WO2017010385A1 - Solar module, solar module manufacturing method, and solar cell wiring method - Google Patents
Solar module, solar module manufacturing method, and solar cell wiring method Download PDFInfo
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- WO2017010385A1 WO2017010385A1 PCT/JP2016/070070 JP2016070070W WO2017010385A1 WO 2017010385 A1 WO2017010385 A1 WO 2017010385A1 JP 2016070070 W JP2016070070 W JP 2016070070W WO 2017010385 A1 WO2017010385 A1 WO 2017010385A1
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- coating layer
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- solar cell
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- solar
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
- H10F19/90—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a solar cell module, a method for manufacturing a solar cell module, and a method for wiring solar cells.
- This application includes Japanese Patent Application No. 2015-139211 filed on July 10, 2015, Japanese Patent Application No. 2015-218976 filed on November 6, 2015, and March 18, 2016. Claims priority based on the filed Japanese Patent Application No. 2016-054790, the entire contents of which are incorporated herein by reference.
- Solar cell modules that convert light energy into electric power are widely used as clean power generators.
- the solar cell module includes a solar cell and a wiring connected to the cell, and the power generated in the cell through the wiring is configured to be supplied to the outside.
- Patent documents 1 to 8 are cited as documents disclosing this type of prior art.
- Patent Documents 1 to 6 relate to a solar cell module in which an n-type electrode is partially disposed on the front surface side of the solar battery cell and a p-type electrode is disposed on the back surface side.
- the present invention relates to a solar cell module that employs a back contact method in which both electrodes are arranged on the back side.
- the structures disclosed in Patent Documents 1 and 2 require that the wiring of solar cells must be individually joined using solder etc. It takes time and there is a limit to improving productivity.
- heating is performed at the time of bonding, such as solder bonding, the characteristics of the cell may be reduced by heating, or the cell may be warped or cracked.
- Solder joints also have a problem of flux contamination.
- the solar cell modules disclosed in Patent Documents 3 and 4 also have the same problems as Patent Documents 1 and 2 because the wires serving as the conductive paths are soldered. Moreover, the said wire is arrange
- the solar cell module described in Patent Document 5 is provided with a pair of sealing sheets having metal wiring on the surface, and sandwiching a plurality of solar cells with the pair of sealing sheets, the metal wiring and the solar cells. Are pressed and heated to electrically connect a plurality of solar cells without requiring solder bonding.
- the conduction between the upper and lower metal wirings includes factors such as securing the contact area and accuracy of alignment, and the conduction state (contact state) of the metal wirings may be impaired by the flow of the sealing resin or the like. is there. These cause deterioration in performance over time, that is, decrease in durability, as a reduction in current collection efficiency and wiring defects.
- Patent Document 6 although the connection reliability is improved by using a conductive film or the like for joining the upper and lower metal wirings, the joint point between the upper and lower metal wirings is a weak point in strength. There are structural limits to improving yield. Thus, with the conventional technical level, it was impossible to achieve both productivity and durability.
- the present invention has been created in view of the above circumstances, and an object thereof is to provide a solar cell module having excellent productivity and improved durability. Another related object is to provide a method for manufacturing such a solar cell module and a method for wiring solar cells.
- a solar cell module provided with a photovoltaic cell.
- This solar cell module includes a conductive portion.
- the conductive portion is partially disposed on the back surface of the solar battery cell.
- the solar cell module further includes a coating layer.
- the covering layer covers the back surface of the solar battery cell over the conductive portion and adheres to the back surface of the solar battery cell.
- the said coating layer is partially arrange
- the coating layer covering the conductive portion from the outside of the cell back surface favorably maintains the contact state between the cell back surface and the conductive portion.
- the coating layer covers the conductive part and is adhered to the back surface of the cell outside the conductive part, the presence of the coating layer makes it possible to use a sealing resin that is usually used for sealing solar cells. Events that adversely affect the contact state between the cell back surface and the conductive portion are prevented.
- the coating layer partially covers the cell back surface, there is a coating layer non-arranged region on the back surface. By providing the covering layer non-arrangement region, the durability of the solar cell module can be further improved as compared with the configuration without the covering layer non-arrangement region.
- the sealing resin usually used for sealing the solar battery cell flows and contacts the back surface of the solar battery cell in the coating layer non-arrangement region, and then adheres to the back surface of the cell by curing (curing adhesion) ) That is, by providing the coating layer non-arrangement region, the contact state between the cell back surface and the conductive portion can be further stabilized by utilizing the action such as the fixing of the sealing resin. As a result, the durability of the solar cell module is improved. ADVANTAGE OF THE INVENTION According to this invention, the solar cell module which is excellent in productivity and can improve durability is provided.
- wiring by contact between the front and back surfaces of the solar battery cell (more specifically, the front and back electrodes of the solar battery cell) and the conductive portion (for example, conductive wire), solder bonding or conductive May be referred to as “physical contact” to distinguish from bonding using bonding means such as adhesive (direct bonding means; also referred to as conductive bonding means; the same shall apply hereinafter).
- Physical contact refers to a contact state or a contact method in which conduction is achieved by contact only by contact without using an adhesive means.
- the coating layer disclosed here may have adhesiveness, it plays the role of assisting and holding the physical contact, and is understood to be different from the bonding means.
- the “solderless wiring” that does not use a low melting point metal such as solder as described above is a typical example of physical contact wiring.
- a solar cell module constructed by such physical contact type wiring is referred to as a physical contact type solar cell module. Since the physical contact type solar cell module can be conducted without heating, cell characteristics can be prevented from being deteriorated due to heating. Moreover, according to the solar cell module that performs solderless wiring (solderless solar cell module), not only the above-mentioned flux contamination can be avoided, but also problems such as leaching and cratering caused by solder bonding can be solved.
- the conductive portion is composed of a plurality of conductive wires.
- the coating layer is composed of a plurality of strip-shaped coating members. Further, in the back surface of the solar battery cell, one of the plurality of belt-shaped covering members covers one conductive wire of the plurality of conductive wires from the outside of the back surface of the solar battery cell, And it adhere
- the coating layer is an adhesive sheet.
- the cell back surface and the conductive portion (for example, a plurality of conductive wires) can be preferably kept conductive by physical contact using the pressure-sensitive adhesive properties of the pressure-sensitive adhesive sheet.
- the adhesive sheet adheres to the back surface of the cell on the outside of the conductive portion (for example, both outer sides of the plurality of conductive lines), and thus prevents, for example, the flow of the sealing resin toward the conductive portion, And the contact state between the conductive portion (for example, a plurality of conductive wires) are better maintained.
- the pressure-sensitive adhesive sheet is a substrate-less pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet includes a base material layer and a pressure-sensitive adhesive layer disposed on at least one surface of the base material layer. By comprising in this way, the durability of the said wiring can be further improved using the rigidity of a base material layer, obtaining the wiring excellent in connection reliability using the adhesion characteristic by an adhesive layer. .
- a sealing resin is disposed on the back surface of the solar battery cell so as to cover the back surface through the coating layer.
- the sealing resin is bonded to the back surface of the solar battery cell in the coating layer non-arrangement region.
- the method of manufacturing a solar cell module includes: a step of partially disposing a conductive portion on a back surface of a solar cell; a step of adhering a covering layer to the back surface of the solar cell on which the conductive portion is disposed; including. Moreover, in the adhesion step of the covering layer, the covering layer is partially disposed on the back surface of the solar battery cell. According to said method, a solar cell module with high contact reliability can be efficiently produced using adhesion
- the wiring method of a photovoltaic cell includes: partially disposing a conductive portion on the back surface of the solar cell; adhering a coating layer over the conductive portion on the back surface of the solar cell on which the conductive portion is disposed; ;including. Moreover, in the adhesion step of the covering layer, the covering layer is partially disposed on the back surface of the solar battery cell. According to said method, the wiring of the photovoltaic cell excellent in durability can be efficiently implement
- FIG. 3 is a view in the direction of arrow III in FIG. 2.
- FIG. 4 is a cross-sectional view taken along line IV-IV of the solar battery cell of FIG.
- It is typical sectional drawing which expands and shows the electroconductive part and coating layer in the photovoltaic cell lower surface which concerns on 2nd Embodiment.
- It is a typical top view of the solar cell module for a test (reference example) used for the heat cycle test.
- 6 is a graph showing the results of a heat cycle test of Reference Example 1.
- 6 is a graph showing the results of a heat cycle test of Reference Example 2.
- 3 is a graph showing the results of a heat cycle test in Example 1-1. It is a graph which shows the result of the heat cycle test of Example 1-2.
- 6 is a graph showing the results of a heat cycle test in Example 2-1. It is a graph which shows the result of the heat cycle test of Example 2-2.
- FIG. 1 is a cross-sectional view schematically showing a main part of the solar cell module according to the first embodiment.
- a solar cell module 1 includes a plurality of solar cells including solar cells 10a, 10b, 10c, and 10d, a sealing resin 150 that covers (surrounds) the plurality of solar cells, and a sealing resin.
- the front surface covering member 160 and the back surface covering member 170 are disposed so as to sandwich the stop resin 150 therebetween.
- a plurality of solar cells including the solar cells 10a, 10b, 10c, and 10d are arranged in a straight line at a predetermined interval to constitute a solar cell group.
- n-type electrode front electrode
- p-type electrode rear surface
- lower surface back surface
- Electrode Electrode
- the upper and lower sides of the solar battery cell in this specification correspond to the front and back of the solar battery cell, and thus correspond to the front and back (upper and lower) of the solar battery module.
- the surface of the solar cell module is a light incident surface (also referred to as a light receiving surface).
- the top and bottom may not necessarily be strictly up and down, so the top and bottom of the solar cells are not limited to exact top and bottom, and are understood to indicate relative positional relationships.
- crystalline Si cells (approximately 15.6 cm ⁇ 15.6 cm) are used as the solar cells 10a, 10b, 10c, and 10d, and an ethylene-vinyl acetate copolymer (EVA) is used as the sealing resin 150.
- EVA ethylene-vinyl acetate copolymer
- a glass plate having a thickness of 3.2 mm is used as the surface covering member 160, and a commercially available back sheet is used as the back surface covering member 170.
- two adjacent solar cells (for example, the solar cell 10a and the solar cell 10b) are electrically connected by one conductive portion 30.
- One of the conductive portions 30 is partially disposed on the surface of the solar battery cell 10a, and extends from the upper surface of the solar battery cell 10a to the lower surface of the solar battery cell 10b.
- the conductive part 30 is also partially disposed on the back surface of the solar battery cell 10b. More specifically, the one conductive portion 30 is disposed on the upper surface of the solar battery cell 10a above the solar battery group, and passes through the space between the solar battery cell 10a and the solar battery cell 10b. It moves below the solar cell group and is disposed on the lower surface of the solar cell 10b.
- the conductive portion 30 extends from the end of the solar cell 10a (the end opposite to the solar cell 10b side) to the end of the solar cell 10b (the end opposite to the solar cell 10a side), It contacts (specifically abuts) the upper surface of the solar battery cell 10a and the lower surface of the solar battery cell 10b.
- the electroconductive part 30 is one member and continues from the upper surface of the solar cell 10a to the lower surface of the solar cell 10b, the connection reliability is high and the durability is also excellent.
- the first coating layer 50 is disposed above the solar cell group. Specifically, one first covering layer 50 is disposed only above one solar battery cell 10a, and is not disposed above another solar battery cell (for example, solar battery cell 10b). A different first covering layer 50 is disposed above another solar battery cell (for example, solar battery cell 10b). Moreover, the 1st coating layer 50 is arrange
- the 1st coating layer 50 is a transparent resin layer, and the surface at the side of a photovoltaic cell has adhesiveness at least.
- the 1st coating layer 50 of this embodiment is a transparent adhesive layer (base material-less adhesive sheet).
- the first covering layer 50 is in contact with the upper surface of the solar battery cell 10 a from above the conductive portion 30 in the non-existing region of the conductive portion 30.
- the conductive portion 30 is reliably and stably brought into contact (specifically, contacted) with the upper surface of the solar battery cell 10a. Details thereof will be described later.
- the first coating layer 50 is not limited to the adhesive layer, but is itself non-adhesive and adheres to the upper surface of the solar battery cell 10a using a known adhesive means such as an adhesive or a pressure-sensitive adhesive. You may do.
- the second coating layer 60 is disposed in the solar cell module 1 below the solar cell group. Specifically, one second covering layer 60 is disposed only below one solar battery cell 10b, and is disposed below other solar battery cells (for example, solar battery cells 10a and 10c). Absent. Different second coating layers 60 are arranged below other solar cells (for example, solar cells 10a and 10c). Moreover, the 2nd coating layer 60 is arrange
- the second coating layer 60 is a transparent pressure-sensitive adhesive layer (baseless pressure-sensitive adhesive sheet).
- the second coating layer 60 is in contact with the lower surface of the solar battery cell 10 b from below the conductive portion 30 in the non-existing region of the conductive portion 30. Thereby, the electroconductive part 30 is made to contact the lower surface of the photovoltaic cell 10b reliably and stably. Details thereof will be described later.
- positioned at the back surface of a photovoltaic cell does not need to be transparent.
- FIG. 2 is a schematic side view showing an enlarged wiring state of two solar cells constituting the solar cell module according to the first embodiment.
- 3 is a view in the direction of the arrow III in FIG.
- FIG. 4 is a cross-sectional view taken along the line IV-IV of the solar battery cell of FIG.
- the wiring in the solar battery module 1 will be described more specifically by taking the wiring of the solar battery cells 10a and 10b as an example. 2 to 4, for convenience of explanation, the conductive portion and the second covering layer disposed on the lower surface of the solar battery cell 10a, and the conductive portion and the first covering layer disposed on the upper surface of the solar battery cell 10b are shown. Omitted.
- one conductive portion 30 is composed of a plurality of conductive wires 40 extending from the upper surface of the solar battery cell 10a to the lower surface of the solar battery cell 10b.
- the plurality of conductive lines 40 extend along the arrangement direction of the solar cells 10a and 10b, and are arranged at intervals. These conductive wires 40 are arranged in a straight line so as to be parallel to each other.
- substantially both ends of the solar cells 10a and 10b ends of the solar cells 10a (solar cells) From the end opposite to the 10b side) to the end of the solar battery cell 10b (the end opposite to the solar battery 10a side).
- the plurality of conductive lines 40 are linearly arranged on the upper surface of the solar battery cell 10a and the lower surface of the solar battery cell 10b so as to be parallel to each other with a space therebetween.
- a copper wire having a width of 0.8 mm and a thickness of 0.25 mm is used as the conductive wire 40.
- the first coating layer 50 covers the plurality of conductive wires 40 as the conductive portion 30 and is bonded to the upper surface of the solar battery cell 10 a through the conductive portion 30. That is, the lower surface (the surface on the solar cell side) of the first coating layer 50 is bonded to the conductive portion 30 (specifically, the plurality of conductive wires 40) and is not bonded to the conductive portion 30. It adheres to the upper surface of the solar battery cell 10a. Thus, the conductive portion 30 is reliably and stably brought into contact (specifically, contacted) with the upper surface of the solar battery cell 10a. Moreover, the 1st coating layer 50 is partially arrange
- the coating layer non-arrangement region 12a exists on the upper surface of the solar battery cell 10a.
- the sealing resin 150 before curing flows into the coating layer non-arrangement region 12a and cures after contacting the upper surface of the solar battery cell 10a.
- the contact state between the solar battery cell 10a and the conductive portion 30 (specifically, the plurality of conductive wires 40) is more stable due to the adhesion by the first coating layer 50 and the fixing (curing adhesion) of the sealing resin 150.
- the conductive portion 30 does not exist in the coating layer non-arrangement region 12a.
- the first covering layer 50 includes a plurality of strip-shaped covering members 52.
- the number of these strip-shaped covering members 52 is the same as that of the conductive wires 40, and each of them is bonded to the upper surface of the solar battery cell 10a through the conductive wire 40 disposed on the upper surface of the solar battery cell 10a.
- the width of each band-shaped covering member 52 is larger than the width of the conductive wire 40.
- the length of each strip-shaped covering member 52 is substantially the same as the length of one side of the solar battery cell 10a.
- Each of the strip-shaped covering members 52 is linearly disposed on the upper surface of the solar battery cell 10a so as to overlap each conductive line 40 and to be parallel to each other.
- Each strip-shaped covering member 52 covers each of the conductive wires 40 arranged on the upper surface of the solar battery cell 10a from above (outside the upper surface) of the solar battery cell 10a, and the width of the conductive wire 40. It is bonded to the upper surface of the solar battery cell 10a on both outer sides in the direction. Further, the plurality of strip-shaped covering members 52 are arranged at intervals. Therefore, a strip-shaped coating layer non-arrangement region 12 a exists between the plurality of strip-shaped coating members 52. By arranging the first coating layer 50 in this way, a wiring excellent in connection reliability is preferably realized.
- the band-shaped covering member 52 constituting the first covering layer 50 is a transparent adhesive layer having a width of about 5 to 10 mm and a thickness of about 0.05 mm in this embodiment, but is not limited thereto.
- the width W1 of the strip-shaped covering member 52 is suitably 1 mm or more larger than the width Wc of the conductive wire 40.
- the difference (W1 ⁇ Wc) between W1 and the width Wc of the conductive wire 40 is preferably 2 mm or more, more preferably 3 mm or more (for example, 7 mm or more).
- the ratio (W1 / Wc) of the width W1 of the band-shaped covering member 52 to the width Wc of the conductive wire 40 is appropriately larger than 1, preferably 3 or more, more preferably 5 or more (for example, 10 Above). Further, from the viewpoint of durability, productivity, translucency, etc., the difference (W1 ⁇ Wc) is suitably about 20 mm or less, preferably 15 mm or less, more preferably 10 mm or less, and still more preferably. It is 7 mm or less (for example, 5 mm or less).
- the ratio (W1 / Wc) of the width W1 of the band-shaped covering member 52 to the width Wc of the conductive wire 40 is suitably 20 or less, preferably 15 or less (for example, 8 or less).
- the width W1 of the belt-shaped covering member 52 is suitably 1.5 mm or more, preferably 3 mm or more, more preferably 4 mm or more (for example, 8 mm or more), and the width W1 is It is suitable that it is 25 mm or less, preferably 18 mm or less, more preferably 12 mm or less (for example, 7 mm or less).
- the interval between the strip-shaped covering members 52 is preferably approximately the same as the interval between the conductive wires 40 arranged on the upper surface of the solar battery cell 10a, but is not limited thereto.
- the interval between the strip-shaped covering members 52 is preferably 0.3 cm or more, more preferably 0.8 cm or more, and further preferably 1.5 cm or more.
- the interval is preferably less than 4.0 cm, more preferably less than 3.0 cm, and even more preferably 2.8 cm or less.
- interval is a pitch and points the distance between the centerlines in the width direction of the strip
- the width of each of the strip-shaped coating layer non-arranged regions 12a existing between the strip-shaped coating members 52 of the first coating layer 50 is a viewpoint of improving durability. Accordingly, the thickness is suitably 1 mm or more, preferably 3 mm or more, more preferably 5 mm or more, still more preferably 8 mm or more, and particularly preferably 10 mm or more (for example, 12 mm or more, further 15 mm or more).
- the width of each of the band-shaped coating layer non-arrangement regions 12a is suitably about 25 mm or less, preferably about 22 mm or less (for example, 16 mm or less). It is.
- the area ratio of the coating layer non-arrangement region 12a on the upper surface of the solar battery cell is not limited to a specific ratio, and is appropriately about 10% or more and is durable. From the viewpoints of lightness and translucency, it is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more, and particularly preferably 60% or more (for example, 70% or more). From the viewpoint of covering the conductive portion 30 with the first coating layer 50, the area ratio is suitably about 90% or less, preferably 85% or less (for example, 65% or less). In another aspect, the area ratio is preferably about 75% or less (for example, 70% or less), and may be 60% or less.
- the second covering layer 60 covers the plurality of conductive wires 40 as the conductive portion 30 and adheres to the lower surface of the solar battery cell 10b through the conductive portion 30. ing. That is, the upper surface (surface on the solar cell side) of the second coating layer 60 is bonded to the conductive portion 30 (specifically, the plurality of conductive wires 40) and is not bonded to the conductive portion 30. It adheres to the lower surface of the solar battery cell 10b. As a result, the conductive portion 30 is reliably and stably brought into contact (specifically, contacted) with the upper surface of the solar battery cell 10b.
- the 2nd coating layer 60 is partially arrange
- the sealing resin 150 before curing flows into the coating layer non-arrangement region 12b and cures after contacting the lower surface of the solar battery cell 10b. Thereby, the contact state between the solar battery cell 10b and the conductive wire 40 is further stabilized by the adhesion by the second coating layer 60 and the fixing (curing adhesion) of the sealing resin 150. Since the lower surface of the conductive portion 30 is covered with the second coating layer 60, the conductive portion 30 does not exist in the coating layer non-arrangement region 12b.
- the second covering layer 60 includes a plurality of strip-shaped covering members 62.
- the number of the strip-shaped covering members 62 is the same as the number of the conductive wires 40, and the lower surface of the solar battery cell 10b is bonded to the lower surface of the solar battery cell 10b through the conductive wire 40 arranged on the lower surface.
- the width of each band-shaped covering member 62 is larger than the width of the conductive wire 40.
- the length of each strip-shaped covering member 62 is substantially the same as the length of one side of the solar battery cell 10b.
- Each of the strip-shaped covering members 62 is linearly arranged on the lower surface of the solar battery cell 10b so as to be parallel to each other while overlapping with the respective conductive wires 40.
- Each strip-shaped covering member 62 covers each of the conductive wires 40 arranged on the lower surface of the solar battery cell 10b from below (outside the lower surface) of the solar battery cell 10b, and the width of the conductive wire 40. It is bonded to the lower surface of the solar battery cell 10b on both outer sides in the direction. Further, the plurality of strip-shaped covering members 62 are arranged at intervals. Therefore, a strip-shaped coating layer non-arrangement region 12 b exists between the plurality of strip-shaped coating members 62. By arranging the second coating layer 60 in this way, a wiring excellent in connection reliability is preferably realized.
- the band-shaped covering member 62 constituting the second covering layer 60 is a transparent adhesive layer having a width of about 5 to 10 mm and a thickness of about 0.05 mm in this embodiment, as in the case of the first covering layer 50.
- the present invention is not limited to this.
- the width W2 of the strip-shaped covering member 62 is suitably 1 mm or more larger than the width Wc of the conductive wire 40.
- the difference (W2 ⁇ Wc) between W2 and the width Wc of the conductive wire 40 is preferably 2 mm or more, more preferably 3 mm or more (for example, 7 mm or more).
- the ratio (W2 / Wc) of the width W2 of the strip-shaped covering member 62 to the width Wc of the conductive wire 40 is appropriately larger than 1, preferably 3 or more, more preferably 5 or more (for example, 10 Above).
- the difference (W2 ⁇ Wc) is suitably about 20 mm or less, preferably 15 mm or less, more preferably 10 mm or less, Preferably it is 7 mm or less (for example, 5 mm or less).
- the ratio (W2 / Wc) of the width W2 of the strip-shaped covering member 52 to the width Wc of the conductive wire 40 is appropriately 20 or less, and preferably 15 or less (for example, 8 or less).
- the width W2 of the band-shaped covering member 62 is suitably 1.5 mm or more, preferably 3 mm or more, more preferably 4 mm or more (for example, 8 mm or more), and the width W2 is It is suitable that it is 25 mm or less, preferably 18 mm or less, more preferably 12 mm or less (for example, 7 mm or less).
- coated member 62 is comparable as the space
- the interval between the strip-shaped covering members 62 is preferably 0.3 cm or more, more preferably 0.8 cm or more, and further preferably 1.5 cm or more.
- the interval is preferably less than 4.0 cm, more preferably less than 3.0 cm, and even more preferably 2.8 cm or less.
- interval is a pitch and points out the distance between the centerlines in the width direction of the strip
- the width of each of the strip-shaped coating layer non-arrangement regions 12b existing between the strip-shaped coating members 62 of the second coating layer 60 is a viewpoint of improving durability.
- the thickness is suitably 1 mm or more, preferably 3 mm or more, more preferably 5 mm or more, still more preferably 8 mm or more, and particularly preferably 10 mm or more (for example, 12 mm or more, further 15 mm or more).
- the width of each of the band-shaped coating layer non-arrangement regions 12b is suitably about 25 mm or less, preferably about 22 mm or less (for example, 16 mm or less). It is.
- the area ratio of the coating layer non-arrangement region 12b on the lower surface of the solar battery cell is not limited to a specific ratio, and is appropriately about 10% or more, and is durable. From the viewpoint of improving the properties, it is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more, and particularly preferably 60% or more (for example, 70% or more). From the viewpoint of covering the conductive portion 30 with the second coating layer 60, the area ratio is suitably about 90% or less, preferably 85% or less (for example, 65% or less). In another aspect, the area ratio is preferably about 75% or less (for example, 70% or less), and may be 60% or less.
- the solar battery module 1 is, from above, the surface coating member 160 / the sealing resin 150 / the first coating layer 50 / the conductive part (surface side conductive part) 30 / solar battery cell.
- 10a / conductive portion (back side conductive portion) 30 / second coating layer 60 / sealing resin 150 / back surface covering member 170 has a cross-sectional structure laminated in this order.
- the conductive portion (surface-side conductive portion) 30 and the first covering layer 50 are partially stacked on the upper surface of the solar battery cell 10a.
- the entire conductive portion (surface-side conductive portion) 30 is covered with the first coating layer 50 from above.
- the conductive part (back side conductive part) 30 and the second coating layer 60 are partially laminated on the lower surface of the solar battery cell 10a.
- the entire conductive portion (back side conductive portion) 30 is covered with the second covering layer 60 from below.
- the solar cell module 1 is the surface coating member 160 / sealing resin 150 / first coating layer 50 / conductive part (surface side conductive part) 30 / solar battery cell from upper direction.
- 10b / conductive portion (back side conductive portion) 30 / second coating layer 60 / sealing resin 150 / back surface covering member 170 has a cross-sectional structure in which the layers are laminated in this order. In the cross-sectional structure, the conductive portion (surface-side conductive portion) 30 and the first covering layer 50 are partially stacked on the upper surface of the solar battery cell 10b.
- the entire conductive portion (surface-side conductive portion) 30 is covered with the first coating layer 50 from above.
- the conductive part (back side conductive part) 30 and the second coating layer 60 are partially laminated on the lower surface of the solar battery cell 10b.
- the entire conductive portion (back side conductive portion) 30 is covered with the second coating layer 60 from below.
- the solar cell module 1 is laminated in this order from the top to the surface covering member 160 / sealing resin 150 / conductive portion 30 / sealing resin 150 / back surface covering member 170. Having a cross-sectional structure.
- the conductive portion (front surface side conductive portion) 30 disposed on the front surface (upper surface) side of the solar cell 10a and the conductive portion (back surface) disposed on the back surface (lower surface) side of the solar cell 10a.
- (Side conductive portion) 30 is a separate member.
- the electroconductive part (surface side electroconductive part) 30 arrange
- the electroconductive part (back surface side electroconductive part) 30 arrange
- the front surface side conductive portion 30 in the solar battery cell 10a and the back surface side conductive portion 30 in the solar battery cell 10b are one continuous member.
- This method includes a step of partially disposing the conductive portion 30 on the lower surface of the solar battery cell 10b; and conducting a coating layer (second coating layer 60) on the lower surface of the solar battery cell 10b on which the conductive portion 30 is disposed. Adhering over part 30. Further, in the bonding step of the coating layer (second coating layer 60), the coating layer (second coating layer 60) is partially disposed on the lower surface of the solar battery cell 10b.
- solar cells 10a and 10b are prepared. And the photovoltaic cell 10b is set so that the lower surface (back surface) faces upwards, and the plurality of conductive lines 40 as the conductive portion 30 are arranged on the lower surface (back surface). At this time, a part of the conductive portion 30 (specifically, a part in the longitudinal direction of the conductive wire 40) is disposed on the lower surface (back surface) of the solar battery cell 10b.
- the arrangement of the conductive wire 40 can be performed using a known means such as a dispenser.
- the conductive portion 30 (the plurality of conductive lines 40) is partially arranged on the lower surface (back surface) of the solar battery cell 10b.
- the second coating layer 60 is adhered to the lower surface (rear surface) of the solar battery cell 10 b on which the conductive wire 40 as the conductive portion 30 is disposed through the conductive portion 30 so as to overlap the conductive portion 30.
- the second covering layer 60 of this embodiment is composed of the same number of strip-shaped covering members 62 as the conductive lines 40, and each width is larger than the width of the conductive lines 40.
- Supply of the 2nd coating layer 60 (arrangement of beltlike covering member 62) can be performed using publicly known means, such as a dispenser.
- the adhesive sheet is used as the second coating layer 60
- the second coating layer 60 itself adheres to the solar battery cell 10b.
- the present invention is not limited to this, and the second coating layer 60 is not adhered.
- the second coating layer 60 may be adhered to the lower surface (rear surface) of the solar battery cell 10b using a known adhesion means such as an adhesive or a pressure-sensitive adhesive. The same applies to the first covering layer 50 described later.
- the said method is the process of arrange
- the solar battery cell 10a disposed adjacent to the solar battery cell 10b is set so that its upper surface (light receiving surface) faces upward. Then, the solar cell 10b to which a part of the conductive wire 40 in the longitudinal direction is attached is turned upside down, and the remaining portion of the conductive wire 40 is arranged on the upper surface (light receiving surface) of the solar cell 10a.
- the first coating layer 50 is adhered to the upper surface (light receiving surface) of the solar battery cell 10 a on which the conductive wire 40 is disposed so as to overlap with the conductive portion 30.
- the first covering layer 50 of this embodiment is composed of the same number of strip-like covering members 52 as the conductive lines 40, as with the second covering layer 60, and each width is larger than the width of the conductive lines 40. large.
- the supply of the first covering layer 50 (arrangement of the belt-like covering member 52) can be performed using a known means such as a dispenser, as in the case of the second covering layer 60.
- a known means such as a dispenser, as in the case of the second covering layer 60.
- solar cells 10c, 10d By repeating this operation by applying it to other solar cells (for example, solar cells 10c, 10d), the upper and lower wirings of the plurality of solar cells 10a, 10b, 10c, 10d as shown in FIG. 1 are completed. .
- the above wiring does not need to be joined by an adhesive means such as solder. Therefore, it is possible to avoid defects (typically cell warpage or cracking, characteristic deterioration, flux contamination) due to solder bonding.
- the solderless solar cell module not only can avoid the above-mentioned flux contamination, but can also solve problems such as leaching and cratering caused by solder joints.
- the upper and lower wirings of the two solar cells (for example, the solar cells 10a and 10b) are provided with the conductive portion 30 (for example, the conductive wire 40) and the covering layers (the first covering layer 50 and the second covering layer 60). Because it is realized only with, it is excellent in wiring workability.
- the contact state of the conductive portion 30 to the solar battery cell (for example, the solar battery cell 10a, 10b) having the above-described configuration has a higher degree of freedom compared to a fixing method such as solder bonding, so it has excellent impact resistance and durability. Also excellent. Furthermore, in this embodiment, since the 1st coating layer 50 and the 2nd coating layer 60 are adhesive layers which have adhesiveness, the photovoltaic cell 10a over the electroconductive part 30 (specifically conductive wire 40), Adhere to 10b. Therefore, a separate bonding means such as a conductive adhesive is not necessary, and the wiring workability is excellent also in this respect.
- the solar cells 10a, 10b, 10c, and 10d (wired solar cell group) to which the conductive portion 30, the first coating layer 50, and the second coating layer 60 are attached as described above are sealed in two sheets.
- Module 1 is constructed.
- the two sheet-like sealing resins 150 are sandwiched between the front surface covering member 160 and the back surface covering member 170, and after being attached with a frame (not shown), they are integrated by heat curing and shown in FIG. The sealing resin 150 is obtained.
- the sealing resin 150 is provided between the front surface covering member 160 constituting the front (front) surface of the solar cell module 1 and the rear surface covering member 170 constituting the back surface.
- the wired solar cell group is housed in a state covered with the above.
- the conductive portion 30 and the second coating layer 60 are disposed on the lower surface (rear surface) of the solar cell 10b, and then the conductive portion 30 and the first coating layer are disposed on the upper surface (light receiving surface) of the solar cell 10a.
- 50 is arranged, it is not limited to this. Since these steps can be carried out continuously, it is possible to efficiently wire solar cells regardless of which step is performed first.
- this specification is a solar cell wiring method or a solar cell module manufacturing method: a step (1A) of partially disposing a conductive portion on the back surface of the solar cell; A step (1B) of adhering a covering layer (second covering layer) to the back surface of the solar cell thus formed through the conductive portion; a step of partially disposing the conductive portion on the surface of the solar cell (2A) And a step (2B) of adhering a coating layer (first coating layer) to the surface of the solar cell on which the conductive portion is disposed over the conductive portion.
- step (1A) and step (1B) may be performed first, then step (2A) and step (2B) may be performed, or step (2A) and step (2B) may be performed first.
- the second coating layer is partially disposed on the back surface of the solar battery cell.
- the first covering layer is preferably partially disposed on the surface of the solar battery cell.
- the solar cells 10a and 10b and the configuration relating to their electrical connection have been described above. However, basically the same applies to other solar cells (for example, the solar cells 10c and 10d) constituting the solar cell group. Since the above configuration is repeated, a duplicate description is omitted.
- the conductive part (more specifically, the conductive wire) disposed on the upper surface or the lower surface of the solar cells located at both ends of the solar cell group is not an electrical connection between the solar cells, but an extraction electrode (not shown) Connected to (terminal bar).
- FIG. 5 is an enlarged schematic cross-sectional view showing the conductive portion and the coating layer on the lower surface of the solar battery cell according to the second embodiment.
- FIG. 5 corresponds to a partially enlarged view of the conductive portion and the covering layer in the cross-sectional view of FIG.
- the solar cell module according to the second embodiment has basically the same configuration as the solar cell module according to the first embodiment except for a covering layer (typically the second covering layer). Therefore, about this embodiment, it explains focusing on the 2nd covering layer, and omits explanation about other points.
- a pressure-sensitive adhesive sheet with a base material layer is used as the second coating layer 60 (more specifically, the belt-shaped coating member 62).
- This pressure-sensitive adhesive sheet (second coating layer 60 (more specifically, band-shaped coating member 62)) is provided with a base layer 64 and a pressure-sensitive adhesive layer 66 disposed on one surface of the base layer.
- the surface of the pressure-sensitive adhesive layer 66 is bonded to the lower surface of the solar battery cell 10b through the conductive portion 30 (typically the conductive wire 40).
- the base material layer 64 of the 2nd coating layer 60 is arrange
- the adhesive property of the adhesive layer 66 is used to obtain wiring excellent in connection reliability, and the rigidity of the base layer 64 is used to further increase the durability of the wiring. Can be improved.
- a single-sided adhesive sheet is used as the second coating layer 60, but is not limited thereto, and a double-sided adhesive sheet with a base material layer may be used.
- a polyester resin film having a thickness of about 50 to 100 ⁇ m is used as the base material layer 64, but is not limited thereto.
- the base material layer may be a peelable support that can be peeled off from various resin films and the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer 66 the same type of pressure-sensitive adhesive as in the first embodiment is used.
- the pressure-sensitive adhesive layer 66 is not limited to this, and can be changed within a range described later.
- the 1st coating layer in this embodiment the 1st coating layer of the same structure as the said 1st Embodiment is used from a translucent viewpoint.
- an electroconductive part is not limited to the shape of the said embodiment, a structure, etc.
- the conductive part is partially arranged on the upper and lower surfaces of the solar cell, and adopts various shapes, structures, etc. that can realize the electrical connection of the solar cell using the conductive part. Is possible.
- the conductive wire may extend in a curved shape.
- the plurality of conductive lines may be separated from each other, connected, or non-parallel to each other (for example, may be crossed or non-parallel so as not to contact each other). ).
- the connection of a plurality of conductive lines includes a mode in which a plurality of parallel conductive lines are spanned by other conductive lines and have a continuous shape (non-separated shape).
- a typical example is a conductive wire arranged in a mesh.
- the number of conductive wires is preferably 2 or more (typically 2 to 20, more preferably 4 to 12, more preferably 6 to 10), Or it may be one.
- each of the second covering layers is composed of a plurality of strip-shaped covering members, but is not limited thereto.
- the second covering layer can be variously modified as long as it covers the back surface of the solar battery cell over the conductive portion and adheres to the lower surface of the solar battery cell.
- the second covering layer may be a sheet-like member having the same shape as the lower surface of the solar battery cell, and may be partially provided with holes or slits (cuts).
- coated member may extend in the shape of a curve.
- the plurality of strip-shaped covering members may be separated from each other, may be connected to each other, or may be non-parallel to each other (for example, may be crossed or do not contact each other). Non-parallel).
- the connection of the plurality of strip-shaped covering members includes an embodiment in which a plurality of parallel strip-shaped covering members are spanned by other strip-shaped covering members and have a continuous shape (non-separating shape).
- a belt-shaped covering member arranged in a mesh shape can be given.
- the width of the belt-shaped covering member may be changed (for example, narrowed) entirely or partially.
- the average value of the widths measured at a plurality of points (for example, 5 points or more) in the longitudinal direction is adopted as the width of the belt-shaped covering member.
- the conductive portion is constituted by a plurality of conductive wires and the second covering portion is constituted by a plurality of strip-shaped covering members
- the number of the conductive wires and the strip-shaped covering members is preferably the same, but the number of the strip-shaped covering members is the conductive wire.
- the number of the conductive wires may be less than the number of the conductive wires, and two or more conductive wires may be covered with one strip-shaped covering member.
- one of the plurality of strip-shaped covering members covers a part of the plurality of conductive wires from the outside of the back surface of the solar battery cell, and the other one of the plurality of strip-shaped covering members. It is also possible that the band-shaped covering member covers the other part of the plurality of conductive lines from the outside of the back surface of the solar battery cell. Therefore, the shape of the covering layer non-arrangement region on the lower surface of the solar battery cell can take various patterns such as a strip shape, a stripe shape, an island shape, a circular shape, and a square shape corresponding to the shape of the covering layer arrangement region.
- the configuration of the lower surface of the solar cell is important for improving the durability, as will be described later in the test, and therefore the first coating layer disposed on the upper surface of the solar cell is particularly It is not limited.
- the first coating layer may not be provided, and even when the first coating layer is provided, the shape of the first coating layer is not particularly limited.
- the first covering layer may be disposed on the entire top surface of the solar battery cell.
- the first coating layer may have almost the same shape (for example, a quadrangular shape) as the solar battery cell, and takes various shapes according to the shape of the solar battery cell, the shape of the conductive portion, and the like. Is possible.
- the first coating layer and the second coating layer may be made of the same material (same composition), or may be made of different materials (having different compositions).
- a substrate-less adhesive sheet may be used as the first coating layer
- a single-sided adhesive sheet with a substrate may be used as the second coating layer, or the first coating layer
- You may use a single-sided adhesive sheet with a base material with a 2nd coating layer.
- a photovoltaic cell is a single-sided light-receiving type, only a 1st coating layer may be transparent and a 2nd coating layer may be non-transparent.
- the second coating layer may specifically be a layer having a total light transmittance of less than 70% (for example, less than 50%, typically less than 30%) described later. Therefore, the first coating layer and the second coating layer may have different total light transmittance. Or when a photovoltaic cell is a double-sided light-receiving type, it is preferable that both a 1st coating layer and a 2nd coating layer are transparent, and it is more preferable to have the total light transmittance more than the predetermined mentioned later.
- the same material and the same shape are used as the band-shaped covering member of the first covering layer and the band-shaped covering member of the second covering layer from the viewpoint of productivity and the like. Therefore, the width of the band-shaped coating member of the first coating layer and the width of the band-shaped coating member of the second coating layer are the same, and the width of each band-shaped coating layer non-arrangement region on the upper surface of the solar cell is also the lower surface of the solar cell.
- belt-shaped coating layer non-arrangement area and the area ratio of the coating layer non-arrangement area
- the interval between the band-shaped covering members of the first covering layer and the interval between the band-shaped covering members of the second covering layer are set to be the same as the interval between the conductive lines.
- the number of solar cells arranged in one solar cell module is not particularly limited, and is at least 1, usually 5 or more (for example, 10 or more, typically 30 or more), May be about 50 or more (50 to 70).
- conductive portions connected to extraction electrodes (terminal bars) can be arranged on the front surface or the back surface.
- positioning) of a several photovoltaic cell is not limited to this, A linear form, a curve It may be a pattern, a regular pattern, or an irregular pattern.
- interval of a photovoltaic cell does not need to be constant.
- the solar cell wiring method and solar cell module manufacturing method disclosed herein are not limited to the method of the above embodiment, and the solar cell wiring structure and solar cell module structure disclosed herein are the same. It is possible to adopt a method that can be realized without limitation. For example, after laminating a conductive part on the coating layer, it is also possible to employ a method of arranging the conductive part arrangement surface of the coating layer with the conductive part on the front surface or the back surface of the solar battery cell.
- the conductive part, the first coating layer, and the second coating layer that constitute the solar cell module are not limited to those of the above-described embodiment, and various modifications can be made within a range in which the effects of the invention are exhibited. The same applies to other components of the solar cell module.
- each element which comprises a solar cell module is demonstrated.
- the conductive portion typically includes a conductive material.
- a metal material such as gold, silver, copper, aluminum, iron, nickel, tin, chromium, bismuth, indium, zinc, or an alloy thereof can be preferably used.
- silver, copper, aluminum, and iron are more preferable, and copper and aluminum are more preferable.
- Conductive paths composed essentially of metal have the advantage of lower resistance.
- the metal wire those having a tensile strength measured according to JIS Z 2241: 2011 of 200 N / mm 2 or more are preferably used from the viewpoint of strength, handling property, and the like.
- a copper metal wire is preferably used.
- coated part using a copper metal wire as a core material is more preferable.
- the film thickness (for example, plating thickness) of the covering portion may be about 10 ⁇ m or less (for example, 5 ⁇ m or less, and further, for example, 3 ⁇ m or less).
- the film thickness is suitably about 0.1 ⁇ m or more (for example, 0.5 ⁇ m or more). From the viewpoint of improving the diffuse reflectance, it is preferably 1.0 ⁇ m or more, more preferably 1.5 ⁇ m or more (for example, 2 ⁇ m). Further, for example, 3 ⁇ m or more).
- a method for forming the covering portion a conventionally known method such as a clad method can be adopted in addition to the above-described plating method.
- a conductive wire typically a metal wire subjected to rust prevention treatment is preferably used as the conductive portion.
- the conductive part may be formed from a conductive sheet.
- the conductive sheet is typically a metal sheet (for example, a metal foil).
- a metal sheet for example, a metal foil
- the metal sheet what gave at least 1 sort (s) of surface treatment of a roughening process, a rust prevention process, and an adhesive improvement process is used preferably.
- Suitable examples of the metal sheet include copper foil (in particular, electrolytic copper foil).
- the conductive portion may be formed from a patterned metal sheet.
- Such a conductive part can be formed by etching a metal sheet. Specifically, a resist is attached to the surface of a metal sheet (typically a metal foil), and a predetermined resist pattern is formed by applying a photolithography technique. Next, the metal sheet is patterned using a known or conventional etching solution. In this way, the conductive portion is formed.
- a similar configuration can be obtained by various vapor deposition methods.
- the conductive portion may be formed, for example, by applying a conductive paste as a conductive material.
- a conductive paste conductive components made of metal materials such as gold, silver, copper, aluminum, iron, nickel, tin, chromium, bismuth, indium, and alloys thereof, and conductive components made of non-metals such as carbon (hereinafter referred to as “conductive paste”) The same)) and a resin component such as polyester or epoxy resin can be used in a suitable solvent.
- conductive paste conductive components made of metal materials such as gold, silver, copper, aluminum, iron, nickel, tin, chromium, bismuth, indium, and alloys thereof, and conductive components made of non-metals such as carbon
- a resin component such as polyester or epoxy resin
- the conductive paste examples include silver paste (trade name “Pertron K-3105”, manufactured by Pernox, conductive component: Ag, resin component: polyester resin, specific resistance: 6.5 ⁇ 10 ⁇ 5 ⁇ ⁇ cm) Is mentioned.
- the specific resistance of the conductive paste at 25 ° C. is about 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less (for example, 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, typically 5.0 ⁇ 10 ⁇ 7 ⁇ ⁇ m or less).
- the specific resistance of the conductive component constituting the conductive paste is preferably 5.0 ⁇ 10 ⁇ 7 ⁇ ⁇ m or less.
- the conductive portion can be formed by applying a conductive paste to the surface of a coating layer, a peelable support or the like using a known dispenser.
- the conductive part formed by applying the conductive paste to the surface of the coating layer overlaps the surface or back surface of the solar cell with the conductive part forming surface of the coating layer.
- the surface of the conductive portion (at least the surface on the solar cell module incident surface side.
- the surface layer portion for example, the portion having a depth of 1 ⁇ m or less from the surface of the conductive portion, the same applies hereinafter) is made of silver.
