Ultrasonic stirring device

Abstract

Provided is an ultrasonic agitation device that can suitably agitate a solution on a substrate without damaging the substrate even if a delicate substrate is used, that can suitably agitate the solution even if the solution is present on both surfaces of the substrate, and that can be applied to roll-to-roll processing. Provided is an ultrasonic agitation device that conveys a long substrate in the lengthwise direction while agitating a solution on the substrate, the ultrasonic agitation device having a first ultrasonic vibrator which is disposed facing the front surface of the substrate and which transmits ultrasonic vibration through the medium of a gas and a second ultrasonic vibrator which is disposed facing the rear surface of the substrate and which transmits ultrasonic vibration through the medium of a gas, wherein the center location of a vibration surface of the second ultrasonic vibrator, when viewed from a direction perpendicular to the main plane of the substrate, is disposed downstream of the center location of a vibration surface of the first ultrasonic vibrator in the conveyance direction of the substrate.

Description

[Technical field]

[0001] The present invention relates to an ultrasonic agitator. [Background technology]

[0002] When forming various layers on the surface of various substrates such as film substrates using a solution, it is necessary to homogenize the reactants in the solution in order to form an appropriate layer. For example, when applying a two-liquid adhesive to a substrate, if the base agent and the curing agent are mixed in advance, the adhesive will harden, so it is necessary to apply the base agent and the curing agent separately. However, if the base agent and the curing agent are applied separately, the base agent and the curing agent will not be mixed sufficiently, which can cause problems such as a long time for curing or a partially weak curing resulting in an uneven layer. Therefore, it is required to stir the solution applied to the substrate, but there are many restrictions when stirring the solution on the substrate. Ultrasonic treatment is known as a technique for stirring such a solution on a substrate.

[0003] For example, Patent Document 1 describes a method for manufacturing an anti-reflective film having a refractive index gradient film on a substrate, in which the refractive index in the visible light region increases continuously from 1.0 to 2.5 from the side farthest from the substrate in the thickness direction to the side closest to the substrate, and the transmittance in the visible light region is 70% or more, in which at least two inorganic materials with different refractive indices are ejected onto the substrate by an inkjet method to form a refractive index gradient film having voids, and in this method, the stage on which the substrate is placed is controlled to ultrasonically treat the substrate in order to promote mixing of the inks that will form the refractive index gradient film (see paragraph

[0052] ). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2012-181292 A Summary of the Invention [Problem to be solved by the invention]

[0005] In the manufacturing method described in Patent Document 1, ultrasonic treatment is applied directly to the substrate (ink) via a stage on which the substrate is placed. However, there is a problem that this method cannot be used when the substrate to be ultrasonically treated is very thin or delicate, such as when it contains brittle materials, such as fibrous materials and inorganic materials. In addition, since the substrate is placed on the stage and ultrasonic treatment is applied, there is a problem that this method cannot be used when a layer is formed by applying a solution to both sides of the substrate.

[0006] In addition, a known efficient method for manufacturing multilayer films is to form layers on a long substrate by conveying the substrate in the longitudinal direction, a process known as roll-to-roll (hereinafter also referred to as RtoR). However, with RtoR, the substrate cannot be placed on a stage, making it difficult to apply ultrasonic treatment.

[0007] The object of the present invention is to solve such problems of the conventional technology, and to provide an ultrasonic stirring device that can properly stir a solution on a substrate without damaging the substrate even when a delicate substrate is used, can properly stir a solution even when the solution exists on both sides of the substrate, and can be applied to roll-to-roll. [Means for solving the problem]

[0008] In order to solve this problem, the present invention has the following configuration. [1] An ultrasonic stirring device that stirs a solution on a long substrate while transporting the substrate in the longitudinal direction, A first ultrasonic transducer is disposed facing the surface of the base material and transmits ultrasonic vibrations through a gas medium; A second ultrasonic transducer is disposed on the back surface of the base material so as to face the back surface of the base material and transmits ultrasonic vibrations through a gas medium. An ultrasonic agitator, wherein the center position of the vibration surface of the second ultrasonic oscillator is disposed downstream in the transport direction of the base material from the center position of the vibration surface of the first ultrasonic oscillator. [2] A solution supply unit is provided that supplies a first solution containing a base material as a reactant and a second solution containing an auxiliary agent that accelerates the reaction of the base material onto a substrate; The ultrasonic stirring device according to [1], wherein the first ultrasonic vibrator and the second ultrasonic vibrator stir the first solution and the second solution. [3] The ultrasonic agitator according to [2], wherein the solution supply unit is a spray device. [4] The ultrasonic stirring device according to any one of [1] to [3], wherein the vibration surfaces of the first ultrasonic transducer and the second ultrasonic transducer each have a convex curved shape facing the base material. [5] A device having a casing that houses a first ultrasonic transducer and a second ultrasonic transducer therein; The ultrasonic agitator according to any one of [1] to [4], further comprising a temperature and humidity control section for controlling the temperature and humidity inside the casing. [6] The ultrasonic agitator according to any one of [1] to [5], wherein the solution is present on both the front and back surfaces of the substrate as it passes through the first ultrasonic transducer and the second ultrasonic transducer. [7] The ultrasonic agitator according to any one of [1] to [6], which accelerates a reaction of a reactant in a solution by agitating the solution. Effect of the Invention

[0009] According to the present invention, an ultrasonic stirring device can be provided that can properly stir a solution on a substrate without damaging the substrate even when a delicate substrate is used, can properly stir a solution even when the solution is present on both sides of the substrate, and can be applied to roll-to-roll. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a diagram conceptually illustrating an example of an ultrasonic stirring device of the present invention. [Diagram 2] 2 is a diagram conceptually illustrating an example of the configuration of a solution supply unit and an ultrasonic transducer of the ultrasonic agitator shown in FIG. [Diagram 3]FIG. 2 is a conceptual diagram for explaining an example of the configuration of an ultrasonic transducer in the ultrasonic stirring device of the present invention. [Figure 4] FIG. 11 is a conceptual diagram for explaining another example of the configuration of the ultrasonic transducer in the ultrasonic stirring device of the present invention. [Diagram 5] FIG. 11 is a conceptual diagram for explaining another example of the configuration of the ultrasonic transducer in the ultrasonic stirring device of the present invention. [Figure 6] 10 is a diagram conceptually illustrating another example of the configuration of the coating unit and ultrasonic transducer of the ultrasonic stirring device of the present invention. FIG. [Figure 7] FIG. 13 is a diagram conceptually illustrating another example of an ultrasonic stirring device of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The ultrasonic agitator of the present invention will now be described in detail with reference to the preferred embodiments shown in the accompanying drawings. In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​before and after "to" as the lower and upper limits.

[0012] [Ultrasonic stirring device] The ultrasonic agitator of the present invention comprises: An ultrasonic stirring device that stirs a solution on a long substrate while transporting the substrate in a longitudinal direction, A first ultrasonic transducer is disposed facing the surface of the base material and transmits ultrasonic vibrations through a gas medium; A second ultrasonic transducer is disposed on the back surface of the base material so as to face the back surface of the base material and transmits ultrasonic vibrations through a gas medium. The ultrasonic agitator is arranged such that the center position of the vibration surface of the second ultrasonic oscillator is located downstream in the transport direction of the base material from the center position of the vibration surface of the first ultrasonic oscillator.

[0013] An example of an ultrasonic agitator of the present invention is conceptually shown in Fig. 1. Fig. 2 conceptually shows an example of the configuration of a solution supply unit and an ultrasonic transducer of the ultrasonic agitator shown in Fig. 1.

[0014] The ultrasonic agitator 10 shown in FIG. 1 is an apparatus for performing various processes while transporting a long substrate Z in the longitudinal direction, and includes, from the upstream side in the transport direction of the substrate Z, a guide roller 12, a solution supply unit 14, a first ultrasonic oscillator 22, a second ultrasonic oscillator 24, a cleaning tank 16, a guide roller 18, and a guide roller 20.

[0015] The guide roller 12, the guide roller 18, and the guide roller 20 are each a conventionally known guide roller that guides the base material Z so as to transport the base material Z along a predetermined transport path.

