate I will provide a.
- the present invention also provides a solar cell module in which electrodes of a plurality of solar cells and metal conductors are electrically connected via the above-described conductive adhesive composition.
- a conductive adhesive composition that is not tacky at room temperature and can be electrically bonded at a low temperature, and a metal wire with a conductive adhesive using the composition. it can.
- the connection body which enabled shortening and the simplification of the process at the time of solar cell module manufacture can be provided by using these conductive adhesive compositions or a metal conducting wire with a conductive adhesive.
- this invention can provide a highly reliable solar cell module by using the conductive adhesive composition which can be joined at a low temperature, or a metal conductor with a conductive adhesive.
- the conductive adhesive composition of the present invention contains (A) conductive particles, (B) a resin, (C) a flux activator, and (D) a solvent.
- the conductive particles those containing a metal having a melting point of 210 ° C. or lower, more preferably those containing a metal having a melting point of 200 ° C. or lower can be used.
- fusing point of the metal in electroconductive particle is not specifically limited, Usually, it is about 120 degreeC.
- conductive particles are used in a conductive adhesive composition, they are melted and fused at a relatively low temperature, that is, a plurality of melted (A) conductive particles are aggregated and integrated to form a unit. It is considered that the fused body directly connects the objects.
- the metal in the conductive particles is preferably composed of a metal other than lead in consideration of environmental problems.
- a metal constituting the conductive particles for example, a simple substance or an alloy containing at least one component selected from tin (Sn), bismuth (Bi), indium (In), zinc (Zn), and the like is used. Can be mentioned.
- the said alloy can obtain more favorable connection reliability, in the range from which melting
- Specific examples of the metal constituting the conductive particles include Sn42-Bi58 solder (melting point 138 ° C.), Sn48-In52 solder (melting point 117 ° C.), Sn42-Bi57-Ag1 solder (melting point 139 ° C.), Sn90-Ag2-Cu0.5-Bi7.5 solder (melting point 189 ° C), Sn96-Zn8-Bi3 solder (melting point 190 ° C), Sn91-Zn9 solder (melting point 197 ° C), etc. have clear solidification behavior after melting This is preferred for the sake of illustration. Solidification behavior means that the metal cools and solidifies after melting.
- Sn42-Bi58 solder or Sn42-Bi57-Ag1 solder is preferably used from the viewpoint of availability and low melting point. These are used singly or in combination of two or more.
- the average particle diameter of the conductive particles is not particularly limited, but is preferably 0.1 to 100 ⁇ m.
- the average particle size is less than 0.1 ⁇ m, the viscosity of the conductive adhesive composition tends to be high and workability tends to be lowered.
- the average particle diameter of electroconductive particle exceeds 100 micrometers, it exists in the tendency for printability to fall and for connection reliability to fall.
- the average particle size is more preferably 1.0 to 50 ⁇ m.
- the average particle diameter is particularly preferably 5.0 to 30 ⁇ m.
- the average particle diameter is a value determined by laser diffraction and scattering method (Kamioka Mining Test Method No. 2).
- the conductive particles are composed only of a metal having a melting point of 210 ° C. or lower, and the surface of particles made of a solid material other than a metal such as ceramics, silica, resin material, etc., has a melting point of 210 ° C. or lower.
- the conductive particles may be coated with a metal film made of a certain metal or a mixture thereof.
- the content of the conductive particles (A) in the conductive adhesive composition is such that the content of the metal constituting the conductive particles is 5 to 95% by mass with respect to the total amount of the conductive adhesive composition. Is preferred.
- content of the said metal is less than 5 mass%, it exists in the tendency for the electroconductivity of the hardened
- the content of the metal exceeds 95% by mass, the viscosity of the conductive adhesive composition tends to increase and workability tends to decrease. Further, since the adhesive component in the conductive adhesive composition is relatively reduced, the mounting reliability of the cured product tends to be lowered.
- the content of the metal with respect to the total amount of the conductive adhesive composition is more preferably 10 to 90% by mass from the viewpoint of improving workability or conductivity, and from the viewpoint of improving the mounting reliability of the cured product.
- the content is more preferably 15 to 85% by mass, and particularly preferably 50 to 85% by mass.
- (A1) electroconductive particle and (a1) electroconductive particle which consists of a metal whose melting
- the metal having a melting point higher than 210 ° C. include, for example, one kind of metal selected from Pt, Au, Ag, Cu, Ni, Pd, Al, or an alloy made of two or more kinds of metals. Specific examples include Au powder, Ag powder, Cu powder, and Ag-plated Cu powder.
- “MA05K” (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a silver bronze powder, is available.
- the blending ratio of (A) :( a1) is 99: 1 to 50: It is preferably in the range of 50, more preferably in the range of 99: 1 to 60:40.
- the resin (A) has a softening point equal to or lower than the melting point of the metal in the conductive particles and is a solid at room temperature. Such a resin liquefies at the temperature below the melting point when heated, and therefore does not hinder the fusion of the conductive particles (A).
- the normal temperature here is 20 ° C.
- tack can be prevented.
- the softening point of the applied resin exceeds 210 ° C., it becomes difficult for the particles to fuse when the metal is melted.