- a metal material for example, copper wire
- the surface of the conductive part is made of silver
- the purity of silver on the surface is not particularly limited, and is suitably about 95% by weight (for example, 99% by weight or more). It is.
- the silver purity is preferably 99.7% by weight or more, more preferably 99.9% by weight or more.
- the concentration of the additive component (component other than silver, such as selenium and antimony) on the surface of the conductive portion is preferably about 0.3% by weight or less (preferably 0.1% by weight or less).
- the purity of silver and the concentration of components other than silver can be measured using an inductively coupled plasma mass spectrometer (ICP-MS) and an inductively coupled plasma emission spectrometer (ICP-AES).
- the conductive portion is formed by hot-melt coating a metal material (typically an alloy) having a low melting point (for example, a melting point of 300 ° C. or lower, preferably 250 ° C. or lower).
- a low-melting-point alloy for example, “SnBi solder” manufactured by Arakawa Chemical Industries, Ltd.), 139 ° C.
- the same configuration as described above can be obtained by employing various printing methods such as screen printing.
- the arithmetic average roughness (Ra) of the surface of the conductive part is preferably 60 nm or more. This tends to increase the diffuse reflectance and improve the power generation efficiency.
- the Ra is more preferably 70 nm or more, further preferably 80 nm or more (for example, 110 nm or more, further for example, 140 nm or more), and particularly preferably 200 nm or more (for example, 220 nm or more, further, for example, 250 nm or more).
- the surface of the conductive portion is composed of silver (typically a silver plating layer), the purity thereof is 99.7% by weight or more (preferably 99.9% by weight or more), and the film thickness of silver
- the diffuse reflectance can be significantly improved.
- the Ra can be adjusted by selecting a metal material type on the surface of the conductive portion, roughening using an embossing roll, or surface treatment such as etching.
- the above Ra is measured by the following method.
- a shape profile is measured for the surface of the conductive portion using an optical interference type shape measuring device.
- the measurement range is about 600 ⁇ m ⁇ 450 ⁇ m.
- an optical interference type shape measuring device manufactured by Veeco, model “Wyko NT9100” or its equivalent may be used.
- Ra of the surface of the conductive portion is calculated.
- Ra is calculated by the above method for any three of the conductive parts, and the value obtained by arithmetically averaging them is defined as Ra on the surface of the conductive part. It is preferable to adopt.
- the surface of the conductive part preferably exhibits a diffuse reflectance of about 60% or more.
- the diffuse reflectance refers to the diffuse reflectance with respect to light having a wavelength of 550 nm (the ratio (%) of diffuse reflection with respect to incident light).
- the diffuse reflectance is more preferably 80% or more, further preferably 85% or more, particularly preferably 87% or more, and particularly preferably 90% or more.
- the ratio of diffuse reflection to the total reflection on the surface of the conductive portion is preferably about 80% or more.
- the diffuse reflection ratio refers to the ratio (%) of diffuse reflection in total reflection (the sum of regular reflection (also referred to as specular reflection) and diffuse reflection) with respect to light having a wavelength of 550 nm.
- the diffuse reflection ratio is more preferably 90% or more, further preferably 95% or more, and particularly preferably 99% or more.
- the above diffuse reflectance and diffuse reflectance ratio can be measured using a commercially available spectrophotometer.
- a commercially available spectrophotometer For example, an integrating sphere unit manufactured by JASCO (for example, product name “ISV-722”), a spectrophotometer manufactured by the same (for example, product name “V-660”), and a standard white plate manufactured by Labsphere (for example, Spectralon ( (Registered trademark) 6916-H422A).
- the measurement is performed on the portion of the conductive portion that is the surface on the light incident surface side of the solar cell module.
- the irradiation area of the electroconductive part for example, conductive wire
- the ratio of the height (H) to the width (W) (H / W) in the cross section orthogonal to the longitudinal direction of the conductive portion (typically conductive wire) is set to be 1 ⁇ 2 or less. preferable. Thereby, excellent performance can be exhibited.
- the ratio (H / W) is preferably about 1/3 or less from the viewpoint of wiring workability and connection reliability, and preferably 1/5 or more (for example, 1/4 or more) from the viewpoint of power generation efficiency. It is.
- the conductive wire has a rectangular shape in a cross section orthogonal to the longitudinal direction. Thereby, almost the whole area of one surface of the conductive wire can be in surface contact with the surface of the solar battery cell.
- the rectangular shape may be chamfered at each corner.
- the cross-sectional shape of the conductive wire is not limited to this, and may be a circular shape, an elliptical shape, a semicircular shape, a trapezoidal shape, a triangular shape, or the like. From the viewpoint of the contact area with the solar battery cell, it is preferable that the conductive portion (typically conductive wire) has a flat portion (typically a surface) in contact with the solar battery cell.
- the width of the conductive line is preferably 0.03 mm or more from the viewpoint of reduction of current collection loss, strength, handling properties, and workability. More preferably, it is 0.1 mm or more, More preferably, it is 0.2 mm or more.
- the width is preferably 1.5 mm or less, more preferably 1.2 mm or less, and further preferably 1.0 mm or less from the viewpoint of reducing shadow loss.
- variety points out the length (width) orthogonal to the longitudinal direction of a conductive wire.
- the distance between the conductive lines is preferably 0.1 cm or more, more preferably 0.8 cm or more, from the viewpoint of reducing shadow loss. More preferably 1.5 cm or more.
- the distance is preferably less than 4.0 cm, more preferably less than 3.0 cm, and even more preferably 2.8 cm or less (for example, 2.5 cm or less) from the viewpoint of reducing current collection loss.
- interval is a pitch and points out the distance between the centerlines in the width direction of a conductive wire.
- the thickness (height) of the conductive portion is 0.01 to 1 mm (for example, 0.02 to 0.5 mm, typically 0.05 to 0.00 mm) from the viewpoints of conductivity, strength, handling properties, and workability. 3 mm) or so is preferable.
- the thickness of the conductive wire is also preferably selected from the same range.
- the first coating layer and the second coating layer (hereinafter collectively referred to as “coating layer”) disclosed herein can function as layers that favorably maintain the contact state between the solar battery cell and the conductive portion.
- the coating layer is typically a resin layer, and is preferably a layer that exhibits the properties of an elastic body or a viscoelastic body in a temperature range near room temperature.
- the viscoelastic body referred to here is a material having both properties of viscosity and elasticity, that is, a material having a property that satisfies the phase of the complex elastic modulus exceeding 0 and less than ⁇ / 2 (typically at 25 ° C. A material having the above properties).
- a coating layer is insulating.
- the coating layer may have a single layer structure or a multilayer structure of two or more layers.
- the storage elastic modulus G ′ (frequency 1 Hz, strain 0.1%, 150 ° C.) of the coating layer (typically a resin layer) disclosed herein is preferably 5,000 Pa or more.
- a coating layer typically a resin layer
- the solar cell and the conductive part are in good contact under high temperature conditions, and under various conditions ( For example, the contact state can be stably maintained under a wide range of temperature conditions.
- the coating layer typically a resin layer
- the 150 ° C. storage elastic modulus G ′ is more preferably 10,000 Pa or more, further preferably 20,000 Pa or more, particularly preferably 25,000 Pa or more (for example, 50,000 Pa or more, typically 80,000 Pa or more). is there.
- the 150 ° C. storage elastic modulus G ′ is usually 1,000,000 Pa or less, preferably 500,000 Pa or less, more preferably 200,000 Pa or less (for example, 150,000 Pa or less, typically 100,000 or less). 000 Pa or less).
- the storage elastic modulus G ′ (frequency 1 Hz, strain 0.1%) of the coating layer (typically a resin layer) is 5,000 Pa to 1,000,000 Pa in the temperature range of 80 ° C. to 150 ° C. It is preferable to be within the range.
- the change in the storage elastic modulus G 'in the high temperature range within a predetermined range may mean that the physical properties of the coating layer (typically a resin layer) are not easily affected by temperature changes.
- the storage elastic modulus G ′ of the coating layer (typically a resin layer) in the temperature range of 80 ° C. to 150 ° C. is more preferably 5,000 Pa to 500,000 Pa, still more preferably 5,000 Pa to 200,000 Pa (for example, 10,000 Pa to 100,000 Pa).
- the storage elastic modulus G ′ (frequency 1 Hz, strain 0.1%) of the coating layer (typically a resin layer) is 5,000 Pa to 10,000,000 Pa in the temperature range of 30 ° C. to 150 ° C. It is preferable to be within the range.
- the change in the storage elastic modulus G ′ in a wide temperature range as described above being within a predetermined range may mean that the physical properties of the coating layer (typically a resin layer) are not easily affected by the temperature change. .
- the storage elastic modulus G ′ of the coating layer (typically a resin layer) in the temperature range of 30 ° C. to 150 ° C. is more preferably 5,000 Pa to 1,000,000 Pa, still more preferably 5,000 Pa to 500,000 Pa. (For example, 10,000 Pa to 200,000 Pa).
- the maximum value of tan ⁇ of the coating layer (typically a resin layer) disclosed herein is preferably less than 0.4 in the temperature range of 80 ° C. to 150 ° C.
- a coating layer typically a resin layer
- the solar cell and the conductive part are in good contact in the high temperature range and various conditions (for example, a wide range of temperature conditions) In (lower), the contact state can be stably maintained.
- the conductive part when the conductive part is pressed against the solar battery cell from the outside of the coating layer when constructing the solar battery module, the conductive part can be satisfactorily brought into contact with the solar battery surface even under high temperature conditions.
- tan ⁇ is a value (G ′′ / G ′) obtained from loss elastic modulus G ′′ / storage elastic modulus G ′.
- the maximum value of tan ⁇ of the coating layer (typically the resin layer) in the temperature range of 80 ° C. to 150 ° C. is more preferably less than 0.3.
- the minimum value of tan ⁇ in the above temperature range can be usually 0.01 or more (for example, 0.1 or more).
- the storage elastic modulus G ′ (frequency 1 Hz, strain 0.1%, 150 ° C.) and tan ⁇ (G ′′ / G ′) and tan ⁇ (G ′′ / G ′) of the coating layer (typically a resin layer) are commercially available rheometers (for example, the device name “ ARES 2KFRT "manufactured by TA Instruments Co., Ltd.) under the conditions of a frequency of 1 Hz and a strain of 0.1%, a predetermined temperature range (temperature range including 80 ° C to 150 ° C, and further 30 ° C to 150 ° C) Temperature range). What is necessary is just to set a measurement temperature range and a temperature increase rate appropriately according to the model etc.
- a temperature range of 30 ° C. to 160 ° C. and a temperature increase rate of about 0.5 ° C. to 20 ° C./min (for example, 10 ° C./min) can be achieved.
- a measurement sample it is preferable to use a sample obtained by punching a coating layer (typically a resin layer) having a thickness of about 2 mm to a diameter of about 8 mm.
- the coating layer (typically a resin layer) may or may not have adhesiveness (typically tackiness).
- the coating layer (typically a resin layer) may be an adhesive layer or a non-adhesive layer.
- the “adhesive layer” refers to a SUS304 stainless steel plate as an adherend in accordance with JIS Z 0237: 2009, and a 2 kg roller is reciprocated once in a measurement environment at 23 ° C. to be bonded to the adherend. 30 minutes later, the peel strength when peeled in the direction of 180 ° at a pulling speed of 300 mm / min is 0.1 N / 20 mm or more.
- non-adhesive layer refers to a layer that does not correspond to the adhesive layer, and typically refers to a layer having a peel strength of less than 0.1 N / 20 mm.
- the layer that does not stick to the stainless steel plate when the 2 kg roller is reciprocated once in a measurement environment of 23 ° C. and pressed against the SUS304 stainless steel plate is a non-adhesive layer here. This is a typical example included in the concept.
- the technique disclosed here is preferably implemented in a form including a resin layer corresponding to an adhesive layer (also referred to as an adhesive layer) formed from an adhesive as a coating layer.
- the resin layer forming composition may be a pressure-sensitive adhesive composition.
- the “pressure-sensitive adhesive” refers to a material that exhibits a soft solid (viscoelastic body) state in a temperature range near room temperature and has a property of easily adhering to an adherend by pressure.
- the adhesive here is generally complex elastic modulus E * (1 Hz) as defined in “C. A. Dahlquist,“ Adhesion: Fundamental and Practice ”, McLaren & Sons, (1966) P. 143”. ⁇ 10 ⁇ 7 > dyne / cm ⁇ 2 > material (typically a material having the above properties at 25 [deg.] C.).
- the surface of the coating layer (typically a resin layer) preferably has adhesiveness.
- the coating layer adheres well to the solar battery cell on both outer sides in the width direction of the conductive part, and maintains a good contact state between the cell surface and the conductive part.
- the surface of the coating layer typically a resin layer
- the coating layer is removed from the conductive part using a known adhesive, pressure-sensitive adhesive, or the like. What is necessary is just to fix to a photovoltaic cell over.
- the surface of the coating layer (typically a resin layer) exhibits a 180-degree peel strength (adhesive power to solar cells) of 3 N / 10 mm or more with respect to the crystalline Si solar cells.
- the adhesive strength to the solar battery cell is more preferably 5 N / 10 mm or more, further preferably 8 N / 10 mm or more (for example, 10 N / 10 mm or more, typically 12 N). / 10 mm or more).
- the surface of the coating layer (typically a resin layer) exhibits a 180 degree peel strength of 15 N / 10 mm or more with respect to the crystalline Si solar battery cell.
- the upper limit of the adhesive force to the solar cell on the surface of the coating layer is not particularly limited, and the above adhesive force is usually 50 N / 10 mm or less (for example, 30 N) from the viewpoint of workability such as reattachment. / 10 mm or less, typically 20 N / 10 mm or less).
- the adherend used for the measurement of the adhesion to solar cells is a crystalline Si solar cell.
- a crystalline Si solar battery cell manufactured by Q CELLS a single crystalline Si cell manufactured by GINTECH, or a polycrystalline Si cell is preferably used.
- Measurement is performed by firmly attaching a coating layer (typically a resin layer) to the adherend by means of lamination or the like, and then commercially available a tensile tester (for example, device name “Autograph AGS-J”, manufactured by Shimadzu Corporation). Can be carried out in an atmosphere of 23 ° C. and 50% RH under the conditions of a tensile speed of 30 mm / min and a peeling angle of 180 degrees.
- the measurement of the adhesive force to solar cells can be performed by, for example, the following method.
- the covering layer is cut into a size of 5 cm ⁇ 10 cm and laminated on an EVA sheet (trade name “EVASKY”, manufactured by Bridgestone) having the same size and a thickness of 450 ⁇ m.
- an EVA sheet (trade name “EVASKY”, manufactured by Bridgestone) having the same size and a thickness of 450 ⁇ m is laminated on a glass of 5 cm ⁇ 10 cm, and a solar cell (single crystal system) cut into 5 cm ⁇ 4 cm on the sheet.
- Si cell Product name “G156S3” (manufactured by GINTECH) is disposed.
- a photovoltaic cell When measuring the adhesive force with respect to the lower surface of a photovoltaic cell, a photovoltaic cell is arrange
- a release liner that has been subjected to release treatment with silicone is placed on the cell non-facing portion of the surface of the coating layer. This release liner is sandwiched between the lower EVA sheet and the coating layer in an area without cells. Further, a PET film is lined on the upper EVA sheet to obtain a test laminate.
- the 180 degree peel strength between the solar power generation cell and the coating layer is measured. Specifically, using a tensile tester (equipment name “Autograph AGS-J”, manufactured by Shimadzu Corporation) under conditions of 23 ° C., 50% RH, tensile speed 30 mm / min, peel angle 180 ° Then, the coating layer is peeled from the adherend (cell), and the peel strength [N / 10 mm] at that time is obtained. It is measured by the same method in the test described later.
- the coating layer typically has translucency.
- the coating layer typically a resin layer
- the coating layer typically a resin layer
- the transparent resin layer refers to a resin layer having a total light transmittance of 70% or more.
- the total light transmittance of the coating layer is more preferably 85% or more, and further preferably 90% or more.
- the total light transmittance of the coating layer (typically a resin layer) can be measured using a commercially available haze meter (for example, trade name “HR-100”, manufactured by Murakami Color Research Laboratory Co., Ltd.).
- the resin layer disclosed herein is preferably composed of a resin material having a melt mass flow rate (MFR) at 150 ° C. of 9 g / 10 min or less.
- the resin layer exhibiting the MFR can exhibit good shape stability.
- the MFR is more preferably 3 g / 10 min or less, further preferably 1 g / 10 min or less, and particularly preferably 0.5 g / 10 min or less (for example, 0.2 g / 10 min or less).
- the above MFR measurement is based on JIS K 7210: 1999 or ASTM D 1238, and the amount of resin flowing out at a constant time under conditions of a temperature of 190 ° C. and a load of 2.16 Kg is weighed with a balance and unit time (10 minutes) This may be done by calculating the amount of resin discharged.
- the linear expansion coefficient of the coating layer (typically a resin layer) is preferably less than 15% in the temperature range of ⁇ 40 ° C. to 85 ° C. According to the coating layer (typically a resin layer) showing the linear expansion coefficient, a wiring with further improved durability is realized.
- the linear expansion coefficient is more preferably 12% or less (for example, 10% or less).
- Each coating layer (typically a resin layer) is cut into a size of 10 mm in length and about 0.5 mm 2 in cross-sectional area to produce a test piece.
- the resin layer as a typical example of the coating layer disclosed here is a resin layer formed from a resin material.
- a resin layer containing a crosslinked resin as a base polymer (for example, a resin layer subjected to crosslinking treatment) is preferable.
- the resin layer has physical properties different from those of the sealing resin, and can typically be formed from a resin material different from the resin material of the sealing resin.
- the resin that forms the resin layer is an acrylic resin, EVA resin, polyolefin resin, rubber, silicone resin, polyester resin, urethane resin, polyether resin, polyamide resin, fluorine resin, etc. 1 type or 2 types or more selected from these resin.
- the acrylic resin is an acrylic polymer as a base polymer (the main component of the polymer component, that is, the component having the largest blending ratio in the polymer component, typically a component that exceeds 50% by weight).
- the resin material The same meaning applies to EVA and other resins.
- the resin layer according to a preferred embodiment is an EVA resin layer formed from an EVA resin.
- the proportion of EVA in the resin layer (which may also be a resin layer forming composition) is not particularly limited and is typically 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight. That's it.
- the EVA resin layer is subjected to a thermosetting treatment at about 80 to 200 ° C. (eg, 100 to 180 ° C., typically 120 to 160 ° C.) from the viewpoint of obtaining desired physical properties. Is preferred.
- the heat curing treatment time is not particularly limited and is usually 5 minutes or longer, preferably 10 minutes or longer, more preferably 20 minutes or longer (for example, 30 minutes or longer, typically 40 minutes to 120 minutes).
- the EVA resin layer is preferably subjected to a press treatment before or during the thermosetting treatment.
- the resin layer may be a layer containing an acrylic polymer as a base polymer, that is, an acrylic resin layer.
- a resin layer having such a composition is preferable because it can be easily adjusted to desired physical properties such as shape stability and flexibility.
- the proportion of the acrylic polymer in the resin layer is not particularly limited, and is typically 50% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more.
- (meth) acrylate” means acrylate and methacrylate comprehensively.
- (meth) acryloyl” means acryloyl and methacryloyl
- “(meth) acryl” generically means acrylic and methacryl.
- the “monomer component constituting the acrylic polymer” refers to a monomer unit constituting the acrylic polymer in the resin material forming the resin layer.
- the monomer component may be contained in the resin layer forming composition used for forming the resin layer in an unpolymerized form (that is, in the form of a raw material monomer in which the polymerizable functional group is unreacted). , May be included in the form of a polymer, or may be included in both forms.
- the resin layer forming composition disclosed herein preferably contains the component (A) as a monomer component constituting the acrylic polymer.
- the component (A) is an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms at the ester end.
- an alkyl (meth) acrylate having an alkyl group having a carbon number of X or more and Y or less at the ester end may be referred to as “C XY alkyl (meth) acrylate”.
- the structure of the C 1-20 alkyl group in the C 1-20 alkyl (meth) acrylate is not particularly limited, and either a linear or branched alkyl group can be used.
- the component (A) one kind of such C 1-20 alkyl (meth) acrylate can be used alone or in combination of two or more kinds.
- C 1-20 alkyl (meth) acrylates having a linear alkyl group at the ester end include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n- Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (Meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-pentadecyl (meth) acrylate,
- C 3-20 alkyl (meth) acrylate having a branched alkyl group at the ester terminal isopropyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, isopentyl (meth) acrylate, t- Pentyl (meth) acrylate, neopentyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) Acrylate, 2-propylheptyl (meth) acrylate, isoundecyl (meth) acrylate, isododecyl (meth) acrylate, isotridecy
- the component (A) can be preferably implemented in an embodiment containing C 4-9 alkyl (meth) acrylate as the component (A1).
- the component (A1) may be one or more selected from C 4-9 alkyl (meth) acrylates. From the viewpoint of compatibility with other monomer components (for example, cyclic nitrogen-containing monomers), C 4-9 alkyl acrylate is preferably used as component (A1).
- Preferable examples of C 4-9 alkyl acrylate include n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate and isononyl acrylate.
- the proportion of the component (A1) in the component (A) is usually 20% by weight or more (eg 20 to 80% by weight), preferably 30% by weight or more. (For example, 30 to 70% by weight), more preferably 40% by weight or more (for example, 40 to 60% by weight).
- the proportion of the component (A1) in the component (A) may be 50% by weight or more (for example, 80% by weight or more, typically 90 to 100% by weight).
- the embodiment in which the component (A) includes C 10-18 alkyl (meth) acrylate as the component (A2) can be preferably carried out.
- the component (A2) may be one or more selected from C 10-18 alkyl (meth) acrylates.
- the component (A2) preferably contains a C 10-18 alkyl (meth) acrylate in which the alkyl group is a branched chain, and more preferably from the viewpoint of compatibility with other monomer components (for example, a cyclic nitrogen-containing monomer). From C10-18 alkyl acrylates in which the alkyl group is branched.
- C 10-18 alkyl (meth) acrylate examples include isodecyl acrylate, isodecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, isomistyryl acrylate, isostearyl acrylate and stearyl methacrylate.
- the proportion of the component (A2) in the component (A) is usually 20% by weight or more (for example, 20 to 80% by weight), preferably 30% by weight or more. (For example, 30 to 70% by weight), more preferably 40% by weight or more (for example, 40 to 60% by weight).
- the proportion of the component (A2) in the component (A) may be 50% by weight or more (for example, 80% by weight or more, typically 90 to 100% by weight).
- the weight ratio (A1: A2) between the component (A1) and the component (A2) is not particularly limited, and is usually 1:
- the ratio is suitably 9 to 9: 1, and preferably 2: 8 to 8: 2 (eg, 3: 7 to 7: 3, typically 4: 6 to 6: 4).
- the component (A) may contain one or more of C 1-3 alkyl (meth) acrylate and C 19-20 alkyl (meth) acrylate as the component (A3).
- the proportion of the component (A3) in the component (A) is usually 30% by weight or less (for example, 15% by weight or less, typically 1 to 5% by weight) is preferable.
- the technique disclosed here is an embodiment in which the component (A) does not substantially contain the component (A3) (the proportion of the component (A3) in the component (A) is less than 1% by weight, and further 0.1% by weight. In an embodiment that is less than).
- the proportion of the component (A) in the monomer component is not particularly limited. From the viewpoint of physical properties of the resin layer and adhesive properties such as adhesive strength, the proportion of the component (A) is usually suitably 30% by weight or more, preferably 50% by weight or more, more preferably 60%. % By weight or more (eg, 75% by weight or more). In addition, the upper limit of the proportion of the component (A) is suitably about 98% by weight or less from the viewpoint of sufficiently obtaining the effects of the later-described components (B) and (C), and is 95% by weight. It is preferable that the amount be less than or equal to (for example, 90% by weight or less, typically 85% by weight or less).
- the resin layer forming composition contains a component (B) as a monomer component constituting the acrylic polymer.
- the component (B) is a heterocycle-containing monomer such as a cyclic nitrogen-containing monomer or a cyclic ether group-containing monomer.
- the component (B) can advantageously contribute to improving the shape stability and transparency of the resin layer.
- the heterocyclic ring-containing monomer can be used alone or in combination of two or more.
- cyclic nitrogen-containing monomer those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a cyclic nitrogen structure can be used without particular limitation.
- the cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure.
- cyclic nitrogen-containing monomers include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone; 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2- Oxazoline group-containing monomers such as oxazoline and 2-isopropenyl-2-oxazoline; vinyl-based compounds having nitrogen-containing heterocycles such as vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, and vinylmorpholine And monomers.
- lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone
- 2-vinyl-2-oxazoline 2-vinyl-5-methyl-2- Oxazoline group-containing monomers such as oxazoline and 2-isopropenyl-2-ox
- the (meth) acryl monomer containing nitrogen-containing heterocyclic rings such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, an aziridine ring.
- nitrogen-containing heterocyclic rings such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, an aziridine ring.
- nitrogen-containing heterocyclic rings such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, an aziridine ring.
- Specific examples include N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine, N-acryloylaziridine and the like.
- lactam vinyl monomers are preferable and N-vinylpyrrolidone is more preferable from the viewpoint
- the monomer having a cyclic ether group a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and a cyclic ether group such as an epoxy group or an oxetane group.
- a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and a cyclic ether group such as an epoxy group or an oxetane group.
- the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like.
- Examples of the oxetane group-containing monomer include 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, and 3-butyl-oxetanylmethyl (meth) acrylate. , 3-hexyl-oxetanylmethyl (meth) acrylate, and the like.
- the proportion of the component (B) in the monomer component is usually 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight. More preferably, it is 10% by weight or more (for example, 12% by weight or more).
- the proportion of the component (B) is suitably about 50% by weight or less, preferably 40% by weight or less (for example, 30% by weight or less), from the viewpoint of sufficiently obtaining the effect of containing the component (A). , Typically 25% by weight or less).
- the resin layer forming composition includes a component (C) as a monomer component constituting the acrylic polymer.
- the component (C) is a monomer having at least one of a hydroxy group and a carboxy group.
- hydroxy group-containing monomer those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxy group can be used without particular limitation.
- the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; -Hydroxyalkylcycloalkane (meth) acrylates such as -hydroxymethylcyclohexyl) methyl (meth) acrylate.
- hydroxyethyl (meth) acrylamide examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. These can be used alone or in combination of two or more. Of these, hydroxyalkyl (meth) acrylate is preferred. For example, a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms can be preferably used. Of these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are more preferable.
- carboxy group-containing monomer a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxy group can be used without particular limitation.
- carboxy group-containing monomers include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate; itaconic acid, maleic acid, fumaric acid, And ethylenically unsaturated dicarboxylic acids such as citraconic acid; metal salts thereof (for example, alkali metal salts); anhydrides of the above ethylenically unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride. These can be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferable.
- the technique disclosed herein can be preferably implemented in a mode in which the component (C) includes a hydroxy group-containing monomer. That is, it is preferable that the component (C) includes only a hydroxy group-containing monomer or includes a hydroxy group-containing monomer and a carboxy group-containing monomer. By increasing the proportion of the hydroxy group-containing monomer in the component (C), metal corrosion caused by the carboxy group can be reduced. From this, the technique disclosed here can be preferably implemented in a mode in which the monomer component does not substantially contain a carboxy group-containing monomer. For example, the proportion of the carboxy group-containing monomer in the monomer component can be less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.2% by weight.
- the proportion of the component (C) in the monomer component is usually suitably 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0, from the viewpoint of the physical properties of the resin layer. .8% by weight or more.
- the proportion of the component (C) may be 3% by weight or more, or 5% by weight or more (for example, 8% by weight or more, typically 10% by weight or more).
- the proportion of the component (C) is suitably about 35% by weight or less, preferably 30% by weight or less, more preferably 25% by weight or less (typically 5% by weight or less, eg 3 % By weight or less).
- the content of the carboxy group-containing monomer is based on the total monomer component used for the synthesis of the acrylic polymer from the viewpoint of achieving both cohesion and cohesion.
- About 0.1% by weight or more for example, 0.2% by weight or more, typically 0.5% by weight or more
- about 10% by weight or less for example, 8% by weight or less, typically Is preferably 5% by weight or less.
- the content of the hydroxy group-containing monomer is the total monomer component used for the synthesis of the acrylic polymer. It is preferably about 0.001% by weight or more (eg, 0.01% by weight or more, typically 0.02% by weight or more), and about 10% by weight or less (eg, 5% by weight or less, typically 2% by weight or less).
- the monomer component constituting the acrylic polymer includes all the components (A), (B), and (C).
- the proportion of component (A) is 50 to 99% by weight (more preferably 60 to 95% by weight, still more preferably Is preferably 70 to 85% by weight, and the proportion of component (B) is 0.9 to 49.9% by weight (more preferably 4.5 to 39.5% by weight, still more preferably 14.2 to 29.2% by weight), and the proportion of component (C) is 0.1 to 35% by weight (more preferably 0.5 to 30% by weight, still more preferably 0.8 to 25% by weight). It is preferable to do.
- the constituent monomer component in the technique disclosed herein may contain a monomer other than the components (A), (B) and (C) (hereinafter also referred to as “optional monomer”) as necessary.
- the optional monomer examples include monomers containing a functional group other than a hydroxy group and a carboxy group. Such a functional group-containing monomer can be used for the purpose of introducing a crosslinking point into the acrylic polymer or increasing the cohesive strength of the acrylic polymer.
- the functional group-containing monomer examples include amide group-containing monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-methylol (meth) acrylamide; cyano group-containing monomers such as acrylonitrile and methacrylonitrile;
- amide group-containing monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-methylol (meth) acrylamide
- cyano group-containing monomers such as acrylonitrile and methacrylonitrile
- sulfonic acid group-containing monomers such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid
- phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate
- Keto group-containing monomers such as acrylamide, diacetone (me
- the optional monomer examples include alicyclic monomers.
- the alicyclic monomer those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having an alicyclic structure-containing group can be used without particular limitation. it can.
- the “alicyclic structure-containing group” refers to a portion containing at least one alicyclic structure.
- the “alicyclic structure” refers to a saturated or unsaturated carbocyclic structure having no aromaticity. In the present specification, the alicyclic structure-containing group is sometimes simply referred to as “alicyclic group”.
- Preferable examples of the alicyclic group include a hydrocarbon group and a hydrocarbon oxy group containing an alicyclic structure.
- Examples of preferred alicyclic monomers include alicyclic (meth) acrylates having an alicyclic group and a (meth) acryloyl group.
- Specific examples of the alicyclic (meth) acrylate include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, and cyclooctyl (meth).
- Examples include acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. These can be used alone or in combination of two or more.
- the monomer component in the technology disclosed herein can be copolymerized with the above components (A), (B), and (C) as the above arbitrary monomer for the purpose of adjusting Tg of acrylic polymer and improving cohesion.
- a copolymerizable monomer other than those exemplified above may be included.
- copolymerizable monomers examples include carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene, substituted styrene ( ⁇ -methylstyrene, etc.), vinyltoluene; ) Aromatic ring-containing acrylate (eg phenyl (meth) acrylate), aryloxyalkyl (meth) acrylate (eg phenoxyethyl (meth) acrylate), arylalkyl (meth) acrylate (eg benzyl (meth) acrylate) ( (Meth) acrylates; olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; for example, methyl vinyl ether, ethyl vinyl ether, and the like Vinyl ether monomers; other, macromonomers, and the like Vinyl
- the amount of these optional monomers used is not particularly limited and can be determined as appropriate. Usually, the total amount of the arbitrary monomers used is suitably less than 50% by weight of the monomer component, preferably 30% by weight or less, and more preferably 20% by weight or less.
- the technique disclosed here can be preferably implemented in an embodiment in which the total amount of any monomer used is 10% by weight or less (for example, 5% by weight or less) of the monomer component.
- the technique disclosed here is an embodiment in which an optional monomer is not substantially used (for example, an embodiment in which the amount of the optional monomer used is 0.3% by weight or less, typically 0.1% by weight or less) of the monomer component. However, it can be preferably implemented.
- the above-described component (A), component (B), component (C) and optional monomer are typically monofunctional monomers.
- the monomer component in the technique disclosed herein can contain a polyfunctional monomer as necessary for the purpose of adjusting the cohesive force of the resin layer.
- the monofunctional monomer in this specification refers to a monomer having one polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and a polyfunctional monomer. As described later, refers to a monomer having at least two polymerizable functional groups.
- the polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
- polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, penta Erythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth)
- a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
- trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used.
- a polyfunctional monomer having two or more acryloyl groups is usually preferable.
- the amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, and the like, but is preferably 3% by weight or less of the above monomer component from the viewpoint of balancing cohesion and adhesion in a balanced manner. Is more preferable, and 1% by weight or less (for example, 0.5% by weight or less) is more preferable. Moreover, the lower limit of the usage-amount in the case of using a polyfunctional monomer should just be larger than 0 weight%, and is not specifically limited. Usually, the effect of improving the cohesive force can be appropriately exhibited by setting the amount of the polyfunctional monomer used to 0.001% by weight or more (for example, 0.01% by weight or more) of the monomer component.
- the proportion of the total amount of the component (A), the component (B) and the component (C) in the monomer component is typically more than 50% by weight, preferably 70% by weight. Above, more preferably 80% by weight or more, still more preferably 90% by weight or more.
- the technique disclosed here can be preferably implemented in an embodiment in which the ratio of the total amount is 95% by weight or more (for example, 99% by weight or more).
- the technology disclosed herein can be preferably implemented in an embodiment in which the ratio of the total amount in the monomer components is 99.999% by weight or less (for example, 99.99% by weight or less).
- the Tg of the polymer corresponding to the composition of the monomer component is preferably ⁇ 20 ° C. or less, preferably ⁇ 25 ° C. or less, from the viewpoints of physical properties and adhesiveness of the resin layer. More preferably -80 ° C or higher, preferably -60 ° C or higher, -50 ° C or higher (eg -40 ° C or higher, typically -35 ° C or higher). It is more preferable.
- the Tg of the polymer corresponding to the composition of the monomer component refers to the Fox based on the Tg of the homopolymer of each monomer contained in the monomer component and the weight fraction of the monomer.
- the formula of Fox is a relational expression between Tg of a copolymer and glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
- Tg is the glass transition temperature (unit: K) of the copolymer
- Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio on a weight basis)
- Tgi is the monomer i.
- the calculation of Tg is performed considering only the monofunctional monomer.
- the total amount of the monofunctional monomer contained in the monomer component is defined as 100% by weight, and the Tg of the homopolymer of each monofunctional monomer and the above total amount of the monofunctional monomer Tg is calculated based on the weight fraction relative to.
- Tg of the homopolymer the following values are adopted for the monomers shown below. 2-Ethylhexyl acrylate -70 ° C n-Butyl acrylate -55 ° C Isostearyl acrylate -18 °C Cyclohexyl acrylate 15 ° C Isobornyl acrylate 94 ° C N-Vinyl-2-pyrrolidone 54 ° C 2-Hydroxyethyl acrylate -15 ° C 4-hydroxybutyl acrylate -40 ° C Acrylic acid 106 °C
- the values described in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) are used as the Tg of the homopolymer. The highest value is adopted for the monomer whose values are described in this document. When not described in the above Polymer Handbook, values obtained by the measurement method described in Japanese Patent Application Publication No. 2007-51271 are used
- composition for resin layer formation includes a monomer component having the above-described composition in the form of a polymer, an unpolymerized product (that is, a form in which the polymerizable functional group is unreacted), or a mixture thereof. Can be included.
- the composition for forming a resin layer is a composition in which an organic solvent contains a resin layer forming component (for example, an adhesive component) (a composition for forming a solvent type resin layer), and a form in which the resin layer forming component is dispersed in an aqueous solvent.
- composition water-dispersed resin layer forming composition
- a composition prepared to cure with active energy rays such as ultraviolet rays and radiation to form a resin layer forming component (active energy ray curable resin layer formation)
- active energy ray curable resin layer formation active energy ray curable resin layer formation
- a hot melt type resin layer forming composition that forms a resin layer when coated in a heated and melted state and cooled to near room temperature.
- the resin layer forming composition typically contains at least part of the monomer components of the composition (may be part of the type of monomer or part of the quantity).
- the polymerization method for forming the polymer is not particularly limited, and various conventionally known polymerization methods can be appropriately employed.
- thermal polymerization such as solution polymerization, emulsion polymerization and bulk polymerization (typically performed in the presence of a thermal polymerization initiator); photopolymerization performed by irradiation with light such as ultraviolet rays (typically It is carried out in the presence of a photopolymerization initiator.); Radiation polymerization carried out by irradiation with radiation such as ⁇ -rays and ⁇ -rays; Of these, photopolymerization is preferred.
- the mode of polymerization is not particularly limited, and conventionally known monomer supply methods, polymerization conditions (temperature, time, pressure, light irradiation amount, radiation irradiation amount, etc.), materials used other than monomers (polymerization initiator) , Surfactant, etc.) can be selected as appropriate.
- a known or commonly used photopolymerization initiator or thermal polymerization initiator can be used depending on the polymerization method, polymerization mode, and the like.
- a polymerization initiator can be used individually by 1 type or in combination of 2 or more types as appropriate.
- the photopolymerization initiator is not particularly limited.
- a polymerization initiator or the like can be used.
- ketal photopolymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, trade name “Irgacure 651” manufactured by BASF).
- acetophenone photopolymerization initiator examples include 1-hydroxycyclohexyl-phenyl-ketone (for example, trade name “Irgacure 184” manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (for example, trade name “Irgacure 2959” manufactured by BASF), 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one (for example, trade name “Darocur 1173” manufactured by BASF), methoxyacetophenone and the like are included.
- benzoin ether photopolymerization initiator examples include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether and benzoin isobutyl ether, and substituted benzoin ethers such as anisole methyl ether.
- acylphosphine oxide photopolymerization initiator examples include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (for example, trade name “Irgacure 819” manufactured by BASF), bis (2,4,6 -Trimethylbenzoyl) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, trade name “Lucirin TPO” manufactured by BASF), bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like.
- ⁇ -ketol photopolymerization initiator examples include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one, and the like. It is.
- aromatic sulfonyl chloride photopolymerization initiator examples include 2-naphthalenesulfonyl chloride and the like.
- photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like.
- benzoin photopolymerization initiator examples include benzoin and the like.
- benzyl photopolymerization initiator examples include benzyl and the like.
- benzophenone photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
- thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone. 2,4-diisopropylthioxanthone, dodecylthioxanthone and the like.
- the thermal polymerization initiator is not particularly limited.
- an azo polymerization initiator, a peroxide initiator, a redox initiator by a combination of a peroxide and a reducing agent, a substituted ethane initiator. Etc. can be used.
- the amount of such a thermal polymerization initiator or photopolymerization initiator used can be a normal amount used according to the polymerization method, polymerization mode, etc., and is not particularly limited.
- a polymerization initiator of 0.001 to 5 parts by weight typically 0.01 to 2 parts by weight, for example, 0.01 to 1 part by weight
- a polymerization initiator of 0.001 to 5 parts by weight typically 0.01 to 2 parts by weight, for example, 0.01 to 1 part by weight
- the resin layer forming composition includes a polymerization reaction product of a monomer mixture containing at least a part of the monomer component (raw material monomer) of the composition. Typically, a part of the monomer component is included in the form of a polymer, and the remainder is included in the form of an unpolymerized substance (unreacted monomer).
- the polymerization reaction product of the monomer mixture can be prepared by at least partially polymerizing the monomer mixture.
- the polymerization reaction product is preferably a partial polymerization product of the monomer mixture.
- Such a partial polymer is a mixture of a polymer derived from the monomer mixture and an unreacted monomer, and typically exhibits a syrup shape (viscous liquid).
- a partially polymerized product may be referred to as “monomer syrup” or simply “syrup”.
- the polymerization method for obtaining the polymerization reaction product is not particularly limited, and various polymerization methods as described above can be appropriately selected and used. From the viewpoints of efficiency and simplicity, a photopolymerization method can be preferably employed. According to photopolymerization, the polymerization conversion rate of the monomer mixture can be easily controlled by polymerization conditions such as the amount of light irradiation (light quantity).
- the polymerization conversion rate (monomer conversion) of the monomer mixture in the partial polymer is not particularly limited.
- the polymerization conversion rate can be, for example, 70% by weight or less, and preferably 60% by weight or less. From the viewpoint of ease of preparation of the resin layer forming composition containing the partial polymer, coating properties, and the like, usually, the polymerization conversion rate is suitably 50% by weight or less, and 40% by weight or less (for example, 35% by weight). % Or less) is preferable.
- the lower limit of the polymerization conversion rate is not particularly limited and is typically 1% by weight or more, and usually 5% by weight or more is appropriate.
- the resin layer forming composition containing a partial polymer of the monomer mixture can be easily obtained by, for example, partially polymerizing a monomer mixture containing all of the raw material monomers by an appropriate polymerization method (for example, photopolymerization method).
- the resin layer forming composition containing the partial polymer may contain other components used as necessary (for example, a photopolymerization initiator, a polyfunctional monomer, a crosslinking agent, an acrylic oligomer described later, and the like).
- the method of blending such other components is not particularly limited, and for example, it may be previously contained in the monomer mixture or added to the partial polymer.
- a complete polymerization product of a monomer mixture containing some types of monomers among the monomer components is converted into the remaining types of monomers or partial polymerization products thereof. It may be in a dissolved form.
- Such a resin layer forming composition is also included in examples of the resin layer forming composition containing a polymerized monomer component and an unpolymerized product.
- the “completely polymerized product” means that the polymerization conversion rate is more than 95% by weight.
- a photopolymerization method can be preferably employed as a curing method (polymerization method) when forming a resin layer from a resin layer forming composition containing a polymerized monomer component and an unpolymerized product.
- the resin layer forming composition containing the polymerization reaction product prepared by the photopolymerization method it is particularly preferable to employ the photopolymerization method as the curing method. Since the polymerization reaction product obtained by the photopolymerization method already contains a photopolymerization initiator, when the resin layer forming composition containing this polymerization reaction product is further cured to form a resin layer, a new photopolymerization start is started. It can be photocured without adding an agent.
- the composition for resin layer formation of the composition which added the photoinitiator as needed to the polymerization reaction material prepared by the photopolymerization method may be sufficient.
- the photopolymerization initiator to be added may be the same as or different from the photopolymerization initiator used for the preparation of the polymerization reaction product.
- the resin layer forming composition prepared by a method other than photopolymerization can be made photocurable by adding a photopolymerization initiator.
- the photocurable resin layer forming composition has an advantage that even a thick resin layer can be easily formed.
- the photopolymerization when forming the resin layer from the resin layer forming composition can be performed by ultraviolet irradiation.
- a known high-pressure mercury lamp, low-pressure mercury lamp, metal halide lamp, or the like can be used for ultraviolet irradiation.
- the resin layer forming composition includes the monomer component of the composition in the form of a completely polymerized product.
- a resin layer forming composition is, for example, a solvent-type resin layer forming composition containing an acrylic polymer, which is a complete polymer of monomer components, in an organic solvent, water in which the acrylic polymer is dispersed in an aqueous solvent. It may be in the form of a dispersion type resin layer forming composition.
- the weight average molecular weight (Mw) of the acrylic polymer that is a complete polymerization product of the monomer component is not particularly limited. From the viewpoint of balancing the adhesive force and the cohesive force in a balanced manner, the Mw is preferably 10 ⁇ 10 4 or more, more preferably 20 ⁇ 10 4 or more, and even more preferably 50 ⁇ 10 4 or more (for example, 100 ⁇ 10 4 or more). , Typically 150 ⁇ 10 4 or more). For the same reason, the Mw is preferably 500 ⁇ 10 4 or less, more preferably 300 ⁇ 10 4 or less (for example, 250 ⁇ 10 4 or less). In addition, in this specification, Mw means the value of standard polystyrene conversion obtained by GPC (gel permeation chromatography).
- the composition for forming a resin layer disclosed herein may contain a (meth) acrylic oligomer from the viewpoint of improving adhesive strength. By including a (meth) acrylic oligomer, the adhesive force of the resin layer can be improved.
- the (meth) acrylic oligomer preferably has a Tg of about 0 ° C. or higher and 300 ° C. or lower, preferably about 20 ° C. or higher and 300 ° C. or lower, more preferably about 40 ° C. or higher and 300 ° C. or lower.
- Tg is within the above range, the adhesive force can be preferably improved.
- the Tg of the (meth) acrylic oligomer is a value calculated based on the Fox equation, similar to the Tg of the acrylic polymer.
- the weight average molecular weight (Mw) of the (meth) acrylic oligomer may typically be 1000 or more and less than 30000, preferably 1500 or more and less than 20000, and more preferably 2000 or more and less than 10,000. It is preferable for Mw to be within the above range because good adhesive force and holding characteristics can be obtained.
