JP2019118868A - Pattern formation method, deposition method and sheet-like product - Google Patents

Abstract

To provide a novel lyophilic and liquid repellent pattern formation method, a deposition method for performing deposition to a lyophilic and liquid repellent pattern formed by the pattern formation method and a sheet-like product formed with the lyophilic and liquid repellent pattern by the pattern formation method.SOLUTION: The problem: is solved by: forming on a surface of a substrate, a particle layer including particles; depressing a pressing plate having a concavoconvex surface onto the particle layer so as to crush a part of the particles of the particle layer with the pressing plate to form a lyophilic area and a liquid repellent area; and performing deposition using an aerosol deposition method to the lyophilic area and the liquid repellent area.SELECTED DRAWING: Figure 1

Description

  In the present invention, a pattern forming method for forming a lyophilic area and a liquid repellent area on the surface of a substrate, a film forming method for forming a film on a substrate on which a pattern is formed by this forming method, and a pattern by this forming method The present invention relates to a sheet-like material formed.

  As a film forming technique for thin film, a raw material liquid containing a film forming material is aerosolized, and the generated aerosol is transported by a carrier gas to be supplied to a substrate to evaporate the solvent in the aerosol attached to the substrate. The technique which forms film-forming material into a film is known. This film formation technique is also called aerosol deposition.

Aerosol deposition forms a film by means of an aerosol that is very small compared to droplets in film formation such as inkjet and spray coating.
Therefore, according to the aerosol deposition, a film having a uniform thickness can be precisely formed with high followability (coverage) to the unevenness of the base material and the like.

By the way, in the film formation by the ink jet, droplets can be selectively landed at the target position. For example, in ink jet, a wiring pattern can be formed by landing ink droplets according to a target wiring pattern.
On the other hand, in aerosol deposition, basically, the aerosol is supplied almost uniformly over the entire surface of the substrate. That is, in aerosol deposition, it is not possible to selectively form a film on a desired position on a substrate.

Such a problem can be solved, for example, by patterning and forming a lyophilic area having lyophilicity and a liquid repellent area having liquid repellency on the surface of the base material.
That is, by adhering and forming the lyophilic area and the liquid repellent area on the surface of the base according to the intended pattern such as a wiring pattern, adhesion of aerosol to the liquid repellent area and film formation are suppressed. As a result, aerosol can be selectively attached to the lyophilic region to form a desired pattern of film formation.

  As a method of patterning and forming a lyophilic area and a liquid repellent area, for example, Patent Document 1 discloses a concavo-convex structure that exerts a lotus effect that repels a liquid by a fine concavo-convex structure on the surface of a sheet A pattern in which a lyophilic area and a lyophobic area are patterned by forming an array across a portion smoother than the structure, and then applying a coating liquid to the smooth portion of the surface of the sheet and solidifying it. A method of making the sheet is described.

JP 2003-190876

  As also described in Patent Document 1, the formation of a pattern having a lyophilic area and a lyophobic area is generally performed by embossing or the like on the surface of a lyophilic substrate to form a lyophobic liquid. It is performed by patterning and forming the concavo-convex structure which expresses sex.

  The object of the present invention is to form a new lyophilic area and liquid repellent area pattern forming method different from the conventional pattern forming method, and to form a film on a film forming surface having a lyophilic area and liquid repellent area formed by this pattern forming method The present invention is directed to providing a film-forming method for forming a lyophilic area and a liquid-repellent area by the pattern forming method.

In order to solve this problem, the present invention has the following configuration.
[1] A particle layer containing particles is formed on the surface of a substrate, and a pressing plate having asperities is pressed against the particle layer, and a part of the particles of the particle layer is crushed by the pressing plate to be a target 1. A pattern forming method comprising: forming a lyophilic area lyophilic to a liquid; and a lyophobic area lyophobic to a liquid to be treated.
[2] The method for forming a pattern according to [1], wherein the particles are hollow particles.
[3] The pattern forming method according to [1] or [2], wherein the particle layer is formed into irregularities by pressing with a pressing plate.
[4] The pressing plate has a plurality of recesses arranged in at least one direction, and the recess has an inclined surface which is inclined in the arrangement direction with respect to the recess forming surface of the pressing plate, [1] to [3] The pattern formation method as described in any of the above.
[5] The pattern forming method according to [4], wherein the depressions of the pressing plate have a square shape in a cross section in the arrangement direction of the depressions.
[6] The pattern forming method according to [5], wherein the depressions of the pressing plate have a trapezoidal shape in a cross section in the arrangement direction of the depressions.
[7] The pattern formation method according to any one of [1] to [6], wherein the surface of the substrate is made lyophilic before the particle layer is formed on the surface of the substrate.
[8] The pattern forming method according to any one of [1] to [7], wherein the base material is a sheet, and a lyophilic area and a liquid repellent area are formed on at least one surface of the sheet-like base .
[9] Film formation by aerosolizing a raw material liquid containing a film forming material and supplying the aerosol to the lyophilic area and the liquid repellent area formed by the pattern forming method according to any one of [1] to [8] Method.
[10] The film forming method according to [9], wherein the aerosol is supplied to the lyophilic area and the liquid repelling area while vibrating the substrate.
[11] The film forming method according to [9] or [10], wherein the aerosol is supplied to the lyophilic area and the liquid repellent area while heating the substrate.
[12] A plurality of projections arranged in at least one direction on at least one surface, wherein the projections have a plane inclined with respect to the arrangement direction and a plane continuous to the plane, What is claimed is: 1. A sheet-like product characterized in that the flat surface of the convex portion is lyophilic with respect to the liquid, and the surface continuous with the flat surface of the convex portion has liquid repellency caused by the unevenness due to particles.
[13] The sheet-like material according to [12], further having a film on the surface of the lyophilic surface.

According to the pattern formation method of the present invention, a new pattern formation method is provided in which a lyophilic region having lyophilicity and a liquid repellent region having liquid repellency are formed by a method different from the conventional method.
Further, according to the film forming method of the present invention, it is possible to form a target pattern by using the lyophilic area and the liquid repellent area formed by the pattern forming method of the present invention as a film forming surface.
Furthermore, the sheet-like material of the present invention is a sheet-like material capable of forming a target pattern having a lyophilic area and a liquid repellent area formed by the pattern forming method of the present invention.

It is a conceptual diagram for demonstrating an example of the pattern formation method of this invention. It is a conceptual diagram for demonstrating another example of the pattern formation method of this invention. It is a conceptual diagram for demonstrating the pattern formation method shown in FIG. It is a conceptual diagram for demonstrating another example of the pattern formation method of this invention. It is a conceptual diagram for demonstrating another example of the pattern formation method of this invention. It is a conceptual diagram for demonstrating the film-forming method of this invention. It is a conceptual diagram for demonstrating another example of the film-forming method of this invention. It is a conceptual diagram for demonstrating the pattern formation method of this invention, and the film-forming method.

Hereinafter, the pattern formation method, the film formation method, and the sheet-like material of the present invention will be described in detail based on the preferred embodiments shown in the attached drawings.
Note that the embodiments shown below illustrate an example of the present invention, and do not limit the scope of the present invention. Further, in order to clearly explain each constituent member, the dimensions of each constituent member in the drawing are appropriately changed. For this reason, the scale in the figure is different from the actual.
Furthermore, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

FIG. 1 conceptually shows an example of the pattern formation method of the present invention.
In the pattern forming method of the present invention, the particle layer 12 containing the particles 12 a is formed on the surface of the substrate 10, and the pressing plate 14 having irregularities is pressed against the particle layer 12 to press the particles 12 a of the particle layer 12. By partially crushing at this time, a lyophilic area having lyophilicity and a liquid repellent area having liquid repellency are formed on the surface of the base material 10 by patterning.
In the following description, the lyophilic area and the lyophobic area formed by patterning are also referred to as a lyophobic pattern.

In the pattern formation method of the present invention, the base material 10 is not limited. For example, various kinds of substances can be used as a film formation target (a film formation material) by aerosol deposition described later. As the base material 10, preferably, a sheet-like material (film, plate-like material) is exemplified.
Examples of the sheet material to be the substrate 10 include polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), and the like. Polyacrylonitrile (PAN), polyimide (PI), transparent polyimide, polymethyl methacrylate resin (PMMA), polycarbonate (PC), polyacrylate, polymethacrylate, polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene Resin materials such as copolymer (ABS), cycloolefin copolymer (COC), cycloolefin polymer (COP), triacetyl cellulose (TAC), and ethylene-vinyl alcohol copolymer (EVOH) Made of a resin film, and, polylactic acid, polyglycolic acid, chitin, and biodegradable film made of chitosan and the like.

Moreover, it is as above-mentioned that the base material 10 is not restrict | limited to a sheet-like thing.
As a substrate 10 other than a sheet-like material, for example, a microchannel chip substrate such as μ-TAS (micro-Total Analysis Systems), various circuit substrates on a silicon wafer, a bio-template substrate, etc. are suitably used. It is illustrated.
That is, in the pattern forming method of the present invention, various members having irregularities on the surface can also be used as the base material 10.

