JP2007152247A - Method and apparatus for manufacturing interlaminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide firstly a method and an apparatus for manufacturing a high-quality interlaminated film effectively at high productivity, and secondly a method and an apparatus for manufacturing effectively a high-quality interlaminated film by a role-to-role way. <P>SOLUTION: The method for manufacturing the interlaminated film enables the execution of a predetermined number of times of each of an immersion treatment process for immersing a base material in a liquid containing a substance having a positive charge and an immersion treatment process for immersing the base material in a liquid containing a substance having a negative charge. The apparatus for manufacturing the interlaminated film comprises an immersion process tank capable of passing the base material and including an immersion treatment tank for storing or introducing the liquid containing the substance having the positive or negative charge, the immersion treatment tank having a slit-like opening provided vertically on a wall for the film-like or sheet-like base material to enter and a slit-like opening provided vertically on the wall for the base material to withdraw. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method and an apparatus for manufacturing an alternately laminated film, and more particularly to a technique that can be used when mass-producing optical elements for displays of various electronic devices, various sensors, filters, and the like.

  As a method for forming a nanometer-scale thin film from a solution, an alternate lamination method (Layer-by-Layer Electrostatic Self-Assembly) has been proposed. The alternate lamination method is described in G.H. This is a method of forming an organic thin film published in 1992 by Decher et al. (See Non-Patent Document 1). In this method, a polycation adsorbed on a substrate by electrostatic attraction by alternately immersing the base material in an aqueous solution of a polymer electrolyte having a positive charge (polycation) and a polymer electrolyte having a negative charge (polyanion). A combination of polyanions is laminated to obtain a composite film (alternate laminated film).

  In the alternating layering method, the film is grown by attracting the charge of the material formed on the substrate and the material having the opposite charge in the solution by electrostatic attraction, so that the adsorption proceeds and the charge is neutralized. When this occurs, no further adsorption occurs. Therefore, when reaching a certain saturation point, the film thickness does not increase any more. Since the adsorption film thickness per one time is thin, it has an excellent feature that the film thickness with high accuracy can be controlled by the number of laminations. I can say that. Furthermore, it is a low-cost and highly accurate thin film forming method that does not require vacuum equipment. In addition, it has a feature not found in other methods, such as the inside of a tube-shaped substrate, the inside of a textile fiber or foam material, and the like, which can be coated on a portion where the solution penetrates.

  Rubner et al. Produced an alternating laminated film of polyacrylic acid and polyallylamine hydrochloride on a substrate, and then immersed the electrostatically adsorbed binding part partially by immersing it in an acid solution adjusted to pH such as hydrochloric acid. There is a report that a void structure is formed by cutting (see Non-Patent Document 2), and an antireflection film using this is proposed (see Patent Document 1 and Non-Patent Document 3).

  In addition, a method of forming a porous film by laminating fine particles has been proposed. Y. Lvov et al. Applied an alternate lamination method to fine particles, and reported a method of laminating a polymer electrolyte having a charge opposite to the surface charge of the fine particles by using an alternate lamination method using silica, titania, and ceria fine particle dispersions. (See Non-Patent Document 4). However, the fine particle laminated film formed by this method has a problem that it is inferior in scratch resistance because the fine particles are adsorbed mainly by a weak electrostatic attraction such as a hydrogen bond.

  The alternating multilayer film thus created is expected to be used for various electronic devices including organic EL (Electro-Luminescence) elements, and the hydrophilicity is controlled by forming the alternating multilayer film on the surface. Therefore, application to coating technology on contact lens surfaces and biomaterials is also attracting attention.

  As an apparatus for producing this alternate laminated film, an automatic apparatus for producing an alternately laminated film having a structure in which a base material is alternately immersed in two water tanks by a robot arm has been proposed (see Non-Patent Document 5). If this apparatus is used, an alternating laminated film is automatically formed on a substrate.

  In addition, as an alternately laminated film manufacturing apparatus, an alternately adsorbed film having a multilayer structure is manufactured by alternately immersing a film forming material in a solution containing positive charged particles and a solution containing negative charged particles multiple times. An apparatus, a first solution tank for containing a solution containing one charged particle, a second solution tank for containing a solution containing the other charged particle, and the first solution tank Directly into the second solution tank directly or through another tank, and again from the second solution tank directly into the first solution tank through another tank. And a transfer device that rotates the annular film-forming material along the circulation path by conveying each part of the annular film-forming material along the return path. An adsorption film manufacturing apparatus has been proposed (see Patent Document 2). Specific examples of the transfer device include an in-tank roller provided in each tank and an out-of-tank roller provided on a circulation path outside the tank.

  In addition, as an apparatus for producing an alternating laminated film that does not require the use of a roll, alternating adsorption in which a positively charged substance having a positive charge and a negatively charged substance having a negative charge are alternately laminated on the surface of the film forming material A film manufacturing apparatus, comprising: a positively charged substance-containing liquid application unit that applies a positively charged substance-containing liquid containing the positively charged substance so as to form a liquid film on the surface of the film forming material; And a negative charge substance-containing liquid coating means for applying the negative charge substance-containing liquid containing the negative charge substance so as to form a liquid film on the surface of the film forming material. In order to form the number of layers required for the alternately adsorbing film, the surface of the film-forming material is processed a plurality of times by the positively charged substance-containing liquid applying unit and the negatively charged substance-containing liquid applying unit. That has been Apparatus for producing alternate adsorption film to symptoms has been proposed (see Patent Document 3).

International Publication WO03 / 082481 JP 2001-62286 A JP 2003-3000274 A Thin Solid Films, 210/211, p831 (1992) Langmuir 16, p5017-5023 (2000) Nature Materials, Vol1 p59-63 (2002) Langmuir, Vol. 13, (1997) p6195-6203 A. C. Fon, O. Onitsuka, M .; Ferreira, B.M. R. Hsieh and M.M. F. Rubner: J.M. Appl. Phys. 79 (10) 15 May 1996

  The above-described alternate layer film formation technology has not yet reached mass production at the present stage, and in order to commercially produce products using the alternate layer film, such as electronic devices, particle sensors, and filters. There are still problems to be solved.

  In the method of Non-Patent Document 5 described above, for example, when producing an alternately laminated film having a size of 1 m square, at least a 1 m square water tank and a robot arm capable of lifting a substrate about 2 m in height from the water tank There is a problem that a large-scale work using a very large apparatus is required.

  The apparatus described in Patent Document 2 has been proposed to solve such a problem, but it is necessary to support the base material with a roll. However, in this patent document, it is proposed to have a structure in which both ends of the transport roll are raised. However, with this technique, there is a risk of generating wrinkles in the film forming material, and the base material may meander, making it difficult to stably produce a high-quality alternating laminated film. Further, in this method, since the roll-shaped base material is cut to form the alternate laminated film, the length at which the alternate laminated film can be formed at a time is about 10 m, and the length is several tens to several hundreds m. However, there is a problem that the alternate laminated film cannot be formed.

  The device described in Patent Document 3 has been proposed in order to solve such problems. In this apparatus, it is preferable that the substrate is transported at an angle of 90 degrees or more and less than 180 degrees with respect to the horizontal plane. However, roll-to-roll can be used to smoothly produce an alternately laminated film without using a transport roll. In order to achieve this, it is considered necessary to transport the sheet at an angle of about 90 degrees with respect to the horizontal plane. However, in this case, since the alternating laminated film is formed by discharging the liquid having the charge substance, there is a possibility that the film thickness unevenness may occur in the alternating laminated film created by the droplets at the time of discharge. -It was difficult to form a high-quality alternating laminated film on a substrate of several tens to several hundreds of meters with high efficiency.

  Therefore, a first object of the present invention is to provide a method and an apparatus for producing a high-quality alternating laminated film with high efficiency and high productivity. Moreover, this invention makes it the 2nd subject to provide the method and apparatus which can manufacture a high quality alternate laminated film efficiently by roll to roll.

