JPWO2015105119A1 - Conductive particles for back contact type solar cell module, conductive material, and solar cell module - Google Patents

Abstract

In a back contact type solar cell module, conductive particles for a back contact type solar cell module capable of improving the conduction reliability between electrodes are provided. The present invention is a conductive particle used in a back contact type solar cell module, comprising: base material particles; and a conductive part disposed on the surface of the base material particle, on the outer surface of the conductive part. Having a plurality of protrusions, the compression recovery rate when compressed by 10% is 40% or more and 80% or less, and the compression recovery rate when compressed by 50% is 3% or more and 18% or less.

Description

  The present invention relates to conductive particles used in a back contact solar cell module. The present invention also relates to a back contact solar cell module conductive material using the conductive particles. The present invention also relates to a back contact type solar cell module using the conductive material.

  Examples of the solar cell module system include a ribbon system and a back contact system. Conventionally, ribbon type solar cell modules have been mainly employed. In recent years, there is an increasing demand for the development of a back contact type solar cell module that can be expected to have high output and high conversion efficiency.

  In the back contact type solar cell module, the solar cell and the flexible printed circuit board are bonded together on the entire surface of the solar cell.

  In Patent Document 1 below, a plurality of solar cells are arranged side by side in the arrangement of the modules with the back surface facing upward, and the P-type electrode and N-type electrode of adjacent solar cells are further electrically connected by an interconnector. The first step of obtaining a series of solar cells connected to each other, and the sealing material, the series of solar cells, the sealing material, and the back side protection member in this order on the front side protection member. The manufacturing method of a solar cell module provided with the 2nd process laminated | stacked and integrated is disclosed. Patent Document 1 describes a method of connecting a wiring electrode of a flexible printed circuit board and an electrode of a solar battery cell with Cu, Ag, Au, Pt, Sn, an alloy containing these, or the like.

  Further, in Patent Document 2 below, one end side of the tab wire is disposed on the surface electrode of the solar battery cell via a conductive adhesive containing spherical conductive particles, and adjacent to the solar battery cell. A step of disposing the other end of the tab wire on the back electrode of the solar battery cell via a conductive adhesive containing conductive particles, and heat-pressing the tab wire to the front electrode and the back electrode. There is disclosed a method for manufacturing a solar cell module including a step of connecting the tab wire to the front electrode and the back electrode by the conductive adhesive. In the tab line, a concavo-convex portion is formed on one surface in contact with the conductive adhesive. The average height (H) of the uneven part and the average particle diameter (D) of the conductive particles satisfy D ≧ H.

  In recent years, it has been proposed to selectively dispose conductive particles on wiring electrodes of a flexible printed circuit board.

  In the following Patent Document 3, a base material, an aluminum wiring disposed on one surface of the base material via an adhesive layer, a solar battery cell having an electrode connected to the aluminum wiring, A method for manufacturing a solar cell module is disclosed that includes a sealing material for sealing a solar battery cell, and a translucent front plate on a surface opposite to the aluminum wiring of the sealing material. The manufacturing method described in Patent Document 3 includes a step of removing the oxide film of the aluminum wiring in advance by a flux, a step of applying aluminum paste solder to the aluminum wiring by printing or a dispenser, the aluminum wiring, and the sun. Connecting the electrodes of the battery cells with the aluminum paste solder. The aluminum paste solder includes aluminum powder and a synthetic resin.

JP 2005-11869 A JP 2012-204388 A JP2013-63443A

  There may be irregularities on the surface of the electrode of the solar battery cell. In addition, irregularities may also exist on the surface of the wiring electrode of the flexible printed board. When the aluminum paste solder described in Patent Document 3 is used, the aluminum paste solder may not sufficiently contact the surface of the electrode due to irregularities on the surface of the electrode. For this reason, the conduction | electrical_connection reliability between electrodes may become low.

  In addition, as described in Patent Document 3, in recent years, since copper wiring electrodes are expensive, there is an increasing demand for using aluminum wiring electrodes. However, an oxide film is easily formed on the surface of the aluminum wiring electrode. For this reason, a decrease in conduction reliability tends to be a big problem. In the conductive materials described in Patent Documents 1 to 3, there is a problem that it is difficult to sufficiently improve the conduction reliability particularly when the aluminum wiring electrodes are electrically connected.

  The objective of this invention is providing the electroconductive particle which can improve the conduction | electrical_connection reliability between electrodes in the solar cell module of a back contact system. Moreover, the objective of this invention is providing the electrically conductive material for solar cell modules of a back contact system using the said electroconductive particle. Moreover, this invention is providing the solar cell module of a back contact system using the said electrically-conductive material.

  According to a wide aspect of the present invention, there are conductive particles used in a back contact solar cell module, comprising: base material particles; and a conductive part disposed on the surface of the base material particles, A plurality of protrusions on the outer surface of the part, the compression recovery rate when compressed by 10% is 40% or more and 80% or less, and the compression recovery rate when compressed by 50% is 3% or more and 18% or less There is provided a conductive particle for a back contact solar cell module.

  On the specific situation with the electroconductive particle which concerns on this invention, the average height of several said processus | protrusion is 50 to 600 nm.

  On the specific situation with the electroconductive particle which concerns on this invention, ratio with respect to the thickness of the said electroconductive part of the average height of several said processus is 0.5 or more and 4.0 or less.

  The conductive particles according to the present invention electrically connect the wiring electrode and the electrode of a flexible printed circuit board having a wiring electrode on the surface or a resin film having a wiring electrode on the surface and a solar battery cell having the electrode on the surface. It is preferably used to connect to

  On the specific situation with the electroconductive particle which concerns on this invention, the said wiring electrode of the said flexible printed circuit board or the said resin film is an aluminum wiring electrode, or the said electrode of the said photovoltaic cell is an aluminum electrode.

  According to a wide aspect of the present invention, there is provided a back contact solar cell module conductive material comprising the above-described back contact solar cell module conductive particles and a binder resin.

  On the specific situation with the electrically-conductive material which concerns on this invention, the said binder resin contains a thermosetting compound and a thermosetting agent.

  According to a wide aspect of the present invention, a flexible printed board having a wiring electrode on its surface or a resin film having a wiring electrode on its surface, a solar battery cell having an electrode on its surface, the flexible printed board or the resin film, and the sun A connecting portion that connects the battery cell, and the connecting portion includes a conductive material for a back contact solar cell module that includes the above-described back contact solar cell module conductive particles and a binder resin. There is provided a back contact type solar cell module that is formed and in which the wiring electrode and the electrode are electrically connected by the conductive particles.