In the pattern formation method of the present invention, a particle layer 12 containing particles 12 a is formed on the surface of such a substrate 10.
In addition, in the pattern formation method of this invention, you may surface-treat on the one surface or both surfaces of the base material 10 in advance of formation of the particle layer 12. As shown in FIG.
There is no restriction on the surface treatment of the substrate 10, and any known surface treatment applied to the film formation surface on which a layer (film) is to be formed can be used. Examples of surface treatment include corona treatment, plasma treatment, UV (Ultra Violet) irradiation, ozone irradiation, and UV ozone cleaning, which improve the lyophilicity (paintability), as an example.
Moreover, as surface treatment of the base material 10, formation of the base layer aiming at improvement or provision of lyophilic property, ensuring of surface smoothness, etc. can also be utilized. The formation of the base layer may be performed by a known method such as a coating method and a printing method depending on the base layer to be formed.

In the pattern formation method of the present invention, a particle layer 12 containing particles 12 a is formed on the surface of a substrate 10 as shown in the second top of FIG. 1.
The particle layer 12 is a layer that exhibits liquid repellency by the so-called Lotus effect (Lotus structure) by having unevenness due to the particles (particulates) 12a.
In the present invention, having lyophilic indicates that the contact angle between the target surface and the target liquid is less than 90 °. On the other hand, having liquid repellency means that the contact angle between the target surface and the target liquid is 90 ° or more. Specifically, in the case of liquid repellency, the target surface is the surface of the substrate 10, the surface of the particle layer 12, the liquid repellent region 10a described later, and the like. Further, in the case of lyophilic, the target surface is a lyophilic area 10 b or the like described later.
Furthermore, the target liquid is, for example, water and a hydrophilic liquid (a liquid that is easily dissolved in water, and water, when the liquid repellent area 10 a is water repellent and the lyophilic area 10 b is hydrophilic. When a film is formed on the base material 10 on which the liquid repellent area 10a and the lyophilic area 10b are formed by the aerosol deposition described later, the raw material liquid L is used.
The contact angle may be measured, for example, using a commercially available device such as Drop Master 700 manufactured by Kyowa Interface Chemical Co., Ltd., in accordance with JIS R 3257. However, the liquid repellent area 10 a and the lyophilic area 10 b are often fine areas, and in many cases the contact angle of water can not be measured directly. In this case, actually, water (water-based ink) may be applied, and the application surface may be observed with an optical microscope or the like to confirm adhesion of water, thereby confirming lyophilicity and liquid repellency. . In addition, the contact angle of water in the liquid repellent area 10 a generally matches the contact angle of water in the particle layer 12.

The lotus effect is also referred to as a lotus leaf effect (a lotus leaf structure).
As well known, the Lotus effect means that as described in Cassie-Baxter theory, when the height and roughness of the asperities are large and the pitch and interval of the asperities are narrow, the liquid is the bottom of the asperity groove by capillary action. It is an effect of expressing a liquid repellency by not being able to reach to the bottom, a void being generated under the droplet, and the liquid and the concavo-convex member being in point contact with each other. On the contrary, when the height and roughness of the unevenness are small and the pitch and interval of the unevenness are wide, the liquid repellency does not appear.

In the present invention, the surface shape of the particle layer 12 is not limited as long as the particle layer 12 exhibits liquid repellency defined by the above-described water contact angle by the Lotus effect.
The surface of the particle layer 12 preferably has an arithmetic mean roughness Ra of 0.05 to 0.2 μm, and preferably has an average spacing Sm of asperities of 0.5 to 20 μm. When the surface shape of the particle layer 12 satisfies the above-described range, the particle layer 12, that is, the liquid repellent region 10 a described later more preferably exhibits liquid repellency by the Lotus effect.
The arithmetic average roughness Ra of the particle layer 12 is more preferably 0.07 to 0.2 μm, and still more preferably 0.1 to 0.2 μm. Moreover, 0.5-10 micrometers is more preferable, and, as for average space Sm of the unevenness | corrugation of the particle layer 12, 0.5-5 micrometers is more preferable.
Arithmetic mean roughness Ra and mean interval Sm of unevenness may be measured in accordance with, for example, JIS B 0601-1994, using a commercially available device such as Surfcom manufactured by Tokyo Precision Co., Ltd.

As described above, the particle layer 12 exhibits liquid repellency by the Lotus effect caused by the unevenness due to the particles 12 a.
Such particle layer 12 prepares a coating liquid (composition) containing particles 12a and a binder as an example, applies the coating liquid on the surface of the substrate 10, cures the binder, and fixes the particles 12a. Form by

Various particles can be used without limitation as long as the particles 12a can form asperities that exhibit liquid repellency due to the Lotus effect and can be crushed by pressing with a pressing plate 14 described later.
Accordingly, there is no limitation on the particle size (particle size) of the particles 12a. 10-200 nm is preferable and, as for the particle size of particle | grains 12a, 30-100 nm is more preferable.
The particles 12a may be hollow particles or solid particles. However, it is preferable that the particles 12 a be hollow particles in terms of ease of crushing by the pressing plate 14 and the like. Solid particles are particles whose inside is clogged.

There is no restriction also in the formation material of particle 12a.
Examples of the material for forming the particles 12a include silica (silicon dioxide), inorganic materials such as silica, organic materials such as acrylic, styrene, melamine and benzoguanamine, organic-inorganic composite materials, and the like.

The binder forming the particle layer 12 is also not limited, and various binders used for forming a layer (film) formed by dispersing particles and the like can be used.
Specific examples of the binder include dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, urethane acrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.
The content of the particles 12a in the coating liquid may be set appropriately in accordance with the particle diameter of the particles 12a and the like, so that the unevenness capable of exhibiting liquid repellency due to the Lotus effect can be formed.

  If necessary, a polymerization initiator, a silane coupling agent, a surfactant, a thickener, and the like may be added to the coating liquid for forming the particle layer 12.

The coating liquid for forming the particle layer 12 may be prepared in the same manner as the coating liquid in which particles are dispersed, for forming a layer containing particles.
As an example, a solution in which a compound serving as a binder is dissolved in a solvent is prepared, and the particles 12a are added to the solution, followed by diffusion and dispersion to prepare a coating solution for forming the particle layer 12. In addition, if necessary, the prepared coating solution may be filtered to remove foreign matter.

The particle layer 12 can be formed by applying such a coating solution to the surface of the substrate 10 and curing the binder.
There are no limitations on the method of applying the prepared coating solution, and known methods such as bar coating, gravure coating, die coating, throttle die coating, and doctor knife can be used.
Next, after drying the coating solution, the binder is cured if necessary. The curing method of the binder is also not limited, and may be performed by a known method such as UV irradiation, electron beam irradiation, and heating depending on the binder.

Next, in the pattern forming method of the present invention, as shown in the third and fifth rows of FIG. The particle layer 12 formed in 10 is pressed, and the particles 12 a of the particle layer 12 are crushed by the convex portion 14 b to separate the pressing plate 14 from the base material 10.
Thereby, the lyophobic pattern having the lyophobic area 10 a and the lyophilic area 10 b can be formed on the surface of the base material 10.

As described above, the particle layer 12 exhibits liquid repellency by the Lotus effect due to the unevenness formed by the particles 12 a.
However, when the particles 12a of the particle layer 12 are crushed, the region where the particles 12a are crushed has no unevenness and can not exhibit liquid repellency due to the Lotus effect.
Therefore, a pressure plate 14 having concave portions 14 a corresponding to the target liquid repellent area and convex portions 14 b corresponding to the target lyophilic area is formed, and the particle layer 12 is pressed by the pressure plate 14, By squeezing the particle 12a with the convex portion 14b, the region corresponding to the concave portion 14a maintains liquid repellency to make the liquid repellent region 10a, and the region corresponding to the convex portion 14b does not have asperities that exhibit the Lotus effect. A target lyophobic pattern can be formed as the lyophilic area 10 b having liquid properties.
For example, in the case of forming a wiring pattern such as a wiring substrate by aerosol deposition to be described later, the pressing plate 14 is formed in which the region for forming the wiring is the convex portion 14b and the region where the wiring is not formed is the concave portion 14a. By pressing the particle layer 12, it is possible to form a lyophobic pattern according to the target wiring pattern.

As described above, according to the conventional lyophilic pattern forming method, the lyophilic surface is formed with the concavities and convexities that exhibit the lyophobicity by the Lotus effect by embossing according to the lyophobic pattern.
On the other hand, according to the pattern forming method of the present invention, first, a particle layer (liquid repellent layer) having irregularities to develop liquid repellency by the Lotus effect by particles is formed, and the particles of this particle layer The lyophilic pattern is formed by squeezing them to be lyophilic in accordance with the above.

In addition, as described above, in the pattern forming method of the present invention, the particle layer 12 is pressed by the pressing plate 14 corresponding to the hydrophilicity repellent pattern to form the hydrophilicity repellent pattern. That is, the liquid repellency in the liquid repellent area 10 a is exhibited by the Lotus effect due to the unevenness of the particle layer 12.
Therefore, in the pattern formation method of the present invention, fine irregularities such as to obtain the Lotus effect like the formation of the conventional hydrophilic / repellant pattern for expressing liquid repellency by the Lotus effect by the formation of the irregularities by embossing etc. There is also no need to make a press plate with it.

In the pattern forming method of the present invention, the pressing force that can crush the particles 12 a may be appropriately set according to the strength of the particles 12 a and the like.
Further, the depth (the size in the thickness direction) of the recess 14 a in the pressing plate 14 may be appropriately set according to the thickness of the particle layer 12 so as not to be in contact with the particle layer 12.

