JP4869013B2 - Multilayer film manufacturing method and film forming apparatus - Google Patents

Description

  According to the present invention, a long film-forming substrate is alternately immersed in a solution containing a first functional material and a solution containing a second functional material, whereby one surface of the film-forming substrate is The present invention relates to a method for efficiently manufacturing a uniform multilayer film, and a multilayer film forming apparatus suitable for carrying out this manufacturing method.

Conventionally, as a method for producing a composite organic thin film, a method using alternating adsorption (Layer-by-Layer Electrostatic Self-Assembly) is known (Non-Patent Document 1).
In this method, an aqueous solution of a positive electrolyte polymer (cation) and an aqueous solution of a negative electrolyte polymer (anion) are prepared in separate containers, and an initial surface charge is applied to these containers (film formation substrate). By alternately immersing the material, a composite organic ultrathin film (alternate adsorption film) having a multilayer structure on the substrate is obtained.

For example, when a glass substrate is used as the deposition target substrate, the surface of the glass substrate OH on the surface to hydrophilic treatment ^- by introducing a group, it has a negative charge as the initial surface charge. Then, when this negatively charged substrate is immersed in a positive electrolyte polymer aqueous solution, the positive electrolyte polymer is adsorbed on the surface by Coulomb force until at least the surface charge is neutralized. It is formed. The surface portion of the ultrathin film thus formed is positively charged. Therefore, this time, if this substrate is immersed in a negative electrolyte polymer aqueous solution, the negative electrolyte polymer is adsorbed by Coulomb force and a single ultrathin film is formed.
In this way, by alternately immersing the substrate in two solutions, an ultra thin film layer made of a positive electrolyte polymer and an ultra thin film layer made of a negative electrolyte polymer can be alternately formed, and a multilayer structure can be formed. A composite organic thin film can be formed.

  Recently, a technique for automating the production of the alternating adsorption film has also been proposed. For example, Non-Patent Document 2 proposes a configuration of an automatic manufacturing apparatus for alternating adsorption films. If this apparatus is used, since the substrate as the film formation substrate is alternately immersed in the two water tanks by the robot arm, the alternate adsorption film is automatically formed on the substrate.

  Non-Patent Document 3 and Patent Document 1 propose a method and a film forming apparatus for forming an alternating adsorption film having a multilayer structure using a long film-forming substrate. That is, as shown in FIG. 8, a positive electrolyte polymer solution is put into the water tank 110, a negative electrolyte polymer solution is put into the water tank 130, and water for the rinse bath is put into the remaining water tanks 120a, 120b, 140a, and 140b. A roll-like (long) fiber material 100 is set in a roll holding part (not shown), one end thereof is drawn out along the introduction path S, drawn along the rolls R1 to R16, and cut at one round. Both ends are stitched to form an annular structure along the circulation path S (→). When the annular fiber material is rotationally driven along the circulation path S (→), the positive electrolyte polymer and the negative electrolyte polymer are alternately adsorbed on the surface of the fiber material, and the alternate adsorption film having a multilayer structure Is formed.

  However, in the forming methods described in these documents, since both surfaces of the substrate to be deposited are in contact with the roll, the formed electrolyte polymer coating film is damaged by the roll, and a uniform multilayer film cannot be formed. There was a case.

  Further, Patent Document 1 describes a mechanism in which only a part of both side surfaces of a base material is in contact with the roll in order to avoid contact between the roll and the coating film. However, it is difficult for such a mechanism to cope with a wide substrate.

JP 2001-62286 A Decher. G, Hong. J. et al. D. and J. et al. Schmit: Thin Solid Films, 210/211, p. 831 (1992). A. C. Fon, O. Onitsuka, M .; Ferreira, B.M. R. Hsieh and M.M. F. Rubner: J.M. Appl. Phys. 79, 10 (1996) Convertech, 2006, N0,6, p67-p75

  The present invention has been made in view of the situation of the prior art as described above. A long film-forming substrate is formed of a solution containing first charged particles, and a charge opposite to the charge of the first charged particles. A method for efficiently producing a uniform multilayer film on one surface of various substrates to be deposited regardless of the width, by alternately immersing in a solution containing second charged particles having It is an object of the present invention to provide a multilayer film forming apparatus suitable for carrying out the method.

