JP3630357B2 - Manufacturing method of laminate - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a laminate comprising a resin layer and a metal thin film layer. In particular, the present invention relates to a method for manufacturing a laminate that is suitable for manufacturing a laminate by laminating a plurality of laminate units each including a resin layer and a metal thin film layer laminated in an arbitrary shape thereon.
[0002]
[Prior art]
A laminate composed of a resin layer and a metal thin film layer is widely used for magnetic recording media such as magnetic tape, packaging materials, and electronic parts.
[0003]
As a method for producing a resin layer used in such a laminate, in addition to a method of obtaining a self-supporting film by melting and forming a resin material, a solution obtained by diluting the resin material with a solvent is applied to the support. Then, a method obtained by drying and curing has been put into practical use. However, the resin layer obtained by these methods has a thickness of up to about 1 μm, and it is difficult to stably obtain a thinner resin layer. In addition, the former method requires a large amount of manufacturing equipment, and the latter method may be environmentally unfavorable depending on the solvent, and the coating film after drying often has defects.
[0004]
On the other hand, a method of forming a resin thin film on a support in vacuum has been proposed as a method in which a thin resin layer can be stably obtained and the above problem does not occur. In this method, after vaporizing a resin material in a vacuum, the resin material is deposited on a support and thinned. According to this method, a resin thin film layer free from void defects can be formed.
[0005]
On the other hand, for the formation of a metal thin film layer, a method of vacuum vapor deposition on a support that moves at high speed is suitable for mass production and has been industrially put into practical use.
[0006]
Further, mainly for electronic component applications, patterning of a metal thin film layer, that is, forming a metal thin film layer only in a specific region is performed. For example, the metal thin film layer having different potentials can be formed in the laminate by dividing the metal thin film layer into a plurality of parts with the portion where the metal thin film layer is not formed as an insulating region.
[0007]
As a method for patterning a metal thin film layer, a method called an oil margin is known. This utilizes the property that a metal thin film layer is not formed on a patterning material when a metal thin film is formed by metal vapor deposition or the like after a patterning material such as oil is previously formed thin on a support.
[0008]
Today's demands for laminates composed of a resin layer and a metal thin film layer are becoming smaller, higher performance, and lower cost. For example, by laminating multiple layers of resin layers and patterned metal thin film layers, various required characteristics can be satisfied, and specific functions can be added to reduce size and increase performance. It has been studied to achieve both. In addition, studies have been made to reduce the cost by continuously laminating a support composed of a resin layer and a metal thin film layer.
[0009]
[Problems to be solved by the invention]
However, when a laminated body is manufactured by sequentially laminating a resin layer and a metal thin film layer on a rotating support, a patterning material is applied after the resin layer is laminated and before the metal thin film layer is laminated. When trying to deposit a metal thin film layer in a specific area by attaching it to a specific shape, the laminated surface is rough, pinholes in the resin layer or metal thin film layer (destacking), destabilization of the laminated area of the metal thin film layer (for example, It has been found that problems such as protrusion from the desired laminated region and vice versa arise. Such a problem is a problem not particularly seen in the conventional method for manufacturing a two-layer laminate in which the process is completed by applying a patterning material to form a metal thin film layer. Moreover, these problems tend to become more prominent as the thickness of each layer is reduced.
[0010]
Accordingly, the object of the present invention is to provide a method for stably producing a laminate comprising a plurality of laminate units each comprising a resin layer and a metal thin film layer laminated only in a specific region. It is to achieve the above-mentioned demands for miniaturization, high performance, and low cost for the laminate.
[0011]
[Means for Solving the Problems]
In order to achieve the above object, the present invention has the following configuration.
[0012]
That is, the manufacturing method of the 1st laminated body of this invention is the following. On the support A step of laminating a resin layer by attaching a resin material, and a patterning material on the resin layer. The distance between the resin layer surface and the patterning material application device is kept substantially constant by measuring the distance between the resin layer surface and the gap measurement means provided in the patterning material application device. By making the process of attaching and the process of laminating the metal thin film layer as a unit, by repeating this a predetermined number of times on the support that circulates, Said With resin layer Said A method for producing a laminate comprising a metal thin film layer, comprising a patterning material Adhesion The The patterning material vaporized from the micropores of the patterning material applying device placed opposite to the resin layer surface is discharged and adhered to the resin layer surface. It is characterized by that.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
(Embodiment 1)
FIG. 1 is a schematic view schematically showing an example of a production apparatus for carrying out the production method of the present invention.
[0016]
A metal thin film layer forming device 14 is disposed below a cylindrical can roller 11 that rotates in the direction of the arrow in the figure at a constant angular velocity or peripheral speed, and a resin layer downstream of the can roller 11 in the rotational direction. The forming device 12 is provided with a patterning material applying device 13 on the upstream side.
[0017]
The outer peripheral surface of the can roller 11 is finished in a smooth, preferably mirror-like shape, and is preferably cooled to −20 to 40 ° C., particularly preferably −10 to 10 ° C. The rotational speed can be freely set, but is about 15 to 70 rpm, and the peripheral speed is preferably 20 to 200 m / min.
[0018]
The resin layer forming apparatus 12 evaporates or atomizes the resin material forming the resin layer and discharges it toward the surface of the can roller 11. The resin material adheres to the outer peripheral surface of the can roller 11 to form a resin layer. The resin material is not particularly limited as long as it can evaporate or atomize, and then can be deposited to form a thin film, and can be appropriately selected according to the use of the laminate, but is a reactive monomer resin. Is preferred. For example, when used for electronic component material applications, those having an acrylate resin or vinyl resin as a main component are preferred. Specifically, polyfunctional (meth) acrylate monomers and polyfunctional vinyl ether monomers are preferred. Pentadiene dimethanol diacrylate, cyclohexane dimethanol divinyl ether monomer, and the like, or monomers substituted with these hydrocarbon groups are preferred in terms of electrical characteristics. As a means for scattering the resin material, a heating means such as a heater, a method of vaporizing or atomizing using ultrasonic waves, sprays or the like is used. In particular, a method of evaporating the resin material by a heating means such as a heater is preferable.
