JPH11209870A - Production of thin film and device for producing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To uniformly and stably form a resin thin film of high quality good in surface properties and free from defects at a high deposition rate by evaporating a resin material when it is fluidized along a heating element in a vacuum and sticking the vapor thereof to a supporter while scattering coarse particles are inhibited. SOLUTION: In a vacuum tank 5 provided with an exhaust system 6, a resin material fed in a liq. state from a feed tube 3 is evaporated under heating while it is flowed down on plural gradient heating boards 11 in succession as a liq. film, and the nonevaporated portion is received in a cup 4. The vapor of the resin material is stuck to the surface of a long size base material 1 running on a can 7 while its diffusion is prevented by an ambient wall 13, and the deposited thin film is furthermore hardened by ultraviolet irradiation by a hardening device 14. At this time, a barrier 12 is arranged, and it is allowed that the part to be stuck with the vapor is not directly seen through from the part in which the resin material is first brought into contact with the heating boards 11, and the sticking of the coarse particles of the evaporating material scattering by the rapid increase of the temp. to the base material 1 is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method and an apparatus for producing a thin film.

[0002]

2. Description of the Related Art Thin films play a very wide role in modern society, and are used in various parts of daily life such as wrapping paper, magnetic tape, capacitors, semiconductors and the like. Without these thin films, it is impossible to talk about the basic trends in technology such as high performance and miniaturization in recent years. At the same time, various methods have been developed for forming thin films in a manner that satisfies industrial demand. For example, in applications such as wrapping paper, magnetic tape, and capacitors, continuous winding is advantageous for high-speed mass production. Vacuum deposition is being performed.
At this time, select the evaporation material and the substrate material according to the purpose of the thin film to be formed, and at the same time, introduce a reactive gas into the vacuum chamber as necessary, and form the thin film with the potential applied to the substrate. Can form a thin film having desired characteristics. For example, in the manufacture of a magnetic recording medium, a long magnetic recording medium is obtained by performing a reactive deposition while introducing an oxygen gas into a vacuum chamber using an evaporation material containing a magnetic element such as Co, Ni, and Fe. Can be done. In a semiconductor, a thin film is formed mainly by a sputtering method. The sputtering method is also particularly effective for forming a thin film using a ceramic material. In many cases, a ceramic thin film is formed by a coating and firing method when the film thickness is several μm or more, and is formed by a sputtering method when the film thickness is 1 μm or less.

On the other hand, a thin film using a resin material is formed by a coating method, and a reverse coat or a die coat is industrially used. In general, a material diluted with a solvent is dried and cured after coating. It is a target. Although the lower limit of the thickness of the resin thin film formed by these methods depends on the material used, it is often about 1 μm, and it is often difficult to obtain a thickness less than that. With a general coating method, the coating thickness immediately after coating is several μm or more, so that a solvent dilution is necessary for forming an ultrathin resin film, and a resin thin film of 1 μm or less cannot be obtained in many cases. . Further, when the solvent is diluted, the coating film after drying tends to have defects, and is not preferable from the viewpoint of environmental protection. Therefore, a method capable of forming a resin thin film without performing solvent dilution and a method capable of stably obtaining an extremely thin resin thin film are desired. As a method for solving this, a method of forming a resin thin film in a vacuum has been proposed. This is a method in which a resin material is vaporized or atomized in a vacuum and then attached to a support. According to these methods, a resin thin film having no void defects can be formed, and there is no need for solvent dilution.

[0004] By laminating different types of thin films on a ceramic thin film or a resin thin film, various composite thin films which could not be obtained conventionally can be obtained, and their industrial application fields are very diverse. Among them, chip-shaped electronic components are very promising. Capacitors, coils, resistors, capacitive batteries, or composite components of these are being formed into extremely small and high-performance products by laminating thin films. Expansion is beginning.

[0005]

What is important when an electronic component or the like is formed using a resin thin film is the surface properties and defects of the resin thin film. If the surface is rough or defective, the effect of the thinning is reduced by half, sometimes leading to poor performance.

On the other hand, it goes without saying that the productivity of the thin film is also important industrially. Therefore, it is important to achieve both productivity and film quality, but the conventional methods have not always been sufficient. That is, Japanese Patent Application No. Hei.
According to JP-A-8-125400, a resin thin film having no defect can be obtained, but the primary vaporization or atomization speed is not always sufficient, and when the material supply speed is increased in order to increase the film formation speed, the mechanical method is not used. In the case of material dripping, ultrasonic waves or a heating method, solidification may be caused, and a high-speed and stable film forming method has been desired.

[0007]

In order to solve these problems, the present invention provides a method for producing a thin film in which a resin material is evaporated in a vacuum to adhere to a support. A method for producing a thin film characterized by being evaporated while flowing along, preferably from the portion where the resin material first contacts the heating body,
A method of manufacturing a thin film, wherein a portion where the resin material adheres to the support is in a positional relationship where it cannot be seen directly, and the heating element along which the resin material flows is a plurality of regions having different temperatures. It is.

[0008]

According to a first aspect of the present invention, there is provided a method for producing a thin film in which a resin material is evaporated in a vacuum to adhere to a support, wherein at least the resin material flows along a heating element. This is a method for producing a thin film, characterized in that evaporation is performed while the film is being formed, whereby a high-speed and stable film formation method can be realized.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(Embodiment 1) FIG. 1 is a diagram showing an example of a method and an apparatus for manufacturing a thin film according to the present invention.