- the softening point of the resin is too low, chipping or peeling of the coating film may occur after application of the metal conductor, and tack remains and the handling tends to be difficult.
- the softening point of resin is 210 degrees C or less, 0 degreeC or more and 180 degrees C or less are more preferable. Furthermore, it is more preferable that it is 30 degreeC or more and 150 degrees C or less. Furthermore, it is particularly preferably 80 ° C. or higher and 150 ° C. or lower.
- the resin has an action of adhering the adherend, and also acts as a binder component for bonding the conductive particles in the conductive adhesive composition and the filler added as necessary.
- a resin include thermosetting organic polymer compounds such as epoxy resins, (meth) acrylic resins, maleimide resins and cyanate resins, and precursors thereof.
- (meth) acrylic resin refers to methacrylic resin and acrylic resin.
- a compound having a polymerizable carbon-carbon double bond represented by (meth) acrylic resin and maleimide resin, or an epoxy resin is preferable.
- thermosetting resins are excellent in heat resistance and adhesiveness, and also can be handled in a liquid state if dissolved or dispersed in an organic solvent as required, so that they are excellent in workability.
- the above-mentioned thermosetting resins are used singly or in combination of two or more.
- (Meth) acrylic resin is composed of a compound having a polymerizable carbon-carbon double bond.
- examples of such compounds include monoacrylate compounds, monomethacrylate compounds, diacrylate compounds, and dimethacrylate compounds.
- Examples of monoacrylate compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, hexadecyl acrylate, stearyl acrylate, isostearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, diethylene glycol acrylate, polyethylene glycol acrylate, polypropyl Pyrene glycol acrylate, 2-methoxyethyl
- Examples of the monomethacrylate compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2- Ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, hexadecyl methacrylate, stearyl methacrylate, isostearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, diethylene glycol methacrylate , Polyethylene glycol
- diacrylate compound examples include ethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,3-butanediol diacrylate, neo Pentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, bisphenol A, bisphenol F or 1 mol of bisphenol AD and glycidyl acrylate 2 Mole reactant, polyethylene of bisphenol A, bisphenol F or bisphenol AD And diacrylates of oxide adducts, diacrylates of polypropylene oxide adducts of bisphenol A, bisphenol F or bisphenol AD, bis (acryloxypropyl) polydimethylsiloxane and bis (acryloxypropyl) methyl
- dimethacrylate compound examples include ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,3-butanediol dimethacrylate, neo Pentyl glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, bisphenol A, bisphenol F or bisphenol AD 1 mole and glycidyl methacrylate 2 Molar reactants, bisphenol A, bisphenol F or Dimethacrylate of a polyethylene oxide adduct of scan phenol AD, polypropylene oxide adduct of bisphenol F or bisphenol AD, bis (methacryloxypropyl
- thermosetting resin when a (meth) acrylic resin is contained as a thermosetting resin, these compounds may be used after being previously polymerized, and these compounds may be used as (A) conductive particles, (C) flux activators. And (D) may be mixed together with a solvent, and polymerization may be performed simultaneously with the mixing.
- the conductive adhesive composition preferably contains a radical polymerization initiator.
- the radical polymerization initiator is preferably an organic peroxide from the viewpoint of effectively suppressing voids.
- the decomposition temperature of the organic peroxide is preferably 70 to 170 ° C., more preferably 80 to 160 ° C. .
- radical polymerization initiator examples include 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis ( t-butylperoxy) cyclododecane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) 3-hexyne and cumene hydroperoxide. These are used singly or in combination of two or more.
- the mixing ratio of the radical polymerization initiator is 0.01 to 20% by mass with respect to the total amount of components other than the conductive particles and the solvent (hereinafter referred to as “adhesive component”) of the conductive adhesive composition. It is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
- a commercially available acrylic resin can be used. Specific examples include FINEDIC A-261 (manufactured by Dainippon Ink and Chemicals, trade name, softening point 105 ⁇ 3 ° C.), FINEDIC A-229-30 (manufactured by Dainippon Ink and Chemicals, product) Name, 109 ⁇ 3 ° C.).
- epoxy resin a known compound can be used without particular limitation as long as it is a compound having two or more epoxy groups in one molecule.
- epoxy resins include, for example, bisphenol A, bisphenol AD, bisphenol S, bisphenol F or condensates of halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, bisphenol A novolac resin. And glycidyl ether.
- an epoxy resin a commercially available product can be used. Specific examples thereof include Epicoat 1004 (softening point 97 ° C.), 1004 AF (softening point 97 ° C.), 1007 (softening point 128 ° C.) which are bisphenol A type epoxy resins (above, manufactured by Mitsubishi Chemical Corporation, trade name) YD-012 (softening point 75-85 ° C.), YD-013 (softening point 85-98 ° C.), YD-014 (softening point 91-102 ° C.) (above, manufactured by Nippon Steel Chemical Co., Ltd., trade name) ), EPICLON 4050 (softening point 96-104 ° C.), EPICLON 7050 (softening point 122-131 ° C.) (above, trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Epicoat 4005P (a product name of bisphenol F epoxy resin Softening point 87 ° C), 4007P
- epoxy resins are used singly or in combination of two or more.