[0016] 1, guide rollers 12 guide substrate Z downward in the vertical direction (arrow v direction). While substrate Z is transported downward in the vertical direction (arrow v direction), solution is supplied to substrate Z in solution supply section 14.

[0017] In the example shown in FIG. 1, the solution is a reaction liquid of two liquids, a main agent which is a reactant and an auxiliary agent which accelerates the reaction of the main agent, and the solution supply unit 14 has a first application unit 14a which applies a first solution containing the main agent and a second application unit 14b which applies a second solution containing the auxiliary agent. In the example shown in FIG. 1, the first application unit 14a and the second application unit 14b are arranged on one main surface (front surface) side and the other main surface (rear surface) side of the substrate Z, respectively. Therefore, the solution supply unit 14 applies the solution to each of the front surface and the rear surface of the substrate Z. In the present invention, the front surface and the rear surface of the substrate Z are referred to in order to distinguish between the two main surfaces, and either main surface may be the front surface.

[0018] 2, the second applicator 14b is disposed upstream of the first applicator 14a in the transport direction of the substrate Z. In the solution supply unit 14, the second applicator 14b first applies a second solution h containing an auxiliary agent to each of both main surfaces of the elongated substrate Z transported in the longitudinal direction, and then the first applicator 14a applies a first solution m containing a main agent to each of both main surfaces of the elongated substrate Z transported in the longitudinal direction.

[0019] There are no particular limitations on the first coater 14a and the second coater 14b as long as they are capable of coating the solution on the substrate Z, and any conventionally known coater may be appropriately used. Examples of the coating method performed by the first coater 14a and the second coater 14b include an inkjet method, a curtain coater method, a roller coater method, a spray method, a bar coater method, a dispenser method, and a die coater method.

[0020] Among these, the spray method is preferably used since the main agent and the auxiliary agent can be suitably mixed on the substrate Z. As the spray method, various known methods such as a one-fluid spray method, a two-fluid spray method, an ultrasonic spray method, a capacitive spray method, and a centrifugal spray method can be used.

[0021] Furthermore, the application methods performed by first application section 14a and second application section 14b may be the same or different, but it is most preferable that both apply by a spray method.

[0022] The first coating section 14a and the second coating section 14b may each have one coating device or multiple coating devices. For example, when a spray-type coating device is used, multiple coating devices may be arranged in the width direction of the substrate Z according to the width of the substrate Z. Alternatively, the first coating section 14a and the second coating section 14b may each have multiple coating devices arranged in the transport direction of the substrate Z. The width direction of the substrate Z is a direction perpendicular to the longitudinal direction of the substrate Z and perpendicular to the transport direction of the substrate Z.

[0023] 1 and 2, first applicator 14a is disposed downstream of second applicator 14b, but the present invention is not limited thereto, and first applicator 14a may be disposed upstream of second applicator 14b. That is, in the example shown in Fig. 1 and 2, first, second solution h containing an auxiliary agent is applied onto substrate Z, and then, first solution m containing a main agent is applied, but it is also possible to apply second solution containing an auxiliary agent after applying first solution containing a main agent onto substrate Z.

[0024] The distance between the second coating section 14b and the first coating section 14a may be appropriately set depending on the conveying speed of the substrate Z, the type of coating layer to be formed, the amount of base material and auxiliary agent applied, the application timing of the auxiliary agent and base material, and the drying speed of the solvent of the auxiliary agent and base material, etc.

[0025] 1, the solution supply unit 14 supplies two reaction liquids of a main agent and an auxiliary agent, but is not limited thereto and may supply one solution containing a reactant. That is, when the solution supply unit 14 supplies a solution by coating, the solution supply unit 14 may have one coating unit.

[0026] In addition, the solution supply unit 14 is preferably disposed at a position where the substrate Z is transported vertically downward. That is, the solution supply unit 14 preferably supplies the solution to the substrate Z at a position where the substrate Z is transported vertically downward. For example, in the example shown in FIG. 1 and FIG. 2, the first application unit 14a and the second application unit 14b are disposed at positions where the substrate Z is transported vertically downward, and supply the second solution containing an auxiliary agent and the first solution containing a main agent to the substrate Z transported vertically downward. This allows the solution to be applied to the substrate Z with a uniform thickness without adhesion of foreign matter or the like and without unevenness.

[0027] The solution supply unit 14 may supply the solution to the entire surface (full width) of the main surface of the base material Z, or may supply the solution to a part of the main surface of the base material Z.

[0028] A first ultrasonic transducer 22 and a second ultrasonic transducer 24 are disposed downstream of the solution supply unit 14 .

[0029] The first ultrasonic transducer 22 is disposed facing the surface of the substrate Z at a predetermined distance, and transmits ultrasonic vibrations to the solution on the substrate Z via gas.

[0030] The second ultrasonic oscillator 24 is disposed facing the rear surface of the base material Z at a predetermined distance, and transmits ultrasonic vibrations to the solution on the base material Z via gas. The ultrasonic vibrations from the first ultrasonic oscillator 22 and the second ultrasonic oscillator 24 may be transmitted via air, or when the space including the first ultrasonic oscillator 22 and the second ultrasonic oscillator 24 is purged with nitrogen gas or the like, the ultrasonic vibrations may be transmitted via this gas.

[0031] The first ultrasonic vibrator 22 and the second ultrasonic vibrator 24 propagate ultrasonic vibrations to the solutions (first solution m and second solution h) on the substrate Z, thereby stirring the solutions and accelerating the reaction of the reactants (main agent) in the solutions. The reactants in the solutions react, hardening them to form a layer (hereinafter referred to as a coating layer).

[0032] There are no particular limitations on the first ultrasonic transducer 22 and the second ultrasonic transducer 24 as long as they are capable of generating ultrasonic vibrations, and conventionally known ultrasonic transducers can be used.

[0033] It is preferable that the first ultrasonic vibrator 22 and the second ultrasonic vibrator 24 have a planar portion that emits ultrasonic vibration. That is, it is preferable that the first ultrasonic vibrator 22 and the second ultrasonic vibrator 24 generate planar ultrasonic vibration. This allows the ultrasonic vibration to be applied uniformly to the solution on the substrate Z.

[0034] Here, as shown in Figures 1 and 2, in the present invention, the center position of the vibration surface 24a of the second ultrasonic transducer 24 is located downstream of the center position of the vibration surface 22a of the first ultrasonic transducer 22 in the transport direction of the base material.

[0035] In the ultrasonic stirring device 10 of the present invention, the first ultrasonic vibrator 22 and the second ultrasonic vibrator 24 are arranged at a distance from the substrate Z, and ultrasonic vibration is applied to the solution via gas. That is, the first ultrasonic vibrator 22 and the second ultrasonic vibrator 24 apply ultrasonic vibration to the solution on the substrate Z without contacting the substrate Z. Therefore, as shown in FIG. 1, a long substrate can be treated by roll-to-roll (RtoR) while being transported in the longitudinal direction. In addition, the ultrasonic stirring device 10 can be used when the substrate is very thin, or when it is a delicate material such as a brittle material including a fibrous material or an inorganic material. In addition, the ultrasonic stirring device 10 can be used when a layer is formed by applying a solution to both sides of the substrate.

[0036] Here, in a configuration in which a long substrate Z is processed while being transported in the longitudinal direction, if an ultrasonic vibrator is arranged only on one main surface side and ultrasonic vibration is applied to the solution on the substrate Z, the substrate Z will vibrate due to the ultrasonic vibration. In a configuration in which the ultrasonic vibrator does not come into contact with the substrate Z and ultrasonic vibration is applied indirectly via gas, a higher output is required to apply ultrasonic vibration to the solution to stir it, but this causes the substrate Z to vibrate more. This causes problems such as an impediment to the transportation of the substrate Z or a change in the distance between the substrate Z (solution) and the ultrasonic vibrator, resulting in variation in the ultrasonic vibration applied to the solution.

[0037] In response to this, a configuration can be considered in which an ultrasonic transducer is disposed on each of the two main surfaces of the base material Z, and the two ultrasonic transducers are disposed at the same position in the transport direction of the base material Z, that is, the two ultrasonic transducers are disposed so as to sandwich the base material Z. However, since the base material Z vibrates slightly while being transported, and the ratio of the distance between one ultrasonic transducer and the base material Z and the distance between the other ultrasonic transducer and the base material Z changes, it is difficult to maintain a constant ratio of the intensity of the ultrasonic vibrations applied from each ultrasonic transducer, and there is a risk that the vibration of the base material Z will be amplified.