In FIG. 1, a resin material is supplied through a supply pipe 3 to a vacuum chamber 5.
Introduced in. The long substrate 1 as a support is unwound from an unwinding roll 15 and passes through a guide roll.
It travels along the cylindrical can 7 and is taken up by the take-up roll 16 via the guide roll 17. Resin vapor for forming a resin thin film on a long substrate is obtained by vaporizing a resin material supplied from a supply pipe. The resin material supplied in a liquid state is supplied to the first heating plate 11 (temperature: 110
C., an inclination angle with respect to the horizontal line: 20 degrees), and a part thereof is vaporized while flowing, and spreads in a thin liquid film along the heating plate. The resin material that has reached the end of the first heating plate is a second heating plate (temperature: 120 ° C., inclination angle to the horizontal line: 10).
) And continue to evaporate further on the second heating plate. That is, by flowing the resin material along the heating element,
The resin material is uniformly heated with a large surface area, and the amount of evaporation is stabilized. When the resin material is stopped in one place and heated, the convection of the resin material is bad and it is not heated uniformly, so the resin material in the vicinity of the heating body is thermoset, or bumping causes many large particles to diverge, The sequentially supplied low-temperature resin material may prevent a rise in the temperature of the resin material, or may not ensure a large amount of stable evaporation.

When a plurality of heating plates are provided as shown in FIG. 1, the evaporation area can be relatively large even if the apparatus is miniaturized. In addition, by changing the heating temperature, the heating temperature is set to an optimum heating pattern according to the material. You can do it. The resin material that has reached the end of the second heating plate is injected into the heating cup 4 and is further evaporated. At that time, as shown in FIG. 1, the inner wall of the heating cup is inclined to guide the resin material along the inner wall, so that the chance of evaporation in the heating cup is increased and the hardening in the cup can be reduced.

Incidentally, the resin material that has just come into contact with the first heating plate may become coarse particles due to a rapid rise in temperature and may be partially scattered. The barrier 12 is provided so that the formation position cannot be seen directly. In addition, the peripheral wall and the barrier were also made to have a heating structure in order to re-evaporate the resin material adhering to the peripheral wall 13 and the barrier. An ultraviolet irradiation device was used as the curing device 14 for curing the resin thin film.

(Embodiment 2) Next, a second embodiment of the present invention will be described with reference to the drawings.

FIG. 2 is a diagram showing an example of the method and apparatus for manufacturing a thin film according to the present invention. In FIG. 2, the resin material is introduced into the vacuum chamber 5 through the supply pipe 3. The substrate 1 as a support moves along the carrier 2, and a resin vapor for forming a resin thin film on the substrate is obtained by vaporizing a resin material supplied from a supply pipe. The resin material supplied in a liquid state spreads in a thin liquid film along the heating plate while a part thereof evaporates while flowing along the heating plate 11. The resin material that has reached the end of the heating plate is dropped onto the heating roller 9 that rotates counterclockwise on the paper surface, and continues to evaporate on the heating roller.

If the heating element is a roller as shown in FIG. 2, a thin liquid film-shaped resin material can be held for a long time, and the evaporation state can be stabilized even if the apparatus is downsized. When the resin material on the heating roller becomes excessive, the excess resin material is dropped from the lowermost portion of the heating roller or scraped off by the blade 8 and dropped into the heating cup 4, and further evaporates.

The resin material that has just come into contact with the heating plate may become coarse particles due to a rapid rise in temperature and may be partially scattered. A barrier 12 is provided so that it cannot be seen directly. In addition, the peripheral wall and the barrier were also made to have a heating structure in order to re-evaporate the resin material adhering to the peripheral wall 13 and the barrier. An ultraviolet irradiation device was used as the curing device 14 for curing the resin thin film.

(Embodiment 3) A third embodiment of the present invention will be described with reference to the drawings.

FIG. 3 is a diagram showing an example of the method and apparatus for manufacturing a thin film according to the present invention. In FIG. 3, the resin material is introduced into the vacuum chamber 5 through the supply pipe 3. The support forms a resin thin film directly on the peripheral surface of the can with the cylindrical can 7. The resin vapor is obtained by vaporizing the resin material supplied from the supply pipe. The resin material supplied in a liquid state spreads in a thin liquid film along the heating roller while a part thereof evaporates while flowing along the heating roller 9 rotating clockwise on the paper surface.
The resin material that has reached the lower end of the heating roller is dropped or scraped off by a blade (not shown), flows on the heating plate 11, and continues to evaporate.

As shown in FIG. 3, even when the heating element is a roller, a thin liquid film-shaped resin material can be held for a long time.
The evaporation state can be stabilized even if the apparatus is downsized. The resin material whose evaporation has not ended is dropped into the cooling cup 4 from the end of the heating plate, and the evaporation ends. The resin material that has just come into contact with the heating roller may become coarse particles due to a rapid rise in temperature and may be partially scattered, so that the position where the resin thin film is formed on the substrate from the contact start point cannot be directly seen. A barrier 12 is provided as described above.

In order to re-evaporate the resin material adhering to the peripheral wall 13 and the barrier, the peripheral wall and the barrier are also heated. An electron beam irradiation device was used as the curing device 14 for curing the resin thin film. FIG. 3 also shows an electron beam (EB) evaporation source 20 used for laminating a metal thin film and a resin thin film.

According to the present embodiment, it is possible to obtain a laminate in which resin thin films and metal thin films are alternately laminated on the outer peripheral surface of the cylindrical can 7. In the process of lamination,
By shielding the EB evaporation source or the resin evaporation source or the like, a layer in which only the resin thin film layer or only the metal thin film layer is continuously laminated can be formed.