- the conductive adhesive composition when the conductive adhesive composition contains the above-mentioned epoxy resin as a thermosetting resin, it may further contain an epoxy compound having only one epoxy group in one molecule as a reactive diluent.
- epoxy compounds are commercially available, and specific examples thereof include, for example, PGE (trade name, manufactured by Nippon Kayaku Co., Ltd.), PP-101 (trade name, manufactured by Tohto Kasei Co., Ltd.), ED-502, ED-509, ED-509S (above, manufactured by Asahi Denka Kogyo Co., Ltd., trade name), YED-122 (manufactured by Yuka Shell Epoxy Co., Ltd., trade name), KBM-403 (Shin-Etsu Chemical Co., Ltd.) Product name), TSL-8350, TSL-8355, TSL-9905 (above, product name, manufactured by Toshiba Silicone Co., Ltd.) and the like. These are used singly or in combination of two or more.
- the blending ratio of the reactive diluent may be in a range that does not hinder the effect of the present invention, and is preferably 0 to 30% by mass with respect to the total amount of the epoxy resin.
- the conductive adhesive composition contains an epoxy resin as the (B) resin, it is more preferable to contain the curing agent or curing accelerator.
- the curing agent is not particularly limited as long as it is conventionally used, and a commercially available one can be obtained.
- Commercially available curing agents include, for example, phenol novolac resin H-1 (trade name, manufactured by Meiwa Kasei Co., Ltd.), VR-9300 (trade name, manufactured by Mitsui Chemicals), and XL, which is phenol aralkyl resin.
- each R 1 independently represents a monovalent hydrocarbon group, preferably a methyl group or an allyl group, and q represents an integer of 1 to 5.
- R 1 2 represents an alkyl group, preferably a methyl group or an ethyl group
- R 3 represents a hydrogen atom or a monovalent hydrocarbon group
- p represents an integer of 2 to 4.
- the mixing ratio of the curing agent is preferably such that the total amount of reactive groups in the curing agent is 0.2 to 1.2 equivalents with respect to 1.0 equivalent of epoxy groups of the epoxy resin.
- the ratio is more preferably 1.0 to 1.0 equivalent, and further preferably 0.5 to 1.0 equivalent.
- the reactive group is a substituent having a reactive activity with an epoxy resin, and examples thereof include a phenolic hydroxyl group.
- the curing accelerator is not particularly limited as long as it is conventionally used as a curing accelerator such as dicyandiamide, and a commercially available product is available.
- commercially available products include ADH, PDH, and SDH (trade names, manufactured by Nippon Hydrazine Kogyo Co., Ltd.), which are dibasic acid dihydrazides represented by the following general formula (III), an epoxy resin and an amine compound.
- examples include NOVACURE (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.), which is a microcapsule type curing agent made of a reaction product.
- R 4 represents a divalent aromatic group or a linear or branched alkylene group having 1 to 12 carbon atoms, preferably an m-phenylene group or a p-phenylene group.
- the blending ratio of the curing accelerator is preferably 0.01 to 90 parts by mass and more preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin. If the blending ratio of this curing accelerator is less than 0.01 parts by mass, the curability tends to decrease, and if it exceeds 90 parts by mass, the viscosity increases and the workability when handling the adhesive component tends to decrease. There is.
- EMZ ⁇ K TPPK (trade name, manufactured by Hokuko Chemical Co., Ltd.) which is an organic boron salt compound, tertiary DBU, U-CAT102, 106, 830, 840 and 5002 which are amines or salts thereof (San Apro Co., Ltd., trade name)
- Cureazole which is an imidazole, 2PZ-CN, 2P4MHZ-PW, C17Z, 2PZ -OK, 2PZ-CNS, and C11Z-CNS (above, trade name, manufactured by Shikoku Kasei Co., Ltd.) may be used.
- the blending ratio of these curing accelerators is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the epoxy resin. Furthermore, it is preferable in it being 15 mass parts or less.
- one kind of each of the curing agent and the curing accelerator may be used alone or in combination of two or more kinds.
- thermoplastic resin that functions as a binder may be added to the conductive adhesive composition of the present embodiment.
- thermoplastic resin include ABS resin (acrylonitrile, butadiene, styrene copolymer synthetic resin), polypropylene resin, polyethylene resin, polyvinyl chloride resin, polystyrene resin, polymethyl methacrylate resin, polybutadiene resin, polyethylene terephthalate resin, polyphenylene ether.
- thermoplastic resins are used singly or in combination of two or more.
- the content of the resin (B) in the conductive adhesive composition is preferably 1 to 60% by mass, more preferably 5 to 40% by mass with respect to the total amount of the adhesive components, and 10 to 30% by mass. % Is more preferable.
- the conductive adhesive composition includes one or more resins having a softening point greater than the melting point of the metal in the conductive particles (A) and / or being liquid at room temperature. May be included.
- the resin having a softening point equal to or lower than the melting point of the metal in the conductive particles (A) include polycarbonate resin, acrylic resin, and polyimide resin.
- the flux activator shows (A) the ability to remove the oxide film formed on the surface of the conductive particles. By using such a flux activator, (A) the oxide film that hinders melting and fusion of the conductive particles is removed.