[0038] In contrast, in the ultrasonic stirring device of the present invention, the center position of the vibration surface 24a of the second ultrasonic oscillator 24 is disposed downstream in the transport direction of the base material from the center position of the vibration surface 22a of the first ultrasonic oscillator 22. In other words, the first ultrasonic oscillator 22 and the second ultrasonic oscillator 24 are disposed at positions offset from each other in the transport direction of the base material Z.

[0039] By arranging the first ultrasonic transducer 22 on the front side of the base material Z and the second ultrasonic transducer 24 on the back side, and arranging the first ultrasonic transducer 22 and the second ultrasonic transducer 24 at positions offset from each other in the conveying direction of the base material Z, the base material Z passing through the first ultrasonic transducer 22 and the second ultrasonic transducer 24 can be maintained in a substantially S-shaped bent state and conveyed in a stable state without amplified vibration. In other words, the first ultrasonic transducer 22 and the second ultrasonic transducer 24 act like non-contact guides, and the base material Z can be conveyed in a stable state.

[0040] In this manner, the ultrasonic agitator of the present invention is an apparatus for treating a long substrate while transporting it in the longitudinal direction, and is capable of agitating the solution on the substrate during transport in a non-contact manner using ultrasonic vibrations.

[0041] From the viewpoints of suitably stirring the solution and stably transporting the base material Z, the frequency of the ultrasonic vibrations generated by the first ultrasonic transducer 22 and the second ultrasonic transducer 24 is preferably 250 kHz to 1 kHz, more preferably 200 kHz to 5 kHz, and even more preferably 150 kHz to 10 kHz.

[0042] Furthermore, the intensity of the ultrasonic vibrations generated by the first ultrasonic vibrator 22 and the second ultrasonic vibrator 24 may be set appropriately depending on the type of solution, the distance from the base material Z, the transport speed of the base material Z, the weight (thickness) of the base material, etc., but from the viewpoint of suitably stirring the solution and stably transporting the base material Z, it is preferably 30 W to 1 W, more preferably 25 W to 3 W, and even more preferably 20 W to 5 W.

[0043] From the viewpoint of stable transportation of the base material Z, it is preferable that the frequency and intensity of the ultrasonic vibrations generated by the first ultrasonic transducer 22 and the second ultrasonic transducer 24 are the same.

[0044] Moreover, the distance d1 between the vibration surface 22a of the first ultrasonic transducer 22 and the substrate Z, and the distance d2 between the vibration surface 24a of the second ultrasonic transducer 24 and the substrate Z (see Figures 3 and 4) are preferably 700 mm to 100 mm, more preferably 500 mm to 150 mm, and even more preferably 400 mm to 200 mm, from the viewpoints of suitably stirring the solution and stably transporting the substrate Z.

[0045] Moreover, the width of the vibration surface 22a of the first ultrasonic transducer 22 and the vibration surface 24a of the second ultrasonic transducer 24 is preferably a width that includes the region in the width direction in which the solution exists from the viewpoint of suitably stirring the solution, and more preferably a width that includes the width of the substrate Z from the viewpoint of suppressing deformation of the substrate Z and stabilizing the transport of the substrate Z. Note that the width of the vibration surface is the width in the direction perpendicular to the transport direction of the substrate Z.

[0046] The lengths of the vibration surface 22a of the first ultrasonic oscillator 22 and the vibration surface 24a of the second ultrasonic oscillator 24 may be appropriately set according to the transport speed of the base material Z, the type of solution, the strength of ultrasonic vibration, etc. From the viewpoint of suitably stirring the solution, stabilizing the transport of the base material Z, etc., the lengths of the vibration surface 22a of the first ultrasonic oscillator 22 and the vibration surface 24a of the second ultrasonic oscillator 24 are preferably 100 mm to 0.1 mm, more preferably 80 mm to 0.5 mm, and even more preferably 60 mm to 1 mm.

[0047] The width and length of the vibration surface 22a of the first ultrasonic transducer 22 and the width and length of the vibration surface 24a of the second ultrasonic transducer 24 may be the same or different, but it is preferable that they are the same from the viewpoint of stabilizing the transportation of the substrate Z, etc.

[0048] Furthermore, when viewed from a direction perpendicular to the main surface of the substrate Z, the vibration surface 22a of the first ultrasonic transducer 22 and the vibration surface 24a of the second ultrasonic transducer 24 may be arranged so as to overlap as shown in FIG. 3, or may be arranged so as to be spaced apart as shown in FIG. 4.

[0049] As shown in FIG. 3, when the vibration surface 22a of the first ultrasonic transducer 22 and the vibration surface 24a of the second ultrasonic transducer 24 are arranged so as to overlap, the distance L2 over which the vibration surface 22a of the first ultrasonic transducer 22 and the vibration surface 24a of the second ultrasonic transducer 24 overlap is preferably equal to or less than 1 / 2 the length of the vibration surface.

[0050] 4, when the vibration surface 22a of the first ultrasonic transducer 22 and the vibration surface 24a of the second ultrasonic transducer 24 are disposed apart from each other, the distance L3 between the vibration surface 22a of the first ultrasonic transducer 22 and the vibration surface 24a of the second ultrasonic transducer 24 is preferably 50 mm to 0.1 mm, more preferably 60 mm to 1 mm, and further preferably 30 mm to 2 mm. If the distance L3 is too large, it may become difficult to control the propagation efficiency of the ultrasonic vibration.

[0051] In addition, the distance L1 (see Figures 3 and 4) between the center position of the vibration surface 22a of the first ultrasonic transducer 22 and the center position of the vibration surface 24a of the second ultrasonic transducer 24 is set according to the length of the vibration surface described above and the distance L2 or the distance L3.

[0052] In addition, the vibration surface 22a of the first ultrasonic transducer 22 and the vibration surface 24a of the second ultrasonic transducer 24 may be flat surfaces or may be curved surfaces convex toward the substrate Z side as shown in FIG. 5. As described above, when the substrate Z passes the positions of the first ultrasonic transducer 22 and the second ultrasonic transducer 24, the substrate Z is bent into a substantially S-shape by the ultrasonic vibrations of the first ultrasonic transducer 22 and the second ultrasonic transducer 24. Therefore, by making the vibration surface 22a of the first ultrasonic transducer 22 and the vibration surface 24a of the second ultrasonic transducer 24 curved surfaces convex toward the substrate Z side, the distance between the substrate Z and the vibration surface can be kept constant in the length direction of the vibration surface. Therefore, the transportation of the substrate Z can be stabilized, and the stirring of the solution can be more suitably performed.

[0053] When the vibration surface 22a of the first ultrasonic transducer 22 and the vibration surface 24a of the second ultrasonic transducer 24 are curved surfaces convex toward the substrate Z side, the radius of curvature R (see FIG. 5) of the vibration surface in a cross section parallel to the transport direction of the substrate Z and perpendicular to the main surface of the substrate Z may be appropriately set depending on the type of substrate Z, the transport speed of the substrate Z, the strength of the ultrasonic transducer, the length of the vibration surface, etc., and is preferably 10 mm to 500 mm, more preferably 30 mm to 300 mm, and even more preferably 50 mm to 100 mm.

[0054] In the example shown in FIG. 1, a cleaning tank 16 and a guide roller 18 are disposed downstream of the second ultrasonic transducer 24.

[0055] The cleaning tank 16 is for immersing the substrate Z covered with the coating layer in the cleaning liquid 16a in the cleaning tank 16. Also, the guide rollers 18 are disposed in the cleaning tank 16, and in the cleaning tank 16, the guide rollers 18 change the conveying direction of the substrate Z to an upward direction.

[0056] By immersing the substrate Z in the cleaning liquid 16a in the cleaning tank 16, foreign matter such as an excess coating layer adhering to the substrate Z is removed. In particular, when the auxiliary agent and the main agent are applied in sequence while the substrate Z is conveyed downward as in the illustrated example, the coating layer, which becomes foreign matter, is swept downward by gravity as described above, so that the foreign matter can be more suitably removed by cleaning in the cleaning tank 16.