(Embodiment 4) Another embodiment of the present invention will be described with reference to the drawings. FIG. 4 is a diagram showing an example of a method and an apparatus for manufacturing a thin film according to the present invention. In FIG. 4, the resin material is introduced into the vacuum chamber 5 through the supply pipe 3. The substrate 1 as a support is moving along the carrier 2,
Resin vapor for forming a resin thin film on a substrate is obtained by vaporizing a resin material supplied from a supply pipe. The resin material supplied in a liquid state is the first heating belt 10
While a part of the liquid flows along the heating belt, a part thereof evaporates, and spreads in a thin liquid film along the heating belt. The resin material that has reached the lowermost portion of the first heating belt drops on the second heating belt, and continues to evaporate on the second heating belt.

When the heating element is a belt as shown in FIG. 4, the evaporation area can be relatively large even if the apparatus is downsized. The resin material whose evaporation is not completed by the second heating belt is blade 8
And is collected in the cooling cup 4 to complete the evaporation. Note that the resin material that has just come into contact with the first heating belt may become coarse particles due to a rapid rise in temperature and may be partially scattered. A barrier 12 is provided so that it cannot be seen directly.
In addition, the peripheral wall and the barrier were also made to have a heating structure in order to re-evaporate the resin material adhering to the peripheral wall 13 and the barrier. Note that an electron beam irradiation device was used as the curing device 14 for curing the resin thin film.

(Comparative Example 1) FIG. 5 is a diagram showing a comparative example of a method for manufacturing a resin thin film. In FIG. 5, the resin material is supplied to the heating cup 4 via the supply pipe 3 and evaporates. Since the resin material that has just come into contact with the heating cup may become partly scattered as coarse particles due to a rapid rise in temperature, the heating roll 9 is installed so that the formation position of the resin thin film cannot be directly seen from the heating cup. I do. The heating roll is rotating, and the resin vapor attached to the heating roll re-evaporates to form a resin thin film on the support.

The peripheral wall 13 is also provided with a heating structure in order to re-evaporate the resin material adhering to the peripheral wall and prevent the wall surface from being stained. The curing device 1 for curing the resin thin film
As No. 4, an ultraviolet irradiation device was used.

Embodiments 1 to 4 and Comparative Example 1
A resin thin film was manufactured with the above configuration, and the relationship between the manufacturing conditions and the film quality was examined. Film formation was performed using three kinds of resin materials while changing the deposition rate of the resin thin film. An area of 5 cm × 5 cm of the prepared film was observed with an optical microscope, and the surface property was evaluated by the number of abnormal grains having a diameter of 3 μm or more. The result

[0028]

[Table 1]

Are shown in FIG. In Table 1, in Examples 1 to 4, the devices described in Embodiments 1 to 4 above were used, respectively.

As can be seen from Table 1, even in the configuration of Comparative Example 1, when the deposition rate of the resin thin film is low, the defect of the produced resin thin film is small. However, when the deposition rate is about 100 nm / s or more, the number of defects increases rapidly.

On the other hand, in the structures of the first to fourth embodiments, even when the deposition rate is 100 nm / s or more, the defect of the resin thin film produced is small. The reason is considered as follows. That is, to increase the deposition rate, it is necessary to increase the supply amount of the resin material. However, in the configuration of Comparative Example 1, the evaporation area becomes insufficient, and the temperature condition is slightly increased to secure the deposition rate. There is a need.

On the other hand, when the supply amount of the resin material increases, the volume with respect to the surface area of the resin before evaporation tends to increase, and in combination with the temperature condition, a part of the resin causes a thermosetting or bumping phenomenon. The defects observed at a high deposition rate in the configuration of Comparative Example 1 are considered to be due to the attachment of some of the bumping particles. Since bumpy particles have high rectilinearity and can be considerably prevented from adhering by providing a barrier at a position where the support cannot be directly seen, it is thought that some of the particles still adhere to the support due to impact reflection or the like.

On the other hand, Embodiments 1 to 4
Is designed to increase the evaporation area, whereby bumping and thermosetting hardly occur even when the supply amount of the resin material is large, that is, when the deposition rate is high. Therefore, it is considered that a resin thin film with few defects can be obtained.

Further, in the configuration of Comparative Example 1, as described above, the rate of thermal curing of the resin at a high deposition rate is large.
Since the evaporation rate of the resin material easily changes with the film formation time,
The control of the film forming conditions was also more difficult than in the first to fourth embodiments. Further, when the resin material is collected in the cooling cup as in the third and fourth embodiments, evaporation from the cup cannot be expected. However, since the resin material does not harden in the cup, the entire film forming apparatus can be used. The amount of evaporation becomes very stable. Therefore, it is preferable to cool the cup if the evaporation rate can be secured.

(Embodiment 5) A resin thin film was formed under the same conditions as in Example 1 of Table 1 by using the same apparatus as in FIG. 1 described in Embodiment 1. However, in the present embodiment, the heating plate 1
In supplying the resin material to No. 1, the resin material was heated in advance by a resin material heating device and then supplied. As the resin material heating device, a device in which a panel heater was attached to the outer peripheral surface of a resin material tank was used. Further, a heat retention heater was wound around the supply pipe 3 connected to the resin material heating device so that the temperature of the resin material did not decrease during the supply process. And
The resin material heated to 60 ° C. was supplied in liquid form to the first heating plate 11 heated to 110 ° C. through the supply pipe 3 maintained at the same temperature.

The surface characteristics of the obtained resin thin film were similarly evaluated.
did. As a result, the number of defects was 2 / m ^TwoExample 1
A resin thin film having a better surface was obtained. In addition,
As compared with the first embodiment, bumping and heat of the resin material on the heating plate 11
The cure was clearly less. Thus, the resin material is reserved.
Heating and then supplying to the heating element, the supplied resin material
Temperature difference between the material and the heating plate
Bumping is unlikely to occur. Also, the resin material on the heating plate
The temperature difference inside the droplets is relatively small, and heating is almost uniform
Only the resin material near the heating plate is rapidly heated
It is not cured by heat. Therefore, the surface properties are good.
It can be seen that a better resin thin film can be obtained.