[0019]
The deposited resin material may be cured to a desired degree of curing by the resin curing device 18 as necessary. Examples of the curing treatment include a treatment for polymerizing and / or crosslinking a resin material. As the resin curing device, for example, an electron beam irradiation device, an ultraviolet irradiation device, or a thermosetting device can be used. The degree of the curing process may be appropriately changed according to the required characteristics of the laminate to be manufactured. It is preferable to carry out a curing treatment until it reaches 75%. If the degree of cure is less than the above range, the laminate obtained by the method of the present invention is easily deformed when an external force is applied in the process of pressing the laminate or mounting it on a circuit board as an electronic component, or a metal thin film layer Will break or short circuit. On the other hand, if the degree of cure is greater than the above range, problems such as cracking when the cylindrical laminate is removed from the can roller after manufacturing the laminate, or when the laminate is pressed to obtain a flat laminate, etc. May occur. The curing degree of the present invention was determined by measuring the absorbance of C = O group and C = C group (1600 cm ^-1 ), Taking the value of the ratio of each monomer to the cured product, and defining the decrease absorbance as 1.
[0020]
In the present invention, the thickness of the resin layer is not particularly limited, but is preferably 1 μm or less, more preferably 0.7 μm or less, and particularly preferably 0.4 μm or less. In order to meet the demands for miniaturization and high performance of the laminate obtained by the method of the present invention, it is preferable that the resin layer is thin. For example, when the laminated body obtained by the manufacturing method of the present invention is used for a capacitor, the thinner the resin layer as the dielectric layer, the larger the capacitance of the capacitor in inverse proportion to its thickness. Further, even if the thickness is reduced, the effect of the present invention can be achieved. If the thickness is rather thin, the effect of the present invention is more remarkably exhibited.
[0021]
The formed resin layer is surface-treated by a resin surface treatment apparatus 19 as necessary. For example, an oxygen plasma treatment or the like can be performed to activate the resin layer surface and improve the adhesion to the metal thin film layer.
[0022]
The patterning material applying device 13 is for attaching the patterning material to the surface of the resin layer in a predetermined shape. A metal thin film is not formed at the location where the patterning material is adhered. In the present embodiment, a predetermined number of patterning materials adhere to the surface of the resin layer formed on the can roller 11 in a predetermined shape in a predetermined position in the circumferential direction.
[0023]
Thereafter, a metal thin film layer is formed by the metal thin film layer forming apparatus 14. As a method for forming the metal thin film, known means such as vapor deposition, sputtering, ion plating, and the like can be applied. In the present invention, vapor deposition, particularly electron beam vapor deposition is preferable in that a film having excellent moisture resistance can be obtained with high productivity. As a material for the metal thin film layer, aluminum, copper, zinc, nickel, a compound thereof, an oxide thereof, an oxide of these compounds, or the like can be used. Among these, aluminum is preferable in terms of adhesiveness and economy. The metal thin film layer may contain components other than those described above.
[0024]
The thickness of the metal thin film layer may be appropriately determined depending on the use of the laminate obtained by the production method of the present invention, but when used for electronic parts, it is 50 nm or less, further 10 to 50 nm, particularly 20 to 40 nm. Is preferred. The membrane resistance is preferably 15 Ω / □ or less, more preferably 10 Ω / □ or less, particularly 1 to 8 Ω / □, and most preferably 2 to 6 Ω / □.
[0025]
Also, when the laminate is used as an electronic component, particularly as a capacitor, if the (resin layer thickness) / (metal thin film layer thickness) is set to 20 or less, particularly 15 or less, the resin layer may have pinholes or the like. When the opposing metal thin film layer is electrically short-circuited, it is preferable because the metal thin film layer disappears or melts due to overcurrent, and the self-recovery function of removing defects is more favorably exhibited.
[0026]
These devices are housed in a vacuum vessel 15, and the inside is kept in a vacuum by a vacuum pump 16. The degree of vacuum in the vacuum vessel 15 is 2 × 10 ^-4 It is about Torr. Note that the inside of the vacuum device 15 may be divided into a plurality of spaces for each process, and each space may be maintained at an optimum degree of vacuum for the process.
[0027]
As described above, the first laminate manufacturing method of the present invention includes a step of laminating a resin layer by attaching a resin material, a step of depositing a patterning material on the resin layer, and laminating a metal thin film layer. Is a method of manufacturing a laminate composed of a resin layer and a metal thin film layer by repeating a predetermined number of times on a support that circulates the substrate, and the patterning material is not contacted with the resin layer surface. It is made to adhere by.
[0028]
As a means for attaching a patterning material called so-called oil margin, a method of directly attaching a liquid patterning material to the surface to be adhered by applying or transferring such as a reverse coat or a die coat is widely used. However, in the manufacturing method of a laminated body in which the resin layer and the metal thin film layer are sequentially laminated on the rotating support as in the present invention, it is possible to easily produce a laminated body having a thinner laminated thickness than before. In such a case, with such a contact type adhesion method, the external force applied to the thin film layer at the time of adhesion cannot be ignored. For example, the deformation of the resin layer or the metal thin film layer due to the external force at the time of adhesion, the accompanying breakage of each layer, the surface roughness of the laminated body, etc. will remarkably occur.
[0029]
As a method for adhering the patterning material to the resin surface in a non-contact manner, the vaporized patterning material is sprayed from the fine holes to be liquefied on the surface of the resin layer, or the liquid patterning material is jetted from the fine holes to be attached. There are methods.
