KR20150032572A - Conductive adhesive for solar cell, solar cell module, and manufacturing method thereof - Google Patents
Conductive adhesive for solar cell, solar cell module, and manufacturing method thereof Download PDFInfo
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- KR20150032572A KR20150032572A KR20157003029A KR20157003029A KR20150032572A KR 20150032572 A KR20150032572 A KR 20150032572A KR 20157003029 A KR20157003029 A KR 20157003029A KR 20157003029 A KR20157003029 A KR 20157003029A KR 20150032572 A KR20150032572 A KR 20150032572A
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- South Korea
- Prior art keywords
- solar cell
- conductive adhesive
- mass
- electrode
- fluorene
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 69
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title description 31
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 77
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Classifications
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- 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
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- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- 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
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Abstract
The present invention relates to a conductive adhesive for solar cells, which is used for connecting an electrode of a solar cell with a tap line and contains at least a fluorene type phenoxy resin, a fluorene type epoxy resin, a curing agent and conductive particles.
Description
The present invention relates to a conductive adhesive for a solar cell, a solar cell module, and a method of manufacturing the same.
Solar cells are expected to be a new energy source because they directly convert sunlight, which is supplied in a clean and limitless manner, into electricity.
The solar cell is used, for example, as a solar cell module in which a plurality of solar cells are connected via a tap wire.
In the conventional tap wire, a type in which solder is applied to the surface of the copper wire has been used. The electrodes and the tab lines of the solar cell were connected via solder. However, since high temperature is required for the solder connection, cracking or bending of the panel on the light receiving surface, shot due to solder pushed out (leaking) from the tap line, and the like have been caused.
Therefore, a conductive adhesive has been used as a connection material in place of solder. For example, a solar cell module has been proposed in which a surface electrode of a solar cell and a tab line are connected via a conductive adhesive (for example, refer to Patent Document 1).
However, the technology of this proposal has a problem that it is difficult to achieve both high adhesiveness of the solar cell and the tab line and high connection reliability.
Therefore, it is desired to provide a conductive adhesive for solar cell, a solar cell module using the conductive adhesive for solar cell, and a manufacturing method thereof, which can both achieve high adhesiveness of a solar cell and a tap line and high connection reliability It is a situation.
SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems and to achieve the following objects. That is, the present invention provides a conductive adhesive for a solar cell capable of achieving both a high adhesiveness of a solar cell and a tab line and a high connection reliability, and a solar cell module using the conductive adhesive for a solar cell and a method of manufacturing the same The purpose.
Means for solving the above problems are as follows. In other words,
≪ 1 > This solar cell is used for connecting an electrode of a solar cell and a tap line,
A fluorene type phenoxy resin, a fluorene type epoxy resin, a curing agent, and conductive particles.
<2> The conductive adhesive for a solar cell according to <1>, wherein the mass ratio (A: B) of the fluorene type phenoxy resin (A) and the fluorene type epoxy resin (B) is 1.0: 3.0 to 3.0: 1.0.
<3> The conductive adhesive for a solar cell according to <1> or <2>, wherein the content of the conductive particles is 2% by mass to 25% by mass.
≪ 4 >, wherein the storage elastic modulus at -40 deg. C after curing is 3.0 x 10 9 to 4.1 x 10 9 Pa and the storage elastic modulus at 170 deg. C after curing is 1.9 x 10 8 Pa to 2.2 x 10 8 Pa. ≫>< 3 >.
<5> The conductive adhesive for a solar cell according to any one of <1> to <4>, wherein the temperature of the main dispersion tan δ peak after curing is 190 ° C. or higher and the peak of the primary dispersion tan δ after curing is 0.40 or higher.
<6> The conductive adhesive for a solar cell according to any one of <1> to <5>, wherein the conductive particles are silver-coated copper powder.
<7> A solar cell comprising a solar cell having an electrode, a tap line, and a cured product of a conductive adhesive,
An electrode of the solar cell and the tap line are connected to each other by using a cured product of the conductive adhesive,
The solar cell module is characterized in that the conductive adhesive is the conductive adhesive for a solar cell according to any one of < 1 > to < 6 >.
A step of arranging the conductive adhesive agent and the tap line so that the electrode and the tap line are connected via the cured product formed by curing the conductive adhesive by heating on the electrode of the solar cell having the electrode, and,
A covering step of covering the solar cell with a sealing resin and further covering the sealing resin with one of a moisture-proof back sheet and a glass plate;
A pressing step of pressing one of the moisture-proof back sheet and the glass plate,
And a heating step of heating the heating stage on which the solar cell is mounted,
Wherein the conductive adhesive is the conductive adhesive for a solar cell according to any one of < 1 > to < 6 >.
According to the present invention, there can be provided a conductive adhesive for a solar cell, which can solve the above-mentioned problems in the prior art and achieve the above object, which can achieve both high adhesiveness of a solar cell and a tap wire and high connection reliability, A solar cell module using a conductive adhesive for a solar cell, and a manufacturing method thereof.
1 is a schematic top view showing an example of a thin film solar cell module.
2 is an exploded perspective view showing an example of a crystalline solar cell module.
3 is a schematic cross-sectional view showing an example of a crystalline solar cell module.
4 is a schematic top view of a solar cell model.
(Conductive adhesive for solar cell)
The conductive adhesive for a solar cell of the present invention contains at least a fluorene type phenoxy resin, a fluorene type epoxy resin, a curing agent, and conductive particles, and further contains other components as necessary.
The conductive adhesive for a solar cell is used for connecting an electrode of a solar cell and a tap line.
