JP2006245175A - Method and device for manufacturing laminate for laminated capacitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an efficient method and a device for manufacturing a high-performance laminate for a laminated capacitor, of which the workability in manufacturing the laminated capacitor is improved, and which is stable in mounting characteristics (avoiding cracking and bending), improved in the interlayer adhesion of a PML strap, and has no contamination. <P>SOLUTION: A laminate is manufactured by laminating two or more resin thin film layers and metal thin film layers on the surface of a rotating drum in a vacuum, and peeled from the surface of the rotating drum. The curved laminate which has been peeled off is preheated in a space of a gas atmosphere. Then, the space is decompressed lower than a gas preheated atmosphere. The curved laminate is pressed and flattened at a temperature equal to or higher than a glass transition temperature of resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a multilayer capacitor laminate by cutting and peeling a laminate produced by laminating two or more resin thin film layers and metal thin film layers on the surface of a rotating drum under vacuum, and It relates to the manufacturing apparatus.

  Conventionally, multilayer capacitors for multilayer capacitors, particularly PML (polymer multilayer) capacitor elements, deposit a dielectric resin layer forming monomer on the cooling surface of a rotating drum under vacuum and cure it to form a resin thin film layer. The process of forming and vapor-depositing a metal on the resin layer, and the process of forming the metal thin film layer are sequentially repeated to produce a laminate by alternately laminating two or more layers, and the laminate is peeled off from the rotating drum. They were manufactured by appropriately cutting the dimensions and attaching external electrodes.

  According to this conventional method, the obtained multilayer structure for the PML type capacitor retains the curved surface shape of the rotating drum, and in the state of the obtained PML strap as it is, it cracks and breaks in the subsequent processes (rough cut, dicing, chip cut). This causes problems such as a deterioration in yield and instability during mounting, resulting in mounting defects.

  Therefore, in order to flatten the curved PML strap in order to prevent cracks and breakage in post-processing, a resin layer and an electrode metal that are dielectrics are alternately laminated on the cooling roll in vacuum, Each time the resin is cured so that the residual ratio of vinyl groups in the resin layer is 40% to 20% to form a laminate, the laminate is removed from the cooling roll, and heat-treated while pressing the laminate in the atmosphere. A method for manufacturing a capacitor is known (see Patent Document 1).

  However, in this method, when the laminate is heat-treated in the air while being pressed, the residual ratio of the vinyl group is 40% to 20% so that the resin layer has flexibility in order to prevent cracking of the laminate. There is a need to. Therefore, it is necessary to control the curing conditions of the resin, and it is necessary to control the heat treatment temperature in order to promote sufficient curing, and the processing accuracy is not stable. In addition, when a laminate is manufactured with a lower degree of cure in this way, the resin layer is insufficiently cured, causing the resin layer to lose the heat of metal evaporation during the metal deposition of the next layer and cause cure shrinkage. , There is a drawback that leads to defects in the resin layer.

  In addition, according to Patent Document 2 filed and published as a divisional application of the above-mentioned Patent Document 1, a resin layer and an electrode metal that are dielectrics are alternately stacked on a cooling roll in a vacuum to form a roll-shaped stack. There is also known a method for manufacturing a capacitor in which a roll laminate is removed from a cooling roll and divided into curved laminates, and the curved laminate is heat-treated while being pressurized (see Patent Document 2).

  However, this method only discloses that the bent laminate is flattened by heat treatment while applying pressure, and is insufficient to enable the flattening to be performed efficiently and effectively. is there. Moreover, it cannot be said that the adhesion between each metal layer and the resin layer is sufficient, and the obtained capacitor characteristics are not excellent.

  Furthermore, as a technology related to the film capacitor manufacturing method, when winding a metallized film on a bobbin, laminating displacement occurs due to shrinkage or wrinkling of the film near the end in the width direction of the metallized film. It is known to eliminate stacking deviations, wrinkles, bubbles, and the like that occur during the lamination of metallized films by pressing the laminated body between elastic bodies (see Patent Document 3).

  However, this method is intended to eliminate misalignment, wrinkles, bubbles, and the like during film capacitor manufacture, and does not suggest a flattening technique for a so-called curved PML capacitor.

  Conventionally, as a method for manufacturing a PML capacitor, a reactive acrylate monomer is deposited on a rotating drum via a heating evaporator to form a thin monomer layer, and the thin monomer layer is crosslinked by electron beam irradiation to form a dielectric. A film layer is formed, and a step of forming a metal-containing layer constituting the internal electrode thereon by vapor deposition is performed a plurality of times, and sandwiched between the metal layer to be a pair of internal electrodes and the internal electrode metal-containing layer. It is known that the polymer dielectric layers are sequentially laminated and external electrodes connected to the respective internal electrodes are provided on both side surfaces of the capacitor multilayer unit by soldering (see Patent Document 4).