The present invention relates to the following.
1. In a method for producing an alternately laminated film in which a substance having a positive charge and a substance having a negative charge are alternately laminated on a base material, the base material is transported in a horizontal direction while the base material is conveyed vertically. A dipping process step of immersing the substrate in a liquid containing a substance and a dipping process step of immersing the substrate in a liquid containing a substance having a negative charge are each performed a predetermined number of times.
2. Item 2. The method for producing an alternately laminated film according to Item 1, further comprising a rinsing step for washing the substrate after each immersion treatment step.
3. Item 2. The method for producing an alternating laminated film according to Item 1, further comprising a step of applying the same liquid used in each immersion treatment step to the substrate from the upper part or from the upper side after each immersion treatment step.
4). After each immersion treatment step, before the rinsing step after each immersion treatment step, including the step of applying the same liquid used in each immersion treatment step to the substrate from above or above Item 3. A method for producing an alternating laminated film according to Item 2.
5. Each immersion treatment step is performed by entering a tank containing a liquid containing a substance having a positive charge or a substance having a negative charge from an opening provided in the tank and from another opening provided in the tank. Item 5. The method for producing an alternating laminated film according to any one of Items 1 to 4, which is carried out by passing a vertically standing substrate so as to exit.
6). Item 6. The method for producing an alternately laminated film according to Item 5, wherein each opening is a slit-like opening provided in the vertical direction.
7). Item 6. The alternating lamination according to item 5 or 6, wherein in each opening of each tank, a pair of columnar members are arranged separately in the vicinity of the inside of the tank of the opening, and the space between the pair of columnar members is passed through the substrate. A method for producing a membrane.
8). Item 9. The method for manufacturing an alternate laminated film according to Item 8, wherein the structure for isolating the pair of columnar members is a structure for isolating the columnar members by sandwiching spacers between the upper and lower portions.
9. Item 9. The method for producing an alternating laminated film according to any one of Items 1 to 8, wherein in the dipping treatment step, the liquid containing the positively charged substance or the negatively charged substance for dipping the substrate is circulated and used.
10. The alternating of any one of Items 1 to 9, wherein the transport of the base material is performed by unwinding the roll-shaped base material before the first step and winding the base material after passing through the last step into a roll shape. Manufacturing method of laminated film.
11. Item 11. The method for producing an alternately laminated film according to any one of Items 1 to 10, wherein the substrate is a woven or nonwoven fabric of a film or a fiber material.
12 It has a slit-like opening provided vertically for a film-like or sheet-like base material to enter the wall and a slit-like opening provided vertically for the base material to exit, positive or negative An alternating film manufacturing apparatus comprising a dipping process tank that contains a dipping treatment tank for containing or introducing a liquid containing a substance having a charge, and that is capable of passing a substrate.
13. Item 13. The alternating laminated film manufacturing apparatus according to Item 12, having a plurality of dipping process tanks.
14 It has a slit-like opening provided vertically for the base material that has passed through the dipping process tank to enter the wall and a slit-like opening provided vertically for the base material to exit, and contains cleaning liquid or Item 14. The apparatus for producing an alternating laminated film according to Item 12 or 13, comprising a rinsing process tank for introduction.
15. It has a slit-like opening provided vertically for the base material that has passed through the last rinsing process tank to enter and a slit-like opening provided vertically for the base material to exit, and is provided with a drying mechanism. Item 15. The alternating laminated film manufacturing apparatus according to Item 14, comprising a drying process tank.
16. A base material holding member that can stand up vertically and hold and unwind a film-like or sheet-like base material wound in a roll;
A guide roll for vertically guiding and unwinding the holding member to the immersion treatment process tank;
Item 16. The alternation according to any one of Items 12 to 15, comprising a guide roll that guides the base material that has passed through the last tank, and a winding roll that is vertically set up to take up the base material guided by the guide roll. Multilayer film manufacturing equipment.
17. Immersion so that the guided substrate can move in a straight line by the guide roll for guiding the unwound holding member to the immersion treatment process tank and the guide roll for guiding the substrate that has passed through the last tank. Item 17. The alternating laminated film manufacturing apparatus according to Item 16, wherein the tanks are arranged by adjusting the positions of the slit-shaped openings of the process tank, the rinse process tank, and the drying process tank.
18. Item 18. The alternately laminated film manufacturing apparatus according to any one of Items 12 to 17, wherein the dipping process tank is composed only of an immersion treatment tank.
19. The immersion process tank according to any one of Items 12 to 17, which has a recovery tank for receiving an immersion liquid flowing out from a slit-like opening through which the base material enters or exits immediately before or after the immersion treatment tank. Alternate film production equipment.
20. Item 18 or 19 has a structure in which a pair of columnar members are arranged separately in the vicinity of the inside of the tank of each of the immersion treatment tanks, and the pair of columnar members are passed through the base material. The alternately laminated film manufacturing apparatus as described.
21. Item 21. The alternating film manufacturing apparatus according to Item 20, wherein the structure for isolating the pair of columnar members is a structure for isolating the columnar members by sandwiching a spacer between the upper portion and the lower portion thereof.
22. Item 20. The alternating laminated film manufacturing apparatus according to Item 19, wherein the recovery tank immediately after the immersion process tank has a mechanism for applying the immersion liquid to the base material from above or from above.
23. Item 23. The alternating film manufacturing apparatus according to Item 19 or 22, wherein the recovery tank has an immersion liquid discharge port on a bottom surface or a side surface.
24. Item 24. The alternating laminated film manufacturing apparatus according to Item 23, which has a mechanism for circulating the immersion liquid discharged from the discharge port of the recovery tank to the immersion treatment tank.
25. The rinsing process tank has a vertically provided slit-like opening for allowing the base material that has passed through the immersion process tank to enter the wall and a vertically provided slit-like opening for the base material to exit, Item 25. The alternating film manufacturing apparatus according to any one of Items 12 to 24, wherein the rinse tank for containing or introducing the cleaning liquid is composed of one tank or a plurality of tanks.
26. Item 26. The alternating laminated film manufacturing apparatus according to Item 25, wherein the rinse tank is provided with a cleaning liquid discharge port on the bottom surface or side surface thereof.
27. Item 27. The alternating laminated film manufacturing apparatus according to Item 26, which has a mechanism for circulating the cleaning liquid discharged from the discharge port of the rinse tank to the rinse tank.

  In the manufacturing method and the manufacturing apparatus of the alternately laminated film according to the present invention, the base material is set up vertically, transported in the horizontal direction, and immersed in a liquid containing a charged substance, and the rinsing process is also performed. This can be performed in the same manner, and a high-quality alternating laminated film can be efficiently produced with high productivity. In the present invention, since it is not necessary to fold the substrate in the liquid, the transport roll is not required in the liquid, and the alternating laminated film formed by contacting the transport roll in a wet state is destroyed. It does not cause problems such as being. Further, since the folding of the base material during the transport process can be reduced, it is easy to transport the base material stably. Furthermore, since there is no transport roll or roll drive unit in the liquid, it is possible to suppress the deterioration of the liquid due to foreign matter mixing.

In the manufacturing method and the manufacturing apparatus of the alternately laminated film according to the present invention, a pair of columnar members are arranged so as to sandwich the substrate in the vicinity of the inside of the opening for passing the substrate provided in the immersion treatment tank, By arranging the spacers at the upper and lower portions of the pair of columnar members, a gap through which the base material passes can be secured, and scratches at the opening can be prevented. Furthermore, the columnar member can also suppress the outflow of liquid from between the opening side wall and the columnar member by bringing the columnar member into contact with the opening side wall by hydraulic pressure.
In the method and apparatus for producing an alternating laminated film according to the present invention, if a collection tank is arranged before and after the immersion treatment tank, the immersion liquid flowing out from the immersion treatment tank can be efficiently recovered. Can be used cyclically.
In the present invention, since the substrate can be transported by roll-to-roll, a high-quality alternating laminated film can be produced efficiently.
In the present invention, the immersion liquid and the cleaning liquid can be recycled.

(Substances with positive charge and substances with negative charge)
As the positively charged substance in the present invention, an ionic polymer having a positive charge, fine particles having a positive charge, and the like can be used. Similarly, as the negatively charged substance in the present invention, an ionic polymer having a negative charge, fine particles having a negative charge, and the like can be used.
It is preferable that the positively charged substance and the negatively charged substance are uniformly dissolved or dispersed in the medium.

