JP6885863B2 - Pattern formation method, film formation method and sheet-like material - Google Patents

Description

The present invention relates to a pattern forming method for forming a parent liquid region and a liquid repellent region on the surface of a base material, a film forming method for forming a film on a base material having a pattern formed by this forming method, and a pattern formed by this forming method. It relates to the sheet-like material which formed.

As a thin film film forming technology, a raw material liquid containing a film forming material is made into an aerosol, and the generated aerosol is supplied to a base material by transporting it with a carrier gas to vaporize the solvent in the aerosol adhering to the base material. Therefore, a technique for forming a film-forming material is known. This film formation technique is also called aerosol deposition.

Aerosol deposition is performed with 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.

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

As an example, such a problem can be solved by patterning and forming a liquid-repellent region having a liquid-repellent property and a liquid-repellent region having a liquid-repellent property on the surface of the base material.
That is, by forming the parent liquid region and the liquid repellent region in a pattern on the surface of the base material according to the target pattern such as the wiring pattern, the adhesion of aerosol to the liquid repellent region and the film formation are suppressed. Then, the aerosol can be selectively adhered to the parent liquid region to form a desired pattern.

As a method of forming the parent liquid region and the liquid repellent region by patterning, for example, Patent Document 1 describes a concave-convex structure on the surface of a sheet-like object, which exhibits a lotus effect of repelling liquid by a fine uneven structure. A pattern in which a parent liquid region and a liquid repellent region are patterned and formed by arranging them with a portion smoother than the structure sandwiched between them, and then applying a coating liquid to the smooth portion on the surface of the sheet to solidify it. The method of manufacturing the sheet is described.

Japanese Unexamined Patent Publication No. 2003-190876

As described in Patent Document 1, the formation of a pattern having a parent liquid region and a liquid repellent region is generally performed by embossing or the like on the surface of a liquid liquid base material to repel liquid by the Lotus effect. This is done by patterning and forming a concavo-convex structure that expresses sex.

An object of the present invention is a new pattern forming method of a parent liquid region and a liquid repellent region, which is different from the conventional pattern forming method, and a film formation on a film forming surface having a parent liquid region and a liquid repellent region formed by this pattern forming method. It is an object of the present invention to provide a film-forming method for performing the above-mentioned method and a sheet-like material having a parent liquid region and a liquid repellent region formed by this 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 base material, a pressing plate having irregularities is pressed against the particle layer, and some of the particles in the particle layer are crushed by the pressing plate. A pattern forming method characterized by forming a liquid-repellent region that is lipophilic to a liquid and a liquid-repellent region that is liquid-repellent to a target liquid.
[2] The pattern forming method 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 recesses have inclined surfaces inclined in the arrangement direction with respect to the concave portion forming surface of the pressing plate [1] to [3]. The pattern forming method according to any one of.
[5] The pattern forming method according to [4], wherein the recesses of the pressing plate are rectangular in cross section in the arrangement direction of the recesses.
[6] The pattern forming method according to [5], wherein the recesses of the pressing plate are trapezoidal in a cross section in the arrangement direction of the recesses.
[7] The pattern forming method according to any one of [1] to [6], wherein the surface of the base material is liquefied before the particle layer is formed on the surface of the base material.
[8] The pattern forming method according to any one of [1] to [7], wherein the base material is in the form of a sheet, and a parent liquid region and a liquid repellent region are formed on at least one surface of the sheet-like base material. ..
[9] Film formation in which the raw material liquid containing the film-forming material is aerosolized and the aerosol is supplied to the parent liquid region and the liquid-repellent region 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 parent liquid region and the liquid repellent region while vibrating the base material.
[11] The film forming method according to [9] or [10], wherein the aerosol is supplied to the parent liquid region and the liquid repellent region while heating the base material.
[12] On at least one surface, there are a plurality of convex portions arranged in at least one direction, and the convex portions have a plane inclined with respect to the arrangement direction and a plane continuous with the plane, and the target is A sheet-like material characterized in that the flat surface of the convex portion is liquid-friendly with respect to the liquid, and the surface continuous with the flat surface of the convex portion has liquid repellency due to unevenness due to particles.
[13] The sheet-like material according to [12], which further has a film on the surface of the surface having a liquidity property.

According to the pattern forming method of the present invention, a new pattern forming method is provided in which a parent liquid region having a liquid repellent property and a liquid repellent region having a liquid repellent property are formed by a method different from the conventional method.
Further, according to the film forming method of the present invention, the desired pattern can be formed by using the parent liquid region and the liquid repellent region formed by the pattern forming method of the present invention as the film forming surface.
Further, the sheet-like material of the present invention is a sheet-like material having a parent liquid region and a liquid-repellent region formed by the pattern forming method of the present invention and capable of forming a desired pattern.

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 formation method of this invention. It is a conceptual diagram for demonstrating another example of the film formation method of this invention. It is a conceptual diagram for demonstrating the pattern formation method and the film formation method of this invention.

Hereinafter, the pattern forming method, the film forming method, and the sheet-like material of the present invention will be described in detail based on the preferred embodiments shown in the accompanying drawings.
The embodiments shown below exemplify an example of the present invention, and do not limit the scope of the present invention. Further, in order to clearly explain each component member, the dimensions of each component member in the drawing are appropriately changed. Therefore, the scale in the figure is different from the actual scale.
Further, the numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

FIG. 1 conceptually shows an example of the pattern forming method of the present invention.
In the pattern forming method of the present invention, the particle layer 12 containing the particles 12a is formed on the surface of the base material 10, the pressing plate 14 having irregularities is pressed against the particle layer 12, and the particles 12a of the particle layer 12 are pressed against the pressing plate 14. By partially crushing the base material 10 with, the parent liquid region having the liquid repellent property and the liquid repellent region having the liquid repellent property are patterned and formed on the surface of the base material 10.
In the following description, the parent liquid region and the liquid repellent region formed by patterning are also referred to as a parent liquid repellent pattern.

In the pattern forming method of the present invention, the base material 10 is not limited, and for example, various materials to be formed by the aerosol deposition described later (material to be formed) can be used. As the base material 10, a sheet-like material (film, plate-like material) is preferably exemplified.
Examples of the sheet-like material serving as the base material 10 include polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), and the like. Polyacrytonitrile (PAN), Polyethylene (PI), Transparent Polyethylene, Polymethylmethacrylate Resin (PMMA), Polycarbonate (PC), Polyacrylate, Polymethacrylate, Polypropylene (PP), Polyethylene (PS), Acrylonitrile-butadiene-styrene A resin film made of a resin material such as a copolymer (ABS), a cycloolefin copolymer (COC), a cycloolefin polymer (COP), a triacetyl cellulose (TAC), and an ethylene-vinyl alcohol copolymer (EVOH). , And a biodegradable film composed of polylactic acid, polyglycolic acid, chitin, chitosan and the like.