Japanese Patent Laid-Open No. 10-32461 JP 2000-348966 A Japanese Patent Laid-Open No. 2-30109 US Pat. No. 6,092,269 (column 3, line 45 to column 5, line 13 and column 9, lines 48 to 57, and FIGS. 1, 2, 6a and 6b)

  The invention of the present application solves the problems of the prior art and effectively flattens the multilayer body for a curved multilayer capacitor, thereby improving the workability of multilayer capacitor manufacturing and stable mounting characteristics (cracking of the capacitor). Efficient manufacturing method and apparatus for high-performance multilayer capacitor-free multilayer capacitors with improved interlayer adhesion (so-called delamination → improvement of moisture resistance), which can contribute to the prevention of bending and the prevention of breakage) The purpose is to provide.

  According to another aspect of the present invention, a thick multilayer capacitor multilayer body can be easily produced by directly stacking a plurality of multilayer bodies and subjecting the different multilayer bodies to close contact with each other by pressure heat treatment. High-performance multilayer capacitors that are simple, efficient, and have strong adhesion (integration), rather than being manufactured by sequentially laminating thick laminates over a long period of time to increase capacity as in the conventional method. The manufacturing method and apparatus which can manufacture the laminated body for manufacture can be provided.

  In the first aspect, the present invention provides a laminate produced by laminating two or more resin thin film layers and metal thin film layers on the surface of the rotating drum under vacuum, and peeling the laminate from the surface of the rotating drum. The peeled laminated body is preheated in a space of a gas atmosphere, and then the inside of the space is depressurized more than the gas preheating atmosphere, and the curved laminated body has a temperature equal to or higher than the glass transition temperature of the resin. The present invention relates to a method for manufacturing a multilayer capacitor multilayer body, characterized by pressing and planarizing at a temperature.

  In a second aspect, the present invention relates to a method for producing a multilayer body for a multilayer capacitor, wherein the preheating temperature is higher than the glass transition temperature of a resin thin film layer with respect to the first aspect.

  In a third aspect, the present invention relates to a method for manufacturing a multilayer capacitor multilayer capacitor, wherein the temperature at the time of pressing and planarizing differs from the preheating temperature with respect to the first or second aspect.

  In a fourth aspect, the present invention relates to a method for producing a multilayer capacitor multilayer body, wherein the temperature at the time of pressing and flattening is higher by 5 ° C. or more than the preheating temperature with respect to the third aspect.

  In a fifth aspect, the present invention relates to any one of the first to fourth aspects, wherein the multilayer body is cooled to a temperature lower than the glass transition temperature of the resin, and then the press is released. It relates to the manufacturing method.

  In a sixth aspect, the present invention relates to any one of the first to fifth aspects, wherein after the planarization, cooling to a temperature lower than the glass transition temperature of the resin is performed by natural heat dissipation or using a cooling means. The present invention relates to a multilayer capacitor manufacturing method.

  In a seventh aspect, the present invention relates to the sixth aspect, wherein the cooling to a temperature lower than the glass transition temperature of the resin is performed in an atmosphere or a reduced pressure atmosphere containing at least a part of an inert gas. The present invention relates to a method for manufacturing a laminate.

  In an eighth aspect, the present invention relates to any one of the first to seventh aspects, wherein the gas in the space at the time of preheating, pressing and cooling the laminate is a gas containing at least a part of an inert gas. The present invention relates to a method of manufacturing a multilayer capacitor multilayer capacitor.

  In a ninth aspect, the present invention relates to any one of the first to eighth aspects, and includes a step of returning the inside of the flattened space to normal pressure after flattening, and the gas introduced at that time is atmospheric air. Alternatively, the present invention relates to a method for manufacturing a multilayer capacitor multilayer capacitor, wherein the multilayer capacitor is a gas containing at least part of an inert gas.

  In a tenth aspect, the present invention relates to any one of the seventh to ninth aspects, wherein the inert gas contains at least one of helium, nitrogen, and argon. About.

  In an eleventh aspect, the present invention relates to a method for manufacturing a multilayer capacitor multilayer body, wherein the multilayer capacitor multilayer body is simultaneously planarized with respect to any one of the first to tenth aspects.

  In a twelfth aspect, the present invention relates to the method for manufacturing a multilayer capacitor multilayer body, wherein the multilayer capacitor multilayer body to be planarized is directly stacked and pressed and planarized with respect to the eleventh aspect. .

  In a thirteenth aspect, the present invention relates to the twelfth aspect, by closely stacking a plurality of multilayer capacitor multilayer bodies to be flattened and subjecting the multilayer bodies to close integration by hot pressing and planarization. The present invention relates to a method of manufacturing a multilayer capacitor multilayer capacitor.

  In a fourteenth aspect, the present invention relates to the eleventh aspect of the multilayer capacitor multilayer body, wherein a plurality of multilayer capacitor multilayer bodies to be planarized are pressed and planarized with a spacer interposed therebetween. It relates to a manufacturing method.

