JP3461751B2 - Laminated body manufacturing method and laminated body manufacturing apparatus - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a manufacturing method and a manufacturing apparatus for a laminate including a resin layer and a metal thin film layer. More specifically, the present invention relates to a method and apparatus for manufacturing a laminated body by alternately laminating a resin layer and a metal thin film layer on an orbiting support.

[0002]

2. Description of the Related Art A resin layer and a metal thin film layer are alternately laminated by repeating a process of laminating a resin layer and a process of laminating a metal thin film layer as one unit on an orbiting support. A method for producing a laminate is disclosed in, for example, Japanese Patent Laid-Open No.
It is known in Japanese Patent Application Laid-Open No. 0-237623 (Japanese Patent Application No. 9-45591).

An example of a method for manufacturing a laminate of a resin layer and a metal thin film layer will be described with reference to the drawings.

FIG. 7 is a schematic cross-sectional view of an example of a manufacturing apparatus for carrying out a conventional method for manufacturing a laminated body.

In FIG. 7, 915 is a vacuum tank, 916 is a vacuum pump for maintaining the inside of the vacuum tank 915 at a predetermined vacuum degree, and 911 is a cylindrical shape installed in the vacuum tank 915 and rotating in the direction of the arrow in the drawing. Can roller, 912 is a resin layer forming device, 913 is a patterning material applying device, 91
4 is a metal thin film forming device, 917 is a patterning material removing device, 918 is a resin curing device, 919 is a surface treatment device,
920a and 920b are partition walls for distinguishing the metal thin film formation region from other regions, 922 is an opening provided in the partition walls 920a and 920b, and 923 is an opening for preventing the metal thin film from being formed except when necessary. A shielding plate for closing 922.

The resin layer forming device 912 evaporates or atomizes the resin material for forming the resin layer and discharges it toward the surface of the can roller 911. Can roller 911
Is cooled to a predetermined temperature, the resin material is cooled and deposited in a film form on the outer peripheral surface of the can roller 911.

The deposited resin material is irradiated with an electron beam, an ultraviolet ray, or the like by a resin curing device 918 as necessary to be cured to a desired hardness.

Next, the resin layer thus formed is subjected to oxygen plasma treatment or the like by a resin surface treatment device 919, if necessary, to activate the surface of the resin layer.

The patterning material applying device 913 is a device for patterning the metal thin film layer into a predetermined shape by a method called an oil margin. If the metal thin film layer is formed by vapor deposition or the like after thinly forming the patterning material on the resin layer, the metal thin film layer is not formed on the patterning material. The metal thin film layer formed in this manner is formed in a state where the patterning portion is omitted, and a metal thin film layer having a desired pattern can be formed. The patterning material is vaporized in the patterning material application device 913 and discharged from the pores formed at predetermined positions toward the outer peripheral surface of the can roller 911.
As a result, the patterning material is thinly applied in advance on the surface on which the metal thin film layer is formed.

After that, a metal thin film forming apparatus 914 forms a metal thin film layer by vapor deposition or the like.

Thereafter, the patterning material removing device 917
This removes the excess patterning material.

According to the above manufacturing apparatus 900, the shielding plate 9
In the state where 23 is retracted, the revolving can roller 91
1, a resin layer formed by the resin layer forming device 912 and a metal thin film layer formed by the metal thin film forming device 914 were alternately laminated on the outer peripheral surface of No. 1, and the shielding plate 923 shielded the opening 922. In this state, a laminate in which resin layers are continuously laminated by the resin layer forming device 912 is manufactured on the outer peripheral surface of the revolving can roller 911. Further, by moving the patterning material application device 913 in a direction parallel to the rotation axis of the can roller 911 in synchronization with the rotation of the can roller 911, it is possible to form metal thin film layers having different pattern positions.

In this way, by forming a multi-layer laminate consisting of the metal thin film layer and the resin layer on the outer peripheral surface of the can roller 911, and then removing the laminate from the can roller 911 and pressing the flat plate, for example, A laminated body element 930 as shown in FIG. 8 can be obtained. In FIG.
931 is a metal thin film layer, 932 is a resin layer, 933 is a pattern position, and an arrow 938 coincides with the traveling direction of the outer peripheral surface of the can roller 911. Laminated body element 930 of FIG.
On the can roller 911, a layer 936a and a layer 935.
It is manufactured by laminating a, layer 934, layer 935b, and layer 936b in this order. Here, the layers 936a and 936b
Is a layer in which the shielding plate 923 is closed and only the resin layers are continuously laminated. The layer 934 and the layers 935a and 935b are layers in which the metal thin film layers and the resin layers are alternately laminated while retracting the shielding plate 923. Is. Further, the layer 934 is formed by the can roller 9
The pattern position is changed every rotation in synchronization with the rotation of 11, and the layers are stacked.

By cutting the laminated body mother element 930 along the cut surfaces 939a and 939b and forming external electrodes on the cut surfaces 939a, a large number of chip capacitors 940 as shown in FIG. 9 can be obtained. In FIG.
941a and 941b are external electrodes formed by being electrically connected to the metal thin film layer 931.

[0015]

In the above, when manufacturing the laminated body mother element 930 shown in FIG.
The shield plate 923 is closed when the layers 36a are stacked, and the shield plate 923 is retracted when the layer 935a is stacked. The layer 935a, the layer 934, and the layer 935b are sequentially stacked with the shield plate 923 retracted, and the shield plate 923 needs to be closed again when stacking of the layer 936b is started. Such opening / closing operation of the shielding plate 923 is generally performed while rotating the can roller 911.

The opening and closing of the shield plate 923 at this time is performed by moving the shield plate 923 in a direction substantially parallel to the moving direction of the outer peripheral surface of the can roller 911 as shown in FIG. Therefore, depending on the relationship between the moving direction and moving speed of the shielding plate 923 and the moving direction and moving speed of the outer peripheral surface of the can roller 911, a metal thin film layer (a stack of metal thin film layers) formed during the opening and closing process of the shielding plate 923 is formed. There has been a problem that the start portion and the end portion of lamination are not formed to have a predetermined thickness, or the thickness is not uniform.