≪ Fluorene type phenoxy resin >
The fluorene-type phenoxy resin is not particularly limited as long as it is a phenoxy resin having a fluorene skeleton and can be appropriately selected depending on the purpose.
Fluorenes are aromatic hydrocarbons having a tricyclic structure and are represented by the following structural formula (1).
The fluorene skeleton means a bivalent organic group containing the fluorene. Examples of the fluorene skeleton include a divalent fluorene group in which two hydrogen atoms at the ninth position of the fluorene are eliminated.
Examples of the fluorene-type phenoxy resin include (i) a phenoxy resin obtained by the reaction of a polyhydric phenol having a fluorene skeleton with epihalohydrin, (ii) a polyhydric phenol having a fluorene skeleton and a bifunctional (Iii) phenoxy resins obtained by the reaction of diglycidyl ether of a polyhydric phenol having a fluorene skeleton with other polyhydric phenols, and the like.
Examples of the polyhydric phenol having a fluorene skeleton include compounds represented by the following formula (1).
However, In the formula (1), the same or different and each ring Z 1 and Z 2 ring represents an aromatic hydrocarbon ring, R 1a, R 1b, R 2a and R 2b are the same or different and each represents a substituent. k1 and k2 are the same or different and each represent an integer of 0 to 4; m1 and m2 each represent 0 or an integer of 1 or more; and n1 and n2 each represent 0 or an integer of 1 or more. When m1, m2, k1 or k2 are each 2 or more, a plurality of R 1a , R 1b , R 2a and R 2b may be the same or different. n1 + n2 is 2 or more.
N1 is preferably 1, and n2 is preferably 1.
Examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring.
Examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group and an ethyl group.
Examples of the compound represented by the above formula (1) include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene and the like. Examples of the 9,9-bis (hydroxyphenyl) fluorene include 9,9-bis (4-hydroxyphenyl) fluorene (a compound represented by the following structural formula (2)). Examples of the 9,9-bis (alkyl-hydroxyphenyl) fluorene include 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9- , 5-dimethylphenyl) fluorene, and the like.
Examples of the epihalohydrin include epichlorohydrin and the like.
The bifunctional epoxy compound is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.
Examples of other polyhydric phenols include bisphenol A, bisphenol F, bisphenol S, and the like.
The method for producing the fluorene-type phenoxy resin is not particularly limited and can be appropriately selected according to the purpose. For example, a known method for producing a phenoxy resin can be referred to. As a method for producing the fluorene-type phenoxy resin, for example, a method for producing a phenoxy resin described in Japanese Patent Application Laid-Open No. 2008-255308 can be referred to.
The fluorene-type phenoxy resin may be a commercially available product. Examples of the commercially available products include FX293 (manufactured by Shin Nittsu Chemical Co., Ltd.) and FX280S (manufactured by Shin Nittsu Chemical Co., Ltd.).
The content of the fluorene-type phenoxy resin is not particularly limited and may be appropriately selected depending on the purpose. The content is preferably 10% by mass to 40% by mass, and more preferably 20% by mass to 30% by mass. If the content is less than 10% by mass, the adhesion may be deteriorated. If the content is more than 40% by mass, the connection reliability may be deteriorated. When the content is within the more preferable range, it is advantageous in that both the adhesiveness and the connection reliability are better.
≪ Fluorene type epoxy resin >
The fluorene-type epoxy resin is not particularly limited as long as it is an epoxy resin having a fluorene skeleton, and can be appropriately selected according to the purpose.
Examples of the fluorene-type epoxy resin include (iv) an epoxy resin obtained by reacting the polyhydric phenol having the fluorene skeleton with the epihalohydrin, (v) the polyhydric phenol having the fluorene skeleton, and An epoxy resin obtained by the reaction of a bifunctional epoxy compound, and (vi) an epoxy resin obtained by the reaction of the diglycidyl ether of a polyhydric phenol having the fluorene skeleton with another polyhydric phenol.
Further, the phenoxy resin and the epoxy resin can be produced by using the same raw materials, and can be produced by controlling reaction conditions (for example, mixing ratio), respectively.
The method for producing the fluorene-type epoxy resin is not particularly limited and can be appropriately selected according to the purpose. For example, a known method for producing an epoxy resin can be referred to. As a method for producing the fluorene-type epoxy resin, for example, a method for producing an epoxy resin described in Japanese Patent Application Laid-Open No. 10-102828 can be referred to.
The fluorene-type epoxy resin may be a commercially available product. Examples of the commercially available products include ozol CG50 (manufactured by Osaka Gas Chemical Co., Ltd.), and ozol CG500 (manufactured by Osaka Gas Chemical Co., Ltd.).
The content of the fluorene-type epoxy resin is not particularly limited and may be appropriately selected according to the purpose. The content is preferably 10% by mass to 40% by mass, and more preferably 20% by mass to 30% by mass. If the content is less than 10 mass%, the connection reliability may be deteriorated. If the content is more than 40 mass%, the adhesive property may be lowered. When the content is within the more preferable range, it is advantageous in that both the adhesiveness and the connection reliability are better.
The mass ratio (A: B) of the fluorene type phenoxy resin (A) to the fluorene type epoxy resin (B) is not particularly limited and may be appropriately selected depending on the purpose, More preferably 1.0: 1.5 to 1.5: 1.0. When the proportion of the fluorene-type phenoxy resin (A) in the mass ratio (A: B) is smaller than the above-mentioned preferable range, the adhesiveness may be lowered. In the mass ratio (A: B) If the ratio of the fluorene-type phenoxy resin (A) is larger than the above preferable range, the connection reliability may be lowered. When the mass ratio (A: B) is within the more preferable range, it is advantageous in that both the adhesiveness and the connection reliability are superior.