  In the fifteenth aspect, the present invention relates to the fourteenth aspect, wherein a spacer is interposed for each multilayer capacitor multilayer unit, and the multilayer bodies for each unit are closely integrated. The present invention relates to a multilayer capacitor manufacturing method.

  In a sixteenth aspect, the present invention relates to a method for manufacturing a multilayer capacitor multilayer body, wherein, in the fourteenth or fifteenth aspect, a plurality of spacers form one unit.

  In a seventeenth aspect, the present invention relates to any one of the fourteenth to sixteenth aspects, and relates to a method of manufacturing a multilayer capacitor multilayer capacitor, wherein the spacer includes at least a stainless steel plate. .

  In an eighteenth aspect, the present invention relates to any one of the fourteenth to seventeenth aspects, wherein the spacer is configured to include at least a glass fiber sheet. About.

  In a nineteenth aspect, the present invention relates to a method for manufacturing a multilayer capacitor multilayer capacitor, wherein the spacer includes at least an elastic body in any one of the fourteenth to eighteenth aspects.

  In a twentieth aspect, the present invention relates to the nineteenth aspect, and relates to a method for manufacturing a multilayer capacitor multilayer capacitor, wherein the elastic body is a glass fiber-containing silicone rubber sheet.

  In a twenty-first aspect, the present invention relates to any one of the fourteenth to sixteenth aspects, and includes a spacer made of a stainless steel plate, a glass fiber sheet, a glass fiber-containing silicone rubber sheet, and a stainless steel plate when flattened. The present invention relates to a method for manufacturing a multilayer capacitor multilayer body, characterized in that a curved multilayer body is sandwiched between the stainless steel plate and the glass fiber sheet, with a spacer group consisting of a combination as one unit.

  In a twenty-second aspect, the present invention relates to any one of the first to twenty-first aspects, and after vapor-depositing a resin-forming monomer on a surface of a rotating drum under vacuum, the resin thin film layer is formed by curing. For a multilayer capacitor including a step of forming a multilayer capacitor multilayer body in which two or more resin thin film layers and metal thin film layers are laminated by sequentially repeating a process and a step of depositing a metal thin film on the resin thin film layer The present invention relates to a method for manufacturing a laminate.

  In a twenty-third aspect, the present invention relates to the twenty-second aspect, wherein the resin thin film layer includes any of a radiation curable resin, an ultraviolet curable resin, and a thermosetting resin. The present invention relates to a method for manufacturing a body.

  In a twenty-fourth aspect, the present invention relates to the twenty-second aspect, wherein the metal thin film layer is a metal selected from the group consisting of aluminum, zinc, copper, silver or nickel, and a metal oxide containing at least one of these metals The present invention also relates to a method for producing a multilayer capacitor multilayer body comprising any one of a metal compound containing at least one of the metals other than these metal oxides and an oxide of the metal compound.

  In a twenty-fifth aspect, the present invention relates to a deaeration device for maintaining the sealed space under vacuum, and depositing two or more resin thin film layers and metal thin film layers on the surface of the rotating drum in the sealed space under vacuum. A device for forming a laminate, a device for preheating the curved laminate peeled from the surface of the rotating drum in a space of a gas atmosphere, a device for depressurizing the space, and pressing the curved laminate. The present invention relates to a multilayer capacitor manufacturing apparatus including a flattening apparatus and a cooling apparatus.

In a twenty-sixth aspect, the present invention relates to the twenty-fifth aspect, 1) an airtight chamber comprising the following apparatus,
2) a press / planarization apparatus including a set of press plates or press blocks provided on both sides of a multilayer capacitor multilayer body of at least one unit;
3) Heating means and cooling medium piping provided in the press plate or press block,
4) an exhaust system connected to the hermetic chamber;
5) a vacuum pump connected to the exhaust system;
6) The present invention relates to a multilayer capacitor manufacturing apparatus including a gas introduction system connected to an airtight chamber.

  Since the present invention has the above-described configuration, it is possible to flatten the curved shape of the multilayer capacitor multilayer body over thousands of resin thin films and metal thin films, so-called PML multilayer capacitor without causing cracks. Along with improved workability and stable mountability, it is possible to produce a multilayer body for PML multilayer capacitors with excellent characteristics.

  In addition, the invention of the present application has the above-described configuration, in particular, the configuration of pressing at a temperature equal to or higher than the glass transition temperature of the resin, thereby improving interlayer adhesion (preventing delamination → improvement of moisture resistance) and eliminating defects due to peeling (moisture resistance) Improved performance). Moreover, the deterioration by thermal oxidation of the resin thin film can be eliminated by pressing in a reduced pressure atmosphere containing at least a part of the atmospheric pressure or an inert gas.

  The present invention has the above-described configuration, particularly the configuration utilizing preheating in an inert gas, so that the thermal conductivity is better than that in a reduced pressure atmosphere in flattening the so-called PML multilayer capacitor multilayer body. It is possible to prevent oxidation of the dielectric layer by oxygen.