[0057] This washing may also be used to stop the reaction between the main agent and the auxiliary agent.

[0058] There are no limitations on the cleaning liquid, and it may be appropriately selected depending on the base material and auxiliary applied to the substrate Z. Examples of the cleaning liquid include a solvent for the base material and auxiliary, a liquid capable of dissolving the components contained in the base material and auxiliary, a liquid that stops the reaction between the base material and auxiliary, and a harmless liquid (e.g., pure water) that does not dissolve the base material and auxiliary.

[0059] The method of cleaning the substrate Z coated with the coating layer is not limited to immersion in the cleaning liquid 16a, and various known methods such as cleaning by spraying the cleaning liquid on the substrate Z, cleaning by spraying gas, and wiping off the cleaning liquid can be used. Depending on the coating layer that covers the substrate Z, after applying the auxiliary agent and the base agent with the solution supply unit 14 and stirring the solution with the first ultrasonic vibrator 22 and the second ultrasonic vibrator 24, drying of the base agent and the auxiliary agent applied to the substrate Z, photo-curing of the coating layer, and heat-curing of the coating layer may be performed instead of cleaning the substrate Z. These treatments may be performed instead of cleaning the substrate Z, before cleaning the substrate Z, or after cleaning the substrate Z. In addition, a plurality of these treatments, including cleaning, may be performed.

[0060] The substrate Z transported upward is transported by guide rollers 20 to the next process.

[0061] There is no limitation on the next process that is applied to the substrate Z coated with the coating layer by the ultrasonic agitator of the present invention. Examples of the next process include a similar coating device, a device for winding up the substrate Z, a device for forming a protective layer, a calendaring device, a slitting device, a device for removing foreign matter, and a dust removing device.

[0062] In the ultrasonic agitator of the present invention, the substrate Z is not limited, and various types of sheet-like objects (plate-like objects, films) can be used. Examples include resin films such as polyethylene terephthalate (PET) film and polyethylene naphthalate (PEN) film, cycloolefin polymer (COP) film, polyimide film, cycloolefin copolymer (COC) film, and triacetyl cellulose (TAC) film, metal foils such as aluminum foil and copper foil, nonwoven fabrics, and paper. There is no limitation on the thickness of the substrate Z, and it may be appropriately selected depending on the application of the substrate Z coated with the coating layer.

[0063] The substrate Z may also have a base layer on its surface. The base layer is formed for the purpose of improving adhesion to the coating layer, improving wettability, etc., depending on the type of coating layer. The coating with the coating layer may be performed on the portion on which the base layer is formed. That is, in the present invention, the base layer of the substrate Z may determine the region on the substrate Z to be coated with the coating layer by the ultrasonic stirring device of the present invention. The base layer may also contain the same material as the coating layer.

[0064] For example, the ultrasonic agitator of the present invention uses a substrate Z having such an underlayer and a two-liquid reaction liquid, and while transporting the substrate Z, first applies an auxiliary agent to the substrate Z, and then applies a base agent to the substrate Z. This makes it possible to mix and react the base agent and the auxiliary agent on the substrate Z, and to coat the substrate Z with a dense coating layer along the underlayer.

[0065] Specifically, for example, when the coating layer is a metal plating, the underlayer may be the metal to be plated. When the coating layer is a hard coat, a layer containing the material of the hard coat may be used as the underlayer. When the coating layer is an adhesive layer or a pressure-sensitive adhesive layer, the underlayer may be a layer containing the material of the adhesive layer or the pressure-sensitive adhesive layer, or the underlayer may be a layer having high adhesion to the base material Z and the coating layer.

[0066] There is no limitation on the method for forming the underlayer, and it may be formed by a known method depending on the material for forming the underlayer, i.e., the coating layer to be coated by the ultrasonic stirring device of the present invention. In addition, as in the example shown in Figure 1, when both sides of the base material Z are coated with a coating layer, the underlayer may be formed on both sides of the base material Z.

[0067] When the underlayer is of the same type as the coating layer, the method of forming the underlayer may be the same as or different from the method of forming the coating layer. For example, when the coating layer is a metal plating, the underlayer may be formed by a metal plating process, or the underlayer of the metal to be plated may be formed by a film forming means capable of forming a thin metal film, such as sputtering.

[0068] There is no limitation on the shape (planar shape) of the underlayer, and various shapes can be used.

[0069] For example, the underlayer may be formed in a layered form covering the entire surface of the base material Z, or the underlayer may be formed in a layered form covering only a portion of the base material Z.

[0070] Alternatively, the underlayer may be formed in a planar pattern with islands spaced apart from one another, such as a polka dot pattern and a checkered pattern. In this case, the planar pattern may be formed regularly or irregularly. Alternatively, the underlayer may be in a lattice pattern, such as a mesh pattern, a square lattice, a triangular lattice, or a hexagonal lattice (honeycomb pattern). Alternatively, the underlayer may be in a striped pattern. The stripes of the striped pattern may have a uniform or non-uniform thickness and / or spacing, or may have a mixture of uniform and non-uniform portions. Alternatively, the underlayer may be in a linear pattern consisting of one or more lines. The underlayer of the linear pattern may be a straight line, a curved line, a line having a bent portion such as a zigzag broken line, or a linear pattern in which these are mixed. The line thickness and spacing may be uniform or non-uniform, or may have a mixture of uniform and non-uniform portions. These underlayers may be formed in an uneven pattern on the substrate Z. Among them, underlayers having a planar pattern with islands separated from one another and underlayers having a linear pattern consisting of one or more lines are preferably used.

[0071] In addition, when the substrate Z has a base layer formed in a pattern, the solution supply unit 14 may supply the solution in the same pattern (design) as the base layer, depending on the shape of the base layer formed on the substrate Z.

[0072] There is no limitation on the conveying speed of the substrate Z, and it may be set appropriately depending on the reactivity and coating amount of the solution (main agent and auxiliary agent), the coating layer to be formed, the state of the undercoat layer, and the like. Considering the productivity, the conveying speed of the substrate Z is preferably 0.1 to 100 m / min, more preferably 1 to 50 m / min, and further preferably 5 to 30 m / min.

[0073] In the example shown in FIG. 2, both sides of the substrate Z are covered with a coating layer, but the present invention is not limited thereto. As in the example shown in FIG. 6, the ultrasonic agitator of the present invention may be configured to cover only one main surface of the substrate Z with a coating layer. That is, the solution supply unit 14 may be disposed only on one main surface side of the substrate Z. Even when only one main surface of the substrate Z is covered with a coating layer, the ultrasonic agitator of the present invention has a first ultrasonic vibrator 22 disposed facing the front surface of the substrate Z and a second ultrasonic vibrator 24 disposed facing the back surface of the substrate Z.

[0074] In the present invention, there are no limitations on the solution that becomes the coating layer that coats the substrate Z, and it may be a two-liquid solution that can produce a coating layer that coats the substrate Z by a two-liquid reaction of a main agent and an auxiliary, or it may be a one-liquid solution that contains a reactant.

[0075] Various types of coating layers can be used as the coating layer formed by the reaction of two liquids, a base agent and an auxiliary agent, including electroless metal plating such as silver plating, copper plating, nickel plating, and cobalt plating, hard coats such as acrylic cured resins and silanol cured resins, and adhesives such as epoxy adhesives and urethane adhesives.

[0076] In the present invention, the base agent includes a material that is the main component of the coating layer, while the auxiliary includes at least one of a component that reacts with the base agent to generate a coating layer, a component that accelerates the generation of the coating layer, a component that accelerates the bonding between the coating layers, a component that stabilizes the coating layers, and a component that causes the coating layers to react with each other.

[0077] For example, when the coating layer is electroless metal plating, the first solution containing the base agent contains metal ions for plating, an additive (stabilizer) for improving the stability of the metal ions, and a pH adjuster, and the second solution containing the auxiliary contains a reducing agent, etc. The type of metal ions for plating contained in the base agent can be appropriately selected according to the type of metal to be deposited, and examples include silver ions, copper ions, nickel ions, and cobalt ions. Compounds that generate these ions when dissolved in water, such as silver nitrate, are added to the base agent.

[0078] When the coating layer is a hard coat, for example when the substrate Z is coated with a silane film, the main agent contains a material that becomes a hard coat, such as an alkoxysilane, and the auxiliary contains a curing agent.

