TW201244915A - Process for producing solar cell sealing sheet - Google Patents

Abstract

The present invention is a process for producing a solar cell sealing sheet, the process comprising conducting the following steps (a), (b), and (c) in the this order: a step (a) in which a resin composition that has been melted by heating is formed into a sheet and then cooled to obtain a web sheet; a step (b) in which at least one surface of the web sheet obtained in the step (a) is heated for 22-55 seconds to elevate, during this heating, the temperature of this surface to a temperature not lower than the melting point of the resin composition that constitutes this surface; and a step (c) in which the surface of the web sheet which has been heated in the step (b) is made to have a temperature within a specific range, and an embossing roller is subsequently pushed against this surface to form an embossed pattern in the surface. Thus, a solar cell sealing sheet which suffers little heat shrinkage and in which a distinct embossed pattern has been formed can be efficiently produced at low cost.

Description

201244915 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of manufacturing a solar cell sealing sheet. More particularly, it relates to a method for producing a sheet which is preferably used for producing a solar cell encapsulating sheet having a small heat shrinkage and having a sharp protrusion formed on the surface. [Prior Art] In recent years, solar cells that directly convert sunlight into electric energy have been developed in various aspects in terms of effective use of resources or prevention of environmental pollution. In general, a solar cell is configured by sealing a solar cell unit with a solar cell sealing sheet (hereinafter referred to as a sealing sheet) between a light-receiving surface protective material represented by a glass substrate and a back surface protective material called a back sheet. As a mainstream of solar cell modules, a crystalline germanium type solar cell is usually manufactured in the following manner. First, a glass substrate, a sealing sheet, a solar cell unit (tantalum power generation element), a sealing sheet, and an underlayer sheet are sequentially laminated. This sealing sheet is usually composed of an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA (ethylene-vinyl acetate copolymer)). Then, the laminated body was heated under vacuum by a vacuum laminator', and the sealing sheet was heated and fused to be cross-linked and hardened. In this way, the solar cell module in which each constituent member is bubble-free is manufactured. In the manufacture of such a solar cell module, "if the sealing sheet shrinks when heated", the power generating element may be broken due to the shrinkage deformation, or the position of the unit may be shifted. Therefore, the sealing sheet is required to have a small shrinkage upon heating. Into 101111289 3 201244915, the year has come, and the resources of the Shishixi are effectively utilized, or the cost is reduced for the popularization of the solar cell module, and (4) the power generation is thick and the material is good, and then it becomes easy to break. Therefore, the requirement that the heat shrinkage of the sealing sheet is small is made four (4). Therefore, various methods for reducing the shrinkage rate of the dense material are being studied. (For example, Patent Document 1) β, in addition to the requirements for the above-mentioned manufacturing, the solar cell module can be used for a long period of time after manufacture, and its reliability is extremely important. The representative anomalies generated in the module are poor appearance such as peeling and expansion between the solar cell unit and the ί& sealing sheet, or a decrease in the amount of power generation accompanying it. The reason for these anomalies is not clear, and research is being conducted on the raw materials constituting the sealing sheet. For example, a method of adjusting the viscosity of the EVA constituting the sealing sheet (a patent document, or a method of adding a decane coupling agent to enhance the adhesion strength between the solar cell unit and the male sheet) (Patent Document 3), etc. Various studies have been conducted on the structure of the sealing sheet. In order to prevent expansion and the like accompanying long-term use, it is important that the constituent members inside the module to be manufactured are as air-free as possible. It is easy to discharge air during vacuum lamination, and attempts to form various protrusions or recesses such as an embossed shape on the surface of the sealing sheet. Moreover, the protrusions or recesses are sometimes used to prevent solar cells from being laminated due to lamination. The pressing pressure is broken, or the sealing sheet is raised for the purpose of rationality, etc. Regarding the embossing pattern, a detailed proposal is proposed for the shape or depth thereof (Patent Documents 4 and 5). 101111289 4 201244915 In the manufacture of the sealing sheet, it is important to reduce the heat shrinkage of the sealing sheet and form a clear embossed shape on the surface of the sealing sheet. The method proposed in the prior art discloses that when a sheet extruded from a τ-shaped die is cast using an extruder such as a twin-screw extruder, an embossed shape is formed on the sheet directly under the nozzle, and the rear view is required to be reduced. Method for annealing treatment by heat shrinkage (Patent Document 6) [Prior Art Document] [Patent Document] Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 Patent Application Patent Publication No. Japanese Laid-Open Patent Publication No. 2000-084996, No. 2002-170971, No. 2000-183382, No. 2006-134970, No. 2002-185027 SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) The manufacturing method of Patent Document 6 is to anneal the sheet after forming an embossed shape on the surface of a sheet (hereinafter referred to as a step sheet) in the manufacturing step. Therefore, if the step sheet is sufficiently heated to reduce the heat shrinkage of the sealing sheet, the embossed shape formed on the surface of the step sheet due to the heating is deformed. On the other hand, if the heating of the step sheet is weakened in order to maintain the embossed shape, the annealing treatment becomes insufficient. Thus, the reduction in the manufacture of 101111289 5 201244915 of Patent Document 6 and the non-method of clearly forming the embossed shape are simultaneously It is often difficult to heat the wall. In addition, as a method of reducing the heat shrinkage of the sealing sheet, it is usually used as follows in the patent order, and the following method is used to transfer the resin film. The person σ is placed on the side of the wheel with a plurality of faces, and the step sheet is contracted, and the peripheral speed is faster than that of the roller on the outlet side, so that the heat shrinkage is particularly high. It must be annealed for a period of 1 to 2 minutes, unless it is not burned. Further, in many cases, the EVA has a cross-linking agent contained in the sealing sheet composed of a ruthenium. Since the forming temperature of the step sheet is low, there is a residual strain remaining in the step sheet. Further, in many cases, the residual strain is uneven in the width direction of the step sheet of the wide towel s. When the step sheet of such a state is annealed as described above, the planarity of the sheet is impaired, the thickness becomes uneven, or the sheet of the step in the annealing process becomes abnormal, such as bending and bending. It is very difficult to perform the embossing process, such as the step of adding/removing the step sheet of the state in a plurality of rolls. Accordingly, an object of the present invention is to provide a method for sufficiently reducing the heat shrinkage of a sealing sheet and forming a clear embossed shape on the surface of the sealing sheet. (Means for Solving the Problems) In order to solve the above problems, the present invention The manufacturing method of the solar cell sealing sheet is characterized in that the following steps (a), (b) and (c) are sequentially performed. 101111289 6 201244915 Step (a): forming a resin composition which is smelted by heating into a sheet form, and then obtaining a step sheet by cooling; Step (b). Obtaining the above obtained in the step (4) At least one surface of the step sheet is heated for 22 to 55 seconds, and the temperature of the surface is brought to a temperature above the melting point of the resin composition constituting the surface portion during the heating; step (c): in the above step ( b) the step of heating the step of the sheet becomes (the melting point of the resin composition constituting the surface portion, 〇 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The step of pressing the embossing surface to form an embossed shape on the surface. (Effect of the Invention) According to the present invention, it is possible to manufacture a solar cell seal having a small heat shrinkage and a clear embossed shape at low cost and with high efficiency. [Embodiment] [Method for Producing Solar Cell Sealing Sheet] The method for producing a solar cell sealing sheet of the present invention is to sequentially perform the following steps (a), (b) and (c). (a): forming a resin composition which is fused by heat of the mouth; forming a sheet, and then obtaining a step sheet by cooling. Step (b): in the above step (a) The at least one of the obtained step sheets is heated to a temperature of 22 to 55 seconds in which the temperature of the surface reaches a temperature higher than a melting point of the resin composition constituting the surface portion. Step (c): The surface of the step of heating in the above step (b) is 101111289 7 201244915 (the melting point of the resin composition constituting the surface portion _10^)~ (the melting point of the resin composition constituting the surface portion +20). The step of pressing the embossing roll on the surface to form an embossed shape on the surface. Hereinafter, the method for producing the solar cell sealing sheet of the present invention will be described with reference to the drawings. 