Further, as described above, the base material 10 is not limited to the sheet-like material.
As the base material 10 other than the sheet-like material, as an example, a microchannel chip base material such as μTAS (micro-Total Analysis Systems), various circuit base materials on a silicon wafer, a biotemplate base material, and the like are preferable. 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 forming method of the present invention, the particle layer 12 containing the particles 12a is formed on the surface of such a base material 10.
In the pattern forming method of the present invention, one or both sides of the base material 10 may be surface-treated prior to the formation of the particle layer 12.
The surface treatment of the base material 10 is not limited, and all known surface treatments applied to the film-forming surface on which some layer (film) is formed can be used. Examples of the surface treatment include corona treatment, plasma treatment, UV (Ultra Violet) irradiation, ozone irradiation, and UV ozone cleaning, which improve liquidity (coatability).
Further, as the surface treatment of the base material 10, the formation of an underlayer is also available for the purpose of improving or imparting liquidity, ensuring surface smoothness, and the like. The base layer may be formed by a known method such as a coating method or a printing method, depending on the base layer to be formed.

In the pattern forming method of the present invention, as shown in the second stage from the top of FIG. 1, a particle layer 12 containing particles 12a is formed on the surface of the base material 10.
The particle layer 12 is a layer that exhibits liquid repellency due to the so-called lotus effect (lotus structure) by having irregularities due to the particles (fine particles) 12a.
In the present invention, having a liquid-like property means 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 base material 10, the surface of the particle layer 12, the liquid repellent region 10a described later, and the like. Further, in the case of parental liquid property, the target surface is a parent liquid region 10b or the like, which will be described later.
Further, the target liquid is, for example, water and a hydrophilic liquid (a liquid that is easily dissolved in water and a liquid that is easily dissolved in water) when the liquid-repellent region 10a is water-repellent and the parent liquid region 10b is hydrophilic. It is a liquid that is easily mixed), and is the raw material liquid L when a film is formed on the base material 10 on which the liquid repellent region 10a and the parent liquid region 10b are formed by the aerosol deposition described later.
The contact angle may be measured in accordance with JIS R 3257 using, for example, a commercially available device such as Drop Master 700 manufactured by Kyowa Surface Chemistry. However, the liquid-repellent region 10a and the parent liquid region 10b are minute regions, and the contact angle of water cannot be directly measured in many cases. In this case, water (water-based ink) may be actually applied, and the coated surface may be observed with an optical microscope or the like to confirm the adhesion of water, thereby confirming the liquidity and liquid repellency. .. The contact angle of water in the liquid-repellent region 10a usually coincides with the contact angle of water in the particle layer 12.

The lotus effect is also called the lotus leaf effect (lotus leaf structure).
As is well known, the Lotus effect, as explained by Cassie-Baxter theory, is when the height and roughness of the unevenness are large and the pitch and spacing of the unevenness are narrow, the liquid flows to the bottom of the uneven groove due to the capillary phenomenon. This is an effect of exhibiting liquid repellency when the liquid and the uneven member come into point contact with each other due to the fact that the liquid cannot reach the area and a void is generated under the droplet. On the contrary, when the height and roughness of the unevenness are small and the pitch and spacing of the unevenness are wide, the liquid repellency is not exhibited.

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

As described above, the particle layer 12 exhibits liquid repellency due to the Lotus effect caused by the unevenness of the particles 12a.
For such a particle layer 12, as an example, a coating liquid (composition) containing the particles 12a and a binder is prepared, the coating liquid is applied to the surface of the base material 10, and the binder is cured to fix the particles 12a. It is formed by converting.

As long as the particles 12a can form irregularities that exhibit liquid repellency due to the Lotus effect and can be crushed by pressing with the pressing plate 14 described later, various particles can be used without limitation.
Therefore, there is no limitation on the particle size (particle size) of the particles 12a. The particle size of the particles 12a is preferably 10 to 200 nm, more preferably 30 to 100 nm.
Further, the particles 12a may be hollow particles or solid particles. However, the particles 12a are preferably hollow particles from the viewpoint that they can be easily crushed by the pressing plate 14. The solid particle is a particle whose inside is clogged.

There are no restrictions on the material for forming the particles 12a.
Examples of the material for forming the particles 12a include inorganic materials such as silica (silicon dioxide) and silica, organic materials such as acrylic, styrene, melamine and benzoguanamine, and organic-inorganic composite materials.

The binder for forming the particle layer 12 is also not limited, and various binders used for forming a layer (film) in which particles and the like are dispersed 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 appropriately set in an amount capable of forming irregularities exhibiting liquid repellency due to the Lotus effect, depending on the particle size of the particles 12a and the like.

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, if necessary.

The coating liquid for forming the particle layer 12 may be prepared in the same manner as the coating liquid in which the particles are dispersed to form the layer containing the particles.
As an example, a coating solution for forming the particle layer 12 may be prepared by preparing a solution in which a compound serving as a binder is dissolved in a solvent, adding particles 12a to the solution, and diffusing and dispersing the particles. Further, if necessary, the prepared coating liquid may be filtered to remove foreign substances.

The particle layer 12 can be formed by applying such a coating liquid to the surface of the base material 10 and curing the binder.
The method for applying the prepared coating liquid is not limited, and known methods such as bar coat, gravure coat, die coat, throttle die coat, and doctor knife can be used.
Then, after the coating liquid is dried, 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.

In the pattern forming method of the present invention, then, as shown in the third to fifth stages of FIG. 1, the base material is formed by the parent liquid region and the liquid repellent region, that is, the pressing plate 14 having irregularities corresponding to the repellent pattern. The particle layer 12 formed on the 10 is pressed, the particles 12a of the particle layer 12 are crushed by the convex portion 14b, and the pressing plate 14 is separated from the base material 10.
As a result, a repellent pattern having a liquid repellent region 10a and a parent liquid region 10b can be formed on the surface of the base material 10.