- the (C) flux activator is preferably a compound that does not inhibit the curing reaction of the (B) resin.
- Examples of (C) flux activators include rosin resins, compounds containing a carboxyl group, phenolic hydroxyl group or alcoholic hydroxyl group in the molecule, 2,4-diethylglutaric acid, 2,2-diethylglutaric acid, 3 -Dibasic acids having an alkyl group in the side chain, such as methyl glutaric acid, 2-ethyl-3-propyl glutaric acid, and 2,5-diethyl adipic acid.
- a compound containing a hydroxyl group and a carboxyl group in the molecule is preferable because it exhibits good flux activity and good reactivity with the epoxy resin that can be used as the resin (B).
- Dihydroxycarboxylic acid is particularly preferred.
- a compound represented by the following general formula (IV) or tartaric acid is preferable.
- R 5 represents an alkyl group having 1 to 5 carbon atoms, and from the viewpoint of more effectively exerting the effect of using the compound represented by formula (IV), methyl group, ethyl Group or propyl group is preferred.
- N and m each independently represents an integer of 0 to 5, and from the viewpoint of more effectively exerting the effect of using the compound represented by formula (IV), is n 0 and m is 1? , N and m are preferably 1.
- Examples of the compound represented by the general formula (IV) include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid, and 2,2-bis (hydroxymethyl) pentane. An acid etc. are mentioned.
- the content of the flux activator is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the conductive particles (A) from the viewpoint of more effectively exhibiting the above-described effects of the present invention. Is preferred. Further, from the viewpoint of storage stability and conductivity, the content is more preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass.
- the solvent is not particularly limited as long as the viscosity can be adjusted in order to improve the workability during preparation of the conductive adhesive composition and the coating workability during use.
- examples of such a solvent include water, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, N-methyl-2-pyrrolidinone, diethylene glycol dimethyl ether (also referred to as diglyme), triethylene glycol dimethyl ether (also referred to as triglyme), Diethylene glycol diethyl ether, 2- (2-methoxyethoxy) ethanol, ⁇ -butyrolactone, isophorone, carbitol, carbitol acetate, 1,3-dimethyl-2-imidazolidinone, 2- (2-butoxyethoxy) ethyl acetate, Ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cell
- boiling point of 20 to 300 ° C. are preferable, and those having a boiling point of 50 to 260 ° C. are more preferable. In particular, a boiling point of 80 ° C. to 220 ° C. is preferable. If the boiling point of the solvent is 300 ° C. or higher, there will be an operational problem that it will be difficult to remove the solvent in the conductive adhesive composition in the drying step, and if it is 20 ° C. or lower, the conductive adhesive composition It becomes difficult to uniformly coat the electrode surface of the solar battery cell.
- the solvent having a preferred boiling point for example, diglyme (boiling point 162 ° C.), triglyme (boiling point 216 ° C.), butyl cellosolve (boiling point 171 ° C.) and the like are preferable. These solvents are used alone or in combination of two or more.
- the solvent is preferably contained in an amount of 0.1 to 95% by mass with respect to the total amount of the conductive adhesive composition. Further, the content is more preferably 1 to 50% by mass, and particularly preferably 5 to 30% by mass. Further, it is particularly preferably contained in an amount of 5 to 20% by mass.
- the amount of the solvent is 0.1% by mass or less, the viscosity becomes high, and the workability in the coating process is lowered.
- the amount of the solvent exceeds 95% by mass, a sufficient conductive particle component cannot be applied, and there is a problem that it takes time for drying.
- the conductive adhesive composition may contain a coupling agent such as a silane coupling agent or a titanium coupling agent for the purpose of improving the adhesive strength.
- a coupling agent such as a silane coupling agent or a titanium coupling agent for the purpose of improving the adhesive strength.
- the silane coupling agent include trade name “KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.
- an anionic surfactant, a fluorosurfactant and the like may be contained.
- you may contain silicone oil etc. as an antifoamer.
- the said adhesive force improver, wettability improver, and antifoamer are used individually by 1 type or in combination of 2 or more types, respectively. These are preferably contained in an amount of 0.1 to 10% by mass with respect to the total amount of components other than the solvent of the conductive adhesive composition.
- the conductive adhesive composition may contain a filler.
- the filler include polymer particles such as acrylic rubber and polystyrene, and inorganic particles such as diamond, boron nitride, aluminum nitride, alumina, and silica. These fillers may be used alone or in combination of two or more.
- the conductive adhesive composition includes, as necessary, a flexible agent for stress relaxation, a diluent for improving workability, an adhesive strength improver, a wettability improver, and an antifoaming agent.
- a flexible agent for stress relaxation e.g., a silicone rubber, a silicone rubber, and a silicone rubber.
- a diluent for improving workability e.g., a silicone rubber, a silicone rubber, and a wettability improver, and an antifoaming agent.
- One or more additives selected from the group consisting of agents may be contained.
- various additives may be included within a range that does not impair the effects of the present invention.
- liquid polybutadiene (trade names “CTBN-1300 ⁇ 31” and “CTBN-1300 ⁇ 9” manufactured by Ube Industries, Ltd.), “NISSO-PB-C-” manufactured by Nippon Soda Co., Ltd. 2000 ").