  As a result of diligent research to solve the above problems, the present inventor alternately dipped a long glass fiber in a solution containing a positive electrolyte polymer and a solution containing a negative electrolyte polymer. In the method of forming an alternating adsorption film composed of multiple layers on one surface, a first solution tank containing a solution containing a positive electrolyte polymer and a second solution tank containing a solution containing a negative electrolyte polymer An operation of immersing the web in the order of a first solution tank, a first rinse tank, a second solution tank, and a second rinse tank while preparing and conveying a long glass fiber in a spiral shape in the lateral direction By repeating the above, it has been found that an alternating adsorption film composed of a uniform multilayer can be efficiently formed regardless of the width of the substrate, and the present invention has been completed.

Thus, according to the first aspect of the present invention, there is provided a method for producing a multilayer film according to the following (1) to (4).
(1) A long film-forming substrate is alternately immersed in a solution containing first charged particles and a solution containing second charged particles having a charge opposite to that of the first charged particles. A method for producing a multilayer film on one surface of the substrate to be deposited,
Preparing a first solution tank containing a solution containing the first charged particles and a second solution tank containing a solution containing second charged particles;
While the long film-forming substrate is spirally conveyed from the first solution tank toward the second solution tank, the film-forming substrate is immersed in the first solution tank,
After immersing the film-forming substrate in the first solution tank and before immersing in the second solution tank, the film-forming substrate is rinsed with a first rinsing liquid,
The surface of the substrate on which the film is formed is dried with a drying device,
Next, the multilayer film manufacturing method is characterized in that the film is immersed in the second solution tank directly or through another tank.
(2) The method for producing a multilayer film according to (1), wherein the coated surface of the film-forming substrate rinsed is dried by the drying device.
(3) The multilayer film according to (2), wherein the deposition target substrate is immersed in a second solution tank, and then the deposition target substrate is rinsed with a second rinse liquid. Production method.
(4) The surface on which the multilayer film of the film-forming substrate is formed is surface-treated before the film-forming substrate is immersed in the first solution tank. The manufacturing method of the multilayer film in any one of.

According to 2nd of this invention, the film-forming apparatus as described in following (5)-(8) is provided.
(5) A long film-forming substrate is alternately immersed in a solution containing first charged particles and a solution containing second charged particles having a charge opposite to that of the first charged particles. A film forming apparatus for forming a multilayer film on one surface of the film forming substrate,
A film-forming substrate feed-out portion for sending a long film-forming substrate to the first tank roll;
A first solution tank containing a solution containing first charged particles;
A second solution tank containing a solution containing second charged particles;
A first outer roll provided on the first solution tank;
A first tank roll provided in the first solution tank;
A second tank outer roll provided on the second solution tank;
A second tank roll provided in the second solution tank;
A first rinse tank provided between the first solution tank and the second solution tank and containing a first rinse liquid;
A third tank roll is provided between the first rinse tank and the second solution tank;
A drying device provided between the first rinsing tank and the roll outside the tank, and drying the surface of the film formation substrate rinsed with the first rinsing liquid with a drying device;
A film-forming substrate recovery unit for recovering a long film-forming substrate immersed in the second solution tank;
The long film-forming substrate is arranged in the order of a first tank roll, a first tank roll, a third tank roll, a second tank roll, and a second tank roll. A film forming apparatus for forming a multilayer film on one surface of the film forming substrate by carrying it in a spiral.
(6) The film forming apparatus according to (5), wherein the drying apparatus dries the coated surface of the rinsed film forming substrate.
(7) A second rinse tank containing a second rinse solution is installed between the second solution tank and the film-depositing substrate recovery unit, and the film-forming substrate is second (6) The film forming apparatus according to (6), wherein the film forming apparatus is immersed in the second rinsing tank after being immersed in the solution tank.
(8) A surface treatment apparatus for surface-treating the surface of the film-forming substrate on which the multilayer film is to be formed is further installed between the film-forming substrate feeding part and the first solution tank. The film forming apparatus according to any one of (5) to (7), which is characterized.