- Mw of the (meth) acrylic oligomer is measured by GPC and can be obtained as a standard polystyrene equivalent value. Specifically, it is measured on a “HPLC 8020” manufactured by Tosoh Corporation using two TSKgelGMH-H (20) columns as a column and a tetrahydrofuran solvent at a flow rate of about 0.5 mL / min.
- a monomer constituting the (meth) acrylic oligomer for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl ( (Meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, is
- Examples of (meth) acrylic oligomers include alkyl (meth) acrylates in which alkyl groups such as isobutyl (meth) acrylate and t-butyl (meth) acrylate have a branched structure; cyclohexyl (meth) acrylate and isobornyl (meth) acrylate, Esters of (meth) acrylic acid and alicyclic alcohols such as dicyclopentanyl (meth) acrylate; cyclic structures such as aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate It is preferable that an acrylic monomer having a relatively bulky structure typified by (meth) acrylate is included as a monomer unit from the viewpoint of further improving adhesiveness.
- an alkyl (meth) acrylate having an ester or an ester with an alicyclic alcohol can be preferably used as a monomer constituting the (meth) acrylic oligomer.
- suitable (meth) acrylic oligomers include, for example, dicyclopentanyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA),
- DCPMA dicyclopentanyl methacrylate
- CHMA cyclohexyl methacrylate
- IBXMA isobornyl methacrylate
- IBXA isobornyl acrylate
- DCPA dicyclopentanyl acrylate
- ADMA 1-adamantyl methacrylate
- ADA 1-adamantyl acrylate
- a copolymer of CHMA and isobutyl methacrylate (IBMA), CHMA and IBXMA Copolymer Copolymer of CHMA and acryloylmorpholine (ACMO), Copolymer of CHMA and diethylacrylamide (DEAA), Copolymer of
- the content thereof is not particularly limited, and is approximately about 100 parts by weight of the monomer component contained in the resin layer forming composition. It is appropriate that the amount is 1 part by weight or more. From the viewpoint of better exhibiting the effect of the (meth) acrylic oligomer, the content of the (meth) acrylic oligomer is 3 parts by weight or more (for example, 5 parts by weight or more, typically 8 parts by weight or more). It is preferable to do.
- the content of the (meth) acrylic oligomer from the viewpoint of the curability of the resin layer forming composition and the compatibility with the partial polymer or the complete polymer of the acrylic polymer (and thus the transparency of the resin layer).
- the technique disclosed here can also be implemented in an embodiment that does not use a (meth) acrylic oligomer.
- the resin layer forming composition disclosed herein may contain a silane coupling agent.
- silane coupling agents that can be preferably used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxy.
- (Meth) acrylic group Isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane; Yes silane coupling agent, and the like. These can be used alone or in combination of two or more.
- the amount of the silane coupling agent is preferably 1 part by weight or less (for example, 0.01 to 1 part by weight), more preferably 0.02 to 100 parts by weight with respect to 100 parts by weight of the monomer component constituting the acrylic polymer. 0.6 parts by weight.
- the composition for resin layer formation disclosed here can contain a crosslinking agent.
- the crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a silicone crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a silane crosslinking agent, an alkyl etherified melamine crosslinking agent, and a metal chelate crosslinking agent. Etc. These can be used alone or in combination of two or more.
- Preferable examples of the crosslinking agent include isocyanate crosslinking agents and epoxy crosslinking agents.
- the amount of the crosslinking agent used is not particularly limited, and is, for example, about 10 parts by weight or less (for example, about 0.005 to 10 parts by weight, preferably about 0.01 to 5 parts by weight) with respect to 100 parts by weight of the acrylic polymer. You can choose from a range. Or the composition for resin layer formation may not contain the above crosslinking agents.
- the resin layer forming composition disclosed herein may contain various additives known in the field of pressure-sensitive adhesives, for example.
- powders such as colorants, pigments, dyes, surfactants, plasticizers, tackifying resins, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, A polymerization inhibitor, an inorganic or organic filler, metal powder, particles, foils, etc. can be appropriately added depending on the application.
- the resin layer disclosed herein can be formed, for example, as a resin layer by applying any of the resin layer forming compositions disclosed herein to a support and drying or curing.
- a coating method of the resin layer forming composition various conventionally known methods can be used. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
- the resin layer forming composition can be dried under heating.
- the drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and further preferably 70 ° C to 170 ° C. By setting the heating temperature within the above range, a resin layer having excellent physical properties can be obtained.
- As the drying time an appropriate time can be adopted as appropriate.
- the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and even more preferably 10 seconds to 5 minutes.
- a crosslinking treatment, a thermosetting treatment, or the like can be further performed.
- a thermosetting treatment can be performed at about 80 to 200 ° C. (eg, 100 to 180 ° C., typically 120 to 160 ° C.) for 5 minutes or more.
- the heat curing treatment time is preferably 10 minutes or longer, more preferably 20 minutes or longer (for example, 30 minutes or longer, typically 40 minutes to 120 minutes).
- the resin layer is preferably subjected to press treatment before or during the thermosetting treatment.
- the resin layer disclosed herein can be obtained from the resin layer forming composition.
- the thickness of the resin layer is not particularly limited, and can be, for example, about 1 to 400 ⁇ m.
- the thickness of the resin layer is preferably 1 to 200 ⁇ m, more preferably 2 to 150 ⁇ m, further preferably 2 to 100 ⁇ m, and particularly preferably 5 to 75 ⁇ m.
- the resin layer before the conductive portion is placed is spirally overlapped with a release liner (support) whose front surface and back surface are both release surfaces (peelable surfaces). It may be in a form wound in a shape. Alternatively, the first surface and the second surface may be respectively protected by two independent release liners (supports). As the release liner, those described below can be preferably used.
- mode is an adhesive sheet containing a base material layer.
- Such an adhesive sheet includes a base material layer and an adhesive layer arranged on at least one surface of the base material layer.
- a single-sided adhesive sheet one-sided pressure-sensitive adhesive sheet with a base material layer
- double-sided adhesive provided with a pressure-sensitive adhesive layer on both sides of the base material layer
- Adhesive sheet double-sided pressure-sensitive adhesive sheet with a base material layer.
- the pressure-sensitive adhesive layer materials that can be used as a pressure-sensitive adhesive layer from those exemplified as the resin layer and those having preferable characteristics can be appropriately selected and used. Therefore, the overlapping description about the pressure-sensitive adhesive layer is omitted here.
- a resin film, paper, cloth, rubber film, foam film, a composite or laminate of these, and the like can be used as the substrate layer disclosed herein.
- a resin film layer is included from viewpoints of durability improvement of a module, workability
- the inclusion of the resin film layer is advantageous from the viewpoint of dimensional stability, thickness accuracy, workability, strength, and the like.
- the “resin film” means a resin film having a non-porous structure and typically containing substantially no bubbles (voidless). Therefore, the said resin film is the concept distinguished from a foam film and a nonwoven fabric.
- a base material layer is a transparent film (for example, transparent resin film) typically.
- the said base material layer When applying a base material layer to the coating layer arrange
- the resin film may have a single layer structure or a multilayer structure of two or more layers.
- resin films examples include polyolefin resin films such as polyethylene (PE), polypropylene (PP), and ethylene / propylene copolymers; polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; Vinyl chloride resin film; vinyl acetate resin film; polyimide resin film; polyamide resin film; fluorine resin film; cellophane; Preferable examples include resin films formed from PE, PP, and PET. Among the resin films, a polyester film is more preferable, and a PET film is more preferable among them.
- additives that can be used for the base material layer of the pressure-sensitive adhesive sheet can be contained as necessary.
- additives such as a light stabilizer such as an ultraviolet absorber, an antioxidant, an antistatic agent, a filler, a plasticizer, a slip agent, and an antiblocking agent can be appropriately blended.
- a light stabilizer such as an ultraviolet absorber, an antioxidant, an antistatic agent, a filler, a plasticizer, a slip agent, and an antiblocking agent
- Each of these additives can be used alone or in combination of two or more. What is necessary is just to set the compounding quantity of an additive suitably from the range of the normal compounding quantity in the said base material layer.
- the coating layer disclosed here is provided with the base material layer which does not contain the component which reduces a total light transmittance from viewpoints, such as electric power generation efficiency.
- the thickness of the base material layer (when there are a plurality of layers, the total thickness of these layers) is not particularly limited, and can be appropriately selected according to the purpose.
- the thickness of the base material layer can generally be 1 to 300 ⁇ m. From the viewpoint of obtaining a predetermined rigidity or more and improving durability, the thickness of the base material layer is preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, further preferably 45 ⁇ m or more (for example, 70 ⁇ m or more, typically 90 ⁇ m or more). ).
- the thickness of the base material layer is preferably about 200 ⁇ m or less (for example, 150 ⁇ m or less).
- a coating layer with a limited thickness of the base material layer can be advantageous in terms of weight reduction, resource saving, and the like.
- the base material layer On the surface of the base material layer (for example, the pressure-sensitive adhesive layer side surface), corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of primer (primer), antistatic treatment, etc., as necessary
- the conventionally known surface treatment may be applied.
- Such a surface treatment may be a treatment for improving the adhesion between the base material layer and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer to the base material layer.
- the back surface of the base material layer (the surface opposite to the surface on which the pressure-sensitive adhesive layer is provided) is subjected to a release treatment with a release treatment agent such as silicone, long-chain alkyl, or fluorine as necessary. May be.
- the thickness of the pressure-sensitive adhesive layer constituting the coating layer is not particularly limited, and may be about 1 ⁇ m or more. From the viewpoint of adhesion with the solar battery cell, the thickness of the pressure-sensitive adhesive layer is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more. The thickness of the pressure-sensitive adhesive layer is usually about 400 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably 75 ⁇ m or less.
- the coating layer in which the thickness of the pressure-sensitive adhesive layer is limited can be advantageous in terms of weight reduction and resource saving. When the pressure-sensitive adhesive layer (first pressure-sensitive adhesive layer and second pressure-sensitive adhesive layer) is provided on both surfaces of the base material layer, the thickness of each pressure-sensitive adhesive layer may be the same or different.
- the total thickness of the coating layer disclosed herein is not particularly limited, and is suitably about 2 ⁇ m or more, preferably Is 5 ⁇ m or more (for example, 10 ⁇ m or more, typically 30 ⁇ m or more).
- the total thickness is suitably about 1000 ⁇ m or less, preferably 500 ⁇ m or less (for example, 300 ⁇ m or less, typically 100 ⁇ m or less).
- a conventional release paper or the like can be used as the release liner for protecting the upper and lower surfaces of the first coating layer and the second coating layer, and is not particularly limited.
- a release liner having a release treatment layer on the surface of a substrate such as a plastic film or paper, or a release made of a low adhesive material such as a fluorine polymer (polytetrafluoroethylene, etc.) or a polyolefin resin (polyethylene, polypropylene, etc.)
- a liner or the like can be used.
- the release treatment layer may be formed by surface-treating the base material with a release treatment agent.
- the release treatment agent include a silicone release treatment agent, a long-chain alkyl release treatment agent, a fluorine release treatment agent, and molybdenum (IV) sulfide.
- the type of the solar battery cell to be used is not particularly limited, and for example, a single crystal type or a polycrystalline type Si cell is suitable.
- the crystalline Si cell may be a p-type cell (a cell in which n-type is added to a p-type substrate) or an n-type cell (a cell in which p-type is added to an n-type substrate).
- the solar battery cell may be an amorphous Si cell, a compound solar battery, an organic solar battery cell or the like. Further, the solar cell may be either a single-sided light receiving type or a double-sided light receiving type.
- the shape of the solar battery cell is not particularly limited, and it may be a wafer having a substantially rectangular plane, or may be a belt shape.
- the thickness of the solar battery cell is preferably about 0.5 mm or less, more preferably about 0.3 mm or less (for example, about 180 to 200 ⁇ m), and further preferably about 160 ⁇ m or less from the viewpoint of lightness and the like.
- the sealing resin disclosed here may be insulative and translucent. For example, it may be a resin layer that can exhibit fluidity by heat or pressure.
- insulating means a specific resistance at 25 ° C. of 1 ⁇ 10 6 ⁇ ⁇ cm or more (preferably 1 ⁇ 10 8 ⁇ ⁇ cm or more, typically 1 ⁇ 10 10 ⁇ ). -Cm or more).
- the electric resistance is a value at 25 ° C. unless otherwise specified.
- “having translucency” means that the total light transmittance defined by JIS K 7375: 2008 is 50% or more (preferably 80% or more, typically 95% or more). That means.
- the sealing resin may preferably be a thermosetting resin.
- the sealing resin made of a thermosetting resin can be well sealed in the solar battery module by, for example, laminating and heating the solar battery cell.
- an ethylene-vinyl acetate copolymer (EVA) is preferably used from the viewpoints of translucency, workability, weather resistance, and the like.
- the above resins include ethylene-vinyl ester copolymers represented by EVA, ethylene-unsaturated carboxylic acid copolymers such as ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid esters, etc.
- An ethylene-unsaturated carboxylic acid ester copolymer, an unsaturated carboxylic acid ester-based polymer such as polymethyl methacrylate, and the like may be used.
- fluoropolymers such as vinylidene fluoride resin and polyethylene tetrafluoroethylene; manufactured using low density polyethylene (LDPE), linear low density polyethylene (LLDPE, typically Ziegler catalyst, vanadium catalyst, metallocene catalyst, etc.
- PE polyethylene
- PP polypropylene
- PP polypropylene
- PP polypropylene
- Polyolefins such as ethylene / ⁇ -olefin copolymers and their modified products (modified polyolefins); Polybutadienes; Polyvinyl acetals such as polyvinyl formal, polyvinyl butyral (PVB resin), and modified PVB; polyethylene Terephthalate (PET); polyimide; amorphous polycarbonate; siloxane sol - gel; polyurethane; polystyrene; polyether sulfone; polyarylate, epoxy resins, may be like; silicone resin; ionomers. These resins may be used alone or in combination of two or more.
- the resin may contain various additives known in the art such as an ultraviolet absorber and a light stabilizer.
- an adhesion improver may be added to the sealing resin in order to improve the adhesion.
- the sealing resin is arranged and heat-treated so that the surface faces the solar cell side, The adhesion between the solar cell and the solar battery cell is improved.
- a silane coupling agent is preferably used as the adhesion improver.
- Various surface treatments such as corona treatment and atmospheric pressure plasma treatment can be applied to the surface of the sheet-shaped sealing resin alone or in combination for the purpose of improving adhesion and the like.
- the thickness of the sheet-shaped sealing resin used for the construction of the solar cell module is about 100 to 2000 ⁇ m (for example, 200 to 1000 ⁇ m, typically 400 to 800 ⁇ m) from the viewpoint of the sealing performance of the solar battery cell. It is preferable.
- ⁇ Surface covering member> As the surface covering member, various materials having translucency can be used.
- Surface covering member is glass plate, fluororesin sheet such as tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride resin, chlorotrifluoroethylene resin, acrylic resin, polyethylene terephthalate It may be a resin sheet composed of a material such as polyester such as (PET) or polyethylene naphthalate (PEN).
- PET polyester
- PEN polyethylene naphthalate
- a flat plate member or a sheet member having a total light transmittance of 70% or more (for example, 90% or more, typically 95% or more) can be preferably used. The total light transmittance may be measured according to JIS K 7375: 2008.
- the thickness of the surface covering member is preferably about 0.5 to 10 mm (for example, 1 to 8 mm, typically 2 to 5 mm) from the viewpoint
- a flat plate member or a sheet member made of various materials exemplified as the material of the surface covering member is preferably used. Especially, it is more preferable to use polyester, such as PET and PEN, as a back surface covering member forming material. Or as a back surface covering member, you may use the metal sheet (for example, aluminum plate) which has corrosion resistance, resin sheets, such as an epoxy resin, and composite sheets, such as silica vapor deposition resin.
- the thickness of the back surface covering member is preferably about 0.1 to 10 mm (for example, 0.2 to 5 mm) from the viewpoints of handleability and lightness. In addition, the back surface covering member may not have translucency.
- the matters disclosed by this specification include the following. (1) a plurality of solar cells arranged at intervals; Conductivity that is connected from the upper surface of one solar cell of two adjacent solar cells to the lower surface of the other solar cell among the plurality of solar cells and electrically connects the two adjacent solar cells. And A first covering layer disposed above one solar cell of the two adjacent solar cells; A second coating layer disposed below the other solar cell of the two adjacent solar cells; With The conductive portion is disposed between the one solar cell and the first coating layer, and between the other solar cell and the second coating layer, and the one solar cell. A solar cell module partially disposed on the upper surface of the solar cell module.
- the conductive portion is composed of a plurality of conductive lines extending from the upper surface of one of the two adjacent solar cells to the lower surface of the other solar cell,
- (6) The solar cell module according to any one of (1) to (5), wherein the conductive wire exhibits a diffuse reflectance of 60% or more.
- Said 1st coating layer is not arrange
- the storage elastic modulus (frequency 1 Hz, strain 0.1%, 150 ° C.) of the first coating layer and the second coating layer are both 5000 Pa or more, and tan ⁇ at 80 ° C. to 150 ° C. is 0.
- an adhesive layer having a thickness of about 23 ⁇ m was obtained.
- the pressure-sensitive adhesive layer thus obtained was used as the coating layer (A).
- a release liner made of a 38 ⁇ m thick polyester film (trade name “Diafoil MRE”, manufactured by Mitsubishi Plastics, Inc.) surface-treated with a silicone-based release agent is applied to the surface of the pressure-sensitive adhesive layer.
- the two release liners were used for protecting the adhesive layer until the coating layer (A) was used.
- the adhesive force with respect to the photovoltaic cell back surface was measured about the coating layer (A), it was 15 N / 10mm.
- ⁇ Preparation Example 2> (Coating layer (B)) After applying corona treatment (made by Kasuga Denki Co., Ltd.) to a 50 ⁇ m thick polyester film (Kasuga Denki Co., Ltd.), the acrylic pressure-sensitive adhesive composition obtained in Preparation Example 1 was treated with corona treatment of the polyester film. It was applied to the surface and heat-treated at 155 ° C. to form an adhesive layer having a thickness of about 23 ⁇ m. This pressure-sensitive adhesive sheet (single-sided adhesive pressure-sensitive adhesive sheet) was used as the coating layer (B).
- a release liner made of a 38 ⁇ m thick polyester film (trade name “Diafoil MRE”, manufactured by Mitsubishi Plastics, Inc.) surface-treated with a silicone release agent is applied to the surface of the pressure-sensitive adhesive layer. Was placed on the pressure-sensitive adhesive layer side. This release liner was used for protecting the pressure-sensitive adhesive layer until the coating layer (B) was used.
- ⁇ Preparation Example 3> (Coating layer (C)) A single-sided adhesive sheet was prepared in the same manner as in Preparation Example 2, except that a polyester film having a thickness of 100 ⁇ m was used as the base material layer. This pressure-sensitive adhesive sheet was used as the coating layer (C).
- a copper wire (width 0.8 mm, thickness 0.25 mm) was prepared, cut to a length of 22 cm, and straightened with a straight line straightening machine (for example, manufactured by WITELS ALBERT) was used.
- Ag was used as the plating type.
- EVA sheet (Sealing resin) EVA sheet (trade name “EVASKY”, manufactured by Bridgestone, thickness 450 ⁇ m)
- Solar cell Si solar cell (polycrystalline Si cell, manufactured by GINTECH, 15.6 cm square)
- Surface covering member Glass plate (white plate heat-treated glass, manufactured by Asahi Glass Co., Ltd., thickness 3.2 mm)
- Back cover member Back sheet (trade name “KOBATEC PV KB-Z1-3”, manufactured by Kobayashi Corporation, thickness 200 ⁇ m)
- a test solar cell module was constructed using the above materials. Specifically, as shown in FIG. 6, two copper wires were arranged in parallel as the conductive portion 230 on the upper surface (light receiving surface) of the solar battery cell 210. The distance between the copper wires was 2 cm.
- the coating layer (A) 260 obtained above was cut into substantially the same size (15.6 cm square) as the solar battery cell 210, and the release liner was removed from the solar battery cell 210 in which the conductive portion 230 was disposed.
- the conductive portion 230 was fixed to the upper surface of the solar battery cell 210.
- a back surface covering member 370 was prepared, and a sheet-shaped sealing resin 350 was disposed on the surface thereof.
- the solar cell 210 with the conductive portion 230 fixed on the sealing resin 350 is placed so that the upper surface (light receiving surface) of the solar cell 210 faces upward (that is, the conductive portion 230 placement surface is on the upper side). Arranged. Further, another sheet-shaped sealing resin 350 was further disposed thereon, and then the surface covering member 360 was superposed on the sealing resin 350.
- This laminate is laminated using a commercially available laminator (manufactured by NPC) under conditions of 150 ° C. and 100 kPa for 5 minutes, cured for 15 minutes, and further, a commercially available blast incubator (Yamato).
- the solar cell module for test 200 was constructed by performing a drying treatment at 150 ° C. for 15 minutes using a science company.
- a test solar cell module was constructed using the above materials. Specifically, as shown in FIG. 6, two copper wires were arranged in parallel as the conductive portion 230 on the lower surface (back surface) of the solar battery cell 210. The distance between the copper wires was 2 cm.
- the coating layer (A) 260 obtained above was cut into substantially the same size (15.6 cm square) as the solar battery cell 210, and the release liner was removed from the solar battery cell 210 in which the conductive portion 230 was disposed.
- the conductive portion 230 was fixed to the lower surface of the solar battery cell 210.
- a surface covering member 360 was prepared, and a sheet-shaped sealing resin 350 was disposed on the surface thereof.
- the solar cell 210 with the conductive portion 230 fixed on the sealing resin 350 is arranged so that the upper surface (light receiving surface) of the solar cell 210 faces downward (surface covering member 360 side) (that is, the conductive portion 230 arrangement surface). Was placed on the top).
- a back surface covering member 370 was superimposed on the sealing resin 350.
- This laminate is laminated using a commercially available laminator (manufactured by NPC) under conditions of 150 ° C. and 100 kPa for 5 minutes, cured for 15 minutes, and further, a commercially available blast incubator (Yamato).
- the solar cell module for test 200 was constructed by performing a drying treatment at 150 ° C. for 15 minutes using a science company.
- solar cells 210 in which the conductive portion 230 and the coating layer (A) 260 are arranged on the lower surface (back surface) are covered with the sealing resin 350 at the upper and lower sides thereof. It is sandwiched between the surface covering member 360 and the back surface covering member 370.
- two copper wires as the conductive portion 230 disposed on the lower surface (back surface) of the solar battery cell 210 protrude from both ends of the test solar battery module 200.
- Example 1-1 As shown in FIG. 7, two copper wires were arranged in parallel as the conductive portion 230 on the lower surface (back surface) of the solar battery cell 210. The distance between the copper wires was 2 cm. Moreover, after preparing two strip
- two strip-shaped covering members 260 cover the copper wire (conductive portion 230) on the lower surface of the solar battery cell 210, and are parallel to each other with a gap therebetween.
- the width of the coating layer non-arrangement region (band region) between the two belt-shaped coating members 260 (coating layer (A)) is about 1 cm.
- Example 1-2 A test solar cell module according to this example was constructed in the same manner as in Example 1-1 except that two strip-shaped covering members cut to 15.6 cm ⁇ 0.5 cm were used as the coating layer (A). In this test solar cell module, the width of the coating layer non-arrangement region (strip region) between the two strip coating members 260 (coating layer (A)) is about 1.5 cm.
- thermo cycle test About the obtained solar cell module for testing, using a thermo-hygrostat (device name “PSL-2J”, manufactured by Espec), in accordance with JIS C 8990: 2009 section 10.11 (temperature cycle test) , A heat cycle test was conducted with -40 ° C to 85 ° C as one cycle. During the test, one end of one copper wire exposed from the test solar cell module (the end portion indicated by symbol A in FIGS. 6 and 7) to the other end of the other copper wire (the end located on the side opposite to the one end) 6 and 7, a DC power source (model name “PMC-185A”) installed outside the thermo-hygrostat using a gold-plated cord with a crocodile clip over the end indicated by the symbol B in FIG.
- PMC-185A DC power source
- a constant current (2 A) was applied from KIKUSUI. Further, a gold-plated alligator clip is attached to one end of the one copper wire and the other end of the other copper wire and between the AB, respectively, and a product name “NIcDAQ-9178 ( I / O module; NI9205) "(manufactured by NATIONAL INSTRUMENTS) was used to measure the voltage. The measurement data was converted into a resistance value by software (LabView) and monitored. Resistance values were recorded at 4 minute intervals.
- FIGS. 8, 9, 10, and 11 The results of the heat cycle tests according to Reference Example 1, Reference Example 2, Example 1-1, and Example 1-2 are shown in FIGS. 8, 9, 10, and 11, respectively. From the comparison between FIG. 8 and FIG. 9, when the coating layer (A) was disposed so as to cover the entire front surface or the entire back surface of the solar battery cell, a tendency for resistance to increase on the back surface side of the solar battery cell was recognized. In particular, a tendency for resistance to increase during heating in the heat cycle test was observed. As the cause, it is considered that the cell contact property of the conductive portion is lowered on the back surface side of the solar battery cell at the time of heating due to the asymmetry of the solar battery cell and the vertical arrangement.
- Example 1-1 and 1-2 where the covering layer partially covers the back surface of the solar cell, the entire cell back surface is covered with the covering layer.
- the covering layer partially covers the back surface of the solar cell, the entire cell back surface is covered with the covering layer.
- an increase in resistance in the heat cycle test was suppressed.
- the conductive portion With the coating layer, the contact state between the back surface of the cell and the conductive portion is well maintained, and by partially covering the back surface of the cell with the coating layer, the sealing resin is disposed in the coating layer non-arranged region. It is presumed that the cell is firmly attached to the back surface of the cell, and the good contact state between the cell back surface and the conductive portion is more firmly maintained, and the durability is improved.
- Example 1-2 in which the band-shaped covering member was made narrower, the increase in resistance tended to be further suppressed.
- Example 2-1> The test solar cell module according to this example is the same as Example 1-1 except that the coating layer (B) (width of the belt-shaped coating member 1 cm) made of a single-sided pressure-sensitive adhesive sheet with a base material layer is used as the coating layer. It was constructed. In this test solar cell module, the coating layer (B) has its adhesive layer side surface bonded to the lower surface of the solar cell through the conductive portion, and its base layer side is outward (downward) of the solar cell. ).
- Example 2-2 The test solar cell module according to this example is the same as Example 2-1, except that the coating layer (C) (1 cm width of the belt-shaped coating member) made of the single-sided adhesive sheet with the base material layer is used as the coating layer. It was constructed.
- Example 2-1 and Example 2-2 The results of the heat cycle test according to Example 2-1 and Example 2-2 are shown in FIGS. 12 and 13, respectively. As FIG. 12 and FIG. 13 showed, the resistance increase in a heat cycle test was further suppressed by using an adhesive sheet with a base material layer as a coating layer. Further, from the comparison between Example 2-1 and Example 2-2, it was recognized that the durability tends to be further improved by increasing the thickness of the base material layer. The reason is considered to be that the rigidity of the coating layer is increased by providing the base material layer, and the good contact state between the back surface of the cell and the conductive portion is more firmly maintained.
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- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、太陽電池モジュール、太陽電池モジュールの製造方法および太陽電池セルの配線方法に関する。
本出願は、2015年7月10日に出願された日本国特許出願2015-139211号、2015年11月6日に出願された日本国特許出願2015-218976号、および2016年3月18日に出願された日本国特許出願2016-054790号に基づく優先権を主張しており、それらの出願の全内容は本明細書中に参照として組み入れられている。
The present invention relates to a solar cell module, a method for manufacturing a solar cell module, and a method for wiring solar cells.
This application includes Japanese Patent Application No. 2015-139211 filed on July 10, 2015, Japanese Patent Application No. 2015-218976 filed on November 6, 2015, and March 18, 2016. Claims priority based on the filed Japanese Patent Application No. 2016-054790, the entire contents of which are incorporated herein by reference.
光エネルギーを電力に変換する太陽電池モジュールは、クリーンな発電装置として幅広く利用されている。太陽電池モジュールは、太陽電池セルと、該セルに接続した配線とを備えており、この配線を通って上記セルにて発電された電力は外部に供給されるように構成されている。この種の従来技術を開示する文献として特許文献1~8が挙げられる。特許文献1~6は、太陽電池セルの表面側にn型電極を部分的に配置し、裏面側にp型電極を配置するタイプの太陽電池モジュールに関するものであり、特許文献7,8は、裏面側に両電極が配置されたバックコンタクト方式を採用する太陽電池モジュールに関するものである。
Solar cell modules that convert light energy into electric power are widely used as clean power generators. The solar cell module includes a solar cell and a wiring connected to the cell, and the power generated in the cell through the wiring is configured to be supplied to the outside.
表裏面に電極を有するタイプの太陽電池モジュールにおいて、例えば特許文献1,2に開示されている構造は、太陽電池セルの配線をはんだ等を用いて個別に接合しなければならず配線作業に手間と時間を要し、生産性の改善に限度がある。はんだ接合等のように接合の際に加熱を行う場合には、加熱によりセルの特性が低下したり、セルに反りや割れが生じるおそれがある。はんだ接合ではフラックス汚染の問題もある。特許文献3,4に開示されている太陽電池モジュールも、導電経路となるワイヤーをはんだ接合しており、特許文献1,2と同様の問題を抱えている。また上記ワイヤーは、樹脂膜上の接着剤層に埋め込むという方法によって配置されている。この方法は部品点数や工程数が多く、生産効率の点で不利益が大きい。
In solar cell modules of the type having electrodes on the front and back surfaces, for example, the structures disclosed in
特許文献5に記載されている太陽電池モジュールは、金属配線を表面に有する封止シートを一対用意し、この一対の封止シートで複数の太陽電池セルを挟んで、上記金属配線と太陽電池セルとを当接させて押圧および加熱することによって、はんだ接合を必要とすることなく複数の太陽電池セルを電気的に接続するとしている。しかし、上下の金属配線の導通は、接触面積の確保、位置合わせの精度等の要素を含み、また、上記金属配線の導通状態(当接状態)は封止樹脂の流動等によって損なわれるおそれがある。これらは、集電効率の低下や配線不良として、経時的な性能劣化、すなわち耐久性の低下をもたらす。特許文献6では、上下の金属配線の接合に導電性フィルム等を利用して接続信頼性の向上を図っているものの、上下の金属配線の接合点は強度上の弱点となるため、耐久性や歩留りの向上には構造的に限界がある。このように、従来の技術水準では、生産性と耐久性とを両立することができなかった。
The solar cell module described in
本発明は、上記の事情に鑑みて創出されたものであり、生産性に優れ、かつ耐久性が向上した太陽電池モジュールを提供することを目的とする。関連する他の目的は、そのような太陽電池モジュールの製造方法および太陽電池セルの配線方法を提供することである。 The present invention has been created in view of the above circumstances, and an object thereof is to provide a solar cell module having excellent productivity and improved durability. Another related object is to provide a method for manufacturing such a solar cell module and a method for wiring solar cells.
本発明によると、太陽電池セルを備える太陽電池モジュールが提供される。この太陽電池モジュールは導電部を備える。この導電部は、前記太陽電池セルの裏面に部分的に配置されている。また、上記太陽電池モジュールは被覆層をさらに備える。この被覆層は、前記太陽電池セルの裏面を前記導電部越しに覆い、かつ該太陽電池セルの裏面と接着する。そして、前記被覆層は、前記太陽電池セルの裏面において部分的に配置されている。
上記の構成によると、太陽電池セル裏面における導電部を用いた配線は、はんだ接合等の直接的な接着手段を必要とせず、セル裏面と導電部との物理接触で実現されるので、生産性に優れる。また、セル裏面の外方から導電部を覆う被覆層は、セル裏面と導電部との接触状態を良好に保持する。例えば、被覆層は導電部を覆い、かつ導電部の外側でセル裏面と接着しているので、上記被覆層が存在することで、太陽電池セルを封止するために通常用いられる封止樹脂がセル裏面と導電部との接触状態に悪影響を及ぼす事象は防止される。さらに、上記被覆層は部分的にセル裏面を覆っているので、当該裏面には被覆層非配置領域が存在する。被覆層非配置領域を設けることによって、被覆層非配置領域のない構成と比べて、太陽電池モジュールの耐久性はさらに向上し得る。具体的には、太陽電池セルを封止するために通常用いられる封止樹脂は、流動して上記被覆層非配置領域にて太陽電池セル裏面と接触後、硬化によってセル裏面に固着(硬化接着)する。すなわち、被覆層非配置領域を設けることによって、上記封止樹脂の固着等の作用を利用して、セル裏面と導電部との接触状態をより安定させることができる。その結果、太陽電池モジュールの耐久性は向上する。本発明によると、生産性に優れ、かつ耐久性を向上し得る太陽電池モジュールが提供される。
According to this invention, a solar cell module provided with a photovoltaic cell is provided. This solar cell module includes a conductive portion. The conductive portion is partially disposed on the back surface of the solar battery cell. The solar cell module further includes a coating layer. The covering layer covers the back surface of the solar battery cell over the conductive portion and adheres to the back surface of the solar battery cell. And the said coating layer is partially arrange | positioned in the back surface of the said photovoltaic cell.
According to the above configuration, the wiring using the conductive portion on the back surface of the solar battery cell is realized by physical contact between the back surface of the cell and the conductive portion without requiring direct bonding means such as solder bonding. Excellent. Moreover, the coating layer covering the conductive portion from the outside of the cell back surface favorably maintains the contact state between the cell back surface and the conductive portion. For example, since the coating layer covers the conductive part and is adhered to the back surface of the cell outside the conductive part, the presence of the coating layer makes it possible to use a sealing resin that is usually used for sealing solar cells. Events that adversely affect the contact state between the cell back surface and the conductive portion are prevented. Furthermore, since the coating layer partially covers the cell back surface, there is a coating layer non-arranged region on the back surface. By providing the covering layer non-arrangement region, the durability of the solar cell module can be further improved as compared with the configuration without the covering layer non-arrangement region. Specifically, the sealing resin usually used for sealing the solar battery cell flows and contacts the back surface of the solar battery cell in the coating layer non-arrangement region, and then adheres to the back surface of the cell by curing (curing adhesion) ) That is, by providing the coating layer non-arrangement region, the contact state between the cell back surface and the conductive portion can be further stabilized by utilizing the action such as the fixing of the sealing resin. As a result, the durability of the solar cell module is improved. ADVANTAGE OF THE INVENTION According to this invention, the solar cell module which is excellent in productivity and can improve durability is provided.
なお、本明細書では、太陽電池セルの表裏面(より具体的には、太陽電池セルの表面電極および裏面電極)と導電部(例えば導電線)との当接による配線を、はんだ接合や導電性接着剤等の接着手段(直接的な接着手段。導電性接着手段ともいう。以下同じ。)を用いた接合と区別する意味で「物理接触」ということがある。物理接触とは、接着手段を用いることなく当接のみで接触し導通が実現された接触状態や接触方法を指す。ここに開示される被覆層は、接着性を有するものであり得るが、上記物理接触を補助および保持する役割を担うものであり、上記接着手段とは異なるものとして把握される。上記のような、はんだ等の低融点金属を使用しない「はんだレス配線」は、物理接触型配線の典型例である。本明細書では、そのような物理接触型配線によって構築された太陽電池モジュールを物理接触型太陽電池モジュールという。物理接触型太陽電池モジュールは、非加熱で導通可能であるので、加熱によるセル特性の低下を防止することができる。また、はんだレス配線を行う太陽電池モジュール(はんだレス太陽電池モジュール)によると、上述のフラックス汚染を回避できるだけでなく、はんだ接合を原因とするリーチングやクレータリング等の問題も解消することができる。 In the present specification, wiring by contact between the front and back surfaces of the solar battery cell (more specifically, the front and back electrodes of the solar battery cell) and the conductive portion (for example, conductive wire), solder bonding or conductive May be referred to as “physical contact” to distinguish from bonding using bonding means such as adhesive (direct bonding means; also referred to as conductive bonding means; the same shall apply hereinafter). Physical contact refers to a contact state or a contact method in which conduction is achieved by contact only by contact without using an adhesive means. Although the coating layer disclosed here may have adhesiveness, it plays the role of assisting and holding the physical contact, and is understood to be different from the bonding means. The “solderless wiring” that does not use a low melting point metal such as solder as described above is a typical example of physical contact wiring. In this specification, a solar cell module constructed by such physical contact type wiring is referred to as a physical contact type solar cell module. Since the physical contact type solar cell module can be conducted without heating, cell characteristics can be prevented from being deteriorated due to heating. Moreover, according to the solar cell module that performs solderless wiring (solderless solar cell module), not only the above-mentioned flux contamination can be avoided, but also problems such as leaching and cratering caused by solder bonding can be solved.
ここに開示される技術(太陽電池モジュール、その製造方法および太陽電池セルの配線方法を包含する。以下同じ。)の好ましい一態様では、前記導電部は、複数の導電線から構成されている。このように構成することで、効率よく集電効率を高めることができる。 In a preferred embodiment of the technology disclosed herein (including a solar cell module, a manufacturing method thereof, and a solar cell wiring method; the same applies hereinafter), the conductive portion is composed of a plurality of conductive wires. By comprising in this way, current collection efficiency can be improved efficiently.
ここに開示される技術の好ましい一態様では、前記被覆層は、複数の帯状被覆部材からなる。また、前記太陽電池セルの裏面において、前記複数の帯状被覆部材のうち一の帯状被覆部材は、該太陽電池セルの裏面外方から前記複数の導電線のうち一の導電線を覆っており、かつ該導電線の幅方向の両外側にて、該太陽電池セルの裏面と接着している。上記のように、被覆層の接着と形状配置とを利用することで、セル裏面と導電線との接触状態はより安定し、接続信頼性に優れた配線が好ましく実現される。 In a preferred aspect of the technology disclosed herein, the coating layer is composed of a plurality of strip-shaped coating members. Further, in the back surface of the solar battery cell, one of the plurality of belt-shaped covering members covers one conductive wire of the plurality of conductive wires from the outside of the back surface of the solar battery cell, And it adhere | attaches with the back surface of this photovoltaic cell in the both outer sides of the width direction of this conductive wire. As described above, by utilizing the adhesion and shape arrangement of the coating layer, the contact state between the cell back surface and the conductive wire is more stable, and wiring excellent in connection reliability is preferably realized.
ここに開示される技術の好ましい一態様では、前記被覆層は粘着シートである。被覆層として粘着シートを用いることで、当該粘着シートの粘着特性を利用して、セル裏面と導電部(例えば複数の導電線)とは、物理接触による導通を好ましく保持することができる。また、上記粘着シートは、導電部の外側(例えば、複数の導電線の各々の両外側)でセル裏面と接着するので、例えば封止樹脂の導電部側への流動等を防止し、セル裏面と導電部(例えば複数の導電線)との接触状態をより良好に保持する。 In a preferred embodiment of the technology disclosed herein, the coating layer is an adhesive sheet. By using the pressure-sensitive adhesive sheet as the coating layer, the cell back surface and the conductive portion (for example, a plurality of conductive wires) can be preferably kept conductive by physical contact using the pressure-sensitive adhesive properties of the pressure-sensitive adhesive sheet. In addition, the adhesive sheet adheres to the back surface of the cell on the outside of the conductive portion (for example, both outer sides of the plurality of conductive lines), and thus prevents, for example, the flow of the sealing resin toward the conductive portion, And the contact state between the conductive portion (for example, a plurality of conductive wires) are better maintained.
ここに開示される技術の好ましい一態様では、前記粘着シートは、粘着剤層からなる基材レス粘着シートである。このように構成することで、粘着剤層による粘着特性を利用して、接続信頼性に優れた配線を得ることができる。他の好ましい一態様では、前記粘着シートは、基材層と、該基材層の少なくとも一方の表面に配置された粘着剤層と、を備える。このように構成することで、粘着剤層による粘着特性を利用して接続信頼性に優れた配線を得つつ、基材層の剛性を利用して上記配線の耐久性をさらに向上させることができる。 In a preferred embodiment of the technology disclosed herein, the pressure-sensitive adhesive sheet is a substrate-less pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer. By comprising in this way, the wiring excellent in connection reliability can be obtained using the adhesion characteristic by an adhesive layer. In another preferable embodiment, the pressure-sensitive adhesive sheet includes a base material layer and a pressure-sensitive adhesive layer disposed on at least one surface of the base material layer. By comprising in this way, the durability of the said wiring can be further improved using the rigidity of a base material layer, obtaining the wiring excellent in connection reliability using the adhesion characteristic by an adhesive layer. .
ここに開示される技術の好ましい一態様では、前記太陽電池セルの裏面には、前記被覆層越しに該裏面を覆う封止樹脂が配置されている。また、前記封止樹脂は、被覆層非配置領域にて該太陽電池セルの裏面と接着している。このように構成することで、セル裏面と導電部(例えば複数の導電線)との接触状態は、被覆層による被覆接着と、封止樹脂とセル裏面との固着作用とによって安定する。そのため、耐久性に優れた構成が好ましく実現される。 In a preferred aspect of the technology disclosed herein, a sealing resin is disposed on the back surface of the solar battery cell so as to cover the back surface through the coating layer. The sealing resin is bonded to the back surface of the solar battery cell in the coating layer non-arrangement region. By comprising in this way, the contact state of a cell back surface and an electroconductive part (for example, several conductive wire) is stabilized by the covering adhesion | attachment by a coating layer, and the adhering effect | action of sealing resin and a cell back surface. Therefore, a configuration excellent in durability is preferably realized.
また、本発明によると、太陽電池モジュールを製造する方法が提供される。前記方法は:太陽電池セルの裏面に、導電部を部分的に配置する工程と;前記導電部が配置された前記太陽電池セルの裏面に、被覆層を該導電部越しに接着させる工程と;を含む。また、前記被覆層の接着工程において、該被覆層を、該太陽電池セルの裏面に部分的に配置する。
上記の方法によると、被覆層の接着と配置を利用して、接触信頼性の高い太陽電池モジュールを効率よく生産することができる。したがって、耐久性が向上した太陽電池モジュールを生産性よく提供し得る太陽電池モジュールの製造方法が提供される。
Moreover, according to this invention, the method of manufacturing a solar cell module is provided. The method includes: a step of partially disposing a conductive portion on a back surface of a solar cell; a step of adhering a covering layer to the back surface of the solar cell on which the conductive portion is disposed; including. Moreover, in the adhesion step of the covering layer, the covering layer is partially disposed on the back surface of the solar battery cell.
According to said method, a solar cell module with high contact reliability can be efficiently produced using adhesion | attachment and arrangement | positioning of a coating layer. Therefore, the manufacturing method of the solar cell module which can provide the solar cell module with improved durability with high productivity is provided.
また、本発明によると、太陽電池セルの配線方法が提供される。前記方法は:前記太陽電池セルの裏面に、導電部を部分的に配置する工程と;前記導電部が配置された前記太陽電池セルの裏面に、被覆層を該導電部越しに接着させる工程と;を含む。また、前記被覆層の接着工程において、該被覆層を、該太陽電池セルの裏面に部分的に配置する。
上記の方法によると、被覆層の接着と配置を利用して、耐久性に優れた太陽電池セルの配線を効率よく実現することができる。
Moreover, according to this invention, the wiring method of a photovoltaic cell is provided. The method includes: partially disposing a conductive portion on the back surface of the solar cell; adhering a coating layer over the conductive portion on the back surface of the solar cell on which the conductive portion is disposed; ;including. Moreover, in the adhesion step of the covering layer, the covering layer is partially disposed on the back surface of the solar battery cell.
According to said method, the wiring of the photovoltaic cell excellent in durability can be efficiently implement | achieved using adhesion | attachment and arrangement | positioning of a coating layer.
以下、本発明の好適な実施形態を説明する。なお、本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、本明細書に記載された発明の実施についての教示と出願時の技術常識とに基づいて当業者に理解され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。また、以下の図面において、同じ作用を奏する部材・部位には同じ符号を付して説明し、重複する説明は省略または簡略化することがある。また、図面に記載の実施形態は、本発明を明瞭に説明するために模式化されており、実際に提供される製品のサイズや縮尺を必ずしも正確に表したものではない。 Hereinafter, preferred embodiments of the present invention will be described. Note that matters other than the matters specifically mentioned in the present specification and necessary for the implementation of the present invention are based on the teachings on the implementation of the invention described in the present specification and the common general technical knowledge at the time of filing. Can be understood by those skilled in the art. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field. Further, in the following drawings, members / parts having the same action are described with the same reference numerals, and overlapping descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are schematically illustrated in order to clearly explain the present invention, and do not necessarily accurately represent the size and scale of a product actually provided.
≪太陽電池モジュールの構造≫
(第1実施形態)
図1は、第1実施形態に係る太陽電池モジュールの主要部を模式的に示す断面図である。
≪Solar cell module structure≫
(First embodiment)
FIG. 1 is a cross-sectional view schematically showing a main part of the solar cell module according to the first embodiment.