- the content is usually preferably 0.01 to 500 parts by mass with respect to 100 parts by mass of the total amount of the thermosetting resin.
- the blending ratio of the adhesive component is a solid content ratio (mass ratio) in the conductive adhesive composition. It is preferably 5/95 to 50/50. Furthermore, from the viewpoints of adhesiveness, conductivity and workability, the blending ratio is more preferably 10/90 to 30/70. When the blending ratio is less than 5/95, the viscosity of the adhesive component becomes high, and it becomes difficult to ensure workability, or the adhesive force tends to decrease. When this mixing ratio exceeds 50/50, the conductivity tends to decrease.
- each of the components described above may be combined with any of those exemplified above.
- the conductive adhesive composition of the present invention contains (D) a solvent, it is generally a liquid conductive adhesive composition.
- the conductive adhesive composition is a paste in which each component is uniformly dispersed by heating, if necessary, by mixing, dissolving, pulverizing kneading, or dispersing each of the above-mentioned components at once or multiple times. It is obtained as a shape.
- the dispersing / dissolving device used in this case include a known stirrer, a leaker, a three roll, a planetary mixer and the like.
- the conductive adhesive composition according to the present embodiment described above can provide a conductive adhesive composition that is not tacky at room temperature and can be electrically joined at a low temperature. Moreover, the connection body which enabled shortening and the simplification of the process at the time of solar cell module manufacture can be provided by using this conductive adhesive composition. Moreover, a highly reliable solar cell module can be provided by using the conductive adhesive composition capable of electrical bonding at a low temperature according to the present embodiment.
- FIG. 1 is a schematic diagram showing a main part of a solar cell module, and shows an outline of a structure in which a plurality of solar cells are connected to each other as an example.
- Fig.1 (a) shows the surface side of a solar cell module
- FIG.1 (b) shows a back surface side
- FIG.1 (c) shows a side surface side.
- the solar cell module 100 includes a grid electrode 7 and a bus electrode (surface electrode) 3a on the front surface side of the semiconductor wafer 6, and a back electrode 8 and a bus electrode (surface electrode) on the back surface side.
- a plurality of solar cells 20 each having a surface electrode 3b are connected to each other by a metal conductor 4.
- the metal conductor 4 is electrically connected to the bus electrode 3a as a surface electrode at one end and the bus electrode 3b as the surface electrode at the other end via the conductive adhesive composition 10 of the present embodiment. It is connected.
- FIG. 2 is a diagram for explaining an embodiment of the method for manufacturing the solar cell module of the present embodiment.
- the solar cell module of the present embodiment includes, for example, a step of arranging the metal conductor 4 and the bus electrodes 3a and 3b so as to face each other via the conductive adhesive composition 10 and producing the connection body 30; The step of laminating the sealing material 2 on both surfaces of the connection body 30, the glass 1 on the sealing material 2 on the light receiving surface side of the solar battery cell 20, and the back sheet 5 on the sealing material 2 on the back surface of the solar battery cell 20. The step of laminating the (protective film) and the resulting laminate at a temperature of 140 to 210 ° C.
- thermocompression bonding step electrical connection between the bus electrodes 3a and 3b of the solar battery cell 20 and the metal conductor 4 and adhesion by curing of the thermosetting resin are performed, and at the same time, sealing of the solar battery cell 20 is performed.
- the solar cell module can be manufactured in a lump.
- the cost can be reduced by shortening the process and improving the productivity as compared with the conventional processes.
- the conductive adhesive composition 10 is dispensed on the bus electrodes 3a and 3b or the metal conductor 4 by a dispensing method or a screen.
- the application method include a printing method and a stamping method.
- the connection body 30 can be obtained by arranging the metal conductor 4 and the bus electrodes 3a and 3b so as to face each other through the conductive adhesive composition 10.
- the metal conductive wire 4 and the bus electrodes 3a and 3b of the solar battery cell are disposed so as to face each other through the conductive adhesive composition 10, and then a temperature of 140 to 210 ° C. (preferably Is (A) a temperature equal to or higher than the melting point of the conductive particles) for 1 to 30 minutes at a pressure of 0.1 to 6.0 MPa, so that the bus electrodes 3a and 3b of the solar battery cell and the metal conductor 4 Temporary pressure bonding may be performed to perform electrical connection.
- the temporary pressure bonding the solar battery cell 20 and the metal conductor 4 are connected to each other, so that the connection body 30 can be easily handled, and workability at the time of manufacturing the solar battery module is improved.
- the sealing material 2 is disposed on both surfaces of the obtained connection body 30, the glass 1 is placed on the sealing material 2 on the light receiving surface side of the solar battery cell 20, and the back surface of the solar battery cell 20 is A back sheet 5 (protective film) is placed on the sealing material 2, and the obtained laminate is thermocompression bonded at a temperature of 140 to 180 ° C. for 1 to 30 minutes at a pressure of 0.1 to 6 MPa.
- a solar cell module can be manufactured by sealing.
- Examples of the glass 1 include white plate tempered glass with dimples for solar cells.
- Examples of the sealing material 2 include sealing resins using ethylene / vinyl acetate copolymer resin (EVA) or polyvinyl butyral.