(6) A first rinsing tank containing a first rinsing liquid is installed between the first solution tank and the second solution tank, and the film formation substrate is used as the first solution tank. The film forming apparatus according to (5), wherein the film forming apparatus is immersed in the first rinsing tank after being immersed in the second solution tank before being immersed in the second solution tank.
(7) A second rinse tank containing a second rinse solution is installed between the second solution tank and the film-depositing substrate recovery unit, and the film-forming substrate is second (6) The film forming apparatus according to (6), wherein the film forming apparatus is immersed in the second rinsing tank after being immersed in the solution tank.
(8) A surface treatment apparatus for surface-treating the surface of the film-forming substrate on which the multilayer film is to be formed is further installed between the film-forming substrate feeding part and the first solution tank. The film forming apparatus according to any one of (5) to (7), which is characterized.

  According to the multilayer film manufacturing method of the present invention, when a multilayer film is continuously formed on one surface of a long film-forming substrate, the surface side on which the multilayer film is formed does not come into contact with the roll. Therefore, the coating film of the solution containing the first or second functional material is not damaged by contact with the roll. Therefore, according to the method for producing a multilayer film of the present invention, a uniform multilayer film can be produced continuously and efficiently without being limited by the width of the substrate.

  The multilayer film produced by the production method of the present invention is expected to be used for various electronic devices including an organic EL (Electro-Luminescence) element, and further, by forming an alternate adsorption film on the surface. Since the hydrophilicity can be controlled, the application to the coating technology on the surface of contact lenses and the application to biomaterials are also attracting attention.

  According to the multilayer film forming apparatus of the present invention, when the multilayer film is continuously formed on one surface of the long film-forming substrate, the surface side on which the multilayer film is formed does not come into contact with the roll. The coating film of the solution containing the first or second functional material is not damaged by contact with the roll. Therefore, according to the multilayer film forming apparatus of the present invention, a uniform multilayer film can be formed continuously and efficiently.

The multilayer film manufacturing method and film forming apparatus of the present invention will be described in detail below.
1) Multilayer Film Manufacturing Method In the multilayer film manufacturing method of the present invention, a long film-forming substrate is charged with a solution containing first charged particles and a charge opposite to the charge of the first charged particles. A method for producing a multilayer film on one surface of the substrate to be deposited by alternately immersing in a solution containing second charged particles having a solution containing the first charged particles. A first solution tank and a second solution tank containing a solution containing second charged particles are prepared, and the long film-forming substrate is directed from the first solution tank to the second solution tank. The substrate to be deposited is immersed in the first solution tank while being spirally conveyed, and then immersed in the second solution tank directly or via another tank.

(1) Film formation substrate The film formation substrate used in the present invention is long (roll-shaped), and a first charged particle layer or a second charged particle layer is formed on the surface by an immersion method. There is no particular limitation as long as it can be formed. In addition, the size (width and length) of the film-forming substrate used in the present invention is not particularly limited, and an appropriate one can be used according to the application.

  Examples of the material for the film-forming substrate used in the present invention include fibers such as polyester, polyamide, acrylic, silk, hair, and glass fiber; polypropylene, polyurethane, polystyrene, polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone And plastics such as polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, and the like.

(2) Multilayer film In the production method of the present invention, a long film-formed substrate is formed by using a solution containing first charged particles and a second charge having a charge opposite to the charge of the first charged particles. In this method, a multilayer film is produced on one surface of the substrate to be deposited by alternately immersing in a solution containing particles. The multilayer film produced by the present invention is an alternating adsorption film formed by utilizing the interaction between molecules such as Coulomb force.

  Specific examples of such alternating adsorption films include optical waveguides, light absorption films, antireflection films, nonlinear optical films, fluorescent films, electrochromic films, photovoltaic / solar cells, conductive films, superhydrophobic films, hydrophilicity A membrane, a filter, a sensor, etc. are mentioned.

  In the present invention, a solution containing first charged particles and a solution containing second charged particles having a charge opposite to that of the first charged particles are used. That is, if the first charged particle is a positive charged particle, the second charged particle is a negative charged particle.

