JP2008188513A - Method and device for manufacturing base material with interlaminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and a device for highly efficiently manufacturing a base material with a high-quality interlaminated film with high productivity, and to provide a method for manufacturing a high-quality interlaminated film effectively with a roll to a roll. <P>SOLUTION: In the method for manufacturing the interlaminated film which keeps a material having a positive electric charge and a material having a negative electric charge alternately overlying the base material, a long base material which can be wound up in a roll shape is reciprocally transferred between a winding up roll and a winding off roll. In this transferring process, the process (1) of bringing the base material into contact with a liquid having the positive electric charge or the negative electric charge, and the process (2) of bringing the base material into contact with a liquid having an electric charge opposed to the process (1) are performed predetermined times. <P>COPYRIGHT: (C)2008,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 alternating lamination method is described in G. 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 electrostatic attraction, and the charge of the material formed on the substrate and the material having the opposite charge in the solution attract each other. 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 device described in Patent Document 2 has been proposed to solve such a problem, but since the roll-shaped base material is cut out to form the alternate laminated film, the alternate laminated film is formed at a time. There is a problem that the length that can be formed is about 10 m, and the alternate laminated film cannot be formed at a time with a length of several tens to several hundreds of meters.

  In order to solve such a problem, a method of forming an alternately laminated film by conveying a flexible base material that can be wound into a roll by roll-to-roll is conceivable. However, the alternate laminated film may need to be laminated several tens to several hundreds of times depending on the application. In order to laminate several tens to several hundreds of times by one conveyance, the processing tank for that was needed, and the enlargement of the apparatus size and the lengthening of the base material conveyance path were problems.

  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.

  As a method for solving such a problem, an alternate laminated film manufacturing apparatus capable of laminating one or more layers is used, and the alternate laminated film is manufactured by repeating a predetermined number of times by performing multiple times in the apparatus. Conceivable. However, in order to perform such repeated processing, it is necessary to perform the work of removing the base material that has been processed once and setting it again in the manufacturing apparatus a plurality of times. It was.

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.
Therefore, an object of the present invention is to provide a method and an apparatus for producing an alternating laminated film that can be laminated several tens to several hundreds of times by roll-to-roll with a relatively compact apparatus.

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 substrate, a long substrate that can be wound into a roll is unwound and a take-up roll. A step (1) of bringing the substrate into contact with a liquid having a positive charge or a substance having a negative charge in the transfer process, and the substrate as a step (1) A process for producing a substrate with alternating laminated films, wherein the step (2) of contacting a liquid containing a substance having an opposite charge is performed a predetermined number of times.
2. Item 2. The method includes the step of bringing the substrate into contact with a liquid containing a substance having a positive charge or a negative charge in the forward path, and the step of bringing the substrate into contact with a liquid containing a substance having a charge opposite to the charge in the return path. The manufacturing method of the base material with an alternating laminated film of.
3. In the forward path, the step of bringing the substrate into contact with a liquid containing a substance having a positive charge or a negative charge and the step of bringing the substrate into contact with a liquid containing a substance having a charge opposite to the above charge are alternately performed evenly or oddly in total. A step of contacting the substrate with a liquid containing a substance having a charge opposite to the charge in the final step of the step of contacting the substrate with a liquid containing a substance having a charge in the forward path in the return path; Item 3. The method for producing a substrate with an alternately laminated film according to Item 1 or 2, wherein the step of bringing into contact with the liquid containing the substance is alternately performed evenly or oddly in total.
4). The production of a substrate with an alternately laminated film according to any one of Items 1 to 3, further comprising a rinsing step of washing the substrate after the step of contacting the substrate with a liquid containing a substance having a positive charge or a negative charge. Method.
5. The manufacturing method of the base material with an alternating laminated film as described in any one of claim | item 1 thru | or 4 which comprises a drying process before winding a base material in roll shape.
6). Item 6. The method for producing a substrate with alternating laminated films according to any one of Items 1 to 5, wherein the substrate is a woven or nonwoven fabric of a film or a fiber material.
7). An apparatus for manufacturing a substrate with alternating laminated films, which enables a long substrate that can be wound into a roll to be reciprocally conveyed between an unwinding roll and a winding roll.
8). Item 8. The substrate with alternating laminated film production according to Item 7, comprising at least one treatment tank for bringing the substrate into contact with a liquid containing a substance having a charge in each of the outward path and the return path in the substrate manufacturing apparatus with alternating laminated film. apparatus.
9. A treatment tank for contacting the substrate with a liquid containing a substance having a positive charge or a negative charge in the forward path; and a treatment tank for bringing the substrate into contact with a liquid containing a substance having a charge opposite to the charge in the return path Item 9. The substrate production apparatus with alternating laminated films according to Item 8, which comprises
10. In the forward path, a treatment tank for bringing the base material into contact with a liquid containing a substance having a positive charge or a negative charge and a treatment tank for bringing the base material into contact with a liquid containing a substance having a charge opposite to the above charge are alternately totaled. A processing tank and a base for contacting a liquid containing a substance having a charge opposite to that in a final processing tank for contacting the substrate with a liquid containing a substance having a charge in the forward path in the return path Item 9. The substrate manufacturing apparatus with alternating laminated films according to Item 8, wherein the processing tanks for bringing the material into contact with a liquid containing a substance having a charge opposite to the charge in the processing tanks are alternately provided in total.
11. Item 11. The method according to any one of Items 8 to 10, comprising a mechanism for preventing a liquid containing a substance having a charge from contacting a base material in a treatment tank for bringing the base material into contact with a liquid containing a substance having a charge. An apparatus for manufacturing a substrate with alternating laminated films.
12 Item 12. The substrate production apparatus with alternating laminated films according to any one of Items 7 to 11, wherein a drying treatment unit is provided at a position before the substrate is wound into a roll shape in the winding roll and the unwinding roll.

In the manufacturing method and the manufacturing apparatus of the alternating laminated film in the present invention, the alternating laminated film is formed by setting the base material on the unwinding roll and the winding roll, and reciprocatingly conveying between the unwinding roll and the winding roll. From the formation, once the substrate is set, a predetermined number of laminations can be obtained by repeating the reciprocating conveyance without removing the substrate. In the present invention, it is only necessary to have at least one step of contacting a liquid containing a substance having a positive charge and one step contacting a liquid containing a substance having a negative charge. Can be stacked several tens to several hundreds of times. In the present invention, since the substrate is transported by roll-to-roll, an alternate laminated film can be formed on a long substrate of several tens of meters or more, and the substrate on which the alternate laminated film is formed is pasted. Post-processing such as punching can be performed efficiently.
In the present invention, the immersion liquid and the cleaning liquid can be recycled.

  In the manufacturing method and the manufacturing apparatus of the alternating laminated film according to the present invention, when performing the step of standing the substrate vertically and transporting it in the horizontal direction and immersing it in the liquid containing the charged substance, the rinsing step can be similarly performed. High-quality alternating laminated films can be efficiently manufactured with high mass 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, when the base material is vertically set and conveyed in the horizontal direction, the base material is provided in the vicinity of the inside of the opening for passing through the base material provided in the immersion treatment tank. By arranging a pair of columnar members so as to sandwich the spacer, and by arranging spacers on the upper and lower portions of the pair of columnar members, a gap through which the substrate passes can be secured, and scratches are generated 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. Moreover, if a collection tank is arrange | positioned before and behind an immersion treatment tank, the immersion liquid which flows out from an immersion treatment tank can be collect | recovered efficiently, and this immersion liquid can be circulated and used.