For example, in the apparatus shown in FIG. 7, the shield plate 923
When the closing operation is performed from the standby state, the shield plate 923
If the moving speed of the outer peripheral surface of the can roller 911 is substantially the same as the moving speed of the outer peripheral surface of the can roller 911, the metal thin film layer formed during the movement of the shielding plate 923 has an opening width in the moving direction of the outer peripheral surface of the can roller 911 of the opening 922. Becomes narrower and the thickness becomes thinner, and as a result, the opening width becomes narrower. As a result, the amount of vapor deposition becomes unstable and the thickness unevenness increases. Moreover, such a metal thin film region is formed with a certain spread in the outer peripheral direction of the can roller 911.

When a metal thin film region having a thickness smaller than a predetermined thickness and large thickness unevenness is present in the laminated body of the laminated body mother element 930, the adhesion at that portion is poor and delamination occurs.
The delamination causes, for example, oxidation of the metal thin film layer, which deteriorates the quality of electronic components and the like finally obtained and reduces the yield.

From the viewpoint of quality control of electronic parts, it is necessary to discard the portion including the unstable metal thin film region formed when the shield plate 923 is opened and closed in the laminated body mother element. As a result, the amount of raw materials has become large and the yield has deteriorated.

The present invention solves the above-mentioned conventional problems,
By suppressing the occurrence of unstable metal thin film regions formed in the laminate mother element due to the movement of the shielding plate or by reducing the size thereof, waste of raw materials is reduced and productivity is improved. It is an object of the present invention to provide a method of manufacturing a laminated body and a manufacturing apparatus capable of manufacturing the same.

[0021]

The present invention has the following constitution in order to achieve the above object.

That is, the method for manufacturing a laminated body according to the present invention includes a step of laminating a resin layer and a step of laminating a metal thin film layer by depositing a metal material by a vacuum process.
When producing a laminate including a resin layer and a metal thin film layer on the support by performing these on a support that circulates, the start or end of the lamination of the metal thin film layer is the metal material supply source and the support. line doctor method for manufacturing a laminated body carried out by moving the installed shielding plate, the movement of the shield plate in the moving direction substantially perpendicular direction of the shielding plate and the opposite sides of the support between the , At the start and end of the lamination of the metal thin film layers
With, the start timing of the movement of the shielding plate and the support
It is characterized in that it is synchronized with the rotational position of .

A laminated body manufacturing apparatus according to the present invention includes a vacuum chamber, a supporting body installed in the vacuum chamber, and a resin layer forming apparatus for laminating a resin layer on the supporting body. A metal thin film forming device for laminating a metal thin film layer on the support by a vacuum process, and a device for producing a laminate comprising a resin layer and a metal thin film layer on the support, A shield plate for preventing stacking of metal thin film layers is provided between the metal thin film forming apparatus and the support so as to be movable in a direction substantially perpendicular to the moving direction of the surface of the support facing the shield plate. And the lamination of the metal thin film layers
At the start and end of the
And the rotational position of the support is synchronized .

According to each of the above-mentioned configurations of the present invention, since the shield plate is moved in a direction substantially perpendicular to the moving direction of the support, the thickness of the metal thin film layer is small at the start and end of the lamination of the metal thin film layers. In addition, it is possible to suppress the occurrence of an unstable region in which the thickness unevenness is large. As a result, productivity is improved, and a high-quality laminate is obtained.

[0025]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below with reference to the drawings.

(Embodiment 1) FIG. 1 is a schematic sectional view showing an example of a laminate manufacturing apparatus for carrying out the laminate manufacturing method of the present invention.

In FIG. 1, 115 is a vacuum tank, 116 is a vacuum pump for maintaining the inside of the vacuum tank 115 at a predetermined degree of vacuum, and 111 is installed in the vacuum tank 115 and rotates in the direction of arrow 111a in the figure. Cylindrical can roller, 1
12 is a resin layer forming device, 113 is a patterning material applying device, 114 is a metal thin film forming device (metal material supply source),
Reference numeral 117 is a patterning material removing device, 118 is a resin curing device, 119 is a surface treatment device, 120 is a partition wall for distinguishing a metal thin film formation region from other regions, and 121 is a partition wall 12.
0 is an opening provided at 0, 130 is a shield plate for closing the opening 121 to prevent the metal thin film from being formed except when necessary, and 131 is an opening provided at the shield plate 130. For convenience of description, as shown in the figure, the horizontal direction of the paper surface (horizontal direction) is the X axis, the vertical direction of the paper surface (vertical direction) is the Y axis, and the vertical direction (the rotational axis direction of the can roller 111) is the paper surface. The Z axis is used.

FIG. 2 is a perspective view showing a schematic configuration of the shield plate 130, the metal thin film forming apparatus 114, and the opening 121 of FIG. In FIG. 2, the partition wall 120 and the opening 121 thereof are drawn by a chain double-dashed line so that the structure of the shielding plate 130 is clear. 3 is a schematic configuration diagram of the shielding plate shown in FIG. 2, where (A) is a plan view and (B) is a side view.

As shown in FIG. 2, the partition wall 120 is formed of metal vapor or metal particles 114 from the metal thin film forming apparatus 114.
It has an opening 121 for passing a and adhering it to a can roller (not shown) with a predetermined width.

On the other hand, the shielding plate 130, as shown in FIG. 3, is made of a substantially rectangular plate-shaped member and has an opening 131 in the center thereof.
Is formed and has shield regions 132a and 132b on both sides thereof. Each of the shielding regions 132a and 132b has a size that can completely cover the opening 121 of the partition wall 120.

The shielding plate 130, as shown in FIG.
It is movably installed in the direction of an arrow 139 parallel to the axis.
When the opening 131 of the shielding plate 130 is arranged so as to coincide with the opening 121 of the partition wall 120, metal vapor or metal particles 114a from the metal thin film forming apparatus 114 can be attached to the surface of the can roller to form a metal thin film. . Further, when one of the shield regions 132a and 132b of the shield plate 130 is arranged so as to coincide with the opening 121 of the partition wall 120, the metal vapor or the metal particles 114a from the metal thin film forming apparatus 114 is shielded by the shield region 132a or 132b. Thus, the formation of the metal thin film layer can be prevented.