1 is a schematic view showing an embodiment of the production method of the present invention. [Step (a): Film forming step] First, the step (a) will be described. In the step (a), the raw material resin is formed into a sheet. The material is shaped and cooled to obtain a step sheet In the following, the step 0) is referred to as a film forming step. In the film forming step in Fig. 1, an extruder 11 is provided which melts and kneads the raw material resin and the additive at a high temperature to reduce the pressure of the resin. The gear pump 31 that stabilizes the thickness of the sheet, the mold 12 that extrudes the kneaded molten resin into a sheet shape, and the step sheet that is extruded at a high temperature is cooled and solidified to form a solid sheet. Polishing rolls 13a, 13b, and 13C. A single-axis extruder or a twin-screw extruder can be used as the extruder 11. In terms of productivity, kneading of the resin and the additive, etc., it is preferable to use a double shaft. In the case of using a single-screw extruder, since the pressure in the mold portion of the extruder front end is relatively small because the extruder is filled with the resin, it is not necessary to provide a quantitative supply device such as the gear pump 31. In the case of using a twin-screw extruder, since the inside of the extruder is not full, it is preferable to provide a quantitative supply device such as a gear pump 31 between the extruder and the mold. 10Π11289 8 201244915 The raw material resin and the additive in the technical-injection machine u can be put into a premixed mixer or the like, or they can be separately supplied. Further, it is also possible to use a side-feed additive in the middle of the extruder or a method of adding it by an injection pump or the like in the case of a liquid additive. The temperature at which the raw material resin and the additive are kneaded is determined depending on the kind or viscosity of the resin to be used, but it is preferably (the raw material resin is the melting point of the raw material resin). The so-called refining point is the endothermic peak temperature of the differential scanning calorimetry (DSC, bribe (10), such as 丨-(4), and the temperature is raised by min. As the sealing sheet, in the case of the commonly used hopping sheet, most In this case, an organic peroxide is contained as an additive for the concealment. Therefore, it is necessary to pay attention to mixing the organic peroxide as much as possible without decomposition. Therefore, as the resin temperature, for example, the refining point is about 7 generations. Preferably, it is in the range of 8G to 13G °C (four), more preferably 100~ 〇C of the standard® is less than 8GC, and there is a lack of kneading and a decrease in the uniformity of the additive. As a result, there is a possibility that the appearance of the sealing sheet is deteriorated. When it exceeds 13 (), the organic peroxide may be decomposed when the organic peroxide is blended, and the quality of the sealing sheet is unstable. In addition, continuous productivity Further, in the step of Fig. 1, an extruder is provided as a method of forming a step sheet, but a known different method such as forming of a profit can be used. 101111289 9 201244915 Using extrusion The machine 11 and the like are used to extrude the raw material tree gold 4 & and the force-purifying Wei Lian refining resin into a sheet shape using the mold 12. ^

Font or circular mold, etc. The flat mold I is used as the mold 12, and the width of the T can be used to form a wide shape. Therefore, the sheet to be extruded is a T-shaped mold on the extruder, and is collectively referred to as a T-shaped mold. In addition, in the T _ and T pre-modes, it is easy to produce a thickness unevenness due to the retention of time or flow rate in the width direction of the mold. The thickness in the width direction is not uniform when the sheet is heated. For solving the problem of 丄, 、, and upper 4, it is preferable to use a cylindrical shape: a circular mold. The circular mold is used to form the tree (four) into a cylindrical shape and to form a sheet-like round-shaped can-like mold by cutting it, and the physical properties of the sheet width tend to become relatively uniform. Moreover, in the case of using a T-shaped mold, κ can extrude different resin compositions by an extruder with a silver number, and can also be stepped by a feed-in module or a multi-mode extrusion method. The material is made into a layered structure, and it is squeezed. « . „ By making such a laminated structure, it is possible to reduce the cost by adding each layer as a sealing sheet, and to reduce the cost. The step sheet __n13b, 13c extruded by the mold 12 is formed into a sheet shape. The polishing roll is used for the inclusion of a pair of smelting resin to sandwich the thickness and surface properties of the sheet material. A sheet conveying device. The device is constructed. Each of the sticks has a mechanism for adjusting the temperature of the molten resin to be cooled or shaped, and the mechanism for adjusting the gap between the rolls and the pressing pressure. Preferably, it is preferable to prevent the adhesion of the step sheet by the inflow of cooling water such as cooling 101111289 201244915 water, etc. It is preferable to adjust the temperature of the cooling water to 0 to 3 (the range of rc. The composition of the resin used is different and sometimes the resin of high temperature is easy The polishing roller 13a on the most upstream side of the polishing roller is preferably wound with a rubber or the like on the surface to improve the mold release property, and further enhances the conveyability, and is preferably located on the most upstream side. The counter roller 13b of the buffing roller 13a is a metal roll having a pear-like surface shape. Preferably, the surface roughness of the pear-like surface is jisb〇6〇1_1994, and the 10-point average roughness rz of the pinch is 2 ～ 左右 左右 左右 左右 左右 左右 左右 左右 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在The thickness of the rubber is preferably from 3 to 10 mm, more preferably from 4 to 8 mm. If the thickness of the rubber is less than 3 mm, the transfer of the skin of the pear skin is sometimes not applied to the sheet of the step. The free roller of the step sheet is conveyed. If the thickness of the stone rubber exceeds 1 Gmm, the resin is adhered to the roller due to the heat accumulated from the sloping heat. [Step (b): Annealing step] + Then Step (8) 绮 Description. The purpose of step (8) is to remove the shape formed in the film forming step The residual strain of the sheet material is reduced, and the heat shrinkage of the step sheet is reduced. In the step (b), the step sheet is heated by the heater 16 provided in the annealing furnace, and the step sheet is passed through the plurality. The method of feeding the roller 17 or the like. Hereinafter, the step (b) is referred to as an annealing step. The heater 16 for heating the sheet of the step is not particularly limited as long as it is a step of heating the sheet > 01111289 201244915, and ceramic heat can be used. Half of the known, such as a half, 6%, Yi, stainless steel heaters, jackets can be added to the thickness of the sheet; force, film ^ use the hot air or steam to use the media;: and better... The method of contact, etc. These heating methods can be used in combination with n and heated rolls. The method of 'can also be used to transfer the sheet of the conveying roller 17 of the step sheet. Therefore, it is preferred to apply the metal in the step of mold release heating by embossing or spraying: or a compound such as metal oxide. The gold is provided with a bump: 乂, a fluororesin coated with a polytetrafluoroethylene, a full i propylene propylene copolymer, a perfluoroalkoxy oxyhydrocarbon, or the like may be used, or may be used for the metal. A roll of a release coated paper or film or the like is attached to the surface. The means for imparting such mold release property is not particularly limited, and a conventionally known method can be used. The degree of release property of the 5 HAI and the like is preferably a material having a peeling strength of 5 N/mm or less for the scotch tape manufactured by Nichiban Co., Ltd. according to the method specified in JIS Z〇237_2009. Further, the conveying roller 17 in the furnace can be individually controlled in accordance with the shrinkage of the step sheet, and it is preferable to remove the heat shrinkage efficiently. It is preferable that the heater 16 and the conveying roller 17 are disposed in the annealing furnace 5 as much as possible to reduce the contact with the outside air, because the temperature in the furnace can be stabilized and the heat treatment of the step sheet is stabilized. Further, one of the preferred aspects is to supply hot air to the furnace for the purpose of uniformly stabilizing the temperature in the furnace. 101111289 12 201244915 Preferably, a pair of rolls 14 are provided upstream of the annealing furnace 15 as needed. It is preferable to set the roll 14 to block the influence of the annealing treatment step on the film forming step. Specifically, it is possible to prevent the shrinkage at the time of heating the sheet from affecting the film forming step or to stabilize the supply of the step sheet to the annealing step. Further, it is preferable to provide a sheet take-out 18 between the exit of the annealing furnace 15 and the embossing roll 20. The sheet is taken out and the Kun Kun 18 functions as a step of taking out the step sheet from the annealing furnace 15. If the sheet take-up roll 18 is not provided, the sheet may be stretched and deformed between the roll on the exit side and the embossing roll 20 in the roll π in the annealing furnace. Further, in the annealing treatment, wrinkles or the like may occur in the width direction of the step sheet during the heat shrinkage of the step sheet, and therefore, it is preferable to remove the wrinkles. 18 is the expansion of the lucky Kun (bow bending roller). Further, the sheet take-up roll 18 is preferably the same as the transfer roll π in the furnace, and is provided with mold release property. Further, when the surface temperature of the sheet take-up roll 18 is too low, the sheet to be supplied to the embossing roll may be cooled, and the transfer property of the embossed shape may be lowered. On the other hand, if the surface temperature is too high, the step sheet may be adhered to the sheet take-up roll 18 and the conveyance of the step sheet may become difficult. Therefore, the surface temperature of the sheet take-up roll 18 is preferably adjusted to a temperature of 20 to 803⁄4. Further, it is preferably set to a surface temperature equal to or lower than the temperature of the step sheet of the annealing furnace outlet. If the surface temperature of the sheet take-up roll 18 is higher than the surface temperature of the step sheet from the annealing, the step sheet sometimes adheres to the roll. 101111289 13 201244915 To prevent the temperature of the step sheet from decreasing, it is preferable that the distance between the annealing furnace 15 and the embossing light 20 is as short as possible. Therefore, the sheet take-up roll 18 may be provided with a plurality of roots, but is preferably less, preferably at most 3 or less, more preferably 1 or 2. In the continuous annealing step and the subsequent step (when the crucible is used, it is preferable to control the surface temperature of the step sheet from which the annealing furnace 15 comes out, and the surface temperature of the step material introduced into the embossing roll in the step (4). In order to accurately grasp the surface temperature of the step sheet, the exit portion of the annealing furnace 15 and the surface temperature of the sheet immediately before the embossing plus I are measured. Therefore, it is preferable to provide a non-contact infrared temperature. Further preferably, a plurality of non-contact thermometers are provided in the annealing furnace 15 to measure the surface temperature of the step sheet. In the annealing step, the highest temperature of at least one surface of the step sheet is heated to become the surface portion. The temperature above the melting point of the resin composition. In the subsequent step (4), the surface of the heated side is subjected to pressure, and the "resin composition constituting the surface portion" as described herein is processed, and the sheet is a single layer in the step. In the case of a material, it means that the resin composition constituting the sheet of the step is heated in the case where the step sheet is a laminated sheet having a plurality of layers laminated. The resin composition of the layer on the side of the surface. Even if the annealing treatment is carried out at a temperature at which the maximum temperature is only the melting point of the resin composition, the effect of reducing the heat shrinkage rate is insufficient, and it is necessary to carry out long-term treatment. The Γ7 / dish degree is preferably (the melting point of the resin composition constituting the surface portion