When the target film thickness and the deposition rate were variously changed, the target film thickness and the target film thickness were larger than those in the first embodiment.
And higher deposition rates.
This is because, in addition to the fact that a part of the supplied resin material was not cured by heat and evaporated without waste, the viscosity of the supplied resin material was reduced, and the supply amount became stable with time.
It is considered that this was due to the fact that the company was able to respond to the large supply. Therefore, it is understood that the deposition efficiency can be improved by heating the resin material in advance and then supplying it to the heater.

Further, when the resin material is heated and supplied to a predetermined temperature, the seasonal fluctuation of the temperature of the supplied resin material is reduced, and it becomes easy to maintain a stable evaporation amount throughout the year.

The heating temperature of the supplied resin material is as follows:
Although it depends on the resin material, it is usually preferably 40 to 100 ° C. When the heating temperature is higher than this range, the resin material is thermoset in the supply pipe, and stable supply may be difficult.

(Embodiment 6) The embodiment shown in FIG. 1 described in Embodiment 1 except that barriers 12a, 30b and 30c having a heating structure as shown in FIG. A resin thin film was formed in the same manner as in Example 1. The barrier 30a and the barrier 30b, and the barrier 30a and the barrier 30c,
Each of them is installed at a predetermined interval with a part thereof facing each other. The evaporated resin material reaches the surface of the support 1 so as to pass through between the opposed portions of the barrier. Also, the barrier 12 of FIG. 1 is installed in such a position that the region where the resin material is first brought into contact with the heating element cannot directly see through the area where the resin material is adhered to the support, whereas the barrier 12 of FIG. Reference numerals 30a, 30b, and 30c are provided such that the region to which the support is adhered cannot be directly seen from the evaporation region of the resin material from the heater.

The surface characteristics of the obtained resin thin film were similarly evaluated.
did. As a result, the number of defects was 3 / m ^TwoExample 1
A resin thin film having a slightly better surface was obtained. Ma
Further, compared with the first embodiment, the resin thinner in the longitudinal direction of the long substrate 1
The thickness unevenness of the film layer was small. In addition, uneven thickness in the width direction
A more uniform resin thin film was obtained.

As shown by the barriers 30a, 30b, and 30c in FIG. 6, the resin material is provided by evaporating the resin material by installing the barrier so that the area to which the support is adhered cannot be directly seen from the evaporation region of the resin material from the heating element. Can prevent the adhesion of bumping particles from the evaporation region other than the portion that first comes into contact with the heating element. Moreover, the barriers 30a, 30b, 30c
Absorbs fluctuations in the amount of evaporation of the resin material over time, and stabilizes the amount of adhesion. Further, the resin material vapor is uniformly diffused also in the width direction. Therefore, it is presumed that a resin thin film having good surface properties and a uniform lamination thickness in both the longitudinal direction and the width direction was obtained.

The arrangement of the barriers 30a, 30b, 30c is not limited to the one shown in FIG. 6, and can be changed as appropriate so as to obtain the above-mentioned effects.

(Embodiment 7) FIG. 7 is a view showing an example of a method and an apparatus for producing a thin film according to the present invention.

The resin material is introduced into the vacuum chamber 5 through the supply pipe 3. The resin material supplied in a liquid state is
The liquid is dropped on a, and while flowing over it, a part thereof evaporates and spreads in a thin liquid film shape. The resin material that has reached the lower end of the heating plate 11a is dropped on the rotating heating roller 9, and while flowing thereover, a part thereof is vaporized and spreads in a thinner liquid film shape. The resin material that has reached the lower end of the heating roller
1b and spreads into a thin liquid film while a part of it is vaporized while flowing over it. The resin material that has reached the lower end of the heating plate 11b is further dropped onto the heating plate 11c, and while flowing over the resin material, a part thereof is vaporized and spreads in a thin liquid film shape. The resin material that has not completely evaporated is dropped into the cooling cup 4 from the lower end of the heating plate 11c, and the evaporation is completed. in this way,
By using three heating plates and heating rollers for the heating element,
Since the resin material can be held in a thin liquid film state for a long time, stable evaporation is possible.

The evaporated resin material is applied to the barriers 30a, 30
b, 30c, and adheres to the long substrate 1 running along the outer peripheral surface of the rotating cylindrical can 7 in the same manner as in the apparatus of FIG. 1 described in the first embodiment. It is formed. In addition, in order to re-evaporate the resin material adhering to the surrounding wall 13 and the barrier, and to prevent the wall from being stained, the surrounding wall and the barrier were also configured to have a heating structure. An ultraviolet irradiation device was used as the curing device 14 for curing the resin thin film.

Using the above apparatus, a target film thickness of 400 nm and a deposition rate of 2,000 were applied on the long substrate 1 using cyclohexane dimethanol divinyl ether as a resin material.
A resin thin film layer was laminated at nm / s. The surface characteristics of the obtained resin thin film were similarly evaluated. As a result, the number of defects was 3 /
m ² , and a resin thin film having a good surface was obtained.
In addition, the long substrate 1 is moved from the evaporation region of the resin material from the heating body.
Walls 30a, 30 so that the area to which the
b, 30c, the above-described Embodiment 6
Similarly to the above, a resin thin film having good surface properties and uniform lamination thickness in both the longitudinal direction and the width direction was obtained.