The combination of the solution containing the first charged particles and the solution containing the second charged particles used in the present invention is not particularly limited, and for example, a solution containing a positive electrolyte polymer exemplified in (a) below: A combination of a solution containing a negative electrolyte polymer exemplified in (b) below, a combination of a solution containing a conductive electrolyte polymer and a solution containing an insulating electrolyte polymer, a ruthenium complex monomer (for example, Ru (bpy) ₃ Cl ₂ ) Solution (positively charged monomer aqueous solution) and polyacrylic acid aqueous solution (negatively charged polymer aqueous solution), inorganic fine particles such as ferrite fine particles, positively charged surfactant (amphiphile) A combination of a dispersion in which a surfactant is dispersed in a solvent and an inorganic fine particle, such as a ferrite fine particle, in which a surfactant (amphiphile) having a negative charge is dispersed in a solvent, etc. Can be mentioned. Here, bpy represents bipyridyl.

(A) Positive electrolyte polymer

(B) Negative electrolyte polymer

  Solvents used for the preparation of these solutions include water; alcohols such as methanol and ethanol; ketones such as acetone; amides such as dimethylformamide; ethers such as tetrahydrofuran; organic amines such as pyridine; Nitriles; and combinations of two or more thereof; and the like.

  In the present invention, the film thickness, density, etc. of the resulting multilayer film are set by setting the concentration, pH, etc. of the solution containing the first charged particles and the solution containing the second charged particles to an arbitrary value. Can be controlled.

  The multilayer film manufacturing method of the present invention prepares a first solution tank containing a solution containing the first charged particles and a second solution tank containing a solution containing second charged particles, While the long film-forming substrate is spirally conveyed from the first solution tank to the second solution tank, the film-forming substrate is immersed in the first solution tank, and then directly Or it is immersed in said 2nd solution tank through another tank, It is characterized by the above-mentioned.

  The above-mentioned “conveying the long film-forming substrate spirally from the first solution tank to the second solution tank” means that the long film-forming substrate is transferred from the first solution tank to the first solution tank. It means that it conveys in the direction of 2 solution tanks so that a spiral may be drawn.

A first solution tank that contains a solution containing the first charged particles and a second solution that contains a solution containing second charged particles while continuously conveying a long film-forming substrate. In order to immerse alternately in the tank, guide rolls (inside the tank and outside the tank) are provided in the first solution tank and the second solution tank, and above the first solution tank and the second solution layer, respectively. Roll) and a long film-forming substrate may be conveyed in a certain direction along the guide roll. At this time, if the long film-forming substrate is transported spirally from the first solution tank to the second solution tank, the portion of the film-forming substrate that contacts the guide roll is always on one side. It can only be a surface. Therefore, according to the multilayer film manufacturing method of the present invention, a uniform multilayer film can be continuously and efficiently manufactured.
The method for producing a multilayer film of the present invention can be preferably carried out by using a film forming apparatus of the present invention described later.

2) Film formation apparatus The second aspect of the present invention is that a long film-forming substrate is formed by using a solution containing first charged particles and a second charge having a charge opposite to the charge of the first charged particles. A film forming apparatus for forming a multilayer film on one surface of the film forming substrate by alternately immersing in a solution containing particles,
A film-forming substrate feed-out portion for sending a long film-forming substrate to the first tank roll;
A first solution tank containing a solution containing first charged particles;
A second solution tank containing a solution containing second charged particles;
A first outer roll provided on the first solution tank;
A first tank roll provided in the first solution tank;
A second tank outer roll provided on the second solution tank;
A second tank roll provided in the second solution tank;
A film-forming substrate recovery unit for recovering a long film-forming substrate immersed in the second solution tank;
By conveying the long film-forming substrate spirally along the order of the first tank roll, the second tank roll, the second tank roll, and the second tank roll. A film forming apparatus for forming a multilayer film on one surface of the film forming substrate.

  In addition, it is also possible to use all the rolls outside the tank as one long roll. In such a case, it is effective for downsizing the film forming apparatus. Moreover, you may arrange | position a roll outside a tank in polygonal shapes, such as a triangle which makes a roll in a tank a vertex. Thereby, the angle of entry into and exit from the solution tank of the base material at the roll portion in the tank can be freely designed.