on the side of the heating + 5 + 〇 ~ Γ椹 α α V and the resin portion of the surface portion of the heating side 101111289 201244915 melting point + 35t) Within the temperature range, if the temperature in the annealing treatment is too high, then ν / in the transfer lighter 'or flatness' is due to the shoulder cause, and there is a sensitivity in the step (c) of the buckwheat horn. For example, In the case of a step sheet composed of a refining point of 71 °c • A-tree, the highest surface temperature in the annealing step is preferably in the range of 76 to 1 G 6 ° C. At the time, even if the step sheet stays in the annealing furnace, the door is in the range of 2 55 U. The heating time is for the step sheet cooled by the polishing rod u, so that the surface temperature of the step sheet reaches the refining point temperature. The time required for the above pounds, After the glaze temperature is reached, the total time for annealing, shrinkage, and shrinkage is reduced. If the heating time is less than η seconds, the heat shrinkage is not sufficiently removed. Even if the heating time exceeds ^ seconds, the heating is performed. Also because of the effect of the wire and only in vain to extend the length of the annealing. The heating time ^ lower limit is preferably 22 seconds or more, more preferably more than Μ seconds. Eight to fill the knife to remove the heat shrinkage, the upper limit of the heating time The shorter one is preferably '45 seconds, less than the clock, more preferably less than 4 seconds. [Step (c). Embossing processing step] Next, step (e) will be explained. Step (e) is a loan a step of forming an embossed shape on the surface of the step sheet by performing embossing on the step sheet which becomes a high temperature state by heating in the annealing step. In the step (c), it is provided to form an embossing on the step sheet. The shape of the embossing roller 2, the secret counter roller 19, and the cooling light 21. Hereinafter, this step (c) is referred to as an embossing step. On the surface of Yu Jian and Wen Qin 20, the engraving of the embossed shape is reversed in accordance with the shape of the embossing 101111289 15 201244915 which is desired to rise in the step sheet. The embossed shape formed on the step sheet is an irregular shape or a geometric pattern, and may be determined as needed. However, if the formation of the embossed shape is insufficient, there is a possibility that adhesion may occur easily during the conveyance of the step sheet or when it is rolled into a shape, or the air may be difficult to be discharged when the solar cell module is formed. Air bubbles are generated inside. The engraved pattern applied to the surface of the embossing roll may be a hemispherical shape, or a triangular pyramid, a quadrangular pyramid, a hexagonal cone, a cone or the like, or a trapezoidal shape which flattens the top. Further, it may be a pattern in which the shapes are mixed. Among these, it is preferably a hemispherical shape and/or a quadrangular pyramid shape. Here, the term "hemispherical and quadrangular pyramidal" means engraving of a pattern in which a hemisphere and a quadrangular pyramid are mixed. The semi-spherical shape is preferable in that it is difficult to apply a concentrated load when the sealing sheet is pressed against the solar cell unit and the load can be uniformly dispersed. Further, in terms of the unevenness of the reflected light of the sealing sheet and the excellent surface quality, it is preferably a quadrangular pyramid. Further, in order to express the characteristics of both the hemispherical shape and the quadrangular pyramid shape, it is preferable to mix the hemispherical shape and the quadrangular pyramid shape. In the case where the hemispherical shape and the tetragonal pyramid are mixed, the respective ratios may be arbitrarily determined depending on which characteristics are sought. It is especially good for all hemispheres. When the ice is overlaid, the pressing pressure is required for the embossing process, and the equipment becomes a gentleman. Therefore, the depth of engraving of the embossing roll is also determined by the early itching of the sheet, but it is preferably in the range of 65 to 350 μm. Furthermore, the so-called embossing roller μ ^ heart to the surface of the 峨 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The difference in the distance between the deepest part of the concave portion (the concave portion) of the engraving. The depth of the engraving is determined by the maximum height Pz ((4) measured according to JIS B〇6〇l (2001) and using the surface rough seam measuring machine.乂 乂 为 为 为 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于As a result, minute protrusions are formed on the surface of the material. As a result, the slidability of the sheet is improved and it becomes easy to handle, and the light is scattered by the minute protrusions to increase the whiteness of the sheet, so the inspection of the domain dissimilar material is performed. It is relatively easy. Such a small recess can be formed by the embossing of the embossed silk ridge, etc., and the depth of the micro (4) can be determined by the particle size or pressure condition when the X is added by spraying. Make adjustments: _19 against pressure _ opposite, to enhance the surface of the embossed stick There is a transfer property of ΓΓΓ, and it is preferable that the metal roll is attached to the roll. The ___, the cut rubber, the nitrile _ = glue, etc., is not particularly limited, but is preferably based on the heart Fu type is a rubber with a hardness of 65 to 85. It is less than 65 or more than 85. The transferability of the embossed shape is reduced. Among these rubbers, it is easy to adhere to it at high temperatures. The step of releasing the sheet is Shi Xi rubber. It is difficult to use the step of adding the pressure to the tempering step, and the temperature is set to (the temperature) is set to (the temperature of the tree) Melting point. Thief) ~ (The composition of the resin constituting the surface is 10111111289 17 201244915 within the range of the degree of the dish. If it is not full (resin composition mi generation), the transfer of the embossed shape is reduced by 1 ± if exceeded (resin The melting point of the composition is such that the temperature of the sheet in the annealing step is too high, and it is easy to generate a slight enemy in the annealing step. For example, the layer on the surface side is composed of EVA resin having a melting point of A 71 ° C. When the surface temperature of the embossing is set to be in the range of 61 to 9 rc. Further, the pressing pressure of the embossing roller 20 Preferably, the line pressure applied to the step sheet is in the range of 150 to 500 N/cm, more preferably in the range of 200 to 1. If the line pressure is less than 150 N/cm, the transfer property of the embossed shape may be lowered. If a line pressure exceeding 5 〇〇 N/cm is to be added, there is a need to increase the size of the apparatus, in which case the life of the facing rubber roller is lowered. In the prior art shown in Fig. 2, embossing It is sufficient that the pressing pressure of the roller 13ly is as high as about 1 〇〇N/cm. The reason is presumed to be as follows: for example, in the case of using an EVA resin having a melting point of 71 ° C, the resin extruded from the τ-shaped mold The temperature is in the range of l〇〇~12〇°c in many cases, and it is sufficient that the transfer line center pressure is about 1 N/cm in the embossed shape due to the high temperature state. On the other hand, in the production method of the present invention, embossing is carried out as described above (the melting point of the resin composition is _10. 〇~ (the melting point of the resin composition + 2 (rc)). When the surface temperature of the step sheet in the embossing process is lowered, it is difficult to transfer the embossed shape. Therefore, it is preferable to increase the pressing pressure necessary for the embossing process. That is, it is preferable to make the line pressure i 5 . 0 N/cm or more. Further, the line pressure in the present invention is a value obtained by dividing the negative load of the roll by 101111289 201244915 by the length of the grain. Further, the embossing at a relatively low temperature as described above. In order to improve the transferability of the embossed shape, it is preferred that the step sheet is wrapped around the embossing roll 20. The body wrap angle of the embossing roll is preferably in the range of 30 to 270. If only the embossing is applied to the embossing, the angle of the package is less than 30. It is also possible to provide a deeper and clearer shape, preferably by setting the angle of the package to 30 or more. The wrap angle can be simply according to the length of the arc of the portion where the step sheet 32 is in contact with the embossing roll 20, and the embossing roll The ratio of the circumference is calculated. For example, in the case where the wrap angle is 90, it means that the step sheet is in contact with a portion corresponding to a length of 1/4 of the circumference of the embossing roll. The surface temperature of the embossing roll 2G is preferably (below the swell point _2 〇 °c of the resin composition constituting the surface portion of the transfer embossing & one side). If the temperature of the embossing roll is low, the step The release property of the sheet is good, and the step sheet is less likely to be entangled on the pros. The result is that the load on the embossing (four) step sheet is reduced, and a solar cell sealing sheet having better quality can be obtained. · After the material is released from the roll, the cooling pro 21 cooling step: #材,使步骤>} the surface temperature of the material is rapidly lowered to near room temperature. 'V-film formation, annealing treatment to remove heat shrinkage, Xing #纹形的步步月 v ^战压月材32 to perform a defect check or to answer the step sheet as i: 宫麻乂& inch''', a after 'winding with a winding machine, etc. Cut into length cut sheets for use in the manufacture of solar cell modules. Battery sealing sheet] 101111289 201244915 Next, a description will be given of a solar cell sealing sheet. The sealing sheet is preferably a protrusion having a height of 6 G to 3 (8) μm on the surface, since the surface of the sealing sheet has an independent height. For the protrusion of 6G handsome, when the vacuum is laminated in the solar module and the pool module, the air remaining between the sealing sheet and the solar battery 7L can be effectively removed from multiple directions, thereby suppressing the generation of bubbles. Further, the pressing pressure of the sealing sheet against the solar cell unit can be dispersed: the occurrence of cracking of the unit can be suppressed. If the shape of the surface of the sealing sheet is not a separate protrusion and is a continuous groove shape, the direction is straight into the groove. The degassing on the surface is insufficient. The residual air forms bubbles. Further, when the height of the projections is 300 μm or less, it is possible to suppress the load from being concentrated on the top portion of the projections during vacuum lamination, thereby preventing the solar cell from being broken. Here, the "independent protrusion" is a protrusion in which the length D of the following bottom side is in the range of % to 〇 μπι when focusing on the bottom surface of the protrusion. Further, regarding the independent protrusion, it is preferable to compress the protrusion by sandwiching the sealing sheet with a flat plate and imparting 5 G kPa in the thickness direction, and the protrusion is extended from the (10) abutment when the top portion of the protrusion is extended to the flat plate. The gap between 2 〇 and 8 〇〇 μχ is ensured between the two ε domains of the protrusion. The independent protrusion is preferably such that the height of the protrusion (7) and the length of the base of the protrusion (d) 〇l are preferably 015 to 〇 8 。. If the t/d ratio is less than 〇.〇5, the cushioning properties of the sealing sheet may be insufficient. If the ratio of (10) exceeds that of Zheng Zheng, there is a case where the load is concentrated on the protrusion and the unit is broken. The south of the protrusion is the following way. First, the case of 101111289 20 201244915 having a protrusion on one side will be described. The surface on which the sealing sheet has the protruding side is referred to as the A surface, and the surface on the side where the sealing sheet is not raised is referred to as the B surface. As jgj) a as shown in Figure 3, will be from the A side