(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, the strip or belt-like substrate having a polar group on the surface is unwound from the unwinding roll and conveyed, and in the meantime, the liquid containing the positively charged substance and the liquid containing the negatively charged substance are alternately brought into contact with each other. An alternating laminated film is produced on the substrate. If the surface charge of the substrate is negative, a step of first contacting the liquid containing a positively charged substance, and if the surface charge of the substrate is positive, a step of contacting a liquid containing a negatively charged substance is performed first. After the step of bringing into contact with the liquid containing the positively charged substance and the liquid containing the negatively charged substance is performed at least once, the substrate is wound up in a roll shape with a winding roll. After performing the above treatment from the part where the alternate laminated film needs to be formed or from the unwinding roll to just before the base material disappears, the base material is unwound from the winding roll and conveyed in the opposite direction to the unwinding roll. Take it up in a roll. If a step of alternately contacting a liquid containing a positively charged substance and a liquid containing a negatively charged substance is provided between the foregoing, an alternate laminated film can be formed efficiently. By repeating the above-described reciprocating conveyance so that the film thickness required for the alternate laminated film is laminated, the intended alternate laminated film can be produced. The step of contacting each liquid containing a charged substance can be carried out by spraying the liquid containing the charged substance by immersion or spraying in the liquid containing the charged substance.

  The base material transport direction that is transported from the unwinding roll to the take-up roll and wound is defined as the forward path, and conversely, the base material transport direction that is transported from the take-up roll to the unwinding roll and wound is defined as the return path. If the surface charge of a base material is minus, the above-mentioned alternately laminated film manufacturing method and manufacturing apparatus include a step of contacting a liquid containing a negatively charged substance, a step of contacting a liquid containing a positively charged substance, and a negatively charged substance It arrange | positions in order of the process made to contact with a liquid. In the forward path, in the step of contacting the liquid containing the negatively charged substance on the unwinding roll side, the process is sequentially carried out in the step of contacting the liquid containing the positively charged substance and the step of contacting the liquid containing the negatively charged substance by performing idle transport. And take up the substrate with a take-up roll. At that time, it is preferable not to perform the step of contacting the liquid containing the negatively charged substance on the unwinding roll side, but there is no particular problem even if it is performed. Next, in the return path, in the step of contacting with the liquid containing the negatively charged substance on the winding roll side, the step of contacting the liquid containing the positively charged substance and the step of bringing into contact with the liquid containing the negatively charged substance in order The treatment is performed, and the substrate is wound up with an unwinding roll. Also in this case, it is preferable not to perform the step of contacting the liquid containing the negatively charged substance on the winding roll side, but there is no particular problem even if it is performed. In the above-described method, each of the forward path and the return path has a structure in which one layer of the positively charged substance and one of the negatively charged substance can be stacked. However, the process may be arranged so that two layers can be stacked. If the steps are arranged so that two or more layers can be laminated, the number of reciprocations of the base material can be reduced, but the apparatus size becomes large, so it is necessary to select appropriately according to the application and purpose. On the other hand, in order to further reduce the size of the apparatus, there is only one step of contacting the liquid containing the charged substance, and the step of contacting the liquid containing the positively charged substance by replacing the liquid containing the charged substance. The step of bringing into contact with a liquid containing a charged substance can be sequentially performed.

  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 treatment time in each of the above treatment steps is appropriately adjusted depending on the material to be laminated, the film thickness to be laminated, and the like. The treatment time can be adjusted according to the conveyance speed of the substrate, the length of the treatment tank, etc. The film thickness per time can be adjusted by adjusting the concentration and pH of a liquid containing a positively charged substance or a negatively charged substance. it can. 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 on the base material, so that the film per time The thickness can be increased. In addition, the treatment time for 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 adsorption state of the charged substance can be confirmed by simultaneously processing the quartz crystal when processing the substrate and confirming the change in the oscillation frequency of the quartz crystal (see International Publication WO00 / 13806). .

  In the step of adsorbing the next charged substance in the same manner as described above after the step of adsorbing the first charged substance, a liquid containing a substance having the opposite charge is used. It is preferable to perform a rinsing step after the step of adsorbing each of these charged substances. 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 there is. 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.

  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 present invention, it is preferable to provide a drying step before winding with a winding roll or a winding roll. After winding the substrate in a wet state, the substrates may dry and adhere to each other, causing the substrate to break during unwinding, or the produced alternating laminated film may be destroyed. There is.

  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.

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

  The above-described apparatus includes an unwinding and winding unit 2 capable of unwinding and winding by extending a strip-shaped or strip-shaped substrate 1 wound in a roll shape in the horizontal direction and raising the surface of the substrate vertically. 3 is immersed in a liquid containing a positively-charged substance and a liquid containing a negatively-charged substance while reciprocally transporting between them. As shown in FIG. 1, the present apparatus is composed of winding and unwinding units 2 and 3 for reciprocating the substrate 1 and a processing unit 4 for forming an alternating laminated film on the substrate 1.

  The base material unwound from the unwinding and winding unit 2 is immersed in a liquid containing a charged substance in the processing unit 4, a rinsing process, a dipping process in a liquid containing the opposite charged substance, a rinsing process, and a drying process. In this order, the substrate is wound up by the unwinding and winding unit 3. After the substrate is transported by the amount necessary for processing, the process from unwinding to winding is performed in the same way in the return path, which is transporting in the direction opposite to that described above. By repeatedly performing the above-described treatments as many times as necessary, it is possible to obtain an alternately laminated film according to the purpose and application.

  The unwinding / winding unit 2 functions as an unwinding device when feeding the substrate, and conversely functions as a winding device when winding the substrate. In the case of functioning as an unwinding device, the roll 21 operates as an uncoiler for vertically feeding the substrate surface vertically, and the roll 22 keeps the strip-like or strip-like substrate fed from the roll 21 constant. It is responsible for introducing the base material into the processing section 4 at the position of. In the case of functioning as a take-up roll, the roll 22 is sent to the roll 21 at a predetermined speed while keeping the base material 1 on which the alternately laminated film that has passed through the processed portion 4 is formed at a fixed position. The roll 21 serves as a recoiler for winding up and collecting the substrate guided by the roll 22. The unwinding / winding unit 3 has the same structure as the unwinding / winding unit 2 and performs the same function. In the present embodiment, the roll 22 and the 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 portion 4 without contacting the wall.