  The back contact type solar cell module conductive particles according to the present invention include base particles and conductive portions arranged on the surfaces of the base particles, and a plurality of conductive particles on the outer surface of the conductive portions. Since it has protrusions, the compression recovery rate when compressed by 10% is 40% or more and 80% or less, and the compression recovery rate when compressed by 50% is 3% or more and 18% or less. Reliability can be increased.

FIG. 1 is a cross-sectional view showing conductive particles for a solar cell module of the back contact system according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing conductive particles for a solar cell module of the back contact system according to the second embodiment of the present invention. FIG. 3: is sectional drawing which shows the electroconductive particle for solar cell modules of the back contact system which concerns on the 3rd Embodiment of this invention. FIG. 4 is a cross-sectional view showing an example of a back contact solar cell module obtained using the back contact solar cell module conductive particles according to the first embodiment of the present invention. 5A to 5C are cross-sectional views for explaining each step of the first manufacturing method of the back contact type solar cell module shown in FIG. FIGS. 6A to 6C are cross-sectional views for explaining each step of the second manufacturing method of the back contact type solar cell module shown in FIG.

  Details of the present invention will be described below.

(Conductive particles for back contact solar cell modules)
The back contact type solar cell module conductive particles according to the present invention include base material particles and a conductive portion disposed on the surface of the base material particles. The back contact solar cell module conductive particles according to the present invention have a plurality of protrusions on the outer surface of the conductive portion. The compression recovery rate is 10% or more and 80% or less when 10% of the back contact solar cell module conductive particles according to the present invention is compressed. The compression recovery rate when the conductive particles for a solar cell module of the back contact type according to the present invention is compressed by 50% is 3% or more and 18% or less.

  In this invention, since the structure mentioned above is provided, the conduction | electrical_connection reliability between electrodes can be improved in the solar cell module of a back contact system.

  For example, in a back contact type solar cell module, the wiring electrode and the electrode of the flexible printed circuit board having the wiring electrode on the surface or the resin film having the wiring electrode on the surface and the solar cell having the electrode on the surface are provided. Electrically connected.

  Since the conductive particles have base particles and conductive portions arranged on the surface of the base particles, the distance between the electrodes can be controlled with high accuracy. In addition, since the conductive particles are easily deformed in response to the change in the interval between the electrodes, the conduction reliability between the electrodes can be improved. As a result, the initial energy conversion efficiency and the energy conversion efficiency after the reliability test can be increased.

  Furthermore, since the conductive particles have a plurality of protrusions on the outer surface of the conductive portion, even if an oxide film is formed on the surface of the conductive portion and the surface of the electrode, the oxide film is broken through by the protrusion. For this reason, the conduction | electrical_connection reliability between electrodes becomes high.

  Furthermore, unevenness may exist on the surface of the electrode of the solar battery cell. Further, irregularities may also exist on the surface of the flexible printed circuit board or the wiring electrode of the resin film. For this reason, the space | interval between electrodes may not be uniform. Furthermore, since the flexible printed circuit board or the resin film is relatively flexible, the distance between the electrodes may not be uniform with the deformation of the flexible printed circuit board or the resin film after connection. On the other hand, the compression recovery rate when compressed by 50% is in the above specific range, so that the repulsive stress due to the deformation of the conductive particles is not excessive in the region where the distance between the electrodes is narrow. It becomes easy to maintain the contact with the stable. In addition, since the compression recovery rate when compressed by 10% is in the above specific range, the conductive particles and the electrodes are easily brought into contact in a region where the distance between the electrodes is wide. Furthermore, since the conductive particles have a plurality of protrusions on the outer surface of the conductive portion, conduction is achieved by the protrusions being crushed or breaking through the electrodes in a region where the distance between the electrodes is narrow. In a region where the interval is wide, conduction is achieved in the vicinity of the tip of the protrusion. For this reason, conduction | electrical_connection reliability can be improved because the said electroconductive particle has several protrusion on the outer surface of an electroconductive part.

  Furthermore, if the conductive particles have a protrusion on the outer surface (conductive surface) of the conductive portion, the protrusion is embedded in the electrode. For this reason, even if an impact is applied to the solar cell module, poor connection is less likely to occur. For this reason, conduction | electrical_connection reliability can be improved effectively and the photoelectric conversion efficiency in a solar cell module can be improved.

  The above effect can be obtained by using conductive particles having protrusions on the outer surface (conductive surface) of the conductive part in order to electrically connect the electrodes of the back contact type solar cell module. For the first time by the present inventors. In particular, when the average height of the plurality of protrusions in the conductive particles is 1 nm or more and 900 nm or less, the above effect is more effectively exhibited. Furthermore, when the average height of the plurality of protrusions in the conductive particle is 50 nm or more and 600 nm or less, the above-described effect is more effectively exhibited. Further, in order to electrically connect the electrodes of the solar cell module of the back contact system, the present inventors have determined the importance and technical significance of the conductive particles having protrusions on the outer surface of the conductive portion. Found for the first time.

  Hereinafter, the conductive particles used in the back contact solar cell module will be described more specifically with reference to the drawings. In the following embodiments, different partial configurations can be replaced with each other.

  FIG. 1 is a cross-sectional view showing conductive particles for a solar cell module of the back contact system according to the first embodiment of the present invention.

  The conductive particle 21 shown in FIG. 1 has a base particle 22 and a conductive portion 23 disposed on the surface of the base particle 22. The conductive part 23 is a conductive layer. The conductive portion 23 covers the surface of the base particle 22. The conductive portion 23 is in contact with the base particle 22. The conductive particle 21 is a coated particle in which the surface of the base particle 22 is coated with the conductive portion 23.

  The conductive particle 21 has a plurality of protrusions 21 a on the outer surface of the conductive portion 23. The conductive portion 23 has a plurality of protrusions 23a on the outer surface.

  The conductive particles 21 have a plurality of core substances 24 on the surface of the substrate particles 22. The conductive portion 23 covers the base particle 22 and the core substance 24. By covering the core substance 24 with the conductive portion 23, the conductive particle 21 has a plurality of protrusions 21 a on the outer surface of the conductive portion 23. The outer surface of the conductive portion 23 is raised by the core substance 24, and a plurality of protrusions 21a and 23a are formed.

  FIG. 2 is a cross-sectional view showing conductive particles for a solar cell module of the back contact system according to the second embodiment of the present invention.

  The conductive particles 21 </ b> A illustrated in FIG. 2 include base material particles 22 and conductive portions 23 </ b> A disposed on the surface of the base material particles 22. The conductive portion 23A is a conductive layer. Only the presence or absence of the core substance 24 is different between the conductive particles 21 and the conductive particles 21A. The conductive particles 21A do not have a core substance.