[0079] When the coating layer is an adhesive, for example when the substrate Z is coated with a urethane film, the main agent contains an adhesive material such as a urethane-based resin, and the auxiliary agent contains a curing agent that accelerates the reaction of the terminal isocyanate group.

[0080] The first solution containing the main agent and the second solution containing the auxiliary agent are solutions in which the components contained therein are dissolved in a solvent.

[0081] There is no limitation on the solvent, and various solvents capable of dissolving the components can be used depending on the coating layer. In consideration of the environment, the solvent is preferably water. That is, the first solution containing the main agent and the second solution containing the auxiliary agent are preferably aqueous solutions.

[0082] In addition, the solvent of the main agent and the auxiliary agent may be the same or different. Considering the control of the atmosphere of the application space where the main agent and the auxiliary agent are applied, which will be described later, it is preferable that the solvent of the main agent and the auxiliary agent be the same. That is, when one type of solvent is used for the main agent and the auxiliary agent, it is preferable that the same solvent is used, and even when multiple types of solvents are used, it is preferable that the same solvent is used for the main agent and the auxiliary agent, and it is more preferable that the ratio of each solvent is the same.

[0083] Examples of one-liquid solutions containing reactants include alkaline saponification solutions that make surfaces hydrophilic or porous, and solutions used in hydrophilization treatments using silanol solutions alone that add functional groups to surfaces (such as the so-called SAM film). The solvent is not limited to water or organic solvents, but the former is a strong alkaline solution with a pH of 11, and the latter is a silane coupling agent.

[0084] In order to allow the base material to react properly with the auxiliary when coating the base material with a coating layer formed by the reaction between the base material and the auxiliary, it is preferable to control the temperature of the base material and the auxiliary on the base material Z. For example, in the case of electroless metal plating, the temperature of the base material and the auxiliary on the base material Z is preferably 15 to 70°C, and more preferably 20 to 50°C.

[0085] Without relying on electroless metal plating, the temperature of the base material and the auxiliary on the substrate Z can be set to a certain predetermined temperature or higher to increase the reaction rate between the base material and the auxiliary, thereby improving productivity. In addition, by setting the temperature of the base material and the auxiliary below a certain predetermined temperature, the evaporation of the solvent from the base material and the auxiliary, which are solutions, can be suppressed, and the generation of a coating layer that does not adhere to the substrate Z and becomes a foreign body can be suppressed. In addition, when the substrate Z has an underlayer and the underlayer reacts with the auxiliary, the auxiliary can be reacted with the underlayer by setting the temperature of the auxiliary above a certain predetermined temperature. In other words, by applying the base material and the auxiliary to the substrate Z while controlling the temperature to an appropriate temperature, the substrate Z can be appropriately coated with the coating layer while preventing foreign bodies from adhering to the surface of the coating layer.

[0086] Here, in an ultrasonic agitator that sequentially applies the auxiliary and the main agent while conveying the substrate Z as in the present invention, it may be difficult to control the temperature of the main agent and the auxiliary on the substrate Z to the desired temperature. In particular, when applying by a spray method, it is difficult to properly control the temperature of the main agent and the auxiliary on the substrate Z. That is, even if the substrate Z is heated and the main agent and the auxiliary are applied, if the temperature of the main agent and the auxiliary is low, the temperature of the main agent and the auxiliary on the substrate Z will immediately become the temperature of the applied main agent and the auxiliary. This tendency becomes more pronounced as the substrate Z becomes thinner and the amount of the main agent and the auxiliary applied increases.

[0087] This tendency is especially pronounced when the base agent and auxiliary are applied by spraying. In other words, the spraying method is a coating method that rapidly increases the specific surface area of ​​the coating. Therefore, even if the temperature of the base agent and auxiliary being sprayed is increased, the temperature of the base agent and auxiliary drops rapidly due to the heat of vaporization. For example, when the base agent and auxiliary are sprayed at room temperature, the temperature of the base agent and auxiliary in the vicinity of the substrate Z becomes much lower than room temperature, and in addition, they take away heat from the substrate Z.

[0088] One example of a method for solving this problem and optimizing the temperature of the base material and auxiliary on the substrate Z is to control the vapor pressure of the solvent of the base material and / or auxiliary in the space where the base material and auxiliary are applied to the substrate Z and stirred.

[0089] For example, when the base agent and the auxiliary are aqueous solutions, the water vapor pressure is controlled in the space in which the base agent and the auxiliary are applied to the substrate Z and stirred. Preferably, the temperature of the space in which the base agent and the auxiliary are applied to the substrate Z and stirred is also controlled. This makes it possible to prevent the base agent and the auxiliary applied to the substrate Z from evaporating, and to appropriately control the temperature of the base agent and the auxiliary on the substrate Z.

[0090] In addition, when the first ultrasonic vibrator and the second ultrasonic vibrator apply ultrasonic vibrations to the main agent and auxiliary agent (solution) applied to the substrate Z to stir and accelerate the reaction, the reactivity between the main agent and auxiliary agent can be increased by adjusting the temperature and humidity of the solution to an appropriate level.

[0091] 7 shows an example of a method for controlling the vapor pressure of the solvent in the space where the base material and the auxiliary are applied to and mixed on the substrate Z, and the temperature of the space. In the following description, for convenience, the space where the base material and the auxiliary are applied to and mixed on the substrate Z is also referred to as the "coating space." In this example, the coating space is covered with a casing 30. That is, in this example, the inside of the casing 30 becomes the coating space.

[0092] A supply unit 32 is connected to the casing 30 via a pipe 32a. In addition, an exhaust unit 34 is connected to the casing 30 via a pipe 34a. In the casing 30, a first application unit 14a, a second application unit 14b, a first ultrasonic vibrator 22, and a second ultrasonic vibrator 24 are arranged.

[0093] The supply unit 32 controls the temperature of a gas containing a solvent for the main agent and the auxiliary agent and supplies the gas into the casing 30. For example, when the main agent and the auxiliary agent are aqueous solutions, the supply unit 32 supplies heated and humidified air into the casing 30. Examples of the gas containing a solvent include air and an inert gas.

[0094] On the other hand, the exhaust section 34 exhausts air from the inside of the casing 30 to keep the pressure inside the casing 30, i.e., the coating space, at an appropriate level and to prevent condensation of the solvent inside the casing 30.

[0095] By using such an apparatus and controlling the temperature of the gas containing the solvent supplied to the casing 30 and the content of the solvent, the temperature in the coating space and the vapor pressure of the solvent of the main agent and auxiliary agent can be kept within a desired range. For example, when the main agent and auxiliary agent are aqueous solutions, the temperature in the coating space and the water vapor pressure can be kept within a desired range by controlling the temperature and humidity of the heated and humidified air supplied into the casing 30. That is, in the example shown in Fig. 7, the supply unit and the exhaust unit are the temperature and humidity control unit of the present invention.

[0096] There are no limitations on the vapor pressure of the solvent in the application space, and it may be set appropriately depending on the application method and application amount of the main agent and auxiliary agent, the temperature of the application space, the concentration of the solvent, and, if the solvent is water, the humidity, etc. The vapor pressure of the solvent in the application space is preferably 50% or more of the saturated vapor pressure, more preferably 60% or more of the saturated vapor pressure, and more preferably saturated vapor pressure or supersaturation.

[0097] The temperature of the coating space may basically be set appropriately depending on the target temperatures of the main agent and auxiliary agent on the substrate Z. For example, in the case of electroless metal plating, the temperature of the coating space is preferably 15 to 70°C, more preferably 20 to 50°C, depending on the temperatures of the main agent and auxiliary agent on the target substrate Z described above.

[0098] However, it is preferable to adjust the temperature of the gas containing the solvent and the content of the solvent in the gas containing the solvent so that the solvent does not condense on the substrate Z.

[0099] In addition, when the solvent of the main agent and the auxiliary agent are different, and when the main agent and / or the auxiliary agent use multiple solvents, the vapor pressure of the solvent that is most supplied to the coating space can be controlled. Considering the vapor pressure of the coating space, it is preferable that the solvent of the main agent and the auxiliary agent are the same. As described above, the solvent of the main agent and the auxiliary agent may be one type or multiple types, as long as they are preferably the same.