<Curing agent>
The curing agent is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include an imidazole-based curing agent, an anion-based curing agent, and a cation-based curing agent. Examples of the imidazole-based curing agent include 2-ethyl 4-methylimidazole and the like. Examples of the anionic curing agent include organic amines and the like. Examples of the cationic curing agent include a sulfonium salt, an onium salt, and an aluminum chelating agent.
Of these, imidazole-based curing agents are preferred.
The curing agent is a curing agent that reacts with the epoxy group of the fluorene type epoxy resin or a curing agent that initiates polymerization of the epoxy group.
The content of the curing agent is not particularly limited and may be appropriately selected according to the purpose. It is preferably 10% by mass to 50% by mass, more preferably 20% by mass to 40% by mass, still more preferably 25% desirable.
<Conductive Particle>
The conductive particles are not particularly limited and may be appropriately selected depending on the purpose. Examples of the conductive particles include gold powder, silver powder, copper powder, nickel powder, gold coated copper powder and silver coated copper powder.
Of these, silver coated copper powder is preferred.
- silver coated copper powder -
The silver-coated copper powder is a copper powder whose surface is covered at least with silver. By using the silver-coated copper powder, connection reliability is better. It is also possible to obtain a conductive adhesive for a solar cell which does not deteriorate power generation efficiency.
The silver-coated copper powder, in other words, at least a part of the surface of the copper powder is coated with silver. The silver-coated copper powder may be such that the entire surface of the copper powder is coated with silver, or a part of the surface of the copper powder is coated with silver. It is preferable that the silver coating is not omnipresent over the whole surface of the copper powder while exposing the surface of the copper powder more than the silver is localized on a part of the surface of the copper powder. By coating without being ubiquitous, a silver-coated copper powder having uniform conductivity can be obtained. In this case, the coated silver is in a state of being attached to the surface of the copper powder in the form of a point shape, a mesh shape, or the like.
The particle size of the copper powder is not particularly limited and may be appropriately selected depending on the purpose.
The silver-coated copper powder may be coated with a fatty acid. Since the silver coated copper powder is covered with the fatty acid, the surface of the silver coated copper powder is smoothed. The fatty acid is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include stearic acid and the like.
The method for producing the silver-coated copper powder is not particularly limited and can be appropriately selected according to the purpose. For example, the following methods [1] to [5] can be given.
[1] A method of precipitating metal silver on the surface of metallic copper powder using a silver complex salt solution of silver nitrate, ammonium carbonate salt and trisodium ethylenediaminetetraacetate (see, for example, Japanese Patent Publication No. 57-59283 Reference).
[2] A method of precipitating metal silver on the surface of a metal copper powder by using a silver complex salt solution of silver nitrate, ammonia water, and EDTA (see, for example, JP-A-61-3802).
[3] A method in which copper powder is dispersed in a chelating agent solution, a silver ion solution is added to the dispersion to promote the reduction reaction, and a reducing agent is further added to completely precipitate the copper powder to precipitate a silver coating on the surface of the copper powder See, for example, Japanese Patent Laid-Open Publication No. 1-119602).
[4] A method of coating silver on the surface of copper particles by a substitution reaction of silver ions and metallic copper in a solution containing silver ions in an organic solvent (see, for example, Japanese Patent Application Laid-Open No. 2006-161081) .
[5] The copper powder processed in the form of a flake is heat treated to oxidize the surface of the copper powder. Then, the copper powder is subjected to removal and washing with water of the surface of the copper powder in the alkaline solution, And then a reducing agent is added to the acid solution in which the copper powder is dispersed to adjust the pH to prepare a copper powder slurry. By continuously adding a silver ion solution to the copper powder slurry, electroless substitution plating and reduction A method of forming a silver layer on the surface of a copper powder by electroless plating (see, for example, Japanese Patent Application Laid-Open No. 2010-174311).
Among them, the method of [5] is preferable.
The average particle diameter of the conductive particles is not particularly limited and may be appropriately selected according to the purpose. The average particle diameter is preferably 1 탆 to 50 탆, more preferably 3 탆 to 30 탆, particularly preferably 5 탆 to 20 탆. If the average particle diameter is less than 1 탆, the connection reliability may be insufficient. If the average particle diameter exceeds 50 탆, the solar cell may be damaged. If the average particle diameter is within the particularly preferable range, it is advantageous in terms of long-term reliability.
The average particle size can be measured by, for example, a particle size distribution measuring apparatus (Microtrac MT3100, manufactured by Nippon Kogaku Co., Ltd.).
The content of the conductive particles is not particularly limited and may be appropriately selected according to the purpose. The content is preferably 2 mass% to 25 mass%, more preferably 2 mass% to 15 mass%, and 2 mass% to 10 mass% , And particularly preferably from 3.5% by mass to 6.5% by mass. If the content is less than 2 mass%, the connection reliability may be deteriorated. When the content is more than 25 mass%, the adhesive property and the connection reliability may be deteriorated. When the content is within the particularly preferable range, it is advantageous in that the adhesive property and the connection reliability are superior.
≪ Other components >
The other components are not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include silane coupling agents, rubbers, fillers, softeners, accelerators, anti-aging agents, organic solvents, ion catchers and the like. The content of the other components is not particularly limited and can be appropriately selected depending on the purpose.
-Rubber-
The rubber is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include acrylic rubber and the like.
The content of the rubber is not particularly limited and may be appropriately selected according to the purpose, but is preferably 5% by mass to 25% by mass, more preferably 10% by mass to 20% by mass.