  The conductive particles 21A have a plurality of protrusions 21Aa on the outer surface of the conductive portion 23A. The conductive portion 23A has a plurality of protrusions 23Aa on the outer surface.

  The conductive portion 23A has a first portion and a second portion that is thicker than the first portion. Accordingly, the conductive portion 23A has a protrusion 23Aa on the outer surface (the outer surface of the conductive layer). A portion excluding the plurality of protrusions 21Aa and 23Aa is the first portion of the conductive portion 23A. The plurality of protrusions 21Aa and 23Aa are the second portions where the conductive portion 23A is thick.

  In order to form the protrusions 21Aa and 23Aa like the conductive particles 21A, it is not always necessary to use a core substance.

  FIG. 3: is sectional drawing which shows the electroconductive particle for solar cell modules of the back contact system which concerns on the 3rd Embodiment of this invention.

  The conductive particles 21 </ b> B illustrated in FIG. 3 include base material particles 22 and conductive portions 23 </ b> B disposed on the surface of the base material particles 22. The conductive portion 23B is a conductive layer. The conductive portion 23B includes a first conductive portion 23Bx disposed on the surface of the base particle 22 and a second conductive portion 23By disposed on the surface of the first conductive portion 23Bx.

  The conductive particles 21B have a plurality of protrusions 21Ba on the outer surface of the conductive portion 23B. The conductive portion 23B has a plurality of protrusions 23Ba on the outer surface.

  The conductive particles 21B have a plurality of core substances 24 on the surface of the first conductive portion 23Bx. The second conductive portion 23By covers the first conductive portion 23Bx and the core substance 24. The substrate particles 22 and the core substance 24 are arranged with a space therebetween. A first conductive portion 23Bx exists between the base particle 22 and the core substance 24. By covering the core substance 24 with the second conductive portion 23By, the conductive particles 21B have a plurality of protrusions 21Ba on the outer surface of the conductive portion 23B. The surface of the conductive portion 23B and the second conductive portion 23By is raised by the core substance 24, and a plurality of protrusions 21Ba and 23Ba are formed.

  Like the conductive particles 21B, the conductive portion 23B may have a multilayer structure. Further, in order to form the protrusions 21Ba and 23Ba, the core material 24 is disposed on the first conductive portion 23Bx of the inner layer, and the core material 24 and the first conductive portion 23Bx are separated by the second conductive portion 23By of the outer layer. It may be coated.

  The conductive particles 21, 21A, 21B all have a plurality of protrusions 21a, 21Aa, 21Ba on the outer surfaces of the conductive portions 23, 23A, 23B. As for electroconductive particle 21,21A, 21B, all have said compression recovery rate in the specific range mentioned above.

  The back contact type solar cell module according to the present invention is manufactured using the conductive particles 21, 21A, 21B and the like as described above. However, the conductive particles have base particles and conductive parts arranged on the surface of the base particles, and have a plurality of protrusions on the outer surface of the conductive parts, and the conductive particles As long as the compression elastic modulus is within the specific range described above, conductive particles other than the conductive particles 21, 21A, and 21B may be used.

  Next, an example of a solar cell module obtained by using the back contact type conductive particles for a solar cell module according to an embodiment of the present invention will be described more specifically with reference to the drawings.

  FIG. 4 is a cross-sectional view of a back contact type solar cell module obtained by using the back contact type solar cell module conductive particles according to an embodiment of the present invention.

  A solar cell module 1 shown in FIG. 4 includes a flexible printed circuit board 2, a solar battery cell 3, and a connection portion 4 that connects the flexible printed circuit board 2 and the solar battery cell 3. The connection part 4 has the 1st connection part formed with the electrically-conductive material containing the electroconductive particle 21, and the 2nd connection part formed with the connection material which does not contain an electroconductive particle. Instead of the conductive particles 21, conductive particles 21A, 21B and the like may be used. The connecting portion may be formed only of a conductive material including the conductive particles 21.

  In the solar cell module 1, the back sheet 5 is disposed on the surface of the flexible printed board 2 opposite to the connection portion 4 side. A sealing material 6 is disposed on the surface opposite to the connection portion 4 side of the solar battery cell 3. A translucent substrate or the like may be disposed on the surface opposite to the solar cell 3 side of the sealing material 6.

  The flexible printed circuit board 2 has a plurality of wiring electrodes 2a on the surface (upper surface). The solar battery cell 3 has a plurality of electrodes 3a on the front surface (lower surface, back surface). The wiring electrode 2 a and the electrode 3 a are electrically connected by one or a plurality of conductive particles 21. Therefore, the flexible printed circuit board 2 and the solar battery cell 3 are electrically connected by the conductive particles 21. The first connection portion is disposed between the wiring electrode 2a and the electrode 3a. The second connection portion is disposed between a portion of the flexible printed board 2 where the wiring electrode 2a is not provided and a portion where the electrode 3a of the solar battery cell 3 is not provided. The second connection portion may be disposed between the wiring electrode 2a and the electrode 3a.

  Instead of the flexible printed circuit board 2 having the wiring electrode 2a on the surface, a resin film having the wiring electrode on the surface may be used.

  The solar cell module shown in FIG. 4 can be obtained, for example, through the steps shown in FIGS. 5 (a) to 5 (c) below.

  A flexible printed circuit board 2 having wiring electrodes 2a on the surface is prepared. Also, a conductive material 4A containing conductive particles 21 and a binder resin is prepared. In the present embodiment, the binder resin includes a thermosetting compound and a thermosetting agent, and a conductive material 4A having thermosetting properties is used. The conductive material 4A is also a connection material. Next, as shown in FIG. 5A, the conductive material 4A is selectively placed on the wiring electrode 2a of the flexible printed board 2 (first placement step). Instead of the wiring electrode 2a of the flexible printed board 2, the conductive material 4A may be selectively disposed on the electrode 3a of the solar battery cell 3.

  In the present embodiment, in the first arrangement step, the conductive material is not uniformly applied on the entire flexible printed board. As much as possible, it is preferable to dispose the conductive material on the wiring electrode, and it is preferable to dispose the conductive material only on the wiring electrode. However, a conductive material may also be disposed in a portion of the flexible printed board where the wiring electrode is not provided. The smaller the conductive material arranged in the portion of the flexible printed circuit board where the wiring electrodes are not provided, the better.

  Therefore, in the first arrangement step, in the entire conductive material disposed on the flexible printed circuit board or the resin film in 100% by weight, or in the entire conductive material disposed on the solar battery cell in 100% by weight. The amount of the conductive material disposed on the wiring electrode or on the electrode is preferably 90% by weight or more, more preferably 99% by weight or more, and further preferably 100% by weight (total amount). However, the conductive material may be uniformly arranged on the flexible printed circuit board or the resin film wiring electrode and on the flexible printed circuit board or the resin film where the wiring electrode is not provided. You may arrange | position a conductive material uniformly on the part in which the electrode of the said photovoltaic cell and the electrode of the said photovoltaic cell are not provided.

