JP4662806B2 - Manufacturing method of adhesive sheet for solar cell - Google Patents

Description

The present invention relates to a method for producing a solar cell adhesive sheet that is preferably used to join a solar cell element and a substrate when a solar cell module is produced.

  As solar cell modules consisting of silicon or selenium semiconductor wafers, an adhesive sheet such as an ethylene copolymer is laminated on both sides of these solar cell elements, with an upper protective material on one side and a lower substrate on the other side. A material is used in which the protective materials are superposed, degassed in vacuum and heated to be bonded together.

  Since the adhesive sheet is required to have transparency, weather resistance, adhesiveness, etc., an adhesive sheet composed of an ethylene copolymer and an organic peroxide has been proposed.

For example, in the protective sheet for a solar cell module made of an ethylene-based copolymer containing an organic peroxide, the organic peroxide is selected from the group consisting of a dialkyl peroxide (A), an alkyl peroxy ester, and a peroxy ketal. Protection for solar cell module using at least one selected peroxide (B) blended at a ratio of (A) / (B) in a ratio of 10/90 to 90/10 Sheets have been proposed, and the one-hour half-life temperature of the dialkyl peroxide (A) is 130 to 160 ° C, and the one-hour half-life temperature of the peroxide (B) is preferably 100 to 135 ° C. (See Patent Document 1). Moreover, as the manufacturing method, an extrusion molding method using a T die is described.
JP 11-26791 A

  However, when the ethylene copolymer is extruded using a T-die, if the ethylene copolymer stays in the extruder or T-die, the cross-linking agent reacts due to a long thermal history and the viscosity increases. Gel formation occurs. In particular, in the T-die, when the ethylene copolymer is developed, the contact area between the ethylene copolymer and the inner surface of the mold is increased, and an ethylene copolymer layer having a slow flow rate and easily staying can be formed.

  When the T die is about 80 to 110 ° C., the melt viscosity of the ethylene copolymer is high, so that the resin tends to stay on the inner surface of the T die. In addition, when an organic peroxide having a one-hour half-life temperature of 100 to 135 ° C. is blended, if it stays at such a temperature for a long time, the crosslinking reaction proceeds and the ethylene copolymer is thickened. Furthermore, it becomes easy to stay.

  In addition, when the T die is about 110 to 130 ° C., when an organic peroxide having a one-hour half-life temperature of 100 to 135 ° C. is used, a part thereof reacts to increase the viscosity of the ethylene copolymer. However, it tends to stay even at this temperature.

  As described above, when the ethylene copolymer stays in the T-die, thickening and gelation of the staying portion further proceeds due to the heat history. If the viscosity of the ethylene copolymer becomes non-uniform due to thickening or gelation, the flow of the ethylene copolymer in the T die becomes non-uniform, causing a thickness defect or further gelling. The ethylene copolymer is solidified in a part of the inside.

The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a method for producing a uniform quality solar cell adhesive sheet that can be stably and efficiently formed.

The method of manufacturing the adhesive sheet for a solar cell of the present invention is composed of an ethylene copolymer and an organic peroxide, an adhesive sheet manufacturing method for a solar cell the three or more layers of the resin sheet is laminated, ethylene system copolymer 100 parts by weight of an organic peroxide 0.05 parts by weight or more, the resin composition for each side outermost layer formed by melt-kneading a less than 0.3 parts by weight, and the ethylene copolymer 100 wt the the parts and the organic peroxide 0.3 part by weight to 3 parts by weight of the resin composition for an inner layer formed by melt-kneading the multilayer T-die such that the sum of both sides outermost layer having a thickness of less than or equal to 20% of the total And extrusion molding.

  The ethylene-based copolymer used in the present invention is a copolymer of ethylene and a copolymerizable monomer that can be copolymerized with ethylene, and the copolymerizable monomer is from the viewpoint of adhesiveness and transparency. , Vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, maleic acid, maleic anhydride, maleic acid ester, etc., and these copolymerizable monomers may be copolymerized with ethylene alone. Two or more kinds of copolymerizable monomers may be copolymerized.