図1に示すように、太陽電池モジュール1は、太陽電池セル10a,10b,10c,10dを含む複数の太陽電池セルと、上記複数の太陽電池セルを覆う(取り囲む)封止樹脂150と、封止樹脂150を挟むように配置された表面被覆部材160および裏面被覆部材170と、を備える。太陽電池セル10a,10b,10c,10dを含む複数の太陽電池セルは、所定の間隔をおいて直線状に一列に配列されており、太陽電池セル群を構成している。太陽電池セル10a,10b,10c,10dの上面(表(おもて)面)にはn型電極(表面電極)が部分的に形成されており、下面(裏面)にはp型電極(裏面電極)が形成されている。なお、本明細書における太陽電池セルの上下は、太陽電池セルの表裏に対応し、ひいては太陽電池モジュールの表裏(上下)に対応する。太陽電池モジュールの表面は入光面(受光面ともいう。)である。太陽電池モジュールは、その設置の仕方によっては表裏が必ずしも厳密な上下とはならないことがあるため、太陽電池セルの上下も厳密な上下に限定されず、相対的な位置関係を示すものとして把握される。また、この実施形態では、太陽電池セル10a,10b,10c,10dとして結晶系Siセル(凡そ15.6cm×15.6cm)を使用し、封止樹脂150としてエチレン-酢酸ビニル共重合体(EVA)を使用し、表面被覆部材160として厚さ3.2mmのガラス板を使用し、裏面被覆部材170として市販のバックシートを使用している。
As shown in FIG. 1, a
上記太陽電池セル群において、隣りあう2つの太陽電池セル(例えば太陽電池セル10aと太陽電池セル10b)は、一の導電部30によって電気的に接続されている。この導電部30の一つは、太陽電池セル10aの表面上に部分的に配置されており、太陽電池セル10aの上面から太陽電池セル10bの下面にかけ渡されている。導電部30は、太陽電池セル10bの裏面上においても部分的に配置されている。より具体的には、一の導電部30は、太陽電池セル群の上方では太陽電池セル10aの上面に配置されており、太陽電池セル10aと太陽電池セル10bとの間の空間を通って、太陽電池セル群の下方に移動し、太陽電池セル10bの下面に配置されている。当該導電部30は、太陽電池セル10aの端(太陽電池セル10b側とは反対側の端)から太陽電池セル10bの端(太陽電池セル10a側とは反対側の端)まで延びており、太陽電池セル10aの上面および太陽電池セル10bの下面に接触(具体的には当接)している。このように、導電部30は一部材で太陽電池セル10aの上面から太陽電池セル10bの下面まで連続しているので、接続信頼性が高く、耐久性にも優れる。
In the solar cell group, two adjacent solar cells (for example, the
太陽電池モジュール1内において、第1被覆層50は、太陽電池セル群の上方に配置されている。具体的には、一の第1被覆層50は、一の太陽電池セル10aの上方にのみ配置されており、他の太陽電池セル(例えば太陽電池セル10b)の上方には配置されていない。他の太陽電池セル(例えば太陽電池セル10b)の上方には、異なる第1被覆層50が配置されている。また、第1被覆層50は、太陽電池セル10aの上方に位置する導電部30よりも上方に配置されている。換言すると、導電部30は、太陽電池セル10aと第1被覆層50との間に配置されている。第1被覆層50は、透明な樹脂層であり、少なくとも太陽電池セル側の表面が接着性を有する。この実施形態の第1被覆層50は透明な粘着剤層(基材レス粘着シート)である。第1被覆層50は、導電部30の上方から、導電部30の非存在領域にて太陽電池セル10aの上面に接触している。これによって、導電部30を太陽電池セル10aの上面に確実かつ安定的に接触(具体的には当接)させている。その詳細については後述する。なお、第1被覆層50は、接着性を有するものに限定されず、それ自体は非接着性で、接着剤、粘着剤等の公知の接着手段を用いて、太陽電池セル10aの上面に接着するものであってもよい。後述の第2被覆層60についても同様である。
In the
一方、第2被覆層60は、太陽電池モジュール1内において、太陽電池セル群の下方に配置されている。具体的には、一の第2被覆層60は、一の太陽電池セル10bの下方にのみ配置されており、他の太陽電池セル(例えば太陽電池セル10a,10c)の下方には配置されていない。他の太陽電池セル(例えば太陽電池セル10a,10c)の下方には、異なる第2被覆層60が配置されている。また、第2被覆層60は、太陽電池セル10bの下方に位置する導電部30よりも下方に配置されている。換言すると、導電部30は、太陽電池セル10bと第2被覆層60との間に配置されている。第2被覆層60は、少なくとも太陽電池セル側の表面が接着性を有する。第2被覆層60は、この実施形態では透明な粘着剤層(基材レス粘着シート)である。第2被覆層60は、導電部30の下方から、導電部30の非存在領域にて太陽電池セル10bの下面に接触している。これによって、導電部30を太陽電池セル10bの下面に確実かつ安定的に接触させている。その詳細については後述する。なお、太陽電池セルの裏面に配置される第2被覆層60は透明でなくてもよい。
On the other hand, the
図2は、第1実施形態に係る太陽電池モジュールを構成する2つの太陽電池セルの配線状態を拡大して示す模式的側面図である。図3は、図2のIII方向矢視図である。図4は、図3の太陽電池セルのIV-IV線における断面図である。これらの図を参照して、太陽電池モジュール1における配線について、太陽電池セル10a,10bの配線を例に、より具体的に説明する。なお、図2~4では、説明の便宜のため、太陽電池セル10aの下面に配置される導電部および第2被覆層、太陽電池セル10bの上面に配置される導電部および第1被覆層は省略している。
FIG. 2 is a schematic side view showing an enlarged wiring state of two solar cells constituting the solar cell module according to the first embodiment. 3 is a view in the direction of the arrow III in FIG. FIG. 4 is a cross-sectional view taken along the line IV-IV of the solar battery cell of FIG. With reference to these drawings, the wiring in the
図2、3に示すように、一の導電部30は、具体的には、太陽電池セル10aの上面から太陽電池セル10bの下面まで延びる複数の導電線40から構成されている。上記複数の導電線40は、太陽電池セル10a,10bの配列方向に沿って延びており、互いに間隔をおいて配置されている。これら導電線40は、互いに平行するように直線状に配置されており、太陽電池セル10a,10bの配列方向において、太陽電池セル10a,10bのほぼ両端(太陽電池セル10aの端(太陽電池セル10b側とは反対側の端)から太陽電池セル10bの端(太陽電池セル10a側とは反対側の端))まで延びている。したがって、複数の導電線40は、太陽電池セル10aの上面および太陽電池セル10bの下面において、互いに間隔をおいて平行するように直線状に配置されている。なお、この実施形態では、導電線40として、幅0.8mmで厚さ0.25mmの銅製のワイヤーが用いられている。
As shown in FIGS. 2 and 3, specifically, one
第1被覆層50は、具体的には、導電部30としての複数の導電線40を覆って、導電部30越しに太陽電池セル10aの上面に接着している。つまり、第1被覆層50の下面(太陽電池セル側の表面)は、導電部30(具体的には複数の導電線40)と接着し、かつ、導電部30と接着していない箇所にて太陽電池セル10aの上面に接着している。これによって、導電部30を太陽電池セル10aの上面に確実かつ安定的に接触(具体的には当接)させている。また、第1被覆層50は、太陽電池セル10aの上面において部分的に配置されている。そのため、太陽電池セル10aの上面には、被覆層非配置領域12aが存在している。この被覆層非配置領域12aに、硬化前の封止樹脂150は流動して太陽電池セル10aの上面と接触後、硬化する。これによって、太陽電池セル10aと導電部30(具体的には複数の導電線40)との接触状態は、第1被覆層50による接着と封止樹脂150の固着(硬化接着)によって、より安定する。なお、導電部30の上面は、第1被覆層50に覆われているので、被覆層非配置領域12aには導電部30は存在しない。
Specifically, the
より具体的には、第1被覆層50は、複数の帯状被覆部材52からなる。これらの帯状被覆部材52の数は導電線40と同数であり、それぞれ、太陽電池セル10aの上面において、当該上面に配置された導電線40越しに太陽電池セル10aの上面に接着している。また、帯状被覆部材52の各々の幅は、導電線40の幅よりも大きい。各帯状被覆部材52の長さは、太陽電池セル10aの一辺の長さとほぼ同じである。帯状被覆部材52の各々は、太陽電池セル10aの上面において、各導電線40と重なりつつ、互いに平行するように直線状に配置されている。各帯状被覆部材52は、太陽電池セル10aの上面において、当該上面に配置された導電線40の各々を太陽電池セル10aの上方(上面の外方)から覆っており、かつ導電線40の幅方向の両外側にて、太陽電池セル10aの上面と接着している。また、複数の帯状被覆部材52は、互いに間隔をおいて配置されている。そのため、複数の帯状被覆部材52の間には、帯状の被覆層非配置領域12aが存在している。このように第1被覆層50を配置することにより、接続信頼性に優れた配線が好ましく実現される。
More specifically, the
第1被覆層50を構成する帯状被覆部材52は、この実施形態では幅約5~10mm、厚さ0.05mm程度の透明な粘着剤層であるが、これに限定されない。セル表面と導電線40との接触状態を良好に保持する観点から、帯状被覆部材52の幅W1は、導電線40の幅Wcよりも1mm以上大きいことが適当であり、帯状被覆部材52の幅W1と導電線40の幅Wcとの差(W1-Wc)は、好ましくは2mm以上、より好ましくは3mm以上(例えば7mm以上)である。同様の理由から、導電線40の幅Wcに対する帯状被覆部材52の幅W1の比(W1/Wc)は1よりも大きいことが適当であり、好ましくは3以上、より好ましくは5以上(例えば10以上)である。また、耐久性、生産性、透光性等の観点から、上記差(W1-Wc)は、凡そ20mm以下とすることが適当であり、好ましくは15mm以下、より好ましくは10mm以下、さらに好ましくは7mm以下(例えば5mm以下)である。同様の理由から、導電線40の幅Wcに対する帯状被覆部材52の幅W1の比(W1/Wc)は20以下が適当であり、好ましくは15以下(例えば8以下)である。具体的には、帯状被覆部材52の幅W1は、1.5mm以上であることが適当であり、好ましくは3mm以上、より好ましくは4mm以上(例えば8mm以上)であり、また上記幅W1は、25mm以下であることが適当であり、好ましくは18mm以下、より好ましくは12mm以下(例えば7mm以下)である。
The band-shaped covering
また、帯状被覆部材52の間隔は、太陽電池セル10aの上面に配置される導電線40の間隔と同程度であることが好ましいが、これに限定されない。例えば、帯状被覆部材52の間隔は、好ましくは0.3cm以上であり、より好ましくは0.8cm以上であり、さらに好ましくは1.5cm以上である。また上記間隔は、好ましくは4.0cm未満であり、より好ましくは3.0cm未満であり、さらに好ましくは2.8cm以下である。なお、上記間隔はピッチであり、帯状被覆部材52の幅方向における中心線間の距離を指す。
Further, the interval between the strip-shaped covering
また、太陽電池セル(例えば太陽電池セル10a)の上面において、第1被覆層50の帯状被覆部材52の間に存在する帯状の被覆層非配置領域12aの各々の幅は、耐久性向上の観点から、1mm以上とすることが適当であり、好ましくは3mm以上、より好ましくは5mm以上、さらに好ましくは8mm以上、特に好ましくは10mm以上(例えば12mm以上、さらには15mm以上)である。上記帯状の被覆層非配置領域12aの各々の幅は、第1被覆層50による導電部30被覆の観点から、凡そ25mm以下であることが適当であり、好ましくは22mm以下(例えば16mm以下)程度である。
Further, on the upper surface of the solar battery cell (for example, the
また、太陽電池セル(例えば太陽電池セル10a)の上面における被覆層非配置領域12aの面積比率は、特定の比率に限定されるものではなく、凡そ10%以上とすることが適当であり、耐久性、透光性等の観点から、好ましくは30%以上、より好ましくは40%以上、さらに好ましくは50%以上、特に好ましくは60%以上(例えば70%以上)である。第1被覆層50による導電部30被覆の観点から、上記面積比率は凡そ90%以下が適当であり、好ましくは85%以下(例えば65%以下)である。他の一態様では、上記面積比率は、凡そ75%以下(例えば70%以下)であることが好ましく、60%以下であってもよい。
Moreover, the area ratio of the coating
また図2~4に示すように、第2被覆層60は、具体的には、導電部30としての複数の導電線40を覆って、導電部30越しに太陽電池セル10bの下面に接着している。つまり、第2被覆層60の上面(太陽電池セル側の表面)は、導電部30(具体的には複数の導電線40)と接着し、かつ、導電部30と接着していない箇所にて太陽電池セル10bの下面に接着している。これによって、導電部30を太陽電池セル10bの上面に確実かつ安定的に接触(具体的には当接)させている。また、第2被覆層60は、太陽電池セル10bの下面において部分的に配置されている。そのため、太陽電池セル10bの下面には、被覆層非配置領域12bが存在している。この被覆層非配置領域12bに、硬化前の封止樹脂150は流動して太陽電池セル10bの下面と接触後、硬化する。これによって、太陽電池セル10bと導電線40との接触状態は、第2被覆層60による接着と封止樹脂150の固着(硬化接着)によって、より安定する。なお、導電部30の下面は、第2被覆層60に覆われているので、被覆層非配置領域12bには導電部30は存在しない。
As shown in FIGS. 2 to 4, specifically, the
より具体的には、第2被覆層60は、複数の帯状被覆部材62からなる。これらの帯状被覆部材62の数は導電線40と同数であり、それぞれ、太陽電池セル10bの下面において、当該下面に配置された導電線40越しに太陽電池セル10bの下面に接着している。また、帯状被覆部材62の各々の幅は、導電線40の幅よりも大きい。各帯状被覆部材62の長さは、太陽電池セル10bの一辺の長さとほぼ同じである。帯状被覆部材62の各々は、太陽電池セル10bの下面において、各導電線40と重なりつつ、互いに平行するように直線状に配置されている。各帯状被覆部材62は、太陽電池セル10bの下面において、当該下面に配置された導電線40の各々を太陽電池セル10bの下方(下面の外方)から覆っており、かつ導電線40の幅方向の両外側にて、太陽電池セル10bの下面と接着している。また、複数の帯状被覆部材62は、互いに間隔をおいて配置されている。そのため、複数の帯状被覆部材62の間には、帯状の被覆層非配置領域12bが存在している。このように第2被覆層60を配置することにより、接続信頼性に優れた配線が好ましく実現される。
More specifically, the
第2被覆層60を構成する帯状被覆部材62は、第1被覆層50の場合と同様、この実施形態では、幅約5~10mm、厚さ0.05mm程度の透明な粘着剤層であるが、これに限定されない。セル裏面と導電線40との接触状態を良好に保持する観点から、帯状被覆部材62の幅W2は、導電線40の幅Wcよりも1mm以上大きいことが適当であり、帯状被覆部材62の幅W2と導電線40の幅Wcとの差(W2-Wc)は、好ましくは2mm以上、より好ましくは3mm以上(例えば7mm以上)である。同様の理由から、導電線40の幅Wcに対する帯状被覆部材62の幅W2の比(W2/Wc)は1よりも大きいことが適当であり、好ましくは3以上、より好ましくは5以上(例えば10以上)である。また、封止樹脂と太陽電池セルとの固着作用を得る観点から、上記差(W2-Wc)は、凡そ20mm以下とすることが適当であり、好ましくは15mm以下、より好ましくは10mm以下、さらに好ましくは7mm以下(例えば5mm以下)である。同様の理由から、導電線40の幅Wcに対する帯状被覆部材52の幅W2の比(W2/Wc)は20以下が適当であり、好ましくは15以下(例えば8以下)である。具体的には、帯状被覆部材62の幅W2は、1.5mm以上であることが適当であり、好ましくは3mm以上、より好ましくは4mm以上(例えば8mm以上)であり、また上記幅W2は、25mm以下であることが適当であり、好ましくは18mm以下、より好ましくは12mm以下(例えば7mm以下)である。
The band-shaped covering
また、帯状被覆部材62の間隔は、太陽電池セル10bの下面に配置される導電線40の間隔と同程度であることが好ましいが、これに限定されない。例えば、帯状被覆部材62の間隔は、好ましくは0.3cm以上であり、より好ましくは0.8cm以上であり、さらに好ましくは1.5cm以上である。また上記間隔は、好ましくは4.0cm未満であり、より好ましくは3.0cm未満であり、さらに好ましくは2.8cm以下である。なお、上記間隔はピッチであり、帯状被覆部材62の幅方向における中心線間の距離を指す。
Moreover, although it is preferable that the space | interval of the strip | belt-shaped coating | coated
また、太陽電池セル(例えば太陽電池セル10b)の下面において、第2被覆層60の帯状被覆部材62の間に存在する帯状の被覆層非配置領域12bの各々の幅は、耐久性向上の観点から、1mm以上とすることが適当であり、好ましくは3mm以上、より好ましくは5mm以上、さらに好ましくは8mm以上、特に好ましくは10mm以上(例えば12mm以上、さらには15mm以上)である。上記帯状の被覆層非配置領域12bの各々の幅は、第2被覆層60による導電部30被覆の観点から、凡そ25mm以下であることが適当であり、好ましくは22mm以下(例えば16mm以下)程度である。
Further, on the lower surface of the solar battery cell (for example, the
また、太陽電池セル(例えば太陽電池セル10b)の下面における被覆層非配置領域12bの面積比率は、特定の比率に限定されるものではなく、凡そ10%以上とすることが適当であり、耐久性向上の観点から、好ましくは30%以上、より好ましくは40%以上、さらに好ましくは50%以上、特に好ましくは60%以上(例えば70%以上)である。第2被覆層60による導電部30被覆の観点から、上記面積比率は凡そ90%以下が適当であり、好ましくは85%以下(例えば65%以下)である。他の一態様では、上記面積比率は、凡そ75%以下(例えば70%以下)であることが好ましく、60%以下であってもよい。
Moreover, the area ratio of the coating
上記の構成を断面構造で説明すると下記のとおりである。すなわち、太陽電池セル10aの配置箇所においては、太陽電池モジュール1は、上方から、表面被覆部材160/封止樹脂150/第1被覆層50/導電部(表面側導電部)30/太陽電池セル10a/導電部(裏面側導電部)30/第2被覆層60/封止樹脂150/裏面被覆部材170がこの順で積層された断面構造を有する。上記断面構造において、導電部(表面側導電部)30と第1被覆層50とは、太陽電池セル10aの上面に部分的に積層されている。また、太陽電池セル10aの上面において、導電部(表面側導電部)30は、その全体が、上方から第1被覆層50に覆われている。同様に、導電部(裏面側導電部)30と第2被覆層60とは、太陽電池セル10aの下面に部分的に積層されている。また、太陽電池セル10aの下面において、導電部(裏面側導電部)30は、その全体が、下方から第2被覆層60に覆われている。
The above configuration will be described in terms of a cross-sectional structure as follows. That is, in the location where the
また、太陽電池セル10bの配置箇所においては、太陽電池モジュール1は、上方から、表面被覆部材160/封止樹脂150/第1被覆層50/導電部(表面側導電部)30/太陽電池セル10b/導電部(裏面側導電部)30/第2被覆層60/封止樹脂150/裏面被覆部材170がこの順で積層された断面構造を有する。上記断面構造において、導電部(表面側導電部)30と第1被覆層50とは、太陽電池セル10bの上面に部分的に積層されている。また、太陽電池セル10bの上面において、導電部(表面側導電部)30は、その全体が、上方から第1被覆層50に覆われている。同様に、導電部(裏面側導電部)30と第2被覆層60とは、太陽電池セル10bの下面に部分的に積層されている。また、太陽電池セル10bの下面において、導電部(裏面側導電部)30は、その全体が、下方から第2被覆層60に覆われている。
Moreover, in the arrangement | positioning location of the
さらに、太陽電池セル10a,10bの間においては、太陽電池モジュール1は、上方から、表面被覆部材160/封止樹脂150/導電部30/封止樹脂150/裏面被覆部材170がこの順で積層された断面構造を有する。なお、上述の構造において、太陽電池セル10aの表面(上面)側に配置される導電部(表面側導電部)30と、太陽電池セル10aの裏面(下面)側に配置される導電部(裏面側導電部)30とは、分離した別部材である。また、太陽電池セル10bの表面(上面)側に配置される導電部(表面側導電部)30と、太陽電池セル10bの裏面(下面)側に配置される導電部(裏面側導電部)30も、分離した別部材である。しかし、太陽電池セル10aにおける表面側導電部30と、太陽電池セル10bにおける裏面側導電部30とは、連続した一部材である。
Furthermore, between the
≪太陽電池セルの配線方法および太陽電池モジュールの製造方法≫
次に、上記のような太陽電池セルの配線方法、ひいては上記のような構成を有する太陽電池モジュールの製造方法の好適例について、2つの太陽電池セル10a,10bを中心に説明する。この方法は、太陽電池セル10bの下面に、導電部30を部分的に配置する工程と;導電部30が配置された太陽電池セル10bの下面に、被覆層(第2被覆層60)を導電部30越しに接着させる工程と;を含む。また、被覆層(第2被覆層60)の接着工程において、被覆層(第2被覆層60)を太陽電池セル10bの下面に部分的に配置する。
<< Solar Cell Wiring Method and Solar Cell Module Manufacturing Method >>
Next, a preferred example of a method for wiring solar cells as described above, and by extension, a method for manufacturing a solar cell module having the above configuration will be described focusing on two
具体的には、まず、太陽電池セル10a,10bを用意する。そして、太陽電池セル10bをその下面(裏面)が上方を向くようにセットし、当該下面(裏面)に、導電部30としての複数の導電線40を配置する。このとき、導電部30の一部(具体的には、導電線40の長手方向の一部)が太陽電池セル10bの下面(裏面)に配置される。導電線40の配置は、ディスペンサ等の公知の手段を用いて行うことができる。これによって、太陽電池セル10bの下面(裏面)に、導電部30(複数の導電線40)が部分的に配置される。
Specifically, first,
次に、上記導電部30としての導電線40が配置された太陽電池セル10bの下面(裏面)に、第2被覆層60を、導電部30と重なるように導電部30越しに接着させる。この実施形態の第2被覆層60は、導電線40と同数の複数の帯状被覆部材62から構成されており、その各々の幅は、導電線40の幅よりも大きい。それら複数の帯状被覆部材62の各々を、導電線40の上に重なるように配置することで、各帯状被覆部材62は、導電線40を覆い、かつ導電線40の幅方向の両端よりも外側にて太陽電池セル10bの下面(裏面)に接着する。第2被覆層60の供給(帯状被覆部材62の配置)は、ディスペンサ等の公知の手段を用いて行うことができる。この実施形態では、第2被覆層60として粘着シートを使用しているので、第2被覆層60自体が太陽電池セル10bに接着するが、これに限定されず、第2被覆層60が非接着性の場合、接着剤、粘着剤等の公知の接着手段を用いて、太陽電池セル10bの下面(裏面)に第2被覆層60を接着させてもよい。後述の第1被覆層50についても同様である。
Next, the
また、上記方法は、太陽電池セル10aの上面に、導電部30を部分的に配置する工程と;導電部30が配置された太陽電池セル10aの上面に、被覆層(第1被覆層50)を導電部30越しに接着させる工程と;を含み得る。被覆層(第1被覆層50)の接着工程において、被覆層(第1被覆層50)を太陽電池セル10aの上面に部分的に配置することが好ましい。
Moreover, the said method is the process of arrange | positioning the
具体的には、太陽電池モジュール1において太陽電池セル10bの隣りに配置される太陽電池セル10aを、その上面(受光面)が上方を向くようにセットする。そこに、導電線40の長手方向の一部が取り付けられた太陽電池セル10bの上下を反転させ、その導電線40の残りの部分を、太陽電池セル10aの上面(受光面)に配置する。
Specifically, in the
そして、上記導電線40が配置された太陽電池セル10aの上面(受光面)に、第1被覆層50を、導電部30と重なるように導電部30越しに接着させる。この実施形態の第1被覆層50は、第2被覆層60と同様、導電線40と同数の複数の帯状被覆部材52から構成されており、その各々の幅は、導電線40の幅よりも大きい。それら複数の帯状被覆部材52の各々を、導電線40の上に重なるように配置することで、各帯状被覆部材52は、導電線40を覆い、かつ導電線40の幅方向の両端よりも外側にて太陽電池セル10aの上面(受光面)に接着する。第1被覆層50の供給(帯状被覆部材52の配置)は、第2被覆層60の場合と同様、ディスペンサ等の公知の手段を用いて行うことができる。この作業を他の太陽電池セル(例えば太陽電池セル10c,10d)にも適用して繰り返すことで、図1に示すような複数の太陽電池セル10a,10b,10c,10dの上下配線が完了する。
Then, the
上記の配線は、はんだ等の接着手段による接合を必要としない。そのため、はんだ接合による不具合(典型的には、セルの反りや割れ、特性低下、フラックス汚染)を回避することが可能である。はんだレス太陽電池モジュールは、上述のフラックス汚染を回避できるだけでなく、はんだ接合を原因とするリーチングやクレータリング等の問題をも解消し得る。また、2つの太陽電池セル(例えば太陽電池セル10a、10b)の上下配線は、導電部30(例えば導電線40)と被覆層(第1被覆層50および第2被覆層60)とを配置するだけで実現されるので、配線作業性に優れる。上記の構成による太陽電池セル(例えば太陽電池セル10a、10b)への導電部30の接触状態は、はんだ接合等の固定方法と比べて自由度が高いので、耐衝撃性に優れ、耐久性にも優れる。さらに、この実施形態では、第1被覆層50および第2被覆層60は、接着性を有する粘着剤層であるので、導電部30(具体的には導電線40)越しに太陽電池セル10a、10bと接着する。そのため、導電性接着剤等の別途の接着手段は不要であり、この点においても配線作業性に優れる。
The above wiring does not need to be joined by an adhesive means such as solder. Therefore, it is possible to avoid defects (typically cell warpage or cracking, characteristic deterioration, flux contamination) due to solder bonding. The solderless solar cell module not only can avoid the above-mentioned flux contamination, but can also solve problems such as leaching and cratering caused by solder joints. In addition, the upper and lower wirings of the two solar cells (for example, the
上記のようにして導電部30、第1被覆層50および第2被覆層60が取り付けられた太陽電池セル10a,10b,10c,10d(配線済み太陽電池セル群)を、2枚のシート状封止樹脂150で挟み、さらにその外方に表面被覆部材160および裏面被覆部材170を配置することで、複数の太陽電池セル10a,10b,10c,10dを、それらを導通した状態で内蔵した太陽電池モジュール1が構築される。なお、2枚のシート状封止樹脂150は、表面被覆部材160および裏面被覆部材170で挟まれ、さらに図示しない枠体が取り付けられた後、加熱硬化することにより、一体化して図1に示す封止樹脂150となる。このようにして得られる太陽電池モジュール1には、太陽電池モジュール1の表(おもて)面を構成する表面被覆部材160と裏面を構成する裏面被覆部材170との間に、封止樹脂150に覆われた状態で、上記配線済み太陽電池セル群が収容されている。
The
なお、上記配線方法では、太陽電池セル10bの下面(裏面)に導電部30と第2被覆層60を配置した後、太陽電池セル10aの上面(受光面)に導電部30と第1被覆層50を配置したが、これに限定されない。これらの工程は、連続的に実施され得るので、いずれの工程を先にしても、太陽電池セルを効率よく配線することが可能である。したがって、この明細書は、太陽電池セルの配線方法または太陽電池モジュールの製造方法であって:太陽電池セルの裏面に、導電部を部分的に配置する工程(1A)と;上記導電部が配置された太陽電池セルの裏面に、被覆層(第2被覆層)を該導電部越しに接着させる工程(1B)と;太陽電池セルの表面に、導電部を部分的に配置する工程(2A)と;上記導電部が配置された太陽電池セルの表面に、被覆層(第1被覆層)を該導電部越しに接着させる工程(2B)と;を含む方法を包含する。この方法において、工程(1A)と工程(1B)を先に実施した後、工程(2A)と工程(2B)を実施してもよく、あるいは、工程(2A)と工程(2B)を先に実施した後、工程(1A)と工程(1B)を実施してもよい。この方法の工程(1B)、すなわち第2被覆層の接着工程において、第2被覆層は該太陽電池セルの裏面に部分的に配置する。また、上記方法の工程(2B)、すなわち第1被覆層の接着工程においても、第1被覆層は該太陽電池セルの表面に部分的に配置することが好ましい。
In the above wiring method, the
以上、太陽電池セル10a,10bと、それらの電気的接続に関わる構成について説明したが、太陽電池セル群を構成する他の太陽電池セル(例えば太陽電池セル10c,10d)についても基本的に同様の構成が繰り返されているので、重複する説明は省略する。なお、太陽電池セル群の両端に位置する太陽電池セルの上面または下面に配置される導電部(より具体的には導電線)は、太陽電池セル同士の電気的接続ではなく、図示しない取出し電極(端子バー)に接続される。
The
(第2実施形態)
図5は、第2実施形態に係る太陽電池セル下面における導電部と被覆層とを拡大して示す模式的断面図である。図5は、図4の断面図における導電部と被覆層とを部分的に拡大した図に対応する。第2実施形態に係る太陽電池モジュールは、被覆層(典型的には第2被覆層)を除いては第1実施形態に係る太陽電池モジュールと基本的に同じ構成を有する。したがって、この実施形態については、第2被覆層を中心に説明し、その他の点についての説明は省略する。
(Second Embodiment)
FIG. 5 is an enlarged schematic cross-sectional view showing the conductive portion and the coating layer on the lower surface of the solar battery cell according to the second embodiment. FIG. 5 corresponds to a partially enlarged view of the conductive portion and the covering layer in the cross-sectional view of FIG. The solar cell module according to the second embodiment has basically the same configuration as the solar cell module according to the first embodiment except for a covering layer (typically the second covering layer). Therefore, about this embodiment, it explains focusing on the 2nd covering layer, and omits explanation about other points.
図5に示すように、この実施形態では、第2被覆層60(より具体的には帯状被覆部材62)として、基材層付き粘着シートが用いられている。この粘着シート(第2被覆層60(より具体的には帯状被覆部材62))は、基材層64と、基材層の一方の表面に配置された粘着剤層66と、を備える片面接着性の粘着シートであり、その粘着剤層66の表面が導電部30(典型的には導電線40)越しに太陽電池セル10bの下面に接着している。また、第2被覆層60の基材層64は太陽電池セル10bの外方(下方)に配置されている。上記のように構成することにより、粘着剤層66による粘着特性を利用して、接続信頼性に優れた配線を得つつ、基材層64の剛性を利用して、上記配線の耐久性をさらに向上させることができる。この実施形態では、第2被覆層60として、片面接着性の粘着シートが用いられているが、これに限定されず、基材層付きの両面接着性の粘着シートを使用してもよい。また、この実施形態では、基材層64として、厚さ50~100μm程度のポリエステル樹脂フィルムが用いられているが、これに限定されない。基材層は、各種樹脂フィルムや、粘着剤層から剥離可能な剥離性支持体であってもよい。粘着剤層66としては、第1実施形態と同種の粘着剤が使用されているが、これに限定されるものではなく、後述する範囲で変更が可能である。なお、この実施形態における第1被覆層については、透光性の観点から、上記第1実施形態と同じ構成の第1被覆層が用いられている。
As shown in FIG. 5, in this embodiment, a pressure-sensitive adhesive sheet with a base material layer is used as the second coating layer 60 (more specifically, the belt-shaped coating member 62). This pressure-sensitive adhesive sheet (second coating layer 60 (more specifically, band-shaped coating member 62)) is provided with a
なお、上記実施形態の導電部は、直線状に延びて且つ互いに平行に配置された複数の導電線であったが、導電部は、上記実施形態の形状、構造等に限定されない。導電部としては、典型的には、太陽電池セルの上面および下面において部分的に配置されており、導電部を利用して太陽電池セルの電気的接続が実現できる種々の形状、構造等を採用することが可能である。例えば、導電部として導電線を使用する場合、当該導電線は曲線状に延びるものであってもよい。複数の導電線を有する場合には、複数の導電線は互いに分離していてもよく、接続していてもよく、互いに非平行(例えば交差していてもよく、あるいは互いに接触しない程度に非平行)であってもよい。複数の導電線が接続していることは、平行する複数の導電線が他の導電線によってかけ渡されて連続した形状(非分離形状)を有する態様を包含する。一典型例としては、網目状に配置された導電線が挙げられる。導電部を導電線で構成する場合、導電線の数は2本以上(典型的には2~20本、より好ましくは4~12本、さらに好ましくは6~10本)であることが好ましく、あるいは1本であってもよい。 In addition, although the electroconductive part of the said embodiment was the some electroconductive wire extended linearly and arrange | positioned in parallel mutually, an electroconductive part is not limited to the shape of the said embodiment, a structure, etc. Typically, the conductive part is partially arranged on the upper and lower surfaces of the solar cell, and adopts various shapes, structures, etc. that can realize the electrical connection of the solar cell using the conductive part. Is possible. For example, when a conductive wire is used as the conductive portion, the conductive wire may extend in a curved shape. In the case of having a plurality of conductive lines, the plurality of conductive lines may be separated from each other, connected, or non-parallel to each other (for example, may be crossed or non-parallel so as not to contact each other). ). The connection of a plurality of conductive lines includes a mode in which a plurality of parallel conductive lines are spanned by other conductive lines and have a continuous shape (non-separated shape). A typical example is a conductive wire arranged in a mesh. When the conductive portion is composed of conductive wires, the number of conductive wires is preferably 2 or more (typically 2 to 20, more preferably 4 to 12, more preferably 6 to 10), Or it may be one.
また、上記実施形態では、第2被覆層は、それぞれ複数の帯状被覆部材から構成されていたが、これに限定されない。第2被覆層は、太陽電池セルの裏面を導電部越しに覆い、かつ太陽電池セルの下面と接着する範囲で様々な変更が可能である。例えば、第2被覆層は、太陽電池セルの下面と同形状を有するシート状部材であって、部分的に孔やスリット(切り込み)が設けられたものであってもよい。また、第2被覆層を帯状被覆部材から構成する場合、当該帯状被覆部材は曲線状に延びるものであってもよい。複数の帯状被覆部材を有する場合には、複数の帯状被覆部材は互いに分離していてもよく、接続していてもよく、互いに非平行(例えば交差していてもよく、あるいは互いに接触しない程度に非平行)であってもよい。複数の帯状被覆部材が接続していることは、平行する複数の帯状被覆部材が他の帯状被覆部材によってかけ渡されて連続した形状(非分離形状)を有する態様を包含する。一典型例としては、網目状に配置された帯状被覆部材が挙げられる。帯状被覆部材の幅は、全体的にまたは部分的に変化(例えば細幅化)するものであってもよい。その場合、帯状被覆部材の幅は、その長手方向の複数点(例えば5点以上)にて測定した幅の平均値が採用される。導電部を複数の導電線で構成し、第2被覆部を複数の帯状被覆部材で構成する場合、導電線と帯状被覆部材とは同数とすることが好ましいが、帯状被覆部材の数を導電線の本数よりも少なくして、一の帯状被覆部材で、2本以上の導電線を覆うように構成してもよい。例えば、複数の帯状被覆部材のうち一の帯状被覆部材が、太陽電池セルの裏面外方から複数の導電線のうち一部の導電線を覆い、上記複数の帯状被覆部材のうち他の一の帯状被覆部材が、太陽電池セルの裏面外方から複数の導電線のうち他の一部の導電線を覆うように構成することも可能である。したがって、太陽電池セル下面における被覆層非配置領域の形状も、被覆層配置領域の形状に対応して、帯状、ストライプ状、島状、円形状、四角形状等の種々のパターンをとり得る。 In the above embodiment, each of the second covering layers is composed of a plurality of strip-shaped covering members, but is not limited thereto. The second covering layer can be variously modified as long as it covers the back surface of the solar battery cell over the conductive portion and adheres to the lower surface of the solar battery cell. For example, the second covering layer may be a sheet-like member having the same shape as the lower surface of the solar battery cell, and may be partially provided with holes or slits (cuts). Moreover, when comprising a 2nd coating layer from a strip | belt-shaped coating | coated member, the said strip | belt-shaped coating | coated member may extend in the shape of a curve. In the case of having a plurality of strip-shaped covering members, the plurality of strip-shaped covering members may be separated from each other, may be connected to each other, or may be non-parallel to each other (for example, may be crossed or do not contact each other). Non-parallel). The connection of the plurality of strip-shaped covering members includes an embodiment in which a plurality of parallel strip-shaped covering members are spanned by other strip-shaped covering members and have a continuous shape (non-separating shape). As a typical example, a belt-shaped covering member arranged in a mesh shape can be given. The width of the belt-shaped covering member may be changed (for example, narrowed) entirely or partially. In that case, the average value of the widths measured at a plurality of points (for example, 5 points or more) in the longitudinal direction is adopted as the width of the belt-shaped covering member. When the conductive portion is constituted by a plurality of conductive wires and the second covering portion is constituted by a plurality of strip-shaped covering members, the number of the conductive wires and the strip-shaped covering members is preferably the same, but the number of the strip-shaped covering members is the conductive wire. The number of the conductive wires may be less than the number of the conductive wires, and two or more conductive wires may be covered with one strip-shaped covering member. For example, one of the plurality of strip-shaped covering members covers a part of the plurality of conductive wires from the outside of the back surface of the solar battery cell, and the other one of the plurality of strip-shaped covering members. It is also possible that the band-shaped covering member covers the other part of the plurality of conductive lines from the outside of the back surface of the solar battery cell. Therefore, the shape of the covering layer non-arrangement region on the lower surface of the solar battery cell can take various patterns such as a strip shape, a stripe shape, an island shape, a circular shape, and a square shape corresponding to the shape of the covering layer arrangement region.
また、ここに開示される技術においては、後述の試験で説明するように、太陽電池セル下面の構成が耐久性向上に重要であるので、太陽電池セル上面に配置される第1被覆層は特に限定されない。第1被覆層はなくてもよく、第1被覆層を設ける場合においても、第1被覆層の形状は特に限定されない。例えば、第1被覆層は、太陽電池セルの上面全体に配置されるものであってもよい。具体的には、第1被覆層は、太陽電池セルとほぼ同形状(例えば四角形状)を有してもよく、太陽電池セルの形状や導電部の形状等にあわせて種々の形状をとることが可能である。また、第1被覆層および第2被覆層は、同じ材料(同一組成)からなるものであってもよく、異なる材料からなるもの(異なる組成を有するもの)であってもよい。例えば、上記第2実施形態のように、第1被覆層として基材レス粘着シートを使用し、第2被覆層として基材付き片面粘着シートを使用してもよく、あるいは、第1被覆層、第2被覆層ともに、基材付き片面粘着シートを使用してもよい。また、太陽電池セルが片面受光型の場合は、第1被覆層のみが透明であり、第2被覆層は非透明であってもよい。その場合、第2被覆層は、具体的には、後述する全光線透過率が70%未満(例えば50%未満、典型的には30%未満)の層であり得る。したがって、第1被覆層と第2被覆層とは、異なる全光線透過率を有するものであり得る。あるいは、太陽電池セルが両面受光型の場合は、第1被覆層と第2被覆層とはともに透明であることが好ましく、後述する所定以上の全光線透過率を有することがより好ましい。 In the technology disclosed herein, the configuration of the lower surface of the solar cell is important for improving the durability, as will be described later in the test, and therefore the first coating layer disposed on the upper surface of the solar cell is particularly It is not limited. The first coating layer may not be provided, and even when the first coating layer is provided, the shape of the first coating layer is not particularly limited. For example, the first covering layer may be disposed on the entire top surface of the solar battery cell. Specifically, the first coating layer may have almost the same shape (for example, a quadrangular shape) as the solar battery cell, and takes various shapes according to the shape of the solar battery cell, the shape of the conductive portion, and the like. Is possible. The first coating layer and the second coating layer may be made of the same material (same composition), or may be made of different materials (having different compositions). For example, as in the second embodiment, a substrate-less adhesive sheet may be used as the first coating layer, and a single-sided adhesive sheet with a substrate may be used as the second coating layer, or the first coating layer, You may use a single-sided adhesive sheet with a base material with a 2nd coating layer. Moreover, when a photovoltaic cell is a single-sided light-receiving type, only a 1st coating layer may be transparent and a 2nd coating layer may be non-transparent. In that case, the second coating layer may specifically be a layer having a total light transmittance of less than 70% (for example, less than 50%, typically less than 30%) described later. Therefore, the first coating layer and the second coating layer may have different total light transmittance. Or when a photovoltaic cell is a double-sided light-receiving type, it is preferable that both a 1st coating layer and a 2nd coating layer are transparent, and it is more preferable to have the total light transmittance more than the predetermined mentioned later.
また、上記実施形態では、生産性等の観点から、第1被覆層の帯状被覆部材および第2被覆層の帯状被覆部材として、同材料かつ同形状のものを使用している。そのため、第1被覆層の帯状被覆部材の幅と第2被覆層の帯状被覆部材の幅は同じであり、太陽電池セル上面における帯状被覆層非配置領域の各々の幅も、太陽電池セル下面における帯状被覆層非配置領域の各々の幅と同じであり、太陽電池セル上面における被覆層非配置領域の面積比率も、太陽電池セル下面における被覆層非配置領域の面積比率と同じである。また、第1被覆層の帯状被覆部材の間隔および第2被覆層の帯状被覆部材の間隔は、導電線の間隔と同じに設定されている。これらの事項は、本発明の効果が実現される範囲で、例えば本明細書に記載される範囲内において変更可能である。 In the above embodiment, the same material and the same shape are used as the band-shaped covering member of the first covering layer and the band-shaped covering member of the second covering layer from the viewpoint of productivity and the like. Therefore, the width of the band-shaped coating member of the first coating layer and the width of the band-shaped coating member of the second coating layer are the same, and the width of each band-shaped coating layer non-arrangement region on the upper surface of the solar cell is also the lower surface of the solar cell. It is the same as each width | variety of a strip | belt-shaped coating layer non-arrangement area, and the area ratio of the coating layer non-arrangement area | region in a photovoltaic cell upper surface is also the same as the area ratio of the coating layer non-arrangement area | region in a photovoltaic cell lower surface. Further, the interval between the band-shaped covering members of the first covering layer and the interval between the band-shaped covering members of the second covering layer are set to be the same as the interval between the conductive lines. These matters can be changed within a range in which the effects of the present invention are realized, for example, within a range described in the present specification.
また、一の太陽電池モジュールに配置される太陽電池セルの個数は、特に限定されず、少なくとも1であり、通常は5以上(例えば10以上、典型的には30以上)であり、典型的には50以上(50~70)程度であり得る。太陽電池セル群の両端に位置する太陽電池セルでは、その表(おもて)面または裏面に、図示しない取出し電極(端子バー)に接続する導電部が配置され得る。また、上記実施形態では、複数の太陽電池セルは一列に配列された太陽電池セル群として構成されていたが、複数の太陽電池セルの配列(配置)はこれに限定されず、直線状、曲線状、規則的なパターン、あるいは不規則的なパターンであってもよい。また、太陽電池セルの間隔は一定でなくてもよい。 The number of solar cells arranged in one solar cell module is not particularly limited, and is at least 1, usually 5 or more (for example, 10 or more, typically 30 or more), May be about 50 or more (50 to 70). In the solar cells located at both ends of the solar cell group, conductive portions connected to extraction electrodes (terminal bars) (not shown) can be arranged on the front surface or the back surface. Moreover, in the said embodiment, although the several photovoltaic cell was comprised as a photovoltaic cell group arranged in a line, the arrangement | sequence (arrangement | positioning) of a several photovoltaic cell is not limited to this, A linear form, a curve It may be a pattern, a regular pattern, or an irregular pattern. Moreover, the space | interval of a photovoltaic cell does not need to be constant.
また、ここに開示される太陽電池セルの配線方法および太陽電池モジュールの製造方法は、上記実施形態の方法に限定されず、ここに開示される太陽電池セルの配線構造および太陽電池モジュールの構造を実現し得る方法を制限なく採用することが可能である。例えば、被覆層に導電部を積層した後、当該導電部付き被覆層の導電部配置面を太陽電池セルの表面や裏面に配置する方法を採用することも可能である。 Further, the solar cell wiring method and solar cell module manufacturing method disclosed herein are not limited to the method of the above embodiment, and the solar cell wiring structure and solar cell module structure disclosed herein are the same. It is possible to adopt a method that can be realized without limitation. For example, after laminating a conductive part on the coating layer, it is also possible to employ a method of arranging the conductive part arrangement surface of the coating layer with the conductive part on the front surface or the back surface of the solar battery cell.
≪太陽電池モジュールの構成要素≫
太陽電池モジュールを構成する導電部や第1被覆層、第2被覆層は、上記実施形態のものに限定されず、発明の効果を発揮する範囲で種々の変更が可能である。太陽電池モジュールの他の構成要素についても同様である。以下、太陽電池モジュールを構成する各要素について説明する。
≪Components of solar cell module≫
The conductive part, the first coating layer, and the second coating layer that constitute the solar cell module are not limited to those of the above-described embodiment, and various modifications can be made within a range in which the effects of the invention are exhibited. The same applies to other components of the solar cell module. Hereinafter, each element which comprises a solar cell module is demonstrated.