As described above, the particle layer 12 exhibits liquid repellency due to the Lotus effect due to the unevenness formed by the particles 12a.
However, when the particles 12a of the particle layer 12 are crushed, the region where the particles 12a are crushed loses unevenness, and the liquid repellency due to the Lotus effect cannot be exhibited.
Therefore, a pressing plate 14 having a concave portion 14a corresponding to the target liquid-repellent region and a convex portion 14b corresponding to the target liquid-repellent region is formed, and the particle layer 12 is pressed by the pressing plate 14. By crushing the particles 12a with the convex portion 14b, the region corresponding to the concave portion 14a is made into a liquid-repellent region 10a while maintaining the liquid repellency, and the region corresponding to the convex portion 14b has no unevenness that exhibits the Lotus effect. The desired repellent pattern can be formed as the liquid parent liquid region 10b.
For example, in the case of forming a wiring pattern such as a wiring board by an aerosol deposition described later, a pressing plate 14 is formed in which a region where wiring is formed is a convex portion 14b and a region where wiring is not formed is a concave portion 14a. By pressing the particle layer 12, a repellent pattern corresponding to the target wiring pattern can be formed.

As described above, in the conventional method for forming a repellent pattern, unevenness is formed on the liquid repellent surface by embossing or the like according to the repellent pattern to exhibit the liquid repellent effect due to the Lotus effect.
On the other hand, in the pattern forming method of the present invention, a particle layer (liquid repellent layer) having irregularities exhibiting liquid repellency due to the Lotus effect is first formed by the particles, and the particles of this particle layer are formed into a repellent pattern. A repellent pattern is formed by crushing the particles to make them liquor-friendly.

Further, 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 repellent pattern to form the repellent pattern. That is, the liquid repellency in the liquid repellent region 10a is exhibited by the Lotus effect due to the unevenness of the particle layer 12.
Therefore, in the pattern forming method of the present invention, fine unevenness that can obtain the lotus effect can be obtained like the conventional formation of a repellent pattern that expresses the liquid repellency due to the lotus effect by forming the unevenness by embossing or the like. It is not necessary to prepare a pressing plate to have.

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

There is no limitation on 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, in the direction perpendicular to the paper surface of FIG.
Therefore, the concave portion 14a and the convex portion 14b of the pressing plate 14 may be long in a direction orthogonal to the arrangement direction of the concave portion 14a and the convex portion 14b. That is, the pressing plate 14 may crush the particles 12a 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 convex portion 14b crushes the particles 12a of the particle layer 12 in the entire area perpendicular to the paper surface of FIG. 1 of the base material 10, the convex portion 14b is continuous, leaving both ends or one end in the same direction. The particles 12a of the particle layer 12 may be crushed so as to form one groove.
Alternatively, the convex portion 14b of the pressing plate 14 may be divided into a plurality of portions in a direction orthogonal to the arrangement direction of the concave portion 14a and the convex portion 14b. That is, the pressing plate 14 may crush the particles 12a of the particle layer 12 at a plurality of separated points in the direction perpendicular to the paper surface of FIG. 1 of the base material 10. That is, the pressing plate 14 may crush the particles 12a 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 pressing plates 18 and 20 that form saw-like irregularities, which will be described later, and the roll pressing plates 14R, which will be described later and correspond to roll-to-roll.

As described above, in the pattern forming method of the present invention, a particle layer (liquid repellent layer) having irregularities that exhibit liquid repellency due to the Lotus effect is formed by the particles, and the particles of this particle layer are pushed according to the repellent pattern. By crushing it to make it lipophilic, a repellent pattern is formed.
According to such a pattern forming method of the present invention, convex portions having an inclined surface are arranged on the surface, and the inclined surface is a parent liquid region having a liquidity property, and the surface continuous with the inclined surface is liquid repellent. It is also possible to form a parent-repellent pattern that becomes a liquid-repellent region having properties.
An example thereof is conceptually shown in FIGS. 2 and 3.

In this example as well, the particle layer 12 having the particles 12a is formed on the surface of the base material 10 as in the above-mentioned example shown in FIG.
In this example, since the particle layer 12 forms a repulsive pattern in which convex portions having an inclined surface are arranged, the particle layer 12 needs to be thicker than the example shown in FIG.

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

In the trapezoidal shape of the recess 18a in the cross section, only one leg a is inclined with respect 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 that is inclined with respect to the concave portion forming surface of the above-mentioned pressing plate 18. In the following description, the inclined surface that is inclined with respect to the concave portion forming surface of the pressing plate 18 is also simply referred to as an “inclined surface”.
Further, in the pressing plate 18, as a preferred embodiment, trapezoidal recesses 18a are continuously arranged in the arrangement direction of the recesses 18a without leaving a gap.

In the example shown in FIG. 2, the particle layer 12 is pressed by the pressing plate 18 so as to mold 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 18a of the pressing plate 18, and has a slightly different shape from the recess 18a.
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 is formed on the pressing plate 18 (recess 18a). It abuts on the forming surface). Therefore, this region 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 the pressing, the unevenness becomes small, and the parent liquid region 10b (broken line) does not exhibit the liquid repellency due to the Lotus effect.
On the other hand, in the particle layer 12, the region corresponding to the trapezoidal upper base c and the region corresponding to the leg b perpendicular to the concave portion forming surface are inclined of the recess 18a described above even if the pressing plate 18 is not in contact with the region. By pressing the particle layer 12 by the surface (leg a), the particle layer 12 is deformed so as to follow the surface (leg a), resulting in a so-called sagging shape in which the corners (shoulders) are rounded. As a result, in this region, most of the region is not pressed by the pressing plate 18 and / or the region where the pressing pressure by the pressing plate 18 is small, and the particles 12a are held without being pressed. As a result, the region corresponding to the trapezoidal upper base c and the leg b becomes a liquid-repellent region 10a that exhibits liquid-repellent property due to the Lotus effect due to the unevenness formed by the particles 12a.

That is, in the repulsion pattern formed by pressing with a pressing plate having such a saw-like uneven shape, a convex portion having a flat (substantially flat) inclined surface is continuously formed and is convex. In the direction of arrangement of the portions, the parent-repellent pattern has an inclined surface that becomes the parent liquid region 10b and a region that is continuous with the inclined surface that becomes the liquid-repellent region 10a alternately. When the base material 10 is a sheet-like material, the base material 10 on which the repulsion pattern is formed is the sheet-like material of the present invention.
By forming a film on such a repellent pattern by aerosol deposition as described later, for example, a member having different surface textures alternately in one direction, a member having different optical characteristics alternately in one direction, and elasticity. And members having different mechanical strengths such as hardness in one direction, gas sensor members having different gas adsorption characteristics in one direction, antenna members having different reflection characteristics in one direction, and Various members having different characteristics alternately in one direction, such as a member having regions having different electromagnetic characteristics in one direction, can be manufactured.

