JP2015168158A - Method of manufacturing thin film laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress generation of winding wrinkles on a thin film laminate by a simple structure.SOLUTION: A method of manufacturing a thin film laminate is provided in which a long resin substrate is continuously transferred by transfer rollers so that a thin film is continuously laminated on the resin substrate. In this method of manufacturing a thin film laminate, when laminating the thin film on the resin substrate, a heating process to heat to a prescribed heated temperature is performed by a heating part 30, and a laminate of the resin substrate and the thin film after the execution of heating process is wound up in a roll shape to a winding roll 28. In the winding process, the winding is performed with the ambient temperature of the laminate being adjusted to the cooling contraction temperature of the resin substrate or higher.

Description

  The present invention relates to a method for manufacturing a thin film laminate.

  As described in Patent Document 1, as a conventional method for producing a thin film laminate, a long transparent resin substrate is continuously conveyed by a conveyance roller, and a transparent thin film is continuously formed thereon by a sputtering method. There has been proposed a method for forming the above. When sputtering is performed, the temperature of the base material rises, a large thermal expansion occurs, and the temperature drops rapidly during winding of the roll, so that the polymer film serving as the base material may shrink and winding wrinkles may occur. was there. In order to prevent this, Patent Document 1 describes that the substrate unwinding chamber, the sputtering chamber, and the substrate winding chamber are adjusted to have a constant temperature.

JP 2013-72112 A JP2012-52170A

  However, in the conventional technique, excessive temperature control is performed in order to suppress the occurrence of winding wrinkles, and there is a problem that the configuration is complicated.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following forms.

  One aspect of the present invention is a method for producing a thin film laminate, in which a thin resin substrate is continuously conveyed by a conveyance roller, and a thin film is continuously laminated on the resin substrate; When laminating the thin film on the base material, a heating step of performing a heat treatment for heating to a predetermined heating temperature; a laminate of the resin base material and the thin film after the heat treatment is performed, A winding step that winds in a shape; and the winding step includes: adjusting the temperature around the laminated body to be equal to or higher than the cooling shrinkage temperature of the resin base material, and performing the winding. It is a manufacturing method. According to this method for manufacturing a thin film laminate, only by adjusting the temperature around the laminate after the heating step to be equal to or higher than the cooling shrinkage temperature of the resin base material, Generation can be suppressed. Therefore, it is possible to suppress the occurrence of winding wrinkles with a simple configuration.

  The present invention can be realized in various forms. For example, the present invention is realized in the form of a manufacturing method of a fuel cell including a manufacturing method of the thin film laminate of the above form, a thin film stack manufacturing apparatus having a configuration corresponding to each step of the manufacturing method of the thin film stack of the above form Can do.

It is explanatory drawing which shows the manufacturing apparatus of the thin film laminated body as 1st Embodiment of this invention. It is a graph for demonstrating cooling shrinkage temperature. It is explanatory drawing which shows the manufacturing apparatus of the thin film laminated body as a reference example. It is explanatory drawing which shows the manufacturing apparatus of the thin film laminated body as 2nd Embodiment.

Next, an embodiment of the present invention will be described.
A. First embodiment:
FIG. 1 is an explanatory view showing an apparatus for manufacturing a thin film laminate as a first embodiment of the present invention. This manufacturing apparatus manufactures an intermediate laminate used when manufacturing a reinforced electrolyte membrane provided in a fuel cell as a thin film laminate. This intermediate laminate is a long (or belt-like, hereinafter the same) sheet in which a back sheet is laminated on one side of the electrolyte membrane and a reinforcing membrane is laminated on the other side of the electrolyte membrane. It is.

  As shown in FIG. 1, the thin film laminate manufacturing apparatus 10 includes a transport unit 20, a heating unit 30, and a temperature control unit 40. The conveyance unit 20 is for realizing a roll-to-roll web handling apparatus, and includes two unwinding (unwinding) rolls 22 and 24, a plurality of conveying rollers 26, and a winding (winding) roll. 28.

On the first unwinding roll 22, an electrolyte membrane 50 with a back sheet in which a back sheet 54 is bonded to an electrolyte membrane 52 is wound. The electrolyte membrane 52 is a precursor polymer resin membrane of a fluorine-based electrolyte resin. For example, an electrolyte precursor resin whose polymer chain end is SO ₂ F is formed to a thickness of about 20 [μm] using an extruder. Molded. The back sheet 54 is, for example, polytetrafluoroethylene (PTFE) and has a thickness of about 100 [μm]. The electrolyte membrane 52 may be a hydrocarbon electrolyte membrane instead of the fluorine electrolyte membrane. The backsheet 54 may be replaced with other fluorine-based resins such as PFA, polyolefin resin (polyethylene, polypropylene, etc.), or polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.) instead of PTFE. ). In addition, the electrolyte membrane 50 with a back sheet is a long sheet. The back sheet 54 corresponds to the “resin substrate” described in the “Summary of the Invention” column.