The distance from the apex of the protrusion to the B surface is set to T imax', and the distance from the portion having no protrusion of the A surface to the surface B is Tmini τ_ and the difference is the directionality T of the protrusion. Next, a case where there are protrusions on both sides will be described. One side of the sealing sheet is set to the A side, and the other side is set to the B side. As shown in Fig. 4, the distance from the top of the A side to the top of the E ^ dog's interest to the non-protruding part of the B side is set to TAmax, which will be from the height of the b side. The distance from the vertex to the portion of the A surface where no protrusion is formed is TBmax, and the distance from the portion where there is no protrusion of the A surface to the portion where the protrusion is not formed on the B surface is Tmin. The difference between the τα_ and Tmin is the height TA of the protrusion A of the A surface, and the difference between Tmin and Tmin is the height TB of the B surface. The length of the bottom edge of the projection is the outer peripheral diameter D as shown in Fig. 5. Further, when the shape of the bottom surface of the protrusion is a polygonal shape such as a triangle or a hexagon, or a _ shape, the length of the bottom side of the protrusion is the diameter of the smallest perfect circle including the shape of the bottom surface. The above-mentioned Tmax, Tmin, and D can be measured by observation of a sheet using a stereoscopic microscope. The height T of the ideal protrusion is 6 〇 to 300 μηη as described above. When the height 突起 of the protrusion is 60 μηι, the length of the bottom edge D of the protrusion is preferably 75 to 1200 μηη, more preferably 75 to 400 μηη. When the height T of the protrusion is 3 〇〇 μιη, the length of the bottom edge of the protrusion is preferably 375 to 6000 μηη, more preferably 375 to 2000 μηι. The number of independent protrusions is preferably that the area of one side of the sheet is 40 101111289 per 1 cm 2 21 201244915 ~ I00 pieces and more preferably 4G to 11 (8) pieces. If there are less than 40 independent protrusions, there is a break in the cell or bubbles. If it exceeds 23 GG/cm2, the above-mentioned T/D ratio may increase, and the unit may be broken due to the concentration of the load on the top of the projection. The sealing sheet is preferably placed in the warm water of the order, and the heat shrinkage rate in the direction in which the sheet is branched is 3% or less. More preferably Μ% or less. Here, ^the stomach is "placed in warm water", when the sealing sheet has a small specific gravity and the sealing sheet is floated on the surface of the dish 7jC, the system does not press the sealing sheet from above to sink it. It is placed in warm water and placed in this floating state. On the other hand, in the case where the proportion of the dense sub-sheet is large and the sealing sheet is in the warm water, it means that the sheet is not sealed from the lower branch and placed in the state of the sinking. Further, the "sheet traveling direction" means the direction in which the material of the sealing coffin is processed. In the usual vacuum lamination step in the manufacture of the solar cell module, the sheet is pressed and the material is not subjected to the load-bearing state during the period in which the sealing sheet is sufficiently melted, and the sealing sheet is melted and degassed. At this time, since the sealing material is exposed to a no-load state at a high temperature of about 80 ° C, shrinkage of the sheet is also caused, resulting in cracking or positional deviation of the unit. The inventors of the present invention conducted research by focusing on the rupture or positional deviation of the unit, and as a result, found that if the step sheet is placed in a no-load state in a vacuum laminator, the sheet is placed in a direction of heating. When the rate is π% or less, the cracking of the unit can be further suppressed. The state reproduced in the vacuum laminator is to place the step sheet at 8G. The state of warm water _. Further, the heat shrinkage ratio in the direction orthogonal to the sheet 101111289 22 201244915 ! is not particularly limited as compared with the traveling direction, but is preferably 5% or less. The shape of the individual protrusions is preferably hemispherical, or a pyramidal cone, a cone or the like, or the top of the elements is 匕 = rtr. Thanks, two = pool 2: the surface shape of the protrusions. It is preferably hemispherical in terms of uniformly distributing the weight of the sun. Further, in terms of unevenness of light and excellent surface quality, it is preferably a quadrangular pyramid. The car ^ is characterized by the characteristics of both the hemispherical and the quadrangular pyramid, and is also in the shape of a mixed shape of four quadrangles. In order to mix the hemispherical shape and the quadrangular pyramid, the ratio of the main self is determined arbitrarily according to the characteristics of which one is pursued. The best is a hemispherical pattern. And the sealing sheet of the present month is preferably a protrusion having an independent protrusion and further having a degree of twist of i 15 μm. It is easy to operate by having such minute protrusions and sheets, and the π dynamic property is improved. Further, since the light is scattered by the minute projections to improve the whiteness of the sheet, the inspection of adhering foreign matter or the like is uniform. Such a small > * + • ^ large can be achieved by performing the pressing process m after the annealing step. In the prior method in which the annealing treatment by heating is performed after the embossing is applied, the height is 10 μηη or more, and the large protrusions of 101111289 23 201244915 remain in the sheet after the heat treatment, but the height is about several angstroms. The minute protrusions disappear with heat treatment. Furthermore, the height of the tiny protrusions is as follows. The surface of the sheet was taken at a magnification of 雷 according to JISB〇6〇1 (2〇〇1) using a well-known laser microscope, a laser microscope VK_X100 manufactured by KEYENCE Co., Ltd., etc. The crude sugar content of the obtained image is set to a value of a small protrusion when the cutoff value is mm. In the present application, as an index for evaluating the cushioning property of the sealing sheet for suppressing cracking of the unit of the solar cell, the rebound stress of the sheet when the sealing sheet is pressed and the steel sheet is compressed in the thickness direction is used. . For the solar η element rupture 舆 sealing sheet, the results of the discovery of the unit rupture are below kpa. Furthermore, the above-mentioned rebound _ force is preferably 70. The use of the compression displacement is obtained by the following five divisions in the following manner: the second plane is 5 μιη or less, and the compression load is

A compression test device with a degree of decomposition below Pa, which presses the flat pressure terminal at a pressurization speed of mm/s. The correction material has a hearing surface pressed in the thickness direction by 1 〇, and the temple is measured. Elastic stress (four). If the rebound of the sealing port is 70 kPa or less, the solar cell can be prevented from being broken by laminating and laminating the surface having the projections in contact with the solar cell. Furthermore, the shape of the surface opposite to the side of the (4) sheet having the protrusion surface is not limited, but the sealing sheet 101111289 24 201244915 is prevented from being adhered when the solar cell module is manufactured. The thickness of the sealing sheet around ΙΟμιη is preferably 5〇~ _, especially preferably ~. It is more preferably (10)~诵 and if m or problems arise from the viewpoint of workability. More than 1500 _, sometimes The decrease in productivity or the decrease in the adhesion is a problem. Moreover, in the case of the lowering of the seal 4, the thickness of the dense thick shirt from the U-shaped prominence is from the apex of the 4 to the The distance from the face of the protrusion is the distance from the apex of the protrusion on the opposite side of the ruler of the self-face protrusion when the protrusion is formed on both sides of the (four) sheet. As described above, for the seal It is preferable to form the sealing sheet by the manufacturing method of the present invention by forming the independent protrusions ' on the surface of the sheet correctly or suppressing the heat shrinkage ratio of the sealing sheet within a specific range. [Constructing the solar cell sealing sheet Raw material] The resin composition constituting the sealing sheet is described. Further, it is preferable that at least the resin composition constituting the surface portion on which the protrusion-side is formed satisfies the grouping of the resin composition of the following (4). The resin composition constituting the step sheet satisfies the composition of the resin composition described in the above-mentioned article. The resin composition constituting the sealing sheet preferably contains a polyolefin resin. Examples of the polyolefin resin include Homopolymeric polypropylene, copolymer with other grasses containing propylene as main component 101111289 25 201244915, polypropylene resin such as ethylene-propylene butene ternary copolymer, low density polyethylene, ultra low density polyethylene, linear Polyethylene-based resin such as a low-density polyethylene, a medium-density polyethylene, a high-density polyethylene, and a copolymer of another monomer containing ethylene as a main component, a polyolefin-based thermoplastic elastomer, etc. Examples of the copolymer of the other monomer include an ethylene-α-olefin copolymer and an ethylene-unsaturated monomer. The α-olefin is an α-olefin. Alkene, propylene, butyl ketone isobutylene, 1-pentene, 2-hydrazino-1-butene, 3-mercapto-indene-butene, fluorene-hexene, heptene, 1-octene, 1- Terpene, 1-decene, etc. Examples of the unsaturated monomer include vinyl acetate, acrylic acid, methacrylic acid, decyl acrylate, methyl methacrylate, ethyl acrylate or vinyl alcohol. Good ^ mentality - in order to make a small amount of copolymerization or modification in the hydrocarbon (tetra) lipids, such as oxime compounds, oxime epoxy propyl compounds, etc. As a solar cell sealing material, U is important for transparency, or adhesion to solar cells, etc.: Luxury is to make (4) B-resistance and Wei compound to ethylene-acetic acid (4) polymer, B-H- riding Agglomerates, low-density polyethylene, and modified. In the case of using ethylene-acetic acid, the copolymerization of the acid A-poly-cutting, the silk synthesis is in the range of 40% by mass of the C. Live horse 15 ~ again, things. Guan 101111289 26 201244915 Anyone who generates free radicals can use any one of them, considering the manufacture of solar cell dense. The temperature at the time of sealing the sheet, the heating and bonding temperature when making the solar cell module, and the storage of the crosslinking agent itself. Select the stability and so on. It is particularly preferable that the decomposition temperature of the half-life is ίο hours is 7 (rc or more. As an example of such an organic peroxide, 'l1-two (peroxide third hexyl) cyclohexane, n-butyl 4 , 4-di-(t-butylperoxy peroxide) valeric acid vinegar, 2,5-dimethyl-2,5-di(t-butylperoxide) hexane,-·second butyl peroxide , bis-thyl hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne _3, bis- _ peroxide - (4_ second butyl Cyclohexyl)peroxydicarbonate, tetradecylbutyl peroxide, 2-ethylhexanoic acid vinegar, third hexyl peroxide, -2-ethylhexanoic acid::::butyl peroxy-2_ethyl Auxiliary, third hexyl peroxy isopropyl (tetra) (tetra), di(tetra)cyclobutylcyclohexyl) peroxydicarbonate, butyl peroxy-3,5,5-trimethylhexanoic acid vinegar, Flute-butyl... Dibutyl peroxy laurate ruthenium butyl peroxy-2-ethylhexyl monocarbonate, third butane-2-ethylhexanoate, tert-butyl peroxide ° Oxidized acetic acid purpose, the first: the child is like 4, red butyl over μ A b _, the third wire peroxide _2 · S purpose, the third n-octyl-amylperoxy = " on a three-pentyl hexyl