  The present invention has the above-described configuration, particularly the preheating configuration, so that the stress on the multilayer body can be relieved during pressurization when the so-called PML multilayer capacitor multilayer body is flattened (that is, cracking prevention). ) Is possible. In particular, this effect can be further improved by setting the preheating temperature to be equal to or higher than the glass transition temperature of the resin thin film layer (the glass transition point can be measured based on the plastic transition temperature measurement method (K7121)). Be improved.

  The invention of the present application can keep the atmosphere during processing constant by having the above-described configuration, in particular, the configuration in which planarization is performed in a reduced-pressure heating atmosphere.

  The present invention has the above-described configuration, particularly a configuration in which the flattening processing environment by heating and pressing is performed under reduced pressure (pump exhaust), thereby preventing contamination of the laminate by gas generated from the laminate during pressurization and heating. it can.

  The present invention can maintain a flattened shape by having the above-described configuration, in particular, the configuration in which the laminate is cooled (to a temperature lower than the glass transition temperature of the resin) and then released from pressure (release of the press). .

  The present invention has the above-described configuration, in particular, a configuration in which a plurality of laminates are directly stacked and subjected to pressure heat treatment, whereby different laminates can be brought into close contact with each other, and there is an effect that can provide a thick laminate. be able to. Also, in order to increase the capacity and increase the capacity with the same breakdown voltage, it is possible to easily manufacture a laminate having strong adhesion (integration) rather than manufacturing a thick laminate over a long period of time.

  The present invention has the above-described configuration, particularly when a plurality of laminates are simultaneously pressed and individually handled, and each has a configuration in which a stainless steel plate, a glass fiber-containing silicone rubber sheet, and a glass fiber sheet are sandwiched. It becomes a cushion and the cracking of the laminated body by press pressure and the adhesion | attachment of laminated bodies can be suppressed.

  In the present invention, the resin thin film layer is a resin layer formed by vapor-depositing a monomer selected from the group consisting of a radiation curable resin, an ultraviolet curable resin, a thermosetting resin, and the like on the surface of the rotating drum and causing a curing reaction. .

  For curing of the monomer (polymerization reaction), ultraviolet rays, radiation, heat and the like can be used.

  When forming a resin layer, additives, such as a crosslinking accelerator, can be added suitably.

  In the present invention, the metal thin film layer is a metal selected from the group consisting of Al, Zn, Cu, Ag and Ni, a metal oxide thereof, a metal compound other than these metal oxides, or a metal thereof. An alloy containing at least one kind, an oxide of the alloy, or a compound other than the oxide of the alloy is deposited on the resin layer formed on the surface of the rotating drum.

The reduced pressure (vacuum) condition when laminating two or more resin thin film layers and metal thin film layers on the surface of the rotating drum is about 10 ⁻⁴ Pa to 10 ² Pa, more preferably about 10 ⁻³ Pa to 1.0 Pa. It is.

  Moreover, it is preferable to select the temperature conditions for the preheating within a range not lower than the glass transition temperature of the resin and causing no melt deformation of the resin layer.

  Moreover, the pressure reduction (vacuum) condition in the space when evacuating and pressing after preheating is 500 Pa (3.75 torr) or less, preferably 50 Pa (0.375 torr) or less.

  Moreover, the pressurization conditions at the time of exhausting and pressing after preheating are 1 kPa to 100 kPa, preferably 1 kPa to 50 kPa.

  One feature of the present invention is that a plurality of multilayer capacitor multilayer bodies to be planarized are pressed and planarized with a spacer interposed therebetween, and the spacer is configured to include at least a stainless steel plate. Can do.

  One feature of the spacer used in the present invention is that the spacer includes at least an elastic body, particularly a glass fiber-containing silicone rubber sheet. By adopting such a configuration, a multilayer body for pressurization and flattening can be maintained in a uniform state during pressing and flattening, avoiding damage during processing, and a multilayer body with good adhesion can be obtained. Obtainable.

  Furthermore, one feature of the spacer used in the present invention is that it includes at least a glass fiber sheet. When the above-mentioned elastic body (glass fiber-containing silicone sheet) is directly stacked on the laminate, the elastic body softened by heat may be in close contact with the laminate. In order to avoid such inconvenience, it is preferable in the present invention to insert a glass fiber sheet between the laminate and the elastic body.

  As described above, the spacer used in the present invention is composed of a combination of a spacer including a stainless steel plate, a glass fiber sheet, a glass fiber-containing silicone rubber sheet, and a stainless steel plate. Cracks of the laminate due to pressure and adhesion between the laminates can be suppressed.