(Eighth Embodiment) In the apparatus shown in FIG. 7 described in the seventh embodiment, the supply pipe 3 is replaced with the supply pipe 31 shown in FIG.
Was replaced. The supply pipe 31 of the present embodiment is formed by connecting a straight hollow pipe 32 to a substantially central portion of one side of a hollow pipe 33 connected in a rectangular shape. On the side of the rectangular hollow tube 33 facing the side where the straight hollow tube 32 is connected, a predetermined number of fine holes 34 are formed at equal intervals. The resin material supplied from the straight hollow tube 32 passes through the inside of the rectangular hollow tube 33 and is dripped almost uniformly onto the heating plate 11a from the plurality of fine holes 34.

Using the apparatus shown in FIG. 7 provided with such a supply pipe 31, a resin thin film layer is deposited on the long substrate 1 running along the outer peripheral surface of the can 7 under the same conditions as in the seventh embodiment. Was. The used supply pipe has a diameter of 0.5 mm and an interval d of 1
It is a supply pipe having 15 micropores of 0 mm.

The surface characteristics of the obtained resin thin film were similarly evaluated. As a result, a wide resin thin film having a width of about 180 mm and a good surface having a defect count of 2 / m ² was obtained on the long substrate 1. Further, the barriers 30a and 30a are provided so that the adhered area of the long substrate 1 cannot be seen directly from the evaporation area of the heating element.
By providing b and 30c, a resin thin film having good surface properties and a uniform lamination thickness in both the longitudinal direction and the width direction was obtained.

As described above, when it is desired to form a wide resin thin film layer, a plurality of resin material supply points are provided according to the width to be formed, and a plurality of evaporation regions are provided. It can be seen that the width of the region should be increased. Furthermore, at this time, by providing a barrier so that the area to which the long substrate 1 is adhered cannot be directly seen from the area of evaporation of the resin material from the heating body, there is little variation in lamination thickness with time, and the vapor of the resin material is reduced. It is possible to form a thin film that is uniformly diffused in the width direction and has less lamination thickness unevenness in the width direction.

(Embodiment 9) FIG. 9 is a view showing another example of the method and apparatus for manufacturing a thin film according to the present invention.

The resin material is supplied to the resin container 42 inside the vacuum layer 5 via the supply pipe 3. The liquid resin material stored in the resin container 42 adheres to the outer peripheral surface of the rotating transfer roll 41, and then transfers to the outer peripheral surface of the rotating heating roller 40 in contact with the outer peripheral surface of the transfer roll 41. According to the present embodiment, since the resin material is transferred to the outer peripheral surface of the heating roller 40 as a thin film having a uniform thickness, the variation with time of the evaporation amount is extremely small, and a thin film having a uniform thickness can be formed. In addition, the transfer roller 41 and the heating roller 40
By changing the length (in the direction perpendicular to the paper of FIG. 9), the width of the evaporation region of the resin material can be changed, and a resin thin film having a desired width can be easily obtained.

The resin container 42 and the transfer roll 41 may or may not be heated. Further, in order to prevent the resin material adhering to the outer peripheral surface of the transfer roll 41 from coming into contact with the outer peripheral surface of the heating roller 40 and being rapidly heated to prevent the coarse particles from scattering around, the contact point between the two rolls is reduced. 4 barriers on the side of attachment
3a and 43b are provided.

The resin material evaporated as described above is applied to the barrier 30
a, 30b, and 30c, and rotates like the apparatus of FIG. 1 described in the first embodiment.
Is adhered onto the long substrate 1 running along the outer peripheral surface of the substrate, and a resin thin film is formed. In addition, in order to re-evaporate the resin material adhering to the surrounding wall 13 and the barrier, and to prevent the wall from being stained, the surrounding wall and the barrier were also configured to have a heating structure. An ultraviolet irradiation device was used as the curing device 14 for curing the resin thin film.

Using the above-described apparatus, a target film thickness of 200 nm and a deposition rate of 1500 were applied on the long substrate 1 using dimethylol tricyclodecane diacrylate as a resin material.
A resin thin film layer was laminated at nm / s. The transfer width of the transfer roll 41 used was 150 mm, and a resin thin film having the same width as this was transferred onto the outer peripheral surface of the heating roller 40 and formed. The barriers 30a, 30b and 30c used were the same dimensions as in the eighth embodiment.

The surface characteristics of the obtained resin thin film were similarly evaluated. As a result, a wide resin thin film having a good surface with a defect number of 3 / m ² and a width of about 170 mm was obtained on the long substrate 1. Further, in addition to the uniform resin thin film being formed on the heating roller 40 by the transfer roll, the barriers 30a, 30b, and 30c are provided so that the adhered area of the long substrate 1 cannot be directly seen from the evaporation area of the heating body. As a result, a resin thin film having a uniform lamination thickness in the longitudinal direction and the width direction was obtained as compared with the eighth embodiment.

As described above, when it is desired to form a wide resin thin film layer, the width of the evaporation region of the resin material may be increased by changing the transfer width of the transfer roll according to the width to be formed. Recognize. Furthermore, at this time, by providing a barrier so that the area to which the long substrate 1 is adhered cannot be directly seen from the area of evaporation of the resin material from the heating body, there is little variation in lamination thickness with time, and the vapor of the resin material is reduced. It is possible to form a thin film that is uniformly diffused in the width direction and has less lamination thickness unevenness in the width direction.

Embodiment 10 In the apparatus of FIG. 1 described in Embodiment 1, the temperatures of the two heating plates 11 were changed. That is, the temperature of the first heating plate was set to 110 ° C, and the temperature of the second heating plate was set to 130 ° C. Except for this, a resin thin film was formed on the substrate 1 in exactly the same manner as in the first embodiment.