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 parent liquid region 10b, the length of the liquid repellent region 10a, the thickness of the uneven repellent pattern to be formed, and the pressing force that can appropriately crush the particles 12a. The thickness at which the particle layer 12 having the desired shape can be obtained is appropriately set according to the pressing conditions such as the condition adjustment, that is, the particles do not collapse (separate) during pressing and the film cracking of the particle layer 12 does not occur. Just do it.

In addition, the shape of the concave portion and the length of the inclined surface also include the length of the parent liquid region 10b, the length of the liquid repellent region 10a, the uneven shape of the target particle layer, and the ease of sagging of the corners (shoulders). That is, the shape may be appropriately set according to the shape in which the particles 12a and 18a are unlikely to come into contact with each other).
For example, if the cross section is a trapezoidal recess 18a, the length of the parent liquid region in the uneven arrangement direction can be adjusted by adjusting the length of the leg a (inclined surface of the recess) that is inclined with respect to the trapezoidal recess forming surface. The length of the liquid repellency in the arrangement direction of the unevenness can be adjusted by adjusting the length of the upper bottom c of the trapezoid.

In the pressing plate having such saw-like unevenness, the shape of the concave portion is not limited to the trapezoidal shape as shown in the illustrated example.
That is, if the concave portion has an inclined surface, that is, if the concave portion has a side inclined from the opening of the concave portion to the concave portion forming surface in the cross section, the flat surface on the closed surface side of the concave portion is the concave portion of the pressing plate. It may be an amorphous quadrangular shape that is not parallel to the forming surface.

Further, the pressing plate having such saw-shaped unevenness is not limited to a quadrangular cross-sectional shape, and may be a triangular concave portion such as the pressing plate 20 conceptually shown in FIG.
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 in the region corresponding to the side perpendicular to the concave portion forming surface of the pressing plate from the vicinity of the apex angle, it does not follow the concave portion. It will be in a slightly sagging state, which is 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 to eliminate unevenness, and the liquid-repellent region due to the Lotus effect is not exhibited. (Dashed line). On the other hand, in the region corresponding to the side perpendicular to the concave portion forming surface of the pressing plate from the vicinity of the apex angle and not following the concave portion 30a, the particles 12a are held and the lotus is formed by the unevenness formed by the particles 12a. It is a liquid-repellent region that exhibits liquid-repellent properties due to the effect.

In the pressing plate having such a saw-shaped recess, there is no limitation on the configuration in which one surface of the recesses in the arrangement direction is perpendicular to the recess forming surface of the pressing plate. That is, the pressing plate having a saw-like uneven shape may have a configuration in which the recesses have two inclined surfaces in the arrangement direction.
For example, in the pressing plate having the concave portion having a trapezoidal cross section shown in FIG. 3, the leg b perpendicular to the concave portion forming surface of the pressing plate may be inclined with respect to the concave portion forming surface of the pressing plate. Further, in the pressing plate 20 having a triangular concave portion shown in FIG. 4, the shape of the concave portion may be a normal triangle instead of a right triangle.
In this case, depending on the angle of the inclined surface with respect to the concave portion forming surface, the region pressed by the inclined surface having a small angle with respect to the concave portion forming surface becomes a parent liquid region by being pressed into particles, and the concave portion forming surface of the pressing plate is formed. The region pressed by the inclined surface having a large angle with respect to the angle is a liquid-repellent region in which the particles are not pressed and the liquid-repellent property due to the unevenness is maintained.

In the example shown in FIG. 2, the pressing plate 18 (20) molded only the particle layer 12, but the present invention is not limited to this.
That is, by press-molding the base material 10 into a concavo-convex shape by the pressing plate 18 having a saw-like concavo-convex shape, a convex portion having a flat (substantially flat) inclined surface is continuously formed and is convex. The base material 10 having a repellent pattern may have an inclined surface serving as a parent liquid region and a region continuous with the inclined surface serving as a liquid repellent region alternately in the direction of arrangement of the portions.
Further, the molding of the particle layer 12 by such a pressing plate can be used not only with the pressing plate 18 having saw-like irregularities, but also with a pressing plate having various shapes of 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 press-molded by a pressing plate 14 having rectangular irregularities to form the particle layer 12 having rectangular irregularities. May be good. At this time, the portion press-molded by the convex portion 14b becomes a parent liquid region in which the particles 12a are crushed to eliminate the unevenness and the liquid repellency due to the Lotus effect is not exhibited. Further, the region corresponding to the recess 14a is a liquid-repellent region that exhibits liquid-repellent properties due to the Lotus effect. Therefore, in this case, it is necessary to prevent the ceiling surface of the recess 14a from coming into contact with the particle layer 12.

The film forming method of the present invention is to form a film on the repellent pattern formed by the pattern forming method of the present invention by aerosol deposition.
In other words, the film forming method of the present invention forms a film on the repellent pattern forming surface of the base material 10 having the repellent pattern formed by the pattern forming method of the present invention by aerosol deposition.

FIG. 6 conceptually shows an example of a film forming apparatus that implements the film forming method of the present invention.
The film forming apparatus 50 shown in FIG. 6 is an apparatus for forming a film on the base material 10 by the above-mentioned aerosol deposition, and has an aerosol generating section 52 and a film forming section 54. The aerosol generation unit 52 and the film forming unit 54 are connected by an induction 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 produced aerosol A to the induction pipe 56. The aerosol A is sent to the film forming section 54 through the induction pipe 56.
In the film forming apparatus 50, the aerosol generation unit 52 includes a raw material container 58 for accommodating the raw material liquid L, a container 60 for accommodating a part of the raw material container 58, and an ultrasonic vibrator 62 arranged on the bottom surface of the container 60. The gas supply means 64 for supplying the carrier gas for sending the aerosol A to the film forming section 54 via the induction pipe 56 is provided.