The temperature (Tg) of the main dispersion tan? Peak after curing of the conductive adhesive for a solar cell is not particularly limited and may be appropriately selected according to the purpose, but is preferably 190 占 폚 or higher, more preferably 190 占 폚 to 225 占 폚, To 215 캜. If the temperature is lower than 190 占 폚, the connection reliability may be lowered.
The peak value of the main dispersion tan? After curing of the conductive adhesive for a solar cell is not particularly limited and may be appropriately selected according to the purpose, but is preferably 0.40 or more, more preferably 0.40 to 0.50, and particularly preferably 0.45 to 0.50. If the peak value is less than 0.40, the adhesiveness may be lowered.
The storage elastic modulus of the conductive adhesive for a solar cell at -40 deg. C after curing is not particularly limited and may be appropriately selected according to the purpose. From the viewpoint of adhesiveness, 3.0 x 10 9 to 4.1 x 10 9 Pa is preferable. The storage elastic modulus at -40 deg. C after curing is considered to be a physical quantity related to adhesion.
The storage elastic modulus at 170 캜 after curing of the conductive adhesive for a solar cell is not particularly limited and may be appropriately selected according to the purpose. From the viewpoint of connection reliability, it is preferably 1.9 × 10 8 to 2.2 × 10 8 Pa. The storage elastic modulus at 170 캜 after curing is considered to be a physical quantity related to the connection reliability.
The temperature (Tg), the main dispersion tan? Peak value, the storage elastic modulus at -40 占 폚 and the storage elastic modulus at 170 占 폚 of the main dispersion tan? Peak after curing of the conductive adhesive for a solar cell can be measured by the following method .
Using the conductive adhesive for solar cell, a conductive adhesive film having an average thickness of 20 占 퐉 is formed on the peeled PET. Subsequently, the conductive adhesive film is placed in a heating furnace at 200 ° C and heated for 30 minutes to cure the conductive adhesive film to obtain a cured product. The cured product was peeled off from the peeled PET, cut into a rectangle of 3.5 mm x 0.4 mm, and used as a measurement sample.
Using a dynamic viscoelasticity measuring instrument (
Examples of the dynamic viscoelasticity measuring instrument include DDV-01FP (manufactured by ORIENTEC).
The conductive adhesive for a solar cell may be in a liquid state or in a film state.
(Solar cell module)
The solar cell module of the present invention has at least a solar battery cell, a tap line, and a cured product of a conductive adhesive, and further includes other members such as a sealing resin, a moisture-proof back sheet, and a glass plate.
The tab lines and the electrodes of the solar cell are connected to each other by using a cured product of the conductive adhesive.
The conductive adhesive is the conductive adhesive for a solar cell of the present invention.
<Solar cell>
The solar cell is not particularly limited as long as it has an electrode and may be appropriately selected according to the purpose. For example, the solar cell may have at least a photoelectric conversion element as a photoelectric conversion unit, a finger electrode, and a bus bar electrode, Member.
Examples of the solar cell include a thin film solar cell and a crystal solar cell. Examples of the thin-film solar cell include an amorphous silicon solar cell, a CdS / CdTe solar cell, a dye-sensitized solar cell, an organic thin film solar cell, a microcrystalline silicon solar cell (tandem solar cell) . Examples of the crystalline solar cell include a single crystal silicon solar cell and a polycrystalline silicon solar cell.
The solar cell may be a bus barrel structure having no bus bar electrode.
The average thickness of the solar cell is not particularly limited and may be appropriately selected depending on the purpose.
- finger electrode -
The finger electrode is an electrode for collecting electricity generated in the photoelectric conversion unit. The finger electrode is formed on the solar cell in a direction substantially orthogonal to the tap line.
The material, shape, size, and structure of the finger electrode are not particularly limited and may be appropriately selected according to the purpose.
- bus bar electrode -
The bus bar electrode is an electrode that further collects electricity collected from the finger electrodes and transmits the collected electricity to the tap lines.
The material, shape, size, and structure of the bus bar electrode are not particularly limited and may be appropriately selected according to the purpose.
Further, in a solar cell having a bus bar structure, electricity is directly transmitted from the finger electrode to the tap line.
<Tap line>
The tap line is not particularly limited as long as it is a line that electrically connects the adjacent portions of the solar cell cells, and can be appropriately selected according to the purpose.
The material, shape, size, and structure of the tap line are not particularly limited and may be appropriately selected according to the purpose.
≪ Sealing resin >
The sealing resin is not particularly limited and may be appropriately selected according to the purpose. Examples of the resin include ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl acetate / triallyl isocyanurate (EVAT), polyvinyl butyrate PVB), polyisobutylene (PIB), silicone resin, and polyurethane resin.
≪
The moisture-proof back sheet is not particularly limited and may be appropriately selected according to the purpose. Examples of the moisture-proof back sheet include polyethylene terephthalate (PET), aluminum (Al), PET, and a laminate of Al and polyethylene (PE).
<Glass plate>
The glass plate is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include soda lime float glass plates and the like.
The solar cell module may be a thin film solar cell module using the thin film solar cell, or a crystal solar cell module using the crystal solar cell.
An example of the solar cell module of the present invention will be described with reference to the drawings.
1 is a schematic top view showing an example of a thin film solar cell module 200. As shown in Fig. In the thin-film solar cell module 200 of Fig. 1, thin-film solar cells 32 composed of thin-film-type photoelectric conversion elements are arranged in series on a substrate 38 in a planar direction. A surface electrode (not shown) of the thin-film solar cell 32c at one end and a surface electrode (not shown) of the thin-film solar cell 32d at the other end are provided with a conductive adhesive layer And a
2 is an exploded perspective view showing an example of a crystalline solar cell module. The crystalline solar cell module 1 has a string 4 in which a plurality of crystalline solar cells 2 are connected in series by a
As shown in Fig. 3, each crystal
The front
(Manufacturing Method of Solar Cell Module)
The method for manufacturing a solar cell module of the present invention includes at least a batch process, a coating process, a pressurizing process, and a heating process, and further includes other processes as necessary.