The surface characteristics of the obtained resin thin film were similarly evaluated.
did. As a result, the number of defects was 2 / m ^TwoExample 1
A resin thin film having a better surface was obtained. In addition,
As compared with the first embodiment, the protrusion of the resin material on the first heating plate 11
Boiling and heat curing were clearly less.

This is considered for the following reason.
The resin material supplied by the supply pipe 3 is first dropped on the first heating plate. At this time, since the first heating plate is maintained at a relatively low temperature (110 ° C.), the temperature difference between the resin material and the first heating plate becomes smaller than that in the first embodiment, and The bumping was prevented. Therefore, the number of coarse particles diverging and adhering to the substrate 1 was reduced, and the number of defects was reduced. Also, the first heating plate is the same as that of the first embodiment.
Since the temperature is lower, the droplets of the resin material on the first heating plate are likely to be uniformly heated as a whole. Therefore, the phenomenon that only the resin material in contact with the first heating plate is rapidly heated, and only that portion is hardened on the heating plate, which is slightly observed in the first embodiment, does not easily occur. Since the temperature difference between the first heating plate and the second heating plate is not so large, the resin material dropped on the second heating plate is rapidly heated and bumps, or the droplets become uneven. The resin material that is heated and is in contact with the heating plate is not cured by heat.

Further, as in the present embodiment, the inclination of the second heating plate maintained at a high temperature is changed to the first heating plate maintained at a low temperature.
If the inclination of the heating plate is set to be larger than that of the heating plate, the speed at which the liquid resin material flows on the high-temperature region (the second heating plate) increases, so that bumping and thermosetting on the second heating plate become more difficult. It can be further prevented. As described above, increasing the inclination of the high-temperature heating plate is particularly effective for a resin material which is easily thermoset at a high temperature or a resin material which can be sufficiently evaporated even at a relatively low temperature.

When the target film thickness and the deposition rate were changed in various ways, the target film thickness and the target film thickness were larger than those in the first embodiment.
And higher deposition rates.

This is considered to be due to the following reasons.
When the resin material is thermally cured on the heating plate, the heating of the sequentially supplied resin material is hindered, and it becomes difficult to maintain a stable evaporation amount. When the temperature of the first heating plate is set to a relatively low temperature as in the present embodiment, the thermosetting of the resin material can be prevented, so that such a problem can be solved. In addition, a part of the resin material heated while flowing on the first heating plate evaporates, and the rest is dropped on the second heating plate. Since the second heating plate is set at a higher temperature than the first heating plate, it is further heated and evaporates. In this way, a part of the supplied resin material evaporates without waste without being thermoset. Therefore, it is understood that the deposition efficiency can be improved by heating the resin material in advance and then supplying it to the heater.

In the present embodiment, the first heating plate is heated to a relatively low temperature and the second heating plate is heated to a relatively high temperature. However, the present invention is not limited to this. For example, one or more heating plates may be further provided between the first heating plate and the second heating plate, and the heating may be performed so that the temperature increases in order. Also, instead of heating all the independent heating plates uniformly, the area where the resin material is first dropped is maintained at a relatively low temperature, and the temperature of the heating element is set along the path along which the resin material flows. May be provided in a single continuous heating body so that the temperature is not gradually increased. Furthermore, a plurality of such heating elements having a plurality of temperature regions may be separately installed, and the resin material may be gradually heated by flowing sequentially over these heating elements. .

Further, in the present embodiment, the inclination of the second heating plate maintained at a high temperature is made larger than the inclination of the first heating plate maintained at a low temperature, but the present invention is not limited to this. For example, contrary to the present embodiment, the inclination of the second heating plate maintained at a high temperature may be smaller than the inclination of the first heating plate maintained at a low temperature. Such a setting of the inclination is particularly effective, for example, for a resin material that has a high viscosity at a relatively low temperature, has poor fluidity, and is difficult to evaporate. By increasing the inclination of the first heating plate maintained at a low temperature, the fluidity of the resin material is ensured, the convection in the liquid droplets is promoted, and a uniform temperature rise is promoted, and at the same time, thermal curing is prevented. This is because, by reducing the inclination of the second heating plate maintained at a high temperature, the flow rate can be reduced and a sufficient amount of evaporation can be secured.

Further, in a heating element having a plurality of different temperature zones in one continuous heating element, the inclination in each temperature zone is continuously or in order to optimize the flow rate of the resin material in each temperature zone. It may be changed stepwise (for example, the inclination is gradually increased or gradually decreased).

When the preheated resin material described in the fifth embodiment is supplied to the device described in the present embodiment,
The temperature difference between the resin material and the first heating plate is further reduced, and the resin material is suddenly heated and bumped, or the droplets are unevenly heated and the resin material in contact with the heating plate is thermally cured. This is preferable because the phenomenon can be further prevented.

The set temperature of the heating element and its inclination are not limited to those in the above-described embodiment. The optimum temperature and gradient can be set appropriately according to the type of the resin used.

(Embodiment 11) In addition to the barriers 30a, 30b and 30c in the apparatus of FIG. 6 described in Embodiment 6, barriers 44a and 44 having a heating structure as shown in FIG.
A resin thin film was formed in the same manner as in Embodiment 6 except that b and 44c were used. The barrier 44a and the barrier 44b, and the barrier 44a and the barrier 44c are installed at predetermined intervals and partly opposed to each other. The evaporated resin material is used as the barrier 44a and the barrier 44b or the barrier 44a and the barrier 4
4c between the opposing portions, and furthermore the barrier 30a
And reaches the surface of the support 1 through the space between the opposed portions of the barrier 30b and the barrier 30a and the barrier 30c. Here, the distance between the opposed portions of the barrier 30a and the barrier 30b and between the barrier 30a and the barrier 30c is d1, and the barrier 44a is
The barriers are installed such that d1> d2, where d2 is the distance between opposing portions of the barrier 44b and the barrier 44a and the barrier 44c.