In the processing unit 4, a drying process tank 411, a rinsing process tank 511, an immersion process tank 611, a rinse process tank 521, an immersion process tank 621, a rinse process tank 531, an immersion process tank 631, a rinse process tank 541, and a drying process tank 421 are provided. Sequentially connected. The immersion treatment tanks 611, 621 and 631 have the same structure, and the rinse tanks 511, 521, 531 and 541 have the same structure.
The immersion process tank includes an immersion treatment tank in which a liquid containing a positively charged substance or a negative charge substance is accommodated and a recovery tank that recovers the liquid that has flowed out of the immersion treatment tank. The recovery tank is disposed before and after the immersion treatment tank. Yes.
In order to perform sufficient rinsing, the rinsing process tank is provided with three tanks and can be rinsed three times.
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-shaped opening through which the substrate 1 conveyed vertically stands also on the walls of the drying tank 411 and the rinse tank 511, the drying tank 421 and the rinse tank 541.

  In this apparatus, the positive charge substance and the negative charge substance are respectively used once in the outward path by using the immersion process tank 621, the rinse process tank 531, the immersion process tank 631, the rinse process tank 541, and the drying process tank 421. Laminating and laminating the positive charge substance and the negative charge substance once each using the immersion process tank 621, the rinse process tank 521, the immersion process tank 611, the rinse process tank 511, and the drying process tank 411 on the return path. It has a configuration. Furthermore, in order to make the process part 4 compact, it is also possible to omit the rinse process tanks 511 and 541 by making the rinse tank common. In this case, first, the immersion process tank 611, the rinse process tank 521, the immersion process tank 621, the rinse process tank 531 and the drying process tank 421 are used in the forward path, and the immersion process tank 631, the rinse process tank 531 in the return path, By using the dipping process tank 621, the rinsing process tank 521, and the drying process tank 411, an alternate laminated film is formed. In addition, there is no problem even if the path is changed by changing the arrangement of the immersion process tank and the rinse process tank.

  In the rinsing process tank, the rinsing liquid is ejected by a nozzle, and the rinsing liquid is applied to the substrate that has been conveyed upright. 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 tanks 411 and 421 are for drying the substrate 1 on which the alternately laminated film is formed.

  As described above, the alternate laminated film manufacturing apparatus according to the present embodiment transports the substrate wound in a roll shape, which is an object forming the alternate laminated film, between the unwinding and winding rolls 2 and 3. By doing so, since the alternate laminated film is formed in the processing section 4, it is possible to obtain a predetermined number of laminations by repeating the reciprocating conveyance without removing the base material. Moreover, in this embodiment, it is possible to obtain an alternating laminated film having a number of laminations of several tens to several hundreds on a strip-like or strip-like base material wound in a roll shape with a relatively compact device.

Next, each component of the alternate laminated film manufacturing apparatus according to the present embodiment will be described in detail.
(1) Unwinding and winding unit 2 and 3
The case where the substrate is wound from the roll 21 onto the unwinding roll 32 will be described. A roll 21 or a strip-like or strip-like base material 1 wound in a roll shape is sent out in the longitudinal direction while being held upright so that the surface thereof is vertical, and the base material 1 is introduced into the processing section 4 via the roll 22. Is done. The 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 is changed, and the base material 1 passes through substantially the center of the plurality of slit-shaped openings of the processed portion 4. It is set like so. An accumulator for keeping the tension constant may be provided between the roll 21 and the roll 22. The roll 31 feeds the base material 1 on which the alternately laminated film is formed in the processing unit 4 to the roll 32. The roll 32 itself has a mechanism that can be controlled to rotate at a constant speed. The roll 32 is set so that the base material 1 passes through the center of each slit-shaped opening of the processing unit 4, and the pass line of the base material 1 is constant. The roll 32 collects the base material 1 that is vertically set up from the roll 31 and wound up in a roll shape. The roll 21 and the roll 32 have functions opposite to each other, and the roll 22 and the roll 31 also have functions opposite to each other, so that the substrate can be unwound from the roll 32 and wound around the roll 21. It has become. In this way, the base material can be reciprocated between the roll 21 and the roll 32.
Since the roll 21 and the roll 32 have a function of performing both winding and unwinding as described above, a drive motor is attached to each roll, and an electromagnetic or pneumatic clutch can be inserted to enable idling. It can be a structure. Further, as a method of giving the roll 22 and the roll 31 both the function of keeping the pass line constant as described above and the function of conveying at a constant speed, the roll 22 and the roll 31 are moved at the same speed by using a servo motor or the like. There are a method of rotating the substrate in the direction in which the substrate is conveyed and a method of rotating a roll close to the roll for unwinding the substrate 1.

(2) Processing part 4
(A) Immersion process tank FIG. 4 is a plan view of the immersion process tank 611 (including part of the adjacent rinse tanks, corresponding to frame A in FIG. 3), and FIG. 5 is a front view of the immersion process tank 611 (both adjacent rinse tanks). (Corresponding to frame A in FIG. 3). 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.
The dipping process tank 611 includes a bottom plate 661, side walls 662, 663, a front wall 664, and a rear wall 665 and is divided into three tanks by two threshold walls 666, 667. The tank 652 and the recovery tank 653 are adjacent to each other to form one immersion process tank.
The immersion treatment tank 652 is a tank for immersing in a liquid containing a charge substance in order to cause the charge substance to be adsorbed on the substrate 1, and a liquid containing the charge substance is accommodated in the tank.
The front wall 664 of the recovery tank 651 through which the substrate 1 first passes, the threshold wall 666 shared by the recovery tank 651 and the immersion tank 652, the threshold wall 667 and the recovery tank 653 shared by the immersion tank 652 and the recovery tank 653. In the rear wall 665, vertically long slit-shaped openings 671, 672, 673, and 674 through which the vertically oriented base material 1 passes are sequentially provided.
The liquid containing the charged substance accommodated in the immersion treatment tank 652 constantly flows out in a parabolic shape from the slit-shaped openings 672 and 673. The liquid that has flowed into the collection tanks 651 and 653 is discharged from the discharge ports 681 and 682. It is preferable to arrange the liquid that flows radially from the immersion treatment tank 652 to the collection tanks 651 and 653 so that most of the liquid flows directly into the discharge ports 681 and 682. Further, 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 651 and 653 does not further flow out from the other slit-shaped openings 671 and 674.
Since the liquid containing the charged substance constantly flows out from the immersion treatment tank 652, 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 652. There is. In this apparatus, it is performed by the liquid supply system. The liquid supply system has a structure in which the liquid stored in the tank 811 is sent to the immersion treatment tank 652 from the nozzle 692 provided at the bottom of the immersion treatment tank 652 by the liquid feed pump 812 via the liquid supply pipe 691. It has become.
In order to continue the liquid feeding, it is necessary to replenish the tank 811 with the liquid. For this purpose, the liquid containing the charged substance prepared in advance may be constantly replenished. However, in this apparatus, the collection tanks 651 and 653 are used. The liquid that has flowed out to the tank 811 is sent to the tank 811 via the recovery pipes 693 and 694 connected to the discharge ports 681 and 682, so that the liquid is recovered and supplemented, and is circulated by the liquid feed pump 812. Yes. The circulation structure using the liquid feed pump, the liquid feed pipe, the recovery pipe, and the tank is the same in the tank 821 and the tank 831.