  From the viewpoint of further improving the placement accuracy, the placement of the conductive material is preferably performed by printing or application by a dispenser. Therefore, the conductive material is preferably a conductive paste. However, the conductive material may be a conductive film. If a conductive film is used, the excessive flow of the conductive film after arrangement | positioning can be suppressed. On the other hand, it is necessary to prepare a conductive film having a predetermined size.

  Moreover, the photovoltaic cell 3 which has the electrode 3a on the surface is prepared. Moreover, the connection material 4B which does not contain electroconductive particle is prepared. The connecting material 4B includes a thermosetting compound and a thermosetting agent. As shown in FIG.5 (b), the connection material 4B which does not contain electroconductive particle is arrange | positioned on the surface of the side by which the electrode 3a of the photovoltaic cell 3 is provided (2nd arrangement | positioning process). When the conductive material 4A is selectively disposed on the electrode 3a of the solar battery cell 3, a flexible printed board having the wiring electrode 2a on the surface is prepared. A connection material 4B that does not contain conductive particles is disposed on the surface of the flexible printed circuit board 2 on which the wiring electrodes 2a are provided (second disposing step). Note that a connection material that does not include conductive particles may not be disposed.

  Next, the flexible printed circuit board 2 obtained in the first arrangement step and provided with the conductive material 4A is bonded to the solar battery cell 3 obtained in the second arrangement step and provided with the connection material 4B. The process of matching is performed. That is, as shown in FIG. 5 (c), the flexible printed circuit board 2 and the solar cell 2 are electrically connected so that the wiring electrode 2 a of the flexible printed circuit board 2 and the electrode 3 a of the solar battery cell 3 are electrically connected by the conductive particles 21. The battery cell 3 is bonded together (bonding process). A conductive material 4A including conductive particles 21 is disposed between the wiring electrode 2a and the electrode 3a. A connecting material 4B that does not contain conductive particles is disposed between a portion of the flexible printed circuit board 2 where the wiring electrode is not provided and a portion of the solar battery cell 3 where the electrode is not provided.

It is preferable to pressurize in the said bonding process. By the pressurization, the protrusions effectively break through the oxide film on the surface of the conductive portion or the surface of the electrode. As a result, the conduction reliability can be further improved. The pressurizing pressure is preferably 9.8 × 10 ⁴ Pa or more, and preferably 1.0 × 10 ⁶ Pa or less. When the pressure of the pressurization is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.

  As described above, the connection portion 4 is formed by the conductive material 4A and the connection material 4B. Moreover, the solar cell module 1 shown in FIG. 4 is obtained by arrange | positioning the back sheet 5 and the sealing material 6 as needed.

  Moreover, in the said bonding process, it is preferable to heat 4A of conductive materials and the connection material 4B. By heating, the conductive material 4 </ b> A and the connection material 4 </ b> B can be cured to form the cured connection portion 4.

  The heating temperature is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 120 ° C. or higher, particularly preferably 150 ° C. or higher, preferably 220 ° C. or lower, more preferably 180 ° C. or lower. When the temperature of the heating is not less than the above lower limit and not more than the above upper limit, curing can be sufficiently advanced and connection reliability can be effectively increased.

  The solar cell module shown in FIG. 4 can also be obtained, for example, through the steps shown in FIGS. 6 (a) to (c) below.

  A flexible printed circuit board 2 having wiring electrodes 2a on the surface is prepared. Also, a conductive material 4A containing conductive particles 21 and a binder resin is prepared. As shown in FIG. 6A, the conductive material 4A is selectively placed on the wiring electrode 2a of the flexible printed board 2 (first placement step). Instead of the wiring electrode 2a of the flexible printed board 2, the conductive material 4A may be selectively disposed on the electrode 3a of the solar battery cell 3.

  Moreover, the connection material 4B which does not contain electroconductive particle is prepared. The connecting material 4B is disposed on the portion of the flexible printed board 2 where the wiring electrode 2a is not provided (second disposing step). In the first arrangement step and the second arrangement step, the first arrangement step may be performed first, or the second arrangement step may be performed first. The first arrangement step and the second arrangement step may be performed simultaneously.

  Moreover, as shown in FIG.6 (b), the photovoltaic cell 3 which has the electrode 3a on the surface is prepared. When the conductive material 4A is selectively disposed on the electrode 3a of the solar battery cell 3, the flexible printed board 2 having the wiring electrode 2a on the surface is prepared.

  Next, the step of bonding the flexible printed circuit board 2 on which the conductive material 4A and the connection material 4B are arranged and the solar cell 3 obtained in the first and second arrangement steps is performed. As shown in FIG. 6 (c), the flexible printed circuit board 2 and the solar battery cell are connected so that the wiring electrode 2 a of the flexible printed circuit board 2 and the electrode 3 a of the solar battery cell 3 are electrically connected by the conductive particles 21. 3 are bonded together (bonding process).

  As described above, the connection portion 4 is formed by the conductive material 4A and the connection material 4B. Moreover, the solar cell module 1 shown in FIG. 4 is obtained by arrange | positioning the back sheet 5 and the sealing material 6 as needed.

  As an electrode (wiring electrode) provided on the flexible printed circuit board or the resin film and an electrode provided on the solar battery cell, a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, Metal electrodes such as a molybdenum electrode and a tungsten electrode can be mentioned. Especially, a copper electrode (copper wiring electrode) or an aluminum electrode (aluminum wiring electrode) is preferable, and an aluminum electrode (aluminum wiring electrode) is especially preferable. It is particularly preferable that the wiring electrode provided on the flexible printed board or the resin film is an aluminum wiring electrode, or the electrode provided on the solar battery cell is an aluminum electrode. In this case, only one of the wiring electrode provided on the flexible printed circuit board or the resin film and the electrode provided on the solar battery cell may be formed of aluminum, both of which are aluminum. May be formed. The wiring electrode provided on the flexible printed circuit board or the resin film may be an aluminum wiring electrode, and the electrode provided on the solar battery cell may be an aluminum electrode. In the case of using an aluminum electrode (aluminum wiring electrode), the effect of the present invention is further exhibited, and in particular, the effect due to the protrusion of the conductive particles is further exhibited.

  Hereinafter, other details of the conductive particles, the conductive material, and the solar cell module will be described.

(Conductive particles)
Examples of the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles. The substrate particles are preferably substrate particles excluding metal particles, and more preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.