That is, in this embodiment, when the metal thin film layer is not laminated, the opening 121 is formed in the shielding region 132.
When shielding is performed with a or 132b and the stacking of the metal thin film layers is started, the shield plate 130 is moved in the moving direction 139 so that the opening 121 is aligned with the opening 131 of the shield plate. Further, when the lamination of the metal thin film layers is finished, the shield plate 130 is moved in the moving direction 139 to shield the opening 121 with the shield region 132a or 132b.

In FIG. 4, using the apparatus shown in FIGS. 1 to 3, the opening 121 is shielded by the shielding region 132a and resin layers are continuously laminated, and then the shielding plate 130 is moved in the positive direction of the Z-axis. It is the figure which showed typically the state of the lamination | stacking start part of the metal thin film layer on a can roller at the time of matching the opening 131 with the opening 121 and starting the lamination of a metal thin film layer. FIG. 4A is a perspective view showing a thin film laminate formed on the can roller, and FIG. 4B is a development view of the thin film laminate of FIG. In the figure, 111a indicates the rotating direction of the can roller 111, and 111b indicates the moving direction of the outer peripheral surface of the can roller 111 at this time. Reference numeral 140 is a continuous layered portion including only resin layers, 141 is an outermost resin layer, 142 is a metal thin film layer laminated on the resin layer 141, and 143 is a layering start portion of the metal thin film layer 142.

As shown in the figure, since the shielding plate is moved in the positive direction of the Z axis, the end 144 of the resin continuous laminating section 140 is moved.
When the stacking of the metal thin film layers is started from the a side and the opening 131 of the shielding plate 130 completely coincides with the opening 121 (that is,
When the opening 121 is fully opened), the stacking of the metal thin film layers near the end 144b is started. During this time, the can roller 11
When the rotation speed of No. 1 and the moving speed of the shielding plate 130 are both kept constant, the stacking start portion 143 of the metal thin film layer 142 is formed.
Is substantially linear on the development view (FIG. 4 (B)).

The openings 121 and 131 each have a rectangular shape and are arranged so that the corresponding sides are substantially parallel to each other, and the shield plate 130 is arranged in the moving direction of the outer peripheral surface of the can roller. Since it is moved in the right-angled direction (Z-axis direction), the width in the moving direction (111b direction) of the outer peripheral surface of the can roller in the region where stacking is newly started is always the width in the moving direction of the outer peripheral surface of the can rollers of the openings 121 and 131. Matches Therefore, the metal thin film layer 142 having a substantially predetermined thickness is formed from the stacking start portion 143. That is, according to the present embodiment, in the stacking start portion 143, an unstable metal thin film layer region having a small thickness or large thickness unevenness as in the conventional case is hardly formed, or even if it is formed, The width is very small.

Further, when an alternating laminated body composed of a metal thin film layer and a resin layer is laminated, the lamination of the metal thin film layers is completed, and a continuous layer composed of only the resin layer is laminated again, the shielding plate 130
Is preferably further moved in the same direction as when the lamination of the metal thin film layer is started to shield the opening 121. That is, in the above example, the shielding plate 130 is moved in the positive direction of the Z axis to shield the opening 121 with the shielding region 132b. FIG. 5 shows the state of the lamination end portion of the metal thin film layer at this time. Figure 5 (A)
[Fig. 5] is a perspective view showing a thin film laminate formed on a can roller, and Fig. 5B is a development view of the thin film laminate of Fig. 5A. In the figure, 140 'is an alternating laminated portion of a resin layer and a metal thin film layer, 141 is an outermost resin layer, 142 is a metal thin film layer, and 143' is a lamination end portion of the metal thin film layer 142.

As shown in the figure, since the shield plate is moved in the positive direction of the Z-axis, the end portion 144a of the alternate laminated portion 140 'is formed.
When the stacking of the metal thin film layers is completed from the side and the opening 121 is completely shielded, the stacking of the metal thin film layers near the end portion 144b is completed. During this time, if the rotational speed of the can roller 111 and the moving speed of the shielding plate 130 are both kept constant, the stacking end portion 143 ′ of the metal thin film layer 142 becomes substantially linear on the developed view (FIG. 5B). .

In this way, by making the moving direction of the shielding plate the same at the time of forming the metal thin film and at the time of forming the metal thin film, the stacking start portion 143 and the stacking end portion 143 'can be inclined in the same direction. . Furthermore, by matching the moving speed of the shielding plate and the rotating speed of the can roller at the start and end of the stacking of the metal thin film layers, the inclination can be matched.

Further, by synchronizing the start timing of the movement of the shielding plate with the rotational position of the can roller at the start and end of the lamination of the metal thin film layers, the lamination start portion 143 and the lamination end portion 143 'are laminated. It is possible to make the positions of the bodies in the stacking direction substantially the same. For example, in the case where an electronic component is manufactured from a laminated body mother element formed on a can roller, it is generally highly likely that the product will be defective if the laminating start portion 143 or the laminating end portion 143 'is included in the product. Therefore, if the stacking start portion 143 and the stacking end portion 143 ′ can be formed at substantially the same position in the thickness direction, the area of defective products can be reduced, and the productivity can be improved.

In the case of FIG. 5 as well, similar to the start of stacking the metal thin film layers of FIG. 4, both the openings 121 and 131 have a rectangular shape and are arranged so that the corresponding sides are substantially parallel. In addition, since the shielding plate 130 is moved in the direction perpendicular to the moving direction of the outer peripheral surface of the can roller (Z-axis direction), the width of the outer peripheral surface of the can roller in the moving direction (111b direction) in the region where lamination is completed. Always matches the width of the openings 121 and 131 in the moving direction of the outer peripheral surface of the can roller. Therefore, the metal thin film layer near the stacking end portion 143 'has a substantially predetermined thickness. That is, according to the present embodiment, an unstable metal thin film layer region having a small thickness or a large thickness unevenness as in the conventional case is hardly formed in the stacking end portion 143 ′, or even if it is formed. Its width is very small.

As is clear from the above, the shield plate 130
However, as shown in FIG. 3, the opening 1 is formed at a substantially central portion in the moving direction.
With the configuration having 31 and shielding regions 132a and 132b on both sides thereof, the operations of shielding, fully opening, and shielding the opening 121 can be performed by moving the shielding plate 130 in the same direction. As a result, the stacking start portion 143 and the stacking end portion 143 'can be formed at substantially the same position in the thickness direction.