In the slit-shaped openings 672 and 673 of the immersion treatment tank 652, 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 alternating laminated film is relatively inferior in scratch resistance, It is preferable to suppress contact at the slit-like openings 672 and 673 in order to prevent the formed alternate laminated film from being broken.
8 is a cross-sectional view taken along the line E-E in FIG. FIG. 9 is a cross-sectional view taken along the line FF in FIG. 8 (in the vicinity of the immersion treatment tank opening) and a plan view corresponding thereto. 9A is a cross-sectional view taken along the line F-F in FIG. 8 when the immersion treatment tank is filled with the liquid (near the immersion treatment tank opening), and FIG. 9B is a plan view corresponding to FIG.
A vertical slit-shaped opening 672 is provided in the threshold wall 666 of the immersion treatment tank 652. The vertically long slit-shaped opening 672 may be opened to the lowermost part of the threshold wall 666, but is not necessarily required, and is opened at an appropriate height, for example, about 20 to 100 mm. .
Two columnar members 695 and 696 are supported by support members 697 and 698 in the vicinity of the slit-shaped opening 672 so as to stand upright in parallel therewith. The support member 697 is attached to the bottom wall 666 so as to be surrounded by the front plate 6971, the side plates 6972, 6973, and the bottom plate 6974 below or below the slit-shaped opening 672. The support member 698 is attached to the slit wall 666 so as to be opened and surrounded by the front plate 6981 and the side plates 6982 and 6983 at the upper part of the slit-shaped opening 672. The two columnar members 695 and 696 are inserted from the support member 698 to the bottom plate 6974 of the support member 697 . The two columnar members 695 and 696 are isolated by rod-shaped spacers 6975 and 6985 so as not to contact each other. The spacer 6975 is supported by the front plate 6971 so as to face the slit-like opening 672, and the spacer 6985 is supported by the front plate 6981 so as to face the slit-like opening 672. Both may be the same shape or different shapes. The columnar members 695 and 696 are not completely fixed and are free in a range limited by the front plates 6971) and 6981), the side plates 6972, 6973, 6982, and 6983), the bottom plate 6974, and the spacers 6975 and 6985. It has become. The positions of the spacers 6975 and 6985 are opposed to the center of the slit-shaped opening 672 in the plan view, and the base material 1 and the columnar members 695 and 696 even when the base material 1 passes substantially along the center line. Spacers 6975 and 6985 having sufficient width so that they do not contact each other are used. When the liquid is stored in the immersion treatment tank 652, the columnar members 695 and 696 are pressed against the wall 666 and the spacers 6975 and 6985 by 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 672 is 10 mm, the widths of the spacers 6975 and 6985 are 1 mm, and the columnar members 695 and 696 are glass round bars having a diameter of 10 mm. The distance between the front plates 6971 and 6981 and the cut wall 666 is 12 mm, the distance between the spacers 6975 and 6985 and the side plates 6972 and 6982, and the distance between the spacers 6975 and 6985 and the side plates 6773 and 6974 is 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 substrate 1 and the columnar members 695 and 696 may come into contact with each other, and the formed alternate laminated film may be destroyed. If the slit width is too wide, liquid outflow from the slit portion increases. The liquid pump 4812 needs to have a large capacity, and the collection tanks 651 and 653 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 of forming the slit through which the substrate passes, there is also a method of fixing the wall 666) of the immersion treatment tank 652) directly to the columnar members 675 and 696). 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, since the small portion of the middle part of the columnar member does not come into contact with the immersion treatment tank 652) and the wall 666), a gap is generated between the walls 666) and the columnar members 695 and 696), 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 666.
Also in the vicinity of the slit opening 673 of the wall 667, the same columnar member, support member and spacer as described above are installed.

  In the recovery tank 653), a liquid having the same charge substance as the liquid used in the dipping process stored in the tank 811 is divided into a pipe 691, a pipe branched from the pipe (not shown), and two feeds branched from the pipe 691. It is supplied to a nozzle (not shown) through a liquid pipe (for example, 6991 in FIG. 10) and sprays from above the base material 1 to prevent drying of the upper portion of the base material 1 in the process of transporting the base material 1, Generation may be prevented. FIG. 10 is a perspective view showing an example of a liquid spray nozzle used in the present apparatus. A polyvinyl chloride pipe member 6992 is horizontally connected to the liquid feed pipe 6991, and a slit-like opening 6993 is horizontally provided on the pipe member 6992 so that a liquid having a charged substance is ejected from the upper part to the lower part of the base material. Drying can be prevented by flowing the liquid. 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 dipping process tanks 621 and 631 have the same structure as that of the dipping process tank 611, but any of the dipping process tanks may not be used depending on the transfer route and the arrangement method of the treatment liquid. In that case, in order to prevent breakage of the formed alternate laminated film and adhesion of the treatment liquid, it is preferable to have a structure in which the gap between the two columnar members can be opened to the extent that it does not contact the substrate. Furthermore, it goes without saying that the reciprocating processing operation can be automated by using a mechanism that can automatically open and close the two cylindrical members.

(B) Rinse process tank Rinse process tanks 511, 521, 531 and 541 have the same structure, and consist of a set of three tanks of a first rinse tank, a second rinse tank and a third rinse tank. Since the first to third configurations are the same, the first rinsing tank of the rinsing process tank 511 will be described.
11 is a plan view of the rinsing process tank 511 including the first rinse tank 5111 before and after (corresponding to the frame B in FIG. 3), and FIG. 12 is a front view thereof. 13 is a GG sectional view of FIG. 12, FIG. 14 is a HH sectional view of FIG. 11, and FIG. 15 is a II sectional view of FIG.
The 1st rinse tank 5111, the 2nd rinse tank 5112, and the 3rd rinse tank (not shown) 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 512 of the first rinsing tank is in contact with the wall of the adjacent drying process tank 411 and is configured so that the slit-shaped opening just overlaps.
The first rinsing tank 5111 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 711 is fed by a liquid feed pump 712 via a liquid feed pipe 513 and branch pipes 514 and 515 connected to the nozzle 516 provided in the upper portion of the first rinse tank 5111. Rinsing liquid is sprayed from 517. The sprayed rinse liquid is circulated from the discharge port 518 at the bottom of the first rinse tank 5111 to the tank 711 through the recovery 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.
Each of the second rinse tank and the third rinse tank is configured in the same manner as the first rinse tank. In addition, the rinsing liquid spraying system in the second rinsing tank, the third rinsing tank, and the circulation structure using the liquid feeding pump, the liquid feeding pipe, the branch pipe, the recovery pipe, and the tank 711 are respectively the rinsing liquid spraying system in the first rinsing tank. In addition, it is configured in the same manner as the circulation structure.
These rinse liquid spraying systems and circulation structures are similarly configured in the rinse tanks 521, 531 and 541.

(C) Drying process tanks 411 and 421
As the drying process tank, 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). Thus, 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 this equipment, it is possible to reduce the number of times that different types of charged substances are stacked or reciprocated by addition of processing tanks and rinse tanks, replacement of processing liquids, selection of processing liquids used, etc. Needless to say. In the case where there is no influence on the alternately laminated film, an unnecessary treatment tank may be operated to transport the substrate.