The length of the concave portion 14a and the convex portion 14b of the pressing plate 14 in the direction orthogonal to the arrangement direction of the concave portion 14a and the convex portion 14b, that is, the direction perpendicular to the paper surface of FIG.
Therefore, the concave portions 14 a and the convex portions 14 b of the pressing plate 14 may be elongated in the direction orthogonal to the arrangement direction of the concave portions 14 a and the convex portions 14 b. That is, the pressing plate 14 may squeeze the particles 12 a of the particle layer 12 so as to form one continuous groove in the direction perpendicular to the paper surface of FIG. 1 of the base material 10. At this time, even if the projections 14b squeeze the particles 12a of the particle layer 12 in the entire region of the base material 10 in the direction perpendicular to the paper surface of FIG. 1, both ends or one end of the same direction remain continuous. The particles 12a of the particle layer 12 may be crushed so as to form a single groove.
Alternatively, the convex portions 14 b of the pressing plate 14 may be divided into a plurality of pieces in the direction orthogonal to the arrangement direction of the concave portions 14 a and the convex portions 14 b. That is, the pressing plate 14 may squeeze the particles 12 a of the particle layer 12 at a plurality of places separated in the direction perpendicular to the paper surface of FIG. 1 of the base material 10. That is, the pressing plate 14 may squeeze the particles 12 a of the particle layer 12 so as to form a plurality of intermittent grooves in the direction perpendicular to the paper surface of FIG. 1 of the base material 10.
In this regard, the same applies to the press plates 18 and 20 forming the saw-like unevenness described later and the roll press plate 14R corresponding to the roll-to-roll described later.

As described above, according to the pattern forming method of the present invention, a particle layer (a liquid repellent layer) having irregularities to develop liquid repellency by the Lotus effect is formed by particles, and the particles of this particle layer are pressed according to the lyophobic pattern. The lyophilic pattern is formed by crushing to make it lyophilic.
According to such a pattern forming method of the present invention, convex portions having inclined surfaces are arrayed on the surface, and the inclined surface is a lyophilic area having lyophilic property, and a surface continuous with the inclined surface is liquid repellent It is also possible to form a lyophobic pattern that results in a lyophobic area having properties.
FIG. 2 and FIG. 3 conceptually show an example thereof.

Also in this example, as in the example shown in FIG. 1 described above, the particle layer 12 having the particles 12 a is formed on the surface of the base material 10.
In the present embodiment, since the hydrophilic layer is formed by arranging the convex portions having inclined surfaces by the particle layer 12, the particle layer 12 needs to be thicker than the example shown in FIG.

Next, as in the previous example, the base 10 on which the particle layer 12 is formed is pressed by the pressing plate 18 having the recess 18 a.
The pressing plate 18 has a concavo-convex shape in which the concave portions 18 a are arranged in one direction. The recess 18 a has a trapezoidal shape in a cross section in the arrangement direction of the recess 18 a. In the following description, the shape of the recess in the cross section in the arrangement direction of the recess is also referred to simply as the “shape of the recess”. Moreover, in the following description, unless otherwise noted, the “cross-section” indicates a cross-section in the arrangement direction of the recesses.
That is, the recess 18 a of the pressing plate 18 has an inclined surface which is inclined with respect to the recess forming surface of the pressing plate 18. In the following description, the concavo-convex shape of a pressing plate in which concave portions having inclined surfaces inclined in the direction of arrangement of the concave portions are arranged with respect to the concave portion forming surface of the pressing plate 18 is Say.
Further, the recess forming surface of the pressing plate 18 is, in other words, a surface connecting the opening of the recess in the pressing plate 18 and the upper end (opening side end) of the protrusion.

The trapezoidal shape of the recess 18a in the cross section is such that only one leg a is inclined to the recess forming surface of the pressing plate 18, and the other leg b is perpendicular to the recess forming surface of the pressing plate 18 (see FIG. 3) ). That is, the portion of the leg a has an inclined surface which is inclined with respect to the recess forming surface of the pressing plate 18 described above. In the following description, the inclined surface which is inclined with respect to the recess forming surface of the pressing plate 18 is also simply referred to as “inclined surface”.
Furthermore, as a preferred embodiment, the pressing plate 18 has trapezoidal concave portions 18 a continuously arranged in the direction of arrangement of the concave portions 18 a without opening a gap.

In the example shown in FIG. 2, the particle layer 12 is pressed by the pressing plate 18 so as to form the particle layer 12.
At this time, the particle layer 12 pressed by the pressing plate 18 does not completely follow the shape of the recess 18 a of the pressing plate 18, and has a slightly different shape from the recess 18 a.
That is, in the particle layer 12, a region corresponding to the inclined surface of the recess 18a, that is, a region corresponding to the leg a inclined with respect to the recess forming surface in the trapezoid of the recess 18a in the cross section Abut on the forming surface). Therefore, this area is pressed by the inclined surface of the pressing plate 18 and is molded following the shape of the recess 18a. Further, in this region, the particles 12a are crushed by pressing, and the unevenness becomes small, so that it becomes a lyophilic region 10b (broken line) which does not express liquid repellency by the Lotus effect.
On the other hand, in the region corresponding to the trapezoid upper bottom c in the particle layer 12 and the region corresponding to the leg b perpendicular to the recess forming surface, the inclination of the recess 18a described above is obtained even if the pressing plate 18 is not in contact. Due to the pressing of the particle layer 12 by the surface (leg a), it is deformed so as to follow, and it becomes a so-called sluggish shape in which the corner (shoulder) is rounded. As a result, in this area, the area where there is no pressure by the pressing plate 18 and / or the area where the pressing force by the pressing plate 18 is small becomes most, and the particles 12a are held without being pressed. As a result, the area corresponding to the trapezoidal upper base c and the leg b becomes a liquid repellent area 10a that exhibits liquid repellency by the Lotus effect due to the unevenness formed by the particles 12a.

That is, in the hydrophilicity repellent pattern formed by pressing with the press plate having such a saw-like concavo-convex shape, convex portions having planar (substantially planar) inclined surfaces are continuously formed, and convex The lyophobic pattern has alternating inclined surfaces to be the lyophilic regions 10b and regions continuous to the inclined surfaces to be the lyophobic regions 10a in the arrangement direction of the parts. In addition, when the base material 10 is a sheet-like thing, the base material 10 in which this lyophilic pattern was formed is a sheet-like thing of this invention.
By forming a film by aerosol deposition on such a lyophilic pattern as described later, for example, a member having different surface characteristics alternately in one direction, a member having different optical characteristics alternately in one direction, elasticity And a member having regions having different mechanical strength such as hardness in one direction, a member for a gas sensor having a region having different gas adsorption properties in one direction, a member for an antenna having a region having different reflection characteristics in one direction, Various members having different characteristics alternately in one direction can be manufactured, such as members having regions having different electromagnetic characteristics in one direction.

  In the example shown in FIG. 2, the thickness of the particle layer 12 is not limited. That is, the thickness of the particle layer 12 is the length of the lyophilic area 10b, the length of the liquid repellent area 10a, the thickness of the uneven lyophobic pattern to be formed, and the pressing force that can crush the particles 12a appropriately. Condition adjustment, that is, the thickness at which the particle layer 12 of the target shape is obtained is appropriately set according to the pressing condition or the like in which the particles do not break (detach) during pressing or the film cracking of the particle layer 12 does not occur. Just do it.

In addition, the shape of the recess and the length of the inclined surface, etc. are also the length of the lyophilic area 10b, the length of the liquid repellent area 10a, the asperity shape of the target particle layer, and the ease of sagging of the corner That is, it may be set as appropriate according to the shape or the like) in which the particles 12a and 18a do not easily abut.
For example, if the cross section is a trapezoidal concave portion 18a, the length of the lyophilic area in the arrangement direction of the concavities and convexities can be adjusted by adjusting the length of the leg a (the inclined surface of the concave portion) inclined to the trapezoidal concave surface By adjusting the length of the upper bottom c of the trapezoid, it is possible to adjust the length of the liquid repellent in the direction of arrangement of the asperities.

In the press plate having such a saw-like unevenness, the shape of the recess is not limited to the trapezoidal shape as shown in the illustrated example.
That is, if the recess has an inclined surface, that is, if it has a side inclined from the opening of the recess to the recess forming surface in the cross section, the plane on the closed surface side of the recess is the recess of the pressing plate It may be an irregular quadrilateral which is not parallel to the formation surface.

Further, the pressing plate having such a saw-like unevenness is not limited to a rectangular cross-sectional shape of the recess, but may be a triangular recess such as the pressing plate 20 conceptually shown in FIG. 4.
Even with such a triangular recess, the particle layer 12 does not completely follow the shape of the pressing plate 20, as conceptually shown in FIG. That is, in the region corresponding to the inclined surface of the pressing plate 20, the shape of the particle layer 12 follows, but does not follow the recess in the region corresponding to the side perpendicular to the recess forming surface of the pressing plate from near the apex angle It is in a slightly dripped state different from the shape of the recess.
As a result, as in the example shown in FIG. 2 described above, in the region corresponding to the inclined surface of the pressing plate 20, the particles 12a are crushed and the unevenness is eliminated, and the lyophilic region does not express liquid repellency by the Lotus effect. (Broken line). On the other hand, in a region which does not follow the recess 30a corresponding to a side perpendicular to the recess forming surface of the pressing plate from near the apex angle, the particles 12a are held, and the unevenness formed by the particles 12a causes the lotus It becomes a liquid repellant area which expresses liquid repellence by an effect.