  The substrate particles are preferably resin particles formed of a resin. When connecting the electrodes, the conductive particles are generally compressed after the conductive particles are arranged between the electrodes. When the substrate particles are resin particles, the conductive particles are easily deformed by compression, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction | electrical_connection reliability between electrodes becomes high.

  Various organic materials are suitably used as the resin for forming the resin particles. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Alkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene Oxide, polyacetal, polyimide, polyamideimide, polyether ether Tons, polyethersulfone, and polymers such as obtained by polymerizing various polymerizable monomers one or more having an ethylenically unsaturated group is used. By polymerizing one or more of various polymerizable monomers having an ethylenically unsaturated group, it is possible to design and synthesize resin particles having any compression property suitable for a conductive material.

  When the resin particles are obtained by polymerizing a monomer having an ethylenically unsaturated group, the monomer having the ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer. And a polymer.

  Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as (meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, dicycle Oxygen atom-containing (meth) acrylates such as pentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1,3-adamantanediol di (meth) acrylate; Nitrile-containing monomers such as acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; acid vinyl esters such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate; ethylene, propylene, isoprene, butadiene, etc. Unsaturated hydrocarbons such as: trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, halogen-containing monomers such as vinyl chloride, vinyl fluoride, and chlorostyrene.

  From the viewpoint of further improving compression characteristics, aliphatic (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Dicyclopentanyl (meth) acrylate or 1,3-adamantanediol di (meth) acrylate is more preferable.

  Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure And silane-containing monomers such as triallyl trimellitate, divinylbenzene, diallyl phthalate, diallylacrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane It is done.

  From the viewpoint of further improving the compression characteristics, polyfunctional (meth) acrylate is preferable, and (poly) tetramethylene glycol di (meth) acrylate or 1,4-butanediol di (meth) acrylate is more preferable.

  The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.

  In the case where the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal particles, examples of the inorganic material that is a material of the substrate particles include silica and carbon black. The inorganic substance is preferably not a metal. The particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle | grains obtained by performing are mentioned. Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

  When the substrate particles are metal particles, examples of the metal that is a material of the metal particles include silver, copper, nickel, silicon, gold, and titanium. However, the substrate particles are preferably not metal particles.

  The average particle diameter of the substrate particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 500 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and particularly preferably 30 μm or less. The average particle diameter of the substrate particles may be 20 μm or less. When the average particle diameter of the base particles is not less than the above lower limit and not more than the above upper limit, when the electrodes are connected using conductive particles, the contact area between the conductive particles and the electrodes becomes sufficiently large, and the conductive particles are conductive. Aggregated conductive particles are less likely to be formed when the layer is formed. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive portion is difficult to peel from the surface of the base particle. From the viewpoint of absorbing the influence of unevenness on the surface of the solar cell circuit, the average particle diameter of the base material particles is preferably 10 μm or more and 30 μm or less.

  The “average particle diameter” of the substrate particles indicates a number average particle diameter. The average particle diameter of the resin particles is obtained by observing 50 arbitrary resin particles with an electron microscope or an optical microscope and calculating an average value.

  The thickness of the conductive part is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, particularly preferably 50 nm or more, preferably 1000 nm or less, more preferably 800 nm or less, still more preferably 500 nm or less, particularly preferably 400 nm or less, most preferably 300 nm or less. When there are a plurality of conductive portions, the thickness of the conductive portion indicates the thickness of the entire plurality of conductive portions. When the thickness of the conductive part is equal to or greater than the lower limit, the conductivity of the conductive particles is further improved. When the thickness of the conductive part is not more than the above upper limit, the difference in the coefficient of thermal expansion between the base particle and the conductive part becomes small, and the conductive part becomes difficult to peel from the base particle.

  Examples of a method for forming the conductive part on the surface of the substrate particle include a method for forming the conductive part by electroless plating and a method for forming the conductive part by electroplating.

  The conductive part preferably contains a metal. The metal that is the material of the conductive part is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, tungsten, molybdenum and cadmium, and alloys thereof. Is mentioned. Further, tin-doped indium oxide (ITO) may be used as the metal. As for the said metal, only 1 type may be used and 2 or more types may be used together.

  The conductive particles have a plurality of protrusions on the outer surface of the conductive part. Since the core substance is embedded in the conductive portion, protrusions can be easily formed on the outer surface of the conductive portion. An oxide film is often formed on the surface of the electrode connected by the conductive particles. When conductive particles having protrusions are used, the oxide film is effectively excluded by the protrusions by placing the conductive particles between the electrodes and pressing them. For this reason, an electrode and electroconductive particle contact more reliably and the connection resistance between electrodes becomes still lower. Furthermore, the protrusion effectively eliminates the binder resin between the conductive particles and the electrode. For this reason, the conduction | electrical_connection reliability between electrodes becomes high.

  As a method for forming protrusions on the surface of the conductive particles, a method of forming a conductive portion by electroless plating after attaching a core substance to the surface of the base particles, and electroless plating on the surface of the base particles Examples include a method of forming a conductive part by, attaching a core substance, and further forming a conductive part by electroless plating. As another method for forming the protrusion, a first conductive part is formed on the surface of the base particle, and then a core substance is disposed on the first conductive part, and then the second conductive part. And a method of adding a core substance in the middle of forming a conductive part on the surface of the base particle. As a method for attaching the core substance to the surface of the substrate particles, a conventionally known method can be adopted. Since the core substance is embedded in the conductive portion, it is easy for the conductive portion to have a plurality of protrusions on the outer surface. However, the core substance is not necessarily used in order to form protrusions on the surfaces of the conductive particles and the conductive part. The core substance is preferably disposed inside or inside the conductive part.

  Examples of the material of the core substance include a conductive substance and a non-conductive substance. Examples of the conductive material include conductive non-metals such as metals, metal oxides, and graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene. Examples of the nonconductive material include silica, alumina, and zirconia. Among them, metal is preferable because conductivity can be increased and connection resistance can be effectively reduced. The core substance is preferably metal particles.

  Examples of the metal include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead. Examples include alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys, and tungsten carbide. Of these, nickel, copper, silver or gold is preferable. The metal that is the material of the core substance may be the same as or different from the metal that is the material of the conductive part. The material of the core substance preferably includes nickel. Examples of the metal oxide include alumina, silica and zirconia.

  The shape of the core material is not particularly limited. The shape of the core substance is preferably a lump. Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.

  The average diameter (average particle diameter) of the core substance is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.6 μm or less, more preferably 0.4 μm or less. The average diameter of the core substance may be 0.9 μm or less, or 0.2 μm or less. When the average diameter of the core substance is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes is effectively reduced.

  The “average diameter (average particle diameter)” of the core substance indicates a number average diameter (number average particle diameter). The average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope and calculating an average value.