  In the present embodiment, the unwinding roll and the winding roll are configured to be able to perform both operations of unwinding and winding of the base material. The base material is unwound by each roll, conveyed, and wound. In between, the immersion in the liquid having the positively charged substance and the immersion in the liquid having the negatively charged substance are each performed once, thereby laminating the positively charged substance and the negatively charged substance one layer at a time. It is a device configuration. The substrate is reciprocated between the unwinding roll and the winding roll so that the alternate laminated film has the required thickness, and immersed in a liquid containing a positively charged substance and immersed in a liquid containing a negatively charged substance. repeat. Therefore, if it is necessary to laminate 10 layers of positively charged substances and negatively charged substances, it is necessary to carry the substrate 10 times.

  In the present invention, a plurality of charge materials can be laminated in multiple layers by further adding an immersion treatment process bath and a rinse process bath to liquids containing different charge materials. For example, when two types of liquids containing negatively charged substances are used, each process tank is arranged in a drying process tank, a rinsing process tank, an immersion treatment process tank 1 in a liquid 1 containing negatively charged substances, and a liquid 2 containing negatively charged substances. Immersion process tank, rinse process tank, process tank into liquid containing positive charge substance, rinse process tank, immersion process process tank in liquid 2 containing negative charge substance, immersion in liquid 1 containing negative charge substance It arrange | positions in order of a process process tank and a rinse process tank. In the case of using the liquid 1 containing a negatively charged substance, the immersion treatment process bath in the liquid 2 containing the negatively charged substance is not used. On the contrary, in the case of using the liquid 2 containing a negatively charged substance, the negatively charged substance is used. By not using the immersion treatment process bath in the liquid 1 containing a substance, different charge substances can be multilayered. A ceria fine particle dispersion capable of forming a thin film having a refractive index of 1.65 to 1.70 is used as the liquid 1 containing a negative charge substance, and a refractive index is 1.28 to 1.35 as the liquid 2 containing a negative charge substance. By using a silica fine particle dispersion that can form a thin film, thin films having different refractive indexes can be multilayered. Moreover, in this embodiment, it is also possible to reduce an immersion process process tank by giving the mechanism which replaces | exchanges a liquid automatically on the way.

The substrate transport method in the present invention is not limited to a method of stretching a strip-like or strip-like substrate wound in a roll shape as described above in the horizontal direction and transporting the substrate with the surface of the substrate standing vertically. It is also possible by a method of conveying with the surface of the material horizontal. FIG. 16 is a perspective view showing an example of an alternate laminated film manufacturing apparatus using a method of transporting the substrate with the surface thereof horizontal. In FIG. 16, the gantry for fixing each tank and roll is not shown. As shown in FIG. 16, an alternate laminated film is formed by carrying out a dipping process by folding and feeding the substrate to a treatment tank storing a liquid containing a charged substance or a rinsing tank storing a rinsing liquid. Is possible. In FIG. 16, the rinsing process tank is structured to be performed once after the immersion treatment in the liquid containing the charged substance, but the rinsing process tank is preferably arranged as necessary. Moreover, when there exists a possibility that the alternating laminated film formed on the base material may be destroyed by contact with a roll, it is preferable to prevent it. As a method for preventing the destruction of the alternate laminated film, rolls that contact only near both ends of the substrate (independent rolls that contact only near both ends of the substrate, a large diameter near both ends of the substrate, In the middle, it is conceivable to carry using a roll having a reduced diameter.
In FIG. 16, first, the base material 1 is unwound from a roll 21 'and wound around a roll 32'. The roll 21 'and the strip-shaped or strip-shaped base material 1 wound in a roll shape are fed out in the longitudinal direction while keeping the surface thereof horizontal, and the base material 1 is introduced into the processing section through the roll 22'. The The roll 22 'is a roll for keeping the pass line of the substrate 1' constant even if the winding diameter of the substrate 1 'changes. An accumulator for keeping the tension constant may be provided between the roll 21 'and the roll 22'. The roll 31 ′ feeds the base material 1 on which the alternately laminated film is formed in the processed portion 4 ′ to the roll 32 ′. The roll 32 'itself has a mechanism that can be controlled to rotate at a constant speed. The roll 32 'is for collecting the base material 1' fed from the roll 31 'by winding it into a roll shape. The roll 21 'and the roll 32' have functions opposite to each other, and the roll 22 'and the roll 31' also have functions opposite to each other. The base material is unwound from the roll 32 'and is transferred to the roll 21'. It can be wound up. In this way, the base material can be reciprocated between the roll 21 'and the roll 32'.
The processing section of the apparatus includes a drying process tank 411 ′, a rinse process tank 511 ′, an immersion process tank 611 ′, a rinse process tank 521 ′, an immersion process tank 621 ′, a rinse process tank 531 ′, an immersion process tank 631 ′, and a rinse. The process tank 541 ′ and the drying process tank 421 ′ are arranged in this order. In addition, transport rolls 911, 912, 913, 914, 915, 916, 917, 918 and transport rolls 92 1, 922, 923 operable up and down are arranged on these tanks.
After passing through the drying process tank 421 ′, the base material 1 ′ is wound around the roll 31 ′ through the roll 32, and at this time, the drying process tank 411 ′ can be eliminated or not operated. On the other hand, after passing through the drying process tank 411 ′, it is wound around the roll 21 ′ through the roll 22 ′. At this time, the drying process tank 421 ′ can be excluded or not operated.
In the forward path, the substrate 1 'is unwound from the roll 21' and sent to the drying process tank 411 'by the roll 22'. Next, the base material 1 ′ is transported to transport rolls 911, 912, and 913, and is sent out by the transport roll 914 to an immersion process tank 611 ′ in which a liquid containing a charged substance is placed. The transport rolls 921, 922, and 923 are arranged above the rinsing process tank 511 ′, the dipping process tank 611 ′, and the rinse process tank 521 ′, respectively, so that they do not come into contact with the rinsing liquid or the liquid containing the charge substance. In the forward path of the material 1, the base material 1 is transported idle. The base material 1 sent to the dipping process tank 611 ′ is sent to the dipping process tank 621 ′ in which a liquid containing a charged substance having the opposite sign to the charged substance in the dipping process tank 611 ′ is placed. Then, it is sent to a transport roll 915 via a transport roll (not shown) in the immersion treatment tank 621 ′. The substrate 1 is immersed in a liquid containing a charged substance in the immersion treatment tank 621 ′, and the charged substance is adsorbed on the substrate 1. Similarly, the base material 1 includes a rinsing process tank 531 ′, a transport roll 916, an immersion process tank 631 ′ containing the same liquid as the immersion process tank 611 ′, a transport roll 917, a rinse process tank 541 ′, and a transport roll 918. Are sequentially fed to the substrate, where charge materials are adsorbed and washed. The base material 1 on which the alternately laminated film is formed is dried in a drying process tank 421 ', and is wound around a roll 32' through a roll 31 '.
In the return path, a transfer roll (not shown) in the rinsing process tank 531 ′, the dipping process tank 631 ′, and the rinsing process tank 541 ′ is moved to the upper side of the respective tanks, and the rinse liquid and the processing liquid are disposed. Carry out empty conveyance so that it does not touch. The transport rolls 921, 922, and 923 are disposed in the rinsing process tank 511 ′, the dipping process tank 611 ′, and the rinse process tank 521 ′, respectively. The charge material is adsorbed to form an alternate laminated film together with the layer containing the charge material. Such a process is repeated so that the film thickness required for the alternately laminated film can be formed.