In addition, in the press plate having such a saw-like recess, the configuration in which one surface of the recess in the arrangement direction is perpendicular to the recess forming surface of the press plate is not limited. That is, in the pressing plate having a saw-like uneven shape, the recess may have two inclined surfaces in the arrangement direction.
For example, in a press plate having a recess having a trapezoidal cross section shown in FIG. 3, the leg b perpendicular to the recess formation surface of the press plate may be inclined with respect to the recess formation surface of the press plate. Further, in the pressing plate 20 having a triangular recess shown in FIG. 4, the shape of the recess may not be a right triangle, but may be a normal triangle.
At this time, according to the angle of the inclined surface with respect to the recess forming surface, the region pressed by the inclined surface having a small angle with respect to the recess forming surface is pressed particles to become a lyophilic region, and the recess forming surface of the pressing plate The region pressed by the inclined surface having a large angle with respect to the surface becomes a liquid repellent region maintaining the liquid repellency caused by the unevenness without pressing the particles.

In the example shown in FIG. 2, the pressing plate 18 (20) has molded only the particle layer 12, but the present invention is not limited thereto.
That is, a convex portion having a flat (substantially planar) inclined surface is continuously formed by pressing the base material 10 in a concave and convex shape with the press plate 18 having a saw-like concave and convex, and a convex It is good also as base material 10 which has a lyophobic pattern which has an inclined surface used as a lyophilic area, and an area which follows an inclined surface used as a lyophobic area alternately in the arrangement direction of the parts.
Further, the molding of the particle layer 12 by such a pressing plate can be used as a pressing plate having irregularities of various shapes in addition to the pressing plate 18 having saw-like irregularities. For example, in the example shown in FIG. 1, the thickness of the particle layer 12 is increased, and the particle layer 12 is pressed and formed by the pressing plate 14 having rectangular asperities to form the particle layer 12 having rectangular asperity. It is also good. At this time, the portion pressed and formed by the convex portion 14 b is a lyophilic area in which the particles 12 a are crushed and the unevenness is eliminated, and the liquid repellency due to the Lotus effect is not expressed. In addition, a region corresponding to the recess 14 a is a liquid repellent region that exhibits liquid repellency by the Lotus effect. Therefore, in this case, it is necessary to prevent the ceiling surface of the recess 14 a from coming into contact with the particle layer 12.

In the film forming method of the present invention, film formation is performed by aerosol deposition on the hydrophilicity pattern formed by the pattern forming method of the present invention.
In other words, in the film forming method of the present invention, film formation is performed by aerosol deposition on the lyophilic pattern forming surface of the substrate 10 having the lyophilic pattern formed by the pattern forming method of the present invention.

In FIG. 6, an example of the film-forming apparatus which enforces the film-forming method of this invention is shown notionally.
The film forming apparatus 50 shown in FIG. 6 is an apparatus for forming a film on the substrate 10 by the above-described aerosol deposition, and includes an aerosol generating unit 52 and a film forming unit 54. The aerosol generating unit 52 and the film forming unit 54 are connected by a guiding pipe 56.

The aerosol generation unit 52 aerosolizes the raw material liquid L obtained by dissolving or dispersing the film forming material in a solvent or a dispersion medium, and supplies the generated aerosol A to the induction pipe 56. The aerosol A is sent to the film forming unit 54 through the induction pipe 56.
In the film forming apparatus 50, the aerosol generating unit 52 includes a raw material container 58 for containing the raw material liquid L, a container 60 for containing a part of the raw material container 58, and an ultrasonic transducer 62 disposed on the bottom of the container 60. And gas supply means 64 for supplying a carrier gas for sending the aerosol A to the film forming unit 54 through the induction pipe 56.

In the container 60, water W is accommodated. The water W is accommodated in the container 60 in order to transmit the ultrasonic waves generated by the ultrasonic transducer 62 to the raw material liquid L. Therefore, the ultrasonic transducer 62 is immersed in the water W. Further, at least a part of the container 60 for containing the raw material container 58 is also immersed in the water W.
When the ultrasonic transducer 62 vibrates, the water W propagates the ultrasonic vibration to ultrasonically vibrate the raw material container 58 to ultrasonically vibrate the raw material liquid L stored in the raw material container 58. By ultrasonically vibrating the raw material liquid L, the raw material liquid L is aerosolized, and an aerosol A of the raw material liquid L is generated. That is, the raw material container 58, the container 60 and the ultrasonic transducer 62 constitute a so-called ultrasonic atomizer.

  In the film forming method of the present invention, the method of ultrasonically vibrating the raw material liquid L is not limited to the method of ultrasonically vibrating the raw material liquid L by propagating ultrasonic waves using water W (intermediate solution). For example, a method of disposing the ultrasonic transducer 62 on the lower surface of the raw material container 58 and ultrasonically vibrating the raw material liquid L through the raw material container 58, and disposing the ultrasonic transducer 62 on the bottom surface of the raw material container 58 A known method may be used which is used for ultrasonic vibration of the raw material liquid L in aerosol deposition, such as a method of ultrasonically vibrating the raw material liquid L directly.

In the film forming method of the present invention, the film forming material (film to be formed) is not limited, and various materials which can be formed by aerosol deposition can be used.
Examples include organic electroluminescent materials, metal alkoxide compounds, silicon compounds such as silicon dioxide (silica) and tetraethoxysilane, ceramic powders such as lead zirconate titanate (PZT) and aluminum oxide (alumina), zinc-based, alumina-based , Metal oxides such as zirconia, silica and probstite, transparent electrode materials such as indium tin oxide (ITO), silver halide and metal nanoparticles, polysaccharides such as gelatin, polyvinyl alcohol, polyvinyl prolydon and starch , Water-soluble resins such as cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, polyhyaluronic acid and carboxycellulose, and oxide semiconductors and organic semiconductors Solution such as a solution containing a molecule or a carbon nanotube serving as is exemplified.

There is no restriction on the solvent or dispersion medium used for preparation of the raw material liquid L, and various liquids can be used as long as the film forming material can be dissolved or dispersed depending on the film forming material.
Examples include amides such as methyl ethyl ketone and N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, heterocyclic compounds such as pyridine, hydrocarbons such as benzene and oxalic acid, alkyl halides such as chloroform and dichloromethane, methyl acetate and butyl acetate And esters thereof such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and 1,2-dimethoxyethane, and organic solvents such as alkyl alcohols such as methanol, ethanol and propanol. Moreover, water is also illustrated as a solvent or a dispersing agent. In addition, as water, it is preferable to use any of ion exchange water, distilled water and pure water.
The solvent and the dispersion medium may be used as a mixture of two or more.

In addition, although mentioned later, in the film-forming method of this invention, the aerosol to the base material 10 is carried out, heating the base material 10 as a preferable response for the purpose of movement of the aerosol A on the base material 10 by the Leidenfrost effect. Supply A.
On the other hand, in the film forming method of the present invention, film formation is performed on the base material 10 having the lyophilic pattern, but when drying of the aerosol A proceeds by heating, the effect of the lyophilic pattern is reduced.
In consideration of this point, the solvent (dispersion medium) used for preparation of the raw material liquid L preferably has a boiling point of 100 ° C. or less.

The raw material liquid L may contain various binders, coupling agents, and the like for the purpose of improving the adhesion of the film after film formation, improving the film strength, and the like, as necessary.
Moreover, the raw material liquid L may also contain a polymerizable monomer in order to raise the film hardness of the film formed as needed.

The ultrasonic transducer 62 is not limited, and various types of ultrasonic transducers (means for generating ultrasonic vibrations) used for aerosolizing (forming into mist) of the raw material liquid L can be used in aerosol deposition.
The frequency of ultrasonic vibration by the ultrasonic transducer 62 is not limited, and the frequency of ultrasonic vibration that can aerosolize the raw material liquid L may be appropriately set according to the composition of the raw material liquid L and the like. The frequency of ultrasonic vibration for aerosolizing the raw material liquid L is about 15 kHz to 3 MHz.

  In the aerosol deposition, the particle size of the aerosol A can be adjusted by adjusting one or more of the density (concentration) of the raw material liquid L, the surface tension of the raw material liquid L, and the frequency of ultrasonic vibration.

In the film forming method of the present invention, the aerosolization of the raw material liquid L is not limited to the ultrasonic vibration of the raw material liquid L, and various known aerosolization methods of the raw material liquid L used in aerosol deposition are used. It is possible.
As an example, there is a method (a pressurized method) of applying pressure and increasing the flow velocity and causing gas to collide with the liquid (pressure method), the liquid dropped on the high speed rotating disc is aerosolized at the end of the disc by centrifugal force. Method (rotary disk type), a method of cutting and aerosolizing a droplet by applying vibration when passing the droplet through an orifice having a fine hole (orifice oscillator type), and direct current to a capillary through which the droplet passes Alternatively, a method (electrostatic type) of applying an alternating voltage to aerosolize a liquid is exemplified.

  The gas supply means 64 is for introducing the carrier gas into the raw material container 58 via the gas supply pipe 64a. The aerosol A suspended in the source container 58 is transported from the source container 58 by the carrier gas supplied from the gas supply means 64, and is transported to the film forming unit 54 through the induction pipe 56.

The gas supply means 64 is not limited, and various known gas supply means used for supply of carrier gas in aerosol deposition, such as fans, blowers, gas cylinders, and compressed air, can be used. Alternatively, the carrier gas may be supplied to the raw material container 58 by suction from the discharge port 70 a of the film forming unit 54 described later.
The amount of gas supplied by the gas supply means 64 is also not limited. Here, it is preferable that the gas supply means 64 supply the carrier gas so that the gas flow in the raw material container 58, the induction piping 56 and the film forming unit 54 (in the casing 70 described later) becomes a laminar flow. By making the gas flow containing an aerosol into a laminar flow, a film of uniform thickness can be formed on the surface of the substrate 10.
The supply amount of the carrier gas by the gas supply unit 64 is preferably 3 × 10 ^{−3 to} 5 × 10 ⁻³ m ³ / min, and more preferably 1 × 10 ^{−3 to} 3 × 10 ⁻³ m ³ / min.