The manufacturing method of the solar cell module of the present invention can be suitably used for manufacturing the solar cell module of the present invention.
<Batch process>
As the arranging step, in the step of disposing the conductive adhesive agent and the tap line so that the electrode and the tab line are connected to each other via the cured product formed by curing the conductive adhesive by heating on the electrode of the solar cell, There is no limitation, and it can be appropriately selected according to the purpose.
Examples of the solar cell include the solar cell described above in the description of the solar cell module of the present invention.
Examples of the above-mentioned tab lines include the above-mentioned tab lines exemplified in the description of the solar cell module of the present invention.
The conductive adhesive is the conductive adhesive for a solar cell of the present invention. The conductive adhesive may be in a liquid state or in a film state.
An example of the arrangement process will be described.
On the bus bar electrode of the solar battery cell, a conductive adhesive (conductive adhesive film) on the film slit having the same width as that of the bus bar electrode is placed. Then, a copper foil (tap line) having the same width as that of the bus bar electrode is placed on the conductive adhesive film. The arrangement step can be performed as described above.
Another example of the arrangement process will be described.
First, an adhesive layer-attached tab line having the same width as the bus bar electrode of the solar cell is prepared. The adhesive layer-adhering tab line can be formed by, for example, placing a film-shaped conductive adhesive (conductive adhesive film) on a copper foil and slicing the copper foil on which the conductive adhesive film is placed so as to have the same width as the bus bar electrode of the solar cell .
The adhesive layer-attaching tab line is placed on the bus bar electrode of the solar cell so that the bus bar electrode and the adhesive layer of the adhesive layer-attaching tab line contact each other. The arrangement step can be performed as described above.
<Coating Step>
The covering step is not particularly limited as long as the step of covering the solar battery cell with a sealing resin and covering the sealing resin with one of the moisture-proof back sheet and the glass plate can be appropriately selected according to the purpose.
The above-described manufacturing method of the solar cell module is preferably performed using a vacuum laminator. The method of using the vacuum laminator can be performed with reference to the method described in, for example, Japanese Patent Application Laid-Open No. 2010-283059.
The sealing resin, the moisture-proof back sheet, and the glass plate are not particularly limited and may be appropriately selected according to the purpose. For example, the sealing resin exemplified in the description of the solar cell module of the present invention, the moisture- A back sheet, and the glass plate, respectively.
≪ Pressure process and heating process >
The pressing step is not particularly limited as long as it is a step of pressing any one of the moisture-proof back sheet and the glass plate, and can be appropriately selected according to the purpose. The pressure to be pressurized and the time to pressurize are arbitrary.
The heating step is not particularly limited as long as it is a step of heating the heating stage on which the solar cell is mounted, and can be appropriately selected according to the purpose. By heating the heating stage, the sealing resin can be heated. Further, the conductive adhesive can be heated.
The heating temperature in the heating step is not particularly limited and may be appropriately selected according to the purpose. The heating temperature is preferably 50 to 250 캜, more preferably 100 to 200 캜. If the heating temperature is less than 50 캜, the sealing may be insufficient. If the heating temperature is more than 250 캜, the organic resin contained in the conductive adhesive, sealing resin, and the like may be thermally decomposed. If the heating temperature is within the more preferable range, it is advantageous in terms of reliability of sealing.
The heating time in the heating step is not particularly limited and may be appropriately selected depending on the purpose. The heating time is preferably 1 second to 1 hour, more preferably 5 seconds to 30 minutes, and particularly preferably 10 seconds to 20 minutes. If the heating time is less than 1 second, the sealing may become insufficient. If the heating time is within the particularly preferable range, it is advantageous in terms of reliability of sealing.
The order of starting the pressurizing step and the heating step is not particularly limited and may be appropriately selected according to the purpose.
The pressing step and the heating step are performed to seal the solar cell and to connect the electrode and the tab line of the solar cell through the cured product of the conductive adhesive.
Thus, the solar cell module of the present invention is manufactured.
Further, for example, a solar cell module of the present invention can be manufactured by forming a matrix in which a plurality of strings in which a plurality of solar cells are directly connected and sealing the same.
Example
Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to these embodiments at all.
In the following embodiments, the average thickness is a value obtained by measuring the thickness of any 10 points of the measurement object and averaging them. The average width is a value obtained by measuring the width of any 10 points of the measurement object and averaging them.
(Production Example 1)
≪ Preparation of silver-coated copper powder &
A copper powder obtained by mechanically pulverizing the atomized copper powder obtained by a method called the atomization method was used. It is also presumed that, during mechanical pulverization, fatty acids are added for the purpose of preventing coarsening by coagulation of copper powders. Specifically, a flake copper powder (AFS-Cu 7 탆) manufactured by Nippon Atomie Chemical Co., Ltd. was used. This copper powder had a weight cumulative particle diameter D 50 of 7.9 탆 according to a laser diffraction scattering particle size distribution measurement method.
500 g of the copper powder on the flakes was subjected to heat treatment at 250 캜 for 5 minutes in the atmosphere (oxidation treatment). Thereafter, the copper powder subjected to the oxidation treatment was added to the mortar and pulverized. 500 g of this copper powder was added to 1,000 ml of a 1% by mass aqueous potassium hydroxide solution and stirred for 20 minutes, followed by primary decantation, 1000 ml of pure water was further added, and the mixture was stirred for several minutes.