[Manufacture of multilayer bodies for multilayer capacitors]
FIG. 1 shows a multilayer capacitor manufacturing apparatus according to the present embodiment. The resin layer forming monomer 9 vaporized by the resin layer forming monomer evaporation chamber 4 having the quantitative monomer supply tube 8 on the rotating drum 2 whose surface is cooled in the vacuum chamber 1 is used as the resin layer forming monomer. Direct vapor deposition through the spray nozzle 3. Subsequently, an electron beam 10 is irradiated by an electron gun 5 positioned in the rotating direction of the rotary drum 2 to cure the resin layer forming monomer thin film deposited on the drum. Further, a metal vapor evaporation source 7 is installed below the rotating drum 2, and the metal vapor is adhered and laminated on the cured resin thin film. Further, when it is desired to provide a linear continuous non-deposition portion on the metal layer on the resin, a margin forming unit 6 provided between the electron beam curing portion and the metal vapor evaporation source is used. Steam can be sprayed onto the resin layer in a pattern, and a metal vapor deposition part and a non-vapor deposition part can be obtained by an oil pattern.

  Using this apparatus, 3300 layers of resin thin films and metal thin films were alternately and alternately laminated to obtain a 2.0 mm thick laminate.

Specifically, after the vacuum chamber was brought to a pressure of 2 × 10 ⁻⁵ Torr (1.33 × 10 ⁻³ Pa), the cooled drum was rotated at a speed of 100 m / min. Next, the resin layer forming monomer 9 vaporized in the resin layer forming monomer evaporation chamber 4 is directly deposited on the drum 2 through the resin forming monomer spray nozzle 3, and then the electron beam 10 of 10 kV and 100 mA. Was irradiated onto the monomer thin film for resin layer formation.

  Next, aluminum vaporized from the resistance heating type metal vapor deposition source 7 was deposited on the resin thin film cured by the electron beam 10. The operations of vapor deposition, curing, and aluminum adhesion of the monomer vapor for resin layer formation were continuously repeated to form a laminate on which the resin thin film and the metal thin film were alternately laminated on the drum. At this time, the thickness per layer of the resin thin film was 0.6 μm, and the vapor deposition resistance value of the metal thin film was 8 to 10Ω / □. In this example, 1,6-hexanediol diacrylate was used as the monomer for forming the resin thin film layer.

  Next, the multilayer plate is divided from the drum 2 at the dividing line 28 to remove the multilayer capacitor multilayer strap, and further divided into five in the length direction to obtain five multilayer capacitor multilayers curved in an arc shape. It was. Since the diameter of the cooled drum used at this time was 1 m and the width was 65 cm, the dimension of the laminated body (laminated body for multilayer capacitor) obtained by division was 60 cm square.

  The glass transition temperature of the resin layer of the multilayer body (multilayer capacitor multilayer body) produced at this time was 60 ° C. (based on the plastic transition temperature measurement method (K7121)). The degree of cure of the resin thin film layer was 92%.

  As shown in FIG. 4, five multilayer capacitors for the multilayer capacitor were laminated via spacers. Although FIG. 3 shows a state where only one multilayer capacitor multilayer body is pressed, the arrangement of the multilayer body and spacers during pressing will be described using this. 3, the stainless steel plate 24, the glass fiber-containing silicone rubber sheet 25, the glass fiber sheet 26, the multilayer capacitor laminate 21, and the stainless steel plate 24 are laminated in this order, and the vacuum heating shown in FIG. 2 is performed. It was arranged in the vacuum heating press chamber 13 of the press device 11.

  Next, the pressing procedure will be described with reference to FIG. FIG. 2 schematically illustrates the case where the multilayer capacitor multilayer body is heated and pressed. Therefore, the spacer is not shown. FIG. 4 shows a case where a plurality of multilayer capacitors are simultaneously pressed individually with a spacer having the same configuration as that shown in FIG. FIG. 5 shows a case where a plurality of multilayer capacitor multilayer bodies are simultaneously integrated and pressed between spacers having the same configuration as that shown in FIG. In any of these cases, heating and pressing can be performed in the same manner as described with reference to FIG. 2A shows a state in which the multilayer capacitor multilayer body is set, and FIG. 2B shows a state in which an inert gas is introduced into the airtight vacuum heating press chamber 13 and then provided on the press plate 14. 2 represents a state in which the multilayer capacitor multilayer body is preheated to a temperature equal to or higher than the glass transition temperature of the resin constituting the resin layer using the heater 17, and C in FIG. 2 represents the preheated multilayer capacitor multilayer capacitor. The air-tight vacuum heating press chamber 13 containing the body is degassed and decompressed, and the multilayer capacitor multilayer body is heated while being maintained at a temperature higher than the glass transition temperature of the resin constituting the resin layer. The state to press is shown. A multilayer capacitor multilayer body is set on the press base plate 15 in the state of FIG. From this state, the vacuum heating press device 11 was stopped to the extent that the press plate 14 was lowered together with the start switch (not shown) and the bent multilayer capacitor multilayer body was not pressed. The press plate 14 has a box shape, and a vacuum heating chamber 23 can be formed with an O-ring 22 provided around the press base plate 15.