<導電部>
導電部(導電線を包含する。以下同じ。)は、典型的には導電性材料を含む。導電部を構成する材料として、金、銀、銅、アルミニウム、鉄、ニッケル、錫、クロム、ビスマス、インジウム、亜鉛、それらの合金等の金属材料が好ましく用いられ得る。なかでも、銀、銅、アルミニウム、鉄がより好ましく、銅、アルミニウムがさらに好ましい。実質的に金属から構成された導電経路は、より低抵抗であるという利点を有する。一典型例として、金属ワイヤーからなる導電線から構成された導電部が挙げられる。上記金属ワイヤーとしては、強度、ハンドリング性等の観点から、JIS Z 2241:2011にしたがって測定される引張強度が200N/mm2以上のものが好ましく用いられる。その具体例としては、銅製の金属ワイヤーが好ましく用いられる。なかでも、銅製の金属ワイヤーを芯材として、被覆部として錫(Sn)や銀(Ag)、ニッケル(Ni)等のめっきが施された金属ワイヤーがより好ましい。その被覆部の膜厚(例えばめっき厚)は10μm以下(例えば5μm以下、さらに例えば3μm以下)程度であり得る。上記膜厚は凡そ0.1μm以上(例えば0.5μm以上)であることが適当であり、拡散反射率向上の観点からは、好ましくは1.0μm以上、さらに好ましくは1.5μm以上(例えば2μm以上、さらに例えば3μm以上)である。被覆部の形成方法としては、上述のめっき法以外にもクラッド法等の従来公知の方法が採用され得る。他の一態様では、導電部として、防錆処理が施された導電線(典型的には金属ワイヤー)が好ましく使用される。
<Conductive part>
The conductive portion (including a conductive line, the same applies hereinafter) typically includes a conductive material. As a material constituting the conductive portion, a metal material such as gold, silver, copper, aluminum, iron, nickel, tin, chromium, bismuth, indium, zinc, or an alloy thereof can be preferably used. Among these, silver, copper, aluminum, and iron are more preferable, and copper and aluminum are more preferable. Conductive paths composed essentially of metal have the advantage of lower resistance. As a typical example, there is a conductive portion made of a conductive wire made of a metal wire. As the metal wire, those having a tensile strength measured according to JIS Z 2241: 2011 of 200 N / mm 2 or more are preferably used from the viewpoint of strength, handling property, and the like. As a specific example, a copper metal wire is preferably used. Especially, the metal wire by which plating, such as tin (Sn), silver (Ag), nickel (Ni), was given as a coating | coated part using a copper metal wire as a core material is more preferable. The film thickness (for example, plating thickness) of the covering portion may be about 10 μm or less (for example, 5 μm or less, and further, for example, 3 μm or less). The film thickness is suitably about 0.1 μm or more (for example, 0.5 μm or more). From the viewpoint of improving the diffuse reflectance, it is preferably 1.0 μm or more, more preferably 1.5 μm or more (for example, 2 μm). Further, for example, 3 μm or more). As a method for forming the covering portion, a conventionally known method such as a clad method can be adopted in addition to the above-described plating method. In another aspect, a conductive wire (typically a metal wire) subjected to rust prevention treatment is preferably used as the conductive portion.
導電部は、導電シートから形成したものであってもよい。導電シートは、典型的には金属シート(例えば金属箔)である。上記金属シートとしては、粗化処理や防錆処理、密着性向上処理の少なくとも1種の表面処理を施したものが好ましく用いられる。金属シートの好適例としては銅箔(なかでも電解銅箔)が挙げられる。導電部が導電シートから形成される場合には、導電部は、パターン化された金属シートから形成されていてもよい。そのような導電部は、金属シートをエッチングすることによって形成することができる。具体的には、金属シート(典型的には金属箔)の表面にレジストを貼り、フォトリソグラフィ技術を適用して所定のレジストパターンを形成する。次いで、公知ないし慣用のエッチング液を用いて金属シートをパターン化する。このようにして導電部は形成される。なお、各種蒸着法によっても同様の構成を得ることができる。 The conductive part may be formed from a conductive sheet. The conductive sheet is typically a metal sheet (for example, a metal foil). As said metal sheet, what gave at least 1 sort (s) of surface treatment of a roughening process, a rust prevention process, and an adhesive improvement process is used preferably. Suitable examples of the metal sheet include copper foil (in particular, electrolytic copper foil). When the conductive portion is formed from a conductive sheet, the conductive portion may be formed from a patterned metal sheet. Such a conductive part can be formed by etching a metal sheet. Specifically, a resist is attached to the surface of a metal sheet (typically a metal foil), and a predetermined resist pattern is formed by applying a photolithography technique. Next, the metal sheet is patterned using a known or conventional etching solution. In this way, the conductive portion is formed. A similar configuration can be obtained by various vapor deposition methods.
あるいは、導電部は、例えば、導電性材料としての導電性ペーストを付与することによって形成してもよい。導電性ペーストとしては、金、銀、銅、アルミニウム、鉄、ニッケル、錫、クロム、ビスマス、インジウム、それらの合金等の金属材料からなる導電成分や、カーボン等の非金属からなる導電成分(以下同じ。)と、ポリエステルやエポキシ樹脂等の樹脂成分とを適当な溶媒を用いて混合してなるペースト状組成物が用いられ得る。なかでも、経時安定性の観点から、導電成分として銀または銅を使用することが好ましい。導電性ペーストの具体例としては、銀ペースト(商品名「ペルトロンK-3105」、ペルノックス社製、導電成分:Ag、樹脂成分:ポリエステル樹脂、比抵抗:6.5×10-5Ω・cm)が挙げられる。導電性ペーストの25℃における比抵抗は、凡そ5×10-4Ω・cm以下(例えば1×10-4Ω・cm以下、典型的には5.0×10-7Ω・m以下)であることが好ましい。また、導電性ペーストを構成する導電成分の比抵抗は5.0×10-7Ω・m以下であることが好ましい。導電部は、公知のディスペンサを用いて導電性ペーストを被覆層や剥離性支持体等の表面に塗布することによって形成することができる。導電性ペーストを被覆層表面に塗布して形成された導電部(被覆層上に部分的に配置された導電部)は、被覆層の導電部形成面を太陽電池セルの表面または裏面に重ねることによって、太陽電池セルの表面または裏面に配置され得る。 Alternatively, the conductive portion may be formed, for example, by applying a conductive paste as a conductive material. As the conductive paste, conductive components made of metal materials such as gold, silver, copper, aluminum, iron, nickel, tin, chromium, bismuth, indium, and alloys thereof, and conductive components made of non-metals such as carbon (hereinafter referred to as “conductive paste”) The same)) and a resin component such as polyester or epoxy resin can be used in a suitable solvent. Especially, it is preferable to use silver or copper as a conductive component from a viewpoint of temporal stability. Specific examples of the conductive paste include silver paste (trade name “Pertron K-3105”, manufactured by Pernox, conductive component: Ag, resin component: polyester resin, specific resistance: 6.5 × 10 −5 Ω · cm) Is mentioned. The specific resistance of the conductive paste at 25 ° C. is about 5 × 10 −4 Ω · cm or less (for example, 1 × 10 −4 Ω · cm or less, typically 5.0 × 10 −7 Ω · m or less). Preferably there is. The specific resistance of the conductive component constituting the conductive paste is preferably 5.0 × 10 −7 Ω · m or less. The conductive portion can be formed by applying a conductive paste to the surface of a coating layer, a peelable support or the like using a known dispenser. The conductive part formed by applying the conductive paste to the surface of the coating layer (the conductive part partially disposed on the coating layer) overlaps the surface or back surface of the solar cell with the conductive part forming surface of the coating layer. Can be disposed on the front or back surface of the solar battery cell.
好ましい一態様では、導電部の表面(少なくとも太陽電池モジュール入光面側表面。典型的には表層部分。例えば、導電部の表面から深さ1μm以下の部分。以下同じ。)は銀からなる。そのような導電部として、銀めっきが施された金属材料(例えば銅線)が挙げられる。導電部の表面が銀で構成されている場合、当該表面における銀の純度(例えば、銀めっきの純度)は特に制限されず、凡そ95重量%以上(例えば99重量%以上)であることが適当である。上記銀の純度は、好ましくは99.7重量%以上であり、より好ましくは99.9重量%以上である。このように高純度の銀を導電部の表面に配することで、拡散反射率が高まり発電効率が向上する。導電部の表面における添加成分(セレン、アンチモン等の銀以外の成分)の濃度は、凡そ0.3重量%以下(好ましくは0.1重量%以下)であることが好ましい。銀の純度および銀以外の成分の濃度は、誘導結合プラズマ質量分析計(ICP-MS)および誘導結合プラズマ発光分光分析計(ICP-AES)を利用して測定することができる。 In a preferred embodiment, the surface of the conductive portion (at least the surface on the solar cell module incident surface side. Typically, the surface layer portion, for example, the portion having a depth of 1 μm or less from the surface of the conductive portion, the same applies hereinafter) is made of silver. As such a conductive part, a metal material (for example, copper wire) subjected to silver plating can be used. When the surface of the conductive part is made of silver, the purity of silver on the surface (for example, the purity of silver plating) is not particularly limited, and is suitably about 95% by weight (for example, 99% by weight or more). It is. The silver purity is preferably 99.7% by weight or more, more preferably 99.9% by weight or more. Thus, by disposing high-purity silver on the surface of the conductive portion, the diffuse reflectance is increased and the power generation efficiency is improved. The concentration of the additive component (component other than silver, such as selenium and antimony) on the surface of the conductive portion is preferably about 0.3% by weight or less (preferably 0.1% by weight or less). The purity of silver and the concentration of components other than silver can be measured using an inductively coupled plasma mass spectrometer (ICP-MS) and an inductively coupled plasma emission spectrometer (ICP-AES).
他の好ましい一態様では、導電部は、低融点(例えば融点300℃以下、好ましくは250℃以下)の金属材料(典型的には合金)をホットメルト塗工することにより形成される。具体的には、被覆層や剥離性支持体等の表面に、市販のホットメルトディスペンサー(例えば武蔵エンジニアリング社製)を用いて低融点合金(例えば、荒川化学工業社製の「SnBiはんだ」、融点139℃)を塗工することにより、導電部を形成することができる。なお、スクリーン印刷等の各種印刷法を採用することによっても、上記と同様の構成を得ることができる。 In another preferred embodiment, the conductive portion is formed by hot-melt coating a metal material (typically an alloy) having a low melting point (for example, a melting point of 300 ° C. or lower, preferably 250 ° C. or lower). Specifically, a low-melting-point alloy (for example, “SnBi solder” manufactured by Arakawa Chemical Industries, Ltd.), 139 ° C.) can be applied to form a conductive portion. Note that the same configuration as described above can be obtained by employing various printing methods such as screen printing.
導電部表面の算術平均粗さ(Ra)は、60nm以上であることが好ましい。これによって、拡散反射率が高まり発電効率が向上する傾向がある。上記Raは、より好ましくは70nm以上、さらに好ましくは80nm以上(例えば110nm以上、さらに例えば140nm以上)であり、特に好ましくは200nm以上(例えば220nm以上、さらに例えば250nm以上)である。特に、導電部の表面が銀(典型的には銀めっき層)で構成されており、その純度が99.7重量%以上(好ましくは99.9重量%以上)であり、かつ銀の膜厚が1.0μm以上(好ましくは1.5μm以上)である構成に対して上記範囲のRaを適用することで、拡散反射率を有意に向上させることができる。上記Raは、導電部表面の金属材料種の選択、エンボスロールを利用した粗化処理、エッチング処理等の表面処理等によって調節することができる。 The arithmetic average roughness (Ra) of the surface of the conductive part is preferably 60 nm or more. This tends to increase the diffuse reflectance and improve the power generation efficiency. The Ra is more preferably 70 nm or more, further preferably 80 nm or more (for example, 110 nm or more, further for example, 140 nm or more), and particularly preferably 200 nm or more (for example, 220 nm or more, further, for example, 250 nm or more). In particular, the surface of the conductive portion is composed of silver (typically a silver plating layer), the purity thereof is 99.7% by weight or more (preferably 99.9% by weight or more), and the film thickness of silver By applying Ra in the above-mentioned range to a configuration in which is 1.0 μm or more (preferably 1.5 μm or more), the diffuse reflectance can be significantly improved. The Ra can be adjusted by selecting a metal material type on the surface of the conductive portion, roughening using an embossing roll, or surface treatment such as etching.
上記Raの測定は、下記の方法で測定される。まず、導電部の表面につき、光干渉型形状測定装置を用いて形状プロファイルを計測する。計測する範囲は約600μm×450μmとする。光干渉型形状測定装置としては、Veeco社製の光干渉型形状測定装置、型式「Wyko NT9100」またはその相当品を使用するとよい。得られた計測結果に含まれるうねりをGaussian処理で除去した後、導電部表面のRaは算出される。導電部が複数(例えば3本以上)の導電線からなる場合、導電部を構成する任意の3本につき、上記の方法でRaを算出し、それらを算術平均した値を導電部表面のRaとして採用することが好ましい。 The above Ra is measured by the following method. First, a shape profile is measured for the surface of the conductive portion using an optical interference type shape measuring device. The measurement range is about 600 μm × 450 μm. As the optical interference type shape measuring device, an optical interference type shape measuring device manufactured by Veeco, model “Wyko NT9100” or its equivalent may be used. After removing the waviness included in the obtained measurement result by Gaussian processing, Ra of the surface of the conductive portion is calculated. When the conductive part is composed of a plurality of (for example, three or more) conductive wires, Ra is calculated by the above method for any three of the conductive parts, and the value obtained by arithmetically averaging them is defined as Ra on the surface of the conductive part. It is preferable to adopt.
導電部表面は、凡そ60%以上の拡散反射率を示すことが好ましい。これによって、発電効率を向上させることができる。ここで拡散反射率とは、波長550nmの光に対する拡散反射率(入射光に対する拡散反射の割合(%))をいう。上記拡散反射率は、より好ましくは80%以上、さらに好ましくは85%以上、殊に好ましくは87%以上、特に好ましくは90%以上である。 The surface of the conductive part preferably exhibits a diffuse reflectance of about 60% or more. Thereby, power generation efficiency can be improved. Here, the diffuse reflectance refers to the diffuse reflectance with respect to light having a wavelength of 550 nm (the ratio (%) of diffuse reflection with respect to incident light). The diffuse reflectance is more preferably 80% or more, further preferably 85% or more, particularly preferably 87% or more, and particularly preferably 90% or more.
また、導電部表面における全反射に占める拡散反射の割合(拡散反射比率)は、凡そ80%以上であることが好ましい。拡散反射比率とは、具体的には、波長550nmの光に対する全反射(正反射(鏡面反射ともいう。)と拡散反射との和)に占める拡散反射の割合(%)をいう。上記拡散反射比率は、より好ましくは90%以上、さらに好ましくは95%以上、特に好ましくは99%以上である。 The ratio of diffuse reflection to the total reflection on the surface of the conductive portion (diffuse reflection ratio) is preferably about 80% or more. Specifically, the diffuse reflection ratio refers to the ratio (%) of diffuse reflection in total reflection (the sum of regular reflection (also referred to as specular reflection) and diffuse reflection) with respect to light having a wavelength of 550 nm. The diffuse reflection ratio is more preferably 90% or more, further preferably 95% or more, and particularly preferably 99% or more.
上記拡散反射率および拡散反射比率は、市販の分光光度計を用いて測定することができる。例えば、JASCO社製の積分球ユニット(例えば製品名「ISV-722」)、同社製の分光光度計(例えば製品名「V-660」)、およびラブスフェア社製の標準白板(例えば、スペクトラロン(登録商標)6916-H422A)を用いて測定される。測定は、導電部において太陽電池モジュールの入光面側の表面となる部分に対して行うものとする。また、測定対象である導電部(例えば導電線)の照射面積が不十分の場合には、複数の導電部を密接するよう並べて測定を行うものとする。 The above diffuse reflectance and diffuse reflectance ratio can be measured using a commercially available spectrophotometer. For example, an integrating sphere unit manufactured by JASCO (for example, product name “ISV-722”), a spectrophotometer manufactured by the same (for example, product name “V-660”), and a standard white plate manufactured by Labsphere (for example, Spectralon ( (Registered trademark) 6916-H422A). The measurement is performed on the portion of the conductive portion that is the surface on the light incident surface side of the solar cell module. Moreover, when the irradiation area of the electroconductive part (for example, conductive wire) which is a measuring object is inadequate, it shall measure by arranging a several electroconductive part closely.
導電部(典型的には導電線)は、その長手方向に直交する断面における高さ(H)と幅(W)との比(H/W)が1/2以下に設定されていることが好ましい。これによって、優れた性能を発揮することができる。上記比(H/W)は、配線作業性や接続信頼性の観点から、好ましくは1/3以下程度であり、また発電効率の観点から、好ましくは1/5以上(例えば1/4以上)である。また、導電部が導電線を有する場合、導電線は、その長手方向に直交する断面において長方形状を有する。これによって、導電線の一面のほぼ全域が太陽電池セル表面と面接触することができる。上記長方形状は、各角にアール等の面取りが施されていてもよい。なお、導電線の断面形状はこれに限定されず、円形、楕円形、半円形、台形、三角形等の形状であってもよい。太陽電池セルとの接触面積の観点から、導電部(典型的には導電線)は、太陽電池セルと接触する部分(典型的には面)が平面となっていることが好ましい。 The ratio of the height (H) to the width (W) (H / W) in the cross section orthogonal to the longitudinal direction of the conductive portion (typically conductive wire) is set to be ½ or less. preferable. Thereby, excellent performance can be exhibited. The ratio (H / W) is preferably about 1/3 or less from the viewpoint of wiring workability and connection reliability, and preferably 1/5 or more (for example, 1/4 or more) from the viewpoint of power generation efficiency. It is. Moreover, when a conductive part has a conductive wire, the conductive wire has a rectangular shape in a cross section orthogonal to the longitudinal direction. Thereby, almost the whole area of one surface of the conductive wire can be in surface contact with the surface of the solar battery cell. The rectangular shape may be chamfered at each corner. The cross-sectional shape of the conductive wire is not limited to this, and may be a circular shape, an elliptical shape, a semicircular shape, a trapezoidal shape, a triangular shape, or the like. From the viewpoint of the contact area with the solar battery cell, it is preferable that the conductive portion (typically conductive wire) has a flat portion (typically a surface) in contact with the solar battery cell.
導電部が導電線を有する場合、導電線の幅(複数の導電線を有する場合は各々の幅)は、集電ロス低減、強度、ハンドリング性および作業性の観点から、好ましくは0.03mm以上であり、より好ましくは0.1mm以上であり、さらに好ましくは0.2mm以上である。また上記幅は、シャドーロス低減等の観点から、好ましくは1.5mm以下であり、より好ましくは1.2mm以下であり、さらに好ましくは1.0mm以下である。なお、上記幅は、導電線の長手方向に直交する長さ(幅)を指す。 When the conductive part has a conductive line, the width of the conductive line (in the case of having a plurality of conductive lines, each width) is preferably 0.03 mm or more from the viewpoint of reduction of current collection loss, strength, handling properties, and workability. More preferably, it is 0.1 mm or more, More preferably, it is 0.2 mm or more. The width is preferably 1.5 mm or less, more preferably 1.2 mm or less, and further preferably 1.0 mm or less from the viewpoint of reducing shadow loss. In addition, the said width | variety points out the length (width) orthogonal to the longitudinal direction of a conductive wire.
また、線状に延びる複数の導電線を間隔をおいて配置する場合、導電線の間隔は、シャドーロス低減等の観点から、好ましくは0.1cm以上であり、より好ましくは0.8cm以上であり、さらに好ましくは1.5cm以上である。また上記間隔は、集電ロス低減の観点からは、好ましくは4.0cm未満であり、より好ましくは3.0cm未満であり、さらに好ましくは2.8cm以下(例えば2.5cm以下)である。なお、上記間隔はピッチであり、導電線の幅方向における中心線間の距離を指す。 In addition, when arranging a plurality of conductive lines extending in a line at intervals, the distance between the conductive lines is preferably 0.1 cm or more, more preferably 0.8 cm or more, from the viewpoint of reducing shadow loss. More preferably 1.5 cm or more. The distance is preferably less than 4.0 cm, more preferably less than 3.0 cm, and even more preferably 2.8 cm or less (for example, 2.5 cm or less) from the viewpoint of reducing current collection loss. In addition, the said space | interval is a pitch and points out the distance between the centerlines in the width direction of a conductive wire.
導電部の厚さ(高さ)は、導電性、強度、ハンドリング性および作業性の観点から、0.01~1mm(例えば0.02~0.5mm、典型的には0.05~0.3mm)程度とすることが好ましい。導電線の厚さも同様の範囲から好ましく選定される。 The thickness (height) of the conductive portion is 0.01 to 1 mm (for example, 0.02 to 0.5 mm, typically 0.05 to 0.00 mm) from the viewpoints of conductivity, strength, handling properties, and workability. 3 mm) or so is preferable. The thickness of the conductive wire is also preferably selected from the same range.
<被覆層>
(被覆層の特性)
ここに開示される第1被覆層および第2被覆層(以下、まとめて「被覆層」ともいう。)は、太陽電池セルと導電部との接触状態を良好に保持する層として機能し得る。被覆層は、典型的には樹脂層であり、室温付近の温度域において弾性体または粘弾性体の性質を示す層であることが好ましい。なお、ここでいう粘弾性体は、粘性と弾性の性質を併せ持つ材料、すなわち、複素弾性率の位相が0を超えてπ/2未満、を満たす性質を有する材料(典型的には25℃において上記性質を有する材料)である。また、被覆層は絶縁性であることが好ましい。被覆層は、単層構造であってもよく、2層以上の多層構造であってもよい。
<Coating layer>
(Characteristics of coating layer)
The first coating layer and the second coating layer (hereinafter collectively referred to as “coating layer”) disclosed herein can function as layers that favorably maintain the contact state between the solar battery cell and the conductive portion. The coating layer is typically a resin layer, and is preferably a layer that exhibits the properties of an elastic body or a viscoelastic body in a temperature range near room temperature. The viscoelastic body referred to here is a material having both properties of viscosity and elasticity, that is, a material having a property that satisfies the phase of the complex elastic modulus exceeding 0 and less than π / 2 (typically at 25 ° C. A material having the above properties). Moreover, it is preferable that a coating layer is insulating. The coating layer may have a single layer structure or a multilayer structure of two or more layers.
ここに開示される被覆層(典型的には樹脂層)の貯蔵弾性率G’(周波数1Hz、歪み0.1%、150℃)は5,000Pa以上であることが好ましい。高温時に所定以上の貯蔵弾性率G’を示す被覆層(典型的には樹脂層)を用いることで、高温条件下において太陽電池セルと導電部とが良好に接触し、かつ様々な条件下(例えば幅広い温度条件下)において、その接触状態が安定的に維持され得る。被覆層(典型的には樹脂層)は、上記貯蔵弾性率G’に加えて、後述のtanδを満足することがより好ましい。例えば、太陽電池モジュールの構築に際して被覆層の外方から導電部を太陽電池セルに押し当てたときに、高温条件下においても導電部を太陽電池セル表面に良好に当接させることができる。上記150℃貯蔵弾性率G’は、より好ましくは10,000Pa以上、さらに好ましくは20,000Pa以上、特に好ましくは25,000Pa以上(例えば50,000Pa以上、典型的には80,000Pa以上)である。また、上記150℃貯蔵弾性率G’は、通常は1,000,000Pa以下であり、好ましくは500,000Pa以下、より好ましくは200,000Pa以下(例えば150,000Pa以下、典型的には100,000Pa以下)であり得る。
The storage elastic modulus G ′ (
また、被覆層(典型的には樹脂層)の貯蔵弾性率G’(周波数1Hz、歪み0.1%)は、80℃~150℃の温度域において、5,000Pa~1,000,000Paの範囲内にあることが好ましい。上記高温域における貯蔵弾性率G’の変化が所定の範囲内にあることは、被覆層(典型的には樹脂層)の物性が温度変化の影響を受けにくいことを意味し得る。80℃~150℃の温度域における被覆層(典型的には樹脂層)の貯蔵弾性率G’は、より好ましくは5,000Pa~500,000Pa、さらに好ましくは5,000Pa~200,000Pa(例えば10,000Pa~100,000Pa)の範囲内である。
In addition, the storage elastic modulus G ′ (
さらに、被覆層(典型的には樹脂層)の貯蔵弾性率G’(周波数1Hz、歪み0.1%)は、30℃~150℃の温度域において、5,000Pa~10,000,000Paの範囲内にあることが好ましい。上記のような広い温度域における貯蔵弾性率G’の変化が所定の範囲内にあることは、被覆層(典型的には樹脂層)の物性が温度変化の影響を受けにくいことを意味し得る。30℃~150℃の温度域における被覆層(典型的には樹脂層)の貯蔵弾性率G’は、より好ましくは5,000Pa~1,000,000Pa、さらに好ましくは5,000Pa~500,000Pa(例えば10,000Pa~200,000Pa)の範囲内である。
Furthermore, the storage elastic modulus G ′ (
また、ここに開示される被覆層(典型的には樹脂層)のtanδの最大値は、80℃~150℃の温度域において0.4未満であることが好ましい。高温域におけるtanδが所定値以下の被覆層(典型的には樹脂層)を用いることで、高温域において太陽電池セルと導電部とが良好に接触し、かつ様々な条件下(例えば幅広い温度条件下)において、その接触状態が安定的に維持され得る。例えば、太陽電池モジュールの構築に際して被覆層の外方から導電部を太陽電池セルに押し当てたときに、高温条件下においても導電部を太陽電池セル表面に良好に当接させることができる。なお、tanδは、損失弾性率G”/貯蔵弾性率G’から求められる値(G”/G’)である。80℃~150℃の温度域における被覆層(典型的には樹脂層)のtanδの最大値は、より好ましくは0.3未満である。また、上記温度域におけるtanδの最小値は、通常は0.01以上(例えば0.1以上)であり得る。 In addition, the maximum value of tan δ of the coating layer (typically a resin layer) disclosed herein is preferably less than 0.4 in the temperature range of 80 ° C. to 150 ° C. By using a coating layer (typically a resin layer) having a tan δ of a predetermined value or less in a high temperature range, the solar cell and the conductive part are in good contact in the high temperature range and various conditions (for example, a wide range of temperature conditions) In (lower), the contact state can be stably maintained. For example, when the conductive part is pressed against the solar battery cell from the outside of the coating layer when constructing the solar battery module, the conductive part can be satisfactorily brought into contact with the solar battery surface even under high temperature conditions. Here, tan δ is a value (G ″ / G ′) obtained from loss elastic modulus G ″ / storage elastic modulus G ′. The maximum value of tan δ of the coating layer (typically the resin layer) in the temperature range of 80 ° C. to 150 ° C. is more preferably less than 0.3. In addition, the minimum value of tan δ in the above temperature range can be usually 0.01 or more (for example, 0.1 or more).
被覆層(典型的には樹脂層)の貯蔵弾性率G’(周波数1Hz、歪み0.1%、150℃)およびtanδ(G”/G’)は、市販のレオメーター(例えば、装置名「ARES 2KFRT」、TAインスツルメント社製)を用いて、周波数1Hz、歪み0.1%の条件で、所定の温度範囲(80℃~150℃を含む温度域、さらには30℃~150℃を含む温度域)で測定すればよい。測定温度域および昇温速度は、測定装置の機種等に応じて適切に設定すればよい。例えば、30℃~160℃の温度域、0.5℃~20℃/分(例えば10℃/分)程度の昇温速度とすることができる。測定サンプルとしては、約2mm厚とした被覆層(典型的には樹脂層)を直径8mm程度に打ち抜いたものを使用することが望ましい。
The storage elastic modulus G ′ (
被覆層(典型的には樹脂層)は、接着性(典型的には粘着性)を有してもよく、有しなくてもよい。換言すると、被覆層(典型的には樹脂層)は、粘着層であってもよく、非粘着層であってもよい。ここで「粘着層」とは、JIS Z 0237:2009に準じて、SUS304ステンレス鋼板を被着体とし、23℃の測定環境下において2kgのローラを1往復させて上記被着体に圧着してから30分後に引張速度300mm/分の条件で180°方向に剥離した場合の剥離強度が0.1N/20mm以上である層をいう。また、「非粘着層」とは、上記粘着層に該当しない層をいい、典型的には上記剥離強度が0.1N/20mm未満である層をいう。23℃の測定環境下において2kgのローラを1往復させてSUS304ステンレス鋼板に圧着した場合に該ステンレス鋼板に貼り付かない層(実質的に粘着性を示さない層)は、ここでいう非粘着層の概念に含まれる典型例である。 The coating layer (typically a resin layer) may or may not have adhesiveness (typically tackiness). In other words, the coating layer (typically a resin layer) may be an adhesive layer or a non-adhesive layer. Here, the “adhesive layer” refers to a SUS304 stainless steel plate as an adherend in accordance with JIS Z 0237: 2009, and a 2 kg roller is reciprocated once in a measurement environment at 23 ° C. to be bonded to the adherend. 30 minutes later, the peel strength when peeled in the direction of 180 ° at a pulling speed of 300 mm / min is 0.1 N / 20 mm or more. The “non-adhesive layer” refers to a layer that does not correspond to the adhesive layer, and typically refers to a layer having a peel strength of less than 0.1 N / 20 mm. The layer that does not stick to the stainless steel plate when the 2 kg roller is reciprocated once in a measurement environment of 23 ° C. and pressed against the SUS304 stainless steel plate is a non-adhesive layer here. This is a typical example included in the concept.
ここに開示される技術は、粘着剤から形成された粘着層(粘着剤層ともいう。)に該当する樹脂層を被覆層として含む形態で好ましく実施される。この場合、樹脂層形成用組成物は粘着剤組成物であり得る。なお、本明細書において「粘着剤」とは、室温付近の温度域において柔らかい固体(粘弾性体)の状態を呈し、圧力により簡単に被着体に接着する性質を有する材料をいう。ここでいう粘着剤は、「C. A. Dahlquist, “Adhesion : Fundamental and Practice”, McLaren & Sons, (1966) P. 143」に定義されているとおり、一般的に、複素引張弾性率E*(1Hz)<107dyne/cm2を満たす性質を有する材料(典型的には、25℃において上記性質を有する材料)である。 The technique disclosed here is preferably implemented in a form including a resin layer corresponding to an adhesive layer (also referred to as an adhesive layer) formed from an adhesive as a coating layer. In this case, the resin layer forming composition may be a pressure-sensitive adhesive composition. In the present specification, the “pressure-sensitive adhesive” refers to a material that exhibits a soft solid (viscoelastic body) state in a temperature range near room temperature and has a property of easily adhering to an adherend by pressure. The adhesive here is generally complex elastic modulus E * (1 Hz) as defined in “C. A. Dahlquist,“ Adhesion: Fundamental and Practice ”, McLaren & Sons, (1966) P. 143”. <10 < 7 > dyne / cm < 2 > material (typically a material having the above properties at 25 [deg.] C.).
被覆層(典型的には樹脂層)の表面は接着性を有することが好ましい。これによって、被覆層は、導電部の幅方向の両外側にて太陽電池セルに良好に接着し、セル表面と導電部との接触状態を良好に保持する。なお、被覆層(典型的には樹脂層)の表面が弱接着性であったり実質的に非接着性である場合は、公知の接着剤、粘着剤等を利用して、被覆層を導電部越しに太陽電池セルに固定すればよい。 The surface of the coating layer (typically a resin layer) preferably has adhesiveness. As a result, the coating layer adheres well to the solar battery cell on both outer sides in the width direction of the conductive part, and maintains a good contact state between the cell surface and the conductive part. In addition, when the surface of the coating layer (typically a resin layer) is weakly adhesive or substantially non-adhesive, the coating layer is removed from the conductive part using a known adhesive, pressure-sensitive adhesive, or the like. What is necessary is just to fix to a photovoltaic cell over.
好ましい一態様では、被覆層(典型的には樹脂層)の表面は、結晶系Si太陽電池セルに対して3N/10mm以上の180度剥離強度(対太陽電池セル接着力)を示す。上記対太陽電池セル接着力は、太陽電池セルや導電部との固定等の観点から、より好ましくは5N/10mm以上、さらに好ましくは8N/10mm以上(例えば10N/10mm以上、典型的には12N/10mm以上)である。特に好ましい一態様では、被覆層(典型的には樹脂層)の表面は、結晶系Si太陽電池セルに対して15N/10mm以上の180度剥離強度を示す。被覆層(典型的には樹脂層)表面の対太陽電池セル接着力の上限は特に限定されず、上記接着力は、貼り直し等の作業性の観点から、通常は50N/10mm以下(例えば30N/10mm以下、典型的には20N/10mm以下)程度である。 In a preferred embodiment, the surface of the coating layer (typically a resin layer) exhibits a 180-degree peel strength (adhesive power to solar cells) of 3 N / 10 mm or more with respect to the crystalline Si solar cells. From the viewpoint of fixing to the solar battery cell or the conductive part, the adhesive strength to the solar battery cell is more preferably 5 N / 10 mm or more, further preferably 8 N / 10 mm or more (for example, 10 N / 10 mm or more, typically 12 N). / 10 mm or more). In a particularly preferred embodiment, the surface of the coating layer (typically a resin layer) exhibits a 180 degree peel strength of 15 N / 10 mm or more with respect to the crystalline Si solar battery cell. The upper limit of the adhesive force to the solar cell on the surface of the coating layer (typically the resin layer) is not particularly limited, and the above adhesive force is usually 50 N / 10 mm or less (for example, 30 N) from the viewpoint of workability such as reattachment. / 10 mm or less, typically 20 N / 10 mm or less).
上記対太陽電池セル接着力の測定に用いられる被着体は、結晶系Si太陽電池セルである。例えば、Qセルズ社製の結晶系Si太陽電池セルや、GINTECH社製の単結晶系Siセル、多結晶系Siセルが好ましく用いられる。測定は、ラミネート等によって被覆層(典型的には樹脂層)を被着体にしっかりと貼り合わせた後、市販の引張試験機(例えば、装置名「オートグラフAGS-J」、島津製作所製)を用いて、23℃、50%RHの雰囲気下、引張速度30mm/分、剥離角度180度の条件で実施することができる。 The adherend used for the measurement of the adhesion to solar cells is a crystalline Si solar cell. For example, a crystalline Si solar battery cell manufactured by Q CELLS, a single crystalline Si cell manufactured by GINTECH, or a polycrystalline Si cell is preferably used. Measurement is performed by firmly attaching a coating layer (typically a resin layer) to the adherend by means of lamination or the like, and then commercially available a tensile tester (for example, device name “Autograph AGS-J”, manufactured by Shimadzu Corporation). Can be carried out in an atmosphere of 23 ° C. and 50% RH under the conditions of a tensile speed of 30 mm / min and a peeling angle of 180 degrees.
対太陽電池セル接着力の測定は、具体的には、例えば下記の方法で行うことができる。被覆層を5cm×10cmのサイズにカットし、同じサイズで厚さ450μmのEVAシート(商品名「EVASKY」、ブリヂストン社製)に積層する。また、5cm×10cmのガラス上に、同じサイズで厚さ450μmのEVAシート(商品名「EVASKY」、ブリヂストン社製)を積層し、その上に5cm×4cmに切断した太陽電池セル(単結晶系Siセル:商品名「G156S3」、GINTECH社製)を配置する。太陽電池セルの下面に対する接着力を測定する場合は、セル上面(受光面)がEVAシートと対向するように太陽電池セルを配置する。そして、上記で用意した被覆層付きEVAシートの被覆層側表面を上記セルの上に積層する。このとき、被覆層表面のセル非対向部分に、シリコーンで剥離処理を行った剥離ライナーを配置する。この剥離ライナーは、セルのない領域にて下側のEVAシートと被覆層との間に挟まれている。さらに、上側のEVAシートの上にPETフィルムを裏打ちして試験用の積層体を得る。その後、市販のラミネータ(NPC社製)を用いて150℃、100KPa、15分間の条件で上記積層体をラミネート処理した後、恒温乾燥機で150℃、15分のポストキュアを行い、試験片を作成する。
この試験片を用いて、太陽発電用のセルと被覆層間の180度剥離強度を測定する。具体的には、引張試験機(装置名「オートグラフAGS-J」、島津製作所製)を使用して、23℃、50%RHの雰囲気下、引張速度30mm/分、剥離角度180度の条件で被着体(セル)から被覆層を剥離し、そのときの剥離強度[N/10mm]を求める。後述の試験においても同様の方法で測定される。
Specifically, the measurement of the adhesive force to solar cells can be performed by, for example, the following method. The covering layer is cut into a size of 5 cm × 10 cm and laminated on an EVA sheet (trade name “EVASKY”, manufactured by Bridgestone) having the same size and a thickness of 450 μm. In addition, an EVA sheet (trade name “EVASKY”, manufactured by Bridgestone) having the same size and a thickness of 450 μm is laminated on a glass of 5 cm × 10 cm, and a solar cell (single crystal system) cut into 5 cm × 4 cm on the sheet. Si cell: Product name “G156S3” (manufactured by GINTECH) is disposed. When measuring the adhesive force with respect to the lower surface of a photovoltaic cell, a photovoltaic cell is arrange | positioned so that a cell upper surface (light-receiving surface) may oppose an EVA sheet | seat. And the coating layer side surface of the EVA sheet with a coating layer prepared above is laminated | stacked on the said cell. At this time, a release liner that has been subjected to release treatment with silicone is placed on the cell non-facing portion of the surface of the coating layer. This release liner is sandwiched between the lower EVA sheet and the coating layer in an area without cells. Further, a PET film is lined on the upper EVA sheet to obtain a test laminate. Then, after laminating the laminate under conditions of 150 ° C., 100 KPa, 15 minutes using a commercially available laminator (manufactured by NPC), post-cure at 150 ° C. for 15 minutes with a constant temperature dryer, create.
Using this test piece, the 180 degree peel strength between the solar power generation cell and the coating layer is measured. Specifically, using a tensile tester (equipment name “Autograph AGS-J”, manufactured by Shimadzu Corporation) under conditions of 23 ° C., 50% RH,
被覆層(典型的には樹脂層)は典型的には透光性を有する。好ましい一態様に係る被覆層(典型的には樹脂層)は、透明樹脂層(例えば透明粘着剤層)である。本明細書において透明樹脂層とは、全光線透過率が70%以上である樹脂層をいう。太陽電池セルの発電効率の観点から、被覆層(典型的には樹脂層)の全光線透過率は、より好ましくは85%以上であり、さらに好ましくは90%以上である。被覆層(典型的には樹脂層)の全光線透過率は、市販のヘーズメーター(例えば、商品名「HR-100」、村上色彩技術研究所社製)を用いて測定することができる。 The coating layer (typically a resin layer) typically has translucency. The coating layer (typically a resin layer) according to a preferred embodiment is a transparent resin layer (for example, a transparent pressure-sensitive adhesive layer). In this specification, the transparent resin layer refers to a resin layer having a total light transmittance of 70% or more. From the viewpoint of power generation efficiency of the solar battery cell, the total light transmittance of the coating layer (typically a resin layer) is more preferably 85% or more, and further preferably 90% or more. The total light transmittance of the coating layer (typically a resin layer) can be measured using a commercially available haze meter (for example, trade name “HR-100”, manufactured by Murakami Color Research Laboratory Co., Ltd.).
ここに開示される樹脂層は、150℃におけるメルトマスフローレート(MFR)が9g/10分以下を示す樹脂材料から構成されていることが好ましい。上記MFRを示す樹脂層は、良好な形状安定性を発揮することができる。上記MFRは、より好ましくは3g/10分以下、さらに好ましくは1g/10分以下、特に好ましくは0.5g/10分以下(例えば0.2g/10分以下)である。上記MFRの測定は、JIS K 7210:1999またはASTM D 1238に準拠し、温度190℃、荷重2.16Kgの条件で一定時間に流れ出てきた樹脂量を天秤で秤量して単位時間(10分間)に吐出した樹脂量を計算することによって行えばよい。 The resin layer disclosed herein is preferably composed of a resin material having a melt mass flow rate (MFR) at 150 ° C. of 9 g / 10 min or less. The resin layer exhibiting the MFR can exhibit good shape stability. The MFR is more preferably 3 g / 10 min or less, further preferably 1 g / 10 min or less, and particularly preferably 0.5 g / 10 min or less (for example, 0.2 g / 10 min or less). The above MFR measurement is based on JIS K 7210: 1999 or ASTM D 1238, and the amount of resin flowing out at a constant time under conditions of a temperature of 190 ° C. and a load of 2.16 Kg is weighed with a balance and unit time (10 minutes) This may be done by calculating the amount of resin discharged.
また、被覆層(典型的には樹脂層)の線膨張率は、-40℃~85℃の温度域において15%未満であることが好ましい。上記の線膨張率を示す被覆層(典型的には樹脂層)によると、耐久性がさらに改善された配線が実現される。上記線膨張率は、より好ましくは12%以下(例えば10%以下)である。被覆層(典型的には樹脂層)の線膨張率としては、下記の方法で測定される引張モードおよび圧縮モードによる値のいずれか一方(好ましくは両方)の値が採用される。
[線膨張率]
(引張モード)
各被覆層(典型的には樹脂層)を長さ10mm×断面積約0.5mm2のサイズに切断して、試験片を作製する。この試験片につき、熱分析装置(商品名「EXSTAR6000」、セイコーインスツル社製)を用いて、引張荷重20mN、昇温速度1.7℃/分の条件で、-40℃~85℃における線膨張率(%)を測定する。上記線膨張率は次式より求められる。
-40℃~85℃における線膨張率(%)=(A-B)/B×100
A:-40℃~85℃における試験片の長さの最大値(mm)
B:-40℃~85℃における試験片の長さの最小値(mm)
(圧縮モード)
各被覆層(典型的には樹脂層)を約5mm角のサイズに切断して、試験片を作製する。この試験片につき、TMA(Thermal Mechanical Analysis)装置(装置名「TMA/SS7100」、エスアイアイ・ナノテクノロジー社製)を用いて下記の条件で、-40℃~85℃における線膨張率(%)を測定する。上記線膨張率は次式より求められる。
-40℃~85℃における線膨張率(%)=(A-B)/B×100
A:-40℃~85℃における試験片の厚さの最大値(μm)
B:-40℃~85℃における試験片の厚さの最小値(μm)
測定条件:
押込試験時の荷重; 9.8mN
プローブ径; φ3.5mm
温度プログラム; -60℃→160℃、10℃/分
測定雰囲気; N2(流量 200mL/分)
The linear expansion coefficient of the coating layer (typically a resin layer) is preferably less than 15% in the temperature range of −40 ° C. to 85 ° C. According to the coating layer (typically a resin layer) showing the linear expansion coefficient, a wiring with further improved durability is realized. The linear expansion coefficient is more preferably 12% or less (for example, 10% or less). As the linear expansion coefficient of the coating layer (typically the resin layer), either one (preferably both) values of the tensile mode and the compression mode measured by the following method are adopted.
[Linear expansion coefficient]
(Tensile mode)
Each coating layer (typically a resin layer) is cut into a size of 10 mm in length and about 0.5 mm 2 in cross-sectional area to produce a test piece. Using this test piece, a line at −40 ° C. to 85 ° C. under the conditions of a tensile load of 20 mN and a temperature increase rate of 1.7 ° C./min using a thermal analyzer (trade name “EXSTAR6000”, manufactured by Seiko Instruments Inc.) The expansion rate (%) is measured. The linear expansion coefficient is obtained from the following equation.
Linear expansion coefficient (%) at −40 ° C. to 85 ° C. = (AB) / B × 100
A: Maximum length of test piece at −40 ° C. to 85 ° C. (mm)
B: Minimum value of length of test piece at −40 ° C. to 85 ° C. (mm)
(Compression mode)
Each coating layer (typically a resin layer) is cut into a size of about 5 mm square to produce a test piece. Using this test piece, a linear expansion coefficient (%) at −40 ° C. to 85 ° C. under the following conditions using a TMA (Thermal Mechanical Analysis) device (device name “TMA / SS7100”, manufactured by SII Nano Technology) Measure. The linear expansion coefficient is obtained from the following equation.