The surface characteristics of the obtained resin thin film were similarly evaluated.
did. As a result, the number of defects was 1 / m ^TwoAnd the form of implementation
A resin thin film having a slightly better surface than that of State 6 was obtained.
Further, compared to the sixth embodiment, the length of the long substrate 1
The thickness unevenness of the resin thin film layer was small. Also, the thickness in the width direction
A more uniform resin thin film was obtained.

This is considered for the following reasons. In the sixth embodiment, the number of the facing portions of the barrier that the evaporated resin material passes through before reaching the adhered region of the support is one, whereas in the present embodiment it is two. The increase in the number of opposing portions of the barrier, through which the resin material must pass, makes it difficult for bumping particles of the resin material generated in the evaporation area to reach the area to be adhered, resulting in a resin thin film having good surface properties. It is thought that it was done. In addition, when the resin material is intermittently supplied in the form of droplets, the partial pressure of the resin material vapor in the evaporation region fluctuates with time. By arranging the barrier so as to have the opposing portion, the variation in the partial pressure of the resin material vapor in the evaporation region is smoothed in the process of reaching the deposition region. By providing the barriers in multiple stages as in the present embodiment, this effect is enhanced, and the temporal variation in the amount of evaporation of the resin material is absorbed, and the amount of adhesion is stabilized. Further, the effect of uniformly diffusing the resin material vapor also in the width direction is enhanced. Therefore, it is presumed that a resin thin film having a uniform lamination thickness in both the longitudinal direction and the width direction was obtained as compared with the sixth embodiment.

The arrangement and number of the barriers are not limited to those shown in FIG.

(Embodiment 12) In the apparatus shown in FIG. 10 described in Embodiment 11, a barrier 30a and a barrier 30b are provided.
The distance d1 between the opposing portions of the barriers 30a and 30c and the distance d2 between the opposing portions of the barriers 44a and 44b and between the opposing walls 44a and 44c are represented by d1.
<D2, that is, the distance d1 in the present embodiment is the same as the distance d2 in the eleventh embodiment,
A resin thin film was formed in the same manner as in Embodiment 11 except that each barrier was provided so that the interval d2 in this embodiment was the same as the interval d1 in Embodiment 11.

The surface characteristics of the obtained resin thin film were similarly evaluated.
did. As a result, the number of defects was 1 / m ^TwoAnd the form of implementation
A resin thin film having a surface equivalent to that of Embodiment 11 was obtained. Ma
In addition, the thickness unevenness of the resin thin film layer in the longitudinal direction of the long substrate 1 is
It was slightly inferior to the eleventh embodiment. Also, in the width direction
The thickness unevenness of the resin thin film layer is slightly smaller than that of the eleventh embodiment.
And it was inferior.

The reason can be considered as follows. As described above, the opposing portion of the barrier has a buffering function of absorbing fluctuations in the partial pressure of the resin material vapor in the evaporation region and smoothing it. The distance between the facing portions of the barriers (the barriers 44a, 44b, 44c in the present embodiment) closer to the evaporation region is set to the distance between the facing portions of the barriers farther than this (the barriers 30a, 30b, 30c in the embodiment of the present invention). When the distance is smaller than the interval, the buffering action of the barrier closer to the source of the variation in the partial pressure is strengthened, and the buffering action of the barrier functions effectively, and the amount of adhesion in the adhered area is more stabilized. It is considered something. Similarly, it is considered that the effect of uniformly diffusing the resin material vapor in the width direction is enhanced.

From the above results, according to the method and apparatus for manufacturing a thin film of the present invention, it is possible to efficiently evaporate a resin material and to perform stable film formation at a high deposition rate while suppressing thermosetting and bumping as much as possible. It is thought that industrial significance is great.

In the above embodiment, the case where an acrylate-based resin material is used as the dielectric has been described. However, other materials such as an epoxy-based material can also be used. Further, in the embodiment, the case where ultraviolet curing and electron beam curing are used as the curing method has been described, but the present invention is not particularly limited by the curing means.

[0079]

As described above, according to the method and apparatus for producing a thin film of the present invention, an excellent resin thin film can be obtained at a high deposition rate.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a method and an apparatus for producing a thin film according to the present invention.

FIG. 2 is a schematic view showing another example of the method and apparatus for manufacturing a thin film according to the present invention.

FIG. 3 is a schematic view showing still another example of the method and apparatus for manufacturing a thin film according to the present invention.

FIG. 4 is a schematic view showing still another example of the method and apparatus for manufacturing a thin film according to the present invention.

FIG. 5 is a schematic view showing an example of a comparative example of a method and an apparatus for manufacturing a thin film.

FIG. 6 is a schematic view showing still another example of the method and apparatus for manufacturing a thin film according to the present invention.

FIG. 7 is a schematic view showing still another example of the method and apparatus for manufacturing a thin film according to the present invention.

FIG. 8 is a schematic perspective view showing an example of a resin supply pipe used in the method and apparatus for manufacturing a thin film according to the present invention.

FIG. 9 is a schematic view showing still another example of the method and apparatus for manufacturing a thin film according to the present invention.

FIG. 10 is a schematic view showing still another example of the method and apparatus for manufacturing a thin film according to the present invention.