  As the ionic polymer, a polymer having a charged functional group in the main chain or side chain can be used. As the ionic polymer having a positive charge, those having a positively charged or chargeable functional group such as a quaternary ammonium group or amino group, such as polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polydiallyldimethylammonium chloride (PDDA), polyvinylpyridine (PVP), polylysine and the like can be used. The ionic polymer having a negative charge is generally one having a negatively charged or chargeable functional group such as sulfonic acid, sulfuric acid, carboxylic acid, such as polystyrene sulfonic acid (PSS), Polyvinyl sulfate (PVS), dextran sulfate, chondroitin sulfate, polyacrylic acid (PAA), polymethacrylic acid (PMA), polymaleic acid, polyfumaric acid and the like are used. Many of these organic polymer ions are water-soluble or soluble in a mixture of water and a water-soluble organic solvent such as alcohol or acetone, and any of the examples exemplified here can be used in such a medium. It is melted.

As fine particles, inorganic fine particles or organic polymer fine particles can be used.
As the inorganic fine particles, magnesium fluoride (MgF ₂ ), aluminum fluoride (AlF ₃ ), lithium fluoride (LiF), sodium fluoride (NaF), silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), Zirconia oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO ₂ ), ceria (CeO ₂ ), Examples thereof include yttrium oxide (Y ₂ O ₃ ) and bismuth oxide (Bi ₂ O ₃ ).

  Examples of the organic polymer fine particles include polyethylene, acrylic polymer, polystyrene, silicon polymer, phenol resin, polyamide, and natural polymer. From liquid phase to solution spray method, solvent removal method, aqueous solution reaction method, emulsion method, suspension polymerization method, dispersion polymerization method, alkoxide hydrolysis method (sol-gel method), hydrothermal reaction method, chemical reduction method, liquid It is synthesized by a manufacturing method such as medium pulse laser ablation.

On the surface of the fine particles of the metal oxide is partially present hydroxyl, it ionized in aqueous solution (-O ^- or -OH 2 ^_+), it is possible to have a positive or negative charge. In addition, a polar group such as a carboxyl group or an amino group or an ionic surfactant may be chemically or physically adsorbed on the fine particles to give a charge to the surface. The polymer fine particles can be charged on the surface by using a polymer as a raw material having the above polar group or ionicity.

  In order to use the alternating laminated film produced according to the present invention as an optical element, the alternating laminated film is preferably transparent. However, when fine particles are used as a substance having a positive charge or a negative charge, the alternating laminated film is transparent. In order to obtain the above, the fine particles dispersed in the medium used in the present invention preferably have an average primary particle diameter of 2 to 100 nm. If the average primary particle size is less than 2 nm, it takes too much time for film growth, and if it exceeds 100 nm, it is difficult to control the film thickness, and light is likely to be scattered, thereby impairing the transparency of the alternately laminated film. Further, when fine particles are used as a substance having a positive charge or a negative charge, the fine particles dispersed in the medium may be primary particles or secondary particles of a type in which primary particles are aggregated. At this time, the average primary particle diameter and average secondary particle diameter of the fine particles can be measured using a known method. When the primary particles are dispersed in the medium without being aggregated, the average primary particle diameter can be measured by a dynamic scattering method. However, in the case of secondary particles or the like in which primary particles are aggregated, what is measured by the dynamic scattering method is not the average primary particles but the average secondary particle diameter. The average primary particle diameter in the secondary particles can be measured by a BET method or an electron microscope method. In the BET method, molecules with an occupied area such as nitrogen gas are adsorbed on the particle surface, the specific surface area is obtained from the relationship between the adsorbed amount and the pressure, and the specific surface area is converted from the conversion table into the particle diameter. The particle size can be measured. In electron microscopy, first, fine particles are scooped up from a fine particle dispersion on a copper mesh on which an amorphous carbon film having a thickness of several tens of nm is formed, or fine particles are adsorbed on the amorphous carbon film. The fine particles are observed with a transmission electron microscope, and then the lengths of a plurality of fine particles in the photographed image are measured, and the arithmetic average is obtained as the average primary particle diameter. When the axial ratios of the particles are greatly different as in the case of columnar particles, the length of the minor axis is generally measured, and the arithmetic average is taken as the average primary particle diameter.

(Base material)
The substrate may be a flexible material that can be wound up into a roll, such as a film, a woven or nonwoven fabric of a fiber material, or a cloth woven with glass fibers. Further, those having extremely hydrophobic and water repellent properties or those having no surface coated with such a film are preferable. In consideration of application development at the present time, a resin transparent film having flexibility is preferably used. Specific examples of the resin transparent film material include triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, polyacrylic resin, polyurethane resin, polyester, polycarbonate, polysulfone, polyether, and polymethyl. Examples include pentene and polyether ketone. In addition, the base material of the present invention includes a base material whose surface is coated with a transparent resin film or inorganic film. Furthermore, a film having an uneven surface can also be applied. As a method of forming an uneven film, a photocurable resin that can be cured by irradiation of active energy rays such as sandblasting, ultraviolet rays, and electron beams is pressed against a mold having an uneven pattern on the surface, ultraviolet rays, Although it can manufacture by the method etc. of irradiating active energy rays, such as an electron beam, there is no limitation in particular in the method.

  In order to form an alternately laminated film on a base material, the base material needs to have a polar group on its surface. Examples of the polar group include a hydroxyl group, a carboxy group, a carbonyl group, a sulfonate group, an amino group, a quaternary ammonium salt, and an isocyanate group. Since they have a positive or negative charge locally by intramolecular polarization or ionization, they adsorb substances having the opposite charge. Accordingly, a base material such as polyethylene terephthalate having a surface hydroxyl group is used as it is, or corona discharge treatment, glow discharge treatment, plasma treatment, ultraviolet irradiation, ozone treatment, chemical etching treatment with alkali or acid, silane, etc. A functional group having polarity is introduced by a coupling treatment or the like to make the surface charge of the substrate negative or positive. As a method for efficiently introducing a positive charge to the surface of the substrate, it is possible to ionize in an aqueous solution and adsorb polydiallyldimethylammonium chloride or polyethyleneimine, which is a strong electrolyte polymer having a positive charge [ Advanced Materials (Advanced Material) 13: 52-54 (issued in 2001)].

  The amount of polar groups on the substrate surface is preferably a zeta potential and an absolute value of 1 to 35 mV. For example, the zeta potential on the surface of a substrate such as glass or polyethylene terephthalate is about −80 to −30 mV, and the zeta potential when polydiallyldimethylammonium chloride is adsorbed on the substrate is about 40 to 60 mV. The zeta potential of the metal oxide fine particles is about 1 to 60 mV in absolute value. The zeta potential can be measured using a laser zeta electrometer ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.) or the like.

(Method for producing alternating laminated film)
In this way, a substrate having a polar group on the surface is vertically conveyed and conveyed in the horizontal direction, and during this time, it is alternately immersed in a liquid containing a positively charged substance and a liquid containing a negatively charged substance, and alternately on the substrate. A laminated film is produced. If the surface charge of the base material is negative, a step of first immersing in a liquid containing a positively charged substance, and if the surface charge of the base material is positive, a step of first immersing in a liquid containing a negatively charged substance is performed. The base material may be used in an appropriate shape, but is preferably in the form of a strip or a belt, and the base material wound in a roll shape is unwound and engaged in the above steps. It is preferable that the base material is wound up in a roll shape after being transported and finished with necessary steps.

  The concentration of the charged substance dissolved or dispersed in the liquid containing the charged substance varies depending on the kind of the charged substance and the medium and the use of the obtained alternating film, but is preferably about 0.1 to 20% by weight. .