- Examples of the metal conductive wire 4 include a TAB wire obtained by dipping or plating a solder on a Cu wire.
- Examples of the back sheet 5 include a PET-based or tedla-PET laminated material, a metal foil-PET laminated material, and the like.
- the conductive adhesive composition of the present embodiment can be connected to the solar cell electrode in the above-described process even when a wiring board in which a metal conductor is formed on a plastic substrate is used. Moreover, also when using a film-form wiring board, it can connect with the electrode of a photovoltaic cell by the process similar to the above using the conductive adhesive composition of this embodiment.
- the cured product of the conductive adhesive composition of the present embodiment can be used as a substrate, an electronic component, and a conductive layer that bonds and electrically connects the substrate and the electronic component. Further, it can also be used as a support layer for mounting a semiconductor, a semiconductor element, and a conductive layer that bonds and electrically connects the support base and the semiconductor element.
- the conductive adhesive composition of the present embodiment can also be used for connection between an electrode of a back electrode type (back contact type) solar cell and a wiring member.
- the conductive adhesive composition is applied on the electrode of the wiring board or the back electrode of the solar battery cell.
- a sealing material formed by hollowing out the electrode part (conductive adhesive composition application part) of the wiring board is laminated on the wiring board, and the solar battery cell is placed on the sealing material, and the back electrode of the solar battery cell and the electrode of the wiring board. It arrange
- a sealing material and glass are disposed on the light receiving surface of the solar battery cell, a back sheet is disposed on the back surface side of the solar battery cell, and the solar battery module is thermocompression-bonded, whereby the back electrode of the solar battery cell and the wiring board The connection and adhesion with the electrodes, and the sealing step of the solar battery cell can be performed at once.
- glass and a sealing material what was mentioned by the manufacturing method of the above-mentioned solar cell module can be used.
- the metal conductor with conductive adhesive of the present embodiment includes a metal conductor and an adhesive layer that covers the metal conductor.
- An adhesive bond layer is formed from the adhesive agent using the above-mentioned conductive adhesive composition.
- the material for the metal conductor is not particularly limited. Particularly desirable is a material having a low specific resistance and mechanical strength, and examples thereof include copper, aluminum, and gold.
- a metal layer such as gold, silver, palladium, nickel, tin, or solder may be deposited or plated, or surface treatment such as acid treatment may be performed.
- Examples of the method of coating the metal conductor with the adhesive layer include a method of applying a conductive adhesive composition to the metal conductor.
- Examples of the method for applying the conductive adhesive composition to the metal conductor include screen printing, stencil printing, dispenser, spraying, and dipping.
- Examples of the method for drying the metal conductor after coating include vacuum drying or heating at a temperature lower than the curing temperature of the curing component. The temperature range for drying by heating needs to be determined appropriately depending on the solvent and the curing temperature of the curing component. When the temperature is low, the evaporation of the solvent component is slow, and sufficient drying cannot be obtained, which may cause peeling during handling. On the other hand, when the drying temperature is higher than the curing temperature, the curing component begins to be cured (A), and the fluidity of the conductive particles is lowered and cannot be fused.
- the metal wire with conductive adhesive of the present embodiment can be suitably used for electrically connecting a plurality of solar cells.
- a solar cell module is manufactured by the same manufacturing method as that using the above-mentioned conductive adhesive composition 10 except that the connection body 30 is manufactured differently. Can be manufactured.
- a connection body can be obtained by arranging and connecting the metal wire with a conductive adhesive on the bus electrodes 3a and 3b.
- Examples of a method for connecting the bus electrodes 3a and 3b and the metal wire with conductive adhesive include a method of heating at a temperature of 140 to 180 ° C. for 1 minute to 30 minutes.
- Example 1 the material used by the Example and the comparative example was produced by the following method, or was obtained.
- An example of the preparation method is shown in Example 1, but the resin compositions and blending ratios of other Examples and Comparative Examples are as shown in Table 1, and the preparation method is the same as Example 1.
- Example 1 Epicoat 1007 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin trade name: softening point 128 ° C.) 12.0 parts by mass, 2P4MHZ-PW (Shikoku Kasei Co., Ltd., 2-phenyl-4-methyl- 5 rolls of 5-hydroxymethylimidazole (trade name), 1.5 parts by weight of BHPA (2,2-bis (hydroxymethyl) propionic acid) and 12.0 parts by weight of butyl cellosolve are mixed to form a 3-roll Was passed through 3 times to prepare an adhesive component.
- 2P4MHZ-PW Sanhikoku Kasei Co., Ltd., 2-phenyl-4-methyl- 5 rolls of 5-hydroxymethylimidazole (trade name)
- BHPA (2,2-bis (hydroxymethyl) propionic acid) 12.0 parts by weight of butyl cellosolve
- the electrically conductive adhesive composition was obtained by performing a defoaming process for 10 minutes at 500 Pa or less using a vacuum stirrer.
- Examples 2 to 3, Comparative Example 1 As described above, conductive adhesive compositions of Examples 2 to 3 and Comparative Example 1 were obtained in the same manner as Example 1 except that the compositions shown in Table 1 were used. In addition, the unit of the mixture ratio of each material in Table 1 is a mass part.