  A reinforcing film 60 is wound around the second unwinding roll 24. The reinforcing membrane 60 is a long PTFE, and is a porous member that can join a softened electrolyte. The reinforcing film 60 is a long sheet having a thickness of about 5 [μm].

  The electrolyte membrane 50 with a back sheet unwound from the first unwinding roll 22 and the reinforcing film 60 unwound from the second unwinding roll 24 are conveyed toward the take-up roll 28 by a plurality of conveying rollers 26. Is done. The electrolyte film 50 with back sheet and the reinforcing film 60 are overlapped with each other so that the surface of the electrolyte film with back sheet 50 on the side of the electrolyte film 52 is in contact with the reinforcing film 60 at the position of the predetermined conveying roller 26a in the middle of the conveyance. Is done.

  The sheet 70 (hereinafter referred to as “superposed sheet”) after being superposed by the conveyance roller 26 a is sent to the heating unit 30 by the conveyance unit 20. The heating unit 30 heats the overlapping sheet 70 to the first temperature T1 or higher. The first temperature T1 is a temperature (for example, 140 [° C.]) at which the electrolyte contained in the electrolyte membrane 50 with a back sheet can be joined. The superposed sheet 70 heated to the first temperature T1 or higher by the heating unit 30 becomes an intermediate laminate 80 when the electrolyte constituting the electrolyte membrane 50 is softened and joined to the reinforcing membrane 60. In the present embodiment, the heating unit 30 includes a heating chamber, and the entire heating chamber is heated by a heater or the like. Instead of a configuration in which the entire room is heated, a configuration may be adopted in which some of the transport rollers are used as hot rollers and heated by the hot rollers.

  The intermediate laminate 80 obtained by heating by the heating unit 30 is then sent to the temperature adjustment unit 40. The temperature control unit 40 includes a temperature control chamber 42 that includes a transport roller 26 downstream of the heating unit 30 and a take-up roll 28, and the temperature inside the temperature control chamber 42 is set to a second temperature by an air conditioner (not shown). Adjust to T2. As a result, the winding of the intermediate laminate 80 by the take-up roll 28 is performed in an atmosphere at the second temperature T2 or higher. That is, the temperature around the intermediate laminate 80 is adjusted to the second temperature T2 or higher, and the intermediate laminate 80 is wound. In the present embodiment, the second temperature T2 is set to 78.5 [° C.]. The reason why the second temperature T2 is set to 78.5 [° C.] will be described next.

  The present inventor cuts a PTFE sheet (thickness 100 [μm]) used as the back sheet 54 into an appropriate test piece and fixes it to a tensile tester (for example, manufactured by Instron), and then from room temperature to 140 [° C.]. The temperature was raised to 50 ° C. and held for 5 minutes, and then cooled to 40 [° C.]. The force [N] applied to the tensile tester from temperature rise to cooling was measured, and the measurement result is shown in the graph of FIG. In the graph, a one-dot chain line is a change in temperature, and a solid line is a change in force applied. As can be seen from the graph, the applied force is almost 0 [N] until the temperature is gradually decreased from about 140 [° C.] to 78.5 [° C.], but 78.5 [° C.] is reduced. Below that point, the added force increases rapidly. As a result, the present inventor has found that the shrinkage stress is generated in the test piece after the temperature falls below 78.5 [° C.] as indicated by the thick broken line in the figure. This 78.5 [° C.] corresponds to the “cooling shrinkage temperature” described in the “Summary of the Invention” column.

  The temperature adjustment unit 40 adjusts the temperature in the temperature adjustment chamber 42 to the second temperature T2 or higher (for example, 80 [° C.]), thereby winding the intermediate laminate 80 around the winding roll 28 as a back sheet. The temperature is adjusted so that the portion 54 does not fall below the above 78.5 [° C.]. This prevents shrinkage stress from being generated in the intermediate laminate 80 during winding. The intermediate laminate 80 wound up on the take-up roll 28 in this way becomes a reinforced electrolyte membrane through subsequent processes (not shown) such as impregnation, hydrolysis, and peeling off the back sheet 54. This reinforced electrolyte membrane is used for fuel cells.