  The number of the protrusions per one conductive particle is preferably 10 or more, more preferably 200 or more, and particularly preferably 500 or more. The number of the protrusions may be 3 or more, or 5 or more. The upper limit of the number of protrusions is not particularly limited. The upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles. The number of the protrusions is preferably 1500 or less, more preferably 1000 or less.

  From the viewpoint of further improving the conduction reliability, the average height of the plurality of protrusions is preferably 50 nm or more, more preferably 200 nm or more, preferably 600 nm or less, more preferably 500 nm or less. The average height of the plurality of protrusions may be 1 nm or more, or 900 nm or less. When the average height of the protrusions is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes is effectively reduced.

  The height of the projection is a virtual line of the conductive portion (dashed line shown in FIG. 1) on the assumption that there is no projection on the line (dashed line L1 shown in FIG. 1) connecting the center of the conductive particles and the tip of the projection. L2) Indicates the distance from the top (on the outer surface of the spherical conductive particles assuming no projection) to the tip of the projection. That is, in FIG. 1, the distance from the intersection of the broken line L1 and the broken line L2 to the tip of the protrusion is shown.

  From the viewpoint of further improving the conduction reliability, the ratio of the average height of the plurality of protrusions to the thickness of the conductive part is preferably 0.5 or more, more preferably 1.0 or more, preferably 4.0 or less. More preferably, it is 2.0 or less.

  The compression recovery rate when the conductive particles are compressed by 10% is 40% or more and 80% or less. From the viewpoint of further improving the conduction reliability, the compression recovery rate when the conductive particles are compressed by 10% is preferably 45% or more, more preferably 50% or more, preferably 70% or less, more preferably 60%. It is as follows.

  The compression recovery rate when the conductive particles are compressed by 50% is 3% or more and 18% or less. From the viewpoint of further improving the conduction reliability, the compression recovery rate when the conductive particles are compressed by 50% is preferably 5% or more, more preferably 7% or more, preferably 15% or less, more preferably 10%. It is as follows.

  The compression recovery rate can be measured as follows.

  Spread conductive particles on the sample stage. For each dispersed conductive particle, using a micro-compression tester, 10% of the conductive particles at 25 ° C. in the center direction of the conductive particles on the end surface of a cylindrical (diameter 50 μm, made of diamond) smooth indenter Alternatively, a load (reverse load value) is applied until 50% compression deformation occurs. Thereafter, unloading is performed up to the origin load value (0.40 mN). The load-compression displacement during this period is measured, and the compression recovery rate can be obtained from the following equation. The load speed is 0.33 mN / sec. As the micro compression tester, for example, “Fischer Scope H-100” manufactured by Fischer is used.

Compression recovery rate (%) = [(L1-L2) / L1] × 100
L1: Compression displacement from the load value for origin to the reverse load value when applying a load L2: Unloading displacement from the reverse load value to the load value for origin when releasing the load

  For example, the compression recovery rate can be controlled within the above range by the composition of the monomers constituting the substrate particles.

(Conductive material and connecting material)
The back contact solar cell module conductive material according to the present invention includes the above-described conductive particles and a binder resin. The binder resin is not particularly limited. As the binder resin, a known insulating resin can be used.

  The binder resin, the conductive material, and the connection material preferably include a thermoplastic component or a thermosetting component. The binder resin, the conductive material, and the connection material may contain a thermoplastic component or may contain a thermosetting component. The binder resin, the conductive material, and the connection material preferably include a thermosetting component. The binder resin, the conductive material, and the connection material preferably include a curable compound (thermosetting compound) that can be cured by heating and a thermosetting agent. The curable compound curable by heating and the thermosetting agent are used in an appropriate blending ratio so that the binder resin is cured.

  Examples of the thermosetting compound include epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the thermosetting agent include an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, an acid anhydride, and a thermal cation curing initiator. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  In 100% by weight of the conductive material, the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 weight% or less. When the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability is further enhanced.

  In 100% by weight of the conductive material, the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, More preferably, it is 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

Example 1
(1) Production of conductive particles Production of polymer seed particle dispersion:
In a separable flask, 2500 g of ion-exchanged water, 250 g of styrene, 50 g of octyl mercaptan, and 0.5 g of sodium chloride were added and stirred under a nitrogen atmosphere. Then, it heated at 70 degreeC, 2.5 g of potassium peroxide was added, and polymer seed particle | grains were obtained by performing reaction for 24 hours.

  5 g of the obtained polymer seed particles, 500 g of ion-exchanged water, and 100 g of a 5% by weight aqueous solution of polyvinyl alcohol were mixed and dispersed by ultrasonic waves, then placed in a separable flask and stirred to disperse the polymer seed particles. A liquid was obtained.

Production of polymer particles:
76 g of isobornyl acrylate, 114 g of polytetramethylene glycol diacrylate, 2.6 g of benzoyl peroxide, 10 g of triethanolamine lauryl sulfate and 130 g of ethanol are added to 1000 g of ion-exchanged water and stirred to obtain an emulsion. It was. The resulting emulsion was added to the polymer seed particle dispersion several times and stirred for 12 hours. Thereafter, 500 g of a 5% by weight aqueous solution of polyvinyl alcohol was added and reacted for 9 hours under a nitrogen atmosphere at 85 ° C. to obtain polymer particles (resin particles, average particle size: 3.0 μm).

Production of conductive particles:
The polymer particles were etched and washed with water. Next, polymer particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Polymer particles were added to a 0.5 wt% dimethylamine borane solution at pH 6 to obtain polymer particles to which palladium was attached.

  The polymer particles to which palladium was attached were stirred and dispersed in 300 mL of ion exchange water for 3 minutes to obtain a dispersion. Next, 1 g of nickel particle slurry (average particle diameter of nickel particles as a core material of 400 nm) was added to the dispersion over 3 minutes to obtain polymer particles to which the core material was adhered.

  A nickel layer was formed on the surface of the polymer particles by electroless plating using the polymer particles to which the core substance was attached. Conductive particles having a plurality of protrusions on the outer surface of the nickel layer were produced. The thickness of the nickel layer was 0.2 μm. The average height of the plurality of protrusions was 400 nm.

(2) Production of conductive material (conductive paste) 20 parts by weight of an epoxy compound (“EP-3300P” manufactured by ADEKA) which is a thermosetting compound and an epoxy compound (“EPICLON HP-” manufactured by DIC) 4032D ") 15 parts by weight, an amine adduct of imidazole as a thermosetting agent (" PN-F "manufactured by Ajinomoto Fine-Techno Co., Ltd.) and 1 part of 2-ethyl-4-methylimidazole as a curing accelerator Part and 20 parts by weight of alumina (average particle diameter 0.5 μm) as a filler were added so that the content in 100% by weight of conductive paste from which conductive particles can be obtained was 10% by weight. Then, the electrically conductive material was obtained by stirring for 5 minutes at 2000 rpm using a planetary stirrer.