  Although content of the copolymerizable monomer contained in an ethylene-type copolymer is not specifically limited, It is preferable that it is 5 to 50 weight%. If the content of the copolymerizable monomer is less than 5% by weight, the transparency after the formation of the solar cell is insufficient, and the power generation performance of the solar cell may not be sufficient. There is a possibility that it is not satisfactory or the strength of the solar cell sheet is insufficient.

  The ethylene copolymer is preferably an ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 5 to 50 parts by weight.

  Examples of the organic peroxide used in the present invention include di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, and 2,5-dimethyl-2,5. -Di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexin-3, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (T-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) ) Cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5 -Dimethyl-2,5-di- (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5- Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4- And di- (t-butylperoxy) valerate. Luo organic peroxides may be used alone, or two or more kinds may be used in combination.

  The adhesive sheet for solar cell of the present invention is an adhesive sheet for solar cell comprising an ethylene copolymer and an organic peroxide and laminated with three or more resin sheets, and the outermost layers on both sides are made of an ethylene copolymer. It consists of 100 parts by weight of polymer and 0.05 parts by weight or more and less than 0.3 parts by weight of organic peroxide.

  When the amount of the organic peroxide added on the outermost layers on both sides is less than 0.05 parts by weight, the solar cell adhesive sheet protrudes from the side surface during the solar cell manufacturing process, or the durability after the solar cell is installed. There is a risk that the sex will be insufficient. Moreover, when 0.3 weight part or more is added, there exists a possibility that it may gel at a retention part at the time of extrusion molding, and a uniform sheet | seat may not be obtained.

  The inner layer comprises 100 parts by weight of an ethylene copolymer and 0.3 to 3 parts by weight of an organic peroxide. If the amount of organic peroxide added is less than 0.3 parts by weight, sufficient durability may not be obtained after the formation of the solar cell. If more than 3 parts by weight is added, the durability will be improved so much. In addition, there is a possibility that problems such as generation of bubbles at the time of manufacturing the solar cell and easy coloring of the sheet may occur.

  In the adhesive sheet for solar cell of the present invention, the sum of the thicknesses of the outermost layers on both sides is 20% or less. If the sum of the thicknesses of the outermost layers on both sides is greater than 20%, sufficient durability may not be obtained.

  One or more additives such as a crosslinking aid, a coupling agent, an antioxidant, and an ultraviolet absorber may be added to the solar cell adhesive sheet of the present invention as necessary. A well-known additive can be used as the additive, and the addition amount may be added within a range not impairing the achievement of the object of the present invention.

  For forming the solar cell adhesive sheet of the present invention, a general multilayer T-die extruder can be used. For example, two or more extruders are used, and the resin composition for both outermost layers and the inner layer are used. The resin composition is melt-kneaded at a temperature at which the organic peroxide is not substantially decomposed, extruded with a multilayer T-die extruder, and the molten resin sheet extruded from the T-die is cooled and solidified with a cooling roll, Wind up.

  The melt-kneading is preferably carried out at a temperature lower by 10 ° C. or more than the one-hour half-life temperature of the organic peroxide used. When two or more organic peroxides are used, it is preferable to melt knead at a temperature that is at least 10 ° C. lower than the lowest one-hour half-life temperature.

  The solar cell bonding sheet of the present invention preferably has an embossed pattern on the surface of the sheet in order to improve the deaeration property in the laminating process of the solar cell module. Examples of the method for shaping the embossed pattern on the surface of the sheet include a method of niping with a cooling roll having an embossed pattern on the surface immediately after the molten resin is extruded from the T die, A known embossing method such as a method of heating and nipping between an embossing roll and a rubber roll can be used.

Since the structure of the manufacturing method of the solar cell bonding sheet | seat of this invention is as the above-mentioned, it can shape | mold stably and efficiently, and the obtained solar cell bonding sheet | seat becomes a thing with uniform quality.