Linear expansion coefficient (%) at −40 ° C. to 85 ° C. = (AB) / B × 100
A: Maximum thickness of test piece at −40 ° C. to 85 ° C. (μm)
B: Minimum thickness of specimen at -40 ° C to 85 ° C (μm)
Measurement condition:
Load during indentation test: 9.8 mN
Probe diameter: φ3.5mm
Temperature program; −60 ° C. → 160 ° C., 10 ° C./min Measurement atmosphere; N 2 (flow
(樹脂層の組成)
ここに開示される被覆層の典型例としての樹脂層は、樹脂材料から形成された樹脂層である。好ましくは、架橋された樹脂をベースポリマーとして含む樹脂層(例えば、架橋処理が施された樹脂層)である。樹脂層は、封止樹脂と異なる物性を有し、典型的には、封止樹脂の樹脂材料とは異なる樹脂材料から形成され得る。樹脂層を形成する樹脂は、アクリル系樹脂、EVA系樹脂、ポリオレフィン系樹脂、ゴム類、シリコーン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、ポリエーテル系樹脂、ポリアミド系樹脂、フッ素系樹脂等の各種の樹脂から選択される1種または2種以上であり得る。また、アクリル系樹脂とは、アクリル系ポリマーをベースポリマー(ポリマー成分のなかの主成分、すなわちポリマー成分のなかで配合割合の最も大きい成分、典型的には50重量%を超えて含まれる成分)とする樹脂材料をいう。EVA系その他の樹脂についても同様の意味である。
(Composition of resin layer)
The resin layer as a typical example of the coating layer disclosed here is a resin layer formed from a resin material. A resin layer containing a crosslinked resin as a base polymer (for example, a resin layer subjected to crosslinking treatment) is preferable. The resin layer has physical properties different from those of the sealing resin, and can typically be formed from a resin material different from the resin material of the sealing resin. The resin that forms the resin layer is an acrylic resin, EVA resin, polyolefin resin, rubber, silicone resin, polyester resin, urethane resin, polyether resin, polyamide resin, fluorine resin, etc. 1 type or 2 types or more selected from these resin. The acrylic resin is an acrylic polymer as a base polymer (the main component of the polymer component, that is, the component having the largest blending ratio in the polymer component, typically a component that exceeds 50% by weight). The resin material. The same meaning applies to EVA and other resins.
(EVA系樹脂)
好ましい一態様に係る樹脂層は、EVA系樹脂から形成されたEVA系樹脂層である。かかる樹脂層(樹脂層形成用組成物でもあり得る。)に占めるEVAの割合は特に限定されず、典型的には50重量%以上であり、好ましくは70重量%以上、より好ましくは80重量%以上である。また、上記EVA系樹脂層は、所望の物性を得る観点から、凡そ80~200℃(例えば100~180℃、典型的には120~160℃)で熱硬化処理が施されたものであることが好ましい。熱硬化処理時間は、特に限定されず、通常は5分以上であり、好ましくは10分以上、より好ましくは20分以上(例えば30分以上、典型的には40分~120分)である。上記EVA系樹脂層は、熱硬化処理前または処理中にプレス処理が行われていることが好ましい。
(EVA resin)
The resin layer according to a preferred embodiment is an EVA resin layer formed from an EVA resin. The proportion of EVA in the resin layer (which may also be a resin layer forming composition) is not particularly limited and is typically 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight. That's it. The EVA resin layer is subjected to a thermosetting treatment at about 80 to 200 ° C. (eg, 100 to 180 ° C., typically 120 to 160 ° C.) from the viewpoint of obtaining desired physical properties. Is preferred. The heat curing treatment time is not particularly limited and is usually 5 minutes or longer, preferably 10 minutes or longer, more preferably 20 minutes or longer (for example, 30 minutes or longer, typically 40 minutes to 120 minutes). The EVA resin layer is preferably subjected to a press treatment before or during the thermosetting treatment.
(アクリル系ポリマー)
好ましい一態様において、樹脂層は、ベースポリマーとしてアクリル系ポリマーを含む層、すなわちアクリル系樹脂層であり得る。かかる組成の樹脂層は、形状安定性や柔軟性など所望の物性に調節しやすいので好ましい。また、樹脂層に占めるアクリル系ポリマーの割合は特に限定されず、典型的には50重量%以上であり、好ましくは70重量%以上、より好ましくは80重量%以上である。
なお、本明細書において「(メタ)アクリレート」とは、アクリレートおよびメタクリレートを包括的に指す意味である。同様に、「(メタ)アクリロイル」とは、アクリロイルおよびメタクリロイルを、「(メタ)アクリル」とはアクリルおよびメタクリルを、それぞれ包括的に指す意味である。
また、本明細書において「アクリル系ポリマーを構成するモノマー成分」とは、樹脂層を形成する樹脂材料においてアクリル系ポリマーを構成するモノマー単位をいう。モノマー成分は、樹脂層を形成するために用いられる樹脂層形成用組成物中に、未重合物の形態(すなわち、重合性官能基が未反応である原料モノマーの形態)で含まれてもよく、重合物の形態で含まれていてもよく、これらの両方の形態で含まれていてもよい。
(Acrylic polymer)
In a preferred embodiment, the resin layer may be a layer containing an acrylic polymer as a base polymer, that is, an acrylic resin layer. A resin layer having such a composition is preferable because it can be easily adjusted to desired physical properties such as shape stability and flexibility. The proportion of the acrylic polymer in the resin layer is not particularly limited, and is typically 50% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more.
In the present specification, “(meth) acrylate” means acrylate and methacrylate comprehensively. Similarly, “(meth) acryloyl” means acryloyl and methacryloyl, and “(meth) acryl” generically means acrylic and methacryl.
Further, in this specification, the “monomer component constituting the acrylic polymer” refers to a monomer unit constituting the acrylic polymer in the resin material forming the resin layer. The monomer component may be contained in the resin layer forming composition used for forming the resin layer in an unpolymerized form (that is, in the form of a raw material monomer in which the polymerizable functional group is unreacted). , May be included in the form of a polymer, or may be included in both forms.
ここに開示される樹脂層形成用組成物は、上記アクリル系ポリマーを構成するモノマー成分として(A)成分を含むことが好ましい。 The resin layer forming composition disclosed herein preferably contains the component (A) as a monomer component constituting the acrylic polymer.
上記(A)成分は、炭素数1~20のアルキル基をエステル末端に有するアルキル(メタ)アクリレートである。以下、炭素数がX以上Y以下のアルキル基をエステル末端に有するアルキル(メタ)アクリレートを「CX-Yアルキル(メタ)アクリレート」と表記することがある。C1-20アルキル(メタ)アクリレートにおけるC1-20アルキル基の構造は特に限定されず、上記アルキル基が直鎖のものおよび分岐鎖のもののいずれも使用可能である。(A)成分としては、このようなC1-20アルキル(メタ)アクリレートの1種を単独でまたは2種以上を組み合わせて用いることができる。 The component (A) is an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms at the ester end. Hereinafter, an alkyl (meth) acrylate having an alkyl group having a carbon number of X or more and Y or less at the ester end may be referred to as “C XY alkyl (meth) acrylate”. The structure of the C 1-20 alkyl group in the C 1-20 alkyl (meth) acrylate is not particularly limited, and either a linear or branched alkyl group can be used. As the component (A), one kind of such C 1-20 alkyl (meth) acrylate can be used alone or in combination of two or more kinds.
直鎖アルキル基をエステル末端に有するC1-20アルキル(メタ)アクリレートとして、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、n-ペンチル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、n-へプチル(メタ)アクリレート、n-オクチル(メタ)アクリレート、n-ノニル(メタ)アクリレート、n-デシル(メタ)アクリレート、n-ウンデシル(メタ)アクリレート、n-ドデシル(メタ)アクリレート、n-トリデシル(メタ)アクリレート、n-テトラデシル(メタ)アクリレート、n-ペンタデシル(メタ)アクリレート、n-ヘキサデシル(メタ)アクリレート、n-ヘプタデシル(メタ)アクリレート、n-オクタデシル(メタ)アクリレート、n-ノナデシル(メタ)アクリレート、n-エイコシル(メタ)アクリレートが挙げられる。また、分岐鎖アルキル基をエステル末端に有するC3-20アルキル(メタ)アクリレートとして、イソプロピル(メタ)アクリレート、t-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、t-ペンチル(メタ)アクリレート、ネオペンチル(メタ)アクリレート、イソヘキシル(メタ)アクリレート、イソへプチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、イソオクチル(メタ)アクリレート、イソノニル(メタ)アクリレート、イソデシル(メタ)アクリレート、2-プロピルヘプチル(メタ)アクリレート、イソウンデシル(メタ)アクリレート、イソドデシル(メタ)アクリレート、イソトリデシル(メタ)アクリレート、イソミスチリル(メタ)アクリレート、イソペンタデシル(メタ)アクリレート、イソヘキサデシル(メタ)アクリレート、イソヘプタデシル(メタ)アクリレート、イソステアリル(メタ)アクリレート、イソノナデシル(メタ)アクリレート、イソエイコシル(メタ)アクリレート等が例示される。これらアルキル(メタ)アクリレートは、1種を単独でまたは2種以上を組み合わせて用いることができる。 Examples of C 1-20 alkyl (meth) acrylates having a linear alkyl group at the ester end include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n- Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (Meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-pentadecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n-heptadecyl (meta) ) Acrylate, n- Examples include octadecyl (meth) acrylate, n-nonadecyl (meth) acrylate, and n-eicosyl (meth) acrylate. Further, as C 3-20 alkyl (meth) acrylate having a branched alkyl group at the ester terminal, isopropyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, isopentyl (meth) acrylate, t- Pentyl (meth) acrylate, neopentyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) Acrylate, 2-propylheptyl (meth) acrylate, isoundecyl (meth) acrylate, isododecyl (meth) acrylate, isotridecyl (meth) acrylate, isomistyryl (meth) Examples include acrylate, isopentadecyl (meth) acrylate, isohexadecyl (meth) acrylate, isoheptadecyl (meth) acrylate, isostearyl (meth) acrylate, isononadecyl (meth) acrylate, and isoeicosyl (meth) acrylate. These alkyl (meth) acrylates can be used alone or in combination of two or more.
(A)成分は、(A1)成分としてC4-9アルキル(メタ)アクリレートを含む態様で好ましく実施され得る。アクリル系ポリマーがモノマー単位として(A1)成分を含むことで、所望の物性を有する樹脂層が得られやすい傾向があり、また粘着性も得られやすい傾向がある。(A1)成分はC4-9アルキル(メタ)アクリレートから選択される1種または2種以上であり得る。他のモノマー成分(例えば環状窒素含有モノマー)との相溶性等の観点から、(A1)成分として、C4-9アルキルアクリレートが好ましく使用される。C4-9アルキルアクリレートの好適例としては、n-ブチルアクリレート、2-エチルヘキシルアクリレート、イソオクチルアクリレートおよびイソノニルアクリレートが挙げられる。 The component (A) can be preferably implemented in an embodiment containing C 4-9 alkyl (meth) acrylate as the component (A1). When the acrylic polymer contains the component (A1) as a monomer unit, a resin layer having desired physical properties tends to be easily obtained, and tackiness tends to be easily obtained. The component (A1) may be one or more selected from C 4-9 alkyl (meth) acrylates. From the viewpoint of compatibility with other monomer components (for example, cyclic nitrogen-containing monomers), C 4-9 alkyl acrylate is preferably used as component (A1). Preferable examples of C 4-9 alkyl acrylate include n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate and isononyl acrylate.
(A)成分が(A1)成分を含む場合、(A)成分に占める(A1)成分の割合は、通常は20重量%以上(例えば20~80重量%)であり、好ましくは30重量%以上(例えば30~70重量%)であり、より好ましくは40重量%以上(例えば40~60重量%)である。(A)成分に占める(A1)成分の割合は、50重量%以上(例えば80重量%以上、典型的には90~100重量%)であってもよい。
When the component (A) includes the component (A1), the proportion of the component (A1) in the component (A) is usually 20% by weight or more (
また、(A)成分は、(A2)成分としてC10-18アルキル(メタ)アクリレートを含む態様でも好ましく実施され得る。アクリル系ポリマーがモノマー単位として(A2)成分を含むことで、所望の物性を有する樹脂層がより得られやすい傾向がある。(A2)成分は、C10-18アルキル(メタ)アクリレートから選択される1種または2種以上であり得る。(A2)成分は、より好ましくはアルキル基が分岐鎖であるC10-18アルキル(メタ)アクリレートを含み、さらに好ましくは、他のモノマー成分(例えば環状窒素含有モノマー)との相溶性等の観点から、アルキル基が分岐鎖であるC10-18アルキルアクリレートを含む。C10-18アルキル(メタ)アクリレートの好適例としては、イソデシルアクリレート、イソデシルメタクリレート、ドデシルメタクリレート、トリデシルメタクリレート、イソミスチリルアクリレート、イソステアリルアクリレート、ステアリルメタクリレートが挙げられる。 Further, the embodiment in which the component (A) includes C 10-18 alkyl (meth) acrylate as the component (A2) can be preferably carried out. When the acrylic polymer contains the component (A2) as a monomer unit, a resin layer having desired physical properties tends to be more easily obtained. The component (A2) may be one or more selected from C 10-18 alkyl (meth) acrylates. The component (A2) preferably contains a C 10-18 alkyl (meth) acrylate in which the alkyl group is a branched chain, and more preferably from the viewpoint of compatibility with other monomer components (for example, a cyclic nitrogen-containing monomer). From C10-18 alkyl acrylates in which the alkyl group is branched. Preferable examples of the C 10-18 alkyl (meth) acrylate include isodecyl acrylate, isodecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, isomistyryl acrylate, isostearyl acrylate and stearyl methacrylate.
(A)成分が(A2)成分を含む場合、(A)成分に占める(A2)成分の割合は、通常は20重量%以上(例えば20~80重量%)であり、好ましくは30重量%以上(例えば30~70重量%)であり、より好ましくは40重量%以上(例えば40~60重量%)である。(A)成分に占める(A2)成分の割合は、50重量%以上(例えば80重量%以上、典型的には90~100重量%)であってもよい。 When the component (A) includes the component (A2), the proportion of the component (A2) in the component (A) is usually 20% by weight or more (for example, 20 to 80% by weight), preferably 30% by weight or more. (For example, 30 to 70% by weight), more preferably 40% by weight or more (for example, 40 to 60% by weight). The proportion of the component (A2) in the component (A) may be 50% by weight or more (for example, 80% by weight or more, typically 90 to 100% by weight).
(A)成分として、(A1)成分と(A2)成分とを併用する場合、(A1)成分と(A2)成分との重量比(A1:A2)は、特に限定されず、通常は1:9~9:1とすることが適当であり、好ましくは2:8~8:2(例えば3:7~7:3、典型的には4:6~6:4)である。 When the component (A1) and the component (A2) are used in combination as the component (A), the weight ratio (A1: A2) between the component (A1) and the component (A2) is not particularly limited, and is usually 1: The ratio is suitably 9 to 9: 1, and preferably 2: 8 to 8: 2 (eg, 3: 7 to 7: 3, typically 4: 6 to 6: 4).
また、(A)成分は、(A3)成分としてC1-3アルキル(メタ)アクリレートおよびC19-20アルキル(メタ)アクリレートの1種または2種以上を含有してもよい。(A)成分が(A3)成分を含む場合、樹脂層の物性の観点から、(A)成分に占める(A3)成分の割合は、通常は30重量%以下(例えば15重量%以下、典型的には1~5重量%)程度とすることが好ましい。ここに開示される技術は、(A)成分が(A3)成分を実質的に含まない態様((A)成分に占める(A3)成分の割合が1重量%未満、さらには0.1重量%未満である態様)で好ましく実施される。 The component (A) may contain one or more of C 1-3 alkyl (meth) acrylate and C 19-20 alkyl (meth) acrylate as the component (A3). When the component (A) includes the component (A3), from the viewpoint of the physical properties of the resin layer, the proportion of the component (A3) in the component (A) is usually 30% by weight or less (for example, 15% by weight or less, typically 1 to 5% by weight) is preferable. The technique disclosed here is an embodiment in which the component (A) does not substantially contain the component (A3) (the proportion of the component (A3) in the component (A) is less than 1% by weight, and further 0.1% by weight. In an embodiment that is less than).
上記モノマー成分に占める(A)成分の割合は特に限定されない。樹脂層の物性や、接着力等の粘着特性の観点から、上記(A)成分の割合は、通常は30重量%以上とすることが適当であり、好ましくは50重量%以上、より好ましくは60重量%以上(例えば75重量%以上)である。また、上記(A)成分の割合の上限は、後述の(B)成分や(C)成分含有による効果を十分に得る観点から、凡そ98重量%以下とすることが適当であり、95重量%以下(例えば90重量%以下、典型的には85重量%以下)とすることが好ましい。 The proportion of the component (A) in the monomer component is not particularly limited. From the viewpoint of physical properties of the resin layer and adhesive properties such as adhesive strength, the proportion of the component (A) is usually suitably 30% by weight or more, preferably 50% by weight or more, more preferably 60%. % By weight or more (eg, 75% by weight or more). In addition, the upper limit of the proportion of the component (A) is suitably about 98% by weight or less from the viewpoint of sufficiently obtaining the effects of the later-described components (B) and (C), and is 95% by weight. It is preferable that the amount be less than or equal to (for example, 90% by weight or less, typically 85% by weight or less).
好ましい一態様では、樹脂層形成用組成物は、上記アクリル系ポリマーを構成するモノマー成分として(B)成分を含む。上記(B)成分は、環状窒素含有モノマー、環状エーテル基含有モノマー等のヘテロ環含有モノマーである。上記(B)成分は、樹脂層の形状安定性や透明性の向上に有利に寄与し得る。ヘテロ環含有モノマーは1種を単独でまたは2種以上を組み合わせて用いることができる。 In a preferred embodiment, the resin layer forming composition contains a component (B) as a monomer component constituting the acrylic polymer. The component (B) is a heterocycle-containing monomer such as a cyclic nitrogen-containing monomer or a cyclic ether group-containing monomer. The component (B) can advantageously contribute to improving the shape stability and transparency of the resin layer. The heterocyclic ring-containing monomer can be used alone or in combination of two or more.
環状窒素含有モノマーとしては、(メタ)アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつ環状窒素構造を有するものを特に制限なく用いることができる。環状窒素構造は、環状構造内に窒素原子を有するものが好ましい。環状窒素含有モノマーとしては、例えば、N-ビニルピロリドン、N-ビニル-ε-カプロラクタム、メチルビニルピロリドン等のラクタム系ビニルモノマー;2-ビニル-2-オキサゾリン、2-ビニル-5-メチル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリンのようなオキサゾリン基含有モノマー;ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルモルホリン等の窒素含有複素環を有するビニル系モノマー等が挙げられる。また、モルホリン環、ピペリジン環、ピロリジン環、ピペラジン環、アジリジン環等の窒素含有複素環を含有する(メタ)アクリルモノマーが挙げられる。具体的には、N-アクリロイルモルホリン、N-アクリロイルピペリジン、N-メタクリロイルピペリジン、N-アクリロイルピロリジン、N-アクリロイルアジリジン等が挙げられる。上記環状窒素含有モノマーのなかでも、凝集性等の点からは、ラクタム系ビニルモノマーが好ましく、N-ビニルピロリドンがより好ましい。 As the cyclic nitrogen-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a cyclic nitrogen structure can be used without particular limitation. The cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure. Examples of cyclic nitrogen-containing monomers include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2- Oxazoline group-containing monomers such as oxazoline and 2-isopropenyl-2-oxazoline; vinyl-based compounds having nitrogen-containing heterocycles such as vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, and vinylmorpholine And monomers. Moreover, the (meth) acryl monomer containing nitrogen-containing heterocyclic rings, such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, an aziridine ring, is mentioned. Specific examples include N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine, N-acryloylaziridine and the like. Among the cyclic nitrogen-containing monomers, lactam vinyl monomers are preferable and N-vinylpyrrolidone is more preferable from the viewpoint of cohesiveness and the like.
環状エーテル基を有するモノマーとしては、(メタ)アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつエポキシ基またはオキセタン基等の環状エーテル基を有するものを特に制限なく用いることができる。エポキシ基含有モノマーとしては、例えば、グリシジル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートグリシジルエーテル等が挙げられる。オキセタン基含有モノマーとしては、例えば、3-オキセタニルメチル(メタ)アクリレート、3-メチル-オキセタニルメチル(メタ)アクリレート、3-エチル-オキセタニルメチル(メタ)アクリレート、3-ブチル-オキセタニルメチル(メタ)アクリレート、3-ヘキシル-オキセタニルメチル(メタ)アクリレート、等が挙げられる。 As the monomer having a cyclic ether group, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and a cyclic ether group such as an epoxy group or an oxetane group. It can be used without particular limitation. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Examples of the oxetane group-containing monomer include 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, and 3-butyl-oxetanylmethyl (meth) acrylate. , 3-hexyl-oxetanylmethyl (meth) acrylate, and the like.
上記モノマー成分に占める(B)成分の割合は、樹脂層の物性の観点から、通常は0.5重量%以上とすることが適当であり、好ましくは1重量%以上、より好ましくは3重量%以上、さらに好ましくは10重量%以上(例えば12重量%以上)である。また、上記(B)成分の割合は、(A)成分含有による効果を十分に得る観点から、凡そ50重量%以下とすることが適当であり、好ましくは40重量%以下(例えば30重量%以下、典型的には25重量%以下)とすることが好ましい。 From the viewpoint of the physical properties of the resin layer, the proportion of the component (B) in the monomer component is usually 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight. More preferably, it is 10% by weight or more (for example, 12% by weight or more). The proportion of the component (B) is suitably about 50% by weight or less, preferably 40% by weight or less (for example, 30% by weight or less), from the viewpoint of sufficiently obtaining the effect of containing the component (A). , Typically 25% by weight or less).
好ましい一態様では、樹脂層形成用組成物は、上記アクリル系ポリマーを構成するモノマー成分として(C)成分を含む。上記(C)成分は、ヒドロキシ基およびカルボキシ基の少なくともいずれかを有するモノマーである。 In a preferred embodiment, the resin layer forming composition includes a component (C) as a monomer component constituting the acrylic polymer. The component (C) is a monomer having at least one of a hydroxy group and a carboxy group.
ヒドロキシ基含有モノマーとしては、(メタ)アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつヒドロキシ基を有するものを特に制限なく用いることができる。ヒドロキシ基含有モノマーとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、8-ヒドロキシオクチル(メタ)アクリレート、10-ヒドロキシデシル(メタ)アクリレート、12-ヒドロキシラウリル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート;(4-ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレート等のヒドロキシアルキルシクロアルカン(メタ)アクリレートが挙げられる。その他、ヒドロキシエチル(メタ)アクリルアミド、アリルアルコール、2-ヒドロキシエチルビニルエーテル、4-ヒドロキシブチルビニルエーテル、ジエチレングリコールモノビニルエーテル等が挙げられる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。これらのなかでもヒドロキシアルキル(メタ)アクリレートが好ましい。例えば、炭素数2~6のヒドロキシアルキル基を有するヒドロキシアルキル(メタ)アクリレートを好ましく使用し得る。なかでも、2-ヒドロキシエチルアクリレート、4-ヒドロキシブチルアクリレートがより好ましい。 As the hydroxy group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxy group can be used without particular limitation. Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; -Hydroxyalkylcycloalkane (meth) acrylates such as -hydroxymethylcyclohexyl) methyl (meth) acrylate. Other examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. These can be used alone or in combination of two or more. Of these, hydroxyalkyl (meth) acrylate is preferred. For example, a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms can be preferably used. Of these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are more preferable.
カルボキシ基含有モノマーとしては、(メタ)アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつカルボキシ基を有するものを特に制限なく用いることができる。カルボキシ基含有モノマーの例としては、アクリル酸、メタクリル酸、クロトン酸、カルボキシエチル(メタ)アクリレート、カルボキシペンチル(メタ)アクリレート等のエチレン性不飽和モノカルボン酸;イタコン酸、マレイン酸、フマル酸、シトラコン酸等のエチレン性不飽和ジカルボン酸;これらの金属塩(例えばアルカリ金属塩);無水マレイン酸、無水イタコン酸等の、上記エチレン性不飽和ジカルボン酸の無水物等;が挙げられる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。これらのなかでも、アクリル酸、メタクリル酸が好ましい。 As the carboxy group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxy group can be used without particular limitation. Examples of carboxy group-containing monomers include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate; itaconic acid, maleic acid, fumaric acid, And ethylenically unsaturated dicarboxylic acids such as citraconic acid; metal salts thereof (for example, alkali metal salts); anhydrides of the above ethylenically unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride. These can be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferable.
ここに開示される技術は、(C)成分がヒドロキシ基含有モノマーを含む態様で好ましく実施することができる。すなわち、(C)成分がヒドロキシ基含有モノマーのみを含むか、ヒドロキシ基含有モノマーおよびカルボキシ基含有モノマーを含むことが好ましい。(C)成分に占めるヒドロキシ基含有モノマーの割合を多くすることにより、カルボキシ基に起因する金属腐食等を低減することができる。このことから、ここに開示される技術は、モノマー成分がカルボキシ基含有モノマーを実質的に含有しない態様で好ましく実施され得る。例えば、モノマー成分に占めるカルボキシ基含有モノマーの割合を、1重量%未満、好ましくは0.5重量%未満、より好ましくは0.2重量%未満とすることができる。 The technique disclosed herein can be preferably implemented in a mode in which the component (C) includes a hydroxy group-containing monomer. That is, it is preferable that the component (C) includes only a hydroxy group-containing monomer or includes a hydroxy group-containing monomer and a carboxy group-containing monomer. By increasing the proportion of the hydroxy group-containing monomer in the component (C), metal corrosion caused by the carboxy group can be reduced. From this, the technique disclosed here can be preferably implemented in a mode in which the monomer component does not substantially contain a carboxy group-containing monomer. For example, the proportion of the carboxy group-containing monomer in the monomer component can be less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.2% by weight.
上記モノマー成分に占める(C)成分の割合は、樹脂層の物性の観点から、通常は0.1重量%以上とすることが適当であり、好ましくは0.5重量%以上、より好ましくは0.8重量%以上である。(C)成分の割合は、3重量%以上であってもよく、5重量%以上(例えば8重量%以上、典型的には10重量%以上)であってもよい。また、上記(C)成分の割合は、凡そ35重量%以下とすることが適当であり、好ましくは30重量%以下、より好ましくは25重量%以下(典型的には5重量%以下、例えば3重量%以下)である。上記アクリル系ポリマーにカルボキシ基含有モノマーが共重合されている場合、粘着力と凝集力との両立の観点から、カルボキシ基含有モノマーの含有量は、アクリル系ポリマーの合成に使用する全モノマー成分中、凡そ0.1重量%以上(例えば0.2重量%以上、典型的には0.5重量%以上)とすることが好ましく、また凡そ10重量%以下(例えば8重量%以下、典型的には5重量%以下)とすることが好ましい。アクリル系ポリマーにヒドロキシ基含有モノマーが共重合されている場合、粘着力と凝集力との両立の観点から、ヒドロキシ基含有モノマーの含有量は、アクリル系ポリマーの合成に使用する全モノマー成分中、凡そ0.001重量%以上(例えば0.01重量%以上、典型的には0.02重量%以上)であることが好ましく、また凡そ10重量%以下(例えば5重量%以下、典型的には2重量%以下)であることが好ましい。 The proportion of the component (C) in the monomer component is usually suitably 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0, from the viewpoint of the physical properties of the resin layer. .8% by weight or more. The proportion of the component (C) may be 3% by weight or more, or 5% by weight or more (for example, 8% by weight or more, typically 10% by weight or more). The proportion of the component (C) is suitably about 35% by weight or less, preferably 30% by weight or less, more preferably 25% by weight or less (typically 5% by weight or less, eg 3 % By weight or less). When a carboxy group-containing monomer is copolymerized with the acrylic polymer, the content of the carboxy group-containing monomer is based on the total monomer component used for the synthesis of the acrylic polymer from the viewpoint of achieving both cohesion and cohesion. About 0.1% by weight or more (for example, 0.2% by weight or more, typically 0.5% by weight or more), and about 10% by weight or less (for example, 8% by weight or less, typically Is preferably 5% by weight or less). When the hydroxy group-containing monomer is copolymerized with the acrylic polymer, from the viewpoint of coexistence of adhesive force and cohesive force, the content of the hydroxy group-containing monomer is the total monomer component used for the synthesis of the acrylic polymer. It is preferably about 0.001% by weight or more (eg, 0.01% by weight or more, typically 0.02% by weight or more), and about 10% by weight or less (eg, 5% by weight or less, typically 2% by weight or less).
特に好ましい一態様では、アクリル系ポリマーを構成するモノマー成分は、上記(A)、(B)および(C)成分をすべて含む。その場合、上記(A)、(B)および(C)成分の総量を100重量%としたときの(A)成分の割合は50~99重量%(より好ましくは60~95重量%、さらに好ましくは70~85重量%)とすることが好ましく、(B)成分の割合は0.9~49.9重量%(より好ましくは4.5~39.5重量%、さらに好ましくは14.2~29.2重量%)とすることが好ましく、(C)成分の割合は0.1~35重量%(より好ましくは0.5~30重量%、さらに好ましくは0.8~25量%)とすることが好ましい。 In a particularly preferred embodiment, the monomer component constituting the acrylic polymer includes all the components (A), (B), and (C). In that case, when the total amount of the above components (A), (B) and (C) is 100% by weight, the proportion of component (A) is 50 to 99% by weight (more preferably 60 to 95% by weight, still more preferably Is preferably 70 to 85% by weight, and the proportion of component (B) is 0.9 to 49.9% by weight (more preferably 4.5 to 39.5% by weight, still more preferably 14.2 to 29.2% by weight), and the proportion of component (C) is 0.1 to 35% by weight (more preferably 0.5 to 30% by weight, still more preferably 0.8 to 25% by weight). It is preferable to do.
ここに開示される技術における上記構成モノマー成分は、上記(A)、(B)成分および(C)成分以外のモノマー(以下「任意モノマー」ともいう。)を必要に応じて含有し得る。 The constituent monomer component in the technique disclosed herein may contain a monomer other than the components (A), (B) and (C) (hereinafter also referred to as “optional monomer”) as necessary.
上記任意モノマーの例として、ヒドロキシ基およびカルボキシ基以外の官能基を含有するモノマーが挙げられる。このような官能基含有モノマーは、アクリル系ポリマーに架橋点を導入したり、アクリル系ポリマーの凝集力を高めたりする目的で使用され得る。官能基含有モノマーとしては、例えば(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド等のアミド基含有モノマー;例えばアクリロニトリル、メタクリロニトリル等のシアノ基含有モノマー; 例えばスチレンスルホン酸、アリルスルホン酸、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸等のスルホン酸基含有モノマー;例えば2-ヒドロキシエチルアクリロイルホスフェート等のリン酸基含有モノマー;例えばジアセトン(メタ)アクリルアミド、ジアセトン(メタ)アクリレート、ビニルメチルケトン、ビニルアセトアセテート等のケト基含有モノマー;例えば2-(メタ)アクリロイルオキシエチルイソシアネート等のイソシアネート基含有モノマー;例えばメトキシエチル(メタ)アクリレート、エトキシエチル(メタ)アクリレート等のアルコキシ基含有モノマー;例えば3-(メタ)アクリロキシプロピルトリメトキシシラン、3-(メタ)アクリロキシプロピルトリエトキシシラン等のアルコキシシリル基含有モノマー;等が挙げられる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。 Examples of the optional monomer include monomers containing a functional group other than a hydroxy group and a carboxy group. Such a functional group-containing monomer can be used for the purpose of introducing a crosslinking point into the acrylic polymer or increasing the cohesive strength of the acrylic polymer. Examples of the functional group-containing monomer include amide group-containing monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-methylol (meth) acrylamide; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; For example, sulfonic acid group-containing monomers such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid; for example, phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; Keto group-containing monomers such as acrylamide, diacetone (meth) acrylate, vinyl methyl ketone, vinyl acetoacetate; for example, isocyanate group-containing monomers such as 2- (meth) acryloyloxyethyl isocyanate; For example, alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; for example, alkoxysilyl groups such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane Containing monomer; and the like. These can be used alone or in combination of two or more.
上記任意モノマーの他の例として、脂環式モノマーが挙げられる。脂環式モノマーとしては、(メタ)アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつ脂環構造含有基を有するものを、特に制限なく用いることができる。ここで「脂環構造含有基」とは、少なくとも一つの脂環構造を含む部分をいう。また、「脂環構造」とは、芳香族性を有しない飽和または不飽和の炭素環構造をいう。本明細書では、脂環構造含有基を単に「脂環式基」ということがある。脂環式基の好適例としては、脂環構造を含む炭化水素基や炭化水素オキシ基が挙げられる。 Other examples of the optional monomer include alicyclic monomers. As the alicyclic monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having an alicyclic structure-containing group can be used without particular limitation. it can. Here, the “alicyclic structure-containing group” refers to a portion containing at least one alicyclic structure. The “alicyclic structure” refers to a saturated or unsaturated carbocyclic structure having no aromaticity. In the present specification, the alicyclic structure-containing group is sometimes simply referred to as “alicyclic group”. Preferable examples of the alicyclic group include a hydrocarbon group and a hydrocarbon oxy group containing an alicyclic structure.
好ましい脂環式モノマーの例として、脂環式基と(メタ)アクリロイル基とを有する脂環式(メタ)アクリレートが挙げられる。脂環式(メタ)アクリレートの具体例としては、シクロプロピル(メタ)アクリレート、シクロブチル(メタ)アクリレート、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、シクロヘプチル(メタ)アクリレート、シクロオクチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート等が挙げられる。これらは、1種を単独でまたは2種以上を組み合わせて用いることができる。 Examples of preferred alicyclic monomers include alicyclic (meth) acrylates having an alicyclic group and a (meth) acryloyl group. Specific examples of the alicyclic (meth) acrylate include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, and cyclooctyl (meth). Examples include acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. These can be used alone or in combination of two or more.
ここに開示される技術におけるモノマー成分は、アクリル系ポリマーのTgの調整や凝集力の向上等の目的で、上記任意モノマーとして、上記(A),(B),(C)成分と共重合可能であって上記で例示した以外の共重合性モノマーを含んでいてもよい。そのような共重合性モノマーとしては、例えば酢酸ビニル、プロピオン酸ビニル等のカルボン酸ビニルエステル;例えばスチレン、置換スチレン(α-メチルスチレン等)、ビニルトルエン等の芳香族ビニル化合物;例えばアリール(メタ)アクリレート(例えばフェニル(メタ)アクリレート)、アリールオキシアルキル(メタ)アクリレート(例えばフェノキシエチル(メタ)アクリレート)、アリールアルキル(メタ)アクリレート(例えばベンジル(メタ)アクリレート)等の芳香族性環含有(メタ)アクリレート;例えばエチレン、プロピレン、イソプレン、ブタジエン、イソブチレン等のオレフィン系モノマー;例えば塩化ビニル、塩化ビニリデン等の塩素含有モノマー;例えばメチルビニルエーテル、エチルビニルエーテル等のビニルエーテル系モノマー;その他、ビニル基を重合したモノマー末端にラジカル重合性ビニル基を有するマクロモノマー等が挙げられる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。 The monomer component in the technology disclosed herein can be copolymerized with the above components (A), (B), and (C) as the above arbitrary monomer for the purpose of adjusting Tg of acrylic polymer and improving cohesion. In addition, a copolymerizable monomer other than those exemplified above may be included. Examples of such copolymerizable monomers include carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene, substituted styrene (α-methylstyrene, etc.), vinyltoluene; ) Aromatic ring-containing acrylate (eg phenyl (meth) acrylate), aryloxyalkyl (meth) acrylate (eg phenoxyethyl (meth) acrylate), arylalkyl (meth) acrylate (eg benzyl (meth) acrylate) ( (Meth) acrylates; olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; for example, methyl vinyl ether, ethyl vinyl ether, and the like Vinyl ether monomers; other, macromonomers, and the like having a radical polymerizable vinyl group in the monomer ends obtained by polymerizing a vinyl group. These can be used alone or in combination of two or more.
これらの任意モノマーの使用量は特に限定されず、適宜決定することができる。通常、任意モノマーの合計使用量は、モノマー成分の50重量%未満とすることが適当であり、30重量%以下とすることが好ましく、20重量%以下とすることがより好ましい。ここに開示される技術は、任意モノマーの合計使用量がモノマー成分の10重量%以下(例えば5重量%以下)である態様で好ましく実施され得る。ここに開示される技術は、任意モノマーを実質的に使用しない態様(例えば、任意モノマーの使用量がモノマー成分の0.3重量%以下、典型的には0.1重量%以下である態様)でも好ましく実施され得る。 The amount of these optional monomers used is not particularly limited and can be determined as appropriate. Usually, the total amount of the arbitrary monomers used is suitably less than 50% by weight of the monomer component, preferably 30% by weight or less, and more preferably 20% by weight or less. The technique disclosed here can be preferably implemented in an embodiment in which the total amount of any monomer used is 10% by weight or less (for example, 5% by weight or less) of the monomer component. The technique disclosed here is an embodiment in which an optional monomer is not substantially used (for example, an embodiment in which the amount of the optional monomer used is 0.3% by weight or less, typically 0.1% by weight or less) of the monomer component. However, it can be preferably implemented.
上述した(A)成分、(B)成分、(C)成分および任意モノマーは、典型的には単官能モノマーである。ここに開示される技術におけるモノマー成分は、このような単官能モノマーの他に、樹脂層の凝集力調整等の目的で、必要に応じて多官能モノマーを含有することができる。ここで、本明細書において単官能モノマーとは、(メタ)アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を1つ有するモノマーを指し、これに対して多官能モノマーとは、後述するように、上記重合性の官能基を少なくとも2つ有するモノマーを指す。 The above-described component (A), component (B), component (C) and optional monomer are typically monofunctional monomers. In addition to such a monofunctional monomer, the monomer component in the technique disclosed herein can contain a polyfunctional monomer as necessary for the purpose of adjusting the cohesive force of the resin layer. Here, the monofunctional monomer in this specification refers to a monomer having one polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and a polyfunctional monomer. As described later, refers to a monomer having at least two polymerizable functional groups.
多官能モノマーは、(メタ)アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を少なくとも2つ有するモノマーである。多官能モノマーの例としては、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、1,2-エチレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート,1,6-ヘキサンジオールジ(メタ)アクリレート、1,12-ドデカンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート等の、多価アルコールと(メタ)アクリル酸とのエステル;アリル(メタ)アクリレート、ビニル(メタ)アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート等が挙げられる。多官能性モノマーは、1種を単独でまたは2種以上を組み合わせて使用することができる。これらのなかでも、トリメチロールプロパントリ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレートを好ましく使用することができる。反応性等の観点から、通常は、2以上のアクリロイル基を有する多官能モノマーが好ましい。 The polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Examples of polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, penta Erythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meth) ) Of acrylate, esters of polyhydric alcohols and (meth) acrylic acid; allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types. Among these, trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used. From the viewpoint of reactivity and the like, a polyfunctional monomer having two or more acryloyl groups is usually preferable.
多官能モノマーの使用量は、その分子量や官能基数等により異なるが、凝集力と接着力とをバランスよく両立する観点から、上記モノマー成分の3重量%以下とすることが好ましく、2重量%以下がより好ましく、1重量%以下(例えば0.5重量%以下)がさらに好ましい。また、多官能モノマーを使用する場合における使用量の下限値は、0重量%より大きければよく、特に限定されない。通常は、多官能モノマーの使用量をモノマー成分の0.001重量%以上(例えば0.01重量%以上)とすることにより、凝集力を向上させる効果が適切に発揮され得る。 The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, and the like, but is preferably 3% by weight or less of the above monomer component from the viewpoint of balancing cohesion and adhesion in a balanced manner. Is more preferable, and 1% by weight or less (for example, 0.5% by weight or less) is more preferable. Moreover, the lower limit of the usage-amount in the case of using a polyfunctional monomer should just be larger than 0 weight%, and is not specifically limited. Usually, the effect of improving the cohesive force can be appropriately exhibited by setting the amount of the polyfunctional monomer used to 0.001% by weight or more (for example, 0.01% by weight or more) of the monomer component.
特に限定するものではないが、上記モノマー成分に占める(A)成分、(B)成分および(C)成分の合計量の割合は、典型的には50重量%超であり、好ましくは70重量%以上、より好ましくは80重量%以上、さらに好ましくは90重量%以上である。ここに開示される技術は、上記合計量の割合が95重量%以上(例えば99重量%以上)である態様で好ましく実施され得る。ここに開示される技術は、上記モノマー成分に占める上記合計量の割合が99.999重量%以下(例えば99.99重量%以下)である態様で好ましく実施され得る。 Although not particularly limited, the proportion of the total amount of the component (A), the component (B) and the component (C) in the monomer component is typically more than 50% by weight, preferably 70% by weight. Above, more preferably 80% by weight or more, still more preferably 90% by weight or more. The technique disclosed here can be preferably implemented in an embodiment in which the ratio of the total amount is 95% by weight or more (for example, 99% by weight or more). The technology disclosed herein can be preferably implemented in an embodiment in which the ratio of the total amount in the monomer components is 99.999% by weight or less (for example, 99.99% by weight or less).
特に限定するものではないが、上記モノマー成分の組成に対応する重合体のTgは、樹脂層の物性、接着性等の観点から、-20℃以下であることが好ましく、-25℃以下であることがより好ましく、また-80℃以上であることが適当であり、-60℃以上であることが好ましく、-50℃以上(例えば-40℃以上、典型的には-35℃以上)であることがより好ましい。 Although not particularly limited, the Tg of the polymer corresponding to the composition of the monomer component is preferably −20 ° C. or less, preferably −25 ° C. or less, from the viewpoints of physical properties and adhesiveness of the resin layer. More preferably -80 ° C or higher, preferably -60 ° C or higher, -50 ° C or higher (eg -40 ° C or higher, typically -35 ° C or higher). It is more preferable.
ここで、モノマー成分の組成に対応する重合体のTgとは、上記モノマー成分に含まれる各モノマーの単独重合体(ホモポリマー)のTgおよび該モノマーの重量分率に基づいて、フォックス(Fox)の式から計算される値をいう。Foxの式とは、以下に示すように、共重合体のTgと、該共重合体を構成するモノマーのそれぞれを単独重合したホモポリマーのガラス転移温度Tgiとの関係式である。
1/Tg=Σ(Wi/Tgi)
なお、上記Foxの式において、Tgは共重合体のガラス転移温度(単位:K)、Wiは該共重合体におけるモノマーiの重量分率(重量基準の共重合割合)、Tgiはモノマーiのホモポリマーのガラス転移温度(単位:K)を表す。ただし、本明細書において、Tgの計算は単官能モノマーのみを考慮して行うものとする。したがって、モノマー成分が多官能モノマーを含む場合には、該モノマー成分に含まれる単官能モノマーの合計量を100重量%として、各単官能モノマーのホモポリマーのTgおよび該単官能モノマーの上記合計量に対する重量分率に基づいてTgを算出する。
Here, the Tg of the polymer corresponding to the composition of the monomer component refers to the Fox based on the Tg of the homopolymer of each monomer contained in the monomer component and the weight fraction of the monomer. The value calculated from the formula. The formula of Fox is a relational expression between Tg of a copolymer and glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
1 / Tg = Σ (Wi / Tgi)
In the above Fox equation, Tg is the glass transition temperature (unit: K) of the copolymer, Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio on a weight basis), and Tgi is the monomer i. Represents the glass transition temperature (unit: K) of the homopolymer. However, in this specification, the calculation of Tg is performed considering only the monofunctional monomer. Therefore, when the monomer component includes a polyfunctional monomer, the total amount of the monofunctional monomer contained in the monomer component is defined as 100% by weight, and the Tg of the homopolymer of each monofunctional monomer and the above total amount of the monofunctional monomer Tg is calculated based on the weight fraction relative to.
ホモポリマーのTgとしては、以下に示すモノマーについては下記の値を採用するものとする。
2-エチルヘキシルアクリレート -70℃
n-ブチルアクリレート -55℃
イソステアリルアクリレート -18℃
シクロヘキシルアクリレート 15℃
イソボルニルアクリレート 94℃
N-ビニル-2-ピロリドン 54℃
2-ヒドロキシエチルアクリレート -15℃
4-ヒドロキシブチルアクリレート -40℃
アクリル酸 106℃
上記で例示した以外のモノマーについては、ホモポリマーのTgとして、「Polymer Handbook」(第3版、John Wiley & Sons, Inc., 1989)に記載の数値を用いるものとする。本文献に複数種類の値が記載されているモノマーについては、最も高い値が採用される。上記Polymer Handbookにも記載されていない場合には、日本国特許出願公開2007-51271号公報に記載の測定方法により得られる値を用いるものとする。
As the Tg of the homopolymer, the following values are adopted for the monomers shown below.
2-Ethylhexyl acrylate -70 ° C
n-Butyl acrylate -55 ° C
Isostearyl acrylate -18 ℃
Isobornyl acrylate 94 ° C
N-Vinyl-2-pyrrolidone 54 ° C
2-Hydroxyethyl acrylate -15 ° C
4-hydroxybutyl acrylate -40 ° C
Acrylic acid 106 ℃
For monomers other than those exemplified above, the values described in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) are used as the Tg of the homopolymer. The highest value is adopted for the monomer whose values are described in this document. When not described in the above Polymer Handbook, values obtained by the measurement method described in Japanese Patent Application Publication No. 2007-51271 are used.