The manufacturing apparatus 100 of FIG. 1 other than the above is described below.
Each of the components will be described.

The inside of the vacuum chamber 115 is kept at a predetermined degree of vacuum by a vacuum pump 116. The preferable degree of vacuum in the vacuum chamber 115 is about 2 × 10 ⁻⁴ Torr. Also,
It is preferable that the space containing the metal thin film forming device 114 partitioned by the partition wall 120 is maintained at a slightly lower pressure than the other spaces. By doing so, it is possible to prevent the metal vapor flow or the metal particle flow from the metal thin film forming apparatus 114 from accidentally leaking out of the space containing the metal thin film forming apparatus 114.

The outer peripheral surface of the can roller 111 is smooth,
It is preferably mirror-finished, preferably -2.
It is cooled to 0 to 40 ° C, particularly preferably -10 to 10 ° C. Rotational speed can be set freely, but 15-100
rpm, peripheral speed is preferably 20 to 300 m / mi
n.

The resin layer forming device 112 evaporates or atomizes the resin material forming the resin layer to form the can roller 1.
11 Release toward the surface. The resin material adheres to the outer peripheral surface of the can roller 111 to form a resin layer. According to such a method, it is possible to obtain a good resin layer which is extremely thin and uniform and has no defects such as pinholes. The resin material is not particularly limited as long as it can be vaporized or atomized in this way and then deposited to form a thin film, and can be appropriately selected depending on the application of the obtained laminate, but the reactive monomer resin Is preferred. For example, when it is used for electronic component materials, those containing acrylate resin or vinyl resin as a main component are preferable, and specifically, polyfunctional (meth) acrylate monomers and polyfunctional vinyl ether monomers are preferable, and among them, Pentadiene dimethanol diacrylate, cyclohexane dimethanol divinyl ether monomer and the like, or monomers in which these hydrocarbon groups are substituted are preferable in terms of electrical characteristics, heat resistance and stability. As a means for scattering the resin material, a heating means such as a heater or a method of vaporizing or atomizing by ultrasonic waves or spray is used. In particular, a method of evaporating the resin material by a heating means such as a heater is preferable from the viewpoints of the thickness and uniformity of the formed resin layer, prevention of defects, and simplification of the apparatus.

The deposited resin material may be cured by the resin curing device 118 to a desired degree of curing, if necessary.
Examples of the curing treatment include a treatment of polymerizing and / or crosslinking a resin material. As the resin curing device, for example, an electron beam irradiation device, an ultraviolet irradiation device, a heat curing device, or the like can be used. The degree of curing treatment may be appropriately changed depending on the required characteristics of the laminated body to be manufactured. For example, in the case of manufacturing a laminated body for electronic parts such as capacitors, the curing degree is 50 to 95%, and further 50 to 95%. It is preferable to carry out a curing treatment to 75%. If the degree of curing is less than the above range, the metal thin film layer may be easily deformed or the metal thin film layer may be broken or short-circuited when an external force or the like is applied in a subsequent step. On the other hand, if the curing degree is higher than the above range, problems such as cracking may occur when an external force or the like is applied in a post process.
The degree of cure of the present invention is reduced by taking the ratio of the absorbance of C = O group and C = C group (1600 cm ^-1 ) with an infrared spectrophotometer and taking the value of the ratio of each monomer to the cured product. Minute absorbance is 1
It is defined as the value subtracted from.

In the present invention, the thickness of the resin layer is not particularly limited, but it is 1 μm or less, more preferably 0.7 μm or less, and particularly preferably 0.
It is preferably 4 μm or less. In order to meet the demand for miniaturization and high performance of the laminate obtained by the method of the present invention, it is preferable that the resin layer be 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 serving as the dielectric layer, the larger the capacitance of the capacitor becomes in inverse proportion to the thickness thereof.

The resin layer thus formed is surface-treated by a surface treatment device 119, if necessary. For example, it is possible to improve the adhesiveness with the metal thin film layer by activating the surface of the resin layer by performing a discharge treatment or an ultraviolet irradiation treatment in an oxygen atmosphere.

The patterning material applying device 113 is for attaching the patterning material to the surface of the resin layer in a predetermined shape. The metal thin film layer is not formed in the portion where the patterning material is attached, but serves as an insulating region (margin portion). As a result, the metal thin film layer is formed in a state where the patterning portion is omitted, and the metal thin film layer having a desired pattern can be formed.

The means for applying the patterning material includes a method of ejecting the vaporized and vaporized patterning material from the fine holes to liquefy it, or a method of ejecting the liquid patterning material in the form of droplets from the fine holes. In addition to the non-contact adhesion means, there is a method by applying a reverse coat, a die coat, etc., but in the present invention, an external force is applied to the resin layer surface, and the resin layer and the metal thin film layer thereunder are deformed, fractured, and roughened A non-contact adhesion means is preferable in order to prevent the occurrence of such problems. In the present embodiment, the patterning material is heated and vaporized in the patterning material application device 113,
A means for ejecting from the fine holes and adhering it in the form of a liquid film in the form of a strip on the surface of the resin layer on the can roller 111 is adopted. The strip-shaped liquid film of the patterning material is formed at a predetermined position in the circumferential direction with a predetermined width and in a predetermined number. At this time, the patterning material application device 113 is moved in parallel with the rotation axis of the can roller 111 in synchronization with the rotation of the can roller 111, whereby metal thin film layers having different pattern positions can be formed.

The patterning material is preferably at least one oil selected from the group consisting of ester oils, glycol oils, fluorine oils and hydrocarbon oils. More preferred are ester-based oils, glycol-based oils, and fluorine-based oils, with fluorine-based oils being particularly preferred. If a patterning material other than the above is used, problems such as roughness of the laminated surface, pinholes in the resin layer or the metal thin film layer, and destabilization of the formation boundary portion of the metal thin film layer may occur.