(Examples 1 and 2 and Comparative Examples 1 to 4)
100 parts by weight of ethylene-vinyl acetate copolymer (vinyl acetate content 28% by weight, MFR 20 g / 10 min), triallyl isocyanurate 0.3 parts by weight, 3-glycidoxypropyltrimethoxysilane 0.1 parts by weight, 2 , 6-di-t-butyl-4-methylphenol 0.1 part by weight, 2-hydroxy-4-methoxybenzophenone 0.3 part by weight and a predetermined amount of organic peroxide shown in Table 1 Were supplied to the feed block from three extruders, and extrusion molded at a resin temperature of 120 ° C. by the T-die method to obtain a three-layer solar cell adhesive sheet having a thickness of 0.5 mm. After extrusion, embossing with a depth of 0.2 mm was performed when cooling and taking. However, since comparative molding 3 could not be stably molded, some evaluation was omitted.

(Examples 1-3, Comparative Examples 1-4)
100 parts by weight of ethylene-vinyl acetate copolymer (vinyl acetate content 28% by weight, MFR 20 g / 10 min), triallyl isocyanurate 0.3 parts by weight, 3-glycidoxypropyltrimethoxysilane 0.1 parts by weight, 2 , 6-di-t-butyl-4-methylphenol 0.1 part by weight, 2-hydroxy-4-methoxybenzophenone 0.3 part by weight and a predetermined amount of organic peroxide shown in Table 1 Were supplied to the feed block from three extruders, and extrusion molded at a resin temperature of 120 ° C. by the T-die method to obtain a three-layer solar cell adhesive sheet having a thickness of 0.5 mm. After extrusion, embossing with a depth of 0.2 mm was performed when cooling and taking. However, since comparative molding 3 could not be stably molded, some evaluation was omitted.

  The gel fraction and the cold / humidity heat cycle test of the obtained solar cell adhesive sheet were conducted by the following methods, and the results are shown in Table 1.

  (1) Gel fraction It measured 2 points | pieces (5 cm and center from an edge part) in the width direction of the adhesive sheet for solar cells obtained 1 hour after the extrusion start, and 24 hours after. In addition, the gel fraction after the solar cell adhesive sheet was sandwiched between release sheets and crosslinked by heating at 150 ° C. for 10 minutes was measured. The gel fraction was determined by immersing 0.2 g of the sample in 50 ml of xylene, heating and dissolving at 110 ° C. for 12 hours, filtering off the insoluble matter with a 200 mesh wire net, drying under reduced pressure at 80 ° C. for 4 hours, and then insoluble. It is expressed in weight% relative to the sample for minutes.

  (2) Cold and wet heat cycle test Between the obtained two solar cell adhesive sheets, a plurality of solar cell silicon semiconductor wafers were arranged in series using an interconnector, and a transparent flat glass was placed on the upper surface of the upper sheet. Then, a polyvinyl fluoride resin sheet was superposed on the lower surface of the lower sheet, and heated and bonded for 10 minutes under a heating temperature of 150 ° C., a reduced pressure of 10 mmHg, and an atmospheric pressure press to produce a solar cell module.

  The obtained solar cell module was allowed to stand at −20 ° C. for 6 hours, then heated from −20 ° C. to + 85 ° C. over 1 hour, left in an atmosphere of + 85 ° C. and 85% RH for 6 hours, and then +85 The process of cooling from 1 ° C. to −20 ° C. for 1 hour was defined as 1 cycle, and the appearance of the solar cell module after 10 cycles was visually observed to determine the presence or absence of abnormalities such as discoloration and peeling.

Claims (1)

A method for producing an adhesive sheet for a solar cell comprising an ethylene copolymer and an organic peroxide, wherein three or more resin sheets are laminated, comprising 100 parts by weight of an ethylene copolymer and 0 organic peroxide .05 parts by weight or more, the resin composition for each side outermost layer formed by melt-kneading a less than 0.3 parts by weight, and the ethylene copolymer 100 parts by weight of an organic peroxide 0.3 part by weight to 3 sun, characterized in that the resin composition for the inner layer obtained by melt-kneading a part by weight, the sum of both sides outermost layer having a thickness of extruded is supplied to the multi-layer T die to less than 20% of the total A method for producing an adhesive sheet for a battery.