(3) Preparation of connecting material (paste) 20 parts by weight of an epoxy compound (“EP-3300P” manufactured by ADEKA) that is a thermosetting compound and an epoxy compound (“EPICLON HP-4032D manufactured by DIC”) that is a thermosetting compound ] 15 parts by weight, 10 parts by weight of an amine adduct of imidazole as a thermosetting agent (“PN-F” manufactured by Ajinomoto Fine Techno Co.), and 1 part by weight of 2-ethyl-4-methylimidazole as a curing accelerator And 20 parts by weight of alumina (average particle size 0.5 μm) as a filler were blended to obtain a connection material.

(4) Production of Solar Cell Module A flexible printed circuit board (L / S = 50 μm / 50 μm) having aluminum wiring electrodes (L / S = 50 μm / 50 μm) on the surface was prepared. Moreover, the photovoltaic cell which has a copper electrode on the surface was prepared.

  A conductive material was selectively applied on the wiring electrode of the flexible printed board using a dispenser to partially form a conductive material layer having a thickness of 25 μm. All of the conductive material on the flexible printed circuit board was disposed on the wiring electrode. That is, the amount of the conductive material disposed on the wiring electrode was 100% by weight out of 100% by weight of the entire conductive material disposed on the flexible printed board.

  Next, the flexible printed circuit board and the solar battery cell were bonded together so that the aluminum wiring electrode of the flexible printed circuit board and the copper electrode of the solar battery cell were electrically connected by conductive particles. At this time, the flexible printed circuit board and the solar battery cell were placed in a vacuum laminate for 5 minutes in an atmosphere of 150 ° C. so as to be sandwiched between the glass substrate and the EVA film. The conductive material layer and the connection material layer were cured by heating during laminating to form a connection portion. A solar cell module was obtained in which the aluminum wiring electrode of the flexible printed board and the copper electrode of the solar cell were electrically connected by conductive particles.

(Examples 2 to 4)
Conductive particles were obtained in the same manner as in Example 1, except that the composition of the monomers at the time of production of the polymer particles was changed as shown in Table 2 below. A solar cell module was obtained in the same manner as in Example 1 using the obtained conductive particles.

(Example 5)
Conductive particles were obtained in the same manner as in Example 1 except that the average particle diameter of the core substance was changed and the average height of the plurality of protrusions of the conductive particles was changed to 50 nm. A solar cell module was obtained in the same manner as in Example 1 using the obtained conductive particles.

(Example 6)
Conductive particles were obtained in the same manner as in Example 1 except that the average particle diameter of the core substance was changed and the average height of the plurality of protrusions of the conductive particles was changed to 600 nm. A solar cell module was obtained in the same manner as in Example 1 using the obtained conductive particles.

(Example 7)
A solar cell module was obtained in the same manner as in Example 1 except that the electrode of the solar cell was changed from a copper electrode to an aluminum electrode.

(Comparative Example 1)
The polymer particles obtained in Example 1 were prepared. Using the polymer particles, a nickel layer was formed on the surface of the polymer particles by electroless plating to produce conductive particles. In Comparative Example 1, no protrusion was formed on the outer surface of the conductive portion of the conductive particles. A solar cell module was obtained in the same manner as in Example 1 using the obtained conductive particles.

(Comparative Example 2)
A solar cell module was obtained in the same manner as in Example 1 except that it was heat-cured at 150 ° C. for 5 seconds using a solder paste (“CP-300” manufactured by Hitachi Chemical Co., Ltd.).

(Comparative Example 3)
A solar cell module was obtained in the same manner as in Example 1 except that Ag paste (“DuPont Solaret PV410” manufactured by DuPont) was heat-cured at 150 ° C. for 30 minutes.

(Comparative Examples 4-7)
Conductive particles having a plurality of protrusions on the outer surface of the conductive portion are obtained in the same manner as in Example 1 except that the composition of the monomers at the time of preparing the polymer particles is changed as shown in Table 2 below. It was. A solar cell module was obtained in the same manner as in Example 1 using the obtained conductive particles.

(Example 8)
Conductive particles were obtained in the same manner as in Example 1 except that the average particle diameter of the polymer particles was changed to 10 μm when the polymer particles were produced. Example except that the obtained conductive particles were used, the electrode configuration when producing the solar cell module was changed to L / S = 300 μm / 300 μm, and the coating thickness of the conductive material was changed to 50 μm. In the same manner as in Example 1, a solar cell module was obtained.

Example 9
Conductive particles were obtained in the same manner as in Example 1 except that the average particle size of the polymer particles was changed to 20 μm when the polymer particles were produced. Example other than using the obtained conductive particles, changing the electrode configuration when producing a solar cell module to L / S = 300 μm / 300 μm, and changing the coating thickness of the conductive material to 75 μm In the same manner as in Example 1, a solar cell module was obtained.

(Example 10)
Conductive particles were obtained in the same manner as in Example 9, except that the average particle diameter of the core substance was changed and the average height of the plurality of protrusions of the conductive particles was changed to 200 nm. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 11)
Conductive particles were obtained in the same manner as in Example 9, except that the average particle diameter of the core substance was changed and the average height of the plurality of protrusions of the conductive particles was changed to 600 nm. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 12)
By using the polymer particles used in Example 1, without using nickel particle slurry, a nickel core material is generated by reaction in the plating bath, and electroless nickel plating is co-deposited together with the generated core material. Thus, conductive particles having a plurality of protrusions on the outer surface of the nickel layer were obtained. The thickness of the nickel layer was 0.1 μm. The average height of the plurality of protrusions was 250 nm. A solar cell module was obtained in the same manner as in Example 9 except that the obtained conductive particles were used.