After depositing the patterning material as required, the metal thin film layer forming device 114 forms a metal thin film layer. As a method for forming the metal thin film layer, well-known vacuum process means such as vapor deposition, sputtering and ion plating can be applied. However, in the present invention, vapor deposition, particularly electron beam vapor deposition, can obtain a film having excellent moisture resistance with high productivity. Is preferred. As the material of the metal thin film layer, aluminum, copper,
Zinc, nickel, iron, cobalt, silicon, germanium or a compound thereof, an oxide thereof, an oxide of a compound thereof, or the like can be used. Of these, aluminum is preferable in terms of adhesiveness and economy. The metal thin film layer may contain components other than the above. In addition, the characteristics may be complemented by mixing the Al thin film and the Cu layer, for example, instead of using one kind of metal thin film layer, and high performance may be achieved depending on use conditions.

The thickness of the metal thin film layer may be appropriately determined depending on the intended use of the obtained laminate, but when used for electronic parts, it is preferably 100 nm or less, more preferably 10 to 50 nm, and particularly preferably 20 to 40 nm. . Also, the membrane resistance is
The upper limit is 20Ω / □ or less, further 15Ω / □ or less, especially 1
It is preferably 0Ω / □ or less, and the lower limit is 1Ω / □
As described above, it is preferably 2Ω / □ or more, and most preferably 3Ω / □ or more.

It is preferable to remove the remaining patterning material after forming the metal thin film layer and before laminating the resin layer. The remaining patterning material causes problems such as roughness of the laminated surface, pinholes in the resin layer or the metal thin film layer (layer missing), and destabilization of the boundary portion where the metal thin film layer is formed. The patterning material is removed by the patterning material removing device 117. The means for removing the patterning material is not particularly limited and may be appropriately selected depending on the type of the patterning material, but can be removed by heating and / or decomposition, for example. As a method for heating and removing, 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. The light here includes far infrared rays and infrared rays. On the other hand, as a method of decomposing and removing, plasma irradiation, ion irradiation, electron irradiation or the like can be used.
At this time, oxygen plasma, argon plasma, nitrogen plasma or the like can be used for plasma irradiation, and oxygen plasma is particularly preferable among them.

According to the above apparatus, when the opening 131 of the shield plate 130 is aligned with the opening 121, the resin layer forming device 112 is formed on the outer peripheral surface of the rotating can roller 111.
On the outer peripheral surface of the revolving can roller 111 in a state where the resin layer according to the above and the metal thin film layer by the metal thin film forming device 114 are alternately laminated, and the shielding plate 130 shields the opening 121. In addition, the resin layer forming apparatus 11
A laminated body in which the resin layers according to No. 2 are continuously laminated is manufactured.

Next, a method of manufacturing the chip capacitor as shown in FIG. 9 using the above apparatus will be described.

While the can roller 111 is being rotated, the layers 936a, 935a and 9 are formed on the can roller 111.
34, the layer 935b, and the layer 936b are sequentially stacked.

When the layer 936a is first laminated, the opening 121 is formed in the shielding region 132a (or 132) of the shielding plate 130.
The can roller 111 is rotated in the state of being shielded in b), and only a predetermined number of resin layers are continuously laminated.

When starting the stacking of layers 935a, the shield plate 1
30 is moved in the positive direction (or negative direction) of the Z axis so that the opening 131 is aligned with the opening 121. At the same time, the patterning material application device 113 applies the patterning material to the surface of the resin layer. In this state, the can roller 11 is rotated a predetermined number of times to form a layer 935a in which patterned metal thin film layers and resin layers are alternately laminated.

Next, the stacking of layer 934 begins. At this stage, the patterning material application device 113 is reciprocated by a predetermined width in the rotation axis direction of the roller 111 every time the can roller 111 makes one rotation. By doing so, a metal thin film layer having different pattern positions adjacent to each other is formed.

Next, the layer 935b is laminated. At this time, a predetermined number of layers are stacked with the patterning material application device 113 fixed at the same position as when the layers 935a were stacked.

Finally, the layer 936b is laminated. At this time, the shielding plate 130 is moved in the same direction (the positive direction (or the negative direction) of the Z axis) as the moving direction of the layer 935a at the start of stacking to open the opening 121 in the shielding region 132b (or 132).
Shield with a). At this time, the movement start timing and movement speed of the shield plate 130 with respect to the rotation angle of the can roller 111 are made to coincide with the movement timing and movement speed at the start of stacking of the layer 935a. Can roller 1 in this state
11 is rotated to form a layer 936b in which only a predetermined number of resin layers are continuously laminated.

As described above, the layers 936a, 935a, 934, and 935 are formed on the outer peripheral surface of the can roller 111.
b, the layer 936b is sequentially stacked to form a stacked body.
Stacking start portion 143 of the metal thin film layer in the stack (see FIG. 4)
And the stacking end portion 143 ′ (see FIG. 5) of the metal thin film layer are formed at substantially the same position in the stacking direction.

Next, the laminated body is cut in the laminating direction to be divided into a plurality of pieces in the circumferential direction, removed from the can roller 111, and flat-plate pressed to obtain a laminated body mother element. At this time, the cutting is performed by the stacking start part 143 and the stacking end part 14
It is performed at a position substantially coincident with 3 ', or a position substantially parallel to the position when expanded.

FIG. 6 is a plan view of an example of the laminated body mother element thus obtained. In the figure, 111b is a moving direction of the outer peripheral surface of the can roller 111, and 151a and 151b are divided surfaces when detached from the can roller 111,
These are substantially the same as or parallel to the stacking start portion 143 and the stacking end portion 143 '. The laminated body element 150 thus obtained is cut along a cutting plane 152 parallel to the arrow 111b in consideration of the relationship with the pattern position of a metal thin film layer (not shown), and the cutting plane is sprayed with an external material. Form electrodes. Next, cutting is performed at a position corresponding to the cutting surface 153, and exterior coating is performed as necessary.
A large number of chip capacitors 940 as shown in FIG.

As described above, the laminating start portion 1 of the metal thin film layer
43 and the stacking end portion 143 ′ are formed at substantially the same position in the stacking direction, and the dividing surfaces 151 a and 151 b are located at positions substantially coincident with these, or at positions substantially parallel to the surfaces when they are expanded, so that finally. The amount of good quality capacitors obtained can be increased, and the productivity can be improved.