  The immersion time in each of the above immersion treatment steps is appropriately adjusted according to the material to be laminated, the film thickness to be laminated, and the like. Immersion time can be adjusted by the transport speed of the substrate, the length of the immersion tank for immersion, etc. The film thickness per time is adjusted by adjusting the concentration and pH of the liquid containing positively charged substance or negatively charged substance Can also be performed. For example, in the case where the positively charged substance or the negatively charged substance is fine particles, the fine particles are aggregated by bringing the pH close to neutral so that the fine particles do not precipitate, and the aggregated fine particles are adsorbed to the base material, so The thickness can be increased. In addition, the immersion time in the liquid containing the positively charged substance or the negatively charged substance is preferably set to be longer than the time when the adsorption of the charged substance is saturated in order to facilitate the film thickness control. The time for which the adsorption of the charged substance is saturated varies depending on the liquid containing the charged substance, but is preferably about 20 to 600 seconds. The adsorbed state of the charged substance can be confirmed by immersing the quartz crystal resonator at the same time when immersing the base material, and confirming the change in the oscillation frequency of the quartz crystal resonator (see International Publication WO00 / 13806). .

  After the first immersion treatment step, a liquid containing a substance having an opposite charge is used in the next immersion treatment step in the same manner as described above. Sequentially, the dipping process is performed as many times as necessary using a liquid containing a substance having the opposite charge. It is preferable to perform the process of rinsing after each of these immersion treatment processes. The charged substance is electrostatically adsorbed on the substrate, but the substance having a charge exceeding that amount and other excess substances can be washed away. Further, it is preferable to rinse in order to prevent a substance to be dissolved or dispersed from being brought into the liquid containing the oppositely charged substance used in the next step. If this is not done, positive charge substances and negative charge substances may be mixed in the solution due to carry-in, and precipitation may occur. The rinsing step can be performed by spraying the rinsing liquid by immersion in the rinsing liquid or spraying. The rinsing liquid used in the present invention is appropriately selected and used depending on the type of liquid containing the charge substance used. Specifically, ion-exchanged water or ultrapure water (specific resistance 18 MΩ · cm), alcohol, a mixed solution of alcohol and water, and the like are appropriately used. The rinsing time is appropriately selected according to the use and the liquid containing the charged substance. Specifically, it is preferable to carry out for a time of about several seconds to several tens of seconds, and the rinsing process may be carried out a plurality of times.

  In the present invention, a drying step may be performed after the rinsing step. This is because the characteristics of the obtained film may differ depending on the presence or absence of drying, and drying may be necessary depending on the type of film. The film thickness that is laminated between the dried substrate and the wet substrate may change, and unevenness may occur in the alternating laminated film due to the generation of dry and undried parts in the transport process. Because. Further, by drying, it is possible to suppress changes in the concentration of the treatment liquid and PH by reducing the amount of water brought into the next immersion treatment tank. The drying step may be performed only once after the last rinsing step.

  In the present invention, after the immersion treatment step in the liquid containing the positively charged substance or the negatively charged substance, before performing the rinsing step, before that, on the substrate on which a thin film of the positively charged substance or the negatively charged substance is formed, It is preferable to perform the step of applying the same liquid as that used in the dipping process. In order to recover the liquid having the charged substance flowing out from the substrate outlet in the immersion treatment process, it is better to collect the liquid flowing out before entering the rinsing process. For that purpose, the bath immersion treatment process and the rinsing process are performed. In some cases, empty transport may be required. During this empty conveyance, the liquid containing the charged substance that is excessively attached to the substrate surface flows from the upper part to the lower part of the substrate, so that the upper part of the substrate is dried depending on the conveyance speed and the empty conveyance distance. There is a possibility that unevenness in film thickness may occur due to the charged substance adhering to the substrate adhering to the substrate. By performing the step of applying the same liquid during empty conveyance, the occurrence of this film thickness unevenness can be prevented. In order to recover the liquid having the charged substance flowing out, it is preferable to provide a recovery tank before and after the immersion treatment step in terms of reuse of the liquid and the cleaning liquid. It is also possible to prevent film thickness unevenness due to drying of the upper part of the base material by carrying out a rinsing process immediately after the immersion treatment process, but in this case, it has a charge substance that flows out from the outlet part of the base material in the immersion process. Since the liquid and the rinsing liquid are mixed, it is necessary to adjust the concentration when the liquid having the charged substance is collected and reused, and in some cases, a new liquid is supplied without being reused.

  In the present invention, the same liquid as that used in the immersion process is applied, and if necessary, the immersion process in the liquid containing the positively charged substance and the negatively charged substance. After repeating the process and the rinsing process as necessary, drying is performed. You may perform drying suitably after each rinse process. After the last drying, it is preferable to roll up the base material on which the alternating laminated film is formed in a roll shape.

  In the production process of the present invention, the kind of the liquid containing the positively charged substance and the liquid containing the negatively charged substance are not limited to one each, depending on the use / function of the alternately laminated film obtained as described above. A plurality of types may be used. Therefore, the number of apparatuses for performing the immersion treatment step in the liquid containing the positively charged substance and the immersion treatment step in the liquid containing the negatively charged substance is the function / use required for the obtained alternately laminated film. It can be changed according to the situation.

In addition, the number of laminations of the alternate laminated film may be several tens to several hundreds depending on the functions and applications required for the obtained alternate laminated film. If it is difficult to prepare equipment that only performs the process corresponding to the number of laminations, the necessary lamination process is repeated by repeating the lamination process from unwinding to winding up the substrate several times to several tens of times. You can also get a number.
According to the present invention, an alternating laminated film can be formed simultaneously on both sides of a substrate, but the substrate does not have a polar group on one side, for example, a group that itself does not have a polar group on one side. It is also possible to form an alternating laminated film only on one side by using a base material such as a material that can be peeled on one side of the base material and a protective film that does not have a polar group on the surface. is there.

(Alternate laminated film manufacturing equipment)
An apparatus for producing such an alternating laminated film will be described. FIG. 1 is a perspective view showing an example of an alternate laminated film manufacturing apparatus according to the present invention, FIG. 2 is a plan view thereof, and FIG. 3 is a front view thereof.

  The above apparatus stretches a strip-shaped or strip-shaped base material wound in a roll shape in the horizontal direction, conveys the base material in a vertical position, and transfers it to a liquid containing a positively charged substance and a liquid containing a negatively charged substance. Is a device that performs the above-mentioned immersion once and winds it up into a roll. In this apparatus, as shown in FIGS. 1-3, in order to hold | maintain the roll-shaped base material 1, the base material unwinding part 2 for unwinding, and the base material 1 on which the alternating laminated film was laminated | stacked and hold | maintained The base material winding unit 3 and the processing unit 4 for forming the alternately laminated film on the base material 1 are located between the base material winding unit 2 and the base material winding unit 3. Yes. The base material unwinding unit 2 continuously feeds the roll-shaped base material 4, and the winding unit 3 continuously winds the base material 4 on which the alternately laminated film is formed in a roll shape. is there.

  The unwinder 2 is provided with an uncoiler 21 for vertically feeding the surface of the substrate 1 wound in a roll shape vertically. Between the uncoiler 21 and the process part 4, the inlet roll 22 for sending out the strip | belt-shaped or strip | belt-shaped base material sent out from the uncoiler 21 to a fixed position is provided. The base material that has passed the inlet roll 12 is introduced into the processing unit 2.

In the winding unit 3, the base material 1 on which the alternately laminated film that has passed through the processing unit 4 is formed is wound around a recoiler 32 in a roll shape and collected via a driving roll 31 for guiding it. . The driving roll 31 plays a role of feeding the base material 1 on which the alternately laminated film is formed to a repositioner 3 at a predetermined speed while keeping the base material 1 at a fixed position.
In the present embodiment, the entrance roll 22 and the drive roll 31 have a role of guiding and guiding the base material 1 so that the base material 1 passes through the plurality of slit-like openings of the processed part 2 without contacting the wall. Yes.