Oxidized mono- _' τ base) cyclohexene, ethyl 3,3-di(t-butyl peroxide) butyric acid vinegar, α 2 (peroxide W) These organic peroxides may be used in combination of two or more kinds. The content of the substance is relative to the polyolefin resin: 1. The peroxidation amount is 101111289. The negative amount is preferably 01 to 5 s. 27 201244915 The best known is 0.1 to 3 parts by mass. 2 parts by mass. If the content of the organic peroxide is not sufficient (M parts by mass, the polyolefin resin may not be crosslinked at the time of the product. Even if it contains more than 5 parts by mass, the effect is low and there is an undecomposed organic The peroxide remains in the sealing sheet and may cause deterioration over the years. The resin composition constituting the sealing sheet may further contain a crosslinking assistant, a sinter coupling agent, a light stabilizer, and an ultraviolet absorbing agent. Agent, antioxidant, etc. The crosslinking assistant is a polyfunctional monomer having a plurality of unsaturated bonds in the molecule for reacting with an active radical compound produced by decomposition of an organic peroxide to cause polymerization The olefin-based resin is uniformly and efficiently crosslinked. Examples of the crosslinking auxiliary agent include: triallyl isocyanurate, triallyl cyanurate, trishydroxypropyl propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and three [ (fluorenyl) propylene oxiranyl ethyl] isocyanurate, thioglycolic acid tetrakis(methyl) propyl acetoacetate, pentaerythritol tetrakis(yl) propyl acrylate, pentaerythritol ethoxy tetra (曱) (A) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinyl benzene, etc. These crosslinking assistants may be used singly or in combination of two or more. In the present invention, "(meth) acrylate" means "acrylate or methacrylic acid S". Among these crosslinking assistants, particularly preferred is isocyanuric triene The vinegar and the trimethyl propyl ketone tris(mercapto) acrylate are preferably 〇 5 parts by mass based on 10 parts by mass of the polyolefin resin when the crosslinking assistant is added. 101111289 28 201244915 preferably 0.1 to 3 parts by mass 'extra good to 0.3 to 3 parts by mass. Even if it contains more than 5 parts by mass The improvement of the effect is also small and becomes a factor of cost increase. The decane coupling agent is preferably used to improve the adhesion of solar cell sealing sheets to various components such as solar cells, underlying sheets, and glass. Adding a decane coupling agent The content in the case of the polyolefin resin is preferably in the range of 5 to 2 parts by mass based on 1 part by mass of the polyolefin resin. If it is less than 5 parts by mass, the effect is small. Even if it contains more than 2 parts by mass. The effect of improving the adhesion is also small. The decane coupling agent is not particularly limited, and examples thereof include a fluorenyloxy group selected from a mercapto propylene group, an acryloxy group, an epoxy group, a sulfhydryl group, and an gland group. A specific example of the alkoxy sulphate, an amine group, and at least one of the functional groups in the group, as a specific example thereof, can be mentioned as follows: γ 曱 丙 丙 氧基 氧基 氧基 氧基 氧基 氧基 f f 了 了 了 _ 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基 氧基a methyl-propionyl-containing silk-based Wei compound 'γ-acryloxypropyltrioxane Kewei et al. (A) anthracene-based alkoxylated compound, γ-glycidoxypropyltrimethoxy (tetra), γ-glycidoxypropyl diethoxy, ρ_(3,4 _Epoxycyclohexyl)ethyltrimethylpyrazine and other silk-based fluorene compounds containing epoxy groups, (iv) propyltrimethoxy#, γ·weipropyl triethoxy Wei, etc.夕炫物 γ-ureidopropyl diethoxy sulphur, ketone propyl trimethyl sulphate, etc., containing urea-based keel-based compounds, γ•iso-counter propyl triethoxy sulphate γ _ Cyanic acid propyl tri-foxy- Wei, γ-isocyanate Ι 011 Ι 1289 29 201244915 propyl f-dimethoxy (IV) and other isocyanate-containing silk-based compound, γ_(2-aminoethyl) Alkoxypropyl P-based bis-oxy decane, γ·(2-aminoethyl)aminopropyltri-f-oxydecane, broadly-aminopropyltrimethoxy decane, etc. a hydroxy alkane compound such as a hydroxy alkane compound, a polyhydroxypropyl group, a oxy decane or a γ-hydroxypropyl diethoxy decane. Among them, from the viewpoint of compatibility with the polyolefin resin, it is preferred to contain a mercaptopropoxy-oxyl-wei compound, and further preferably a mercaptopropenyloxypropyltrimethoxy group. Decane. The resin composition constituting the sealing sheet preferably further contains an ultraviolet absorber. The ultraviolet absorbing agent absorbs harmful ultraviolet rays in the illuminating light and converts them into harmless heat energy in the molecule, thereby preventing the active species of the light in the polymer from being excited. As the ultraviolet absorber, a known one can be used. For example, a diphenyl ketone type, a benzotrisal system, a tris, a salicylic acid type, an aryl acrylate vinegar type, etc. can be used. One type of these may be used, and two or more types may be used in combination, and 0 may be used as the diphenyl ketone-based ultraviolet absorber. For example, 2, 2, di-diyl ruthenium (m-methyl) may be mentioned. Diphenyl hydrazine, 2 upper di-based groups from di(tetra)ethyl): benzyl, 2'2'-di-diyl-3,3'-dimethoxy-5,5 Ι_bis (thiol) Phenyl ketone, 2,2'·dimensyl·3 3'- **A prepared a soil 3,3 monomethoxy _5,5 丨 _ bis (2 hydroxyethyl) diphenyl hydrazine , 2,2'_di-based _3,3·_ two (by fluorenyl) your di-oxydiphenyl steel, n-secret-3,3, · two (2·ethyl)_5, 5••Dimethoxydiphenyl ketone, π-dipyridyl-methoxy-diphenyl ketone, and the like. 101111289 201244915 As the ultraviolet absorber of the present invention, for example, 2_[2,_transyl-5'-(hydroxymethyl)phenyl]·2Η_benzotriazole, 2_[2,_ Hydroxy _5, 2 hydroxyethyl) phenyl] 2 Η - Benzene η sit, 2_[2'-radio- 5'-(3-propyl) phenyl]_2η_benzotriazole, 2 -[2,-hydroxy_3|·methyl_5,_(hydroxymethyl)phenyl]_2 benzotriazole, 2_[2,·hydroxy-3·-methyl·5·_(2_ Hydroxyethyl)phenyl]_2Η_benzotriazole, 2[2·_hydroxy-3Lindolyl-5,-(3-hydroxypropyl)phenyl]-2Η-benzotriazole, 2-[2 , hydroxy·3,·t-butyl-5'-(hydroxymethyl)phenyl]_2Η_benzotriazole, 2_[2,_hydroxy_3,_t-butyl-5-(2- Ethyl)benzyl]_2Η-benzotriazine, 2-[2'-carbyl-3,_t-octyl-5'-(hydroxymethyl)phenyl;|_2H-benzotriazole , 2-[2,-hydroxy·3,_t-octyl-5'-(2-hydroxyethyl)phenyl]_2Η-benzotriazole, 2_[2,_hydroxy_3•-third octane -5-(3-Technylpropyl)benzyl]-2Η-benzoquinone tris[beta] or the like, or 2 2'·indolyl bis[6-(2Η-benzotriazol-2-yl)-4- (hydroxymethyl) phenol], 2, 2, _ fluorenylene bis [6-(2H- stupid Triazol-2-yl) winter (2-hydroxyethyl)phenol], methylene bis[6-(2H-benzotriazol-2-yl)-4-(3-hydroxypropyl)phenol], 2,2,_methylenebis[6-(2H-benzotriazol-2-yl)-4-(4-hydroxybutyl)phenol], 3,3_{22,·double [6-(2H -benzotriazol-2-yl)-1 -hydroxy_4_(2-hydroxyethyl)phenyl]indole propane, 2,2-{2,2'-bis[6-cation-benzotriazine- 2-yl)-1_transcarbyl|(2_ethyl)phenyl]}butyring, 2,2-oxybis[6-(2H-benzotrisyl-2-yl)_4_(2· Ethyl) Benzene], 2,2,-bis[6-(musobenzotrisin-2-yl)_4_(2_erythryl)benzene]amine. Examples of the second-tillage ultraviolet absorber include: 2-(2-hydroxyindoleylphenyl)-4,6-diphenyl--tris-trimium, 2-(2-hydroxy hydroxy hydroxy phenyl) 101111289 31 201244915 M,6-bis(2,4-dimercaptophenyl)_all three ♦, imprinted by warthene _4♦ by ethyl) phenyl]-4,6-monophenyl-average tillage, 2 Must be based on _4_(2-ethyl)phenyl]♦ bis(2,4-dimethylphenyl-tris-morphine, 2_[2-trans-iso-p-ethylethoxy)phenyl]-4, 6-diphenyl-average three-plowing, 2·[2-hydroxy_4_(2·hydroxyethoxy)phenylhydrazine, 6-bis(2,4-dimethylphenyl)_-s-tri-β well, 2_[2_经基·4_(3_Pyrylpropoxy)phenylhydrazine, 6-diphenyl-s-tris-β丼, 2_[2_trans-based-4(3-pyridyloxy)benzene 4-[6,6-bis(2,4-dimethylphenyl)-distributed, 2 [2_carbyl-4-(4)-butylbutyl)phenyl]-4,6-diphenyl _Homotriene, 2_[2_ via acetyl (4-hydroxybutyl) phenyl hydrazine, 6-bis (2,4-dimethylphenyl) _ three tillage, 2_[2_ via base ice (4) Butyloxy)phenyl]-4,6-diphenyl-average three-pile, 2_[2_trans-iso-butyryloxy)phenylindole, 6·bis(2,4-diyl) Phenyl)--tri-ephthyl, 2-(2-based 4-methyl-phenyl)-4,6-bis(2-yl--4 -Methylphenyl)_all three sigma wells, 2_[2_transcarbyl_4·(2·hydroxyethyl)phenylhydrazine, 6·bis(2-hydroxylmethylphenyl)_three tillage, 2_[2•transyl 4-(2-hydroxyethoxy)phenyl]_4,6-bis(2-hydroxy-'mercaptophenyl)·-trientrine, 2-[2-hydroxy-4-( 3-hydroxypropyl)phenyl]_4,6-bis(2-hydroxy-4-indolylphenyl)-memenorphin, 2-[2-hydroxy-4-(3-hydroxypropoxy)phenyl ]_4,6_bis(2-hydroxy-4-indolylphenyl)_all three wells and the like. Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like. Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl 2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3, Diphenyl acrylate and the like. 101111289 32 201244915 It is preferably a diphenyl fluorene-based ultraviolet absorber from the viewpoint of the ultraviolet absorbing effect and the coloring of the ultraviolet absorbing agent itself. In the case where the above ultraviolet absorber is added, it is preferably from 0.5 to 3 parts by mass based on the amount of the polyolefin resin * 1 〇 0 f. More preferably, it is 0.05 to 2. 