  In the film forming method of the present invention, the carrier gas is also not limited, and inert gas such as argon and nitrogen, air, gas itself obtained by aerosolizing a film forming material, and gas formed by aerosolizing another film forming material A variety of known gases are available, such as those used as carrier gases in aerosol deposition.

On the other hand, the film forming unit 54 includes a casing 70, a support 72 that supports the base material 10, and an oscillating device 74. The support 72 is disposed in the casing 70. In addition, the base material 10 is a base material in which the lyophilic area and the liquid repellent area (the lyophobic pattern) are formed by the pattern forming method of the present invention described above.
The vibrating device 74 is provided as a preferred embodiment, and in the illustrated example, is fixed in contact with the lower surface of the casing 70. In a preferred embodiment, the support 72 incorporates a heating means.

In the film forming method of the present invention, the substrate 10 has a lyophobic pattern in which a lyophilic lyophilic area and a lyophobic liquid repellent area are formed on the film formation surface.
As described above, in the aerosol deposition, the aerosol A is uniformly supplied to the entire surface of the substrate 10, unlike the ink jet that can selectively land droplets on the desired position of the substrate, basically, It is not possible to perform film formation patterned in a pattern.
On the other hand, adhesion of the aerosol A to the liquid repellent area 10a is suppressed by forming a lyophobic pattern on the film formation surface of the base material 10, and the aerosol A is selectively adhered to the lyophilic area 10b. It is possible to perform film formation patterned in a target pattern.

In the film forming method of the present invention, the particle size of the aerosol A is not limited, but is preferably 20 to 50 μm, more preferably 10 to 20 μm, and still more preferably 1 to 10 μm.
As described above, the particle size of the aerosol can be adjusted by adjusting one or more of the density of the raw material liquid L, the surface tension of the raw material liquid L, and the frequency of ultrasonic vibration.

In the film forming method of the present invention, the particle diameter of the aerosol A may be measured by a known method of measuring the particle diameter (particle diameter of particles).
A method of measuring the particle size of the aerosol A by, as an example, injecting laser sheet light into a space where the aerosol A exists using a laser sheet light source for visualization, imaging with a high-speed camera, and analyzing an image Is illustrated. Alternatively, the particle size of the aerosol A may be measured by visualizing the aerosol A using a commercially available fine particle visualization system (for example, ViEST manufactured by Shin Nippon Air Conditioning Co., Ltd.). When the aerosol A is visualized to measure (calculate) the particle size, image processing may be performed as necessary.
Moreover, when performing aerosolization of the raw material liquid L by ultrasonic vibration, the particle size of the aerosol A may be calculated | required by the following formula. In the following equation, ρ represents the density of the raw material liquid L, σ represents the surface tension of the raw material liquid L, and f represents the frequency of ultrasonic vibration.
D = 0.68 [(π * σ) / (ρ * f ² )] ^1/2
This formula is described in J. Accousticai Sot. Amer. 34 (1962) 6.

The particle size of the aerosol A is from generation of the aerosol A to movement in the induction pipe 56 to arrival at the substrate 10, except when the particle size of the aerosol A unexpectedly changes due to collisions between the aerosols A, etc. Basically, it is considered the same.
In addition, the particle size of the aerosol A arriving at the substrate 10 is basically considered to be uniform over the entire surface of the substrate 10 except in the case where the particle size of the aerosol A unexpectedly changes.

The support 72 is a support means for mounting and supporting the substrate 10.
In the film forming method of the present invention, the support means for the base material 10 is not limited to the support 72 on which the base material 10 is placed, and any known sheet such as a support means for holding the end of the sheet Various means for supporting the sheet (plate, film) can be used.
In the case of roll-to-roll, which will be described later, a roller (a conveying roller, a conveying roller pair, etc.) for conveying the base material 10 in the supply unit (film forming unit) of the aerosol A A drum (can) or the like for winding and conveying the substrate 10 acts as a support means for the substrate 10.

In the film forming method of the present invention, the substrate 10 is preferably heated when the aerosol A is being supplied. Corresponding to this, in the film forming apparatus 50, the support 72 incorporates a heating means.
By supplying the aerosol A to the base material 10 while heating the base material 10, the aerosol A moves on the base material 10 by the Leidenfrost phenomenon (Leidenfrost effect), so the liquid repellent area 10a to the lyophilic area The movement of the aerosol A to 10 b can be promoted to further improve the patterning accuracy of the film formation.
There is no restriction | limiting in the heating temperature of the base material 10, According to the solvent used for the raw material liquid L, what is necessary is just to set the temperature which a Leidenfrost phenomenon produces suitably. The heating of the substrate 10 is preferably performed so that the surface of the substrate 10 is 100 ° C. or more, and more preferably 150 ° C. or more.

It is preferable to set the heating of the substrate 10 to a temperature at which the substrate 10 is not damaged or less, depending on the forming material of the substrate 10.
Here, when the drying of the aerosol A proceeds by heating, the effect of the lyophilic pattern formed on the substrate 10 is reduced. In consideration of this point, the surface temperature of the substrate 10 by heating is preferably 300 ° C. or less, and more preferably 200 ° C. or less.
Furthermore, in view of this point, the solvent (dispersion medium) used for the preparation of the raw material liquid L is preferably a liquid having a boiling point of 100 ° C. or less, as described above.

As a heating method of the support 72, various known heating methods such as a method using a heater can be used.
Moreover, the heating method of the base material 10 can utilize various well-known heating methods of a sheet-like thing, such as direct heating by heating with a lamp and a heater other than heating of the support 72.

The film forming apparatus 50 in the illustrated example is provided with a vibrating apparatus 74 on the lower surface of the support 72. The vibration apparatus 74 is provided as a preferable embodiment, and vibrates the base 10 when the aerosol A is supplied to the base 10.
In the film forming unit 54, the support 72 is provided in contact with the bottom surface (inner wall surface) of the casing 70. The excitation device 74 is provided in contact with the lower surface of the casing 70. Therefore, when the vibration device 74 vibrates the casing 70, the support 72 vibrates, and the base 10 supported by the support 72 vibrates.

The film forming method of the present invention uses the substrate 10 having the lyophobic pattern (the liquid repellent area 10a and the lyophilic area 10b) in the film formation by aerosol deposition to adhere the aerosol A to the liquid repellent area 10a. By suppressing the aerosol A selectively adhering to the lyophilic area 10b, a film formed by patterning in a target pattern is performed.
Therefore, by supplying the aerosol A to the substrate 10 while vibrating the substrate 10, the movement of the aerosol A attached to the liquid repellent region 10a to the lyophilic region 10b is promoted, and the patterning accuracy of the film formation is It can improve more.

Moreover, the film-forming speed can also be improved by supplying the aerosol A to the base material 10 while vibrating the base material 10.
In the aerosol deposition, the aerosol A adheres to the substrate 10 and is dried to form a film in a sea-island manner. Here, the aerosol A which has not been fixed to the substrate 10 is discharged from the substrate 10 as it falls. Therefore, in the conventional aerosol deposition, many aerosols A are not effectively used for film formation, and the film formation speed is slow. On the other hand, by supplying the aerosol A while vibrating the base material 10, it is possible to prevent the aerosol A from rolling down from the base material, and the aerosol A moves on the base material 10 and the aerosols A collide with each other. As a result, droplets of the aerosol A aggregate. As a result, the aerosol A is likely to be fixed on the substrate 10, and the film forming rate is considered to be improved.

In the film forming method of the present invention, there is no limitation on the frequency of vibration of the substrate 10 when the substrate 10 is vibrated.
In order to suitably obtain the effect of vibrating the substrate 10, the frequency of vibration of the substrate 10 is preferably 50 Hz or more, more preferably 100 Hz or more, and still more preferably 200 Hz or more.

In the film forming method of the present invention, when the substrate 10 is vibrated, the frequency of vibration of the substrate 10 is preferably 10 kHz or less, more preferably 5 kHz or less, and still more preferably 1 kHz or less.
When the aerosol A adheres to the substrate 10, the aerosols A combine to become a liquid close to the raw material liquid L. Here, when the substrate 10 is vibrated at a frequency of more than 10 kHz, a liquid close to the raw material liquid L attached to the substrate 10 is ultrasonically vibrated, and is again converted into an aerosol A, and from the surface of the substrate 10 There is a possibility that the deposition rate may be reduced due to detachment.

When the substrate 10 is vibrated in the film forming method of the present invention, the speed of vibration of the substrate 10 is not limited.
However, in order to suitably obtain the effect of vibrating the substrate 10, it is preferable to vibrate the substrate 10 at a certain speed or more. The speed of vibration of the substrate 10 is preferably 0.1 mm / sec or more, more preferably 0.5 mm / sec or more, and still more preferably 1 mm / sec or more.
Conversely, if the speed of vibration of the substrate 10 is too fast, the load on the device increases, the load on the substrate 10 increases, the aerosol A easily falls from the substrate 10, and before the aerosol A moves Problems such as drying out may occur. Therefore, 10 mm / s or less is preferable, as for the amplitude of a vibration of the base material 10, 8 mm / s or less is more preferable, and 5 mm / s or less is more preferable.