  FIG. 3 is an explanatory view showing a thin film laminate manufacturing apparatus as a reference example. The thin film laminate manufacturing apparatus 910 as a reference example is different from the thin film stack manufacturing apparatus 10 as the first embodiment in that it does not include the temperature control unit 40, and the other configurations are the same. In this configuration, the intermediate laminate 80 obtained by softening the electrolyte at a high temperature of 140 [° C.] or more by the heating unit 30 and bonding the electrolyte to the reinforcing film 60 is naturally cooled gradually, and is wound on the winding roll 28. Before reaching the temperature, it falls below the cooling shrinkage temperature of 78.5 [° C]. When the PTFE sheet as a back sheet included in the intermediate laminate 80 is less than 78.5 [° C.], a large shrinkage stress is generated, and a wrinkle CR is generated when the roll is wound around the winding roll 28. I will let you.

  On the other hand, according to the apparatus for manufacturing a thin film laminate as the first embodiment, when the intermediate laminate 80 is wound around the take-up roll 28 in a roll shape by the temperature control unit after heating by the heating unit 30. The temperature adjustment is performed so that the portion of the back sheet 54 does not fall below the second temperature T2. For this reason, generation | occurrence | production of the winding wrinkle of the intermediate | middle laminated body 80 by the cooling shrinkage | contraction of the part of the back seat | sheet 54 can be suppressed.

B. Second embodiment:
FIG. 4 is an explanatory view showing an apparatus for manufacturing a thin film laminate as a second embodiment. Compared with the thin film laminate manufacturing apparatus 10 according to the first embodiment, the thin film laminate manufacturing apparatus 210 according to the second embodiment does not include the temperature control unit 40 and the intermediate where the heating unit 30 is carried out. The laminated body 80 is different in that it is immediately wound by the winding roll 28. The intermediate laminated body 80 transported out of the heating unit 30 is gradually cooled as shown in the temperature graph TG, but the timing of reaching the second temperature T2 (= cooling shrinkage temperature) of 78.5 [° C.] is reached. The timing of winding onto the winding roll 28 is reached. Since the other configurations in the second embodiment are the same as those in the first embodiment, the same components are denoted by the same reference numerals in FIG. 4 as those in FIG.

  According to the thin film laminate manufacturing apparatus 210 as the second embodiment having such a configuration, after the heating by the heating unit 30, before the intermediate laminate 80 falls below the second temperature T <b> 2, Winding is performed. For this reason, like the first embodiment, it is possible to suppress the occurrence of winding wrinkles of the intermediate laminate 80 due to the cooling shrinkage of the portion of the back sheet 54.

C. Variation:
・ Modification 1:
In the embodiment and the modification thereof, the second temperature T2 is set to 78.5 [° C.] corresponding to the cooling shrinkage temperature. On the other hand, the cooling shrinkage temperature is not necessarily 78.5 [° C.], but the thickness of the PTFE sheet used as the back sheet 54, the thickness of other materials, and the like are changed, and the cooling shrinkage temperature of the PTFE sheet is changed. Will fluctuate. For this reason, it is good also as a structure which determines 2nd temperature T2 to the value of the cooling shrinkage temperature according to embodiment defined by material etc.

Modification 2
In the embodiment and the modification thereof, the resin base material is the back sheet 54. On the other hand, in a modification, the resin base material may be the electrolyte membrane itself.

  The present invention is not limited to the above-described embodiments, examples, and modifications, and can be realized with various configurations without departing from the spirit thereof. For example, the technical features in the embodiments, examples, and modifications corresponding to the technical features in each embodiment described in the summary section of the invention are to solve some or all of the above-described problems, or In order to achieve part or all of the above effects, replacement or combination can be performed as appropriate. Moreover, elements other than the elements described in the independent claims among the constituent elements in the above-described embodiments and modifications are additional elements and can be omitted as appropriate.

DESCRIPTION OF SYMBOLS 10 ... Manufacturing apparatus of thin film laminated body 20 ... Conveying part 22 ... 1st unwinding roll 24 ... 2nd unwinding roll 26 ... Conveying roller 28 ... Winding roll 30 ... Heating part 40 ... Temperature control part 42 ... Conditioning room DESCRIPTION OF SYMBOLS 50 ... Electrolyte membrane with a back sheet 52 ... Electrolyte membrane 54 ... Back sheet 60 ... Reinforcement membrane 70 ... Overlapping sheet 80 ... Intermediate laminated body 210 ... Manufacturing apparatus of a thin film laminated body

Claims (1)

A method for producing a thin film laminate, in which a thin resin substrate is continuously conveyed by a conveyance roller while a thin film is continuously laminated on the resin substrate,
When laminating the thin film on the resin base material, a heating step of performing a heat treatment to heat to a predetermined heating temperature;
A winding step of winding the laminate of the resin base material and the thin film into a roll after the heat treatment is performed,
With
The winding step
The manufacturing method of a thin film laminated body which adjusts the temperature around the said laminated body more than the cooling shrinkage temperature of the said resin base material, and performs the said winding.

Images