In the process part 4, the 1st immersion process tank 410, the 1st rinse process tank 500, the 2nd immersion process tank 710, the 2nd rinse process tank 800, and the drying process tank 900 are connected in order.
In the first immersion process tank 410, a recovery tank 411, an immersion treatment tank 412 in which a liquid containing a positively charged substance or a negatively charged substance is accommodated, and a recovery tank 413 are sequentially connected. In the first rinse process tank 500, the first rinse is performed. The tank 510, the second rinse tank 520, and the third rinse tank 530 are sequentially connected. In the second immersion process tank 710, an immersion treatment tank 712 and a recovery tank 713 that store a liquid containing a charge substance having a charge opposite to that of the charge substance contained in the liquid stored in the recovery tank 711 and the immersion treatment tank 412 are sequentially provided. It is lined up. In the 2nd rinse process tank 800, the 1st rinse tank 810, the 2nd rinse tank 820, and the 3rd rinse tank 830 are connected in order.
In each of the above-mentioned tanks, a vertically long slit-like opening through which a base material that is vertically conveyed is passed is provided on a wall adjacent to the tanks through the tanks. A vertically long slit-like opening through which the substrate 1 conveyed vertically stands also on the wall on the side where the adjacent tanks of the recovery tank 411 and the air knife drying tank 900 do not exist.

  In the first and second immersion process tanks, the recovery tanks 411, 413, 711, and 713 arranged before and after the immersion treatment tank 412 and the immersion treatment tank 712 flow out from the slit-shaped openings provided in the immersion treatment tank. It is a tank for recovering the liquid containing the charged substance.

  A total of six rinsing tanks 510, 520, 530, 810, 820, and 830 of the first and second rinsing process tanks are formed by spraying the rinsing liquid from the nozzles and applying the rinsing liquid to the substrate conveyed upright. A rinse is to be implemented. The rinsing method may be carried out by a method of immersing in a rinsing solution, similar to a liquid containing a charged substance, and is not particularly limited as long as it does not damage the substrate or the laminated film, such as directly touching the substrate. . When the immersion method is used, a recovery tank similar to the recovery tank for the immersion treatment tank is provided before and after the rinse tank.

  The drying process tank 900 is for drying the base material 1 on which the alternately laminated film is formed.

  As described above, the alternate laminated film manufacturing apparatus according to the present embodiment efficiently bases the substrate wound in a roll shape, which is an object for forming the alternate laminated film, by vertically conveying it in the longitudinal direction. Alternately laminated films can be formed on the material. Furthermore, since the processing unit 4 does not require a transport roll, problems such as destruction of the alternately laminated film due to the transport roll contact and contamination of the liquid due to dust generation from the roll drive unit do not occur.

Next, each component of the alternate laminated film manufacturing apparatus according to the present embodiment will be described in detail.
(1) Substrate unwinding part 2
The uncoiler 21 feeds the strip-shaped or strip-shaped substrate 1 wound in a roll shape in the longitudinal direction while holding the substrate 1 upright so that the surface thereof is vertical. 2 is introduced. The inlet roll 22 is a roll for keeping the pass line of the base material 1 constant even when the winding diameter of the base material 1 changes, and the base material 1 passes through almost the center of the plurality of slit-like openings of the processed portion 4. Is set to do. The substrate unwinding unit 2 may be provided with an accumulator for keeping the tension constant between the uncoiler 21 and the inlet roll 22.

(2) Processing part 4
(A) Immersion process tank FIG. 4 is a plan view of the first immersion process tank 410, and FIG. 5 is a front view of the first immersion process tank 410. 6 is a cross-sectional view taken along the line CC in FIG. 5, and FIG. 7 is a cross-sectional view taken along the line DD in FIG. These correspond to part A of FIG.
The first immersion process tank 410 includes a bottom plate 421, side walls 422, 423, a front wall 424, and a rear wall 425, and is divided into three tanks by two threshold walls 426, 427. A recovery tank 411, The immersion treatment tank 412 and the collection tank 413 are adjacent to each other to form one immersion process tank.
The immersion treatment tank 412 is a tank for immersing in a liquid containing a charged substance in order to cause the charged substance to be adsorbed on the substrate 1, and a liquid containing the charged substance is accommodated in the tank.
The front wall 424 of the recovery tank 411 through which the substrate 1 first passes, the threshold wall 426 shared by the recovery tank 411 and the immersion treatment tank 412, the threshold wall 427 shared by the immersion treatment tank 411 and the recovery tank 413, and the recovery tank 413. In the rear wall 425, vertically long slit-like openings 431, 432, 433, and 434 through which the vertically standing base material 1 passes are sequentially provided.
The liquid containing the charged substance stored in the immersion treatment tank 412 constantly flows out in a parabolic shape from the slit-shaped openings 432 and 433. The liquid that has flowed into the collection tanks 411 and 413 is discharged from the discharge ports 441 and 442. It is preferable to arrange the liquid that flows radially from the immersion treatment tank 411 to the collection tanks 411 and 413 so that most of the liquid flows directly into the discharge ports 441 and 442. In addition, it is preferable that the height of the slit-shaped opening, the length of the collection tank, and the like are adjusted so that the liquid that has flowed into the collection tanks 411 and 413 does not further flow out from the other slit-shaped openings 431 and 434.
In order to collect the liquid containing the charged substance flowing out from the immersion treatment tank 412 and reduce the amount of liquid brought into the first rinsing tank 510, the size of the collection tanks 411 and 413 is the outflow of the liquid containing the charged substance in the transport direction. It is preferable to make it longer than the distance. For example, if the length of the slit-shaped openings 522 and 523 is about 150 mm, the length of the collection tanks 411 and 413 is preferably about 150 mm with respect to the transport direction, and the length of the slit-shaped openings 432 and 433 If the length is about 300 mm, the length of the recovery tanks 411 and 413 is preferably about 250 mm in the transport direction.
Since the liquid containing the charged substance constantly flows out of the immersion treatment tank 412, it is necessary to replenish the liquid to be discharged in order to always store a sufficient amount of the liquid containing the charged substance in the tank of the immersion treatment tank 412. There is. In this apparatus, it is performed by the liquid supply system. In the liquid supply system, the liquid stored in the tank 451 is sent to the immersion treatment tank 412 from the discharge port 455 of the nozzle 454 provided at the bottom of the immersion treatment tank 412 by the liquid feed pump 452 via the liquid feed pipe 453. It is structured to liquefy.
In order to continue the liquid feeding, it is necessary to replenish the tank 451 with the liquid. For this purpose, the liquid containing the charged substance prepared in advance may be constantly replenished. The liquid that has flowed out to the tank 451 is sent to the tank 451 via the recovery pipes 456 and 457 connected to the discharge ports 441 and 442, so that the liquid is recovered and supplemented, and is circulated by the liquid feed pump 452. Yes.

In the slit-like openings 432 and 433 of the immersion treatment tank 412, it is preferable that there are few gaps to flow out in order to reduce the outflow of the liquid, but as described above, the alternately laminated film is relatively inferior in scratch resistance, It is preferable to suppress contact at the slit-like openings 432 and 433 in order to prevent the formed alternating laminated film from being broken. The structure for this will be described with reference to the drawings.
8 is an EE cross-sectional view of FIG. 4, and FIG. 9 is an FF cross-sectional view of FIG. 10A is a cross-sectional view taken along the line G-G in FIG. 8 when the immersion treatment tank is filled with a liquid (FIG. 10B), and FIG. 10B is a plan view corresponding to FIG. 8.
A vertically long slit-shaped opening 432 is provided in the threshold wall 426 of the immersion treatment tank 412. The vertically long slit-shaped opening 432 may open to the lowermost part of the threshold wall 426, but is not necessarily required, and is opened at an appropriate height, for example, about 20 to 100 mm. .
Two columnar members 461 and 462 are supported by support members 470 and 480 in the vicinity of the slit-shaped opening 432 so as to stand upright in parallel therewith. The support member 470 is attached to the bottom wall 426 so as to be surrounded by the front plate 471, the side plates 472 and 473, and the bottom plate 474 below or below the slit-like opening 432. The support member 480 is attached to the top wall 426 so as to be opened and surrounded by the front plate 481 and the side plates 482 and 483 at the upper part of the slit-shaped opening 432. The two columnar members 461 and 462 are inserted from the support member 480 to the bottom plate 474 of the support member 470. The two columnar members 461 and 462 are separated by bar-shaped spacers 475 and 485 so that they do not contact each other. The spacer 475 is supported on the front plate 471 so as to face the slit-like opening 432, and the spacer 485 is supported on the front plate 481 so as to face the slit-like opening 432. Both may be the same shape or different shapes. The columnar members 461 and 462 are not completely fixed, and are free in a range limited by the front plates 471 and 481, the side plates 472, 473, 482 and 483, the bottom plate 474 and the spacers 475 and 485. Yes. The positions of the spacers 475 and 485 are opposed to the center of the slit-like opening in the plan view, and the base material 1 and the columnar members 461 and 462 are located even when the base material 1 passes substantially along the center line. Spacers 475, 485 having sufficient width so as not to contact are used. When the liquid is stored in the immersion treatment tank 412, the columnar members 461 and 462 are pressed against the threshold wall 426 and the spacers 475 and 485 due to the liquid pressure to form slits having the same width as the spacer, thereby reducing the outflow of the liquid. be able to.
For example, the slit width of the slit-shaped opening 432 is 10 mm, the widths of the spacers 475 and 485 are 1 mm, and the columnar members 461 and 462 are glass round bars having a diameter of 10 mm. The distance between the front plates 471 and 481 and the cut-off wall 426 is 12 mm, the distance between the spacers 475 and 485 and the side plates 472 and 482, and the distance between the spacers 475 and 485 and the side plates 473 and 483 are also 12 mm.
Although it depends on the thickness of the base material on which the alternately laminated film is formed, the slit width formed by the spacer is preferably 0.5 to 2 mm if the thickness is about 100 μm. If the slit width is too narrow, the base material 4 and the columnar members 461 and 462 may come into contact with each other, and the formed alternate laminated film may be destroyed. If the slit width is too wide, the liquid outflow from the slit portion increases. The liquid pump 452 needs to have a large capacity, and the collection tanks 411 and 413 may need to be increased in size.