An example of the film forming apparatus of the present invention is shown in FIG.
The film forming apparatus shown in FIG. 1 is a film forming substrate sending part 15 for sending a long film forming substrate 1 wound up in a roll shape to a conveyance path, and a first containing a solution containing positive charged particles. 1 solution tank 2, a first rinse tank 3 that contains a first rinse liquid, a second solution tank 4 that contains a solution containing negatively charged particles, and a second rinse that contains a second rinse liquid Provided on the tank 5, the outside roll 6 provided on the first solution tank 2, the inside roll 7 provided on the first solution tank 2, and the first rinse tank 3 The outside roll 8 provided, the inside roll 9 provided in the first rinse tank 3, the outside roll 10 provided on the second solution tank 4, and the second solution tank. 4 in the tank, the roll 12 outside the tank provided on the second rinse tank 5, and the second rinse tank 5. The inner roll 13, the outer roll 14 provided between the second rinsing tank 5 and the film formation substrate recovery unit 16, and the long film formation substrate 1 on which a multilayer film is formed. The film-forming base material collection | recovery part 16 which winds up in roll shape.

  The film forming apparatus shown in FIG. 1 includes a long film-forming substrate 1 that includes a tank roll 6, a tank roll 7, a tank roll 8, a tank roll 9, a tank roll 10, a tank roll 11, While the outer roll 12, the inner roll 13, and the outer roll 14 are transported spirally in the lateral direction, the long film-forming substrate 1 is transferred to the first solution tank 2, the first By immersing in the rinsing tank 3, the second solution tank 4, and the second rinsing tank 5 in this order, an alternate adsorption film composed of two layers is formed on one surface of the long film-forming substrate 1. To form.

  Hereinafter, an operation procedure for forming an alternating adsorption film composed of two layers on one surface of a long film-forming substrate 1 using the film forming apparatus shown in FIG. 1 will be described in detail.

  First, a long film-forming substrate 1 is prepared. Here, a long glass fiber is used as the film formation substrate 1.

  The long film-forming substrate 1 wound up in a roll shape contains a first charged particle containing solution containing the first charged particles from the film-forming substrate delivery unit 2 via the tank roll 6. It is sent into the solution tank 2.

  In this case, as shown in FIG. 2, it is preferable to install a surface treatment device 17 on the upper part of the out-of-tank roll 6 to surface-treat the surface portion of the surface on which the multilayer film of the film formation substrate 1 is formed. . As a result, a large number of hydrophilic groups such as OH groups are formed on the surface of the substrate 1 on which the multilayer film is to be formed, and the first charged particles are easily adsorbed, resulting in uniform and high quality. A multilayer film can be formed.

  Although it does not restrict | limit especially as said surface treatment apparatus 17, For example, a corona discharge treatment apparatus, a plasma discharge treatment apparatus, etc. are mentioned.

  The film-forming substrate 1 sent into the first solution tank 2 containing the solution containing the first charged particles passes through the solution containing the first charged particles through the tank roll 7. Thus, as shown in FIG. 3 ((a) → (b)), a layer of first positive charged particles is formed on the surface of the substrate to be deposited.

In this case, when it is desired to promote micelle formation when the first charged particle solution is a micelle solution, or when the first charged particles are components that are difficult to uniformly disperse, Or you may install the ultrasonic generator for giving the vibration by an ultrasonic wave to a 2nd solution tank.
In addition, depending on the solution, in the case where the components are easily dispersed uniformly by increasing the temperature, the solution in the first solution tank 2 and / or the second solution tank 4 is heated. A heating device (not shown) can be added.

  In FIG. 4, the schematic diagram of the 1st solution tank 2 is shown. 4A is a cross-sectional view of the first solution tank 2 viewed from the side, and FIG. 4B is a top view of the first solution tank 2 viewed from above. In the tank of the 1st solution tank 2, the solution A containing the 1st charged particle is accommodated. In this embodiment, an aqueous solution of a positive electrolyte polymer is used as the solution A containing the first charged particles.

  In the 1st solution tank 2, the roll 7 in a tank for sending the to-be-film-formed base material through the roll 6 outside a tank from the inside of the 1st solution tank 2 to the roll 8 outside a tank is installed. . An enlarged view of the tank roll 7 is shown in FIG. Rotating shafts 7a are provided at both ends of the tank roll 7, and are rotatably fitted in a rotating bearing (not shown) in the tank.

  In addition, the 1st rinse tank 3, the 2nd solution tank 4, and the 2nd rinse tank 5 have the same structure as the 1st solution tank 2 except the kind of solution accommodated differs. Yes. In addition, the roll inside the tank and the roll outside the tank other than the roll 7 inside the tank have the same structure as the roll 7 inside the tank.