[0100] In the ultrasonic agitator of the present invention, the temperature of the base agent and auxiliary agent on the substrate Z can be controlled by controlling only one of the vapor pressure of the solvent in the coating space and the temperature of the coating space. However, in order to more suitably control the temperature of the base agent and auxiliary agent on the substrate Z, it is preferable to control both the vapor pressure of the solvent in the coating space and the temperature of the coating space.

[0101] In the ultrasonic agitator of the present invention, the temperature of the base material Z carried into the coating space may be controlled as necessary. Furthermore, in the ultrasonic agitator of the present invention, the temperature of the base agent supplied to the first coating section 14a and / or the temperature of the auxiliary agent supplied to the second coating section 14b may be controlled as necessary. The temperatures in both temperature controls are basically similar to the temperature of the coating space described above.

[0102] The ultrasonic agitator of the present invention has been described in detail above, but the present invention is not limited to the above-mentioned aspects, and various improvements and modifications may be made without departing from the gist of the present invention. EXAMPLES

[0103] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the specific examples shown below.

[0104] [Example 1] <Formation of substrate and undercoat layer> A PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 40 μm, a width of 10 cm, and a length of 100 m was prepared. This PET film was used as the substrate.

[0105] A thin silver film was formed on the entire surface of one of the main surfaces of the substrate using a commercially available sputtering device to serve as an underlayer. The thickness of the thin silver film was estimated to be about 1 nm.

[0106] <Preparation of main agent and auxiliary agent> 30 mM (mol) silver nitrate, 120 mM ammonia water, and 140 mM ethylenediamine were dissolved in pure water to prepare 200 mL (liters) of a base solution (first solution) for electroless silver plating.

[0107] Also, 150 mM hydrazine hydrate was dissolved in pure water to prepare 200 mL of an auxiliary (second solution) for electroless silver plating.

[0108] <Substrate material transport device> An apparatus for transporting a substrate having a base layer formed thereon along a predetermined transport path as shown in FIG. 1 was prepared.

[0109] <Preparing the spray device> A two-fluid spray head (Atmax, AM6) was prepared, and a commercially available compressed air device (As One) and a diaphragm pump (Tacmina, QI-100-6T-PS) were connected to each spray head with a PTFE (polytetrafluoroethylene) tube (φ6 mm). A ribbon heater was wrapped around the PTFE tube from the pump to the spray head, and the liquid temperature was adjusted to 30°C.

[0110] The spray head was positioned in the path of transport of the substrate, facing the surface of the substrate.

[0111] Specifically, three two-fluid spray heads were arranged in the width direction of the substrate as the second coating section, and three were arranged in the width direction downstream of the second coating section as the first coating section. The distance between the upper and lower sections was 100 mm in the substrate transport direction. The distance between each spray head and the substrate was 70 mm for both the first and second coating sections.

[0112] The auxiliary agent was adjusted to be sprayed at 10 ml / min per head from the three spray heads in the second coating section, and the main agent was adjusted to be sprayed at 10 ml / min per head from the three spray heads in the first coating section.

[0113] <Preparing the ultrasonic transducer> As an ultrasonic transducer, a stainless steel ultrasonic horn was fabricated and attached to the tip of a Branson ultrasonic transducer. The width of the vibration surface of this ultrasonic transducer was 100 mm, the length was 10 mm, and the radius of curvature was 300 mm.

[0114] Two ultrasonic transducers were disposed downstream of the spray head in the transport path of the substrate, facing the front and back surfaces of the substrate, respectively.

[0115] Specifically, the ultrasonic vibrator was disposed facing the surface of the substrate as the first ultrasonic vibrator. The distance between the first ultrasonic vibrator and the first application section was 500 mm in the transport direction of the substrate. The distance d1 between the first ultrasonic vibrator and the substrate was 0.5 mm. The ultrasonic vibrator was disposed facing the back surface of the substrate as the second ultrasonic vibrator. The center-to-center distance L1 between the vibration surfaces of the second ultrasonic vibrator and the first ultrasonic vibrator was 5 mm in the transport direction of the substrate. The distance d2 between the second ultrasonic vibrator and the substrate was 0.5 mm. In this case, when viewed from a direction perpendicular to the main surface of the substrate, the vibration surface of the first ultrasonic vibrator and the vibration surface of the second ultrasonic vibrator overlap, and the overlap distance L2 was 5 mm.

[0116] <Coating space> The base material was coated with the base material and the auxiliary agent with the spray head, and the space in which the base material and auxiliary agent coated on the base material were stirred with the ultrasonic vibrator (coating space), i.e., the space in which the first coating part, the second coating part, the first ultrasonic vibrator, and the second ultrasonic vibrator were arranged, was covered with a casing (see Figure 7). Heated and humidified air was supplied to the inside of the casing, and the atmosphere inside the casing was adjusted to a temperature of 30°C and a humidity of 60% RH (vapor pressure of 60% of the saturated vapor pressure).

[0117] <Electroless silver plating> While conveying the substrate at 0.5 m / min, the auxiliary agent was sprayed from the spray head of the second coating section, and the main agent was sprayed from the spray head of the first coating section, and the substrate was coated with the auxiliary agent and the main agent in that order. The coating amounts of the auxiliary agent and the main agent were adjusted so that the coating thickness of the liquid before drying was about 30 μm.

[0118] The first ultrasonic transducer and the second ultrasonic transducer were driven to apply ultrasonic vibrations to the main agent and auxiliary agent applied to the substrate to stir them. The frequency and intensity of the ultrasonic vibrations generated by the first ultrasonic transducer and the second ultrasonic transducer were 200 kHz and 15 W, respectively.

[0119] A cleaning tank was placed downstream of the second ultrasonic transducer, and the substrate was washed with pure water to stop the reaction, thereby coating the substrate with electroless silver plating. The thickness of the silver plating was confirmed to be 1 μm.

[0120] [Example 2] The same procedure was followed as in Example 1, except that the ultrasonic transducer was changed as follows.

[0121] The width of the vibration surface of the ultrasonic vibrator was 100 mm, the length was 10 mm, and the radius of curvature was 0 mm. As the first ultrasonic vibrator, the ultrasonic vibrator was arranged facing the surface of the substrate. The distance between the first ultrasonic vibrator and the first application section was 500 mm in the transport direction of the substrate. The distance d1 between the first ultrasonic vibrator and the substrate was 0.5 mm. As the second ultrasonic vibrator, the ultrasonic vibrator was arranged facing the back surface of the substrate. The center-to-center distance L1 between the vibration surfaces of the second ultrasonic vibrator and the first ultrasonic vibrator was 5 mm in the transport direction of the substrate. The distance d2 between the second ultrasonic vibrator and the substrate was 0.5 mm. In this case, when viewed from a direction perpendicular to the main surface of the substrate, the vibration surface of the first ultrasonic vibrator and the vibration surface of the second ultrasonic vibrator overlap, and the overlap distance L2 was 5 mm.

[0122] [Example 3] The same procedure was followed as in Example 1, except that the ultrasonic transducer was changed as follows.

[0123] The width of the vibration surface of the ultrasonic vibrator was 100 mm, the length was 10 mm, and the radius of curvature was 300 mm. As the first ultrasonic vibrator, the ultrasonic vibrator was arranged facing the surface of the substrate. The distance between the first ultrasonic vibrator and the first application section was 500 mm in the transport direction of the substrate. The distance d1 between the first ultrasonic vibrator and the substrate was 0.5 mm. As the second ultrasonic vibrator, the ultrasonic vibrator was arranged facing the back surface of the substrate. The center-to-center distance L1 between the vibration surfaces of the second ultrasonic vibrator and the first ultrasonic vibrator was 15 mm in the transport direction of the substrate. The distance d2 between the second ultrasonic vibrator and the substrate was 0.5 mm. In this case, when viewed from a direction perpendicular to the main surface of the substrate, the vibration surface of the first ultrasonic vibrator and the vibration surface of the second ultrasonic vibrator were separated, and the distance L3 between them was 5 mm.

[0124] [Example 4] The same procedure was followed as in Example 1, except that the frequencies of the ultrasonic vibrations generated by the first ultrasonic transducer and the second ultrasonic transducer were changed as follows.