Thereafter, secondary decantation treatment was carried out, 2,500 mL of a sulfuric acid aqueous solution having a sulfuric acid concentration of 15 g / L was added, and the mixture was stirred for 30 minutes (acid washing). Further, the acid cleaning with the aqueous sulfuric acid solution was repeated one more time. Further, tertiary decantation treatment was performed, 2,500 mL of pure water was added, and the mixture was stirred for several minutes. The copper powder and the solution on the flakes were separated by filtration by filtration washing and suction dewatering, and the copper powder on the flakes was dried at 90 ° C for 2 hours.
Then, 2,500 mL of a sulfuric acid aqueous solution having a sulfuric acid concentration of 7.5 g / L was added to the copper powder on the dried flakes, and the mixture was stirred for 30 minutes. Further, a fifth decantation treatment was carried out, 2,500 mL of pure water was added, and the mixture was stirred for several minutes.
Further, a sixth decantation treatment was carried out, 2,500 mL of a 1 mass% potassium sodium tartrate solution was added, and the mixture was stirred for several minutes to form a copper slurry. Sulfuric acid or potassium hydroxide solution was added to the copper slurry to adjust the pH of the copper slurry to 3.5 to 4.5.
To the copper slurry whose pH was adjusted, 1,000 mL of an ammonia solution of ammonium nitrate (87.5 g of silver nitrate was added to water and ammonia water was added thereto and adjusted to 1,000 mL) was slowly added over 30 minutes to carry out a substitution reaction and a reduction reaction, Followed by stirring for 30 minutes to obtain a silver-coated copper powder.
Thereafter, 7th order decantation treatment was performed, 3,500 mL of pure water was added, and the mixture was stirred for several minutes. Further, an eighth decantation treatment was performed, 3,500 mL of pure water was added, and the mixture was stirred for several minutes. The silver coated copper powder and the solution were separated by filtration by filtration washing and suction dewatering, and the silver coated copper powder was dried at 90 ° C for 2 hours.
500 g of the silver-coated copper powder obtained above was placed in a tubular furnace, and heat-treated at 200 캜 for 30 minutes in a reducing atmosphere in a hydrogen stream (3.0 L / minute to 3.5 L / minute). The heat treated silver coated copper powder was pulverized in induction. 500 g of the silver-coated copper powder after the pulverization was dispersed in 1,000 mL of a 0.5 mass% stearic acid isopropyl alcohol solution and stirred for 30 minutes.
Then, silver-coated silver powder treated with heat treatment and suction dewatering by suction filtration and solution were separated by filtration and dried at 90 ° C for 2 hours to obtain silver coated copper powder treated with stearic acid.
Further, the above-described method for producing the silver-coated copper powder can be performed with reference to Japanese Patent Application Laid-Open No. 2010-174311.
(Example 1)
<Fabrication of solar cell module model>
- Preparation of conductive adhesive film -
, 25 parts by mass of a fluorene-type phenoxy resin (FX293, manufactured by Shin-Etsu Chemical Co., Ltd.), 25 parts by mass of a fluorene-type epoxy resin (Oakzol CG50, manufactured by Osaka Gas Chemical Co., 30 parts by mass of a curing agent (imidazole-based curing agent, Nova Cure HX3941HP, manufactured by Asahi Kasei Imperialties Co., Ltd.) and 15 parts by mass of a conductive particle (silver coated copper obtained in Production Example 1) Powder,
Then, the obtained conductive adhesive composition was coated on a polyethylene terephthalate film (release film) having a thickness of 50 mu m which had been subjected to a surface-exfoliation treatment. Followed by heat treatment in an oven at 80 DEG C for 5 minutes to form a conductive adhesive film having an average thickness of 25 mu m.
- Laminate and Slit -
The above-mentioned conductive adhesive film was laminated to a copper foil (average thickness of 150 mu m) to prepare a copper foil in which the conductive adhesive film was laminated. Then, the copper foil having the conductive adhesive film laminated thereon was slit with an average width of 1.5 mm to prepare a tab line with an adhesive layer.
- Production of solar cell model -
As a solar cell model 2 ', a glass substrate having a
- Production of solar module model -
An adhesive layer attaching tab line was attached on the
Subsequently, the above-mentioned tab line was heated and pressed through a silicone rubber buffer material (200 mu m) with a heating tool at a pressing force of 2 MPa and a heating temperature of 180 DEG C for 15 seconds to form the bus bar electrode and the tab line, As shown in Fig. Thus, a tap-line mounted solar battery cell model was obtained.
The tap line-mounted solar cell model obtained was covered with a sealing resin, and the sealing resin was covered with a moisture-proof back sheet. As the sealing resin, an ethylene / vinyl acetate copolymer having a thickness of 500 mu m was used. A PET film was used for the back sheet.
Then, the sealing resin was sealed by using a vacuum laminator. Concretely, after vacuuming at 100 ° C for 5 minutes, the laminate was pressed at 0.1 MPa for 5 minutes, and then cured at 155 ° C for 45 minutes in an oven.
Thus, a solar cell module model was obtained.
<Evaluation>
The following evaluation was conducted. The results are shown in Table 1.
- peak dispersion tan? Peak value, main dispersion tan? Peak temperature (Tg), storage elastic modulus at -40 占 폚 and storage elastic modulus at 170 占 폚 -
[Sample preparation]
A conductive adhesive film having an average thickness of 20 占 퐉 was formed on the peeled PET. Subsequently, the conductive adhesive film was placed in a heating furnace at 200 ° C and heated for 30 minutes to cure the conductive adhesive film to obtain a cured product. The cured product was peeled off from the peeled PET and cut into a rectangle of 3.5 mm x 0.4 mm to obtain a measurement sample.