The vibrating device 74 is not limited, and various known vibrating means capable of vibrating the support 72 depending on the support 72 supporting the substrate 10 may be used. In the present invention, the support (support means) for supporting the base material 10 includes a roller and the like in roll-to-roll as described above.
As the vibration device 74, as an example, a vibration means using a piezo element, a vibration motor (eccentric motor), a vibration means using a movable coil, a vibration means using an air actuator, a hydraulic actuator or the like are exemplified. Moreover, the vibration exciter 74 can also utilize suitably a commercially available vibrator (vibration exciter).

In the film forming method of the present invention, the method of vibrating the substrate 10 is not limited to the method of vibrating the supporting means of the substrate 10.
For example, when the substrate 10 is supported by supporting means for holding the end, or when the substrate 10 is transported by a pair of transport rollers in roll-to-roll described later, the aerosol A to the substrate 10 When the substrate 10 is in a vibratable state of the substrate 10 at the supply position, ie, the film formation position, as a vibration means of the substrate 10, a blower for blowing and vibrating the substrate 10, and a speaker A means or the like that vibrates by irradiating a sound wave to the base material 10 such as is also suitably usable as a vibration means of the base material 10.

In the film forming method of the present invention, when vibrating the substrate 10, there is no limitation on the timing to start the vibration, but before the supply of the aerosol A to the substrate 10 is started, the vibration of the substrate 10 is It is preferable to start. For example, in the case of the film forming apparatus 50 shown in FIG. 6, after starting the vibration of the base 10 (support 72) by the vibrating apparatus 74, the driving of the ultrasonic transducer 62 is started. It is preferred to initiate aerosolization.
When the substrate 10 is vibrated, it is preferable to always vibrate the substrate 10 in a state where the aerosol A is supplied to the substrate 10 in order to suitably obtain the effect of the vibration. By starting the vibration of the substrate 10 before the supply of the aerosol A to the substrate 10 is started, the substrate 10 can be reliably vibrated when the aerosol A is supplied.

In the film forming method of the present invention, the vibration of the substrate 10 may be in the plane direction of the main surface (maximum surface) of the substrate 10 or in the direction orthogonal to the main surface of the substrate 10. The vibration may include both the surface direction of the main surface and the direction orthogonal to the main surface of the substrate 10.
Also, the vibration of the base material 10 may be a linear reciprocating motion, or may be a vibration of a trace that draws a shape such as a circle, an ellipse, and a polygon.

Hereinafter, the operation of the film forming apparatus 50 shown in FIG. 6 will be described.
In the film-forming apparatus 50 shown in FIG. 6, the base material 10 in which the liquid repelling pattern was formed is mounted in the support body 72. As shown in FIG.
Thereafter, when the ultrasonic transducer 62 ultrasonically vibrates in a state where the raw material liquid L is stored in the raw material container 58, the ultrasonic wave is transmitted to the raw material liquid L via the water W, and the raw material liquid L ultrasonically vibrates.
By ultrasonic vibration of the raw material liquid L, the raw material liquid L is aerosolized. Thereby, in the inside of the raw material container 58, the aerosol A produced | generated by aerosolization of the raw material liquid L will be in the state which floated above.

Next, the carrier gas is supplied from the gas supply means 64 into the raw material container 58 via the gas supply pipe 64a. The aerosol A floating in the raw material container 58 is conveyed from the raw material container 58 to the induction pipe 56 by the carrier gas, and is conveyed from the induction pipe 56 into the casing 70 of the film forming unit 54. In addition, the aerosol A may be concentrated, for example, by heating the induction piping 56, if necessary.
When the aerosol A is transported into the casing 70 of the film forming unit 54, the aerosol A is supplied to the base 10 placed on the support 72. Furthermore, the solvent is evaporated from the aerosol A supplied (adhered) to the substrate 10, and the film forming material contained in the aerosol A (raw material liquid L) is deposited on the substrate 10. In addition, the aerosol A which was not used for film-forming is discharged | emitted from the discharge port 70a of the casing 70. As shown in FIG.

Here, in the film forming method of the present invention, the hydrophilic pattern is formed on the substrate 10.
Therefore, as described above, the aerosol A arriving at the liquid repellent area 10a moves, and the aerosol A selectively adheres to the lyophilic area 10b. As a result, a film patterned in a target pattern can be formed with high patterning accuracy. Preferably, the substrate 10 is vibrated by the vibration device 74 and heated by the heating means contained in the support 72, so that the film formation patterned with higher accuracy can be performed.

In the film forming method of the present invention, after forming a film on the substrate 10 as necessary, UV, electron beam and radiation such as α ray, β ray and γ ray are formed on the formed film. And the like may be irradiated with actinic radiation.
For example, when the film forming material is a polymerizable liquid crystal compound, the film may be formed on the substrate 10, and then the film may be irradiated with UV to cure (polymerize) the polymerizable liquid crystal compound. As a light source which generate | occur | produces an ultraviolet-ray, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, LED etc. are illustrated, for example.

The film forming method of the present invention can also use roll-to-roll film formation. In particular, as described above, since the film forming rate can be improved by vibrating the substrate 10, roll-to-roll can be more suitably used by vibrating the substrate 10.
As well known, the roll-to-roll means that the base material 10 is fed from a base material roll in which the long base material 10 is wound in a roll, and the long base material 10 is conveyed in the longitudinal direction. It is a manufacturing method which processes treatment, such as membrane formation, continuously to substrate 10, and rolls processing-treated substrate 10 again in roll shape. By using roll-to-roll, productivity can be greatly improved.
In the following description, roll-to-roll is also referred to as "RtoR".

  FIG. 7 conceptually shows an example in which the film forming method of the present invention is used for RtoR. The film forming apparatus shown in FIG. 7 uses the same members as the film forming apparatus 50 shown in FIG. 6 in many cases, so the same members are denoted by the same reference numerals and description will be mainly made on different parts.

In the film forming apparatus 78 shown in FIG. 7, the long base material 10 is transported by the transport roller 80 and the transport roller 82 in the longitudinal direction (arrow x direction in the figure). In addition, it may replace with a conveyance roller and may use a conveyance roller pair.
The casing 70A of the film forming unit 54A is a rectangular casing whose lower surface is open. In addition, the vibrating device 74 is disposed below the base 10 so as to sandwich the base 10 together with the casing 70A. The casing 70 </ b> A is provided between the transport roller 80 and the transport roller 82 in the transport direction of the substrate 10. Therefore, in the film forming apparatus 78, the transport roller 80 and the transport roller 82 serve as a support for the substrate 10.

In the film forming apparatus 78, the base material 10 having the lyophilic pattern is supplied in the longitudinal direction by the transport roller 80 and the transport roller 82, and is supplied with the aerosol A when passing under the casing 70A. Be filmed.
Preferably, the substrate 10 is vibrated by a vibration device 74 disposed below the casing 70A. As a result, it becomes possible to form a film patterned with higher accuracy, and the film forming speed can be improved.
In RtoR, as the vibrating device 74, an air blower that blows and vibrates the base material 10 and a means that irradiates and vibrates a sound wave to the base material 10 such as a speaker are preferably usable as described above. That's right. Further, the base 10 may be vibrated by vibrating the carrying roller 80 and / or the carrying roller 82 as the supporting means.

As described above, the vibration of the base material 10 is preferably started before the supply of the aerosol A is started.
Therefore, in the film forming apparatus 78 of the illustrated example using RtoR, it is preferable that the vibration exciting apparatus 74 vibrate the base material 10 from the upstream side of the casing 70A. It is preferable to vibrate the substrate 10 from immediately downstream.

As described above, in the film forming method of the present invention, film formation patterned by aerosol deposition is performed on the base material 10 having the lyophilic pattern.
Here, when the present invention is used for RtoR, a particle layer forming means and a pressing plate are provided upstream of the casing 70A, and the pattern forming method of the present invention and the film forming method of the present invention are processed by RtoR. It may be performed continuously.

For example, as conceptually shown in FIG. 8, a roller pressing plate 14R having a convex portion 14Rb and a concave portion 14Ra on the week surface is provided upstream of the film forming device 78 (casing 70A). And a particle layer forming means 86 for forming the particle layer 12. For example, the particle layer forming unit 86 applies a coating solution for forming the particle layer 12 to the substrate 10, a drying unit for drying the coating solution applied to the substrate 10, and a binder of the coating film Effect means for curing.
At this time, while the base material 10 is conveyed in the longitudinal direction (arrow x direction), first, a coating liquid containing a binder and particles 12 a is applied by the particle layer forming means 86, and then a solvent of the coating liquid Are dried, and the binder is cured by UV irradiation or the like to form the particle layer 12 on the surface of the substrate 10.
Next, while conveying the base material 10 in the longitudinal direction, the convex portions 14Rb of the roller pressing plate 14R are pressed against the base material 10, and the particles 12a of the particle layer 12 are crushed by the convex portions 14Rb. As a result, a lyophobic pattern is formed on the surface of the base material 10, having a lyophobic area 10a corresponding to the concave portion 14Ra and a lyophilic area 10b in which the particles 12a are pressed and granulated by the convex portion 14Rb.
Thereafter, while the base material 10 is transported, a film is formed on the base material 10 on which such a hydrophilic pattern is formed by the film forming apparatus 78 which performs the film forming method of the present invention. As a result, patterning can be performed only on the lyophilic area to attach the aerosol A, and the film formation material can be patterned to form a film.