Water W is contained in the container 60. The water W is housed in the container 60 in order to transmit the ultrasonic waves generated by the ultrasonic vibrator 62 to the raw material liquid L. Therefore, the ultrasonic vibrator 62 is immersed in water W. Further, at least a part of the container 60 accommodating the raw material container 58 is also immersed in water W.
When the ultrasonic vibrator 62 vibrates, the water W propagates the ultrasonic vibration to cause the raw material container 58 to be ultrasonically vibrated, and the raw material liquid L contained in the raw material container 58 to be ultrasonically vibrated. When the raw material liquid L is ultrasonically vibrated, the raw material liquid L is converted into an aerosol, and the aerosol A of the raw material liquid L is generated. That is, the raw material container 58, the container 60, and the ultrasonic vibrator 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 in which an ultrasonic vibrator 62 is arranged on the lower surface of the raw material container 58 and the raw material liquid L is ultrasonically vibrated via the raw material container 58, and an ultrasonic vibrator 62 is arranged on the bottom surface of the raw material container 58. A known method used for ultrasonic vibration of the raw material liquid L in the aerosol deposition, such as a method of directly ultrasonically vibrating the raw material liquid L, can be used.

In the film forming method of the present invention, there is no limitation on the film forming material (film to be formed), and various materials capable of forming a film by aerosol deposition can be used.
As an example, organic electroluminescence material, metal alkoxide compound, silicon compound such as silicon dioxide (silica) and tetraethoxysilane, ceramic powder such as lead zirconate titanate (PZT) and aluminum oxide (alumina), zinc-based, alumina-based. , Metal oxides such as zirconia, silica and probskite, transparent electrode materials such as indium tin oxide (ITO), silver halide and metal nanoparticles, polysaccharides such as gelatin, polyvinyl alcohol, polyvinyl proridone and starch. , Cellulose and its derivatives, polyethylene oxide, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyargicic acid, polyhyaluronic acid, carboxycellulose and other water-soluble resins, as well as molecules and carbon nanotubes that become oxide semiconductors and organic semiconductors. Examples include solutions containing.

The solvent or dispersion medium used for preparing the raw material liquid L is not limited, 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 methyl ethyl ketone, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, heterocyclic compounds such as pyridine, hydrocarbons such as benzene and wall acid, alkyl halides such as chloroform and dichloromethane, methyl acetate and butyl acetate. Etc., ketones 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 are exemplified. Water is also exemplified as the solvent or dispersant. As the water, it is preferable to use any of ion-exchanged water, distilled water and pure water.
As the solvent and the dispersion medium, two or more kinds may be mixed and used.

As will be described later, in the film forming method of the present invention, for the purpose of moving the aerosol A on the base material 10 by the Leidenfrost effect, as a preferable measure, the aerosol to the base material 10 while heating the base material 10 Supply A.
On the other hand, in the film forming method of the present invention, the film is formed on the base material 10 having the repellent pattern, but when the aerosol A is dried by heating, the effect of the repellent pattern is reduced.
Considering this point, the solvent (dispersion medium) used for preparing the raw material liquid L is preferably a liquid having a boiling point of 100 ° C. or lower.

If necessary, 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.
Further, the raw material liquid L may contain a polymerizable monomer in order to increase the film hardness of the film formed, if necessary.

The ultrasonic vibrator 62 is not limited, and various ultrasonic vibrators (means for generating ultrasonic vibration) used for aerosolizing (misting) the raw material liquid L can be used in the aerosol deposition.
The frequency of the ultrasonic vibration by the ultrasonic vibrator 62 is also not limited, and the frequency of the ultrasonic vibration capable of converting the raw material liquid L into an aerosol 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 methods for aerosolizing the raw material liquid L used in the aerosol deposition can be used. It is possible.
As an example, a method of aerosolizing by colliding a gas whose flow velocity is increased by applying pressure with a liquid (pressurized type), a liquid dropped on a disk rotating at high speed is aerosolized at the edge of the disk by centrifugal force. (Rotating disk type), a method of cutting a droplet and making it into an aerosol by applying vibration when passing the droplet through an orifice with fine holes (operator vibration type), and a DC to the thin tube through which the droplet is passed. Alternatively, a method (electrostatic type) in which a liquid is aerosolized by applying an AC voltage is exemplified.

The gas supply means 64 introduces the carrier gas 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 by the carrier gas supplied from the gas supply means 64, and is conveyed to the film forming section 54 through the induction pipe 56.

The gas supply means 64 is not limited, and various known gas supply means used for supplying carrier gas in the aerosol deposition such as a fan, a blower, a gas cylinder, 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 70a of the film forming portion 54, which will be described later.
There is no limitation on the amount of gas supplied by the gas supply means 64. Here, the gas supply means 64 preferably supplies the carrier gas so that the gas flow in the raw material container 58, the induction pipe 56, and the film forming portion 54 (inside the casing 70 described later) becomes a laminar flow. By using a gas flow containing an aerosol as a laminar flow, a film having a uniform thickness can be formed on the surface of the base material 10.
The amount of carrier gas supplied by the gas supply means 64 ^{is preferably 3 × 10 -3 to} 5 × 10 ^-3 m ³ / min, 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 is an inert gas such as argon and nitrogen, air, the gas itself obtained by aerosolizing the film forming material, and the gas obtained by aerosolizing another film forming material. Etc., various known gases used as carrier gases in aerosol deposition can be used.

On the other hand, the film forming portion 54 has a casing 70, a support 72 for supporting the base material 10, and a vibration device 74. The support 72 is arranged in the casing 70. The base material 10 is a base material on which a parent liquid region and a liquid repellent region (parent repellent 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, the vibrating device 74 is in contact with and fixed to the lower surface of the casing 70. Further, as a preferred embodiment, the support 72 has a built-in heating means.

In the film forming method of the present invention, the base material 10 has a pro-repellent pattern in which a lipophilic region and a liquid-repellent liquid-repellent region are formed on the surface to be filmed.
As described above, unlike the inkjet that can selectively land the droplets at the desired position of the base material, in the aerosol deposition, the aerosol A is uniformly supplied to the entire surface of the base material 10, and basically, the desired position is obtained. It is not possible to form a film patterned in a pattern.
On the other hand, by forming a repellent pattern on the film-forming surface of the base material 10, the adhesion of the aerosol A to the liquid-repellent region 10a is suppressed, and the aerosol A is selectively attached to the liquid-repellent region 10b. Then, a film formation patterned in a desired pattern can be performed.

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, 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 size of aerosol A may be measured by a known method for measuring the particle size (particle size of particles).
As an example, a method of measuring the particle size of aerosol A by injecting laser sheet light into a space in which aerosol A exists using a laser sheet light source for visualization and imaging the image with a high-speed camera to analyze the image. Is exemplified. Further, the aerosol A may be visualized and the particle size of the aerosol A may be measured by using a commercially available fine particle visualization system (for example, ViEST manufactured by Shin Nippon Air Technologies Co., Ltd.). When the aerosol A is visualized and the particle size is measured (calculated), image processing may be performed as necessary.
Further, when the raw material liquid L is made into an aerosol by ultrasonic vibration, the particle size of the aerosol A may be obtained by the following formula. In the following formula, ρ indicates the density of the raw material liquid L, σ indicates the surface tension of the raw material liquid L, and f indicates the frequency of ultrasonic vibration.
D = 0.68 [(π * σ) / (ρ * f ² )] ^1/2
This equation is described in J.Accousticai Sot.Amer.34 (1962) 6.