According to the above method, the dividing surface 151
Since a and 151b are inclined with respect to the arrow 111b, when a capacitor having a substantially rectangular parallelepiped shape is obtained, the dividing surface 1
It is unavoidable that a wasteful part in which the shape of the capacitor cannot be formed is generated in the vicinity of 51a and 151b. However, in view of the size of the unstable region of the metal thin film layer that has occurred at the start and end of the formation of the conventional metal thin film layer, the useless portion that cannot be the capacitor of this embodiment is negligibly small. , The product yield will be significantly improved compared to the past.

In the above embodiment, the cylindrical can roller is illustrated as the support, but the present invention is not limited to this. For example, it may be a belt-shaped support that revolves between two or more rolls, or a rotating disc-shaped support. Even when such a support is used, the effect of the present invention can be obtained by moving the shield plate in the direction perpendicular to the moving direction of the support.

Although the shielding plate 130 has a flat plate shape as an example, the cross section may be deformed into a substantially arcuate shape in accordance with the curvature of the outer peripheral surface of the can roller 111.

Furthermore, it is preferable to apply a release agent to the outer peripheral surface of the can roller 111 prior to the start of stacking, since the work of removing the stack after the stacking is facilitated. As the release agent, for example, a fluorine-based release agent (for example,
Product names: "Daifree", manufactured by Daikin Industries, Ltd., etc. can be used. As a method of applying the release agent, it is preferable to appropriately select a method suitable for the release agent material and process conditions such as a spraying method, a sputtering method, and a vapor deposition method.

[0071]

Example 1 A chip capacitor having the structure shown in FIG. 9 was manufactured using the manufacturing apparatus shown in FIG.

The inside of the vacuum chamber 115 was set to 2 × 10 ⁻⁴ Torr by the vacuum pump 116, and the outer peripheral surface of the can roller 111 was cooled to 5 ° C. The diameter of the can roller 111 was 500 mm, and the moving speed of the outer surface was 50 m / min.

Prior to the lamination, a fluorine-based release agent ("Die Free" manufactured by Daikin Industries, Ltd.) was spray-coated on the outer peripheral surface of the can roller 111, and then thinly spread with a non-woven fabric.

First, a portion to be a layer (protective layer) 936a in which only resin layers were continuously laminated was laminated. Layer 936
Although a does not generate a capacitance as a capacitor, it is a layer that effectively functions to prevent the layer (element layer) 934, which is a capacitance generation portion, from being damaged by a heat load or an external force.

Dicyclopentadiene dimethanol diacrylate was used as the material of the layer 936a, which was vaporized and deposited on the outer peripheral surface of the can roller 111 by the resin layer forming device 112. The laminated thickness per layer is 0.6 μm
Is. Next, an ultraviolet curing device was used as the resin curing device 118, and the resin layer material deposited as described above was polymerized and cured until the curing degree reached 70%. This operation is repeated by rotating the can roller 111, and the layer 9 having a thickness of 15 μm is formed on the outer peripheral surface of the can roller 111.
The 36a part was formed. During this time, the opening 121 was shielded by the shielding region 132a.

Next, a portion to be a layer (reinforcing layer) 935a in which the resin layer and the metal thin film layer were alternately laminated was laminated.
The layer 935a is a layer (element layer) 934 that is a capacitance generating portion.
Is a layer that effectively functions to prevent being damaged by heat load or external force. Further, by having the metal thin film layer, it contributes to the improvement of the adhesion strength of the external electrode.

The resin layer material of the layer 935a is the same as the above-mentioned layer 93.
The same material as 6a was used. The laminated thickness per resin layer is 0.6 μm. Next, the resin curing device 118
The resin layer was cured until the degree of curing reached 70%.
Then, the surface was treated with oxygen plasma by the surface treatment device 119. Next, the patterning material application device 113 ejected the vaporized patterning material from the fine holes and deposited it in a strip shape on the surface of the resin layer. Fluorine-based oil was used as the patterning material. The temperature at which the vapor pressure of this patterning material becomes 0.1 torr is 100.
℃. The average molecular weight of the oil is 1500. The adhesion width of the band-shaped patterning material was 150 μm. Next, the shield plate 130 is moved in the positive direction of the Z axis to move the opening 12
Opened one. Then, aluminum was vapor-deposited from the metal thin film forming apparatus 114. The laminated thickness was 300 Å. Then, the patterning material removing apparatus 1
17, heating with a far infrared heater and plasma discharge treatment were performed to remove the remaining patterning material. The above operation is repeated 500 times by rotating the can roller 111, and the layer 93 having a total thickness of 315 μm is obtained.
The 5a part was formed.

Next, a portion to be a layer (element layer) 934 to be a capacitance generating portion as a capacitor was laminated. The same resin layer material as described above was used, and the laminated thickness per layer was 0.4 μm. Next, the resin layer was cured by the resin curing device 118 until the degree of curing reached 70%. Then, the surface was treated with oxygen plasma by the surface treatment device 119. Next, the same patterning material as described above was applied in a strip shape with the same width as the above by the patterning material application device 113. Next, aluminum was vapor-deposited from the metal thin film forming apparatus 114. The laminated thickness was 300 Å. Then, the patterning material removing apparatus 1
17, the remaining patterning material was removed. The above operation is repeated about 2000 times by rotating the can roller 111, and the layer 934 having a total thickness of 860 μm is obtained.
The part was formed. During this period, the patterning material application device 113 was reciprocated by 1000 μm in the rotation axis direction for each rotation in synchronization with the rotation of the can roller 111.

Next, the movement of the patterning material application device 113 is stopped, and a layer (reinforcing layer) 935 having a thickness of 315 μm is formed.
Formed part b. The forming method was the same as that of the layer 935a.

Finally, a layer (protective layer) 93 having a thickness of 15 μm
Formed part 6b. At this time, the shield plate 130 is moved in the positive direction of the Z-axis to open the opening 121 in the shield region 132b.
Shielded with. At this time, the movement start timing and movement speed of the shielding plate 130 with respect to the rotation angle of the can roller 111 were made to coincide with the movement timing and movement speed at the start of stacking of the layer 935a. The method of forming the layer 936b was the same as that of the layer 936a.