[0125] The ultrasonic vibration generated by the first ultrasonic transducer had a frequency of 200 kHz and an intensity of 15 W, and the ultrasonic vibration generated by the second ultrasonic transducer had a frequency of 20 kHz and an intensity of 5 W.

[0126] [Example 5] When forming an underlayer on the substrate, silver was sputtered using a mask having striped openings 5 ​​μm wide and spaced 200 μm apart, and then the mask was positioned so that the stripes were perpendicular to each other and silver was sputtered in the same manner to form a mesh-like silver underlayer. A substrate was coated with electroless silver plating in the same manner as in Example 1, except that the substrate on which this undercoat was formed was used.

[0127] [Example 6] 24.6 g of silver nitrate, 46.2 g of sodium sulfite, and 40.5 g of sodium thiosulfate were dissolved in 700 g of pure water to prepare a base material for electroless silver plating. In addition, 47.52 g of sodium sulfite, 14.49 g of methylhydroquinone, 39.6 g of T-50 dispersant, 8.29 g of potassium carbonate, and 1.07 g of potassium hydroxide were dissolved in 600 g of pure water to prepare an auxiliary for electroless silver plating. A substrate was coated with electroless silver plating in the same manner as in Example 1, except that the base material and auxiliary were used.

[0128] [Comparative Example 1] The substrate was coated with electroless silver plating in the same manner as in Example 1, except that only the first ultrasonic transducer was provided facing the surface of the substrate, and the second ultrasonic transducer was not provided. [Comparative Example 2] The substrate was coated with electroless silver plating in the same manner as in Example 1, except that the first ultrasonic transducer and the second ultrasonic transducer were disposed at the same position in the substrate transport direction.

[0129] [evaluation] The condition of the substrate during transportation was evaluated. In addition, the substrate coated with electroless silver plating was evaluated for electrical conductivity and surface properties.

[0130] <Status during transport> In all of the examples, the substrate fluttered little when passing through the first ultrasonic transducer and the second ultrasonic transducer, and was transported appropriately. On the other hand, in Comparative Examples 1 and 2, the substrate fluttered when passing through the ultrasonic transducer, causing wrinkles and deformation in the substrate. In addition, the gloss of the plating varied accordingly, resulting in uneven plating.

[0131] <Surface texture> Using an optical microscope, sea-island-like gloss unevenness was evaluated within a 10 mm square field of view. The evaluation criteria are as follows: A is when the sea is so uniform that no islands are visible, B: Small localized sea-island irregularities; C: Localized sea-island unevenness. The case where the entire surface was an island in the sea was rated D. <Conductivity> The surface resistance of a substrate that had been electrolessly silver plated was measured using Loresta GP. The denser the silver plating that covers the substrate, the lower the surface resistance. The evaluation criteria are as follows: A: Surface resistance is less than 50 Ω. B: Surface resistance is 50 Ω or more but less than 100 Ω. C: Surface resistance is 100 or more but less than 300 Ω. A surface resistance of 300 Ω or more was rated as D. The results are shown in Table 1 below.

[0132] [Table 1]

[0133] As shown in Table 1, the ultrasonic stirring device of the present invention can coat a substrate with silver plating with good electrical conductivity, with no uneven gloss and good surface properties. The small amount of uneven gloss indicates that the main agent and auxiliary agent are mixed well by the ultrasonic vibration. It can also be seen that the electrical conductivity changes in proportion to the uneven gloss. In other words, it can be seen that by mixing the main agent and auxiliary agent well, silver plating with good electrical conductivity can be formed.

[0134] Moreover, by comparing Example 1 and Example 2, it is understood that it is preferable that the vibration surface of the ultrasonic transducer has a curved shape. Furthermore, a comparison between Example 1 and Example 3 reveals that it is preferable for the vibration planes of the first ultrasonic transducer and the second ultrasonic transducer to overlap when viewed from a direction perpendicular to the main surface of the substrate. Furthermore, a comparison between Example 1 and Example 4 reveals that it is preferable that the frequency and intensity of the first ultrasonic transducer and the second ultrasonic transducer are the same.

[0135] [Example 7] <Formation of substrate and undercoat layer> A PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 40 μm, a width of 10 cm, and a length of 100 m was prepared. This PET film was used as the substrate.

[0136] A trimethoxy(2-phenylethyl)silane film was formed as an underlayer on the entire surface of one of the main surfaces of the substrate.

[0137] First, 1 mL of trimethoxy(2-phenylethyl)silane (Tokyo Chemical Industry Co., Ltd.) was placed in a 3 mL vial. Next, this vial and the substrate were placed in a 130°C oven and heated for 3 hours. As a result, the trimethoxy(2-phenylethyl)silane in the vial evaporated, and a trimethoxy(2-phenylethyl)silane film was formed on the surface of the substrate as a base. The film had a thickness of 1 nm.

[0138] <Preparation of main agent and auxiliary agent> As the alkoxysilane, 3-glycidoxypropyltriethoxysilane (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.) and tetraethoxysilane (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.) were used. First, while vigorously stirring an aqueous solution of acetic acid as acidic water at 40°C, 3-glycidoxypropyltriethoxysilane was dropped into this aqueous solution of acetic acid over a period of 3 minutes. The aqueous solution of acetic acid had an acetic acid concentration of 1% by mass. Next, tetraethoxysilane was added to the aqueous solution of acetic acid over a period of 5 minutes while vigorously stirring, and then the mixture was stirred at 40°C for 3 hours to prepare an aqueous solution of silanol. This aqueous solution of silanol was used as the main agent for forming a hard coat.

[0139] A curing agent (aluminum chelate (Kawaken Fine Chemicals, Aluminum Chelate D)) and a surfactant (NOF Corp., Lapisol A90, and Sanyo Chemical Industries, Ltd., Naroacty CL-95) were added sequentially to an aqueous acetic acid solution to prepare an auxiliary for forming a hard coat.

[0140] The main agent and auxiliary agent were each 200 mL, making the total amount 400 mL. In terms of the breakdown, in the total amount of coating liquid, the amount of 3-glycidoxypropyltriethoxysilane added was 67.5 parts by mass, the amount of tetraethoxysilane added was 22.5 parts by mass, the amount of curing agent added was 9 parts by mass, and the amount of surfactant added was 1 part by mass (0.5 parts by mass added each time).

[0141] <Substrate material transport device> A conveying device similar to that in Example 1 was prepared.

[0142] <Preparing the spray device> A spray device similar to that in Example 1 was prepared. However, the spray amount was adjusted so that the auxiliary agent was sprayed at 20 ml / min per head from the three spray heads in the second application section, and the main agent was sprayed at 5 ml / min per head from the three spray heads in the first application section.

[0143] <Preparing the ultrasonic transducer> An ultrasonic transducer was prepared similarly to that in Example 1. The first ultrasonic transducer and the second ultrasonic transducer were arranged in the same manner as in Example 1.

[0144] <Coating space> As in Example 1, the atmosphere in the space (application space) in which the base material was applied with the main agent and auxiliary agent by the spray head was adjusted.

[0145] <Hard coat formation> While moving the substrate at 0.5 m / min, the auxiliary agent was sprayed from the spray head of the second coating section, and the main agent was sprayed from the spray head of the first coating section, and the substrate was coated with the auxiliary agent and the main agent in that order. The coating amounts of the auxiliary agent and the main agent were adjusted so that the coating thickness of the liquid before drying was about 20 μm.

[0146] In addition, the first ultrasonic transducer and the second ultrasonic transducer were driven to apply ultrasonic vibration to the main agent and auxiliary agent applied to the base material to mix them. The frequency of the ultrasonic vibration generated by the first ultrasonic transducer and the second ultrasonic transducer was 20 kHz, and the strength was 5 W.

[0147] A heating device was placed at a position 1 m away from the second ultrasonic transducer in the conveying direction, and the substrate was dried at 130° C. for 5 minutes to coat the substrate with a hard coat. It was confirmed that the thickness of the hard coat was 1 μm.

[0148] [Example 8] The same procedure was followed as in Example 7, except that the ultrasonic transducer was changed as follows.