[0030]
First, a method for injecting vaporized patterning material from fine holes to liquefy the resin layer surface will be described. This method has an advantage that the patterning material can be stably deposited in a predetermined range with a necessary and sufficient thickness and is structurally simple.
[0031]
FIG. 2 shows a front view of an example of a patterning material applying apparatus capable of discharging vaporized patterning material. On the front surface of the patterning material applying device 13, a predetermined number of fine holes 21 are arranged at predetermined intervals. The patterning material applying device 13 is installed so that the micro holes 21 face the adherend surface and the direction of the arrow 22 coincides with the traveling direction of the adherend surface. Then, by evaporating the vaporized patterning material from the micro holes 21, the patterning material adheres to the surface to be adhered, and is cooled and liquefied to form an adhesion film of the patterning material. Therefore, the interval and the number of the fine holes 21 in the figure correspond to the interval and the number in the case where the patterning material is attached to the surface of the resin layer in a band shape.
[0032]
FIG. 3 is a cross-sectional view as seen from the direction of arrows I-I in FIG. The fine hole 21 is connected to the nozzle 23, and the nozzle 23 is further connected to the container 24. In this example, the patterning material is supplied to the container 24 from the outside.
[0033]
The shape of the fine hole 21 of the nozzle may be round (circular) as shown in FIG. 2, but may be other shapes. In FIG. 4, the example of the shape of the micropore seen from the front of the patterning material provision apparatus was shown. For example, in addition to the round shape shown in FIG. 5A, an elliptical shape such as (b), a long hole shape such as (c), and a rectangular shape such as (d) can be used. In this case, if the maximum diameter D of the fine holes is 10 to 500 μm, particularly 30 to 100 μm, an adhesion film of a patterning material with a clear boundary can be obtained with an appropriate adhesion thickness. In addition, it is good to arrange | position so that the largest radial direction (up-down direction of the figure) of a micropore may correspond with the advancing direction of a to-be-adhered surface. Further, a plurality of fine holes having various shapes above may be provided close to each other to form one patterning material adhesion position. In this case, when a plurality of fine holes are arranged side by side along the traveling direction of the surface to be adhered, a good adhesion film of a patterning material is often formed. The shape, size, number, and arrangement of the fine holes as described above are appropriately selected according to various conditions such as the type of patterning material, the adhesion width, and the traveling speed of the adherend surface.
[0034]
The vaporized patterning material diffuses with a certain directivity when released from the fine holes. In order to stably form the deposition film of the patterning material so as to have a predetermined width and to make the boundary clear, it is preferable that the diffusion width of the released patterning material is narrow. For this reason, when the maximum diameter of the fine holes is D and the depth of the fine holes is L (see FIG. 3), L / D is preferably 1 to 10, more preferably 2 to 8, particularly 3 to 7. When L / D is smaller than the above range, the patterning material diffuses widely, and it becomes difficult to form the preferable adhesion film. On the other hand, if it is larger than the above range, the directivity of the diffusion of the patterning material is not improved so much, and the processing of the fine holes becomes difficult and the cost increases.
[0035]
When the maximum diameters D and L / D of the fine holes satisfy the above ranges at the same time, it is particularly preferable because a good patterning material can be stably obtained.
[0036]
Next, a method for supplying the patterning material to the patterning material applying apparatus will be described.
[0037]
FIG. 5 is a schematic view showing an example of a configuration in the case of supplying vaporized patterning material to the patterning material applying apparatus. The liquid patterning material 33 is stored in the reserve tank 31 and supplied to the vaporizer 32 through a pipe 35a having a valve 34a. The vaporizer 32 raises the temperature of the patterning material and vaporizes it. The patterning material in the gaseous state is sent to the container 24 of the patterning material applying apparatus 13 through the pipe 35b having the valve 34b. Thereafter, the patterning material is discharged toward the surface to be adhered through the nozzle 23 and its fine holes 21. In this case, the pipe 35b and the patterning material applying device 13 are heated and kept at a predetermined temperature so that the patterning material is not liquefied. The reserve tank 31 and the vaporizer 32 are placed outside the vacuum device 15 (see FIG. 1). According to this example, since the patterning material is vaporized in advance by the vaporization device 32 before the patterning material applying device 13, a patterning material vapor that is stable over time can be obtained.
[0038]
FIG. 6 is a schematic view showing another example of the configuration in the case where the vaporized patterning material is supplied to the patterning material applying apparatus. This example is different from the case of FIG. 5 only in that a patterning material application device 13 ′ having no container 24 is used as the patterning material application device. That is, the gaseous patterning material vaporized by the vaporizing device 32 is directly supplied to the nozzle 23 ′ of the heated patterning material applying device 13 ′. Although this example is susceptible to the pressure fluctuation of the patterning material supplied from the vaporization device 32 and has the disadvantage that the fluctuation of the discharge amount is likely to occur, the structure of the patterning material applying device is simplified and the manufacturing cost is reduced. It has the advantage that it can be lowered.
[0039]
FIG. 7 is a schematic diagram illustrating an example of a configuration in the case where the patterning material is supplied to the patterning material applying apparatus in a liquid state. The patterning material 33 in a liquid state is stored in the reserve tank 31 and supplied to the container 24 of the patterning material applying apparatus 13 through a pipe 35c having a valve 34c. The patterning material application device 13 is heated to the boiling point or more of the patterning material, and the patterning material is vaporized in the container 24. Thereafter, the patterning material is discharged toward the surface to be adhered through the nozzle 23 and its fine holes 21. In this case, the reserve tank 31 is placed outside the vacuum device 15 (see FIG. 1). The patterning material may be supplied from the reserve tank 31 at any time during the manufacturing process of the laminate, and is supplied to the container 24 before the start of the manufacturing process, and from the reserve tank 31 during the manufacturing process. The supply may be stopped. According to this example, since the patterning material application device also serves as a vaporization device, there is an advantage that the equipment is simplified. On the other hand, the amount of discharge tends to be unstable due to the influence of the pressure fluctuation of the patterning material vapor in the container 24.