  Next, the deposition target substrate 1 having the first charged particle layer formed on the surface is sent to the first rinsing tank 3 via the outer roll 8 and is then transferred to the first rinse tank 3 via the inner roll 9. Through this, the solution containing the first charged particles that have adhered excessively to the surface of the substrate 1 to be deposited is washed away.

  Here, as the first rinsing liquid, the same solvent as the solvent used for preparing the solution containing the first charged particles can be used. However, the solvent used as the rinse liquid is preferably a high-purity solvent from the viewpoint of preventing impurities from being mixed. For example, if the solvent is water, it is preferable to use ultrapure water.

In this case, for example, as shown in FIG. 6, a drying device 18 (for example, a device for blowing nitrogen gas) is installed between the first rinsing tank 3 and the third outer roll 10, and the first It is also preferable to dry the deposition target substrate surface on which one charged particle layer is formed. In addition, in FIG. 6, the drying apparatus 18 dries the coating surface (a white surface in a figure) of a back surface side.

  Further, in the present invention, a dedicated tank for drying (for example, a drying chamber equipped with a mechanism for blowing warm air) is provided, and water droplets adhering to the surface of the film formation substrate 1 are sufficiently dried and removed. A second charged particle layer may be formed.

  Note that the rinsing step is not limited to the method of immersing the film formation substrate in the rinsing liquid, but may be a method of performing a shower with the rinsing liquid.

  Next, the film formation target substrate 1 from which the solution containing the first charged particles adhering to the surface is removed is fed into the second solution tank 4 through the tank roll 10.

  The film-forming substrate 1 sent into the second solution tank 4 containing the solution containing the second charged particles (negative charged particles) receives the second charged particles through the tank roll 11. As shown in FIG. 3 ((b) → (c)), the second charged particles are immersed on the layer of the first charged particles on the surface of the substrate 1 to be deposited. A layer is formed.

  Next, the deposition target substrate 1 on which the layer of the second charged particles is formed on the surface is sent into the second rinse tank 5 through the tank roll 12, and through the tank roll 13, Through the second rinsing liquid, the solution containing the second charged particles that are excessively attached to the surface of the film formation substrate 1 is washed away.

  Also in this case, drying is performed between the second rinsing tank 5 and the outer roll 14 in the same manner as a drying device is installed between the first rinsing tank 3 and the outer roll 10. An apparatus can be installed to dry the deposition target substrate surface on which the second charged particle layer is formed.

As described above, an alternate adsorption film having two layers as shown in FIG. 3C can be formed.
The film forming apparatus shown in FIG. 1 forms an alternating adsorption film consisting of a total of two layers, but a solution containing the first charged particles between the second rinse tank 5 and the recovery unit 16. By installing a third solution tank containing a third solution tank, a third rinse tank, a fourth solution tank containing a solution containing second charged particles, and a fourth rinse tank, alternating adsorption consisting of a total of four layers A film can also be formed. Similarly, an alternate adsorption film composed of a multilayer film of six layers or more can be formed. It is also possible to use odd-numbered layers such as three layers and five layers.

In the present invention, after forming an alternating adsorption film of a desired number of layers, as shown in FIG. 7, a solution containing a solution containing an ionizing curable resin between the second rinse tank 5 and the recovery unit 16 The tank 20 may be installed, and an ionizing radiation irradiation device 19 such as an ultraviolet irradiation device may be installed between the solution tank 20 and the outside roll 22. By setting it as such a structure, an ionization hardening resin layer (hard-coat layer) can be formed on the formed alternate adsorption film.
In FIG. 7, the ionizing radiation irradiation device 19 cures the coating surface on the back side (white surface in the figure) with ionizing radiation.