The particle size of the aerosol A is the generation of the aerosol A, the movement in the induction pipe 56, and the arrival at the base material 10, except when the particle size of the aerosol A is suddenly changed due to a collision between the aerosols A and the like. Basically, it is considered the same.
Further, the particle size of the aerosol A arriving at the base material 10 is considered to be basically uniform over the entire surface of the base material 10 except when the particle size of the aerosol A suddenly changes.

The support 72 is a support means on which the base material 10 is placed and supported.
In the film forming method of the present invention, the supporting means for the base material 10 is not limited to the support 72 on which the base material 10 is placed, and known sheets such as supporting means for sandwiching the end portion of the sheet-like material are known. Various means for supporting the shaped object (plate-shaped object, film-shaped object) can be used.
In the case of roll-to-roll, which will be described later, in the roller (conveying roller, transfer roller pair, etc.) that conveys the base material 10 in the aerosol A supply section (film formation section), and in the aerosol A supply section. A drum (can) or the like around which the base material 10 is wound and conveyed acts as a supporting means for the base material 10.

In the film forming method of the present invention, it is preferable to heat the base material 10 while supplying the aerosol A. Correspondingly, in the film forming apparatus 50, the support 72 has a built-in 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 due to the Leidenfrost phenomenon (Leidenfrost effect), so that the liquid repellent region 10a to the parent liquid region The movement of the aerosol A to 10b can be promoted, and the patterning accuracy of the film formation can be further improved.
The heating temperature of the base material 10 is not limited, and the temperature at which the Leidenfrost phenomenon occurs may be appropriately set according to the solvent used in the raw material liquid L. The heating of the base material 10 is preferably performed so that the surface of the base material 10 is 100 ° C. or higher, and more preferably 150 ° C. or higher.

The heating of the base material 10 is preferably set to a temperature or lower at which the base material 10 is not damaged, depending on the material for forming the base material 10.
Here, if the aerosol A is dried by heating, the effect of the repellent pattern formed on the base material 10 is reduced. Considering this point, the surface temperature of the base material 10 by heating is preferably 300 ° C. or lower, more preferably 200 ° C. or lower.
Further, in consideration of this point, the solvent (dispersion medium) used for preparing the raw material liquid L is preferably a liquid having a boiling point of 100 ° C. or lower, as described above.

As a heating method of the support 72, various known heating methods such as a method using a heater or the like can be used.
Further, as a method for heating the base material 10, in addition to heating the support 72, various known methods for heating a sheet-like material such as heating with a lamp and direct heating with a heater can be used.

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

In the film formation method of the present invention, in the film formation by aerosol deposition, the base material 10 having the repellent pattern (liquid repellent region 10a and repellent region 10b) is used to attach the aerosol A to the liquid repellent region 10a. By suppressing and selectively adhering the aerosol A to the parent liquid region 10b, a film formation patterned in a target pattern is performed.
Therefore, by supplying the aerosol A to the base material 10 while vibrating the base material 10, the movement of the aerosol A adhering to the liquid-repellent region 10a to the parent liquid region 10b is promoted, and the patterning accuracy of the film formation is improved. Can be improved further.

Further, by supplying the aerosol A to the base material 10 while vibrating the base material 10, the film forming speed can be improved.
In the aerosol deposition, the aerosol A adheres to the base material 10 and dries to form a sea-island-like film. Here, the aerosol A that is not fixed to the base material 10 is discharged from the base material 10 as it is by rolling down. Therefore, in the conventional aerosol deposition, many aerosols A are not effectively subjected to film formation, and the film formation rate 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 so that the aerosols A collide with each other. By doing so, the droplets of aerosol A are aggregated. As a result, it is considered that the aerosol A is easily fixed on the base material 10 and the film formation rate is improved.

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

Further, in the film forming method of the present invention, when the base material 10 is vibrated, the vibration frequency of the base material 10 is preferably 10 kHz or less, more preferably 5 kHz or less, still more preferably 1 kHz or less.
When the aerosol A adheres to the base material 10, the aerosols A are bonded to each other to form a liquid close to the raw material liquid L. Here, when the base material 10 is vibrated at a frequency of more than 10 kHz, the liquid close to the raw material liquid L adhering to the base material 10 is in a state of being ultrasonically vibrated, and is converted into aerosol A again from the surface of the base material 10. There is a possibility that the film formation speed will be slowed down due to the detachment.

When the base material 10 is vibrated in the film forming method of the present invention, there is no limitation on the vibration speed of the base material 10.
However, in order to preferably obtain the effect of vibrating the base material 10, it is preferable to vibrate the base material 10 at a certain speed or higher. The vibration rate of the base material 10 is preferably 0.1 mm / sec or more, more preferably 0.5 mm / sec or more, still more preferably 1 mm / sec or more.
On the contrary, if the vibration speed of the base material 10 is too high, the load on the device becomes large, the load on the base material 10 becomes large, the aerosol A easily falls off the base material 10, and before the aerosol A moves. There is a possibility that problems such as drying out may occur. Therefore, the vibration amplitude of the base material 10 is preferably 10 mm / sec or less, more preferably 8 mm / sec or less, and further preferably 5 mm / sec or less.

The vibration device 74 is not limited, and various known vibration means capable of vibrating the support 72 depending on the support 72 that supports the base material 10 can be used. As described above, in the present invention, the support (supporting means) for supporting the base material 10 includes rollers and the like in roll-to-roll.
Examples of the vibrating device 74 include a vibrating means using a piezo element, a vibrating motor (eccentric motor), a vibrating means using a movable coil, a vibrating means using an air actuator, a hydraulic actuator, and the like. Further, as the vibrating device 74, a commercially available vibrating device (vibration device) can also be preferably used.

In the film forming method of the present invention, the method of vibrating the base material 10 is not limited to the method of vibrating the supporting means of the base material 10.
For example, when the base material 10 is supported by a support means that sandwiches the end portion, or when the base material 10 is conveyed by a transfer roller pair in a roll-to-roll described later, the aerosol A to the base material 10 When the base material 10 is in a state where it can vibrate by itself at the supply position, that is, the film formation position, the base material 10 is vibrated by blowing air to the base material 10 to vibrate the base material 10 and a speaker. Means such as those for irradiating the base material 10 with sound waves to vibrate the base material 10 can also be suitably used as the means for vibrating the base material 10.