[0040]
FIG. 8 is a schematic view showing another example of the configuration in the case where the patterning material is supplied in a liquid state to the patterning material applying apparatus. This example is different from the case of FIG. 7 only in that the patterning material applying device 13 ″ without the container 24 is used as the patterning material applying device. That is, the liquid patterning material is heated. The patterning material applying apparatus 13 ″ is directly supplied to the nozzle 23 ″. In this example, compared with the case of FIG. Tends to destabilize. On the other hand, there is an advantage that the structure of the patterning material applying apparatus is simplified and the manufacturing cost can be reduced.
[0041]
In FIG. 7 and FIG. 8, the liquid patterning material is supplied to the heated patterning material application apparatus. However, after the liquid patterning material is supplied to the room temperature patterning material application apparatus, the patterning material application apparatus is heated to increase the patterning material application apparatus. After the patterning material is evaporated and vaporized therein, the vapor may be released from the fine holes. However, since the vaporization of the patterning material tends to vaporize from the one having a low molecular weight, the vapor components that are vaporized may be different at the beginning and the end of the process. Therefore, it is necessary to perform patterning after vaporization is stabilized.
[0042]
The distance Dw (see FIG. 1) between the fine holes of the patterning material application device and the adherend surface (resin layer surface) is preferably 500 μm or less, more preferably 400 μm or less, and particularly preferably 300 μm or less. The lower limit is preferably 50 μm or more, more preferably 100 μm or more, and particularly preferably 200 μm or more. As described above, when the vaporized patterning material is released from the micropores, it diffuses with a certain directivity. Therefore, in order to stably form an adhesion film of the patterning material with an intended width and a clear boundary, it is preferable that the distance between the fine hole and the adherend surface is small. On the other hand, if it is too close, it becomes difficult to control the thickness of the adhesion film, the difference in the thickness of the adhesion film between the central part and the peripheral part becomes large, or the ratio of vapor that diffuses without adhering increases. To do.
[0043]
Next, a method of spraying and attaching a liquid patterning material from the fine holes will be described.
[0044]
FIG. 9 shows a front view of an example of a patterning material applying apparatus capable of injecting a liquid patterning material from a fine hole. The patterning material application device 13 is installed so that the direction of the arrow 22 coincides with the traveling direction of the adherend surface. A predetermined number of nozzle heads 41 are arranged at predetermined intervals on the front surface of the patterning material application device 13 so as to form an angle of approximately 45 ° with the arrow 22.
[0045]
FIG. 10 shows a partially enlarged view of the nozzle head 41 of FIG. 9 as viewed from the front. In the figure, the arrow 22 coincides with the direction of the arrow 22 in FIG. Fine holes 42 are arranged on the surface of the nozzle head. In the example of FIG. 10, a set of three micro holes arranged at a predetermined interval in the direction perpendicular to the arrow 22 is set as one set, and a predetermined number of them are arranged at a predetermined interval in the nozzle head. These micro holes 42 are arranged at equal intervals when viewed on a plane perpendicular to the arrow 22.
[0046]
Needless to say, the arrangement of the fine holes is not limited to that shown in FIGS.
[0047]
FIG. 11 shows a front view of another example of a patterning material applying apparatus capable of injecting a liquid patterning material from a fine hole. The patterning material application device 13 is installed so that the direction of the arrow 22 coincides with the traveling direction of the adherend surface. A nozzle head 41 ′ is disposed on the front surface of the patterning material application device 13 so as to be perpendicular to the arrow 22.
[0048]
FIG. 12 shows a partially enlarged view of the nozzle head 41 ′ of FIG. 11 as viewed from the front. In the figure, the arrow 22 coincides with the direction of the arrow 22 in FIG. Fine holes 42 are arranged on the surface of the nozzle head. In the example of FIG. 12, a set of three micro holes arranged at a predetermined interval so as to form an angle of about 45 ° with the arrow 22 is arranged as a set at a predetermined interval in the nozzle head. Yes. These micro holes 42 are arranged at equal intervals when viewed on a plane perpendicular to the arrow 22.
[0049]
FIG. 13 is a partial cross-sectional view of the micropore viewed from the direction of arrows II-II in FIG. The micropores shown in FIG. 12 have the same structure as this.
[0050]
A cylinder 48 is machined in the base plate 43 at a portion corresponding to the position of the fine hole 42, and a piezoelectric element 44 and a piston head 45 are inserted into the cylinder 48 in this order. An orifice plate 46 is disposed on the front surface of the base plate 43, and a patterning material 47 in a liquid state is filled therebetween. The diameter of the fine holes 42 can be designed as appropriate, but is about 70 μm, for example.
[0051]
The liquid patterning material is ejected from the micro holes 42 as follows. Due to the piezoelectric effect of the piezoelectric element 44, the piezoelectric element 44 is contracted, and the piston head 45 is retracted in the left direction in the figure. As a result, the front surface of the piston head 45 becomes negative pressure and the patterning material 47 is sucked into the cylinder 48 of the base plate. Thereafter, by returning the piezoelectric element to the original state, the patterning material stored in the cylinder 48 is discharged through the micro holes 42. In this method, the patterning material is discontinuously discharged as droplets. Accordingly, the patterning material adheres to the adherend surface (resin layer surface) as one dot by one discharge. The patterning material can be deposited as a continuous liquid film by adjusting the discharge amount (size of droplets) and interval of the patterning material per one time.