Peak value of the main dispersion tan delta when the temperature of the sample to be measured was raised from -60 DEG C to 200 DEG C at a heating rate of 3 DEG C per minute using a dynamic viscoelastometer (DDV-01FP, manufactured by ORIENTEC CO., LTD. , The storage elastic modulus at -40 ° C and the storage elastic modulus at 170 ° C.
- Adhesion -
The peel strength (N / mm) when the tab lines were peeled from the tab line-mounted solar battery cell model in the 90 占 direction at a tensile strength of 50 cm / min was measured using a peel strength tester (Tensilon, Orientech) And evaluated by the following evaluation criteria.
〔Evaluation standard〕
?: 2.0 N / mm or more
?: 1.5 N / mm or more and less than 2.0 N / mm
?: 1.0 N / mm or more and less than 1.5 N / mm
X: less than 1.0 N / mm
- Connection reliability -
A portion of 2 mm at the tip of each of two tab lines (Cu foil, 1.5 mm in width and 200 탆 in thickness) was thermocompression bonded (180 DEG C, 2 MPa, 10 Sec) to prepare a measurement sample. The distance between the tip portions of the two tab lines was 3 mm.
The initial and the resistance of the obtained test sample after the cycle test were measured using a digital multimeter (Digital Multimeter 7555, manufactured by Yokogawa Electric KK) and evaluated according to the following evaluation criteria. Further, the temperature was raised from -40 DEG C to 100 DEG C (at a heating rate of 2 DEG C / minute), held at 100 DEG C for 35 minutes, decreased at 100 DEG C to -40 DEG C Minute holding was set as one cycle, and the test was carried out for 1,000 cycles and for the test for 3,000 cycles.
〔Evaluation standard〕
◎: Less than 4mΩ
○: 4 mΩ or more and less than 5 mΩ
Δ: 5 mΩ or more and less than 6 mΩ
×: 6 mΩ or more
(Examples 2 to 5)
In the production of the conductive adhesive film of Example 1, while maintaining the total amount (50 parts by mass) of the fluorene type phenoxy resin and the fluorene type epoxy resin, the mass of the fluorene type phenoxy resin and the fluorene type epoxy resin A conductive adhesive film, a tap wire-mounted solar cell model, and a solar cell module model were produced and evaluated in the same manner as in Example 1 except that the ratios were changed to the mass ratios shown in Table 1. The results are shown in Table 1.
(Examples 6 and 7)
In the production of the conductive adhesive film of Example 1, 25 parts by mass of the fluorene type phenoxy resin, 25 parts by mass of the fluorene type epoxy resin, 15 parts by mass of the acryl rubber and 30 parts by mass of the curing agent, A conductive adhesive film, a tap wire-mounted solar cell model and a solar cell module model were produced in the same manner as in Example 1, except that the amount of the conductive particles was changed so that the content of the conductive particles in the conductive particles , And evaluation. The results are shown in Table 1.
(Examples 8 and 9)
In the production of the conductive adhesive film of Example 1, while maintaining the total amount (50 parts by mass) of the fluorene type phenoxy resin and the fluorene type epoxy resin, the mass of the fluorene type phenoxy resin and the fluorene type epoxy resin A conductive adhesive film, a tap wire-mounted solar cell model, and a solar cell module model were produced and evaluated in the same manner as in Example 1 except that the ratios were changed to the mass ratios shown in Table 2. The results are shown in Table 2.
(Examples 10 and 11)
In the production of the conductive adhesive film of Example 1, 25 parts by mass of the fluorene type phenoxy resin, 25 parts by mass of the fluorene type epoxy resin, 15 parts by mass of the acrylic rubber and 30 parts by mass of the curing agent, A conductive adhesive film, a tap wire-mounted solar cell model and a solar cell module model were produced in the same manner as in Example 1 except that the amount of the conductive particles was changed so that the content in the conductive adhesive composition was as shown in Table 2 , And evaluation. The results are shown in Table 2.
(Example 12)
A conductive adhesive film of Example 1 was produced in the same manner as in Example 1 except that fluorene-type phenoxy resin was changed to fluorene-type phenoxy resin (FX280S, manufactured by Shin-Nittetsu Kagaku Kabushiki Kaisha) An adhesive film, a tap wire mounted solar cell model, and a solar cell module model were manufactured and evaluated. The results are shown in Table 2.
(Example 13)
In the same manner as in Example 1 except that a fluorene type epoxy resin was changed to a fluorene type epoxy resin (ozol CG500, manufactured by Osaka Gas Chemical Co., Ltd.) in the production of the conductive adhesive film of Example 1, Film and tap-line mounted solar cell models and solar cell module models were manufactured and evaluated. The results are shown in Table 2.
(Example 14)
A conductive adhesive film, a tap-line-mounted solar cell model, and a solar cell were prepared in the same manner as in Example 1, except that the conductive particles were changed to nickel particles (HCA-1, A battery module model was produced and evaluated. The results are shown in Table 2.
(Comparative Examples 1 to 6)
A conductive adhesive film, a tap-line-mounted solar cell model, and a solar cell module model were prepared in the same manner as in Example 1 except that the phenoxy resin and the epoxy resin in Example 1 were replaced by the phenoxy resin and the epoxy resin shown in Table 3 And evaluation was performed. The results are shown in Table 3.
The bisphenol-type phenoxy resin used in Comparative Examples 1, 5, and 6 is PKHH (manufactured by InChem).
The fluorene-type phenoxy resin used in Comparative Examples 2 to 4 was FX293 (manufactured by Shin-Nittsu Chemical Co., Ltd.).