- YD-014 bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd .: softening point 91-102 ° C
- YL983U Bisphenol F type epoxy resin, manufactured by Mitsubishi Chemical Corporation: Resin Sn42-Bi57-Ag1 which is liquid at normal temperature Soldering point: 139 ° C.
- the conductive adhesive compositions obtained in Examples 1 to 3 and Comparative Example 1 were subjected to surface electrode (material: silver glass paste) formed on the light receiving surface of a solar battery cell (125 mm ⁇ 125 mm, thickness 310 ⁇ m). 2 mm ⁇ 125 mm) was printed using a metal mask (thickness 100 ⁇ m, opening size 1.2 mm ⁇ 125 mm), and dried on a hot plate at 100 ° C. for 3 minutes to prepare a coating cell.
- surface electrode material: silver glass paste
- 2 mm ⁇ 125 mm was printed using a metal mask (thickness 100 ⁇ m, opening size 1.2 mm ⁇ 125 mm), and dried on a hot plate at 100 ° C. for 3 minutes to prepare a coating cell.
- the tackiness of the coating cell is as follows. When the tab wire falls when the coated tab wire (trade name “A-TPS” manufactured by Hitachi Cable, Ltd.) is overlaid on the coated surface and lifted, If it is, it was determined that there was tackiness. Connectivity is achieved by placing a solder-coated tab wire (trade name “A-TPS” manufactured by Hitachi Cable Ltd.) as a metal conductor on the conductive adhesive composition formed on the light receiving surface of the coating cell. The plate was heated at 160 ° C. for 10 minutes to confirm the possibility of electrical connection of the metal conductors. The measurement was performed using a solar simulator (trade name: WXS-155S-10, AM: 1.5G, manufactured by Wacom Denso). The fused state of the conductive particles was confirmed with an X-ray fluoroscope (manufactured by Shimadzu Corporation, microfocus X-ray fluoroscope SMX-1000).
- the tackiness of metal conductors with conductive adhesive is tacky when the tab wire drops when the coated tab wire (trade name “A-TPS” manufactured by Hitachi Cable Ltd.) is overlaid on the coated surface and lifted. When there is no property and it remains attached, it is determined that there is tackiness.
- a metal wire with conductive adhesive is placed on a surface electrode (material: silver glass paste, 2 mm ⁇ 125 mm) formed on the light receiving surface of a solar cell (125 mm ⁇ 125 mm, thickness 310 ⁇ m). Then, it was heated on a hot plate at 160 ° C. for 10 minutes to confirm the possibility of electrical connection of the metal conductors.
- the measurement was performed using a solar simulator (trade name: WXS-155S-10, AM: 1.5G, manufactured by Wacom Denso).
- the fused state of the conductive particles was confirmed with an X-ray fluoroscope (manufactured by Shimadzu Corporation, microfocus X-ray fluoroscope SMX-1000).
- the coating cells of Examples 1 to 3 and the metal conductive wire with conductive adhesive were not tacky and had good handleability. Moreover, it was connected also with the photovoltaic cell by the heating for 10 minutes at 160 degreeC, and fusion
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Abstract
Description
なお、本明細書において、「タック性がない」とは、実施例に記載の所定の試験の結果タック性が認められないことをいう。