[0052]
In this method, the patterning material can be released by arbitrarily selecting from a plurality of fine holes arranged in the direction perpendicular to the moving direction of the surface to be adhered (resin layer surface), so the patterning material adhesion area can be changed. Becomes easier. Moreover, since each operation | movement and a stop can be performed easily, it is also easy to attach patterning material to arbitrary shapes (for example, discontinuous shape) other than strip | belt shape. Furthermore, compared to the method of discharging the vaporized patterning material described above and liquefying on the adherend surface, the directionality of the released patterning material is sharp, and the patterning material can be attached exactly as intended. Easy. In addition, since the distance between the micropores and the surface to be adhered can be increased (for example, about 500 μm), the degree of freedom in designing the apparatus is increased, and precise control such as retraction of the patterning material applying apparatus described later can be simplified. There is a possibility.
[0053]
In this method, it is preferable that the droplet particles of the discharged patterning material are further charged to form an electric field in the discharged space. When the direction of the electric field is matched with the direction of the adherend surface from the micropore, the droplet particles of the patterning material are accelerated toward the adherend surface. Therefore, the directivity of the emitted patterning material particles becomes sharp, and the distance between the micropores and the adherend surface can be further increased. In addition, the direction of the electric field can be set to other directions, and the trajectory of the droplet particles can be bent in an arbitrary direction. Thereby, the freedom degree of apparatus design can be improved. In order to charge the droplet particles, for example, electron beam irradiation, ion irradiation, plasma ionization, or the like can be used.
[0054]
In addition, the manufacturing method of the laminated body of this invention laminates | stacks a predetermined number of resin layers and the patterned metal thin film layer on the surrounding support body. Therefore, as the number of stacked layers increases, the distance between the fine holes and the adherend surface (resin layer surface) becomes gradually narrower. Therefore, in order to maintain the distance between the two in the above range, it is preferable to retract the patterning material application device 13 as the lamination proceeds.
[0055]
The patterning material applying device 13 can be retracted by, for example, an apparatus shown in FIG. That is, the actuator A52 is fixed on the movable base 51, and the patterning material applying device 13 is attached to the moving end of the actuator A52. The patterning material application device 13 is installed on the movable base 51 so as to be movable in the direction of an arrow 53 by an actuator A52. The patterning material application device 13 is provided with a gap measuring device 54 that measures the distance from the surface of the can roller 11 (in the laminate formation process, the outer peripheral surface of the laminate). As the gap measuring device 54, for example, a non-contact distance measuring device using a laser can be used. The gap measuring device 54 always measures the distance between the surface of the can roller 11 and the outer peripheral surface of the laminated body during the production of the laminated body, and the signal is sent to the gap measuring circuit 55. The gap measuring circuit 55 always checks whether the distance between the fine hole of the patterning material applying device 13 and the surface of the can roller 11 (in the laminated body formation process, the outer circumferential surface of the laminated body) is within a predetermined range. If it is determined that the distance is smaller than the predetermined range, the actuator A52 is instructed to move the patterning material applying device 13 backward by a predetermined amount, and based on this, the patterning material applying device 13 moves backward by a predetermined amount. Thus, the lamination proceeds while the distance Dw between the fine hole end of the patterning material applying device 13 and the outer peripheral surface of the laminated body on the can roller 11 is always maintained at a constant interval.
[0056]
In addition, without performing control using the gap measuring device 54 and the gap measuring circuit 55 as described above, the amount is sequentially set by a preset amount based on the stacking thickness according to the number of rotations of the can roller 11 (for example, one rotation). It may be designed to retreat. Further, the distance measurement by the gap measuring device 54 may be used together for confirmation, and fine adjustment may be added as appropriate.
[0057]
In the manufacturing method of the present invention, the patterning material is attached in a direction parallel to the adherend surface of the support in a direction perpendicular to the movement direction of the adherend surface each time the circulating support member rotates a predetermined number of times. You may make it move only a predetermined amount. If it does in this way, in the laminated body by which the resin layer and the metal thin film layer were laminated | stacked one by one, the laminated body which changed the position of the non-lamination part of a metal thin film layer for every layer can be obtained. For example, when the laminate is used as an electronic component, it is possible to easily realize the upper and lower metal thin film layers sandwiching the resin layer as electrodes having different potentials.
[0058]
For example, the apparatus shown in FIG. 14 can be used to change the deposition position of the patterning material. That is, the actuator B57 is fixed on the fixed base 56, and the movable base 51 is attached to the moving end of the actuator B57. The movable base 51 is installed on the fixed base 56 so as to be movable in the direction of the arrow 58 by an actuator B57. The rotation of the can roller 11 is monitored by a rotation detector (not shown), and a rotation signal S1 is sent to the rotation detection circuit 59 every time the can roller 11 rotates once. Each time the rotation detection circuit 59 detects the rotation signal S1 a predetermined number of times (for example, once), the rotation detection circuit 59 instructs the actuator B57 to move the movable base 51 in a predetermined direction in the direction of the arrow 58 based on this. The movable base 51, that is, the patterning material applying device 13 moves by a predetermined amount in a predetermined direction in the direction of the arrow 58. Thus, the deposition position of the patterning material is changed by a predetermined amount in the direction perpendicular to the rotational movement direction of the surface of the can roller 11 every time the can roller 11 rotates a predetermined number of times.
[0059]
As described above, the second laminate manufacturing method of the present invention includes a step of laminating a resin layer by adhering a resin material, a step of adhering a patterning material on the resin layer, and laminating a metal thin film layer. Is a method of manufacturing a laminate composed of a resin layer and a metal thin film layer by repeating a predetermined number of times on a support that circulates the unit, and after the step of laminating the metal thin film layer Then, the method has a step of removing the remaining patterning material before the step of laminating the resin layers.