In the film forming method of the present invention, when the base material 10 is vibrated, the timing at which the vibration is started is not limited, but the base material 10 is vibrated before the supply of the aerosol A to the base material 10 is started. It is preferable to start. For example, in the film forming apparatus 50 shown in FIG. 6, after the vibration device 74 starts the vibration of the base material 10 (support 72), the ultrasonic vibrator 62 is started to be driven to obtain the raw material liquid L. It is preferable to initiate aerosolization.
When the base material 10 is vibrated, in order to preferably obtain the effect of vibration, it is preferable that the base material 10 is always vibrated while the aerosol A is being supplied to the base material 10. By starting the vibration of the base material 10 before starting the supply of the aerosol A to the base material 10, the base material 10 can be surely in a vibrating state when the aerosol A is supplied.

In the film forming method of the present invention, the vibration of the base material 10 may be in the plane direction of the main surface (maximum surface) of the base material 10 or in the direction orthogonal to the main surface of the base material 10, and the base material 10 may be vibrated. The vibration may include both the surface direction of the main surface and the direction orthogonal to the main surface of the base material 10.
Further, the vibration of the base material 10 may be a linear reciprocating motion, or may be a vibration of a locus that draws a shape such as a circle, an ellipse, or 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 on which the liquid-repellent pattern is formed is placed on the support 72.
After that, when the ultrasonic vibrator 62 ultrasonically vibrates while the raw material liquid L is contained in the raw material container 58, the ultrasonic waves are transmitted to the raw material liquid L via the water W, and the raw material liquid L vibrates ultrasonically.
The raw material liquid L is ultrasonically vibrated, so that the raw material liquid L becomes an aerosol. As a result, inside the raw material container 58, the aerosol A produced by the aerosolization of the raw material liquid L is suspended above.

Next, the carrier gas is supplied into the raw material container 58 from the gas supply means 64 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 portion 54. If necessary, the aerosol A may be concentrated, for example, by heating the induction pipe 56.
When the aerosol A is conveyed into the casing 70 of the film forming portion 54, the aerosol A is supplied to the base material 10 placed on the support 72. Further, the solvent evaporates from the aerosol A supplied (adhered) to the base material 10, and the film-forming material contained in the aerosol A (raw material liquid L) is formed on the base material 10. The aerosol A that has not been subjected to the film formation is discharged from the discharge port 70a of the casing 70.

Here, in the film forming method of the present invention, a repellent pattern is formed on the base material 10.
Therefore, as described above, the aerosol A that has arrived at the liquid-repellent region 10a moves, and the aerosol A selectively adheres to the parent liquid region 10b. As a result, a film patterned in a target pattern can be formed with high patterning accuracy. Preferably, the base material 10 is vibrated by the vibrating device 74 and heated by the heating means built in the support 72, so that a more accurate patterned film can be formed.

In the film forming method of the present invention, if necessary, the film is formed on the base material 10, and then the film is irradiated with UV, electron beams, and radiation such as α rays, β rays, and γ rays. Etc. may be irradiated with active radiation.
For example, when the film-forming material is a polymerizable liquid crystal compound, the film may be formed on the base material 10 and then the film may be irradiated with UV to cure (polymerize) the polymerizable liquid crystal compound. Examples of the light source that generates ultraviolet rays include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, and an LED.

The film formation method of the present invention can also be used for film formation by roll-to-roll. In particular, as described above, since the film formation rate can be improved by vibrating the base material 10, roll-to-roll can be more preferably used by vibrating the base material 10.
As is well known, roll-to-roll means that the base material 10 is sent out from a base material roll in which a long base material 10 is wound in a roll shape, and the long base material 10 is conveyed in the longitudinal direction while being conveyed. This is a manufacturing method in which the base material 10 is continuously subjected to a treatment such as film formation, and the treated base material 10 is wound again in a 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. Since the film forming apparatus shown in FIG. 7 uses the same members as those of the film forming apparatus 50 shown in FIG. 6, the same members are designated by the same reference numerals, and the description will be mainly given to different parts.

In the film forming apparatus 78 shown in FIG. 7, the long base material 10 is conveyed in the longitudinal direction (arrow x direction in the drawing) by the transfer roller 80 and the transfer roller 82. A pair of transport rollers may be used instead of the transport rollers.
The casing 70A of the film forming portion 54A is a rectangular housing with an open lower surface. Further, the vibration device 74 is arranged below the base material 10 so as to sandwich the base material 10 together with the casing 70A. The casing 70A is provided between the transport roller 80 and the transport roller 82 in the transport direction of the base material 10. Therefore, in the film forming apparatus 78, the transfer roller 80 and the transfer roller 82 serve as supporting means for the base material 10.

In the film forming apparatus 78, the base material 10 having a repellent pattern is supplied with aerosol A as it passes under the casing 70A while being conveyed in the longitudinal direction by the transfer roller 80 and the transfer roller 82. Be filmed.
Preferably, the substrate 10 is vibrated by a vibrating device 74 located below the casing 70A. As a result, it is possible to form a patterned film with higher accuracy, and it is possible to improve the film forming speed.
In RtoR, as the vibrating device 74, a blowing means for blowing air to the base material 10 to vibrate and a means for irradiating the base material 10 such as a speaker with sound waves to vibrate can be preferably used as described above. That's right. Further, the base material 10 may be vibrated by vibrating the transport roller 80 and / or the transport roller 82 which are the supporting means.

As described above, it is preferable that the vibration of the base material 10 is 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 vibrating apparatus 74 vibrates the base material 10 from the upstream side of the casing 70A, and specifically, the transfer roller 80 on the upstream side. It is preferable to vibrate the base material 10 from immediately downstream.