(樹脂層形成用組成物)
ここに開示される樹脂層形成用組成物は、上述のような組成のモノマー成分を、重合物、未重合物(すなわち、重合性官能基が未反応である形態)、あるいはこれらの混合物の形態で含み得る。上記樹脂層形成用組成物は、有機溶媒中に樹脂層形成成分(例えば粘着成分)を含む形態の組成物(溶剤型樹脂層形成用組成物)、樹脂層形成成分が水性溶媒に分散した形態の組成物(水分散型樹脂層形成用組成物)、紫外線や放射線等の活性エネルギー線により硬化して樹脂層形成成分を形成するように調製された組成物(活性エネルギー線硬化型樹脂層形成用組成物)、加熱溶融状態で塗工され、室温付近まで冷えると樹脂層を形成するホットメルト型樹脂層形成用組成物等の、種々の形態であり得る。
(Composition for resin layer formation)
The composition for forming a resin layer disclosed herein includes a monomer component having the above-described composition in the form of a polymer, an unpolymerized product (that is, a form in which the polymerizable functional group is unreacted), or a mixture thereof. Can be included. The composition for forming a resin layer is a composition in which an organic solvent contains a resin layer forming component (for example, an adhesive component) (a composition for forming a solvent type resin layer), and a form in which the resin layer forming component is dispersed in an aqueous solvent. Composition (water-dispersed resin layer forming composition), a composition prepared to cure with active energy rays such as ultraviolet rays and radiation to form a resin layer forming component (active energy ray curable resin layer formation) And a hot melt type resin layer forming composition that forms a resin layer when coated in a heated and melted state and cooled to near room temperature.
上記樹脂層形成用組成物は、典型的には、該組成物のモノマー成分のうち少なくとも一部(モノマーの種類の一部であってもよく、分量の一部であってもよい。)を重合物の形態で含む。上記重合物を形成する際の重合方法は特に限定されず、従来公知の各種重合方法を適宜採用することができる。例えば、溶液重合、エマルション重合、塊状重合等の熱重合(典型的には、熱重合開始剤の存在下で行われる。);紫外線等の光を照射して行う光重合(典型的には、光重合開始剤の存在下で行われる。);β線、γ線等の放射線を照射して行う放射線重合;等を適宜採用することができる。なかでも光重合が好ましい。これらの重合方法において、重合の態様は特に限定されず、従来公知のモノマー供給方法、重合条件(温度、時間、圧力、光照射量、放射線照射量等)、モノマー以外の使用材料(重合開始剤、界面活性剤等)等を適宜選択して行うことができる。 The resin layer forming composition typically contains at least part of the monomer components of the composition (may be part of the type of monomer or part of the quantity). In the form of a polymer. The polymerization method for forming the polymer is not particularly limited, and various conventionally known polymerization methods can be appropriately employed. For example, thermal polymerization such as solution polymerization, emulsion polymerization and bulk polymerization (typically performed in the presence of a thermal polymerization initiator); photopolymerization performed by irradiation with light such as ultraviolet rays (typically It is carried out in the presence of a photopolymerization initiator.); Radiation polymerization carried out by irradiation with radiation such as β-rays and γ-rays; Of these, photopolymerization is preferred. In these polymerization methods, the mode of polymerization is not particularly limited, and conventionally known monomer supply methods, polymerization conditions (temperature, time, pressure, light irradiation amount, radiation irradiation amount, etc.), materials used other than monomers (polymerization initiator) , Surfactant, etc.) can be selected as appropriate.
重合にあたっては、重合方法や重合態様等に応じて、公知または慣用の光重合開始剤や熱重合開始剤を使用し得る。このような重合開始剤は、1種を単独でまたは2種以上を適宜組み合わせて用いることができる。 In the polymerization, a known or commonly used photopolymerization initiator or thermal polymerization initiator can be used depending on the polymerization method, polymerization mode, and the like. Such a polymerization initiator can be used individually by 1 type or in combination of 2 or more types as appropriate.
光重合開始剤としては、特に限定されるものではないが、例えばケタール系光重合開始剤、アセトフェノン系光重合開始剤、ベンゾインエーテル系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤、α-ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、チオキサントン系光重合開始剤等を用いることができる。 The photopolymerization initiator is not particularly limited. For example, ketal photopolymerization initiator, acetophenone photopolymerization initiator, benzoin ether photopolymerization initiator, acylphosphine oxide photopolymerization initiator, α- Ketol photoinitiator, aromatic sulfonyl chloride photoinitiator, photoactive oxime photoinitiator, benzoin photoinitiator, benzyl photoinitiator, benzophenone photoinitiator, thioxanthone light A polymerization initiator or the like can be used.
ケタール系光重合開始剤の具体例には、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(例えば、BASF社製の商品名「イルガキュア651」)等が含まれる。
アセトフェノン系光重合開始剤の具体例には、1-ヒドロキシシクロヘキシル-フェニル-ケトン(例えば、BASF社製の商品名「イルガキュア184」)、4-フェノキシジクロロアセトフェノン、4-t-ブチル-ジクロロアセトフェノン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン(例えば、BASF社製の商品名「イルガキュア2959」)、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(例えば、BASF社製の商品名「ダロキュア1173」)、メトキシアセトフェノン等が含まれる。
ベンゾインエーテル系光重合開始剤の具体例には、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾインエーテルおよびアニソールメチルエーテル等の置換ベンゾインエーテルが含まれる。
アシルホスフィンオキサイド系光重合開始剤の具体例には、ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド(例えば、BASF社製の商品名「イルガキュア819」)、ビス(2,4,6-トリメチルベンゾイル)-2,4-ジ-n-ブトキシフェニルホスフィンオキシド、2,4,6-トリメチルベンゾイルジフェニルホスフィンオキシド(例えば、BASF社製の商品名「ルシリンTPO」)、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルホスフィンオキシド等が含まれる。
α-ケトール系光重合開始剤の具体例には、2-メチル-2-ヒドロキシプロピオフェノン、1-[4-(2-ヒドロキシエチル)フェニル]-2-メチルプロパン-1-オン等が含まれる。芳香族スルホニルクロリド系光重合開始剤の具体例には、2-ナフタレンスルホニルクロライド等が含まれる。光活性オキシム系光重合開始剤の具体例には、1-フェニル-1,1-プロパンジオン-2-(o-エトキシカルボニル)-オキシム等が含まれる。ベンゾイン系光重合開始剤の具体例にはベンゾイン等が含まれる。ベンジル系光重合開始剤の具体例にはベンジル等が含まれる。
ベンゾフェノン系光重合開始剤の具体例には、ベンゾフェノン、ベンゾイル安息香酸、3,3’-ジメチル-4-メトキシベンゾフェノン、ポリビニルベンゾフェノン、α-ヒドロキシシクロヘキシルフェニルケトン等が含まれる。
チオキサントン系光重合開始剤の具体例には、チオキサントン、2-クロロチオキサントン、2-メチルチオキサントン、2,4-ジメチルチオキサントン、イソプロピルチオキサントン、2,4-ジクロロチオキサントン、2,4-ジエチルチオキサントン、イソプロピルチオキサントン、2,4-ジイソプロピルチオキサントン、ドデシルチオキサントン等が含まれる。
Specific examples of the ketal photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, trade name “Irgacure 651” manufactured by BASF).
Specific examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl-phenyl-ketone (for example, trade name “Irgacure 184” manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (for example, trade name “Irgacure 2959” manufactured by BASF), 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one (for example, trade name “Darocur 1173” manufactured by BASF), methoxyacetophenone and the like are included.
Specific examples of the benzoin ether photopolymerization initiator include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether and benzoin isobutyl ether, and substituted benzoin ethers such as anisole methyl ether.
Specific examples of the acylphosphine oxide photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (for example, trade name “Irgacure 819” manufactured by BASF), bis (2,4,6 -Trimethylbenzoyl) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, trade name “Lucirin TPO” manufactured by BASF), bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like.
Specific examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one, and the like. It is. Specific examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride and the like. Specific examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like. Specific examples of the benzoin photopolymerization initiator include benzoin and the like. Specific examples of the benzyl photopolymerization initiator include benzyl and the like.
Specific examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, and the like.
Specific examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone. 2,4-diisopropylthioxanthone, dodecylthioxanthone and the like.
熱重合開始剤としては、特に限定されるものではないが、例えばアゾ系重合開始剤、過酸化物系開始剤、過酸化物と還元剤との組合せによるレドックス系開始剤、置換エタン系開始剤等を使用することができる。より具体的には、例えば2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2-メチルプロピオンアミジン)二硫酸塩、2,2’-アゾビス(2-アミジノプロパン)ジヒドロクロライド、2,2’-アゾビス[2-(5-メチル-2-イミダゾリン-2-イル)プロパン]ジヒドロクロライド、2,2’-アゾビス(N,N’-ジメチレンイソブチルアミジン)、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]ハイドレート等のアゾ系開始剤;例えば過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩;ベンゾイルパーオキサイド、t-ブチルハイドロパーオキサイド、過酸化水素等の過酸化物系開始剤;例えばフェニル置換エタン等の置換エタン系開始剤;例えば過硫酸塩と亜硫酸水素ナトリウムとの組合せ、過酸化物とアスコルビン酸ナトリウムとの組合せ等のレドックス系開始剤;等が例示されるが、これらに限定されない。なお、熱重合は、例えば20~100℃(典型的には40~80℃)程度の温度で好ましく実施され得る。 The thermal polymerization initiator is not particularly limited. For example, an azo polymerization initiator, a peroxide initiator, a redox initiator by a combination of a peroxide and a reducing agent, a substituted ethane initiator. Etc. can be used. More specifically, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (2-amidinopropane) dihydrochloride 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (N, N′-dimethyleneisobutylamidine), 2,2 ′ -Azo initiators such as azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate; persulfates such as potassium persulfate and ammonium persulfate; benzoyl peroxide, t-butyl hydroperoxide Peroxide initiators such as hydrogen peroxide; substituted ethane initiators such as phenyl substituted ethane; persulfates and sulfites Combination of sodium hydrogen, redox initiators such as a combination of a peroxide and sodium ascorbate; but the like, without limitation. The thermal polymerization can be preferably carried out at a temperature of, for example, about 20 to 100 ° C. (typically 40 to 80 ° C.).
このような熱重合開始剤または光重合開始剤の使用量は、重合方法や重合態様等に応じた通常の使用量とすることができ、特に限定されない。例えば、重合対象のモノマー成分100重量部に対して重合開始剤0.001~5重量部(典型的には0.01~2重量部、例えば0.01~1重量部)を用いることができる。 The amount of such a thermal polymerization initiator or photopolymerization initiator used can be a normal amount used according to the polymerization method, polymerization mode, etc., and is not particularly limited. For example, a polymerization initiator of 0.001 to 5 parts by weight (typically 0.01 to 2 parts by weight, for example, 0.01 to 1 part by weight) can be used with respect to 100 parts by weight of the monomer component to be polymerized. .
(モノマー成分の重合物と未重合物とを含む樹脂層形成用組成物)
好ましい一態様に係る樹脂層形成用組成物は、該組成物のモノマー成分(原料モノマー)の少なくとも一部を含むモノマー混合物の重合反応物を含む。典型的には、上記モノマー成分の一部を重合物の形態で含み、残部を未重合物(未反応のモノマー)の形態で含む。上記モノマー混合物の重合反応物は、該モノマー混合物を少なくとも部分的に重合させることにより調製することができる。
上記重合反応物は、好ましくは上記モノマー混合物の部分重合物である。このような部分重合物は、上記モノマー混合物に由来する重合物と未反応のモノマーとの混合物であって、典型的にはシロップ状(粘性のある液状)を呈する。以下、かかる性状の部分重合物を「モノマーシロップ」または単に「シロップ」ということがある。
(Composition for forming a resin layer containing a polymerized monomer component and an unpolymerized product)
The resin layer forming composition according to a preferred embodiment includes a polymerization reaction product of a monomer mixture containing at least a part of the monomer component (raw material monomer) of the composition. Typically, a part of the monomer component is included in the form of a polymer, and the remainder is included in the form of an unpolymerized substance (unreacted monomer). The polymerization reaction product of the monomer mixture can be prepared by at least partially polymerizing the monomer mixture.
The polymerization reaction product is preferably a partial polymerization product of the monomer mixture. Such a partial polymer is a mixture of a polymer derived from the monomer mixture and an unreacted monomer, and typically exhibits a syrup shape (viscous liquid). Hereinafter, such a partially polymerized product may be referred to as “monomer syrup” or simply “syrup”.
上記重合反応物を得る際の重合方法は特に制限されず、上述のような各種重合方法を適宜選択して用いることができる。効率や簡便性の観点から、光重合法を好ましく採用し得る。光重合によると、光の照射量(光量)等の重合条件によって、上記モノマー混合物の重合転化率を容易に制御することができる。 The polymerization method for obtaining the polymerization reaction product is not particularly limited, and various polymerization methods as described above can be appropriately selected and used. From the viewpoints of efficiency and simplicity, a photopolymerization method can be preferably employed. According to photopolymerization, the polymerization conversion rate of the monomer mixture can be easily controlled by polymerization conditions such as the amount of light irradiation (light quantity).
上記部分重合物におけるモノマー混合物の重合転化率(モノマーコンバーション)は、特に限定されない。上記重合転化率は、例えば70重量%以下とすることができ、60重量%以下とすることが好ましい。上記部分重合物を含む樹脂層形成用組成物の調製容易性や塗工性等の観点から、通常、上記重合転化率は、50重量%以下が適当であり、40重量%以下(例えば35重量%以下)が好ましい。重合転化率の下限は特に制限されず、典型的には1重量%以上であり、通常は5重量%以上とすることが適当である。 The polymerization conversion rate (monomer conversion) of the monomer mixture in the partial polymer is not particularly limited. The polymerization conversion rate can be, for example, 70% by weight or less, and preferably 60% by weight or less. From the viewpoint of ease of preparation of the resin layer forming composition containing the partial polymer, coating properties, and the like, usually, the polymerization conversion rate is suitably 50% by weight or less, and 40% by weight or less (for example, 35% by weight). % Or less) is preferable. The lower limit of the polymerization conversion rate is not particularly limited and is typically 1% by weight or more, and usually 5% by weight or more is appropriate.
上記モノマー混合物の部分重合物を含む樹脂層形成用組成物は、例えば、原料モノマーの全部を含むモノマー混合物を適当な重合方法(例えば光重合法)により部分重合させることにより容易に得ることができる。上記部分重合物を含む樹脂層形成用組成物には、必要に応じて用いられる他の成分(例えば、光重合開始剤、多官能モノマー、架橋剤、後述するアクリル系オリゴマー等)が配合され得る。そのような他の成分を配合する方法は特に限定されず、例えば上記モノマー混合物にあらかじめ含有させてもよく、上記部分重合物に添加してもよい。 The resin layer forming composition containing a partial polymer of the monomer mixture can be easily obtained by, for example, partially polymerizing a monomer mixture containing all of the raw material monomers by an appropriate polymerization method (for example, photopolymerization method). . The resin layer forming composition containing the partial polymer may contain other components used as necessary (for example, a photopolymerization initiator, a polyfunctional monomer, a crosslinking agent, an acrylic oligomer described later, and the like). . The method of blending such other components is not particularly limited, and for example, it may be previously contained in the monomer mixture or added to the partial polymer.
また、ここに開示される樹脂層形成用組成物は、モノマー成分(原料モノマー)のうち一部の種類のモノマーを含むモノマー混合物の完全重合物が、残りの種類のモノマーまたはその部分重合物に溶解した形態であってもよい。このような形態の樹脂層形成用組成物も、モノマー成分の重合物と未重合物とを含む樹脂層形成用組成物の例に含まれる。なお、本明細書において「完全重合物」とは、重合転化率が95重量%超であることをいう。 Further, in the resin layer forming composition disclosed herein, a complete polymerization product of a monomer mixture containing some types of monomers among the monomer components (raw material monomers) is converted into the remaining types of monomers or partial polymerization products thereof. It may be in a dissolved form. Such a resin layer forming composition is also included in examples of the resin layer forming composition containing a polymerized monomer component and an unpolymerized product. In the present specification, the “completely polymerized product” means that the polymerization conversion rate is more than 95% by weight.
このようにモノマー成分の重合物と未重合物とを含む樹脂層形成用組成物から樹脂層を形成する際の硬化方法(重合方法)としては、光重合法を好ましく採用することができる。光重合法によって調製された重合反応物を含む樹脂層形成用組成物では、その硬化方法として光重合法を採用することが特に好ましい。光重合法により得られた重合反応物は、すでに光重合開始剤を含むので、この重合反応物を含む樹脂層形成用組成物をさらに硬化させて樹脂層を形成する際、新たな光重合開始剤を追加しなくても光硬化し得る。あるいは、光重合法により調製された重合反応物に、必要に応じて光重合開始剤を追加した組成の樹脂層形成用組成物であってもよい。追加する光重合開始剤は、重合反応物の調製に使用した光重合開始剤と同じでもよく、異なってもよい。光重合以外の方法で調製された樹脂層形成用組成物は、光重合開始剤を添加することにより光硬化性とすることができる。光硬化性の樹脂層形成用組成物は、厚手の樹脂層であっても容易に形成し得るという利点を有する。好ましい一態様において、樹脂層形成用組成物から樹脂層を形成する際の光重合は、紫外線照射により行うことができる。紫外線照射には、公知の高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ等を用いることができる。 As described above, a photopolymerization method can be preferably employed as a curing method (polymerization method) when forming a resin layer from a resin layer forming composition containing a polymerized monomer component and an unpolymerized product. In the resin layer forming composition containing the polymerization reaction product prepared by the photopolymerization method, it is particularly preferable to employ the photopolymerization method as the curing method. Since the polymerization reaction product obtained by the photopolymerization method already contains a photopolymerization initiator, when the resin layer forming composition containing this polymerization reaction product is further cured to form a resin layer, a new photopolymerization start is started. It can be photocured without adding an agent. Or the composition for resin layer formation of the composition which added the photoinitiator as needed to the polymerization reaction material prepared by the photopolymerization method may be sufficient. The photopolymerization initiator to be added may be the same as or different from the photopolymerization initiator used for the preparation of the polymerization reaction product. The resin layer forming composition prepared by a method other than photopolymerization can be made photocurable by adding a photopolymerization initiator. The photocurable resin layer forming composition has an advantage that even a thick resin layer can be easily formed. In a preferred embodiment, the photopolymerization when forming the resin layer from the resin layer forming composition can be performed by ultraviolet irradiation. A known high-pressure mercury lamp, low-pressure mercury lamp, metal halide lamp, or the like can be used for ultraviolet irradiation.
(モノマー成分を完全重合物の形態で含む樹脂層形成用組成物)
好ましい他の一態様に係る樹脂層形成用組成物は、該組成物のモノマー成分を完全重合物の形態で含む。このような樹脂層形成用組成物は、例えば、モノマー成分の完全重合物であるアクリル系ポリマーを有機溶媒中に含む溶剤型樹脂層形成用組成物、上記アクリル系ポリマーが水性溶媒に分散した水分散型樹脂層形成用組成物、等の形態であり得る。
(Composition for forming a resin layer containing a monomer component in the form of a completely polymerized product)
The resin layer forming composition according to another preferred embodiment includes the monomer component of the composition in the form of a completely polymerized product. Such a resin layer forming composition is, for example, a solvent-type resin layer forming composition containing an acrylic polymer, which is a complete polymer of monomer components, in an organic solvent, water in which the acrylic polymer is dispersed in an aqueous solvent. It may be in the form of a dispersion type resin layer forming composition.
上記モノマー成分の完全重合物であるアクリル系ポリマーの重量平均分子量(Mw)は、特に限定されない。粘着力と凝集力とをバランスよく両立する観点から、上記Mwは、好ましくは10×104以上、より好ましくは20×104以上、さらに好ましくは50×104以上(例えば100×104以上、典型的には150×104以上)である。同様の理由から、上記Mwは、好ましくは500×104以下、より好ましくは300×104以下(例えば250×104以下)である。なお、この明細書においてMwとは、GPC(ゲルパーミエーションクロマトグラフィー)により得られた標準ポリスチレン換算の値をいう。 The weight average molecular weight (Mw) of the acrylic polymer that is a complete polymerization product of the monomer component is not particularly limited. From the viewpoint of balancing the adhesive force and the cohesive force in a balanced manner, the Mw is preferably 10 × 10 4 or more, more preferably 20 × 10 4 or more, and even more preferably 50 × 10 4 or more (for example, 100 × 10 4 or more). , Typically 150 × 10 4 or more). For the same reason, the Mw is preferably 500 × 10 4 or less, more preferably 300 × 10 4 or less (for example, 250 × 10 4 or less). In addition, in this specification, Mw means the value of standard polystyrene conversion obtained by GPC (gel permeation chromatography).
((メタ)アクリル系オリゴマー)
ここに開示される樹脂層形成用組成物には、接着力向上の観点から、(メタ)アクリル系オリゴマーを含有させることができる。(メタ)アクリル系オリゴマーを含有させることにより、樹脂層の接着力は向上し得る。
((Meth) acrylic oligomer)
The composition for forming a resin layer disclosed herein may contain a (meth) acrylic oligomer from the viewpoint of improving adhesive strength. By including a (meth) acrylic oligomer, the adhesive force of the resin layer can be improved.
上記(メタ)アクリル系オリゴマーは、Tgが約0℃以上300℃以下、好ましくは約20℃以上300℃以下、さらに好ましくは約40℃以上300℃以下であることが望ましい。Tgが上記範囲内であることにより、接着力を好ましく向上することができる。なお(メタ)アクリル系オリゴマーのTgは、上記アクリル系ポリマーのTgと同様、Foxの式に基づいて計算される値である。 The (meth) acrylic oligomer preferably has a Tg of about 0 ° C. or higher and 300 ° C. or lower, preferably about 20 ° C. or higher and 300 ° C. or lower, more preferably about 40 ° C. or higher and 300 ° C. or lower. When Tg is within the above range, the adhesive force can be preferably improved. Note that the Tg of the (meth) acrylic oligomer is a value calculated based on the Fox equation, similar to the Tg of the acrylic polymer.
(メタ)アクリル系オリゴマーの重量平均分子量(Mw)は、典型的には1000以上30000未満、好ましくは1500以上20000未満、さらに好ましくは2000以上10000未満であり得る。Mwが上記範囲内にあることで、良好な接着力や保持特性が得られるため好ましい。(メタ)アクリル系オリゴマーのMwは、GPCにより測定し、標準ポリスチレン換算の値として求めることができる。具体的には、東ソー社製「HPLC8020」に、カラムとしてTSKgelGMH-H(20)×2本を用いて、テトラヒドロフラン溶媒で流速約0.5mL/分の条件にて測定される。 The weight average molecular weight (Mw) of the (meth) acrylic oligomer may typically be 1000 or more and less than 30000, preferably 1500 or more and less than 20000, and more preferably 2000 or more and less than 10,000. It is preferable for Mw to be within the above range because good adhesive force and holding characteristics can be obtained. Mw of the (meth) acrylic oligomer is measured by GPC and can be obtained as a standard polystyrene equivalent value. Specifically, it is measured on a “HPLC 8020” manufactured by Tosoh Corporation using two TSKgelGMH-H (20) columns as a column and a tetrahydrofuran solvent at a flow rate of about 0.5 mL / min.
(メタ)アクリル系オリゴマーを構成するモノマーとしては、例えばメチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、s-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ウンデシル(メタ)アクリレート、ドデシル(メタ)アクリレートのようなアルキル(メタ)アクリレート;シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレートのような(メタ)アクリル酸と脂環族アルコールとのエステル;フェニル(メタ)アクリレート、ベンジル(メタ)アクリレートのようなアリール(メタ)アクリレート;テルペン化合物誘導体アルコールから得られる(メタ)アクリレート;等が挙げられる。このような(メタ)アクリレートは、1種を単独でまたは2種以上を組み合わせて使用することができる。 As a monomer constituting the (meth) acrylic oligomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl ( (Meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl Alkyl (meth) acrylates such as meth) acrylate, dodecyl (meth) acrylate; (meth) acrylic acid and alicyclic such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate Examples include esters with alcohols; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; (meth) acrylates obtained from terpene compound derivative alcohols; and the like. Such (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.
(メタ)アクリル系オリゴマーとしては、イソブチル(メタ)アクリレートやt-ブチル(メタ)アクリレートのようなアルキル基が分岐構造を有するアルキル(メタ)アクリレート;シクロヘキシル(メタ)アクリレートやイソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレートのような(メタ)アクリル酸と脂環式アルコールとのエステル;フェニル(メタ)アクリレートやベンジル(メタ)アクリレートのようなアリール(メタ)アクリレート等の環状構造を有する(メタ)アクリレートに代表される、比較的嵩高い構造を有するアクリル系モノマーをモノマー単位として含んでいることが、接着性をさらに向上させることができる観点から好ましい。また、(メタ)アクリル系オリゴマーの合成の際や樹脂層の作製の際に紫外線を採用する場合には、重合阻害を起こしにくいという点で、飽和結合を有するものが好ましく、アルキル基が分岐構造を有するアルキル(メタ)アクリレート、または脂環式アルコールとのエステルを、(メタ)アクリル系オリゴマーを構成するモノマーとして好ましく用いることができる。 Examples of (meth) acrylic oligomers include alkyl (meth) acrylates in which alkyl groups such as isobutyl (meth) acrylate and t-butyl (meth) acrylate have a branched structure; cyclohexyl (meth) acrylate and isobornyl (meth) acrylate, Esters of (meth) acrylic acid and alicyclic alcohols such as dicyclopentanyl (meth) acrylate; cyclic structures such as aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate It is preferable that an acrylic monomer having a relatively bulky structure typified by (meth) acrylate is included as a monomer unit from the viewpoint of further improving adhesiveness. In addition, when ultraviolet rays are used in the synthesis of a (meth) acrylic oligomer or in the production of a resin layer, those having a saturated bond are preferred in that polymerization inhibition is unlikely to occur, and the alkyl group has a branched structure. An alkyl (meth) acrylate having an ester or an ester with an alicyclic alcohol can be preferably used as a monomer constituting the (meth) acrylic oligomer.
このような点から、好適な(メタ)アクリル系オリゴマーとしては、例えば、ジシクロペンタニルメタクリレート(DCPMA)、シクロヘキシルメタクリレート(CHMA)、イソボルニルメタクリレート(IBXMA)、イソボルニルアクリレート(IBXA)、ジシクロペンタニルアクリレート(DCPA)、1-アダマンチルメタクリレート(ADMA)、1-アダマンチルアクリレート(ADA)の各単独重合体のほか、CHMAとイソブチルメタクリレート(IBMA)との共重合体、CHMAとIBXMAとの共重合体、CHMAとアクリロイルモルホリン(ACMO)との共重合体、CHMAとジエチルアクリルアミド(DEAA)との共重合体、ADAとメチルメタクリレート(MMA)の共重合体、DCPMAとIBXMAとの共重合体、DCPMAとMMAの共重合体、等が挙げられる。 From this point, suitable (meth) acrylic oligomers include, for example, dicyclopentanyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), In addition to dicyclopentanyl acrylate (DCPA), 1-adamantyl methacrylate (ADMA), and 1-adamantyl acrylate (ADA) homopolymers, a copolymer of CHMA and isobutyl methacrylate (IBMA), CHMA and IBXMA Copolymer, Copolymer of CHMA and acryloylmorpholine (ACMO), Copolymer of CHMA and diethylacrylamide (DEAA), Copolymer of ADA and methyl methacrylate (MMA), DCPMA and IB Copolymers of MA, copolymers of DCPMA and MMA, and the like.
ここに開示される樹脂層形成用組成物に(メタ)アクリル系オリゴマーを含有させる場合、その含有量は特に限定されず、樹脂層形成用組成物に含まれるモノマー成分100重量部に対して凡そ1重量部以上とすることが適当である。(メタ)アクリル系オリゴマーの効果をよりよく発揮させる観点からは、上記(メタ)アクリル系オリゴマーの含有量は、3重量部以上(例えば5重量部以上、典型的には8重量部以上)とすることが好ましい。また、樹脂層形成用組成物の硬化性やアクリル系ポリマーの部分重合物や完全重合物との相溶性(ひいては樹脂層の透明性)等の観点から、上記(メタ)アクリル系オリゴマーの含有量は、樹脂層形成用組成物に含まれるモノマー成分100重量部に対して70重量部以下(例えば40重量部以下、典型的には20重量部以下)とすることが適当である。ここに開示される技術は、(メタ)アクリル系オリゴマーを使用しない態様でも実施され得る。 When the (meth) acrylic oligomer is contained in the resin layer forming composition disclosed herein, the content thereof is not particularly limited, and is approximately about 100 parts by weight of the monomer component contained in the resin layer forming composition. It is appropriate that the amount is 1 part by weight or more. From the viewpoint of better exhibiting the effect of the (meth) acrylic oligomer, the content of the (meth) acrylic oligomer is 3 parts by weight or more (for example, 5 parts by weight or more, typically 8 parts by weight or more). It is preferable to do. In addition, the content of the (meth) acrylic oligomer from the viewpoint of the curability of the resin layer forming composition and the compatibility with the partial polymer or the complete polymer of the acrylic polymer (and thus the transparency of the resin layer). Is suitably 70 parts by weight or less (for example 40 parts by weight or less, typically 20 parts by weight or less) with respect to 100 parts by weight of the monomer component contained in the resin layer forming composition. The technique disclosed here can also be implemented in an embodiment that does not use a (meth) acrylic oligomer.
(シランカップリング剤)
さらに、ここに開示される樹脂層形成用組成物は、シランカップリング剤を含有することができる。好ましく用いられ得るシランカップリング剤としては、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基含有シランカップリング剤;3-アミノプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチルブチリデン)プロピルアミン、N-フェニル-γ-アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤;3-アクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン等の(メタ)アクリル基含有シランカップリング剤;3-イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤;等が挙げられる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。シランカップリング剤の配合量は、アクリル系ポリマーを構成するモノマー成分100重量部に対して、好ましくは1重量部以下(例えば0.01~1重量部)であり、より好ましくは0.02~0.6重量部である。
(Silane coupling agent)
Further, the resin layer forming composition disclosed herein may contain a silane coupling agent. Examples of silane coupling agents that can be preferably used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxy. (Cyclohexyl) ethyltrimethoxysilane and other epoxy group-containing silane coupling agents; 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- ( Amino group-containing silane coupling agents such as 1,3-dimethylbutylidene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. (Meth) acrylic group Isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane; Yes silane coupling agent, and the like. These can be used alone or in combination of two or more. The amount of the silane coupling agent is preferably 1 part by weight or less (for example, 0.01 to 1 part by weight), more preferably 0.02 to 100 parts by weight with respect to 100 parts by weight of the monomer component constituting the acrylic polymer. 0.6 parts by weight.
(架橋剤)
ここに開示される樹脂層形成用組成物は、架橋剤を含有することができる。架橋剤としては、例えば、エポキシ系架橋剤、イソシアネート系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤等が挙げられる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。架橋剤の好適例としては、イソシアネート系架橋剤、エポキシ系架橋剤が挙げられる。架橋剤の使用量は特に制限されず、例えば、アクリル系ポリマー100重量部に対して凡そ10重量部以下(例えば凡そ0.005~10重量部、好ましくは凡そ0.01~5重量部)の範囲から選択することができる。あるいは、樹脂層形成用組成物は、上述のような架橋剤を含まないものであってもよい。
(Crosslinking agent)
The composition for resin layer formation disclosed here can contain a crosslinking agent. Examples of the crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a silicone crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a silane crosslinking agent, an alkyl etherified melamine crosslinking agent, and a metal chelate crosslinking agent. Etc. These can be used alone or in combination of two or more. Preferable examples of the crosslinking agent include isocyanate crosslinking agents and epoxy crosslinking agents. The amount of the crosslinking agent used is not particularly limited, and is, for example, about 10 parts by weight or less (for example, about 0.005 to 10 parts by weight, preferably about 0.01 to 5 parts by weight) with respect to 100 parts by weight of the acrylic polymer. You can choose from a range. Or the composition for resin layer formation may not contain the above crosslinking agents.
(その他の添加剤)
その他、ここに開示される樹脂層形成用組成物には、例えば粘着剤の分野において公知の各種添加剤を含有させることができる。例えば、着色剤、顔料等の粉体、染料、界面活性剤、可塑剤、粘着付与樹脂、表面潤滑剤、レベリング剤、軟化剤、酸化防止剤、老化防止剤、光安定剤、紫外線吸収剤、重合禁止剤、無機または有機の充填剤、金属粉、粒子状、箔状物等を、用途に応じて適宜添加することができる。
(Other additives)
In addition, the resin layer forming composition disclosed herein may contain various additives known in the field of pressure-sensitive adhesives, for example. For example, powders such as colorants, pigments, dyes, surfactants, plasticizers, tackifying resins, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, A polymerization inhibitor, an inorganic or organic filler, metal powder, particles, foils, etc. can be appropriately added depending on the application.
(形成方法等)
ここに開示される樹脂層は、例えば、ここに開示されるいずれかの樹脂層形成用組成物を支持体に塗布して乾燥または硬化させることにより樹脂層として形成することができる。樹脂層形成用組成物の塗布方法としては、従来公知の各種の方法を使用可能である。具体的には、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーター等による押出しコート法等の方法が挙げられる。
(Formation method, etc.)
The resin layer disclosed herein can be formed, for example, as a resin layer by applying any of the resin layer forming compositions disclosed herein to a support and drying or curing. As a coating method of the resin layer forming composition, various conventionally known methods can be used. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
樹脂層形成用組成物の乾燥は加熱下で行うことができる。乾燥温度は、40℃~200℃が好ましく、50℃~180℃がより好ましく、70℃~170℃がさらに好ましい。加熱温度を上記の範囲とすることによって、優れた物性を有する樹脂層を得ることができる。乾燥時間は、適宜、適切な時間が採用され得る。上記乾燥時間は、5秒~20分が好ましく、5秒~10分がより好ましく、10秒~5分がさらに好ましい。 The resin layer forming composition can be dried under heating. The drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and further preferably 70 ° C to 170 ° C. By setting the heating temperature within the above range, a resin layer having excellent physical properties can be obtained. As the drying time, an appropriate time can be adopted as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and even more preferably 10 seconds to 5 minutes.
樹脂層の形成にあたっては、所望の物性を得るため、さらに架橋処理、熱硬化処理等が施され得る。例えば、凡そ80~200℃(例えば100~180℃、典型的には120~160℃)で、5分以上の熱硬化処理が施され得る。熱硬化処理時間は、好ましくは10分以上、より好ましくは20分以上(例えば30分以上、典型的には40分~120分)である。上記樹脂層は、熱硬化処理前または処理中にプレス処理を行うことが好ましい。 In forming the resin layer, in order to obtain desired physical properties, a crosslinking treatment, a thermosetting treatment, or the like can be further performed. For example, a thermosetting treatment can be performed at about 80 to 200 ° C. (eg, 100 to 180 ° C., typically 120 to 160 ° C.) for 5 minutes or more. The heat curing treatment time is preferably 10 minutes or longer, more preferably 20 minutes or longer (for example, 30 minutes or longer, typically 40 minutes to 120 minutes). The resin layer is preferably subjected to press treatment before or during the thermosetting treatment.
(樹脂層の厚さ)
ここに開示される樹脂層は、上記樹脂層形成用組成物から得ることができる。樹脂層の厚さは特に制限されず、例えば1~400μm程度であり得る。通常、樹脂層の厚さは、1~200μmが好ましく、2~150μmがより好ましく、2~100μmがさらに好ましく、5~75μmが特に好ましい。
(Resin layer thickness)
The resin layer disclosed herein can be obtained from the resin layer forming composition. The thickness of the resin layer is not particularly limited, and can be, for example, about 1 to 400 μm. Usually, the thickness of the resin layer is preferably 1 to 200 μm, more preferably 2 to 150 μm, further preferably 2 to 100 μm, and particularly preferably 5 to 75 μm.
導電部をあらかじめ樹脂層に積層する態様において、導電部を配置する前の樹脂層は、前面および背面がいずれも剥離面(剥離性の表面)である剥離ライナー(支持体)と重ね合わされて渦巻き状に巻回された形態であり得る。あるいは、第1表面および第2表面が2枚の独立した剥離ライナー(支持体)によりそれぞれ保護された形態であってもよい。剥離ライナーとしては、後述のものを好ましく使用し得る。 In a mode in which the conductive portion is laminated on the resin layer in advance, the resin layer before the conductive portion is placed is spirally overlapped with a release liner (support) whose front surface and back surface are both release surfaces (peelable surfaces). It may be in a form wound in a shape. Alternatively, the first surface and the second surface may be respectively protected by two independent release liners (supports). As the release liner, those described below can be preferably used.
(基材層付き粘着シート)
他の好ましい一態様に係る被覆層は、基材層を含む粘着シートである。かかる粘着シートは、基材層と、基材層の少なくとも一方の表面に配置された粘着剤層と、を備える。その構成例としては、基材層の片面に粘着剤層が設けられた片面接着性の粘着シート(基材層付き片面粘着シート)、基材層の両面に粘着剤層が設けられた両面接着性の粘着シート(基材層付き両面粘着シート)が挙げられる。粘着剤層としては、上記樹脂層として例示したもののなかから粘着剤層となり得る材料や、好ましい特性を有するものを適宜選択して使用することができる。したがって、粘着剤層についての重複する説明はここでは省略する。
(Adhesive sheet with base material layer)
The coating layer which concerns on another preferable one aspect | mode is an adhesive sheet containing a base material layer. Such an adhesive sheet includes a base material layer and an adhesive layer arranged on at least one surface of the base material layer. As a configuration example, a single-sided adhesive sheet (one-sided pressure-sensitive adhesive sheet with a base material layer) provided with a pressure-sensitive adhesive layer on one side of the base material layer, and double-sided adhesive provided with a pressure-sensitive adhesive layer on both sides of the base material layer Adhesive sheet (double-sided pressure-sensitive adhesive sheet with a base material layer). As the pressure-sensitive adhesive layer, materials that can be used as a pressure-sensitive adhesive layer from those exemplified as the resin layer and those having preferable characteristics can be appropriately selected and used. Therefore, the overlapping description about the pressure-sensitive adhesive layer is omitted here.
ここに開示される基材層としては、例えば、樹脂フィルム、紙、布、ゴムフィルム、発泡体フィルム、これらの複合体や積層体等を用いることができる。なかでも、モジュールの耐久性向上や作業性等の観点から、樹脂フィルム層を含むことが好ましい。樹脂フィルム層を含むことは、寸法安定性、厚さ精度、加工性、強度等の観点からも有利である。ここで「樹脂フィルム」は、非多孔質の構造であって、典型的には実質的に気泡を含まない(ボイドレスの)樹脂フィルムを意味する。したがって、上記樹脂フィルムは、発泡体フィルムや不織布とは区別される概念である。また、基材層は、典型的には透明フィルム(例えば透明樹脂フィルム)であることが好ましい。太陽電池セルの下面に配置される被覆層に基材層を適用する場合、当該基材層は透明でなくてもよく、有色かつ不透明の樹脂フィルムであり得る。上記樹脂フィルムは、単層構造であってもよく、2層以上の多層構造であってもよい。 As the substrate layer disclosed herein, for example, a resin film, paper, cloth, rubber film, foam film, a composite or laminate of these, and the like can be used. Especially, it is preferable that a resin film layer is included from viewpoints of durability improvement of a module, workability | operativity, etc. The inclusion of the resin film layer is advantageous from the viewpoint of dimensional stability, thickness accuracy, workability, strength, and the like. Here, the “resin film” means a resin film having a non-porous structure and typically containing substantially no bubbles (voidless). Therefore, the said resin film is the concept distinguished from a foam film and a nonwoven fabric. Moreover, it is preferable that a base material layer is a transparent film (for example, transparent resin film) typically. When applying a base material layer to the coating layer arrange | positioned at the lower surface of a photovoltaic cell, the said base material layer does not need to be transparent and can be a colored and opaque resin film. The resin film may have a single layer structure or a multilayer structure of two or more layers.
樹脂フィルムの例としては、ポリエチレン(PE)、ポリプロピレン(PP)、エチレン・プロピレン共重合体等のポリオレフィン系樹脂フィルム;ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂フィルム;塩化ビニル系樹脂フィルム;酢酸ビニル系樹脂フィルム;ポリイミド系樹脂フィルム;ポリアミド系樹脂フィルム;フッ素系樹脂フィルム;セロハン;等が挙げられる。好適例としては、PE、PP、PETから形成された樹脂フィルムが挙げられる。樹脂フィルムのなかでは、ポリエステルフィルムがより好ましく、そのなかでもPETフィルムがさらに好ましい。 Examples of resin films include polyolefin resin films such as polyethylene (PE), polypropylene (PP), and ethylene / propylene copolymers; polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; Vinyl chloride resin film; vinyl acetate resin film; polyimide resin film; polyamide resin film; fluorine resin film; cellophane; Preferable examples include resin films formed from PE, PP, and PET. Among the resin films, a polyester film is more preferable, and a PET film is more preferable among them.
基材層には、例えば粘着シートの基材層に用いられ得る公知の添加剤を必要に応じて含有させることができる。例えば、紫外線吸収剤等の光安定剤、酸化防止剤、帯電防止剤、充填材、可塑剤、スリップ剤、アンチブロッキング剤等の添加剤を適宜配合することができる。これら添加剤は、それぞれ1種を単独でまたは2種以上を組み合わせて用いることができる。添加剤の配合量は、上記基材層における通常の配合量の範囲内から適宜設定すればよい。ここに開示される被覆層は、発電効率等の観点から、全光線透過率を低下させる成分を実質的に含まない基材層を備えるものであることが好ましい。 In the base material layer, for example, known additives that can be used for the base material layer of the pressure-sensitive adhesive sheet can be contained as necessary. For example, additives such as a light stabilizer such as an ultraviolet absorber, an antioxidant, an antistatic agent, a filler, a plasticizer, a slip agent, and an antiblocking agent can be appropriately blended. Each of these additives can be used alone or in combination of two or more. What is necessary is just to set the compounding quantity of an additive suitably from the range of the normal compounding quantity in the said base material layer. It is preferable that the coating layer disclosed here is provided with the base material layer which does not contain the component which reduces a total light transmittance from viewpoints, such as electric power generation efficiency.
基材層の厚さ(複数の層を有する場合には、それらの層の合計厚さ)は特に限定されず、目的に応じて適宜選択できる。基材層の厚さは、一般的には1~300μmであり得る。所定以上の剛性を得て耐久性を向上させる観点から、基材層の厚さは、好ましくは10μm以上、より好ましくは30μm以上、さらに好ましくは45μm以上(例えば70μm以上、典型的には90μm以上)である。基材層が所定以上の厚さを有することで、被覆層の加工性や取扱い性、作業性も向上する傾向がある。また、基材層の厚さは、凡そ200μm以下(例えば150μm以下)であることが好ましい。基材層の厚さが制限された被覆層は、軽量化、省資源化等の点で有利なものとなり得る。 The thickness of the base material layer (when there are a plurality of layers, the total thickness of these layers) is not particularly limited, and can be appropriately selected according to the purpose. The thickness of the base material layer can generally be 1 to 300 μm. From the viewpoint of obtaining a predetermined rigidity or more and improving durability, the thickness of the base material layer is preferably 10 μm or more, more preferably 30 μm or more, further preferably 45 μm or more (for example, 70 μm or more, typically 90 μm or more). ). When the base material layer has a thickness greater than or equal to a predetermined thickness, the processability, handleability, and workability of the coating layer tend to be improved. Further, the thickness of the base material layer is preferably about 200 μm or less (for example, 150 μm or less). A coating layer with a limited thickness of the base material layer can be advantageous in terms of weight reduction, resource saving, and the like.
基材層の表面(例えば粘着剤層側表面)には、必要に応じて、コロナ放電処理、プラズマ処理、紫外線照射処理、酸処理、アルカリ処理、下塗り剤(プライマー)の塗布、帯電防止処理等の、従来公知の表面処理が施されていてもよい。このような表面処理は、基材層と粘着剤層との密着性、言い換えると粘着剤層の基材層への投錨性を向上させるための処理であり得る。また、基材層の背面(粘着剤層が設けられる面とは反対側の面)には、必要に応じて、シリコーン系、長鎖アルキル系、フッ素系等の剥離処理剤による剥離処理が施されていてもよい。 On the surface of the base material layer (for example, the pressure-sensitive adhesive layer side surface), corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of primer (primer), antistatic treatment, etc., as necessary The conventionally known surface treatment may be applied. Such a surface treatment may be a treatment for improving the adhesion between the base material layer and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer to the base material layer. In addition, the back surface of the base material layer (the surface opposite to the surface on which the pressure-sensitive adhesive layer is provided) is subjected to a release treatment with a release treatment agent such as silicone, long-chain alkyl, or fluorine as necessary. May be.