[0060]
Most of the patterning material deposited by the patterning material applying apparatus is re-evaporated and disappears when the metal thin film is formed. However, some remain after the formation of the metal thin film layer, resulting in problems such as roughness of the laminated surface, pinholes in the resin layer and metal thin film layer (lamination omission), and destabilization of the laminated region of the metal thin film layer. Originally, the patterning material should have the minimum amount of adhesion so that it does not remain after the formation of the metal thin film layer, but if it is slightly insufficient, the non-laminated portion of the metal thin film layer is not formed as intended, Its control is extremely difficult. Therefore, it is necessary to remove the patterning material remaining after the metal thin film layer is laminated and before the resin layer is laminated.
[0061]
Specifically, the patterning material removing step can be realized by installing a patterning material removing device 17 between the metal thin film layer forming device 14 and the resin layer forming device 12 in the apparatus of FIG.
[0062]
The removal means for the patterning material is not particularly limited, and may be appropriately selected according to the type of the patterning material. For example, the patterning material can be removed by heating and / or decomposition. As a method of removing by heating, for example, a method using light irradiation or an electric heater can be exemplified, but the method using light irradiation has a simple apparatus and high removal performance. Here, the light includes far infrared rays and infrared rays. On the other hand, plasma irradiation, ion irradiation, electron irradiation, or the like can be used as a method of removing by decomposition. At this time, oxygen plasma, argon plasma, nitrogen plasma, or the like can be used for plasma irradiation. Among these, oxygen plasma is particularly preferable.
[0063]
The third laminate manufacturing method of the present invention includes a step of laminating a resin layer by attaching a resin material, a step of depositing a patterning material on the resin layer, and a step of laminating a metal thin film layer. A method of manufacturing a laminate comprising a resin layer and a metal thin film layer by repeating a predetermined number of times on a support that circulates as a unit, wherein the patterning material is ester oil, glycol oil, fluorine It is characterized by using at least one kind of oil selected from the group consisting of oil and hydrocarbon oil.
[0064]
Similar to the oil used for the conventional oil margin, the patterning material needs to withstand the thermal load during the formation of the metal thin film and prevent the metal thin film from being reliably formed in the adhesion region. However, the present invention is not limited to this, and needs to be able to adhere to the resin layer surface in a non-contact manner, in a vaporized state or in a liquid state. At that time, the fine holes of the patterning material applying apparatus should not be clogged. Furthermore, it must be compatible with the resin layer formed by the method of the present invention and have appropriate wettability. Furthermore, it must be easily removable by heating or decomposition in a vacuum. When such special conditions are added, the patterning material used in the present invention needs to be a specific type of oil. If a patterning material other than the above is used, problems such as roughness of the laminated surface, pinholes in the resin layer or metal thin film layer, and destabilization of the laminated region of the metal thin film layer occur.
[0065]
More preferably, the patterning material is ester oil, glycol oil, fluorine oil, particularly fluorine oil.
[0066]
The patterning material preferably has a temperature at which the vapor pressure becomes 0.1 torr within a range of 80 to 250 ° C. The patterning material that does not satisfy this condition may cause the above problem.
[0067]
The average molecular weight of the oil is preferably 200 to 3000, more preferably 300 to 3000, and particularly preferably 350 to 2000. If the average molecular weight is larger than this range, clogging of micropores is likely to occur. Conversely, if the average molecular weight is smaller than this range, margin formation may be insufficient.
[0068]
(Embodiment 2)
FIG. 15 is a schematic view schematically showing another example of a manufacturing apparatus for carrying out the manufacturing method of the present invention.
[0069]
The manufacturing apparatus of FIG. 15 uses a belt-like support body 20 that circulates between two rolls instead of the cylindrical drum of the manufacturing apparatus of FIG. Is different. The belt-like support 20 can be made of metal, resin, cloth, or a composite thereof.
[0070]
As devices other than those described above, those described in the first embodiment can be used as they are.
[0071]
In addition to the cylindrical drum shown in FIG. 1 and the belt shown in FIG. In this case, the patterning material is deposited concentrically. The method for manufacturing a laminate of the present invention includes a step of laminating a resin layer by attaching a resin material, a step of depositing a patterning material on the resin layer, and a step of laminating a metal thin film layer as a unit. By repeating this a predetermined number of times on a support that circulates, a laminate composed of a resin layer and a metal thin film layer is produced. Either before or during or during the production process, either a resin layer or a metal thin film layer is produced. There may be a step of continuously laminating only the metal thin film layer or only the resin layer without laminating them. Moreover, you may have the process of laminating | stacking the other layer which is different from either the resin layer of this invention, or the metal thin film layer in the middle of the manufacturing process of a laminated body.
[0072]
【Example】
(Example 1)
A capacitor laminate was manufactured using the apparatus shown in FIG.
[0073]
Inside the vacuum vessel 15 is 2 × 10 ^-4 Torr, the outer surface of the can roller 11 is maintained at 5 ° C.
[0074]
First, a portion to be a protective layer (a layer made only of a resin layer) was laminated on the outer peripheral surface of the can roller 11. Dicyclopentadiene dimethanol diacrylate was used as the protective layer material, which was vaporized and deposited on the outer peripheral surface of the can roller 11 from the resin layer forming apparatus 12. Next, an ultraviolet curing device was used as the resin curing device 18, and the protective layer material deposited as described above was polymerized and cured. This operation was repeated by rotating the can roller 11 to form a protective layer having a thickness of 15 μm on the outer peripheral surface of the can roller 11.