  When the vacuum heating chamber 23 was formed (that is, where the sealed space was formed), the vacuum heating chamber 23 was evacuated to 50 Pa (0.375 torr) or less by the vacuum pump 20. After evacuation for a fixed time, the electromagnetic switching valve 19 was switched, and argon gas was introduced into the vacuum heating chamber 23 through the gas inlet 18 until the atmospheric pressure was reached. In order to completely replace the inside of the vacuum heating chamber 23 with argon gas, it is preferable to repeat this operation several times.

  When the inside of the vacuum heating chamber 23 becomes atmospheric pressure with argon gas, heating in the vacuum heating chamber 23 is started by the heater 17 provided in the press plate 14 and the press base plate 15, and after reaching the preheating temperature, it is curved. The laminated body for a multilayer capacitor was kept at the above heating temperature for 30 minutes so that it was sufficiently heated. The heating temperature at this time was set to 150 ° C.

After 30 minutes, the inside of the vacuum heating chamber 23 was heated to the press temperature (160 ° C.) of the multilayer capacitor multilayer body (see B in FIG. 2). After reaching the pressing temperature, the inside of the vacuum heating chamber 23 was again evacuated by the vacuum pump 20, and at the same time, the pressing plate 14 was slowly lowered to start pressing so that the multilayer capacitor multilayer body 21 became flat. The pressing was performed for 12 hours (see C in FIG. 2). The pressing pressure at this time was 0.1 kgf / cm ² (10 × 10 ³ Pa). After the press time elapses, heating by the heater 17 is stopped, and water is passed through the press plate 14 and the cooling solvent pipe 16 provided in the press base plate 15, so that the press plate 14, the press base plate 15, the vacuum heating chamber 23, and the lamination are stacked. The capacitor laminate 21 was cooled.

  When the temperature of the multilayer capacitor multilayer body 21 reaches a temperature lower than the glass transition temperature (room temperature), the exhaust in the vacuum heating chamber 23 is stopped, and argon gas is introduced through the gas inlet 18 to obtain atmospheric pressure. Then, the multilayer capacitor multilayer body 21 was slowly released from the press later.

  When the degree of curvature of the multilayer capacitor multilayer body after the press was measured in the same manner as in the method shown in FIG. 6, no curvature of the multilayer body was observed. The results are shown in Table 1. Further, the finally obtained multilayer capacitor multilayer body was cut into thin pieces (7 mm width), and the bending stress (breaking strength) was measured with reference to a method defined in JIS6911 with a distance between fulcrums of 40 mm. The results are shown in Table 2.

  In the present invention, rather than forcing the press to flatten only by pressure, by pressing the glass thin film layer beyond the glass transition point, the flat shape is memorized, and the glass transition point from that state is stored. It is characterized in that its flattened shape is maintained by cooling it to a temperature below (finally normal temperature).

  When hot pressing is performed, for example, a high pressure of 100 kPa or more is not necessary because there is a possibility of causing cracks in the multilayer capacitor multilayer body. In particular, applying a high pressure in a state below the glass transition temperature promotes cracking of the multilayer capacitor multilayer body. In the present invention, pressing is performed at a temperature higher than the glass transition temperature of the resin thin film layer, and the press is released at a temperature lower than the glass transition temperature. Therefore, it is only necessary to keep the laminate flat during pressing. Accordingly, the pressure of the press of the present invention depends on the material constituting the multilayer body, the thickness and number of the multilayer body, the number of multilayer body units, etc., the spacer structure, and the characteristics and properties of the multilayer capacitor multilayer body obtained. In consideration of the above, an appropriate range can be selected. As a guideline, it is 1 kPa to 100 kPa, and preferably about 1 kPa to 50 kPa is sufficient.

  When a multilayer capacitor multilayer body was formed in the same manner as in Example 1 and the two multilayer capacitor multilayer structures were placed in the vacuum heating press apparatus 11, no spacer was interposed between the multilayers (see FIG. 5). ).

  When the degree of curvature of the multilayer capacitor multilayer body after the press was measured by the same method as shown in FIG. 6, the multilayer capacitor multilayer body was hardly bent. The results are shown in Table 1. Moreover, the adhesiveness between each laminated body was favorable, and could not be easily peeled off by hand. Further, the finally obtained multilayer capacitor multilayer body was cut into thin pieces (7 mm width), and the bending stress was measured with a distance between fulcrums of 40 mm with reference to a method defined in JIS6911. The results are shown in Table 2.

  A laminate was formed in the same manner as in Example 1, but in this example, tripropylene glycol diacrylate was used as the resin thin film layer. The glass transition temperature of this resin was 52 ° C., and the degree of cure of the resin thin film layer was 90%.

  The pressing conditions were a preheating temperature of 100 ° C., a pressing temperature of 110 ° C., and a 12 hour press. The press pressure was 5 kPa.