上記被覆層(例えば基材層付き粘着シート)を構成する粘着剤層の厚さは特に制限されず、凡そ1μm以上であり得る。太陽電池セルとの密着性の観点から、粘着剤層の厚さは、好ましくは5μm以上、より好ましくは10μm以上である。また、粘着剤層の厚さは、通常は凡そ400μm以下であり、好ましくは200μm以下、より好ましくは150μm以下、さらに好ましくは100μm以下、特に好ましくは75μm以下である。粘着剤層の厚さが制限された被覆層は、軽量化、省資源化等の点で有利なものとなり得る。基材層の両面に粘着剤層(第一粘着剤層および第二粘着剤層)が設けられている場合、各粘着剤層の厚さは同じであってもよく、異なっていてもよい。 The thickness of the pressure-sensitive adhesive layer constituting the coating layer (for example, the pressure-sensitive adhesive sheet with a base material layer) is not particularly limited, and may be about 1 μm or more. From the viewpoint of adhesion with the solar battery cell, the thickness of the pressure-sensitive adhesive layer is preferably 5 μm or more, more preferably 10 μm or more. The thickness of the pressure-sensitive adhesive layer is usually about 400 μm or less, preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, and particularly preferably 75 μm or less. The coating layer in which the thickness of the pressure-sensitive adhesive layer is limited can be advantageous in terms of weight reduction and resource saving. When the pressure-sensitive adhesive layer (first pressure-sensitive adhesive layer and second pressure-sensitive adhesive layer) is provided on both surfaces of the base material layer, the thickness of each pressure-sensitive adhesive layer may be the same or different.
(被覆層の総厚さ)
ここに開示される被覆層(例えば粘着剤層と基材層とを含むが、剥離ライナーは含まない。)の総厚さは特に限定されず、凡そ2μm以上とすることが適当であり、好ましくは5μm以上(例えば10μm以上、典型的には30μm以上)である。また、上記総厚さは、凡そ1000μm以下とすることが適当であり、好ましくは500μm以下(例えば300μm以下、典型的には100μm以下)である。
(Total thickness of coating layer)
The total thickness of the coating layer disclosed herein (for example, including the pressure-sensitive adhesive layer and the base material layer but not including the release liner) is not particularly limited, and is suitably about 2 μm or more, preferably Is 5 μm or more (for example, 10 μm or more, typically 30 μm or more). The total thickness is suitably about 1000 μm or less, preferably 500 μm or less (for example, 300 μm or less, typically 100 μm or less).
<剥離ライナー>
第1被覆層や第2被覆層の上下面を保護する剥離ライナーとしては、慣用の剥離紙等を使用することができ、特に限定されない。例えば、プラスチックフィルムや紙等の基材の表面に剥離処理層を有する剥離ライナーや、フッ素系ポリマー(ポリテトラフルオロエチレン等)やポリオレフィン系樹脂(ポリエチレン、ポリプロピレン等)の低接着性材料からなる剥離ライナー等を用いることができる。上記剥離処理層は、上記基材を剥離処理剤により表面処理して形成されたものであり得る。剥離処理剤の例としては、シリコーン系剥離処理剤、長鎖アルキル系剥離処理剤、フッ素系剥離処理剤、硫化モリブデン(IV)等が挙げられる。
<Release liner>
A conventional release paper or the like can be used as the release liner for protecting the upper and lower surfaces of the first coating layer and the second coating layer, and is not particularly limited. For example, a release liner having a release treatment layer on the surface of a substrate such as a plastic film or paper, or a release made of a low adhesive material such as a fluorine polymer (polytetrafluoroethylene, etc.) or a polyolefin resin (polyethylene, polypropylene, etc.) A liner or the like can be used. The release treatment layer may be formed by surface-treating the base material with a release treatment agent. Examples of the release treatment agent include a silicone release treatment agent, a long-chain alkyl release treatment agent, a fluorine release treatment agent, and molybdenum (IV) sulfide.
<太陽電池セル>
使用される太陽電池セルの種類は特に限定されず、例えば単結晶型や多結晶型の結晶系Siセルが好適である。結晶系Siセルは、p型セル(p型基板にn型が付加されたセル)であってもよく、n型セル(n型基板にp型が付加されたセル)であってもよい。また、太陽電池セルは、アモルファス系Siセル、化合物系、有機系等の太陽電池セルであってもよい。また、太陽電池セルは片面受光型、両面受光型のいずれであってもよい。太陽電池セルの形状も特に限定されず、ほぼ四角形状平面を有するウエハであってもよく、帯状等であってもよい。太陽電池セルの厚さは、軽量性等の観点から、好ましくは0.5mm以下程度であり、より好ましくは0.3mm以下(例えば180~200μm程度)、さらに好ましくは160μm以下程度であり得る。
<Solar cell>
The type of the solar battery cell to be used is not particularly limited, and for example, a single crystal type or a polycrystalline type Si cell is suitable. The crystalline Si cell may be a p-type cell (a cell in which n-type is added to a p-type substrate) or an n-type cell (a cell in which p-type is added to an n-type substrate). Further, the solar battery cell may be an amorphous Si cell, a compound solar battery, an organic solar battery cell or the like. Further, the solar cell may be either a single-sided light receiving type or a double-sided light receiving type. The shape of the solar battery cell is not particularly limited, and it may be a wafer having a substantially rectangular plane, or may be a belt shape. The thickness of the solar battery cell is preferably about 0.5 mm or less, more preferably about 0.3 mm or less (for example, about 180 to 200 μm), and further preferably about 160 μm or less from the viewpoint of lightness and the like.
<封止樹脂>
ここに開示される封止樹脂は、絶縁性であり、かつ透光性を有するものであり得る。また例えば、熱や圧力によって流動性を示し得る樹脂層であり得る。なお、本明細書において「絶縁性である」とは、25℃における比抵抗が1×106Ω・cm以上(好ましくは1×108Ω・cm以上、典型的には1×1010Ω・cm以上)であることをいう。また、本明細書において電気抵抗(例えば比抵抗)は、特記しないかぎり25℃における値をいうものとする。また、本明細書において「透光性を有する」とは、JIS K 7375:2008で規定される全光線透過率が50%以上(好ましくは80%以上、典型的には95%以上)であることをいう。
<Sealing resin>
The sealing resin disclosed here may be insulative and translucent. For example, it may be a resin layer that can exhibit fluidity by heat or pressure. In this specification, “insulating” means a specific resistance at 25 ° C. of 1 × 10 6 Ω · cm or more (preferably 1 × 10 8 Ω · cm or more, typically 1 × 10 10 Ω). -Cm or more). In this specification, the electric resistance (for example, specific resistance) is a value at 25 ° C. unless otherwise specified. Further, in the present specification, “having translucency” means that the total light transmittance defined by JIS K 7375: 2008 is 50% or more (preferably 80% or more, typically 95% or more). That means.
封止樹脂は、好ましくは熱硬化性樹脂であり得る。熱硬化性樹脂からなる封止樹脂は、例えば太陽電池セルに積層し加熱することで、太陽電池モジュールにおいて太陽電池セルを良好に封止することができる。上記樹脂としては、透光性、加工性、耐候性等の観点から、エチレン-酢酸ビニル共重合体(EVA)が好ましく使用される。上記樹脂は、EVAに代表されるエチレン-ビニルエステル共重合体の他、エチレン-(メタ)アクリル酸共重合体等のエチレン-不飽和カルボン酸共重合体、エチレン-(メタ)アクリル酸エステル等のエチレン-不飽和カルボン酸エステル共重合体、ポリメタクリル酸メチル等の不飽和カルボン酸エステル系重合体等であってもよい。あるいは、フッ化ビニリデン樹脂、ポリエチレンテトラフルオロエチレン等のフッ素樹脂;低密度ポリエチレン(LDPE)、直鎖状低密度ポリエチレン(LLDPE。典型的にはチーグラー触媒、バナジウム触媒、メタロセン触媒等を用いて製造され得るLLDPE)等のポリエチレン(PE)、ポリプロピレン(PP。例えば、チーグラー触媒、フィリップス触媒、メタロセン触媒等を用いて製造され得るPP)、チーグラー触媒、バナジウム触媒、メタロセン触媒等を用いて製造することができるエチレン・α-オレフィン共重合体、それらの変性物(変性ポリオレフィン)等のポリオレフィン類;ポリブタジエン類;ポリビニルホルマール、ポリビニルブチラール(PVB樹脂)、変性PVB等のポリビニルアセタール;ポリエチレンテレフタレート(PET);ポリイミド;非晶質ポリカーボネート;シロキサンゾル-ゲル;ポリウレタン;ポリスチレン;ポリエーテルサルフォン;ポリアリレート;エポキシ樹脂;シリコーン樹脂;アイオノマー;等であってもよい。これらの樹脂は単独で使用してもよく、2種以上を混合して使用してもよい。上記樹脂は、紫外線吸収剤や光安定剤等の、この分野に公知の各種添加剤を含み得る。 The sealing resin may preferably be a thermosetting resin. The sealing resin made of a thermosetting resin can be well sealed in the solar battery module by, for example, laminating and heating the solar battery cell. As the resin, an ethylene-vinyl acetate copolymer (EVA) is preferably used from the viewpoints of translucency, workability, weather resistance, and the like. The above resins include ethylene-vinyl ester copolymers represented by EVA, ethylene-unsaturated carboxylic acid copolymers such as ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid esters, etc. An ethylene-unsaturated carboxylic acid ester copolymer, an unsaturated carboxylic acid ester-based polymer such as polymethyl methacrylate, and the like may be used. Alternatively, fluoropolymers such as vinylidene fluoride resin and polyethylene tetrafluoroethylene; manufactured using low density polyethylene (LDPE), linear low density polyethylene (LLDPE, typically Ziegler catalyst, vanadium catalyst, metallocene catalyst, etc. Can be produced using polyethylene (PE) such as LLDPE), polypropylene (PP. For example, PP that can be produced using Ziegler catalyst, Phillips catalyst, metallocene catalyst, etc.), Ziegler catalyst, vanadium catalyst, metallocene catalyst, etc. Polyolefins such as ethylene / α-olefin copolymers and their modified products (modified polyolefins); Polybutadienes; Polyvinyl acetals such as polyvinyl formal, polyvinyl butyral (PVB resin), and modified PVB; polyethylene Terephthalate (PET); polyimide; amorphous polycarbonate; siloxane sol - gel; polyurethane; polystyrene; polyether sulfone; polyarylate, epoxy resins, may be like; silicone resin; ionomers. These resins may be used alone or in combination of two or more. The resin may contain various additives known in the art such as an ultraviolet absorber and a light stabilizer.
また、封止樹脂には、密着性を高めるため、密着性向上剤が付与されていてもよい。例えば、加熱硬化前のシート状封止樹脂の表面に密着性向上剤を付与した後、当該表面が太陽電池セル側を向くように封止樹脂を配置し、加熱処理することで、封止樹脂と太陽電池セルとの密着性は向上する。封止樹脂としてEVAシートが用いられる場合には、密着性向上剤としてシランカップリング剤が好ましく使用される。また、上記シート状封止樹脂の表面には、密着性向上その他を目的として、コロナ処理、大気圧プラズマ処理等の各種表面処理を単独でまたは組み合わせて施すことができる。 In addition, an adhesion improver may be added to the sealing resin in order to improve the adhesion. For example, after applying an adhesion improver to the surface of the sheet-shaped sealing resin before heat curing, the sealing resin is arranged and heat-treated so that the surface faces the solar cell side, The adhesion between the solar cell and the solar battery cell is improved. When an EVA sheet is used as the sealing resin, a silane coupling agent is preferably used as the adhesion improver. Various surface treatments such as corona treatment and atmospheric pressure plasma treatment can be applied to the surface of the sheet-shaped sealing resin alone or in combination for the purpose of improving adhesion and the like.
太陽電池モジュールの構築に用いられるシート状封止樹脂の厚さは、太陽電池セルの封止性等の観点から、100~2000μm(例えば200~1000μm、典型的には400~800μm)程度とすることが好ましい。 The thickness of the sheet-shaped sealing resin used for the construction of the solar cell module is about 100 to 2000 μm (for example, 200 to 1000 μm, typically 400 to 800 μm) from the viewpoint of the sealing performance of the solar battery cell. It is preferable.
<表面被覆部材>
表面被覆部材としては、透光性を有する各種材料が使用され得る。表面被覆部材は、ガラス板や、テトラフルオロエチレン-エチレン共重合体、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、フッ化ビニリデン樹脂、クロロトリフルオロエチレン樹脂等のフッ素樹脂シート、アクリル樹脂、ポリエチレンテレフタレート(PET)やポリエチレンナフタレート(PEN)等のポリエステル等の材料から構成された樹脂シートであり得る。例えば、全光線透過率が70%以上(例えば90%以上、典型的には95%以上)の平板状部材またはシート状部材が好ましく用いられ得る。上記全光線透過率は、JIS K 7375:2008に基づいて測定すればよい。表面被覆部材の厚さは、保護性や軽量性等の観点から、0.5~10mm(例えば1~8mm、典型的には2~5mm)程度とすることが好ましい。
<Surface covering member>
As the surface covering member, various materials having translucency can be used. Surface covering member is glass plate, fluororesin sheet such as tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride resin, chlorotrifluoroethylene resin, acrylic resin, polyethylene terephthalate It may be a resin sheet composed of a material such as polyester such as (PET) or polyethylene naphthalate (PEN). For example, a flat plate member or a sheet member having a total light transmittance of 70% or more (for example, 90% or more, typically 95% or more) can be preferably used. The total light transmittance may be measured according to JIS K 7375: 2008. The thickness of the surface covering member is preferably about 0.5 to 10 mm (for example, 1 to 8 mm, typically 2 to 5 mm) from the viewpoint of protection and light weight.
<裏面被覆部材>
裏面被覆部材としては、表面被覆部材の材料として例示した各種材料からなる平板状部材またはシート状部材が好ましく使用される。なかでも、裏面被覆部材形成材料として、PETやPEN等のポリエステルを使用することがより好ましい。あるいは、裏面被覆部材として、耐食性を有する金属板(例えばアルミニウム板)や、エポキシ樹脂等の樹脂シート、シリカ蒸着樹脂等の複合シートを用いてもよい。裏面被覆部材の厚さは、取扱い性や軽量性等の観点から、0.1~10mm(例えば0.2~5mm)程度とすることが好ましい。なお、裏面被覆部材は透光性を有していなくてもよい。
<Backside coating member>
As the back surface covering member, a flat plate member or a sheet member made of various materials exemplified as the material of the surface covering member is preferably used. Especially, it is more preferable to use polyester, such as PET and PEN, as a back surface covering member forming material. Or as a back surface covering member, you may use the metal sheet (for example, aluminum plate) which has corrosion resistance, resin sheets, such as an epoxy resin, and composite sheets, such as silica vapor deposition resin. The thickness of the back surface covering member is preferably about 0.1 to 10 mm (for example, 0.2 to 5 mm) from the viewpoints of handleability and lightness. In addition, the back surface covering member may not have translucency.
本明細書により開示される事項には以下のものが含まれる。
(1) 間隔をおいて配列される複数の太陽電池セルと、
前記複数の太陽電池セルのうち隣りあう2つの太陽電池セルの一方の太陽電池セルの上面から他方の太陽電池セルの下面にかけ渡されて該隣りあう2つの太陽電池セルを電気的に接続する導電部と、
前記隣りあう2つの太陽電池セルの一方の太陽電池セルの上方に配置される第1被覆層と、
前記隣りあう2つの太陽電池セルの他方の太陽電池セルの下方に配置される第2被覆層と、
を備え、
前記導電部は、前記一方の太陽電池セルと前記第1被覆層との間、および前記他方の太陽電池セルと前記第2被覆層との間に配置されており、かつ前記一方の太陽電池セルの上面に部分的に配置されている、太陽電池モジュール。
(2) 前記導電部は、前記隣りあう2つの太陽電池セルの一方の太陽電池セルの上面から他方の太陽電池セルの下面まで延びる複数の導電線から構成されており、
前記複数の導電線は、互いに間隔をおいて配置されている、上記(1)に記載の太陽電池モジュール。
(3) 前記導電線は、めっきが施された銅線である、上記(2)に記載の太陽電池モジュール。
(4) 前記めっきは銀めっきである、上記(3)に記載の太陽電池モジュール。
(5) 前記銀めっきの純度は99.7重量%以上である、上記(4)に記載の太陽電池モジュール。
(6) 前記導電線は60%以上の拡散反射率を示す、上記(1)~(5)のいずれかに記載の太陽電池モジュール。
(7) 前記第1被覆層は前記他方の太陽電池セルの上方には配置されておらず、前記第2被覆層は前記一方の太陽電池セルの下方には配置されていない、上記(1)~(6)のいずれかに記載の太陽電池モジュール。
(8) 前記第1被覆層および前記第2被覆層は、いずれも粘着剤層である、上記(1)~(7)のいずれかに記載の太陽電池モジュール。
(9) 前記第1被覆層および前記第2被覆層は、いずれも架橋された粘着剤層である、上記(1)~(8)のいずれかに記載の太陽電池モジュール。
(10) 前記第1被覆層および前記第2被覆層の貯蔵弾性率(周波数1Hz、歪み0.1%、150℃)は、いずれも5000Pa以上であり、かつ80℃~150℃におけるtanδは0.4未満である、上記(1)~(9)のいずれかに記載の太陽電池モジュール。
The matters disclosed by this specification include the following.
(1) a plurality of solar cells arranged at intervals;
Conductivity that is connected from the upper surface of one solar cell of two adjacent solar cells to the lower surface of the other solar cell among the plurality of solar cells and electrically connects the two adjacent solar cells. And
A first covering layer disposed above one solar cell of the two adjacent solar cells;
A second coating layer disposed below the other solar cell of the two adjacent solar cells;
With
The conductive portion is disposed between the one solar cell and the first coating layer, and between the other solar cell and the second coating layer, and the one solar cell. A solar cell module partially disposed on the upper surface of the solar cell module.
(2) The conductive portion is composed of a plurality of conductive lines extending from the upper surface of one of the two adjacent solar cells to the lower surface of the other solar cell,
The solar cell module according to (1), wherein the plurality of conductive lines are arranged at intervals.
(3) The solar cell module according to (2), wherein the conductive wire is a plated copper wire.
(4) The solar cell module according to (3), wherein the plating is silver plating.
(5) The solar cell module according to (4), wherein the silver plating has a purity of 99.7% by weight or more.
(6) The solar cell module according to any one of (1) to (5), wherein the conductive wire exhibits a diffuse reflectance of 60% or more.
(7) Said 1st coating layer is not arrange | positioned above said other photovoltaic cell, and said 2nd coating layer is not arrange | positioned below said one photovoltaic cell, said (1) The solar cell module according to any one of (6) to (6).
(8) The solar cell module according to any one of (1) to (7), wherein each of the first coating layer and the second coating layer is an adhesive layer.
(9) The solar cell module according to any one of (1) to (8), wherein each of the first coating layer and the second coating layer is a crosslinked adhesive layer.
(10) The storage elastic modulus (
以下、本発明に関する効果確認実験について説明する。なお、以下の説明中の「部」および「%」は、特に断りがない限り重量基準である。 Hereinafter, an effect confirmation experiment regarding the present invention will be described. In the following description, “parts” and “%” are based on weight unless otherwise specified.
≪使用材料≫
<調製例1>
(被覆層(A))
冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器に、アクリル酸ブチル94.9部、アクリル酸5部およびアクリル酸2-ヒドロキシエチル0.1部と、上記モノマー(固形分)100部に対してジベンゾイルパーオキサイド0.3部とを、酢酸エチルとともに加えて、窒素ガス気流下にて、60℃で7時間反応させた。その反応液に酢酸エチルを加えて、重量平均分子量約220万のアクリル系ポリマーを含有する溶液を得た。このアクリル系ポリマー溶液の固形分100部あたり0.6部のトリメチロールプロパントリレンジイソシアネート(商品名「コロネートL」、東ソー社製)と、0.075部のγ-グリシドキシプロピルメトキシシラン(商品名「KBM-403」、信越化学工業社製)を配合して、アクリル系粘着剤組成物を得た。
上記で得たアクリル系粘着剤組成物を、シリコーン系剥離剤で表面処理したポリエステルフィルム(商品名「ダイアホイルMRF」、三菱樹脂社製)からなる剥離ライナーに塗布し、155℃で加熱処理して厚さ約23μmの粘着剤層を得た。このようにして得た粘着剤層を被覆層(A)として用いた。なお、上記粘着剤層の表面に、シリコーン系剥離剤で表面処理した厚さ38μmのポリエステルフィルム(商品名「ダイアホイルMRE」、三菱樹脂社製)からなる剥離ライナーを、当該フィルムの剥離処理面が上記粘着剤層側になるようにして被せた。上記2枚の剥離ライナーは、被覆層(A)の使用時まで粘着剤層の保護に用いた。なお、被覆層(A)について、太陽電池セル裏面に対する接着力を測定したところ、15N/10mmであった。
≪Used materials≫
<Preparation Example 1>
(Coating layer (A))
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 94.9 parts of butyl acrylate, 5 parts of acrylic acid and 0.1 part of 2-hydroxyethyl acrylate, the above monomer (solid content) To 100 parts, 0.3 part of dibenzoyl peroxide was added together with ethyl acetate and allowed to react at 60 ° C. for 7 hours under a nitrogen gas stream. Ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer having a weight average molecular weight of about 2.2 million. 0.6 parts of trimethylolpropane tolylene diisocyanate (trade name “Coronate L”, manufactured by Tosoh Corporation) and 0.075 part of γ-glycidoxypropylmethoxysilane (100 parts by solid content of this acrylic polymer solution) A trade name “KBM-403” (manufactured by Shin-Etsu Chemical Co., Ltd.) was blended to obtain an acrylic pressure-sensitive adhesive composition.
The acrylic pressure-sensitive adhesive composition obtained above was applied to a release liner made of a polyester film (trade name “Diafoil MRF”, manufactured by Mitsubishi Plastics, Inc.) surface-treated with a silicone release agent, and heat-treated at 155 ° C. Thus, an adhesive layer having a thickness of about 23 μm was obtained. The pressure-sensitive adhesive layer thus obtained was used as the coating layer (A). A release liner made of a 38 μm thick polyester film (trade name “Diafoil MRE”, manufactured by Mitsubishi Plastics, Inc.) surface-treated with a silicone-based release agent is applied to the surface of the pressure-sensitive adhesive layer. Was placed on the pressure-sensitive adhesive layer side. The two release liners were used for protecting the adhesive layer until the coating layer (A) was used. In addition, when the adhesive force with respect to the photovoltaic cell back surface was measured about the coating layer (A), it was 15 N / 10mm.
<調製例2>
(被覆層(B))
厚さ50μmのポリエステルフィルム(基材層)にコロナ処理(春日電気社製)を施し、投錨性を高めた後、上記調製例1で得たアクリル系粘着剤組成物を上記ポリエステルフィルムのコロナ処理面に塗布し、155℃で加熱処理して厚さ約23μmの粘着剤層を形成した。この粘着シート(片面接着性の粘着シート)を被覆層(B)として用いた。また、上記粘着剤層の表面に、シリコーン系剥離剤で表面処理した厚さ38μmのポリエステルフィルム(商品名「ダイアホイルMRE」、三菱樹脂社製)からなる剥離ライナーを、当該フィルムの剥離処理面が上記粘着剤層側になるようにして被せた。この剥離ライナーは、被覆層(B)の使用時まで粘着剤層の保護に用いた。
<Preparation Example 2>
(Coating layer (B))
After applying corona treatment (made by Kasuga Denki Co., Ltd.) to a 50 μm thick polyester film (Kasuga Denki Co., Ltd.), the acrylic pressure-sensitive adhesive composition obtained in Preparation Example 1 was treated with corona treatment of the polyester film. It was applied to the surface and heat-treated at 155 ° C. to form an adhesive layer having a thickness of about 23 μm. This pressure-sensitive adhesive sheet (single-sided adhesive pressure-sensitive adhesive sheet) was used as the coating layer (B). A release liner made of a 38 μm thick polyester film (trade name “Diafoil MRE”, manufactured by Mitsubishi Plastics, Inc.) surface-treated with a silicone release agent is applied to the surface of the pressure-sensitive adhesive layer. Was placed on the pressure-sensitive adhesive layer side. This release liner was used for protecting the pressure-sensitive adhesive layer until the coating layer (B) was used.
<調製例3>
(被覆層(C))
基材層として、厚さ100μmのポリエステルフィルムを使用した他は調製例2と同様にして、片面接着性の粘着シートを作製した。この粘着シートを被覆層(C)として用いた。
<Preparation Example 3>
(Coating layer (C))
A single-sided adhesive sheet was prepared in the same manner as in Preparation Example 2, except that a polyester film having a thickness of 100 μm was used as the base material layer. This pressure-sensitive adhesive sheet was used as the coating layer (C).
(導電部)
銅ワイヤー(幅0.8mm、厚さ0.25mm)を用意し、22cmの長さにカットして直線矯正機(例えばWITELS ALBERT社製)で矯正したものを使用した。銅ワイヤーとしては、幅公差±10%、厚さ公差±4%、めっき厚さ1μm(公差±15%)、引張強度が200N/mm2以上であるものを用いた。めっき種としてはAgを用いた。
(封止樹脂)
EVAシート(商品名「EVASKY」、ブリヂストン社製、厚さ450μm)
(太陽電池セル)
Si系太陽電池セル(多結晶Siセル、GINTECH社製、15.6cm角)
(表面被覆部材)
ガラス板(白板熱処理ガラス、旭硝子社製、厚さ3.2mm)
(裏面被覆部材)
バックシート(商品名「コバテックPV KB-Z1-3」、コバヤシ社製、厚さ200μm)
(Conductive part)
A copper wire (width 0.8 mm, thickness 0.25 mm) was prepared, cut to a length of 22 cm, and straightened with a straight line straightening machine (for example, manufactured by WITELS ALBERT) was used. A copper wire having a width tolerance of ± 10%, a thickness tolerance of ± 4%, a plating thickness of 1 μm (tolerance of ± 15%), and a tensile strength of 200 N / mm 2 or more was used. Ag was used as the plating type.
(Sealing resin)
EVA sheet (trade name “EVASKY”, manufactured by Bridgestone, thickness 450 μm)
(Solar cell)
Si solar cell (polycrystalline Si cell, manufactured by GINTECH, 15.6 cm square)
(Surface covering member)
Glass plate (white plate heat-treated glass, manufactured by Asahi Glass Co., Ltd., thickness 3.2 mm)
(Back cover member)
Back sheet (trade name “KOBATEC PV KB-Z1-3”, manufactured by Kobayashi Corporation,
≪実験1≫
<参考例1>
上記材料を用いて、試験用太陽電池モジュールを構築した。具体的には、図6に示すように、太陽電池セル210の上面(受光面)に、導電部230として2本の銅ワイヤーを平行に配置した。銅ワイヤーの間隔は2cmとした。また、上記で得た被覆層(A)260を太陽電池セル210とほぼ同サイズ(15.6cm角)にカットし、剥離ライナーを除去したものを、上記導電部230を配置した太陽電池セル210の上面に貼り合わせ、導電部230を太陽電池セル210上面に固定した。
次いで、裏面被覆部材370を用意し、その表面にシート状封止樹脂350を配置した。その封止樹脂350上に、導電部230を固定した太陽電池セル210を、太陽電池セル210の上面(受光面)が上方を向くように(すなわち導電部230配置面が上側となるように)配置した。その上に、別のシート状封止樹脂350をさらに配置した後、該封止樹脂350上に表面被覆部材360を重ね合わせた。この積層物に対して、市販のラミネータ(NPC社製)を用いて150℃、100kPa、5分間の条件でラミネートを行い、15分間のキュアを実施し、さらに、市販の送風定温恒温器(ヤマト科学社製)を用いて150℃、15分間の乾燥処理を行うことにより、試験用太陽電池モジュール200を構築した。この試験用太陽電池モジュール200では、上面(受光面)に導電部230と被覆層(A)260とが配置された太陽電池セル210が、その上下で封止樹脂350に覆われており、それらが表面被覆部材360と裏面被覆部材370とで挟み込まれている。また、太陽電池セル210の上面(受光面)に配置された導電部230としての2本の銅ワイヤーは、それらの両端が試験用太陽電池モジュール200の外部にはみ出している。
≪
<Reference Example 1>
A test solar cell module was constructed using the above materials. Specifically, as shown in FIG. 6, two copper wires were arranged in parallel as the
Next, a back surface covering member 370 was prepared, and a sheet-shaped sealing resin 350 was disposed on the surface thereof. The
<参考例2>
上記材料を用いて、試験用太陽電池モジュールを構築した。具体的には、図6に示すように、太陽電池セル210の下面(裏面)に、導電部230として2本の銅ワイヤーを平行に配置した。銅ワイヤーの間隔は2cmとした。また、上記で得た被覆層(A)260を太陽電池セル210とほぼ同サイズ(15.6cm角)にカットし、剥離ライナーを除去したものを、上記導電部230を配置した太陽電池セル210の下面に貼り合わせ、導電部230を太陽電池セル210下面に固定した。
次いで、表面被覆部材360を用意し、その表面にシート状封止樹脂350を配置した。その封止樹脂350上に、導電部230を固定した太陽電池セル210を、太陽電池セル210の上面(受光面)が下方(表面被覆部材360側)を向くように(すなわち導電部230配置面が上側となるように)配置した。その上に、別のシート状封止樹脂350を配置した後、該封止樹脂350上に裏面被覆部材370を重ね合わせた。この積層物に対して、市販のラミネータ(NPC社製)を用いて150℃、100kPa、5分間の条件でラミネートを行い、15分間のキュアを実施し、さらに、市販の送風定温恒温器(ヤマト科学社製)を用いて150℃、15分間の乾燥処理を行うことにより、試験用太陽電池モジュール200を構築した。この試験用太陽電池モジュール200では、下面(裏面)に導電部230と被覆層(A)260とが配置された太陽電池セル210が、その上下で封止樹脂350に覆われており、それらが表面被覆部材360と裏面被覆部材370とで挟み込まれている。また、太陽電池セル210の下面(裏面)に配置された導電部230としての2本の銅ワイヤーは、それらの両端が試験用太陽電池モジュール200の外部にはみ出している。
<Reference Example 2>
A test solar cell module was constructed using the above materials. Specifically, as shown in FIG. 6, two copper wires were arranged in parallel as the
Next, a surface covering member 360 was prepared, and a sheet-shaped sealing resin 350 was disposed on the surface thereof. The
<例1-1>
図7に示すように、太陽電池セル210の下面(裏面)に、導電部230として2本の銅ワイヤーを平行に配置した。銅ワイヤーの間隔は2cmとした。また、上記で得た被覆層(A)を15.6cm×1cmにカットした帯状体(帯状被覆部材260)を2つ用意し、剥離ライナーを除去した後、それぞれ、2本の銅ワイヤーに重ね、銅ワイヤー越しに太陽電池セル210の下面に貼り合わせて、導電部230を太陽電池セル210下面に固定した。その他は参考例2と同様にして、本例に係る試験用太陽電池モジュール200を構築した。この試験用太陽電池モジュール200では、太陽電池セル210の下面にて、2本の帯状被覆部材260(被覆層(A))が銅ワイヤー(導電部230)を覆い、かつ間隔をおいて平行に配置されている。2本の帯状被覆部材260(被覆層(A))間の被覆層非配置領域(帯状領域)の幅は約1cmである。
<Example 1-1>
As shown in FIG. 7, two copper wires were arranged in parallel as the
<例1-2>
被覆層(A)として、15.6cm×0.5cmにカットした帯状被覆部材を2本使用した他は例1-1と同様にして、本例に係る試験用太陽電池モジュールを構築した。この試験用太陽電池モジュールにおいて、2本の帯状被覆部材260(被覆層(A))間の被覆層非配置領域(帯状領域)の幅は約1.5cmである。
<Example 1-2>
A test solar cell module according to this example was constructed in the same manner as in Example 1-1 except that two strip-shaped covering members cut to 15.6 cm × 0.5 cm were used as the coating layer (A). In this test solar cell module, the width of the coating layer non-arrangement region (strip region) between the two strip coating members 260 (coating layer (A)) is about 1.5 cm.
[ヒートサイクル試験]
得られた試験用太陽電池モジュールにつき、恒温恒湿器(装置名「PSL-2J」、エスペック社製)を用いて、JIS C 8990:2009の10.11項(温度サイクル試験)に準拠して、-40℃から85℃を1サイクルとするヒートサイクル試験を実施した。
試験中、試験用太陽電池モジュールから露出した一方の銅ワイヤーの一端(図6,7中、符号Aで示す端部)から他方の銅ワイヤーの他端(上記一端とは反対側に位置する端部。図6,7中、符号Bで示す端部)にかけて、金めっきされたワニ口クリップ付きのコードを使用して、恒温恒湿器の外に設置した直流電源(モデル名「PMC-185A」、KIKUSUI社製)から定電流(2A)を流した。さらに、上記一方の銅ワイヤーの一端および他方の銅ワイヤーの他端であって上記A-B間の内側の部分に、金めっきされたワニ口クリップをそれぞれ取り付けて、商品名「NIcDAQ-9178(I/Oモジュール;NI9205)」(NATIONAL INSTRUMENTS社製)を用いて電圧を計測した。計測データをソフトウエア(LabView)にて抵抗値に変換してモニターした。抵抗値は4分間隔で記録した。
[Heat cycle test]
About the obtained solar cell module for testing, using a thermo-hygrostat (device name “PSL-2J”, manufactured by Espec), in accordance with JIS C 8990: 2009 section 10.11 (temperature cycle test) , A heat cycle test was conducted with -40 ° C to 85 ° C as one cycle.
During the test, one end of one copper wire exposed from the test solar cell module (the end portion indicated by symbol A in FIGS. 6 and 7) to the other end of the other copper wire (the end located on the side opposite to the one end) 6 and 7, a DC power source (model name “PMC-185A”) installed outside the thermo-hygrostat using a gold-plated cord with a crocodile clip over the end indicated by the symbol B in FIG. A constant current (2 A) was applied from KIKUSUI. Further, a gold-plated alligator clip is attached to one end of the one copper wire and the other end of the other copper wire and between the AB, respectively, and a product name “NIcDAQ-9178 ( I / O module; NI9205) "(manufactured by NATIONAL INSTRUMENTS) was used to measure the voltage. The measurement data was converted into a resistance value by software (LabView) and monitored. Resistance values were recorded at 4 minute intervals.
参考例1、参考例2、例1-1および例1-2に係るヒートサイクル試験の結果を図8、図9、図10、図11にそれぞれ示す。図8と図9との対比から、被覆層(A)を太陽電池セルの表面全体または裏面全体を覆うように配置した場合、太陽電池セルの裏面側において抵抗が増大する傾向が認められた。特に、ヒートサイクル試験の加熱時に抵抗が増大する傾向が認められた。その原因としては、太陽電池セルの非対称性、上下配置等のために、加熱時に太陽電池セル裏面側で導電部のセル接触性が低下したことが考えられる。 The results of the heat cycle tests according to Reference Example 1, Reference Example 2, Example 1-1, and Example 1-2 are shown in FIGS. 8, 9, 10, and 11, respectively. From the comparison between FIG. 8 and FIG. 9, when the coating layer (A) was disposed so as to cover the entire front surface or the entire back surface of the solar battery cell, a tendency for resistance to increase on the back surface side of the solar battery cell was recognized. In particular, a tendency for resistance to increase during heating in the heat cycle test was observed. As the cause, it is considered that the cell contact property of the conductive portion is lowered on the back surface side of the solar battery cell at the time of heating due to the asymmetry of the solar battery cell and the vertical arrangement.
図9、図10、図11に示されるように、太陽電池セル裏面において被覆層がセル裏面を部分的に覆うように構成した例1-1,1-2では、セル裏面全体を被覆層で覆った参考例2と比べて、ヒートサイクル試験における抵抗増加が抑制された。被覆層で導電部を覆うことで、セル裏面と導電部との接触状態が良好に保持され、また被覆層で部分的にセル裏面を覆うことで、被覆層非配置領域にて封止樹脂がセル裏面と固着し、セル裏面と導電部との良好な接触状態がより強固に保持され、耐久性が向上したものと推察される。帯状被覆部材をより細幅化した例1-2では、抵抗増加がより抑制される傾向が認められた。 As shown in FIGS. 9, 10, and 11, in Examples 1-1 and 1-2 where the covering layer partially covers the back surface of the solar cell, the entire cell back surface is covered with the covering layer. Compared with the covered reference example 2, an increase in resistance in the heat cycle test was suppressed. By covering the conductive portion with the coating layer, the contact state between the back surface of the cell and the conductive portion is well maintained, and by partially covering the back surface of the cell with the coating layer, the sealing resin is disposed in the coating layer non-arranged region. It is presumed that the cell is firmly attached to the back surface of the cell, and the good contact state between the cell back surface and the conductive portion is more firmly maintained, and the durability is improved. In Example 1-2 in which the band-shaped covering member was made narrower, the increase in resistance tended to be further suppressed.
≪実験2≫
<例2-1>
被覆層として、基材層付き片面粘着シートからなる被覆層(B)(帯状被覆部材の幅1cm)を使用した他は例1-1と同様にして、本例に係る試験用太陽電池モジュールを構築した。この試験用太陽電池モジュールでは、被覆層(B)は、その粘着剤層側表面が導電部越しに太陽電池セルの下面に接着しており、その基材層側が太陽電池セルの外方(下方)となるように配置されている。
≪Experiment 2≫
<Example 2-1>
The test solar cell module according to this example is the same as Example 1-1 except that the coating layer (B) (width of the belt-shaped
<例2-2>
被覆層として、基材層付き片面粘着シートからなる被覆層(C)(帯状被覆部材の幅1cm)を使用した他は例2-1と同様にして、本例に係る試験用太陽電池モジュールを構築した。
<Example 2-2>
The test solar cell module according to this example is the same as Example 2-1, except that the coating layer (C) (1 cm width of the belt-shaped coating member) made of the single-sided adhesive sheet with the base material layer is used as the coating layer. It was constructed.
例2-1および例2-2に係るヒートサイクル試験の結果を図12、図13にそれぞれ示す。図12、図13に示されるように、被覆層として、基材層付き粘着シートを使用することにより、ヒートサイクル試験における抵抗増加はさらに抑制された。また、例2-1と例2-2との対比から、基材層の厚さを大きくすることにより、耐久性がより向上する傾向が認められた。その理由としては、基材層を設けることにより被覆層の剛性が高まり、セル裏面と導電部との良好な接触状態をより強固に保持したためと考えられる。 The results of the heat cycle test according to Example 2-1 and Example 2-2 are shown in FIGS. 12 and 13, respectively. As FIG. 12 and FIG. 13 showed, the resistance increase in a heat cycle test was further suppressed by using an adhesive sheet with a base material layer as a coating layer. Further, from the comparison between Example 2-1 and Example 2-2, it was recognized that the durability tends to be further improved by increasing the thickness of the base material layer. The reason is considered to be that the rigidity of the coating layer is increased by providing the base material layer, and the good contact state between the back surface of the cell and the conductive portion is more firmly maintained.
以上、本発明の具体例を詳細に説明したが、これらは例示にすぎず、特許請求の範囲を限定するものではない。特許請求の範囲に記載の技術には、以上に例示した具体例を様々に変形、変更したものが含まれる。 Specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.
1 太陽電池モジュール
10a、10b、10c、10d 太陽電池セル
12a、12b 被覆層非配置領域
30 導電部
40 導電線
50 第1被覆層
52 帯状被覆部材
60 第2被覆層
62 帯状被覆部材
64 基材層
66 粘着剤層
150 封止樹脂
160 表面被覆部材
170 裏面被覆部材
DESCRIPTION OF
Claims (9)
前記太陽電池セルの裏面に部分的に配置された導電部と、
前記太陽電池セルの裏面を前記導電部越しに覆い、かつ該太陽電池セルの裏面と接着する被覆層と、
を備え、
前記被覆層は、前記太陽電池セルの裏面において部分的に配置されている、太陽電池モジュール。 Solar cells,
A conductive portion partially disposed on the back surface of the solar cell;
A covering layer that covers the back surface of the solar battery cell over the conductive portion and adheres to the back surface of the solar battery cell;
With
The said coating layer is a solar cell module partially arrange | positioned in the back surface of the said photovoltaic cell.
前記太陽電池セルの裏面において、前記複数の帯状被覆部材のうち一の帯状被覆部材は、該太陽電池セルの裏面外方から前記複数の導電線のうち一の導電線を覆っており、かつ該導電線の幅方向の両外側にて、該太陽電池セルの裏面と接着している、請求項2に記載の太陽電池モジュール。 The covering layer is composed of a plurality of strip-shaped covering members,
In the back surface of the solar battery cell, one of the plurality of belt-shaped cover members covers one conductive wire of the plurality of conductive wires from the outside of the back surface of the solar battery cell, and The solar cell module according to claim 2, wherein the solar cell module is bonded to the back surface of the solar cell on both outer sides in the width direction of the conductive wire.
前記封止樹脂は、被覆層非配置領域にて該太陽電池セルの裏面と接着している、請求項1~6のいずれか一項に記載の太陽電池モジュール。 On the back surface of the solar battery cell, a sealing resin that covers the back surface is disposed over the coating layer,
The solar cell module according to any one of claims 1 to 6, wherein the sealing resin is bonded to the back surface of the solar cell in a region where the coating layer is not disposed.
前記方法は:
太陽電池セルの裏面に、導電部を部分的に配置する工程と;
前記導電部が配置された前記太陽電池セルの裏面に、被覆層を該導電部越しに接着させる工程と;
を含み、
前記被覆層の接着工程において、該被覆層を、該太陽電池セルの裏面に部分的に配置する、太陽電池モジュールの製造方法。 A method for manufacturing a solar cell module, comprising:
The method is:
A step of partially disposing the conductive portion on the back surface of the solar cell;
Adhering a coating layer to the back surface of the solar cell in which the conductive portion is disposed over the conductive portion;
Including
The method for manufacturing a solar cell module, wherein in the adhesion step of the coating layer, the coating layer is partially disposed on a back surface of the solar battery cell.
前記方法は:
前記太陽電池セルの裏面に、導電部を部分的に配置する工程と;
前記導電部が配置された前記太陽電池セルの裏面に、被覆層を該導電部越しに接着させる工程と;
を含み、
前記被覆層の接着工程において、該被覆層を、該太陽電池セルの裏面に部分的に配置する、太陽電池セルの配線方法。 A solar cell wiring method comprising:
The method is:
A step of partially disposing a conductive portion on the back surface of the solar cell;
Adhering a coating layer to the back surface of the solar cell in which the conductive portion is disposed over the conductive portion;
Including
The solar cell wiring method, wherein in the step of bonding the coating layer, the coating layer is partially disposed on the back surface of the solar cell.
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| JP2015139211 | 2015-07-10 | ||
| JP2015-139211 | 2015-07-10 | ||
| JP2015-218976 | 2015-11-06 | ||
| JP2015218976 | 2015-11-06 | ||
| JP2016-054790 | 2016-03-18 | ||
| JP2016054790 | 2016-03-18 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018150887A1 (en) * | 2017-02-17 | 2018-08-23 | パナソニックIpマネジメント株式会社 | Solar cell module and interconnector for solar cell modules |
| TWI743361B (en) * | 2017-07-06 | 2021-10-21 | 日商琳得科股份有限公司 | Resin layer forming film and resin layer forming composite sheet |
| JP7450089B1 (en) | 2023-01-16 | 2024-03-14 | ジョジアン ジンコ ソーラー カンパニー リミテッド | Photovoltaic module and its manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013140623A1 (en) * | 2012-03-23 | 2013-09-26 | 三洋電機株式会社 | Solar cell module and method for manufacturing same |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013140623A1 (en) * | 2012-03-23 | 2013-09-26 | 三洋電機株式会社 | Solar cell module and method for manufacturing same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018150887A1 (en) * | 2017-02-17 | 2018-08-23 | パナソニックIpマネジメント株式会社 | Solar cell module and interconnector for solar cell modules |
| TWI743361B (en) * | 2017-07-06 | 2021-10-21 | 日商琳得科股份有限公司 | Resin layer forming film and resin layer forming composite sheet |
| JP7450089B1 (en) | 2023-01-16 | 2024-03-14 | ジョジアン ジンコ ソーラー カンパニー リミテッド | Photovoltaic module and its manufacturing method |
| JP2024100722A (en) * | 2023-01-16 | 2024-07-26 | ジョジアン ジンコ ソーラー カンパニー リミテッド | Photovoltaic module and method of manufacturing same |
| JP2024100651A (en) * | 2023-01-16 | 2024-07-26 | ジョジアン ジンコ ソーラー カンパニー リミテッド | Photovoltaic module and method of manufacturing same |
| US12302646B2 (en) | 2023-01-16 | 2025-05-13 | Zhejiang Jinko Solar Co., Ltd. | Photovoltaic module and preparation method thereof |
| JP7676598B2 (en) | 2023-01-16 | 2025-05-14 | ジョジアン ジンコ ソーラー カンパニー リミテッド | Photovoltaic module and method of manufacturing same |
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