  The columnar member in the present invention includes a cylindrical member having the same outer shape. The cross-sectional shape of the columnar member in the present invention includes a circular shape, an elliptical shape, a quadrangular shape such as a quadrilateral shape, a pentagonal shape, and the like. And a circular or elliptical shape, which is considered to be less disturbed by the outflow of liquid, is preferable. The columnar member is preferably made of a material that is not affected by the liquid containing the charged substance and that does not break due to the hydraulic pressure and causes less warping. Examples thereof include metals such as glass and stainless steel. As the spacer, there are a metal rod and plate such as stainless steel, a resin plate and rod such as polypropylene and PVC, and a material which is not affected by a liquid containing a charged substance is preferable.

As a method for forming the slit through which the substrate passes, there is a method in which the columnar members 461 and 462 are directly fixed to the wall 426 in the immersion treatment tank 412. In addition, there is a structure in which the upper end and the lower end of the columnar member are made larger than the middle thereof. In this case, the small portion of the middle part of the columnar member does not come into contact with the wall 426 of the immersion treatment tank 412, so a gap is generated between the wall 426 and the columnar member, and the outflow of liquid increases. In order to suppress this outflow, it is preferable to reduce the gap by sandwiching a plate-like member in the gap between the intermediate portion of the columnar member and the wall 426.
Also in the vicinity of the slit opening 433 of the wall 427, the same columnar member, support member and spacer as described above are installed.

  In the recovery tank 413, a nozzle 494 passes through a pipe 453, a pipe 491 branched from the pipe 453, and a liquid feed pipe 492, 493 branched from the pipe 453. 495 is sprayed from above the base material 1 to prevent drying of the upper part of the base material 1 during the transport process of the base material 1 and to prevent occurrence of film thickness unevenness. FIG. 11 is a perspective view showing an example of a liquid spray nozzle used in the present apparatus. A polyvinyl chloride pipe member 496 is connected horizontally to the liquid supply pipe 492 or 493, and a slit-like opening 497 is provided horizontally to the liquid supply pipe 492 or 493. Drying can be prevented by flowing a liquid over the lower part. The nozzle can be made by closing both ends of a polyvinyl chloride piping joint cheese provided with slit-shaped openings and combining with the piping pipe, but the material is affected by the liquid containing the charged substance and the rinsing liquid. If it is a material which does not receive, it will not specifically limit. Further, the shape of the nozzle is not particularly limited as long as no problem such as damage to the formed alternate laminated film occurs.

The configuration of the second immersion process tank 710 is the same as that of the first immersion process tank 410. The immersion treatment tank 712 is a tank for immersing in a liquid having a charge substance in order to adsorb the charge substance to the base material 4, and has a charge opposite to the charge substance in the liquid contained in the immersion treatment tank 412. A liquid containing the substance is contained. Recovery tanks 711 and 713 are adjacent to each other before and after the immersion treatment tank 712. The configurations of the recovery tank 711, the immersion treatment tank 712, and the recovery tank 713 are the same as those of the recovery tank 411, the immersion treatment tank 412, and the recovery tank 413 described above. However, the opposite side of the recovery tank 711 from the immersion treatment tank 712 is different in that the recovery tank 411 is adjacent to the third rinse tank 530 and the recovery tank 411 has no corresponding adjacent tank. The details will be apparent from the following description.
The liquid supply system in the second immersion process tank 710 is the same as the liquid supply system in the first immersion process tank 410. Note that the tank 751, liquid feed pump 752, pipe 753, pipe 756, and pipe 757 in the liquid supply system in the second immersion process tank 710 are the tank 451 and liquid feed pump in the liquid supply system in the first immersion process tank 410, respectively. 452, a pipe 453, a pipe 456, and a pipe 457.

(B) Rinse process tank The first rinse process tank 500 in this apparatus is a set of three tanks of a first rinse tank 510, a second rinse tank 520, and a third rinse tank 530, and the second rinse process tank 800 is a first rinse tank. 810, the 2nd rinse tank 820, and the 3rd rinse tank 830 consist of 1 set of 3 tanks. Since both structures are the same, the 1st rinse process tank 500 is demonstrated.
FIG. 12 is a plan view of the front and rear including the first rinse tank 221, and FIG. 13 is a front view thereof. 14 is a cross-sectional view taken along line HH in FIG. 13, FIG. 15 is a cross-sectional view taken along line II in FIG. 12, and FIG. 16 is a cross-sectional view taken along line JJ in FIG. These correspond to part B in FIG.
The first rinsing process tank 500 includes a bottom plate, a side wall, a front wall, and a rear wall like the above-described dipping process tank 410, and is divided into three tanks by two threshold walls. That is, the first rinsing process tank 22 includes a bottom plate 611, side walls 612 and 613, a front wall 614, and a rear wall (not shown), and three tanks include a threshold wall 616 and another threshold wall (not shown). The 1st rinse tank 510, the 2nd rinse tank 520, and the 3rd rinse tank 530 are connected in order from the front.
The 1st rinse tank 510, the 2nd rinse tank 520, and the 3rd rinse tank 530 share the threshold wall between the mutually adjacent tanks. In those walls, slit-like openings for allowing the substrate 1 to pass are formed in the same manner as in the immersion treatment tank. The other opposite front wall 614 of the first rinse tank 510 is in contact with the wall (rear wall 425) of the adjacent collection tank 413, and is configured such that the slit-shaped opening portion just overlaps.
The first rinsing tank 510 incorporates a rinsing liquid spraying system for spraying the rinsing liquid onto the substrate 1. In the rinse liquid spraying system, a liquid stored in a tank 511 is fed by a liquid feed pump 512 via a liquid feed pipe 513 and branch pipes 514 and 515 connected to the nozzle 516 provided at the upper portion of the first rinse tank 510. Rinsing liquid is sprayed from 517. The sprayed rinse liquid is sent from the discharge port 518 at the bottom of the first rinse tank 510 to the tank 511 through the liquid feed pipe 519.
The nozzles 516 and 517 are set with nozzles having a structure in which slit-like openings similar to the liquid spray nozzles implemented after the above-described immersion treatment are provided.
The second rinse tank 520 and the third rinse tank 530 are each configured in the same manner as the first rinse tank 510. The rinse liquid spray system in the second rinse tank 520 and the rinse liquid spray system in the third rinse tank 530 are configured in the same manner as the rinse liquid spray system in the first rinse tank 510, respectively.
The tank 511, the liquid feed pump 512, the liquid feed pipe 513, and the liquid feed pipe 519 in the first rinse tank 510 are the tank 521, the liquid feed pump 522, the liquid feed pipe 523, and the liquid feed pipe 529 of the second rinse tank 520, respectively. , Corresponding to the tank 531, the liquid feed pump 532, the liquid feed pipe 533, and the liquid feed pipe 539 of the third rinse tank 530.