  When the degree of curvature of the multilayer capacitor multilayer body after the press was measured by the same method as shown in FIG. 6, the multilayer capacitor multilayer body was hardly bent. The results are shown in Table 1. Further, the finally obtained multilayer capacitor multilayer body was cut into thin pieces (7 mm width), and the bending stress (breaking strength) was measured with reference to a method defined in JIS6911 with a distance between fulcrums of 40 mm. The results are shown in Table 2.

Comparative Example 1
The multilayer capacitor multilayer body produced in the same manner as in Example 1 was sandwiched between metal plates, pressed at a pressure of 10 kPa at room temperature, and maintained at 160 ° C. while maintaining the pressure with a clamp. Left in it for 12 hours.

  When the multilayer capacitor multilayer body after pressing was confirmed, the multilayer capacitor multilayer body was started to be pressed at room temperature, but cracks were found in a part of the multilayer capacitor multilayer body.

  Further, the finally obtained multilayer capacitor multilayer body was cut into thin pieces (7 mm width), and the bending stress (breaking strength) was measured with reference to a method defined in JIS6911 with a distance between fulcrums of 40 mm. The results are shown in Table 2. The stress was weaker than that of Example 1 measured in the same manner. This is presumably because the resin thin film layer was oxidized and decomposed by oxygen in the atmosphere and became brittle.

Comparative Example 2
The laminate produced in the same manner as in Example 1 was pressed for 12 hours at room temperature without heating (the method without heating in Example 1). The laminated body after the press was cracked and the curvature was not eliminated.

Comparative Example 3
The laminate produced in the same manner as in Example 1 was pressed in the same manner as in Example 1 without any spacers except for the stainless steel plate (to remove the glass fiber sheet and the glass fiber-containing silicone rubber sheet). went. Some cracks were observed in the laminate after the press.

Comparative Example 4
The laminated body produced similarly to Example 1 was made into the structure of the spacer except a glass fiber sheet, and the same press as Example 1 was performed. Although the laminated body after the press was flat, the glass fiber-containing silicone rubber sheet and the laminated body adhered to each other, and when peeled off, the resin thin film layer on the surface of the laminated body was peeled off.

FIG. 1 is an explanatory diagram of a laminated body manufacturing apparatus. FIG. 2 is an explanatory diagram of a vacuum heating press apparatus. FIG. 3 is an explanatory diagram of a setting method when there is one laminate unit. FIG. 4 is an explanatory diagram of a setting method in the case where there are a plurality of laminate units and individual simultaneous pressing is performed. FIG. 5 is an explanatory diagram of a setting method in the case where there are a plurality of laminate units and the plurality are simultaneously pressed and integrated. FIG. 6 is an explanation of a method for measuring the curvature of a laminate.

Explanation of symbols

1 Vacuum chamber 2 Rotating drum (cooling drum)
DESCRIPTION OF SYMBOLS 3 Resin layer formation monomer spray nozzle 4 Resin layer formation monomer evaporation chamber 5 Electron gun 6 Margin (metal non-deposition part) formation unit 7 Metal vapor evaporation source 8 Fixed monomer supply tube 9 Vaporized resin layer formation monomer 10 Electron Wire 11 Vacuum heating press device 12 Hydraulic cylinder 13 Vacuum heating press chamber 14 Press plate 15 Press base plate 16 Cooling solvent piping 17 Heater 18 Gas inlet 19 Electromagnetic switching valve 20 Vacuum pump 21 Multilayer capacitor 22 O-ring 23 Vacuum Heating chamber 24 Stainless steel plate 25 Glass fiber-containing silicone rubber sheet 26 Glass fiber sheet 27 Laminate 28 Dividing line 29 Ruler

Claims (26)