It is the schematic of the film-forming apparatus of this invention. It is a figure which shows the state which installed the surface treatment apparatus 17 which performs the surface treatment of the film-forming base material surface on the roll 6 outside a tank. FIG. 3 is a diagram schematically illustrating a state in which a layer of positive charged particles is formed on a deposition target substrate 1 and a layer of negative charged particles is formed on the layer of positive charged particles. FIG. 3 is a schematic view of a first solution tank 2. (A) is sectional drawing, (b) is a top view. It is a figure of the roll 7 in a tank. It is a figure which shows the state which installed the drying apparatus 18 between the 1st rinse tank 3 and the roll 10 outside a tank. A solution tank 20 containing an ionizing radiation curable resin solution is installed between the outer tank roll 14 and the recovery unit 16, and further, an ionizing radiation irradiation device 19 is provided between the solution tank 20 and the outer roll 22. It is a figure which shows the state which installed. It is a schematic diagram of the apparatus which forms the conventional alternating adsorption film continuously.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Film-forming base material, 2 ... 1st solution tank, 3 ... 1st rinse tank, 4 ... 2nd solution tank, 5 ... 2nd rinse tank, 6, 8, 10, 12, 14, DESCRIPTION OF SYMBOLS 22 ... Roll outside a tank, 7, 9, 11, 13, 21 ... Roll inside tank, 15 ... Film-forming base material sending part, 16 ... Film-forming base material collection | recovery part, 17 ... Surface treatment apparatus, 18 ... Drying apparatus , 19 ... ionizing radiation irradiation device, 20 ... solution tank containing a solution of ionizing radiation curable resin, 100 ... long fiber material, 110, 130 ... water tank, 120a, 120b, 140a, 140b ... rinse bath, R1 R16 ... roll

Claims (8)

By alternately immersing a long film-forming substrate in a solution containing first charged particles and a solution containing second charged particles having a charge opposite to that of the first charged particles, A method for producing a multilayer film on one surface of the substrate to be deposited,
Preparing a first solution tank containing a solution containing the first charged particles and a second solution tank containing a solution containing second charged particles;
While the long film-forming substrate is spirally conveyed from the first solution tank toward the second solution tank, the film-forming substrate is immersed in the first solution tank,
After immersing the film-forming substrate in the first solution tank and before immersing in the second solution tank, the film-forming substrate is rinsed with a first rinsing liquid,
The surface of the substrate on which the film is formed is dried with a drying device,
Next, the multilayer film manufacturing method is characterized in that the film is immersed in the second solution tank directly or through another tank. The method for producing a multilayer film according to claim 1, wherein the drying apparatus dries the coated surface of the substrate on which the film is formed.   3. The method for producing a multilayer film according to claim 2, wherein the film-forming substrate is immersed in a second solution tank, and then the film-forming substrate is rinsed with a second rinsing liquid.   The surface on which the multilayer film of the film formation base material is formed is surface-treated before immersing the film formation base material in the first solution tank. A method for producing a multilayer film. By alternately immersing a long film-forming substrate in a solution containing first charged particles and a solution containing second charged particles having a charge opposite to that of the first charged particles, A film forming apparatus for forming a multilayer film on one surface of a film forming substrate,
A film-forming substrate feed-out portion for sending a long film-forming substrate to the first tank roll;
A first solution tank containing a solution containing first charged particles;
A second solution tank containing a solution containing second charged particles;
A first outer roll provided on the first solution tank;
A first tank roll provided in the first solution tank;
A second tank outer roll provided on the second solution tank;
A second tank roll provided in the second solution tank;
A first rinse tank provided between the first solution tank and the second solution tank and containing a first rinse liquid;
A third tank roll is provided between the first rinse tank and the second solution tank;
A drying device provided between the first rinsing tank and the roll outside the tank, and drying the surface of the film formation substrate rinsed with the first rinsing liquid with a drying device;
A film-forming substrate recovery unit for recovering a long film-forming substrate immersed in the second solution tank;
The long film-forming substrate is arranged in the order of a first tank roll, a first tank roll, a third tank roll, a second tank roll, and a second tank roll. A film forming apparatus for forming a multilayer film on one surface of the film forming substrate by carrying it in a spiral. The film-forming apparatus according to claim 5, wherein the drying apparatus dries the coated surface of the film-forming substrate to be rinsed.   A second rinsing tank containing a second rinsing liquid is installed between the second solution tank and the film forming substrate recovery part, and the film forming substrate is used as the second solution tank. The film forming apparatus according to claim 6, wherein the film forming apparatus is immersed in the second rinsing tank after being immersed in the film.   A surface treatment apparatus for surface-treating a surface of the film-forming substrate on which the multilayer film is formed is installed between the film-forming substrate feeding part and the first solution tank. The film forming apparatus according to claim 5.

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