  In this invention, you may perform the process made to contact the liquid containing each charge substance by spraying the liquid containing a charge substance by spray etc. In FIG.

  The substrate transport method in the present invention is not limited to a method of stretching a strip-like or strip-like substrate wound in a roll shape as described above in the horizontal direction and transporting the substrate with the surface of the substrate standing vertically. It is also possible by a method of conveying with the surface of the material horizontal. In this case, the alternate laminated film is formed by carrying out the dipping process by folding the substrate and sending it out to the treatment tank in which the liquid containing the charged substance is stored or the rinse tank in which the rinsing liquid is stored. It is possible.

  In the present invention, a process tank that does not need to be processed may be generated and transported empty. In the case of performing the empty conveyance, it is preferable that the liquid containing the charge substance or the rinsing liquid does not contact the substrate in the empty conveyance process tank. In the case where the substrate is transported upright as in the present embodiment, the structure may be such that the two columnar members can be opened so that the slits are about 10 mm at the time of empty transport or can be easily removed. Conceivable. In the method of transporting with the surface of the substrate horizontal, the transport roll in the immersion treatment tank can be moved up or down, or the treatment tank can be moved up and down, and the roll outside the treatment tank during empty transport Can be considered. When the transport roll and the processing tank are moved up and down, it is preferable to provide a mechanism for cleaning the transport roll, a cover for preventing the liquid adhering to the roll from dripping and adhering to the substrate being transported, and the like.

  In the present invention, the switching of the conveyance direction of the base material may be visually confirmed and manually performed, but is preferably performed automatically. In the case of automatically switching the conveyance direction of the substrate, it is necessary to automatically recognize the timing for switching the conveyance direction and switch the immersion treatment process tank and the rinsing process tank to be operated. There are a method of setting the length to be processed in advance and a method of marking the substrate as a mark for the timing of switching the transport direction. As a method of setting the length to be processed and switching the conveyance direction, there is a case where confirmation is made by the number of rotations of the motors of the rolls 21 and 21 'and the rolls 31 and 31'. When switching the conveyance direction by marking the base material, it is possible to perform marking according to the presence or absence of light shielding by marking the base material so as to shield the light and installing a photoelectric sensor in the unwinding part or winding part. is there.

  As a liquid containing a positively charged substance, an aqueous solution of diallyldimethylammonium chloride (PAS-H, manufactured by Nitto Boseki Co., Ltd., water-soluble cationic polymer, PAS-H-10L, average molecular weight 200000), a liquid containing a negatively charged substance as silica A fine particle-dispersed aqueous solution (ST-UP, manufactured by Nissan Chemical Industries, Ltd., colloidal silica, Snowtex UP, average primary particle size 7.5 nm) was used. A polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., 150 mm × 20 m × 125 μm thickness) was used as the substrate.

In the apparatus as shown in FIG. 1, a 0.3 wt% PAS-H aqueous solution is stored in a tank 821 and 2 wt% ST-UP aqueous solution is stored in tanks 811 and 831, and the immersion process tanks 611, 621 and 631 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 state in which a belt-shaped PET film (base material 1) wound in a roll shape is vertically unwound from the winding unit 2 through each slit-shaped opening of the processing unit 4 and can be set and transported to the unwinding unit 3 It was. In this conveyance path, conveyance from the unwinding / winding unit 1 to the unwinding / winding unit 3 is defined as an outward path, and conversely, conveyance from the unwinding / winding unit 3 to the unwinding / winding unit 1 is defined as a return path. In the outward path, the immersion process tank 621, the rinse process tank 531, the immersion process tank 631, the rinse process tank 541, and the drying process tank 421 are used to perform the immersion process in the PAS-H aqueous solution and the ST-UP aqueous solution. The alternating laminated film was formed. In the return path, the immersion process tank 621, the rinse process tank 521, the immersion process tank 611, the rinse process tank 511, and the drying process tank 411 are used to soak the PAS-H aqueous solution and the ST-UP aqueous solution. The alternating laminated film was formed.
First, the substrate 1 is conveyed without processing in the drying process tank 411, the rinsing process tank 511, the immersing process tank 611, and the rinsing process tank 521, and a PAS-H film is formed in the immersing process tank 621. did. Next, in the rinsing process tank 531, the substrate 1 was subjected to a rinsing process in which rinsing ultrapure water (18 MΩ) was sprayed from the upper and upper portions by a nozzle three times. Next, an ST-UP film was formed on the PAS-H film of the base material 1 in the dipping process tank 531, and a rinse process with ultrapure water was subsequently performed in the rinse process tank 541 in the same manner as described above. . In a drying process tank 421, drying was performed by blowing air with a blower using a pair of air knives arranged so as to sandwich the substrate 1 conveyed vertically. The base material 1 that passed through the processed portion 4 was wound into a roll by the unwinding and winding portion 3.
Next, the same process as the forward path was performed on the return path. In the return path, the drying process tank 421, the rinsing process tank 541, the dipping process tank 631, and the rinsing process tank 531 convey the base material 1 without any treatment, and the dipping process tank 621, the rinsing process tank 521, and the dipping process tank. 611, the rinse process tank 511, and the drying process tank 411 were used, and the alternate laminated film was formed.
A total of 4.5 reciprocations were performed with the above-described treatment as one reciprocation, and an alternate laminated film was formed in which PAS-H and ST-UP were laminated 9 times each in the vicinity of the center 10 m with respect to the substrate transport direction. As a result of measuring the surface reflectance of the formed alternating laminated film with an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation), the surface reflectance is minimum at a wavelength of 490 nm, and the surface reflectance at that wavelength is 0.5%. It was confirmed that there was. Therefore, in this apparatus, an antireflection film could be formed on the PET film.

In the above, the total length of the processing part 4 is about 4100 mm, and the width of the treatment tank and the rinse tank is 150 mm and the height is 500 mm.
The immersion treatment tank was 300 mm in length with respect to the transport direction, and the recovery tank was 250 mm in length with respect to the transport direction.
The slit opening of each layer was 400 mm long and 10 mm wide from the upper end at the center (plan view) of the wall where it was provided. Two glass round bars having a diameter of 10 mm were used at the slit opening of the dipping process tank, and the slit formed by the two glass bars was 0.9 mm. In addition, the slit opening part of the tank which is not used was made into 10 mm slit width by removing a glass rod.
The substrate 1 (PET film) was conveyed at a speed of 0.6 m / min, and the time during which the substrate was immersed in each immersion process tank was 30 seconds.
A pump capable of feeding at a flow rate of 50 to 60 liters / minute was used to replenish the dipping process tank to be filled with a liquid containing a charged substance (PAS-H or ST-UP). Moreover, in order to circulate and spray the rinse liquid, a pump capable of feeding at a flow rate of 40 to 50 liters / minute was used.
The length of the drying tank was 350 mm, and a pair of air knives were placed on the good side of the film, and drying was performed by blowing air with a blower.