[Explanation of symbols]

 Reference Signs List 1 long substrate 2 carrier 3 supply pipe 4 cup 5 vacuum tank 6 exhaust system 7 can 8 blade 9 heating roller 10 heating belt 11, 11a, 11b, 11c heating plate 12 barrier 13 peripheral wall 14 curing device 15 unwinding roll 16 winding Take-up roll 17 Guide roll 18 Moving direction 19 Partition wall 20 EB evaporation source 30a, 30b, 30c Barrier wall 31 Supply pipe 32 Straight hollow pipe 33 Rectangular hollow pipe 34 Micro hole 40 Heating roller 41 Transfer roll 42 Resin container 43a, 43b Barrier 44a, 44b, 44c

Continuation of the front page (72) Inventor Nobuki Sunaru 1006 Kazuma Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.

Claims (32)

[Claims] 1. A method for producing a thin film, wherein a resin material is evaporated in a vacuum to adhere to a support, wherein at least the resin material is evaporated while flowing along a heating element. 2. The position according to claim 1, wherein a portion where the resin material first comes into contact with the heating element has a positional relationship where a portion where the resin material adheres to the support is not directly visible. Manufacturing method of thin film. 3. The method according to claim 1, wherein the heating element along which the resin material flows comprises a plurality of regions having different temperatures. 4. The method for producing a thin film according to claim 3, wherein at least a part of the other portion of the heating element is higher in temperature than the temperature of the heating element that the resin material contacts first. . 5. The heating method according to claim 1, wherein the resin material flows along the heating element, then leaves the heating element in a liquid state, and flows again along another part of the heating element. The method for producing a thin film according to any one of the above. 6. The method according to claim 1, wherein the heating element along which the resin material flows comprises a plurality of regions having different inclinations. 7. The method for producing a thin film according to claim 1, wherein at least a part of the heating element performs a movement, a rotation, or both operations. 8. The method according to claim 1, wherein a part of the resin material flowing along the heating plate is accumulated in a liquid state at a temperature lower than a maximum temperature of the heating element. A method for producing the thin film according to the above. 9. When supplying a resin material to a heating element,
2. The method according to claim 1, wherein the resin material is heated in advance.
3. The method for producing a thin film according to item 1. 10. The method for producing a thin film according to claim 1, wherein the resin material is evaporated such that the region to which the support is adhered cannot be directly seen from the evaporation region of the resin material. 11. The apparatus according to claim 1, wherein the evaporated resin material reaches a region to which the support is adhered at a predetermined interval through a barrier provided to form an opposing portion. 11. The method for producing a thin film according to item 10. 12. The method for producing a thin film according to claim 11, wherein there are a plurality of opposing portions of the barrier wall through which the evaporated resin material passes before reaching the adhesion region of the support. 13. The space according to claim 12, wherein an interval between certain opposing portions of the plurality of opposing portions of the barrier is larger than an interval between the opposing portions closer to the vapor deposition region of the resin material. Manufacturing method of thin film. 14. The method for producing a thin film according to claim 1, wherein the evaporation region of the resin material has a width according to the width of the resin material attached to the support. 15. The method for manufacturing a thin film according to claim 1, wherein a plurality of evaporation regions of the resin material are provided according to a width of the resin material attached to the support. 16. The method according to claim 1, wherein a resin material is supplied to the heating element by a transfer roll. 17. The method for producing a thin film according to claim 1, wherein the thin film is laminated by rotating the support. 18. A vacuum vessel, a supply device for supplying a resin material in the vacuum vessel, an evaporator for evaporating the resin material, and a resin thin film formed by adhering the evaporated resin material. An apparatus for manufacturing a thin film having a support for performing the above, wherein the evaporator has means for evaporating while moving the resin material. 19. The apparatus according to claim 18, wherein the means for evaporating the resin material while moving the resin material comprises at least a heating plate. 20. The apparatus according to claim 18, wherein the means for evaporating the resin material while moving the resin material comprises at least a heating roller. 21. The apparatus for manufacturing a thin film according to claim 18, wherein the means for evaporating the resin material while moving the resin material comprises at least a heating belt. 22. The thin film manufacturing apparatus according to claim 18, wherein a barrier is provided to block a straight line connecting a resin material supply position and a resin thin film formation position. 23. The apparatus according to claim 18, wherein a part of the resin material is collected in a cooling container. 24. The method according to claim 18, wherein a part of the resin material is guided to the inclined inner wall surface of the heating vessel and collected.
3. The apparatus for producing a thin film according to any one of 2. 25. The thin film manufacturing apparatus according to claim 18, further comprising a resin material heating device for heating the resin material in advance when supplying the resin material. 26. The thin film manufacturing apparatus according to claim 18, wherein a barrier is provided so that a region to which the support is adhered cannot be directly seen from an evaporation region of the resin material. 27. The thin-film manufacturing apparatus according to claim 22, wherein the barrier is provided so as to form a portion facing each other at a predetermined interval. 28. The barrier according to claim 27, wherein the barrier is provided such that the evaporated resin material passes through the facing portions of the plurality of barriers before reaching the adhesion area of the support. Thin film manufacturing equipment. 29. The barrier according to claim 29, wherein the distance between certain opposing portions of the plurality of opposing portions through which the resin material passes is greater than the distance between the opposing portions on the resin material deposition region side. 29. The method of claim 28, wherein
2. The apparatus for producing a thin film according to claim 1. 30. The apparatus for manufacturing a thin film according to claim 18, wherein a plurality of supply points of the resin material are provided according to a width of the resin material adhered to the support. 31. The apparatus for manufacturing a thin film according to claim 18, wherein the supply of the resin material is performed by a transfer roll. 32. The apparatus for producing a thin film according to claim 18, wherein the support rotates.