Next, the cylindrical laminated body was removed by dividing it into 8 sections in the circumferential direction at the cut surfaces along the stacking start portion and stacking end portion of the metal thin film layer and at the cut surfaces at equal intervals, and pressed under heating. Then, a flat plate-shaped laminated body mother element 1 as shown in FIG.
Got 50. This was cut along the cut surface 152, and brass was metal-sprayed on the cut surface to form an external electrode. Further, a conductive paste prepared by dispersing an alloy of copper, Ni, silver or the like in a thermosetting phenolic resin was applied on the surface of the metal sprayed, cured by heating, and then the surface of the resin was subjected to molten solder plating. After that, cutting is performed at a position corresponding to the cutting surface 153, and the outer surface is coated by dipping in a silane coupling agent solution,
A chip capacitor as shown in FIG. 9 was obtained.

The obtained chip capacitor had a thickness in the stacking direction of about 1.5 mm, a depth of about 1.6 mm and a width (between both external electrodes) of about 3.2 mm.
It was μF. The withstand voltage was 50V. Further, the insulation resistance value at a DC applied voltage of 16 V was 10 ¹¹ Ω, and no short circuit between the metal thin film layers or breakage of the metal thin film layers was observed.

The degree of curing of the resin layers of the layer 934, the layers 935a and 935b, and the layers 936a and 936b is 95, respectively.
%, 95% and 90%.

The metal thin film layers of the layer 934 and the layers 935a and 935b have a thickness of 300 Å and a film resistance of 6
It was Ω / □.

In the laminated body mother element 150, the layer 9
The margin width of the metal thin film layer of 34 parts is 150 μm, and the margin width of the metal thin film layers of layers 935a and 935b is 15 μm.
It was 0 μm.

Example 2 A chip capacitor having the structure shown in FIG. 9 was manufactured in exactly the same manner as in Example 1 except that the moving direction of the shielding plate 130 was changed.

That is, the steps up to the step of laminating the reinforcing layer 935b are performed in exactly the same manner as in Example 1, and when shifting to the layer laminating of the protective layer 936b, the shield plate 130 is moved in the negative direction of the Z axis to form the opening 121. Was shielded by the shielding region 132a. The moving speed of the shielding plate at this time was the same as the moving speed at the time of moving in the positive direction of the Z axis. Then, the lamination process was completed in the same manner as in Example 1. The obtained cylindrical laminated body was divided into eight in the circumferential direction at the cut surface along the stacking end portion of the metal thin film layer and the cut surfaces at equal intervals, and the chip capacitor was obtained in the same manner as in Example 1. Obtained.

(Comparative Examples 1 and 2) The movement of the shielding plate at the start and end of the formation of the metal thin film layer is parallel to the movement direction of the outer peripheral surface of the can roller as in the conventional manufacturing apparatus shown in FIG. A chip capacitor having the structure shown in FIG. 9 was manufactured in the same manner as in Example 1 except that the above step was performed.

At this time, the moving speed of the shield plate 923 is changed in two ways until the opening 922 is fully opened from the fully closed state (referred to as opening operation) and from the fully opened state to fully closed (referred to as closing operation). It was That is, in Comparative Example 1, both the opening operation and the closing operation are performed in 15% of the rotation cycle of the can roller 911, and in Comparative Example 2, the opening operation and the closing operation are performed in 30% of the rotation cycle of the can roller 911. I did.

(Evaluation) From the chip capacitors obtained in Examples 1 and 2 and Comparative Examples 1 and 2, 200 pieces were randomly extracted and left in an atmosphere of 60 ° C. and 95% RH for 1000 hours. Shape evaluation of the chip capacitor after leaving,
The defect rate was calculated assuming that the layer with delamination was defective. The results are shown in Table 1.

[0091]

[Table 1]

As is clear from a comparison between Examples 1 and 2 and Comparative Examples 1 and 2, according to the method of the present invention, the metal thin film layer is generated in the vicinity of the stacking start portion and the stacking end portion of the metal thin film layer. It can be seen that since the size of the unstable region in which the thickness is smaller than the design value or the thickness unevenness is large can be made extremely small, the product defect rate is remarkably improved.

The reason why the defective rate of Example 2 is inferior to that of Example 1 is considered to be as follows. In the second embodiment, since the moving directions of the shielding plate 130 when opening and closing the opening 121 are opposite, it is possible to make the stacking start portion and the stacking end portion of the metal thin film layers substantially coincide with each other in the stacking direction. could not. Since the metal thin film layer was cut at the lamination end portion and a direction parallel to the lamination end portion, the chip capacitor slightly including the lamination start portion of the metal thin film layer was included. The defect rate of Example 2 was larger than that of Example 1,
It is considered that this is due to the inclusion of the chip capacitor including the stacking start portion inside.

The defective rate of Comparative Example 2 was inferior to that of Comparative Example 1 because the time required for the opening / closing operation of the opening 922 was long with respect to the rotation cycle of the can roller 911, and therefore the shielding plate 923 was used. It is presumed that this is because the unstable region of the metal thin film layer generated at the time of moving becomes larger than that in Comparative Example 1.

As a result of detailed examination of defective products slightly contained in Examples 1 and 2, all of these defective products were concentrated in the vicinity of the laminating start portion and laminating end portion of the metal thin film layer. Therefore, it was found that there were almost no defective products from other areas. According to the method of the present invention, it is possible to detect the positions on the can roller 111 of the stacking start portion and the stacking end portion of the metal thin film layer. It is possible to reduce the defect rate to almost 0%.

[0096]

As described above, according to the present invention, since the shielding plate is moved in a direction substantially perpendicular to the moving direction of the support, the thickness of the metal thin film layer is increased at the start and end of the lamination of the metal thin film layers. It is possible to suppress the occurrence of an unstable region where the thickness is thin or the thickness is uneven. As a result, productivity is improved, and a high-quality laminate is obtained.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing apparatus for carrying out the method for manufacturing a laminated body of the present invention.

FIG. 2 is a perspective view showing a schematic configuration of a shield plate, a metal thin film forming device, and an opening in the manufacturing apparatus of FIG.

FIG. 3 is a schematic configuration diagram of the shielding plate shown in FIG. 2, (A) is a plan view, and (B) is a side view.