Subsequently, the part used as a reinforcement layer was laminated | stacked. The resin layer material used was the same as the above protective layer material, which was vaporized and deposited on the protective layer from the resin layer forming apparatus 12. Next, an ultraviolet curing device was used as the resin curing device 18, and the resin layer material deposited as described above was polymerized and cured until the degree of curing reached 70%. The resin layer formed at this time is 0.6 μm. Thereafter, the surface was subjected to oxygen plasma treatment by a resin surface treatment device 19. Next, a patterning material was adhered by the patterning material applying device 13. Fluorine oil was used as a patterning material. The temperature at which the vapor pressure of the patterning material becomes 0.1 torr is 100 ° C. The average molecular weight of the oil is 1500. The patterning material was supplied by the method shown in FIG. 5 after being previously vaporized by the vaporizer 32 and then supplied to the patterning material applying apparatus maintained at 170 ° C. The apparatus shown in FIGS. 2 and 3 was used as a patterning material applying apparatus, and a gaseous patterning material was ejected from a round nozzle having a diameter of 50 μm and a depth of 300 μm to be attached in a band shape having a width of 150 μm. Next, aluminum was vapor-deposited from the metal thin film forming apparatus 14. The deposition thickness is 300 Å and the film resistance is 3Ω / □. After that, the remaining patterning material was removed by heating with a far infrared heater and plasma discharge treatment by the patterning material removing device 17. The above operation was repeated 500 times by rotating the can roller 11 to form a reinforcing layer having a total thickness of 315 μm. Note that the movement of the patterning material application apparatus in the direction perpendicular to the movement direction of the outer peripheral surface of the can roller 11 (in the direction of the arrow 58 in FIG. 14) was performed in the following pattern using the apparatus shown in FIG. That is, when the can roller 11 rotates once, it moves 60 μm in a certain direction, moves 60 μm in the same direction after the next one rotation, moves 60 μm in the reverse direction after the next one rotation, and moves in the same direction after the next one rotation 60 μm. This movement was repeated below, with the movement of moving as one cycle. In addition, the distance Dw between the fine hole of the patterning material applying apparatus and the surface to be adhered was controlled so as to always maintain 250 to 300 μm.
[0075]
Next, a capacitance generating portion (element layer portion) as a capacitor was laminated. As the resin layer (dielectric layer) material, the same material as the resin layer of the protective layer and the reinforcing layer was used, and this was vaporized and deposited on the reinforcing layer. Next, using the ultraviolet curing device as the resin curing device 18, the dielectric layer material deposited as described above was polymerized and cured until the curing degree reached 70%. The dielectric layer formed at this time is 0.4 μm. Thereafter, the surface was subjected to oxygen plasma treatment by a resin surface treatment device 19. Next, a patterning material was adhered by the patterning material applying device 13. Fluorine oil was used as a patterning material. The temperature at which the vapor pressure of the patterning material becomes 0.1 torr is 130 ° C. The average molecular weight of the oil is 1800. The patterning material was supplied by the method shown in FIG. 5 after being previously vaporized by the vaporizer 32 and then supplied to the patterning material applying apparatus maintained at 170 ° C. The apparatus shown in FIGS. 2 and 3 was used as a patterning material applying apparatus, and a gaseous patterning material was ejected from a round nozzle having a diameter of 50 μm and a depth of 300 μm to be attached in a band shape having a width of 150 μm. Next, aluminum was vapor-deposited from the metal thin film forming apparatus 14. The deposition thickness is 300 Å and the film resistance is 3Ω / □. Thereafter, the remaining patterning material was removed by heating with an infrared heater and plasma discharge treatment by the patterning material removing device 17. The above operation was repeated about 2000 times by rotating the can roller 11 to form an element layer portion having a total thickness of 860 μm. Note that the movement of the patterning material application apparatus in the direction perpendicular to the movement direction of the outer peripheral surface of the can roller 11 (in the direction of the arrow 58 in FIG. 14) was performed in the following pattern using the apparatus shown in FIG. . That is, when the can roller 11 makes one rotation, it moves 1000 μm in a certain direction, moves 940 μm in the reverse direction after the next one rotation, moves 1000 μm in the reverse direction after the next one rotation, and 940 μm in the reverse direction after the next one rotation. Moves, moves 1000 μm in the reverse direction after the next rotation, moves 1060 μm in the reverse direction after the next rotation, moves 1000 μm in the reverse direction after the next rotation, and moves 1060 μm in the reverse direction after the next rotation This movement was repeated in the following. In addition, the distance Dw between the fine hole of the patterning material applying apparatus and the surface to be adhered was controlled so as to always maintain 250 to 300 μm.
[0076]
Next, a reinforcing layer portion having a thickness of 315 μm was formed on the surface of the element layer portion. The forming method was exactly the same as the forming method of the reinforcing layer.
[0077]
Finally, a protective layer portion having a thickness of 15 μm was formed on the reinforcing layer surface. The formation method was exactly the same as the formation method of the protective layer.
[0078]
Next, the obtained cylindrical laminate was removed by dividing it into eight in the radial direction (cut every 45 °) and pressed under heating to obtain a flat laminate mother element 60 as shown in FIG. . In the figure, an arrow 61 indicates the moving direction of the outer peripheral surface of the can roller 11. This was cut at a cut surface 65a, and brass was metal sprayed on the cut surface to form an external electrode. Further, a conductive paste in which copper, Ni, silver alloy or the like was dispersed in a thermosetting phenolic resin was applied to the metal sprayed surface, heat-cured, and further, molten solder plating was applied to the resin surface. Then, it cut | disconnected in the location corresponding to the cut surface 65b of FIG. 16, was immersed in the silane coupling agent solution, and coated the outer surface, and the chip capacitor 70 as shown in FIG. 17 was obtained.
[0079]
The obtained chip capacitor had a thickness in the stacking direction of about 1.5 mm, a depth of about 1.6 mm, a width (direction between both external electrodes) of about 3.2 mm, and a capacitance of 0.47 μF despite being small. The withstand voltage was 50V. No short circuit between the metal thin film layers or breakage of the metal thin film layer was observed. When the chip capacitor was disassembled and the surface roughness Ra of the dielectric layer surface and the metal thin film layer surface of the element layer portion was measured, it was 0.005 μm and 0.005 μm in order, and smooth and coarse protrusions were not found. The degree of cure of the resin layer (dielectric layer) of the element layer, the resin layer of the reinforcing layer, and the protective layer was 95%, 95%, and 90%, respectively. The width of the non-laminated portion of the metal thin film layer of the element layer portion 62 is 150 μm, the width of the non-laminated portion of the metal thin film layer of the reinforcing layers 63a and 63b is 150 μm, and the margin width as originally designed is a constant width. Formed.