(C) Adsorption of opposite charge Next, a substance having a positive charge and a negative charge are obtained by adsorbing in the immersion process tank 710 an electrified substance having a charge opposite to that of the charged substance adsorbed on the substrate 1 in the immersion process tank 410. It becomes possible to laminate the materials one by one.

(D) Drying process tank 900
As the drying process tank 900, for example, an air knife drying tank can be adopted, which is provided with a pair of air knives sandwiching the substrate 1, and blows air by a blower (not shown). By doing so, the alternate laminated film formed on the substrate 1 is dried. The drying method may be hot air or ultra-dry air, and is not particularly limited as long as it does not cause problems such as destruction of the formed alternate laminated film.

  In the processing unit 4, one set of one dipping process tank and one rinse process tank is used as a set, and there are two sets of repetition. However, this set can be added as appropriate. In this case, it is preferable that the number of sets is a plurality of sets in order to produce the alternately laminated film.

(3) Winding unit 3
The drive roll 31 sends the base material 1 on which the alternately laminated film is formed in the processing unit 2 to the recoiler 32. The recoiler 32 itself has a mechanism that can be controlled to rotate at a constant speed. The recoiler 32 is set so that the base material 1 passes through the center of each slit-shaped opening of the processed part 2, and the pass line of the base material 1 is constant. The recoiler 32 takes up and collects the base material 1 that is vertically raised from the drive roll 31 in a roll shape.

  In this embodiment, the apparatus configuration in which the positively charged substance and the negatively charged substance are stacked one by one by immersing in the liquid having the positively charged substance and the immersion in the liquid having the negatively charged substance once each. It has become. When it is necessary to laminate a plurality of times in order to obtain the film thickness required for the alternately laminated film, it is necessary to repeatedly carry out the process from unwinding to winding until the film thickness that requires treatment is obtained. Moreover, in this embodiment, it cannot be overemphasized that said repetition frequency can be reduced by further adding an immersion treatment process tank and a rinse process tank.

  As a liquid containing a positively charged substance, an aqueous solution of polydiallyldimethylammonium chloride (PDDA, average molecular weight 100000, manufactured by Aldrich), an aqueous silica fine particle dispersion (ST-PS-S, manufactured by Nissan Chemical Industries, colloidal silica, Snowtex PS-S, average) A particle diameter of 20 nm) was used. As the substrate, a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., 150 mm × 10000 mm × 125 μm thickness) was used.

In an apparatus as shown in FIGS. 1 to 3, a 0.3 wt% PDDA aqueous solution is stored in a tank 451 and a 0.3 wt% ST-PS-S aqueous solution is stored in a tank 751, and the immersion treatment tanks 412 and 712 are stored. By sending the solution, the immersion treatment tank was filled with the solution. The liquid that flows out from the immersion treatment tank to the collection tanks before and after the immersion treatment tank is collected in the tank and used in a circulating manner.
A roll of a belt-shaped polyethylene terephthalate (PET) film (base material 1) is vertically set up and conveyed from the unwinding part 2 through each slit-like opening of the processing part 2 to the winding part 3 for winding. In the meantime, the alternate lamination film was formed by performing the immersion treatment in the PDDA aqueous solution and the immersion treatment in the ST-PS-S aqueous solution.
First, a PDDA film was formed on the substrate 1 in the immersion process bath 410. After passing through the recovery tank 411, the base material 1 is subjected to immersion treatment in the PDDA aqueous solution in the immersion processing tank 412. In order to prevent drying in the recovery tank 413, the PDDA aqueous solution is supplied from above and above the base material by the nozzles 494 and 495. It was sprayed. Next, in the rinsing process tank 500, the substrate 1 is supplied three times by three tanks of rinsing tanks 510, 520, and 530 to the rinsing process in which ultrapure water (18 MΩ) for rinsing is sprayed from above and above the nozzle. It was done.
Next, in the immersion process tank 710, an ST-PS-S film was formed on the PDDA film of the substrate 1 in the same manner as the immersion process tank 410. The immersion process in the aqueous solution, the spraying of the liquid for preventing the drying, and the subsequent rinsing process with ultrapure water are the same as described above. The last process in the processing unit 4 is a drying process in the drying process tank 900. The drying process tank 900 has a mechanism in which a pair of air knives are vertically arranged so as to sandwich the substrate 1 conveyed vertically and air is blown by a blower to perform drying. The base material 1 that passed through the processed portion 4 was wound into a roll by the winding portion 3. This operation from unwinding to winding was repeated four times to form an alternately laminated film in which four PDDA films and ST-PS-S films were alternately laminated. The formed alternating laminated film was not visually observed and scratched.

In the above description, the total length of the processed portion 4 is about 2000 mm, the width is 150 mm, and the height is 250 mm.
The immersion treatment tanks 412 and 712 have a length of 100 mm with respect to the transport direction, and the recovery tanks 411, 413, 711, and 713 have a length of 150 mm with respect to the transport direction.
The slit opening of each layer was 200 mm long and 10 mm wide from the upper end at the center (plan view) of the wall where it was provided. A glass round bar having a diameter of 10 mm was used as the columnar member disposed in the slit openings of the immersion treatment tanks 412 and 712, and a stainless steel bar having a diameter of 0.9 mm was used as the spacer.
As the nozzles for spraying the recovery tanks 413 and 713 and the rinsing tanks 510, 520, 530, 810, 820, and 830, nozzles having a slit length of 50 mm as shown in FIG. 11 were used. . The outlet of the nozzle slit was arranged at a position about 3 mm higher than the upper end of the film and about 20 mm away from the film.
The substrate 1 (PET film) was conveyed at a speed of 0.2 m / min, and the time during which the substrate was immersed in each immersion treatment tank was 30 seconds.
In order to replenish the immersion treatment tank 412 with a liquid containing a charged substance (PDDA or ST-PS-S), a pump capable of feeding at a flow rate of 50 to 60 liters / minute is used to replenish the liquid after the immersion treatment. For the application, a pump capable of feeding at a flow rate of 10 to 20 liters / minute was used. Moreover, in order to circulate and spray the rinse liquid, a pump capable of feeding at a flow rate of 10 to 20 liters / minute was used.
The length of the drying tank was 150 mm, a pair of air knives were placed on the good side of the film, and air was blown by a blower for drying.

Comparative Example 1
While the roll-shaped PET film is vertically set up and conveyed from the unwinding unit to the winding unit and wound, a 0.3 wt% PDDA aqueous solution and a 0.3 wt% ST-PS-S aqueous solution are applied from the top of the film. The alternate laminated film was formed by spraying. First, a rinsing step of spraying an aqueous PDDA solution from the upper part of the film using the nozzle of FIG. 11 and then spraying ultrapure water (18 MΩ) for rinsing with the nozzle from the upper part of the film was performed three times. Similarly, the ST-PS-S aqueous solution was sprayed and rinsed, dried by a pair of air knives, and wound into a roll. This operation from unwinding to winding was repeated four times to form an alternately laminated film in which four layers of PDDA and ST-PS-S were laminated. In the formed alternate laminated film, spotted appearance irregularities that could be visually confirmed occurred.

Comparative Example 2
The roll-shaped PET film is laid sideways and conveyed from the unwinding unit to the winding unit while the film is brought into contact with a urethane conveyance roll. In the transport path, a container in which 0.3 wt% PDDA aqueous solution was stored, a container in which 0.3 wt% ST-PS-S aqueous solution and rinsing ultrapure water (18 MΩ) were stored were stored. The container was arrange | positioned and it was made to immerse by feeding a film into each container with a conveyance roll, and the alternating laminated film was formed. First, a rinsing step in which the unwound film was fed and immersed in a container in which the PDDA aqueous solution was stored by a transport roll and then was immersed in a container in which ultrapure water was stored was performed three times. Similarly, it was immersed in an ST-PS-S aqueous solution and rinsed, dried by a pair of air knives, and wound into a roll. This operation from unwinding to winding was repeated four times to form an alternately laminated film in which four layers of PDDA and ST-PS-S were laminated. In the alternately laminated film formed, dot-like dents that could be visually confirmed occurred.