  Under vacuum, a laminate produced by laminating two or more resin thin film layers and metal thin film layers on the surface of the rotating drum is peeled off from the surface of the rotating drum, and the peeled folded laminate is gasified. Preheating in an atmosphere space, then reducing the pressure in the space as compared with the gas preheating atmosphere, and pressing and flattening the curved laminate at a temperature equal to or higher than the glass transition temperature of the resin. A method for producing a multilayer body for a multilayer capacitor.   The method for producing a multilayer capacitor multilayer body according to claim 1, wherein the preheating temperature is higher than a glass transition temperature of the resin thin film layer.   The method for producing a multilayer body for a multilayer capacitor according to claim 1 or 2, wherein a temperature at the time of pressing and flattening is different from a preheating temperature.   The method for producing a multilayer capacitor multilayer capacitor body according to claim 3, wherein the temperature at the time of pressing and flattening is higher by 5 ° C or more than the preheating temperature.   The method for manufacturing a multilayer capacitor multilayer body according to any one of claims 1 to 4, wherein the multilayer body is cooled to a temperature lower than a glass transition temperature of the resin, and then the press is released.   The multilayer capacitor multilayer laminate according to any one of claims 1 to 5, wherein after the planarization, cooling to a temperature lower than a glass transition temperature of the resin is performed by natural heat dissipation or using a cooling means. Body manufacturing method.   The method of manufacturing a multilayer capacitor for a multilayer capacitor according to claim 6, wherein the cooling to a temperature lower than the glass transition temperature of the resin is performed in a reduced pressure atmosphere containing at least a part of air or an inert gas.   The multilayer capacitor according to any one of claims 1 to 7, wherein the gas in the space during preheating, pressing, and cooling of the multilayer body is a gas that includes at least a part of an inert gas. A manufacturing method of a layered product.   2. The method according to claim 1, further comprising a step of returning the space in which the planarization has been performed to normal pressure after the planarization, wherein the gas introduced is a gas containing at least a part of the atmosphere or an inert gas. The manufacturing method of the multilayer body for multilayer capacitors as described in any one of Claims 8.   The method for manufacturing a multilayer capacitor multilayer capacitor body according to any one of claims 7 to 9, wherein the inert gas contains at least one of helium, nitrogen, and argon.   The method for producing a multilayer capacitor multilayer body according to any one of claims 1 to 10, wherein a plurality of multilayer capacitor multilayer bodies are planarized simultaneously.   The method for manufacturing a multilayer capacitor multilayer body according to claim 11, wherein a plurality of multilayer capacitor multilayer bodies to be planarized are directly stacked and pressed and planarized.   The multilayer capacitor multilayer body according to claim 12, wherein a plurality of multilayer capacitor multilayer bodies to be planarized are directly stacked and hot-pressed / flattened to closely adhere to each other. Manufacturing method.   12. The method for manufacturing a multilayer capacitor multilayer body according to claim 11, wherein a plurality of multilayer capacitor multilayer bodies to be planarized are pressed and planarized with a spacer interposed therebetween.   15. The multilayer capacitor multilayer body according to claim 14, wherein a spacer is interposed for each multilayer capacitor multilayer body unit, and the multilayer bodies for each unit are closely integrated with each other. Production method.   The method for producing a multilayer capacitor multilayer body according to claim 14, wherein a plurality of spacers form one unit.   The method for producing a multilayer body for a multilayer capacitor according to any one of claims 14 to 16, wherein the spacer includes at least a stainless steel plate.   The method for producing a multilayer capacitor multilayer body according to any one of claims 14 to 17, wherein the spacer includes at least a glass fiber sheet.   The method for producing a multilayer body for a multilayer capacitor according to any one of claims 14 to 18, wherein the spacer includes at least an elastic body.   The method for manufacturing a multilayer capacitor multilayer body according to claim 19, wherein the elastic body is a glass fiber-containing silicone rubber sheet.   When pressing and flattening, the curved laminate is made of the stainless steel plate and a spacer group consisting of a combination of a glass fiber sheet, a glass fiber-containing silicone rubber sheet and a stainless steel plate as one unit. The method for producing a multilayer capacitor multilayer body according to any one of claims 14 to 16, wherein the multilayer capacitor body is sandwiched between a sheet-made sheet and the glass fiber sheet.   Under vacuum, after vapor-depositing a resin-forming monomer on the surface of a rotating drum, a step of forming a resin thin film layer by curing and a step of depositing a metal thin film on the resin thin film layer are sequentially repeated. The manufacturing method of the laminated body for multilayer capacitors as described in any one of Claims 1-21 including the process of forming the laminated body for multilayer capacitors which laminated | stacked two or more layers of the resin thin film layer and the metal thin film layer.   The method for producing a multilayer capacitor multilayer body according to claim 22, wherein the resin thin film layer includes any of a radiation curable resin, an ultraviolet curable resin, and a thermosetting resin.   The metal thin film layer is a metal selected from the group consisting of aluminum, zinc, copper, silver or nickel, a metal oxide containing at least one of these metals, and a metal containing at least one of the metals other than these metal oxides The method for producing a multilayer capacitor multilayer capacitor body according to claim 22, comprising any one of a compound and an oxide of the metal compound.   A deaeration device that maintains the sealed space under vacuum, a device that forms a laminate by depositing two or more resin thin film layers and metal thin film layers on the surface of the rotating drum in the sealed space under the vacuum, and the rotation Including a device for preheating the curved laminate peeled from the surface of the drum in a space of a gas atmosphere, a device for depressurizing the space, a device for pressing and flattening the curved laminate, and a cooling device. Multilayer manufacturing equipment for multilayer capacitors. 1) An airtight chamber equipped with the following devices:
2) a press / planarization apparatus including a set of press plates or press blocks provided on both sides of a multilayer capacitor multilayer body of at least one unit;
3) Heating means and cooling medium piping provided in the press plate or press block,
4) an exhaust system connected to the hermetic chamber;
5) a vacuum pump connected to the exhaust system;
6) The multilayer capacitor manufacturing apparatus for a multilayer capacitor according to claim 25, comprising a gas introduction system connected to the hermetic chamber.

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