As a liquid containing a positively charged substance, a PAS-H aqueous solution, and as a liquid containing a negatively charged substance, a ceria fine particle dispersed aqueous solution (P-10, Niedral, manufactured by Taki Chemical Co., Ltd., Niedral P-10, average primary particle size 8 nm) ) Was used. A PET film (150 mm × 20 m × 125 μm thickness) was used as the substrate.
In the apparatus as shown in FIG. 1, a 0.3 wt% PAS-H aqueous solution is stored in a tank 821 and a 0.2 wt% P-10 aqueous solution is stored in tanks 811 and 831, and dipping process tanks 611, 621 and By sending the solution to 631, 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.
In the same process as in Example 1, the process of laminating PAS-H and P-10 once each in a single forward or backward transport is performed 9 reciprocations, and 10 m near the center with respect to the transport direction of the substrate. An alternately laminated film in which PAS-H and P-10 were laminated 18 times each was formed. As a result of measuring the surface reflectance of the formed alternating laminated film with an ultraviolet-visible spectrophotometer, it was confirmed that the surface reflectance was 7.1 to 8.7% in the wavelength range of 400 nm to 800 nm. Since the surface reflectance of the PET film alone in the wavelength range of 400 nm to 800 nm is 3.9 to 5.1%, a laminated film of PAS-H and P-10 is formed on the PET film, and the reflection increases. It was confirmed that

As a liquid containing a positively charged substance, a PAS-H aqueous solution, and as a liquid containing a negatively charged substance, a silica fine particle dispersed aqueous solution (ST-UP, manufactured by Nissan Chemical Industries, Ltd., colloidal silica, Snowtex UP, average primary particle size 7 0.5 nm) and a ceria fine particle-dispersed aqueous solution (P-10, Niedral, manufactured by Taki Chemical Co., Ltd., Niedral P-10, average primary particle size 8 nm). A PET film (150 mm × 20 m × 125 μm thickness) was used as the substrate.
In the apparatus as shown in FIG. 1, a 0.3 wt% PAS-H aqueous solution is stored in a tank 821 and 2 wt% ST-UP aqueous solution is stored in tanks 811 and 831, and the immersion process tanks 611, 621 and 631 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.
In the same process as in Example 1, the process of laminating PAS-H and ST-UP once for each transfer in each forward path or return path is performed 4.5 times, near the center with respect to the transport direction of the substrate An alternating laminated film in which PAS-H and ST-UP were laminated 9 times each in 10 m was formed.
Next, the ST-UP aqueous solution in the tanks 811 and 831 is extracted, and the tanks 811 and 831 and the dipping process tanks 611 and 631 are washed, and then stored in the tanks 811 and 831 with 0.2 wt% P-10 aqueous solution. The liquid can be fed into the dipping process tanks 611, 621, and 631. In the same process as in Example 1, the process of laminating PAS-H and P-10 once in each forward / rearward transport is performed 9 times, and PAS-H and ST-UP are each 9 times. An alternating laminated film in which PAS-H and P-10 were laminated 18 times each was formed on the laminated base material.
As a result of measuring the surface reflectance of the formed alternate laminated film with an ultraviolet-visible spectrophotometer, a laminated film having a maximum surface reflectance of 21.4% at a wavelength of 575 nm was formed. As a result of simulation calculation based on the measurement results, a thin film having a refractive index of 1.30 and a film thickness of 95 nm and a thin film having a refractive index of 1.67 and a film thickness of 95 nm are laminated on the PET film. It was confirmed that a film was formed.

(Embodiment)
The present invention includes the following aspects.
(A1) 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 substrate, a long substrate that can be wound in a roll shape is unwound and wound. A dipping process step of immersing the base material in a liquid containing a substance having a positive charge while transporting the base material vertically and horizontally in the transport process, A method for producing an alternating laminated film, wherein the dipping process step of dipping a substrate in a liquid containing a substance having a negative charge is performed a predetermined number of times.
(A2) The method for producing an alternating laminated film according to (A1), which includes a rinsing step for washing the base material after each immersion treatment step.
(A3) The method for producing an alternating laminated film according to item (A1), including a step of applying the same liquid used in each immersion treatment step to the base material from above or above after each immersion treatment step .
(A4) After each immersion treatment step, before the rinsing step after each immersion treatment step, the same liquid used in each immersion treatment step is applied to the substrate from above or above. The manufacturing method of the alternating laminated film of the term (A2) including a process.
(A5) In each immersion treatment step, a tank containing a liquid having a substance having a positive charge or a substance having a negative charge is introduced from an opening provided in the tank and another tank provided in the tank. The method for producing an alternating laminated film according to any one of Items (A1) to (A4), which is performed by passing a vertically upright base so as to exit from the opening.
(A6) The method for producing an alternately laminated film according to item (A5), wherein each opening is a slit-like opening provided in the vertical direction.
(A7) 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 (A5) or (A6) The manufacturing method of the alternating laminated film as described.
(A8) The method for producing an alternately laminated film according to item (A8), 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.
(A9) Alternately according to any one of the items (A1) to (A8), wherein in the immersion treatment step, the positively charged substance or the liquid containing the negatively charged substance for immersing the substrate is circulated and used. Manufacturing method of laminated film.
(A10) A term (A1) in which the substrate is conveyed (outward or return) by unwinding the roll-shaped substrate before the first step and winding the substrate after passing through the last step into a roll. ) To (A9).
(A11) The method for producing an alternating laminated film according to any one of Items (A1) to (A10), wherein the base material is a woven or nonwoven fabric of a film or a fiber material.
(B1) It has a slit-like opening portion provided vertically for a film-like or sheet-like base material to enter the wall and a slit-like opening portion provided vertically for the base material to exit. Alternatively, an alternate laminated film manufacturing apparatus including an immersion treatment tank for containing or introducing a liquid containing a substance having a negative charge, and including an immersion process tank through which a substrate can pass.
(B2) The apparatus for producing an alternating laminated film according to item (B1), wherein the apparatus has a plurality of dipping process tanks.
(B3) A cleaning liquid having a vertically provided slit-like opening for allowing the base material that has passed through the dipping process tank to enter the wall and a vertically provided slit-like opening for exiting the base material, The alternating film production apparatus according to item (B1) or (B2), comprising a rinsing process tank for containing or introducing the material.
(B4) 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 dried. The alternating laminated film manufacturing apparatus according to item (B3), comprising a drying process tank having a mechanism.
(B5) A base material holding member for a forward path or a return path, which can hold and unwind a film-like or sheet-like base material that is vertically set and wound in a roll shape,
A guide roll for vertically guiding and unwinding the holding member to the rinsing process tank or the dipping process tank;
Terms (B1) 12 to (12) comprising a guide roll for guiding the base material that has passed through the last tank in the forward path or the return path, and a vertically winding roll for winding the base material guided by the guide roll B4) The alternating laminated film manufacturing apparatus according to any one of 15.
(B6) The guided base material can be moved 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 apparatus for producing an alternating laminated film according to item (B5), wherein the tanks are arranged by adjusting the positions of the slit-shaped openings of the dipping process tank, the rinse process tank, and the drying process tank.
(B7) The alternating laminated film manufacturing apparatus according to any one of Items (B1) to (B6), wherein the dipping process tank includes only an immersion treatment tank.
(B8) Items (B1) to (B1), wherein the immersion process tank has a recovery tank for receiving the immersion liquid flowing out from the slit-like opening for entering or exiting the base material immediately before or after the immersion treatment tank. The alternating laminated film manufacturing apparatus according to any one of B6).
(B9) In each opening of the immersion treatment tank, a pair of columnar members are arranged separately in the vicinity of the inner side of the opening, and the structure is configured to pass between the pair of columnar members through the base material. The alternating laminated film manufacturing apparatus according to (B7) or (B8).
(B10) The alternating film manufacturing apparatus according to item (B9), 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.
(B11) The alternating film manufacturing apparatus according to item (B8), 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.
(B12) The alternating laminated film manufacturing apparatus according to (B8) or (B11), which has an immersion liquid discharge port on the bottom surface or side surface of the recovery tank.
(B13) The alternating laminated film manufacturing apparatus according to item (B12), having a mechanism for circulating the immersion liquid discharged from the discharge port of the recovery tank to the immersion treatment tank.
(B14) The slit-shaped opening provided vertically for the base material that the rinsing process tank has passed through the dipping process tank to enter the wall and the slit-shaped opening provided vertically for the base material to exit. The apparatus for producing an alternate laminated film according to any one of Items (B1) to (B13), wherein the rinsing tank for storing or introducing the cleaning liquid is composed of one tank or a plurality of tanks.
(B15) The alternating film manufacturing apparatus according to item (B14), wherein the rinse tank is provided with a cleaning liquid discharge port on a bottom surface or a side surface thereof.
(B16) The alternating laminated film manufacturing apparatus according to item (B15), having a mechanism for circulating the cleaning liquid discharged from the discharge port of the rinse tank to the rinse tank.