エピコート1007(三菱化学(株)製、ビスフェノールA型エポキシ樹脂の商品名:軟化点128℃)12.0質量部と、2P4MHZ-PW(四国化成(株)製、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールの商品名)0.5質量部と、BHPA(2,2-ビス(ヒドロキシメチル)プロピオン酸)1.5質量部と、ブチルセロソルブ12.0質量部を混合し、3本ロールを3回通して接着剤成分を調製した。
上述したように、表1に示す組成とした以外は実施例1と同様にして、実施例2~3、比較例1の導電性接着剤組成物を得た。
なお、表1中の各材料の配合割合の単位は質量部である。
YD-014:ビスフェノールA型エポキシ樹脂、新日鐵化学(株)製:軟化点91~102℃
YL983U:ビスフェノールF型エポキシ樹脂、三菱化学(株)製:常温で液状の樹脂
Sn42-Bi57-Ag1はんだ:融点139℃
実施例1~3及び比較例1で得られた導電性接着剤組成物を、太陽電池セル(125mm×125mm、厚さ310μm)の受光面上に形成された表面電極(材質:銀ガラスペースト、2mm×125mm)上にメタルマスク(厚み100μm、開口寸法1.2mm×125mm)を用いて印刷し、ホットプレート上で100℃で3分間乾燥し、塗布セルを作製した。
Sn96.5-Ag3.0-Cu0.5はんだを、上述と同様に太陽電池セルの受光面上に形成された表面電極に印刷し、100℃で3分間乾燥し、塗布セルを作製した。
上記実施例1~3、比較例1、2の塗布セルについて、下記の条件で、タック性、接続性及び導電性粒子の融合の有無について評価した。その結果を表2にまとめて示した。
接続性は、塗布セルの受光面上に形成された導電性接着剤組成物上に金属導線としてはんだ被覆タブ線(日立電線(株)製商品名「A-TPS」)を配置させて、ホットプレート上で160℃で10分間加熱し、金属導線の電気的な接続の可否を確認した。測定はソーラシミュレータ(ワコム電創社製、商品名:WXS-155S-10、AM:1.5G)を用いて行った。
導電性粒子の融合状態は、X線透視装置(島津製作所(株)製、マイクロフォーカスX線透視装置SMX-1000)で確認した。
実施例1~3及び比較例1で得られた導電性接着剤組成物を、被覆タブ線(日立電線(株)製、商品名:A-TPS)に幅400mμ厚さ200μmで塗布し、ホットプレート上で100℃で3分間加熱し、導電性接着剤付金属導線を作製した。
上記実施例1~3、比較例1の導電性接着剤付金属導線について、下記の条件で、タック性、接続性及び導電性粒子の融合の有無について評価した。その結果を表3にまとめて示した。
接続性は、導電性接着剤付金属導線を、太陽電池セル(125mm×125mm、厚さ310μm)の受光面上に形成された表面電極(材質:銀ガラスペースト、2mm×125mm)に配置させて、ホットプレート上で160℃で10分間加熱し、金属導線の電気的な接続の可否を確認した。測定はソーラシミュレータ(ワコム電創社製、商品名:WXS-155S-10、AM:1.5G)を用いて行った。
導電性粒子の融合状態は、X線透視装置(島津製作所(株)製、マイクロフォーカスX線透視装置SMX-1000)で確認した。
太陽電池セルの受光面及び裏面の表面電極上にフラックス剤(千住金属(株)製商品名「デルタラックス533」)を塗布した後、Sn96.5-Ag3.0-Cu0.5はんだ(融点217℃)被覆タブ線(日立電線(株)製商品名「A-TPS」)を配置し、ホットプレート上で160℃で10分間加熱し、金属導線の電気的な接続の可否を確認した。測定はソーラシミュレータ(ワコム電創社製、商品名:WXS-155S-10、AM:1.5G)を用いて行った。その結果を表3に示す。
Claims (13)
- (A)融点が210℃以下である金属を含む導電性粒子、(B)軟化点が該導電性粒子における金属の融点以下であり、かつ常温で固体である樹脂、(C)フラックス活性剤、及び(D)溶媒を含む導電性接着剤組成物。
- 前記(A)導電性粒子における金属が、ビスマス、インジウム、スズ及び亜鉛から選ばれる少なくとも1種の成分を含有する、請求項1記載の導電性接着剤組成物。
- 前記(B)樹脂が熱硬化性樹脂を含有する、請求項1又は2に記載の導電性接着剤組成物。
- 前記熱硬化性樹脂がエポキシ樹脂である、請求項3に記載の導電性接着剤組成物。
- 硬化剤又は硬化促進剤をさらに含有する、請求項3又は4に記載の導電性接着剤組成物。
- 前記(C)フラックス活性剤が、水酸基及びカルボキシル基を有する化合物を含有する、請求項1乃至5のいずれか一項に記載の導電性接着剤組成物。
- 前記(D)溶媒の沸点が20℃以上300℃以下である、請求項1乃至6のいずれか一項に記載の導電性接着剤組成物。
- 太陽電池セルの電極と金属導線とを電気的に接続するために用いられる、請求項1乃至7のいずれか一項に記載の導電性接着剤組成物。
- 複数の太陽電池セルが金属導線を介して接続される接続体であって、
該太陽電池セルの電極と金属導線とが、請求項1乃至8のいずれか一項に記載の導電性接着剤組成物を介して接続されている接続体。 - 金属導線と、該金属導線を被覆してなる接着剤層と、からなる導電性接着剤付金属導線であって、
前記接着剤層は、請求項1乃至8のいずれか一項に記載の導電性接着剤組成物を用いた接着剤からなる導電性接着剤付金属導線。 - 複数の太陽電池セルと、該太陽電池セルの電極面に配置され、複数の太陽電池セルを電気的に接続するための導電性接着剤付金属導線と、からなる接続体であって、
該導電性接着剤付金属導線が請求項10記載の導電性接着剤付金属導線である接続体。 - 請求項9又は11に記載の接続体の両面に封止材を積層する工程と、
前記太陽電池セルの受光面側の前記封止材上にガラス、前記太陽電池セルの裏面の前記封止材上に保護フィルムを積層する工程と、
得られた積層体を加熱することにより前記太陽電池セルと金属導線とを電気的に接続するとともに接着しながら、前記太陽電池セルを封止する工程と、を含む太陽電池モジュールの製造方法。 - 請求項1乃至8のいずれか一項に記載の導電性接着剤組成物を介して、複数の太陽電池セルの電極と金属導線とが電気的に接続された太陽電池モジュール。
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US13/981,820 US20130333744A1 (en) | 2011-01-27 | 2012-01-11 | Conductive binder composition, metal wire with conductive binder, bonded unit, and solar cell module |
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JP6508292B2 (ja) | 2019-05-08 |
JP2018080333A (ja) | 2018-05-24 |
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CN103328595A (zh) | 2013-09-25 |
TW201233763A (en) | 2012-08-16 |
JPWO2012102076A1 (ja) | 2014-06-30 |
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