〇 mass. If the wound contains less than 0.05 parts by mass, the effect is low, and if it exceeds 3 parts by mass, the coloring tendency tends. The resin composition constituting the sealing sheet preferably further contains a light stabilizer. Light stabilizers are those that capture the harmful effects of the polymer and do not produce new free radicals. As the light stabilizer, a hindered amine light stabilizer is preferably used. Examples of the:-resistance-based light stabilizer include bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) sebacate, and The reaction product of mercaptoethyl hydroperoxide and octane is 70% by mass and the polypropylene is 3% by mass, and double (U, 2, 6, 6-pentamethyl L-based; ^3, 5. double. Dimethylethyl) 4 phenylphenyl] decyl] butyl malonate, bis(1,2,2,6,6-pentacylidene-4-piperidinyl); sebacate Methyl-1,2,2,6,6-pentamethyl-4_piperidinyl sebacate mixture • Bis(2,2,6,6-tetradecyl-4-piperidinyl) Sebacate, tetrakis(2,2,6,6-tetradecyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate, tetra^2,2,6,6 - 曱, ,, -4-, 4-butane, tetrabutyl phthalate, 1,2,6,6-tetradecyl-piperidinyl-1,2,3, 4-butane tetracarboxylate and tridecylbutane tetracarboxylate/«j, 1,2,2,6,6-pentamethyl_4_σ bottom bite _i,2,3 , a mixture of 4-butane sulphate and thirteen-yard-1,2,3,4-butane tetracarboxylate, poly[^(丨丄^四101111289 33 201244915 decylbutyl)amine -1,3,5-three-talk-2,4-diyl}{(2,2,6,6-tetramethyl-4-indanyl)imine }六亚曱基{(2,2,6,6-tetradecyl-4-piperidinyl)imido}], dinonyl succinate and 4-hydroxy-2,2,6,6-tetra Polymers, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine曱基基旅基冰基)Amino)-三耕-2·yl)-4,7-diazadecane_ι,10-diamine with the above-mentioned acenaphthyl quinone and 4-carbyl- 2,2,6,6-tetramethyl-Ι-d bottom bite ethanol polymer mixture, dibutylamine_1,3,5-three tillage·Ν,Ν,-double (2,2,6 a polycondensate of 6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and [SK2,2,6,6-tetramethyl-4-pyridinyl)butylamine The hindered amine-based light stabilizer may be used singly or in combination of two or more. In the case of s 玄#, as a hindered amine-based light stabilizer, it is preferably used: double (1, 2, a mixture of 2,6,6-pentamethyl-4-0 bottom bite) azelaic acid vinegar with methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate And methyl 4-(piperidinyl azelaic acid bismuth, bis(2,2,6,6-tetramethyl-4-Benbityl) azelaic acid. Further, hindered amine light stabilizer It is preferred to use a melting point of 6〇 (In the case where the hindered amine-based light stabilizer is added, the content is preferably 0. 05 to 3 parts by mass based on 100 parts by mass of the polyolefin-based resin. More preferably 〇 〜 5 to 1.0 parts by mass. When the content is less than 5.00 parts by mass, the stabilizing effect is insufficient, and even if it contains more than 3.0 parts by mass, it becomes a cause of coloring or cost increase. Further, as a known additive, an antioxidant, a flame retardant, a flame retardant auxiliary, a plasticizer, a lubricant, a colorant or the like may be contained as needed within a range not inhibiting the effects of the present invention. 101111289 34 201244915 [Solar battery module] The solar cell module is composed of a light-receiving surface protective material, a back protective material, and a solar cell unit that is disposed between the quartz and the surface protective material and the back protective material and sealed with a sealing sheet. The layer is composed. As the sealing sheet used herein, a sealing sheet obtained by the production method of the present invention can be used, and a sealing sheet having independent projections as described above can also be used. In the sealing sheet obtained by the production method of the present invention, the heat shrinkage when the above-mentioned constituent materials are laminated is small. Therefore, the residual stress between the solar cell unit and the sealing sheet, between the light-receiving surface protective material and the sealing sheet, and between the back surface protective material and the sealing sheet is small, forming a sun having excellent durability over a long period of time. Battery module. Further, since the sealing sheet having the independent projections on the surface thereof can disperse the pressing force of the solar battery cells when the materials of the above-described constituent layers are integrated, the residual between the solar battery cells and the sealing sheets can be caused. The stress is small. Moreover, there is no residual of the bubbles in the male and the sealing materials. Therefore, a solar cell module excellent in durability over a long period of time is formed. [Examples] The assays used in the examples are shown below. Unless otherwise specified, the number of measured η was set to 5, and the average value was used. (1) Thickness of sheet The thickness of the formed sealing sheet was measured at any two turns in the width direction to determine the average end. The measuring device is a thick product specification 101111289 35 201244915 (model 547-301) manufactured by Mitutoyo Corporation. Regarding the thickness of the sealing sheet, when a projection is formed only on one surface of the sealing sheet, the distance from the vertex of the projection to the surface opposite to the surface having the projection is measured. In the case where protrusions are formed on both surfaces of the sealing sheet, the distance from the apex of the protrusion of one surface to the apex of the protrusion of the opposite surface is measured. (2) Protrusion height The sealing sheet is cut by the top of the projection in a direction (width direction) at right angles to the moving direction of the sheet at the time of manufacture (hereinafter simply referred to as the MD direction). The thickness direction cross section of the cut sealing sheet was observed by a stereo microscope across the entire width of the sheet. When there is a projection on one surface of the sealing sheet, the surface on the side where the sealing sheet has the projection is the A surface, and the surface on the side where the projection is not formed is the B surface. As shown in Fig. 3, the distance from the vertex of the protrusion on the A surface to the surface B is Tmax, and the distance from the portion of the A surface where there is no protrusion to the surface B is Tmin. Then, the height T of the protrusion is calculated using the formula (1). • Τ (μιη) = Tmax-Tmin· * - (i) When there are protrusions on both sides of the sealing sheet, one side of the sealing sheet is set to the A side and the other side is the B side. As shown in FIG. 4, the distance from the vertex of the protrusion of the A surface to the portion of the B surface where no protrusion is formed is set to TAmax, and the distance from the vertex of the protrusion of the B surface to the portion of the A surface where no protrusion is formed is TBmax. The distance from the non-protrusion portion of the A surface to the non-protrusion portion of the B surface is set to Tmin. Then, the height of the protrusion of the A surface is calculated by the formula (ii) 101111289 36 201244915 ΤΑ, and the height TB of the protrusion of the B surface is calculated by the formula (iii). • TA(pm)=TAmax-Tmin...(1)) • TB(pm) = TBmax_Tmin. ·.(out). (3) The depth of the embossing roller is determined according to JIS B0601 (2001)'. The surface of the embossing roller is measured under the conditions of a reference length of 2 mm, a load of 〇75 mN, and a measuring speed of 〇·3 mm/s. . The measurement was carried out using a small plastic surface roughness measuring device SJ401 manufactured by Mitutoyo Co., Ltd., and a cone of 60 was used. The diamond stylus with a front end radius of curvature of 2 μη is measured. The measured value is used as the embossing depth ρ ζ (μιη) of the embossing roll. (4) The embossing transfer rate is determined by dividing the protrusion height τ (μιη) (or the height 宍 (μιη) or the protrusion height τ Β (μιη)) measured in the above (2) by the above-mentioned (3) The value of the pattern depth ρ 压 of the embossing roller is used as the embossing transfer rate. • Embossing transfer rate (%) = Τ / Ρζχ 100. (5) Heat shrinkage rate Test piece of a flat square of 120 mm on one side of the sealing sheet. On the test piece, at the center of the TD direction at the time of manufacture, a straight line (5 cm) in the direction of two parallel TEs was drawn at intervals of 100 mm. Then, the positions where the respective straight lines 6 are equally divided (5 places respectively) are marked. The test piece was then heated to 80. (: The warm water is placed for 60 seconds. When the sealing sheet has a small specific gravity and the sealing sheet floats on the surface of the warm water, 101111289 37 201244915, it is placed in the floating state. The ratio of the sealing sheet is smoked. When the sealing sheet is large and sinks into warm water, it is placed in the state of sinking. After 60 seconds, the test piece is taken out from the warm water, and it is immersed and cooled in a room temperature of 2 Torr. After a second, remove the moisture on the surface of the sheet. Using a vernier caliper, measure the interval A from each of the five marks marked on one of the straight lines on the test piece to the opposite mark marked on the other line ( (mm) The heating shrinkage rate is calculated based on the following formula, and the average value of the five points is obtained. • The heat shrinkage rate (%) = (100 - Α) / 100 χ 100. (6) Melting of the resin composition constituting the sealing sheet The flow rate is based on JISK7210 (1999) "Test method for MFR 'melt mass-flow rate and melt volume flow rate, meh volume-flow rate" at a temperature of 19 Torr. (: The resin composition was measured under the test conditions of a load of 2.16 kg. (7) Length of the bottom side of the protrusion (D) The surface of the sheet having the protrusion was observed by a stereoscopic microscope, and the length of the bottom side (D) was measured. When the shape of the bottom surface is a polygonal shape such as a triangle or a hexagon, or an elliptical shape, the diameter of the smallest perfect circle including the above shape is measured. (8) Unit rupture The two sides of the self-sealing sheet are cut into 180 mm. Test piece of flat square. Soldering joint (thickness 280, width 101111289 38 201244915 2 mm) on a polycrystalline solar cell unit (3 types of busbars 'i56mm square, thickness 200 μπι) Solar cell with connector. Prepare glass plate (180 mm square, thickness 3 mm) and polyester solar cell back sheet (180 mm square, thickness 24 〇μιη). The laminated sealing sheet, the solar cell sheet, the sealing sheet, and the bottom layer were laminated. At this time, the sealing sheet was laminated so that the surface of the sealing sheet was in contact with the solar cell unit. The laminated body was placed at a temperature of 145. (:, The solar cell module was fabricated by vacuuming for 30 seconds, pressing for 1 minute, and pressure S for 10 minutes to form a solar cell module. Using a solar cell £L (Electroluminescence) image detecting device for the solar electric field of Saki Group _ hair image, and measure the length (mm) of the total crack of the unit rupture u 。. Repeat the test three times to find the average value of the total crack length. (9) Number of bubbles by visual number The number of bubbles in the solar cell module produced in the above (8) was determined. The average value of the three tests was obtained. (10) Rebound stress A test piece of a flat square having a side of 120 mm cut from the sealing sheet Then, using the compression tester KES FB_3 manufactured by Kato Tech Co., Ltd., the flat pressure terminal of diameter 16 111111 was pressed at a speed of 2 〇/ muscle from the test piece with a protrusion facing the sealing sheet, and measured in the thickness direction. The rebound stress (kpa) of the sheet when the pressure was increased by 1 〇〇μηη. The average value of the rebound stress was obtained by repeating the test three times. (Example 1) 101111289 39 201244915 According to FIG. Method for making solar cell sealing sheet (a) : film making step _