  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 before and behind the immersion treatment tank of FIG. The front view before and behind the immersion treatment tank of FIG. The top view before and behind the immersion process tank 611. FIG. The front view before and behind the immersion process tank 611. FIG. CC sectional drawing of FIG. DD sectional drawing of FIG. EE sectional drawing of FIG. FF sectional drawing (immersion processing tank opening part vicinity) of FIG. 8 and a top view corresponding to it. The perspective view which shows an example of the nozzle for liquid spraying. The top view before and behind the rinse tank. The front view before and behind the rinse tank. GG sectional drawing of FIG. HH sectional drawing of FIG. II sectional drawing of FIG. The perspective view which shows an example of the alternate laminated film manufacturing apparatus which applies the method of conveying by making the surface of a base material horizontal.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2, 3 ... Unwinding winding part 4 ... Processing part 21, 32 ... Uncoiler and recoiler 22, 31 ... Roll 411,421 ... Drying process tank 511 521, 531, 541 ... Rinse tanks 516, 517 ... Nozzles 611, 621, 631 ... Immersion process tank 651 ... Recovery tank 652 ... Immersion treatment tank 653 ... Recovery tank 671, 672 , 673, 674 ... slit-like opening 692 ... nozzle 695 provided at the bottom of the immersion treatment tank 652 ... cylindrical member 696 ... spacers 711, 721, 731, 741 ... rinsing liquid Tank 811, 821, 831 ... Liquid tank 712 ... Liquid feed pump 812 ... Liquid feed pump 911, 912, 913, 914, 915, 916, 917, 91 ... transport rolls 921, 922, 923 ... operation that can be transported roll up and down

Claims (12)

  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 substrate, a long substrate that can be wound into a roll is unwound and a take-up roll. A step (1) of bringing the substrate into contact with a liquid having a positive charge or a substance having a negative charge in the transfer process, and the substrate as a step (1) A process for producing a substrate with alternating laminated films, wherein the step (2) of contacting a liquid containing a substance having an opposite charge is performed a predetermined number of times.   The method according to claim 1, further comprising the step of contacting the substrate with a liquid containing a substance having a positive charge or a negative charge in the outward path, and contacting the substrate with a liquid containing a substance having a charge opposite to the charge in the return path. The manufacturing method of the base material with an alternating laminated film of description.   In the forward path, the step of bringing the substrate into contact with a liquid containing a substance having a positive charge or a negative charge and the step of bringing the substrate into contact with a liquid containing a substance having a charge opposite to the above charge are alternately performed evenly or oddly in total. A step of contacting the substrate with a liquid containing a substance having a charge opposite to the charge in the final step of the step of contacting the substrate with a liquid containing a substance having a charge in the forward path in the return path; The manufacturing method of the base material with an alternating laminated film of Claim 1 or 2 which performs the process made to contact the liquid containing the substance which has it alternately alternately in total even number times or odd number times.   The substrate with an alternately laminated film according to any one of claims 1 to 3, further comprising a rinsing step of washing the substrate after the step of bringing the substrate into contact with a liquid containing a substance having a positive charge or a negative charge. Production method.   The manufacturing method of the base material with an alternating laminated film as described in any one of Claims 1 thru | or 4 which comprises a drying process before winding a base material in roll shape.   The method for producing a substrate with alternating laminated films according to any one of claims 1 to 5, wherein the substrate is a woven or nonwoven fabric of a film or a fiber material.   An apparatus for manufacturing a substrate with alternating laminated films, which enables a long substrate that can be wound into a roll to be reciprocally conveyed between an unwinding roll and a winding roll.   8. The substrate with alternating laminated films according to claim 7, comprising at least one treatment tank for bringing the substrate into contact with a liquid containing a substance having a charge in each of the outward path and the return path in the substrate manufacturing apparatus with alternating laminated films. Manufacturing equipment.   A treatment tank for contacting the substrate with a liquid containing a substance having a positive charge or a negative charge in the forward path; and a treatment tank for bringing the substrate into contact with a liquid containing a substance having a charge opposite to the charge in the return path The base-material manufacturing apparatus with an alternating laminated film of Claim 8 containing this.   In the forward path, a treatment tank for bringing the base material into contact with a liquid containing a substance having a positive charge or a negative charge and a treatment tank for bringing the base material into contact with a liquid containing a substance having a charge opposite to the above charge are alternately totaled. A processing tank and a base for contacting a liquid containing a substance having a charge opposite to that in a final processing tank for contacting the substrate with a liquid containing a substance having a charge in the forward path in the return path The base material manufacturing apparatus with an alternating laminated film according to claim 8, further comprising a total of even or odd number of treatment tanks for bringing the material into contact with a liquid containing a substance having a charge opposite to the charge in the treatment tank.   The processing tank for bringing a base material into contact with a liquid containing a substance having a charge, comprising a mechanism for preventing the liquid containing a substance having a charge from coming into contact with the base material. The base material manufacturing apparatus with an alternating laminated film of description.   In the winding roll and the unwinding roll, the base material manufacturing apparatus with an alternately laminated film according to any one of claims 7 to 11, wherein a drying processing unit is provided at a position before the base material is wound into a roll shape.

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