  The alternate laminated film according to the present invention is a technique that can be used for mass production of optical elements for various electronic devices such as antireflection films, various sensors, filters, and the like.

The perspective view which shows an example of the alternate laminated film manufacturing apparatus which concerns on this invention. The top view of the alternate laminated film manufacturing apparatus of FIG. The front view of the alternate laminated film manufacturing apparatus of FIG. The top view before and behind the immersion treatment tank of FIG. The front view before and behind the immersion treatment tank of FIG. CC sectional drawing of FIG. DD sectional drawing of FIG. EE sectional drawing of FIG. FF sectional drawing of FIG. Sectional drawing and top view of immersion processing tank opening vicinity vicinity. The perspective view which shows an example of a nozzle. The top view before and behind the 1st rinse tank. The front view before and behind the 1st rinse tank. HH sectional drawing of FIG. II sectional drawing of FIG. JJ sectional drawing of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Unwinding part 3 ... Winding part 4 ... Processing part 21 ... Uncoiler 22 ... Inlet roll 31 ... Drive roll 32 ... Recoiler 410- .. First immersion process tank 411... Recovery tank 412... Immersion process tank 413 .. recovery tank 432... Slit-like opening 451. Provided nozzles 461, 462 ... columnar member 470 ... support member 475 ... spacer 480 ... support member 485 ... spacer 494, 495 ... nozzle 500 for spraying liquid ... 1st rinse process tank 510 ... 1st rinse tank 511 ... Tank 516, 517 ... Nozzle 520 ... 2nd rinse tank 521 ... Tank 530 ... 3rd rinse tank 531 ... Tank 710 ... 2 immersion process tank 711 ... recovery tank 712 ... immersion treatment tank 713 ... recovery tank 751 ... tank 800 ... second rinse process tank 810 ... first rinse tank 811 ... tank 820 ... 2nd rinse tank 821 ... Tank 830 ... 3rd rinse tank 831 ... Tank

Claims (27)

  In a method for producing an alternately laminated film in which a substance having a positive charge and a substance having a negative charge are alternately laminated on a base material, the base material is transported in a horizontal direction while the base material is conveyed vertically. A dipping process step of immersing the substrate in a liquid containing a substance and a dipping process step of immersing the substrate in a liquid containing a substance having a negative charge are each performed a predetermined number of times.   The manufacturing method of the alternating laminated film of Claim 1 including the rinse process which wash | cleans a base material after each of each immersion treatment process.   The method for producing an alternating laminated film according to claim 1, further comprising a step of applying the same liquid used in each immersion treatment step to the substrate from above or above after each immersion treatment step.   After each immersion treatment step, before the rinsing step after each immersion treatment step, including the step of applying the same liquid used in each immersion treatment step to the substrate from above or above The manufacturing method of the alternating laminated film of Claim 2.   Each immersion treatment step is performed by entering a tank containing a liquid containing a substance having a positive charge or a substance having a negative charge from an opening provided in the tank and from another opening provided in the tank. The manufacturing method of the alternating laminated film in any one of Claims 1-4 performed by letting the base material stood up vertically to pass out.   6. The method for producing an alternate laminated film according to claim 5, wherein each opening is a slit-like opening provided in a vertical direction.   7. The alternation according to claim 5 or 6, wherein in each opening of each tank, a pair of columnar members are arranged separately in the vicinity of the inside of the tank of the opening, and the space between the pair of columnar members is passed through the base material. Manufacturing method of laminated film.   9. The method for producing an alternating laminated film according to claim 8, wherein the structure for isolating the pair of columnar members is a structure for isolating the columnar members by sandwiching a spacer between the upper portion and the lower portion thereof.   The method for producing an alternately laminated film according to any one of claims 1 to 8, wherein in the dipping treatment step, a liquid containing the substance having a positive charge or the substance having a negative charge for dipping the substrate is circulated.   The conveyance of a base material is performed by unwinding the roll-shaped base material before the 1st process, and winding up the base material after the passage of the last process in roll shape. A method for producing an alternating laminated film.   The method for producing an alternately laminated film according to any one of claims 1 to 10, wherein the base material is a woven or non-woven fabric of a film or a fiber material.   It has a slit-like opening provided vertically for a film-like or sheet-like base material to enter the wall and a slit-like opening provided vertically for the base material to exit, positive or negative An alternating film manufacturing apparatus comprising a dipping process tank that contains a dipping treatment tank for containing or introducing a liquid containing a substance having a charge, and that is capable of passing a substrate.   The alternating laminated film manufacturing apparatus of Claim 12 which has two or more immersion process tanks.   It has a slit-like opening provided vertically for the base material that has passed through the dipping process tank to enter the wall and a slit-like opening provided vertically for the base material to exit, and contains cleaning liquid or The alternating laminated film manufacturing apparatus of Claim 12 or 13 provided with the rinse process tank for introducing.   It has a slit-like opening provided vertically for the base material that has passed through the last rinsing process tank to enter and a slit-like opening provided vertically for the base material to exit, and is provided with a drying mechanism. The apparatus for producing an alternating laminated film according to claim 14, comprising a drying process tank. A base material holding member that can stand up vertically and hold and unwind a film-like or sheet-like base material wound in a roll;
A guide roll for vertically guiding and unwinding the holding member to the dipping process tank;
The guide roll which guide | induces the base material which passed the last tank, and the winding roll set up vertically for winding up the base material guided by the guide roll are provided in any one of Claims 12-15 Alternating film production equipment.   The dipping process so that the guided base material can move in a straight line by the guide roll for guiding the unwound holding member to the dipping process tank and the guide roll for guiding the base material that has passed through the last tank. The alternating laminated film manufacturing apparatus of Claim 16 which adjusts the position of the slit-shaped opening part of a tank, a rinse process tank, and a drying process tank, and arranges each tank.   The alternating film production apparatus according to any one of claims 12 to 17, wherein the dipping process tank comprises only an immersion treatment tank.   The immersion process tank has a recovery tank for receiving an immersion liquid flowing out from a slit-like opening for entering or leaving the base material immediately before or after the immersion treatment tank. The alternately laminated film manufacturing apparatus as described.   19. In each opening of the immersion treatment tank, a pair of columnar members are arranged separately in the vicinity of the inside of the tank of the opening, and the space between the pair of columnar members is passed through the base material. 19. The apparatus for producing an alternating laminated film according to 19.   21. The apparatus for producing an alternate laminated film according to claim 20, wherein the structure for isolating the pair of columnar members is a structure for isolating the columnar members by sandwiching a spacer between an upper portion and a lower portion thereof.   The alternating laminated film manufacturing apparatus according to claim 19, wherein the recovery tank immediately after the immersion process tank has a mechanism for applying the immersion liquid to the substrate from above or from above.   The alternating laminated film manufacturing apparatus according to claim 19 or 22, further comprising an immersion liquid discharge port on a bottom surface or a side surface of the collection tank.   The alternating laminated film manufacturing apparatus according to claim 23, further comprising a mechanism for circulating the immersion liquid discharged from the discharge port of the recovery tank to the immersion treatment tank.   The rinsing process tank has a vertically provided slit-like opening for allowing the base material that has passed through the immersion process tank to enter the wall and a vertically provided slit-like opening for the base material to exit, The apparatus for producing an alternating laminated film according to any one of claims 12 to 24, wherein the rinsing tank for containing or introducing the cleaning liquid is composed of one tank or a plurality of tanks.   26. The apparatus for manufacturing an alternate laminated film according to claim 25, wherein the rinse tank is provided with a cleaning liquid discharge port on a bottom surface or a side surface thereof. 27. The alternating laminated film manufacturing apparatus according to claim 26, further comprising a mechanism for circulating the cleaning liquid discharged from the discharge port of the rinsing tank to the rinsing tank.

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