Using a twin-screw extruder as A for extruder 11, it will contain EVA (ethyl acetate content: 28 mass. /0, melt flow rate: 15 g/10 min, melting point: 71 °C) Part, second τ Gan. monobutyl peroxy-2-ethylhexyl monocarbonate (1 hour and half-life temperature: 11 ^. # ^ C) 0·7 parts by mass, triallyl isocyanurate 0.3 Lizhi, γ-methyl-endo-oxypropyltrimethoxy oxime, mass fraction, 2-perylene 4-methoxydiphenyl _ Q3 parts by mass, bis(1,2,(10)-penta The resin composition of the base of the adipic acid 癸 量 量 供给 is supplied to an extruder η (four) row (four) scale set to 8 ° ° C. The resin composition of the squama is extruded from the extruder 11 and held by the stencil. Furthermore, the opening width of the Τ font used is i fine, and the opening gap is 〇8 赖. The resin composition extruded in the above manner is formed into a sheet shape by being cooled and solidified by the polishing rolls 13a, 13b, and 13c of TC. Further, the temperature of the sheet when the film is ejected from the τ font is 1Grc. Further, the step sheet at this time has a width of 1150 mm, a thickness of 450 μm, a transport speed of 1 μm/mine, and a step (b): an annealing treatment step followed by an annealing treatment under the conditions described in Table 1. The ceramic heater 16 is used, and the transfer roller π is provided with a diameter of 15 mm and coated with "Teflon (registered trademark) on the surface, and the metal rolls are provided at intervals of a center pitch of the rolls of 200 mm. The 15 series is used for the insulation of the casing made of SUS. In addition, the hot air is blown at a wind speed of 1 m/sec from the lower part of the annealing furnace η 101111289 40 201244915 and the lower part of the outlet. Step (c). The processing steps are performed according to the conditions described in Table 1, and the embossing is performed after the annealing treatment. The embossing process is performed by passing the step sheet conveyed from the annealing furnace through the embossing roll 2 of the pattern depth of 120 μm, and wound with The hardness of 1〇mm is 75. The embossing of the glue was carried out between the opposed rolls 19. The heat shrinkage rate and the embossing transfer rate of the obtained solar cell sealing sheet were evaluated. The results are shown in Table 1. As shown in Table 1, The heat shrinkage rate is not small and the embossed solar cell sealing sheet is clearly transferred. (Example 2) The temperature of the hot air in the step (b) was 87 ΐ, and the heater temperature was set to 320 ° C. The sealing sheet was formed in the same manner as in Example i except that the residence time in the furnace was set to 29 seconds. Since the surface temperature of the step sheet was lowered, the heat shrinkage ratio was slightly increased, and the embossing transfer rate was increased. It is slightly lower. However, it can be heated in the same manner as in Example 1 (4) to turn the solar cell sealing sheet which is often small and clearly transferred with an embossed pattern. (Example 3) Except the temperature of the hot air in the step (b) It is set as a thief, and the temperature of the heater is set to 300 ° C, the residence time in the furnace is set to 30 seconds, and the line pressure is set to be U 〇 N / cm. The method of reading Example 丨 (4) is sealed. The surface temperature of the sheet is further lowered, so that the heat shrinkage surface becomes slightly larger, 101111289 41 20124 Further, in the same manner as in Example 1, a solar cell sealing sheet having a very small heat shrinkage ratio and clearly transferred with an embossed pattern was obtained in the same manner as in Example 1. (Example 4) c) The pressure of the line was set to 200 N/cm, and a sealing sheet was produced in the same manner as in Example 3. The embossing transfer rate was slightly lowered, but the transfer was clearly obtained in the same manner as in Example 3. An embossed solar cell sealing sheet. (Example 5) The hot line temperature in the step (b) was set to 110 ° C, the residence time in the furnace was set to 27 seconds, and the line pressure in the step (4) was used. A sheet was produced in the same manner as in Example 1 except that it was set to 200 N/cm. Since the surface temperature of the step sheet rises, a solar cell sealing sheet having a very small heat shrinkage ratio and a clear embossing transfer rate can be obtained. (Example 6) The wrap angle of the embossing roll in the step (c) was set to 45. A sealing sheet was produced in the same manner as in Example 5 except for the method. Since the wrap angle becomes shallow, the embossing transfer rate becomes slightly shallow, but it is a sheet having a good appearance. (Example 7) The holding speed of the sheet in the step (b) was set to 7 m/min, the hot air temperature was set to 110 ° C, the heater temperature was set to 300 ° C, and the residence time in the furnace was set. A sealing sheet was prepared in the same manner as in Example 1 except that the line pressure in the step (4) was set to 120 N/cm to 101111289 42 201244915. Since the heating time of the step sheet becomes long and the surface temperature becomes high, the heat shrinkage rate is greatly lowered, and even if the line pressure is low, a clear embossed sheet can be produced. (Comparative Examples 1 to 5) A solar cell sealing sheet was produced in the same manner as in Example 1 except that the conditions shown in Table 2 were used. (Comparative Examples 6 and 7) Using the previous production method shown in Fig. 2, embossing was immediately performed after extrusion from the T-die, followed by annealing treatment. The annealing treatment apparatus was set to be the same as in the first embodiment, and the embossing roll 13b' immediately after the T-shaped mold used a protruding depth of 120 μm. 101111289 43 201244915 [II Example 7 Inch Bu CO (N 〇8 cn 〇OS 〇〇v〇00 00 Example 6 δ § 〇cn CN 〇T-Η 〇tn m 〇Os On ON α; 00 00 o CN 3 Embodiment 5 Inch 〇CO CN 〇ο m 8 〇\ON 〇\ON 00 〇〇8 CN r—Η Example 4 〇ο ΓΛ CN ο m ΓΛ P 〇 VO ο o CN Example 3 δ 〇ο m CN g 8 m rn ΓΛ (N <7; ο inch, _·Η Example 2 〇ο m CN SS 闵m ir> 00 m 00 in 〇\ i〇m Example 1 **Η 〇ο m CN ΓΟ as沄mv〇cK oo 沄m 〇CN »-Η S3 Item M at the exit of the stencil mold M (°c) Step thickness of the sheet _ Step sheet conveying speed (m/min) Step at the entrance of the annealing furnace 15 Sheet surface temperature (°C) Hot air miscellaneous (°〇 Surface temperature of heater 16 (°C) The maximum temperature of the surface of the sheet in the annealing furnace (°C) The surface of the sheet at the exit of the annealing furnace Temperature (°C) Retention time of the sheet in the annealing furnace (seconds) Step speed of the sheet at the exit of the annealing furnace 15 (m/min) Step sheet at the entrance of the embossing roller 20 Surface temperature (°C) Temperature of embossing roll 20 (°C) Line pressure of embossing roll 20 (N/cm) Wrap angle of embossing pro 20 (°) Depth of embossing roll Τηι(μχη Heating shrinkage rate (%) embossing transfer rate (%) film forming step annealing process step embossing processing step sheet property sheet making step inch; s-UIOl 201244915 [(Nd than car case 7 inch inch —^ m <N 00 VO ο (Ν CS Ο; 1 1 Ο <Ν 1 3 pj Comparative Example 6 〇〇m (N § ο ΓΟ rn CS cK 1 1 Ο f—Η 1 | Comparative Example 5 1 inch Cn CN S τ—Η 8 inch 14·4 1 m oo VO m CR Comparative Example 4 〇Ο m CN ρ CN 00 CN 〇< Q Γ—^ 寸 r»H 00 m Comparative Example 3 ! inchο m CN ο Ο ^Τ) ο CN Os ON Ό uo ir> Inch TH rH in <N Comparative Example 2 Inch ο ^Η cn CN 00 s (Ν s <N α< OO <n § rH No sample i no sample丨Comparative example 1 〇ο rH CO (N 00 VO g (Ν vo CN cK oo inch temperature of the resin at the exit of the T-die) (°C) Step sheet ^J?·degree (μηι) Step sheet conveying speed (m/min) Step at the entrance of the annealing furnace 15 Sheet surface temperature (°C) Hot air temperature (°C) Surface temperature of heater 16 (°C) Maximum temperature of the surface of the sheet in the annealing furnace (°C) Step sheet at the exit of the annealing furnace Surface temperature (°C) Step in the annealing furnace Residual time of the moon (seconds) Step speed of the sheet at the exit of the annealing furnace 15 (m/min) Step surface of the embossing pro 20 inlet sheet (° C) embossing pro 20 temperature (°C) embossing report 20 line pressure (N / cm) embossing report 20 wrap angle (°) embossed report depth Tm (pm) heating shrinkage ( %) embossing transfer rate (%) film forming step annealing treatment step embossing processing step sheet property sheet forming step 5 inch 68-11101 201244915 (Results) As shown in Table 1, Examples 1 to 7 The prepared solar cell sealing sheet has a small heat shrinkage ratio, a high embossing transfer rate, and a clear transfer of the embossed shape. Using these solar cell sealing sheets and forming a solar battery module by a conventionally known method, as a result, no abnormality such as cell offset, cell breakage, or bubble mixing occurred during the manufacture of the module. In Comparative Example 1, since the temperature at the time of the annealing treatment and the sheet temperature at the entrance of the embossing roll 20 were both low, the heat shrinkage ratio was large and the embossing transfer rate was low. In Comparative Example 3 t, since the temperature between the annealing furnace outlet and the embossing roller inlet was enlarged, the temperature of the sheet was lowered, and the embossing transfer rate was lowered. In Comparative Example 4, since the surface temperature of the sheet in the annealing furnace was low, the heat shrinkage ratio could not be sufficiently reduced. In Comparative Example 2, the step sheet was wound around the embossing roll, and the sample could not be obtained. In Comparative Example 5, since the annealing treatment time was short, the heat shrinkage of the solar cell sealing sheet could not be sufficiently reduced. In Comparative Examples 6 and 7, the embossed shape was obtained by the use of the buffing roll, and the embossed shape was clear. However, if the heat shrinkage was to be reduced, the embossed shape was deformed, and if the embossed shape was to be maintained, the heat shrinkage could not be reduced. (Example 8) Step (a): The film forming step will contain EVA (ethylene hydride content: 28% by mass, melt flow rate: 101111289 46 201244915 15 g/l 〇 min (190 ° C), melting point: 7 Γ〇 1 part by mass, tert-butylperoxy-2-ethylhexyl monocarbonate (1 time half-life temperature: 119. 匸) 〇 7 mass. Parts, isocyanuric acid tris-propyl hydrazine. Parts by mass, γ-methacryloxyloxy; 0.2 parts by weight of trimethoxycarbazide, L-hydroxy-4-methoxydipyridyl ketone 3. Part by mass, bis (丨, 2, 2, 6 The resin composition of 1 part by mass of hexamethylene-4-piperidinyl) sebacate was supplied to a twin-screw extruder set to 8 Torr. The melt-kneading was carried out by mixing the resin. The material was extruded from a twin-axis extruder maintained at 105 ° C. Further, the opening of the Τ-shaped mold was 13 〇〇 mm, and the opening gap was 0.8 mm. The EVA sheet was maintained by The polishing roller of 2 ° ° C is cooled and solidified. Further, the sheet temperature of the EVA sheet when ejected from the τ-shaped mold is i 〇 7 ° C. Further, the sheet width at this time is 1150 mm, and the thickness of the sheet is 450 μπι, The material conveying speed is 10 m/min. Then, the annealing treatment and the embossing processing are continuously performed. Step (b): Annealing treatment step The annealing treatment is performed by winding a heat insulating material through a casing made of SUS! It is carried out in a furnace equipped with a ceramic heater having a surface temperature of 350 ° C and a metal having a diameter of 150 mm and coated with "Teflon(registered trademark)" The center-to-center spacing is set at intervals of 250 mm. Further, hot air is blown at a wind speed of 1 m/sec from the lower part of the inlet of the furnace and the lower part of the outlet. Step (c): embossing processing step 101111289 47 201244915 By embossing The sheet taken out from the annealing furnace passes through a embossing pattern having a grain depth of 180 μm and having a diameter of 450 Å μm of 450/cm 2 and a concave shape of a hemispherical concave shape and a hardness of 75 mm wound with a thickness of 75 mm. The eccentric rubber is applied between the opposing rolls. Further, the details of the above manufacturing conditions are as follows.