  In addition, the manufacturing method as shown in FIG. 8 uses a transfer means such as a belt conveyer and a roller conveyer, and as shown in FIG. A plurality of sheets are arranged in the transport direction, and while being transported by the transport means, the formation of the particle layer 12 by the particle layer forming means 86 is sequentially performed on the substrate 10 which is transported, and the lyophobicity by the roller pressing plate 14R. The present invention can also be used in a manufacturing method in which a film is formed by the film forming apparatus 78 that performs the film forming method of the present invention after forming a pattern.

Moreover, the processing by RtoR as shown in FIG. 8 can also be used when only the pattern formation method of the present invention is implemented.
As an example, in the apparatus shown in FIG. 8, the particle layer forming means is carried while conveying the base material 10 in the longitudinal direction as a configuration having only the particle layer forming means 86 and the roller pressing plate 14R without providing the film forming device 78. The formation of the particle layer 12 by 86 and the formation of the lyophobic pattern by crushing of the particles 12a of the particle layer 12 by the roller pressing plate 14R may be performed by RtoR.

  As mentioned above, although the pattern formation method, the film-forming method, and the sheet-like material of the present invention have been described in detail, the present invention is not limited to the above-described example, and various improvements and modifications can be made without departing from the scope of the present invention. Of course you may do it.

  The features of the present invention will be more specifically described below with reference to examples. However, the scope of the present invention should not be construed as limited by the specific examples shown below.

<Pressing plate A>
A press plate A having saw-like irregularities (see FIGS. 2 and 3) on the surface was prepared.
The pressing plate A has a trapezoidal recess in a cross section in the arrangement direction of the asperities, and the recess is continuously formed in the asperity arrangement direction. In the following description, the trapezoidal shape of the pressing plate A indicates a trapezoidal shape in a cross section in the arrangement direction of the concavities and convexities.
The trapezoidal shape had a lower base of 20 μm, an upper base of 5 μm, and a height of 2 μm. The lower base of the trapezoid is the length of the concave-convex arrangement direction of the concave plate forming surface side of the pressing plate A, that is, the formation pitch of the concaves. Further, the upper bottom of the trapezoid is the length in the concave / convex arrangement direction of the concave portion forming surface on the closed side of the concave portion, and the height is the depth of the concave portion.
Also, one of the trapezoidal legs was inclined with respect to the recess forming surface, and the other of the trapezoidal legs was perpendicular to the recess forming surface. That is, the recess of this pressing plate has an inclined surface.
The concave portion is elongated in a direction perpendicular to the arrangement direction of the concavities and convexities (a method perpendicular to the paper surface in FIGS. 2 and 4).

<Pressing plate B>
A pressure plate B having rectangular asperities (see FIG. 1) on its surface was prepared.
The pressing plate B has a concavo-convex shape in which rectangular recesses and protrusions are alternately formed in a cross section in the arrangement direction of the concavities and convexities. The length of the depressions in the arrangement direction of the asperities was 5 μm, the length of the asperities was 15 μm, and the formation pitch of the asperities was 20 μm. Further, the height of the convex portion, that is, the depth of the concave portion was 2 μm.
In addition, a recessed part is elongate in the direction (perpendicular to the paper surface in FIG. 1) orthogonal to the sequence direction of unevenness | corrugation. That is, this uneven | corrugated shape is uneven | corrugated shape like a line and space.

<Preparation of Coating Solution A>
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was diluted with 285.0 g of methyl isobutyl ketone. Further, 15.0 g of a polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) was added and mixed and stirred.
Subsequently, 60.0 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) was added and stirred for 120 minutes with an air disper to completely dissolve the solute.
Further, to this solution was added 240 g of a 40% methyl isobutyl ketone dispersion of hollow silica particles (Silinx, manufactured by Nittetsu Mining Co., Ltd.) dispersed with a Polytron disperser at 10000 rpm for 20 minutes. Thereafter, 112.5 g of methyl ethyl ketone and 112.5 g of propylene glycol were added, and the mixture was stirred by an air disper for 10 minutes.
The dispersion obtained by dispersing the hollow silica particles was filtered with a polypropylene filter having a pore size of 30 μm to prepare a coating solution A.

<Formation of particle layer A>
As a substrate, a triacetyl cellulose film (TAC-TD80U manufactured by Fujifilm Corporation) having a thickness of 80 μm and a width of 300 mm was facilitated.
The coating solution A was applied to the base material to a 5.2 g / m ² using a slot die coater, and dried at 30 ° C. for 30 seconds and 90 ° C. for 40 seconds. After drying, the coated layer was cured by irradiation with ultraviolet light of 160 W / cm ² under a nitrogen purge to form a particle layer A having a thickness of 1.8 μm on the surface of the substrate.
The base on which the particle layer A was formed had a surface roughness Ra of 0.15 μm and an Sm of 3 μm. Moreover, when water was dripped at the base material in which the particle layer A was formed, it was a contact angle of 120 degrees, and it confirmed that there was liquid repellency. In addition, the surface shape was measured by the surf com made by Tokyo Seimitsu Co., Ltd., and the measurement of the contact angle was measured by Drop Master 700 made by Kyowa Interface Chemical Co., Ltd.

Example 1
The base material on which the particle layer A was formed was cut into 50 × 50 mm.
The pressing plate A is brought into contact with the formation surface of the particle layer A of the cut substrate with the depression forming surface facing, and is pressed under the conditions of a pressure of 3 kg / cm ² and a temperature of 120 ° C. It was crushed to form a lyophobic pattern.

The particle layer A pressed by the pressing plate A was observed by a field emission scanning electron microscope (FE-SEM). As a result, in the portion corresponding to the leg (the inclined surface of the recess) inclined with respect to the recess forming surface of the pressing plate A, the particles were completely crushed. The particles were completely left on the upper bottom of the trapezoidal shape of the pressing plate A and the portions corresponding to the legs perpendicular to the recess forming surface.
Since the unevenness of the pressure plate A is fine, the contact angle of water in the lyophilic area and the liquid repellent area formed by the unevenness of the pressure plate A can not be measured.
Instead, water-based ink was dropped on the surface pressed by the pressing plate A and observed with an optical microscope. As a result, there is no ink in the portions corresponding to the legs perpendicular to the upper bottom of the trapezoidal shape of the pressing plate A and the recess forming surface, and the portions corresponding to the legs inclined to the recess forming surface of the pressing plate A Ink was attached collectively.
From this result, the particles of the particle layer A are crushed and lyophilic in the portions corresponding to the legs (inclined surface of the recess) inclined with respect to the recess forming surface of the pressing plate A. And the part corresponding to the leg perpendicular | vertical to a recessed part formation surface has maintained the liquid repellency which the particle layer A has, without particle | grains being crushed, and it turned out that the lyophobic pattern is formed. In the region corresponding to the leg inclined with respect to the recess formation surface, the pressing plate A squeezes the particles to flatten the height and roughness of the unevenness of the particles, and the pitch and interval of the unevenness of the particles It is considered that the liquid repellent property was lost.

A raw material liquid (lyophilic ink) having the following composition was prepared.
The density of the prepared raw material liquid was 1.1 g / cm ³ and the surface tension was 46 mN / m. The density of the raw material solution was measured in accordance with JIS Z 8804: 2012. In addition, the surface tension of the raw material liquid was measured by the hanging drop method (pendant drop method).
In addition, in order to make observation easy, the raw material liquid contained Blue No. 1 as a pigment.
――――――――――――――――――――――――――――――――――――――――
・ 25.05 g of water
-Glycerin 4.65g
・ Diethylene glycol 3g
・ Orphin (Nisshin Chemical Industry Co., Ltd. E1010) 0.03 g
・ Blue No. 1 0.27 g
――――――――――――――――――――――――――――――――――――――――

The substrate on which the lyophobic pattern is formed is placed on the support of the film forming unit of the film forming apparatus as shown in FIG. 6 with the lyophobic pattern formed surface up, and film formation by aerosol deposition is performed. The
As a vibrating device of the film forming unit, LW139.141-75 manufactured by Air Brown Ltd. was used. The substrate (support) was vibrated at a frequency of 500 Hz and a vibration speed of 2 mm / sec by this vibration excitation device.
After vibration of the base material was started, the ultrasonic transducer of the aerosol generation unit was vibrated at 500 kHz to start aerosolization of the raw material liquid. As an ultrasonic transducer, IM4-36D manufactured by Hoshi Kogakuen Co., Ltd. was used.

The produced | generated aerosol was conveyed to the film-forming chamber from the raw material container through induction piping using air as carrier gas. The flow rate of the carrier gas was 2.8 × 10 ⁻³ m ³ / min.
Under such conditions, film formation was performed by supplying an aerosol to the substrate for 60 seconds.
In addition, it was 5.5 micrometers when the particle size of the aerosol was computed by the above-mentioned formula (D = 0.68 [(π * σ) / (rho * f ² )] ^1/2 ).

After the film formation was completed, the substrate was removed from the aerosol supply unit, dried, and the film formation surface was observed with a microscope.
As a result, adhesion of Blue No. 1 was not confirmed in the liquid repellent area detected by the above-described confirmation of the lyophobic pattern, and only the lyophilic area corresponding to the inclined surface of the pressure plate A was crushed. The adhesion of Blue No. 1 was confirmed, and a good pattern could be formed.

Example 2
The base material on which the particle layer A was formed was cut into 50 × 50 mm.
The pressing plate B was pressed against the formation surface of the particle layer A of the cut-out base material, with the depression forming surface facing the surface. The pressing conditions were the same as in Example 1.