(Example 13)
Conductive particles were obtained in the same manner as in Example 9 except that the composition of the monomers at the time of production of the polymer particles was changed as shown in Table 2 below. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 14)
Conductive particles were obtained in the same manner as in Example 9 except that the thickness of the nickel layer was changed to 800 nm. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 15)
Conductive particles were obtained in the same manner as in Example 9 except that the thickness of the nickel layer was changed to 105 nm. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 16)
The conductive particles obtained in Example 9 were subjected to gold plating using electroless gold plating to obtain conductive particles having a gold layer on the outermost surface and a plurality of protrusions on the outer surface of the gold layer. The total of the nickel layer and the gold layer was 0.25 μm (nickel layer 0.2 μm). The average height of the plurality of protrusions was 400 nm. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 17)
Conductive particles were obtained in the same manner as in Example 9, except that the conductive particle plating layer was changed to only the copper layer. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 18)
Conductive particles were obtained in the same manner as in Example 16 except that the outermost layer of the plated layer of conductive particles was changed to a palladium layer. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 19)
Conductive particles were obtained in the same manner as in Example 16 except that the nickel layer, which is a plating layer of conductive particles, was changed to a copper layer and the outermost layer, which was a plating layer, was changed to a palladium layer. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 20)
Conductive particles were obtained in the same manner as in Example 16 except that the outermost layer of the plated layer of conductive particles was changed to a silver layer. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 21)
Conductive particles were obtained in the same manner as in Example 9 except that the composition of the monomers at the time of production of the polymer particles was changed as shown in Table 2 below. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 22)
Conductive particles were obtained in the same manner as in Example 9 except that the thickness of the nickel layer was changed to 1333 nm. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 23)
Conductive particles were obtained in the same manner as in Example 9 except that the thickness of the nickel layer was changed to 89 nm. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Example 24)
Conductive particles were obtained in the same manner as in Example 9 except that the composition of the monomers at the time of production of the polymer particles was changed as shown in Table 2 below. Using the obtained conductive particles, a solar cell module was obtained in the same manner as in Example 9.

(Evaluation)
(1) Compression recovery rate of conductive particles The compression recovery rate when the obtained conductive particles were compressed by 10% and the compression recovery rate when compressed by 50% were determined by the above-described method using a micro compression tester (Fischer Corporation). It was measured using “Fischer Scope H-100”).

  Conductive particles were sprayed on the sample stage. For each dispersed conductive particle, using a micro-compression tester, 10% of the conductive particles at 25 ° C. in the center direction of the conductive particles on the end surface of a cylindrical (diameter 50 μm, made of diamond) smooth indenter Alternatively, a load (reverse load value) was applied until 50% compression deformation occurred. Thereafter, unloading was performed up to the load value for origin (0.40 mN). The load-compression displacement during this period was measured, and the compression recovery rate was determined from the above formula.

(2) Initial energy conversion efficiency The energy conversion efficiency in the obtained solar cell module was measured. The initial energy conversion efficiency was determined according to the following criteria.

[Evaluation criteria for initial energy conversion efficiency]
XX: Energy conversion efficiency exceeds 22% XX: Energy conversion efficiency exceeds 20% and 22% or less XX: Energy conversion efficiency exceeds 18% and 20% or less O: Energy conversion efficiency is 16% 18% or less △: Energy conversion efficiency exceeds 14% and 16% or less ×: Energy conversion efficiency is 14% or less

(3) Energy conversion efficiency after reliability test About the obtained solar cell module, cycle test of −40 ° C. to 90 ° C., holding time 30 minutes, temperature change rate 87 ° C./hour is performed 200 cycles with a cycle tester. After doing, energy conversion efficiency was measured. The energy conversion efficiency after the reliability test was determined according to the following criteria.

[Evaluation criteria for energy conversion efficiency after reliability test]
XX: Energy conversion efficiency exceeds 22% XX: Energy conversion efficiency exceeds 20% and 22% or less XX: Energy conversion efficiency exceeds 18% and 20% or less O: Energy conversion efficiency is 16% 18% or less △: Energy conversion efficiency exceeds 14% and 16% or less ×: Energy conversion efficiency is 14% or less

  The results are shown in Table 1 below. The composition is shown in Table 2 below.

  In Example 1, a copper electrode was used for the solar battery cell, and in Example 7, an aluminum electrode was used for the solar battery cell. In Example 1 and Example 7, the evaluation results based on the above criteria for the initial energy conversion efficiency and the energy conversion efficiency after the reliability test were the same, but in the aluminum electrode, the conductivity provided with the configuration of the present invention. By using the particles, it was confirmed that the effects of the present invention were more effectively exhibited as compared with the case of using conductive particles not having the configuration of the present invention. In addition, the number of protrusions per single particle in Examples 1 to 24 and Comparative Examples 4 to 7 was about 300 to about 900.

DESCRIPTION OF SYMBOLS 1 ... Solar cell module 2 ... Flexible printed circuit board 2a ... Wiring electrode 3 ... Solar cell 3a ... Electrode 4 ... Connection part 4A ... Conductive material 4B ... Connection material 5 ... Back sheet 6 ... Sealing material 21, 21A, 21B ... Conductivity 21a, 21Aa, 21Ba ... projection 22 ... base particle 23, 23A, 23B ... conductive portion 23a, 23Aa, 23Ba ... projection 23Bx ... first conductive portion 23By ... second conductive portion 24 ... core substance

Claims (8)

Conductive particles used for back contact solar cell modules,
Substrate particles,
A conductive portion disposed on the surface of the base particle,
A plurality of protrusions on the outer surface of the conductive portion;
The compression recovery rate when compressed by 10% is 40% or more and 80% or less,
Conductive particles for a solar cell module of a back contact system, wherein the compression recovery rate when compressed by 50% is 3% or more and 18% or less.   2. The conductive particle for a back contact solar cell module according to claim 1, wherein an average height of the plurality of protrusions is 50 nm or more and 600 nm or less.   3. The conductive particle for a back contact solar cell module according to claim 1, wherein a ratio of an average height of the plurality of protrusions to a thickness of the conductive portion is 0.5 or more and 4.0 or less.   A flexible printed circuit board having a wiring electrode on its surface or a resin film having a wiring electrode on its surface, and a solar battery cell having an electrode on its surface, used to electrically connect the wiring electrode and the electrode. Item 4. The conductive particle for a solar cell module according to any one of Items 1 to 3.   The back contact solar cell module according to claim 4, wherein the wiring electrode of the flexible printed circuit board or the resin film is an aluminum wiring electrode, or the electrode of the solar battery cell is an aluminum electrode. Conductive particles.   The electrically conductive material for solar cell modules of a back contact system containing the electroconductive particle for solar cell modules of a back contact system of any one of Claims 1-5, and binder resin.   The conductive material for back contact solar cell modules according to claim 6, wherein the binder resin contains a thermosetting compound and a thermosetting agent. A flexible printed circuit board having wiring electrodes on the surface or a resin film having wiring electrodes on the surface;
A solar battery cell having an electrode on its surface;
A connecting portion connecting the flexible printed circuit board or the resin film and the solar battery cell;
The said connection part is formed with the electroconductive material for solar cell modules of a back contact system of the back contact system solar cell module of any one of Claims 1-5, and binder resin. And
A back contact type solar cell module in which the wiring electrode and the electrode are electrically connected by the conductive particles.

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