Sheet surface temperature at the inlet of the annealing furnace: 23 °C Hot air temperature: 93 °C Maximum temperature of the surface of the sheet in the annealing furnace: 90 °C Surface temperature at the exit of the annealing furnace: 90 °C Annealing furnace Sheet residence time: sheet speed at the exit of the annealing furnace 15 at 28 seconds: 9.6 m/min. Sheet surface temperature at the entrance of the embossing roll: 78. 〇 embossing roll temperature: 15 °C Line pressure of embossing roll: 350 N/cm Wrap angle of embossing roll: 120. . The heat shrinkage ratio, the rebound stress, the cell cracking property at the time of module manufacture, and the number of bubbles were evaluated for the obtained sealing sheet. The results are shown in Table 3. As shown in Table 3, it is a sealing sheet in which the sheet heat shrinkage rate is small and the unit is broken and bubbles are small at the time of module manufacture. (Example 9) In addition to changing the embossing roll in the step (c) to a pattern depth of 120 and having a diameter of 450/cm 2 of 460 μm and a hemispherical concave pattern of 101111289 48 201244915 A sealing sheet was produced in the same manner as in Example 8. The obtained sealing sheet was as shown in Table 3, and was a sealing sheet in which the sheet heat shrinkage rate was small and the unit was broken at the time of manufacture of the mold, and the bubbles were small. • (Example 10) • Except that the embossing roll in step (e) was changed to an embossing roll having a pattern depth of 300 μm and having a diameter of 450/cm 2 46〇μηι and a hemispherical concave pattern. A sealing sheet was produced in the same manner as in Example 8. The obtained sealing sheet was as shown in Table 3, and was a sealing sheet in which the heat shrinkage rate of the sheet was small and the unit was broken and bubbles were small at the time of manufacture of the module. (Example 11) Except that the embossing roll in the step (e) was changed to the depth of the pattern, and the embossed pattern having a diameter of 0.3 Å/cm and a concave shape of a hemispherical shape was used, A sealing sheet was prepared in the same manner as in Example 8. The obtained sealing sheet was as shown in Table 3, and was a sealing sheet having a small heat shrinkage rate of the sheet and a cell breakage and less bubbles in the manufacture of the module. (Example 12), except that the embossing roll in the step (4) was changed to an embossing roll having a embossed pattern having a groove depth of 180 μm and having a peripheral diameter of 46 Å/cm 2 and a square pyramid shape A sealing sheet was produced in the same manner as in Example 8. The obtained sealing sheet was as shown in Table 3, in order to cause a number of cells to be broken during the manufacture of the module, but the sheet had a smaller heat shrinkage ratio and a smaller bubble. (10) The sealing sheet was prepared in the same manner as in the example (3) except that the annealing treatment was not carried out, and the surface temperature of the sheet was heated by an infrared heater except "outside". The sealing sheet obtained by the household is as shown in Table 3, which is a sheet having a large heat shrinkage ratio and a sealing sheet in which a plurality of cells are broken but bubbles are small at the time of module manufacture. (Example 14) A sealing sheet was formed in the same manner as in Example 8 except that the EVA resin was changed to an eva resin having a melt flow rate of 1 〇 g / i. The obtained sealing sheet was as shown in Table 3, which was a sealing sheet in which a plurality of unit cracks were produced at the time of module manufacture, but the sheet had a small heat shrinkage ratio and a small number of bubbles. (Example 15) Except that the embossing roll in the step (c) was changed to a embossing roll having a embossed pattern of a pattern depth of ι8 〇μηη and having a peripheral diameter of 2000 μm and having a square pyramid shape of a rectangular shape, A sealing sheet was produced in the same manner as in Example 8. The obtained sealing sheet was as shown in Table 3, and was a sealing sheet having a small heat shrinkage rate of the sheet and a number of cell cracks but less bubbles in the manufacture of the module. (Reference Example 1) A sealing sheet which was subjected to annealing treatment was prepared and evaluated for evaluation in the same manner as in Example 8 except that embossing was not carried out. The obtained sealing sheet was as shown in Table 4, and was a sealing sheet in which the heat shrinkage rate of the sheet was small but the unit was broken at the time of manufacture of the module, and a large amount of bubbles were generated. (Reference Example 2) Except the engraved pattern in which the embossing roll in the step (c) is changed to the embossing depth of 18 111 111 and has a semicircular groove (groove width μιη) continuous in the rotation direction of the roll. A sealing sheet was produced in the same manner as in Example 8 except for the embossing roll. The obtained sealing sheet was as shown in Table 4, and was a sealing sheet in which the sheet was heated at a small (four) rate and the unit was broken at the time of module manufacture but the bubbles were large. (Reference Example 3) In addition to changing the embossing in the step (4) to a grain depth of 5 () and having a diameter of 45 WW, which is a hemispherical concave pattern, the pattern is lighter than A sealing sheet was produced in the same manner as in Example 8. The obtained sealing sheet was as shown in Table 4, and the heat shrinkage rate of the sheet was small, but the module manufacturing unit broke the H-k sealing sheet. (Reference Example 4) A sealing sheet was produced in the same manner as in Example 8 except that the roll in the step (4) was changed to the pattern depth i8Q_ and 4r5〇〇^^^. The obtained sealing sheet was as shown in Table 4, and was a sealing sheet in which the sheet had a small heat shrinkage ratio and a small number of bubbles but the unit was broken at the time of module manufacture. 101111289 201244915 (Reference Example 5) Except that the embossing roll in the step (c) is changed to an embossing roll having a pattern depth of 180 μm and having a diameter of 3800 μm and a hemispherical concave pattern, A sealing sheet was produced in the same manner as in Example 8. The obtained sealing sheet was as shown in Table 4, and was a sealing sheet in which the sheet had a small heat shrinkage ratio but the unit was broken and the bubbles were large at the time of module manufacture. 101111289 52 201244915 [Example] Example 15 Quadrilateral I 〇 2000 0.08 in CO ο Example 14 Hemisphere 450 460 0.33 Example 13 Hemisphere 450 460 0.33 ο Example 12 » Ti Teeth 840 I 0.33 < N m ο Example 11 1 Hemisphere 980 250 330 0.76 cn 〇ο Example 10 1 Hemisphere | 450 250 460 0.54 o ο Example 9 1 Hemisphere 1 450 〇 460 0.22 | (Ν »no ο | Example 8 1 1 Hemisphere 1 450 150 460 | 0.33 | o ο unit | g/10 min / cm2 ί 1 kPa i EVA resin melt flow rate protrusion shape protrusion number of protrusions Τ length of the bottom side of the protrusion D Τ / D ratio heating shrinkage Rebound stress unit rupture (crack length) Number of bubbles 1 Reference Example 5 I l Hemisphere I Bu 3800 I 0.04 I 215 inch | Reference Example 4 1 1 Hemisphere | 4500 I 1.00 I (Ν CN σ\ 〇〇〇| Reference Example 3 1 | Hemisphere | 450 〇460 0.09 CN 00 00 Inch Reference Example 2 Continuous groove shape t Γ-Η 1 1 m (N CN 〇ΓΛ Reference example 1 No protrusion 1 1 1 1 (N 220 unit 1 g/ 10 min / cm2 1 I kPa 1 Learn the melt flow of EVA resin The height of the number of protrusions of the shape protrusions Τ The length of the bottom side of the protrusions DT/D ratio Heat shrinkage rate Rebound stress unit rupture (crack length) Number of bubbles [inch 1 -s-llsl 201244915 (Industry UTILITY) The present invention can be suitably used in a method for manufacturing a solar cell sealing sheet. In particular, since the heat shrinkage is reduced and a clear embossing pattern is provided, the positional deviation of the unit during module manufacturing can be prevented. Fig. 1 is a schematic view showing an example of a method for producing a solar cell sealing sheet of the present invention. Fig. 2 is a schematic view showing an example of a method for producing a solar cell sealing sheet of the present invention. A schematic view showing an example of a method for producing a solar cell sealing sheet of the prior art. Fig. 3 is a view for explaining a method of measuring the height of a projection of a solar cell sealing sheet having a protrusion formed on one surface. A diagram of a method of forming the height of the protrusion of the protruding solar cell sealing sheet on both sides. Fig. 5 is a view showing the length d of the bottom side of the protrusion. [Description of main component symbols] 1 Step sheet 11 Double-axis extruder 12 Mold 13a Polishing roller (surface without engraving) 13b Polishing roller (no engraving on the surface) 13b' Embossing roller (surface engraving) 101111289 54 201244915 13c Polishing roller (surface without engraving) 14 Roller 15 Annealing furnace 16 Heater 17 Transfer roller 18 Sheet removal report 19 Embossed counter roller 20 Embossing roller 21 Cooling roller 31 Gear fruit 32 Sheet conveying direction 33 Non-contact infrared Thermometer 101111289 55

Claims (1)

201244915 VII. Patent application scope: - A method for manufacturing a solar cell sealing sheet, which is according to step (4), step (b) and step (c): step by heating the resin composition, and then cooling Step of obtaining a step sheet; sheet step (b): heating the surface of the step (a) in the above step (a) for four seconds, and forming a flop of the surface of the rhyme composition of the surface portion (4): heating in the above step (b): step: degree sheet:: the table is (the sleek point of the resin composition constituting the surface portion) ~ (the enchantment of the resin composition constituting the surface portion described above. The temperature, which in turn presses the embossing roll against the surface to form an embossed shape on the surface. 2. The method for manufacturing a solar cell sealing sheet according to the invention of claim i, wherein in the step (c), when the surface of the step sheet is pressed by the ink mark, the surface is applied to the surface The line pressure is (9) ~ gamma N / cm. 3', the method for manufacturing a solar cell sealing sheet according to claim 1 or 2, wherein the embossing roller is used in the above step (4), and the surface of the sheet is pressed by the above-mentioned step. The surface temperature is equal to or lower than the melting point of the resin composition constituting the surface portion. 4', such as Uli fcS), the solar cell sealing material of any one of items 1 to 3, wherein in the above step (4), the shaft or the biaxial 101111289 56 201244915 extruder will be heated by the above The molten resin composition is extruded from a mold and formed into a sheet shape. 5. If you apply for a patent scope! The method for producing a solar cell encapsulating sheet according to any one of the preceding claims, wherein the resin la composition constituting the surface portion contains a polyolefin resin and an organic peroxide. 6. A solar cell sealing sheet obtained by using the solar cell sealing sheet obtained by the manufacturing method of the patent application No. 1-5 to 5, and the resin composition constituting the surface portion contains a poly-smoke system The resin, the surface on which the embossed shape is formed has a height of 60 · 23 〇〇 / cm 2 of the independent protrusion, and the ratio of the height (τ) of the independent protrusion to the length of the base (D) (T/D) is 〇.〇5~〇8〇. — 7. The solar cell sealing sheet according to item 6 of the patent scope of May, wherein, when the solar cell is sealed in the warm water of _ for a minute, the direction of the sheet of the sealing sheet is The heat shrinkage ratio is as follows. 8. The solar cell sealing sheet of claim 6 or claim 7, wherein the independent protrusions have a hemispherical shape and/or a quadrangular pyramid shape. 9. The solar cell encapsulating sheet according to any one of claims 6 to 8 wherein the solar cell sealing sheet has the above-mentioned protrusion surface is compressed in the thickness direction of the sealing sheet. When the sheet has a rebound stress of 70 kPa or less. 10. The solar cell sealing sheet according to any one of claims 6 to 9, wherein the solar cell sealing sheet has a raised surface and further has a protrusion of 101111289 57 201244915 having a twist of 1 to 15 μm. u.—The solar cell module, the light-receiving surface protection material, and the surface protection material, and the system thereof are composed of the following parts: disposed between the light-receiving surface protection material and the back surface protection material, and the application patent scopes 6 to 1 A solar cell sealing sheet according to any one of the preceding claims, wherein the layer of the solar cell unit is sealed. 101111289 58