[0080]
【The invention's effect】
According to the method for producing a laminate of the present invention, even if the laminate thickness is reduced, there are problems such as roughness of the laminate surface, pinholes in the resin layer and metal thin film layer, and destabilization of the laminate region of the metal thin film layer. Can be obtained. Therefore, the laminate obtained by the production method of the present invention has a wide range of uses such as magnetic recording media such as magnetic tape, packaging materials, electronic parts, etc. that require miniaturization, high performance, and low cost. Can be used for
[Brief description of the drawings]
FIG. 1 is a schematic view schematically showing an example of a production apparatus for carrying out a production method of the present invention.
FIG. 2 is a front view of an example of a patterning material applying apparatus.
3 is a cross-sectional view as seen from the direction of arrows I-I in FIG. 2;
FIG. 4 is a schematic view showing an example of the shape of a microscopic hole as viewed from the front of the patterning material applying apparatus.
FIG. 5 is a schematic view showing an example of a configuration in the case where a vaporized patterning material is supplied to a patterning material applying apparatus.
FIG. 6 is a schematic view showing another example of a configuration in the case where a vaporized patterning material is supplied to the patterning material applying apparatus.
FIG. 7 is a schematic view showing an example of a configuration when a patterning material is supplied in a liquid state to the patterning material applying apparatus.
FIG. 8 is a schematic view showing another example of the configuration in the case where the patterning material is supplied to the patterning material applying apparatus in a liquid state.
FIG. 9 is a front view of another example of a patterning material applying apparatus.
10 is a partially enlarged view of the nozzle head of the patterning material application apparatus of FIG. 9 as viewed from the front.
FIG. 11 is a front view of still another example of a patterning material applying apparatus.
12 is a partially enlarged view of the nozzle head of the patterning material application apparatus of FIG. 11 as viewed from the front.
13 is a partial cross-sectional view of a microscopic hole as viewed from the direction of arrows II-II in FIG.
FIG. 14 is a schematic view showing an example of an apparatus for moving the patterning material applying apparatus backward and moving the patterning material deposition position.
FIG. 15 is a schematic view schematically showing another example of a production apparatus for carrying out the production method of the present invention.
FIG. 16 is a partial perspective view showing an example of a schematic configuration of a flat laminated mother element.
FIG. 17 is a perspective view showing a schematic configuration of a chip capacitor.
[Explanation of symbols]
11 Can Roller
12 Resin layer forming device
13, 13 ', 13 "patterning material applying device
14 Metal thin film layer forming device
15 Vacuum container
16 Vacuum pump
17 Patterning material removal device
18 Resin curing device
19 Resin surface treatment equipment
20 Belt-like support
21, 21a, 21b, 21c, 21d
22 Support movement direction
23, 23 ', 23 "nozzle
24 containers
31 Reserve tank
32 Vaporizer
33 Patterning material
34a, 34b, 34c Valve
35a, 35b, 35c Piping
41, 41 'Nozzle head
42 micropores
43 Base plate
44 Piezoelectric elements
45 Piston head
46 Orifice plate
47 Patterning material
48 cylinders
51 Movable base
52 Actuator A
53 Arrow (moving direction)
54 Gap measuring device
55 Gap measurement circuit
56 fixed base
57 Actuator B
58 Arrow (movement direction)
59 Rotation detection circuit
60 Laminated body element
61 arrow
62 Element layer
63a, 63b reinforcement layer
64a, 64b protective layer
65a, 65b cut surface
70 chip capacitor
71a, 71b External electrode

Claims (11)

A step of laminating a resin layer by adhering a resin material on a support, and measuring a distance between the patterning material on the resin layer and a surface of the resin layer by a gap measuring unit provided in a patterning material applying apparatus. And the step of adhering while keeping the distance between the resin layer surface and the patterning material application device substantially constant and the step of laminating the metal thin film layer as a unit, on the support that goes around this A method for producing a laminate comprising the resin layer and the metal thin film layer by repeating a predetermined number of times,
The patterning material is attached by discharging the patterning material vaporized from the micropores of the patterning material application device disposed opposite to the resin layer surface and attaching the patterning material to the resin layer surface. A method for manufacturing a laminate. The method for producing a laminate according to claim 1, wherein the maximum diameter D of the fine holes is 10 μm to 500 μm. The method for producing a laminate according to claim 1, wherein L / D is 1 to 10, where D is the maximum diameter of the micropores and L is the depth of the micropores. The laminate according to claim 1, wherein D is 10 μm to 500 μm and L / D is 1 to 10 where D is the maximum diameter of the micropores and L is the depth of the micropores. Body manufacturing method. The method for producing a laminate according to claim 1, wherein the distance between the surface of the resin layer to which the patterning material is adhered and the fine holes is maintained at 50 to 500 µm. The method for manufacturing a laminate according to claim 1, wherein the deposition position of the patterning material is changed each time the support rotates a predetermined number of times. The method for producing a laminate according to claim 1, wherein the patterning material is at least one oil selected from the group consisting of ester oils and fluorine oils. The method for producing a laminate according to claim 7, wherein the temperature at which the vapor pressure of the patterning material is 0.1 torr is in the range of 80 to 250 ° C. The average molecular weight of oil is 200-3000, The manufacturing method of the laminated body of Claim 7 characterized by the above-mentioned. The method for manufacturing a laminate according to claim 1, wherein the gap measuring means is a non-contact distance measuring device. The method for manufacturing a laminate according to claim 10, wherein the non-contact distance measuring device is a laser sensor.

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