FIG. 4 is a diagram schematically showing a state of a lamination start portion of a metal thin film layer on a can roller obtained by the manufacturing apparatus of FIG. 1, and FIG. 4 (A) shows a thin film laminate on the can roller. 4B is a developed view of the thin film laminate of FIG.

5 is a diagram schematically showing a state of a lamination end portion of a metal thin film layer on a can roller obtained by the manufacturing apparatus of FIG. 1, and FIG. 5 (A) shows a thin film laminate on the can roller. 5B is a developed view of the thin film laminate of FIG.

FIG. 6 is a plan view showing an example of a laminated body mother element obtained by the present invention.

FIG. 7 is a schematic cross-sectional view showing an example of a manufacturing apparatus for carrying out a conventional laminated body manufacturing method.

FIG. 8 is a perspective view showing an example of a layered body mother element obtained by a conventional method.

FIG. 9 is a schematic perspective view showing an example of a general configuration of a chip capacitor.

[Explanation of symbols]

100 laminated body manufacturing apparatus 115 vacuum tank 116 vacuum pump 111 can roller 111a can roller rotating direction 111b can roller outer peripheral surface moving direction 112 resin layer forming apparatus 113 patterning material applying apparatus 114 metal thin film forming apparatus 114a metal thin film forming apparatus Metal vapor or metal particles 117 from patterning material removing device 118 resin curing device 119 surface treatment device 120 partition wall 121 partition wall opening 130 shield plate 131 openings 132a and 132b provided in the shield plate shielding region 139 shield plate moving direction 140 resin Layer-only continuous laminated portion 140 ′ Alternate laminated portion 141 of resin layer and metal thin film layer 141 Outermost resin layer 142 Metal thin film layer 143 Metal thin film layer laminating start portion 143 ′ Metal thin film layer laminating end portion 150 Laminate mother Element 151a, 151b Dividing surface 152, 53 Cut Surface 900 Laminate Manufacturing Device 911 Can Roller 912 Resin Layer Forming Device 913 Patterning Material Applying Device 914 Metal Thin Film Forming Device 915 Vacuum Tank 916 Vacuum Pump 917 Patterning Material Removing Device 918 Resin Curing Device 919 Surface Treatment Devices 920a, 920b Partition Walls 922 Opening 923 Shielding plate 930 Laminated body element 931 Metal thin film layer 932 Resin layer 933 Pattern position 938 Running direction of the outer surface of the can roller 939a, 939b Cutting surface 940 Chip capacitors 941a, 941b External electrodes

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinki Sunagure 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Toru Miyake 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. (56) References JP-A-8-269710 (JP, A) JP-A-6-93428 (JP, A) JP-A-3-104865 (JP, A) JP-A-10-237623 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) H01G 4/30 C23C 14/34

Claims (13)

(57) [Claims] 1. A step of laminating a resin layer, and a step of depositing a metal material by a vacuum process to laminate a metal thin film layer, which are carried out on a support which circulates the support on the support. When manufacturing a laminate including a resin layer and a metal thin film layer, the lamination of the metal thin film layer is started or ended by moving a shielding plate installed between a metal material supply source and a support. a method of manufacturing a body, the had the row in the moving direction substantially vertical shielding plate facing the side of the support the movement of the shield plate, the start of lamination of the metal thin film layer
And the start timing of the movement of the shielding plate at the time and the end time.
A method for manufacturing a laminated body, characterized in that the rotational position of the support is synchronized . 2. The method for producing a laminated body according to claim 1, wherein the direction of movement of the shielding plate when starting the lamination of the metal thin film layer and the direction of movement of the shielding plate when ending the lamination are the same. 3. The method for producing a laminated body according to claim 1, wherein the shielding plate has an opening for forming a metal thin film layer at a substantially central portion in the moving direction. 4. The method for producing a laminated body according to claim 1, wherein the moving speed of the shielding plate and the rotating speed of the support are made to match at the start and end of the lamination of the metal thin film layers. 5. A boundary portion between the metal thin film layers formed by moving the shield plate for starting the stacking of the metal thin film layers, and a metal formed by moving the shield plate for ending the stacking of the metal thin film layers. The method for manufacturing a laminated body according to claim 1, wherein the shielding plate is moved so that the boundary portion of the thin film layers is substantially at the same position in the laminating direction. 6. When cutting a laminated body formed on a support body in the laminating direction to divide the laminated body, the cutting is performed at the boundary portion of the metal thin film layer formed by the movement of the shielding plate or in parallel with this. The method for producing a laminate according to claim 1, which is performed. 7. The production of a laminate according to claim 1, wherein the positions of the lamination start portion and the lamination end portion of the metal thin film layer on the support are detected, and the product is collected while avoiding the lamination start portion and the lamination end portion. Method. 8. The method for producing a laminate according to claim 1, wherein the orbiting support is a cylindrical drum, a disc-shaped support, or an endless belt. 9. The method for producing a laminate according to claim 1, wherein the laminate is an electronic component laminate. 10. The method for producing a laminated body according to claim 1, wherein the laminated body is a laminated body for capacitors. 11. A vacuum chamber, an orbiting support installed in the vacuum chamber, a resin layer forming apparatus for laminating a resin layer on the support, and a metal thin film layer on the support by a vacuum process. And a metal thin film forming apparatus for laminating a metal thin film forming apparatus, wherein the metal thin film forming apparatus and the support are provided between the metal thin film forming apparatus and the support. In, the shielding plate for preventing the lamination of the metal thin film layers, is installed movably in a direction substantially perpendicular to the moving direction of the surface of the support facing the shielding plate, the lamination of the metal thin film layers. Start and end
At the end, the start timing of the movement of the shielding plate and the support
An apparatus for manufacturing a laminated body, characterized in that the rotational position of a holding body is synchronized . 12. The apparatus for manufacturing a laminate according to claim 11 , wherein the shield plate is moved in a direction substantially perpendicular to the moving direction of the support at the start or end of the formation of the metal thin film layer. 13. The apparatus for manufacturing a laminate according to claim 11 , wherein the shielding plate has an opening at a substantially central portion in the moving direction and has shielding regions on both sides thereof.