After pressing, it confirmed by FE-SEM like Example 1. FIG. As a result, in the portion corresponding to the convex portion of the pressing plate B, the particles were completely crushed. In addition, in the part corresponding to the recessed part of the press plate B, particle | grains remained completely.
Further, similar to Example 1, when the water-based ink is dropped on the surface pressed by the pressing plate B and observed with an optical microscope, there is no ink in the region corresponding to the concave portion of the pressing plate B, and the convex of the pressing plate B The ink was collectively attached to the area corresponding to the part.
From this result, the particles of the particle layer are crushed and lyophilicized in the portion corresponding to the convex portion of the pressing plate B, and in the portion corresponding to the recess of the pressing plate B, the particles are not crushed but the liquid repellant possessed by the particle layer It turned out that the nature was maintained and the lyophobic pattern was formed. Similarly, in the region corresponding to the convex portion of the pressing plate B, the particles are crushed by the pressing plate B, and the height and roughness of the unevenness of the particles are flattened, and the pitch and interval of the unevenness of the particles It is considered that the liquid repellent property was lost.

In the same manner as in Example 1, a film was formed by aerosol deposition on the substrate on which the hydrophilicity pattern was formed in this manner.
As a result, adhesion of Blue No. 1 is not confirmed in the liquid repellent area detected by the above-described confirmation of the lyophilic pattern, and the particle is crushed and corresponds to the leg inclined with respect to the recess forming surface. Adhesion of Blue No. 1 was confirmed only in the liquid region, and a good pattern could be formed.

<Preparation of Coating Solution B>
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was diluted with 285.0 g of methyl isobutyl ketone. Further, 15.0 g of a polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) was added and mixed and stirred.
Subsequently, 60.0 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) was added and stirred for 120 minutes with an air disper to completely dissolve the solute.
Further, to this solution was added 240 g of a 60% methyl isobutyl ketone dispersion of solid silica particles (AEROSIL 50 manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of 30 nm dispersed by a polytron disperser at 10000 rpm for 20 minutes. Thereafter, 112.5 g of methyl ethyl ketone and 112.5 g of propylene glycol were added, and the mixture was stirred for 10 minutes with an air disper.
The dispersion obtained by dispersing the solid silica particles was filtered with a polypropylene filter having a pore size of 30 μm to prepare a coating solution B.

<Formation of particle layer B>
As a substrate, a triacetyl cellulose film (TAC-TD80U manufactured by Fujifilm Corporation) having a thickness of 80 μm and a width of 300 mm was prepared.
The coating solution B was applied to this base material to 4.2 g / m ² using a slot die coater, and dried at 30 ° C. for 30 seconds and 90 ° C. for 40 seconds. After drying, the coated layer was cured by irradiation with ultraviolet light of 160 W / cm ² under a nitrogen purge to form a particle layer B with a thickness of 1.4 μm on the surface of the substrate.
The base on which the particle layer B was formed had a surface roughness Ra of 0.11 μm and Sm of 1 μm. Moreover, when water was dripped at the base material in which the particle layer B was formed, it was a contact angle of 130 degrees, and it confirmed that there was liquid repellency. In addition, the surface shape was measured by the surf com made by Tokyo Seimitsu Co., Ltd., and the measurement of the contact angle was measured by Drop Master 700 made by Kyowa Interface Chemical Co., Ltd.

[Example 3]
The base on which the particle layer B was formed was cut into 50 × 50 mm.
The pressing plate A was pressed against the substrate having the cut particle layer B with the recess forming surface facing. The pressing conditions were the same as in Example 1.

The particle layer B in which the pressing plate A was pressed was observed by FE-SEM in the same manner as in Example 1. As a result, in the region corresponding to the leg (the inclined surface of the recess) that is inclined with respect to the recess forming surface of the pressing plate A, most of the particles are crushed, but the particle is not crushed and remains I was spotted. Since the fine particles were not hollow, it is considered that a partial crushing failure occurred. The particles remained completely in the upper bottom of the trapezoidal shape of the pressing plate A and in the region corresponding to the leg perpendicular to the recess forming surface.
Further, similar to Example 1, when the water-based ink was dropped and confirmed by the optical microscope, there was no ink in the upper bottom of the trapezoidal section of the pressing plate A and the part corresponding to the leg perpendicular to the recess forming surface The ink was collectively attached to the part corresponding to the leg which inclines with respect to the recessed part formation surface of the press plate A. FIG. From this result, it can be judged that the surface of the base material acts as a lyophobic pattern.

In the same manner as in Example 1, a film was formed by aerosol deposition on the substrate on which the hydrophilicity pattern was formed in this manner.
As a result, although a slight disorder is observed in the film formation pattern, no adhesion of Blue No. 1 is confirmed in the liquid repellent area detected by the above-described confirmation of the lyophilic pattern, and the inclined surface of the pressure plate A is supported. The adhesion of Blue No. 1 was confirmed only in the lyophilic area where the particles were crushed, and a good pattern could be formed.

Example 4
The base on which the particle layer B was formed was cut into 50 × 50 mm.
The pressing plate B was pressed against the base material having the cut particle layer B with the recess forming surface facing. The pressing conditions were the same as in Example 1.

After pressing, it confirmed by FE-SEM like Example 1. FIG. As a result, in the region corresponding to the convex portion of the pressing plate B, most of the particles were crushed, but portions where the particles were not crushed were scattered. Since the fine particles were not hollow, it is considered that a partial crushing failure occurred. In addition, in the part corresponding to the recessed part of the press plate B, the particle | grains remained completely.
Further, as in Example 1, when the water-based ink was dropped and confirmed by the optical microscope, there was no ink in the portion corresponding to the concave portion of the pressure plate B, and the portion corresponding to the convex portion of the pressure plate B The ink was attached collectively. From the result, it can be judged that the surface of the base material acts as a hydrophilicity repellent pattern.

In the same manner as in Example 1, a film was formed by aerosol deposition on the substrate on which the hydrophilicity pattern was formed in this manner.
As a result, although a slight disorder is observed in the film formation pattern, no adhesion of Blue No. 1 is confirmed in the liquid repellent area detected by the above-described confirmation of the lyophilic pattern, and the inclined surface of the pressure plate B is supported. The adhesion of Blue No. 1 was confirmed only in the lyophilic area where the particles were crushed, and a good pattern could be formed.
The results are shown in the following table.

As shown in Table 1, according to the present invention, it is possible to form a target lyophilic pattern and to form a target pattern of film formation by the unevenness of the pressing plate.
In Examples 3 and 4 in which solid particles were used for the particle layer, some disturbance was observed in the film formation pattern, but there was no problem in quality.

  For example, it can be suitably used for the production of an optical element, the production of a semiconductor element, the production of an electric element, the production of a solar cell, and the like.

DESCRIPTION OF SYMBOLS 10 base material 10a liquid repellent area 10b lyophilic area 12 particle layer 12a particle 14, 18, 20 pressing plate 14a, 18a recessed part 14b convex part 14R roller pressing plate 50, 78 film forming apparatus 52 aerosol generation part 54, 54A film forming part 56 Induction piping 58 Raw material container 60 Container 62 Ultrasonic transducer 64 Gas supply means 64a Gas supply pipe 70, 70A Casing 72 Support body 74 Vibrating device 80, 82 Conveying roller 86 Particle layer forming means A Aerosol L Raw material liquid W Water

Claims (13)

  A particle layer containing particles is formed on the surface of a substrate, and a pressing plate having asperities is pressed against the particle layer, and a part of the particles of the particle layer is crushed by the pressing plate. 9. A pattern forming method comprising: forming a lyophilic area that is lyophilic with respect to a liquid; and a liquid repellent area that is repellent with respect to a liquid of interest.   The pattern formation method according to claim 1, wherein the particles are hollow particles.   The pattern formation method of Claim 1 or 2 which shape | molds the said particle layer into an unevenness | corrugation by the press by the said press plate.   4. The pressure plate according to claim 1, wherein the pressing plate has a plurality of recesses arranged in at least one direction, and the recess has an inclined surface which is inclined in the arranging direction with respect to the recess forming surface of the pressing plate. The pattern formation method of any one term.   The pattern formation method according to claim 4, wherein the concave portion of the pressing plate has a rectangular shape in a cross section in the arrangement direction of the concave portion.   The pattern formation method according to claim 5, wherein the concave portion of the pressing plate has a trapezoidal shape in a cross section in the arrangement direction of the concave portion.   The pattern formation method according to any one of claims 1 to 6, wherein the surface of the substrate is made lyophilic before the particle layer is formed on the surface of the substrate.   The pattern formation according to any one of claims 1 to 7, wherein the base material is a sheet, and the lyophilic area and the liquid repellent area are formed on at least one surface of the sheet-like base material. Method. By aerosolizing the raw material liquid containing the film forming material,
The film-forming method of supplying the said aerosol to the said lyophilic area | region and the said liquid repelling area | region which were formed by the pattern formation method of any one of Claims 1-8.   The film forming method according to claim 9, wherein the aerosol is supplied to the lyophilic area and the liquid repellent area while vibrating the base material.   The film forming method according to claim 9, wherein the aerosol is supplied to the lyophilic area and the liquid repellent area while the substrate is heated. At least one surface has a plurality of projections arranged in at least one direction,
The convex portion has a plane which is inclined with respect to the arrangement direction, and a plane which is continuous with the plane,
For the liquid to be processed, the flat surface of the convex portion is lyophilic, and the surface continuous to the flat surface of the convex portion has a liquid repellant property due to unevenness due to particles. object.   The sheet-like material according to claim 12, further comprising a membrane on the surface of the lyophilic surface.