The fluorene-type epoxy resin used in Comparative Example 1 is Oak sol CG50 (manufactured by Osaka Gas Chemical Co., Ltd.).
The naphthalene type epoxy resin used in Comparative Examples 2 and 6 is HP4710 (manufactured by DIC Co.).
The phenol novolak type epoxy resin used in Comparative Example 3 is N540 (manufactured by DIC Co.).
The bisphenol A type epoxy resin used in Comparative Examples 4 and 5 is YL980 (manufactured by Mitsubishi Chemical Corporation).
It was confirmed that the solar cell module models produced in Examples 1 to 14 were excellent in adhesiveness and connection reliability.
The mass ratio (A: B) of the fluorene type phenoxy resin (A) to the fluorene type epoxy resin (B) is particularly preferably 1.0: 1.5 to 1.5: 1.0 because both the adhesiveness and the connection reliability are very excellent (See, for example, Examples 1, 8 and 9).
As the content of the conductive particles, it was confirmed that 2 parts by mass to 10 parts by mass was particularly preferable because both of the adhesiveness and the connection reliability were excellent (see, for example, Examples 1, 10 and 11).
It was confirmed that the silver-coated copper powder was particularly preferable as the kind of the conductive particles since both the adhesiveness and the connection reliability were excellent (see, for example, Example 1).
On the other hand, in Comparative Examples 1 to 6 in which a resin other than the fluorene type was used for either the phenoxy resin or the epoxy resin, at least one of adhesion and connection reliability was insufficient ("x" in the evaluation standard).
≪ Industrial applicability >
The solar cell module of the present invention is particularly suitable for a solar cell module requiring durability because of its excellent adhesiveness and connection reliability.
1 crystal solar cell module
2 crystal solar cell
3-tap line
4 Strings
5 matrix
6 sheets
7 Surface cover
8 back sheet
9 metal frame
10 crystal system photoelectric conversion element
11 bus bar electrode
12 finger electrodes
13 Al electrode
17 conductive adhesive film
32 Thin Film Solar Cell
38 substrate
200 Thin Film Solar Cell Module
Claims (8)
A conductive adhesive for a solar cell, which comprises at least a fluorene type phenoxy resin, a fluorene type epoxy resin, a curing agent, and conductive particles.
An electrode of the solar cell and the tap line are connected to each other by using a cured product of the conductive adhesive,
Wherein the conductive adhesive is the conductive adhesive for a solar cell according to any one of claims 1 to 6.
A covering step of covering the solar cell with a sealing resin and further covering the sealing resin with one of a moisture-proof back sheet and a glass plate;
A pressing step of pressing one of the moisture-proof back sheet and the glass plate,
And a heating step of heating the heating stage on which the solar cell is mounted,
Wherein the conductive adhesive is the conductive adhesive for a solar cell according to any one of claims 1 to 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012153656A JP5877133B2 (en) | 2012-07-09 | 2012-07-09 | Conductive adhesive for solar cell, solar cell module, and manufacturing method thereof |
| JPJP-P-2012-153656 | 2012-07-09 | ||
| PCT/JP2013/067310 WO2014010404A1 (en) | 2012-07-09 | 2013-06-25 | Conductive adhesive for solar cell, solar cell module, and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20150032572A true KR20150032572A (en) | 2015-03-26 |
Family
ID=49915870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR20157003029A KR20150032572A (en) | 2012-07-09 | 2013-06-25 | Conductive adhesive for solar cell, solar cell module, and manufacturing method thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5877133B2 (en) |
| KR (1) | KR20150032572A (en) |
| CN (1) | CN104412392A (en) |
| TW (1) | TW201410838A (en) |
| WO (1) | WO2014010404A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6175935B2 (en) * | 2013-06-25 | 2017-08-09 | 日立化成株式会社 | Solar cell connection material, solar cell module using the same, and manufacturing method thereof |
| JP6231394B2 (en) * | 2014-02-03 | 2017-11-15 | デクセリアルズ株式会社 | Method for measuring reaction rate of acrylic adhesive and acrylic adhesive |
| CN106018965B (en) * | 2016-05-16 | 2018-11-23 | 云南瑞博检测技术股份有限公司 | A kind of detection method of the precision resistance prepared on optical glass |
| JP6438102B2 (en) * | 2017-10-19 | 2018-12-12 | デクセリアルズ株式会社 | Connection body and method of manufacturing connection body |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008135654A (en) * | 2006-11-29 | 2008-06-12 | Sanyo Electric Co Ltd | Solar battery module |
| JP5029691B2 (en) * | 2007-06-13 | 2012-09-19 | 日立化成工業株式会社 | Film adhesive for circuit connection |
| JP5045803B2 (en) * | 2010-09-29 | 2012-10-10 | 横浜ゴム株式会社 | Conductive composition and solar battery cell |
| JP5565277B2 (en) * | 2010-11-09 | 2014-08-06 | デクセリアルズ株式会社 | Anisotropic conductive film |
-
2012
- 2012-07-09 JP JP2012153656A patent/JP5877133B2/en active Active
-
2013
- 2013-06-25 KR KR20157003029A patent/KR20150032572A/en not_active Application Discontinuation
- 2013-06-25 WO PCT/JP2013/067310 patent/WO2014010404A1/en active Application Filing
- 2013-06-25 CN CN201380035411.8A patent/CN104412392A/en active Pending
- 2013-07-02 TW TW102123656A patent/TW201410838A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014010404A1 (en) | 2014-01-16 |
| JP2014017368A (en) | 2014-01-30 |
| CN104412392A (en) | 2015-03-11 |
| JP5877133B2 (en) | 2016-03-02 |
| TW201410838A (en) | 2014-03-16 |
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