[0149] The width of the vibration surface of the ultrasonic vibrator was 100 mm, the length was 10 mm, and the radius of curvature was 0 mm. As the first ultrasonic vibrator, the ultrasonic vibrator was arranged facing the surface of the substrate. The distance between the first ultrasonic vibrator and the first application section was 500 mm in the transport direction of the substrate. The distance d1 between the first ultrasonic vibrator and the substrate was 0.5 mm. As the second ultrasonic vibrator, the ultrasonic vibrator was arranged facing the back surface of the substrate. The center-to-center distance L1 between the vibration surfaces of the second ultrasonic vibrator and the first ultrasonic vibrator was 5 mm in the transport direction of the substrate. The distance d2 between the second ultrasonic vibrator and the substrate was 0.5 mm. In this case, when viewed from a direction perpendicular to the main surface of the substrate, the vibration surface of the first ultrasonic vibrator and the vibration surface of the second ultrasonic vibrator overlap, and the overlap distance L2 was 5 mm.

[0150] [Example 9] The same procedure was followed as in Example 7, except that the ultrasonic transducer was changed as follows.

[0151] The width of the vibration surface of the ultrasonic vibrator was 100 mm, the length was 10 mm, and the radius of curvature was 300 mm. As the first ultrasonic vibrator, the ultrasonic vibrator was arranged facing the surface of the substrate. The distance between the first ultrasonic vibrator and the first application section was 500 mm in the transport direction of the substrate. The distance d1 between the first ultrasonic vibrator and the substrate was 0.5 mm. As the second ultrasonic vibrator, the ultrasonic vibrator was arranged facing the back surface of the substrate. The center-to-center distance L1 between the vibration surfaces of the second ultrasonic vibrator and the first ultrasonic vibrator was 15 mm in the transport direction of the substrate. The distance d2 between the second ultrasonic vibrator and the substrate was 0.5 mm. In this case, when viewed from a direction perpendicular to the main surface of the substrate, the vibration surface of the first ultrasonic vibrator and the vibration surface of the second ultrasonic vibrator were separated, and the distance L3 between them was 5 mm.

[0152] [Example 10] The same procedure was followed as in Example 7, except that the frequencies of the ultrasonic vibrations generated by the first ultrasonic transducer and the second ultrasonic transducer were changed as follows.

[0153] The ultrasonic vibration generated by the first ultrasonic transducer had a frequency of 200 kHz and an intensity of 15 W, and the ultrasonic vibration generated by the second ultrasonic transducer had a frequency of 20 kHz and an intensity of 5 W.

[0154] [Example 11] The substrate was coated with a hard coat in the same manner as in Example 7, except that the atmosphere inside the casing was changed to a temperature of 25° C. and a humidity of 20% RH (vapor pressure of 20% of the saturated vapor pressure).

[0155] [Comparative Example 3] The substrate was coated with a hard coat in the same manner as in Example 7, except that only the first ultrasonic transducer facing the surface of the substrate was provided, and the second ultrasonic transducer was not provided. [Comparative Example 4] The substrate was coated with a hard coat in the same manner as in Example 7, except that the first ultrasonic oscillator and the second ultrasonic oscillator were disposed at the same position in the substrate transport direction.

[0156] [evaluation] The condition of the substrate during transportation was evaluated. In addition, the substrate coated with the hard coat was evaluated for hard coat properties and surface properties.

[0157] <Status during transport> In all of the examples, the substrate fluttered little when passing through the first ultrasonic transducer and the second ultrasonic transducer, and was transported appropriately. On the other hand, in Comparative Examples 3 and 4, the substrate flapped when passing through the ultrasonic transducer, which resulted in the hard coat layer curing in a wrinkled state, and the marks did not disappear. <Surface texture> The surface properties were evaluated in the same manner as in Example 1.

[0158] <Hard coat properties (pencil hardness)> The pencil hardness was measured in accordance with JIS K 5600. The higher the pencil hardness, the denser the hard coat and the better the hard coat properties. The results are shown in Table 2 below.

[0159] [Table 2]

[0160] As shown in Table 2, the ultrasonic stirring device of the present invention can coat a substrate with a hard coat that has little gloss unevenness, good surface properties, and high pencil hardness. The little gloss unevenness indicates that the base material and auxiliary are mixed well by ultrasonic vibration. It can also be seen that the pencil hardness changes in proportion to the gloss unevenness. In other words, it can be seen that a hard coat with high pencil hardness can be formed by mixing the base material and auxiliary well.

[0161] Moreover, a comparison between Example 7 and Example 8 reveals that it is preferable for the vibration surface of the ultrasonic transducer to have a curved shape. Furthermore, a comparison between Example 7 and Example 9 reveals that it is preferable for the vibration planes of the first ultrasonic transducer and the second ultrasonic transducer to overlap when viewed from a direction perpendicular to the main surface of the substrate. Moreover, a comparison between Example 7 and Example 10 reveals that it is preferable that the frequency and intensity of the first ultrasonic transducer and the second ultrasonic transducer are the same. Moreover, a comparison between Example 7 and Example 11 reveals that the vapor pressure of the solvent in the application space is preferably 50% or more of the saturated vapor pressure. From the above results, the effects of the present invention are clear. [Explanation of symbols]

[0162] 10, 10b Ultrasonic stirring device 12,18,20 Guide rollers 14 Solution supply section 14a First coating section 14b Second coating section 16 Cleaning tank 16a Cleaning solution 22 First ultrasonic transducer 22a, 24a Vibration surface 24 Second ultrasonic transducer 30 Casing 32 Supply section 34 Exhaust section Z base material h Second solution m 1st solution r mixture d1: distance between the substrate and the first ultrasonic transducer d2 is the distance between the substrate and the second ultrasonic transducer L1: Distance between the center position of the vibration surface of the first ultrasonic transducer and the center position of the vibration surface of the second ultrasonic transducer L2: The length of the overlapping portion between the vibration surface of the first ultrasonic transducer and the vibration surface of the second ultrasonic transducer L3: Distance between the vibration surface of the first ultrasonic transducer and the vibration surface of the second ultrasonic transducer R Vibration surface of ultrasonic transducer

Claims

1. An ultrasonic stirring device that stirs a solution on a long substrate while transporting the substrate in a longitudinal direction, A first ultrasonic transducer that is disposed facing the surface of the base material and transmits ultrasonic vibrations through a gas medium; A second ultrasonic transducer is disposed on the back surface of the base material so as to face the back surface of the base material and transmits ultrasonic vibrations through a gas medium. a center position of a vibration surface of the second ultrasonic transducer is disposed downstream of a center position of a vibration surface of the first ultrasonic transducer in a transport direction of the base material; A solution supply unit is provided that supplies, as the solutions, a first solution containing a base material that is a reactant and a second solution containing an auxiliary agent that accelerates the reaction of the base material onto the base material; The first ultrasonic vibrator and the second ultrasonic vibrator agitate the first solution and the second solution.

2. 2. The ultrasonic agitator of claim 1, wherein the solution supply is a spray device.

3. 3. The ultrasonic stirring device according to claim 1, wherein the vibration surfaces of the first ultrasonic transducer and the second ultrasonic transducer each have a curved shape that is convex toward the base material.

4. a casing that accommodates the first ultrasonic transducer and the second ultrasonic transducer therein; 4. The ultrasonic stirring device according to claim 1, further comprising a temperature and humidity control section for controlling the temperature and humidity inside the casing.

5. 5. The ultrasonic stirring device according to claim 1, wherein the solution is present on the front and back surfaces of the base material when passing through the first ultrasonic transducer and the second ultrasonic transducer.

6. The ultrasonic agitator according to any one of claims 1 to 5, wherein the ultrasonic agitator accelerates a reaction of a reactant in the solution by agitating the solution.

7. An ultrasonic stirring device for stirring a solution on a long substrate while transporting the substrate in a longitudinal direction, comprising: A first ultrasonic transducer that is disposed facing the surface of the base material and transmits ultrasonic vibrations through a gas medium; A second ultrasonic transducer is disposed on the back surface of the base material so as to face the back surface of the base material and transmits ultrasonic vibrations through a gas medium. a center position of a vibration surface of the second ultrasonic transducer is disposed downstream of a center position of a vibration surface of the first ultrasonic transducer in a transport direction of the base material; the vibration surfaces of the first ultrasonic vibrator and the second ultrasonic vibrator each have a curved shape that is convex toward the base material.

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