As described above, in the film forming method of the present invention, a film is formed on the base material 10 having a repellent pattern by patterning with an aerosol deposition.
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 subjected to 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 weekly surface is provided upstream of the film forming apparatus 78 (casing 70A), and further upstream of the roller pressing plate 14R. Is provided with a particle layer forming means 86 for forming the particle layer 12. As an example, the particle layer forming means 86 includes a coating means for applying a coating liquid for forming a particle layer 12 to a base material 10, a drying means for drying the coating liquid applied to the base material 10, and a binder for a coating film. Has effective means of curing.
At this time, while transporting the base material 10 in the longitudinal direction (arrow x direction), first, the coating liquid containing the binder and the particles 12a is applied by the particle layer forming means 86, and then the solvent of the coating liquid is applied. Is further dried, and the binder is further cured by UV irradiation or the like to form a particle layer 12 on the surface of the base material 10.
Next, while transporting the base material 10 in the longitudinal direction, the convex portion 14Rb of the roller pressing plate 14R is pressed against the base material 10, and the particles 12a of the particle layer 12 are crushed by the convex portion 14Rb. As a result, a repellent pattern is formed on the surface of the base material 10 having a liquid repellent region 10a corresponding to the concave portion 14Ra and a parent liquid region 10b in which the particles 12a are pressed by the convex portion 14Rb.
Then, while transporting the base material 10, a film is formed on the base material 10 on which such a repulsion pattern is formed by a film forming apparatus 78 that performs the film forming method of the present invention. As a result, the aerosol A can be patterned and adhered only to the parent liquid region, and the film-forming material can be patterned and formed.

In the manufacturing method as shown in FIG. 8, a transport means such as a belt conveyor and a roller conveyor is used, and a single-wafer type (cut sheet-like) base material 10 having a repellent pattern as shown in FIG. 1 is used. , A plurality of sheets are arranged in the transport direction, and while being transported by the transport means, the particle layer 12 is sequentially formed on the substrate 10 to be transported by the particle layer forming means 86, and the repellent is repelled by the roller pressing plate 14R. It can also be used in a manufacturing method in which a pattern is formed and a film is formed by a film forming apparatus 78 that performs the film forming method of the present invention.

Further, the treatment by RtoR as shown in FIG. 8 can also be used when only the pattern forming method of the present invention is carried out.
As an example, in the apparatus shown in FIG. 8, the particle layer forming means 86 and the roller pressing plate 14R are provided without the film forming apparatus 78, and the particle layer forming means is conveyed while the base material 10 is conveyed in the longitudinal direction. The formation of the particle layer 12 by 86 and the formation of the repulsion pattern by crushing the particles 12a of the particle layer 12 by the roller pressing plate 14R may be performed by RtoR.

Although the pattern forming method, the film forming method and the sheet-like material of the present invention have been described in detail above, the present invention is not limited to the above-mentioned examples, and various improvements and modifications are made without departing from the gist of the present invention. Of course, you may do.

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

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

<Press plate B>
A pressing plate B having rectangular irregularities (see FIG. 1) on the surface was prepared.
The pressing plate B has a concave-convex shape in which rectangular concave portions and convex portions are alternately formed in a cross section in the uneven arrangement direction. The length of the concave portion in the arrangement direction of the unevenness was 5 μm, the length of the convex portion was 15 μm, and the formation pitch of the unevenness was 20 μm. The height of the convex portion, that is, the depth of the concave portion was set to 2 μm.
The concave portion is long in the direction orthogonal to the arrangement direction of the unevenness (method perpendicular to the paper surface in FIG. 1). That is, this uneven shape is a concave-convex shape such as line and space.

<Preparation of coating liquid A>
285.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was diluted with 175.0 g of methyl isobutyl ketone. Further, 15.0 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) was added, and the mixture was mixed and stirred.
Subsequently, 60.0 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred with an air disper for 120 minutes to completely dissolve the solute.
Further, 240 g of a 40% methyl isobutyl ketone dispersion of hollow silica particles (Sirinax, manufactured by Nittetsu Mining Co., Ltd.) having an average particle size of 105 nm dispersed by a polytron disperser at 10000 rpm for 20 minutes was added to this solution. Then, 112.5 g of methyl ethyl ketone and 112.5 g of propylene glycol were added, and the mixture was stirred with an air disper for 10 minutes.
The dispersion liquid in which the hollow silica particles were dispersed was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating liquid A.

<Formation of particle layer A>
As a base material, a triacetyl cellulose film (manufactured by Fujifilm, TAC-TD80U) having a thickness of 80 μm and a width of 300 mm was facilitated.
The coating liquid A was applied to this substrate using a slot die coater so as to have a concentration of 5.2 g / m ^2, and dried at 30 ° C. for 30 seconds and at 90 ° C. for 40 seconds. After drying, the coating layer was cured by irradiating with ultraviolet rays 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 base material.
The base material on which the particle layer A was formed had a surface roughness Ra of 0.15 μm and Sm of 3 μm. Further, when water was dropped on the base material on which the particle layer A was formed, the contact angle was 120 °, and it was confirmed that the particle layer A had liquid repellency. The surface shape was measured by Surfcom manufactured by Tokyo Seimitsu Co., Ltd., and the contact angle was measured by Drop Master 700 manufactured by Kyowa Surface Chemistry Co., Ltd.

[Example 1]
The base material on which the particle layer A was formed was cut out to a size of 50 × 50 mm.
The pressing plate A is brought into contact with the formed surface of the particle layer A of the cut-out base material with the concave portion forming surface facing, ^{and pressed under the conditions of a pressure of 3 kg / cm 2} and a temperature of 120 ° C. to press the particles of the particle layer A. It was crushed to form a repellent pattern.

The particle layer A on which the pressing plate A was pressed was observed with a field emission scanning electron microscope (FE-SEM). As a result, the particles were completely crushed at the portion corresponding to the leg (inclined surface of the recess) inclined with respect to the concave portion forming surface of the pressing plate A. The particles were completely left on the upper bottom of the trapezoid of the pressing plate A and the portion corresponding to the leg perpendicular to the concave portion forming surface.
Since the unevenness of the pressing plate A is fine, the contact angle of water in the parent liquid region and the liquid repellent region formed by the unevenness of the pressing plate A cannot be measured.
Instead, the 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 trapezoidal upper bottom of the pressing plate A and the portion corresponding to the leg perpendicular to the concave portion forming surface, and the portion corresponding to the leg inclined with respect to the concave portion forming surface of the pressing plate A is formed. The ink was collectively attached.
From this result, the particles of the particle layer A are crushed and liquefied in the portion corresponding to the leg (inclined surface of the recess) inclined with respect to the concave portion forming surface of the pressing plate A, and the trapezoidal upper bottom of the pressing plate A is formed. It was found that the portion corresponding to the leg perpendicular to the concave portion forming surface maintained the liquid repellency of the particle layer A without crushing the particles, and a repellent pattern was formed. In the region corresponding to the leg inclined with respect to the concave portion forming surface, the particles are crushed by the pressing plate A to flatten the height and roughness of the unevenness of the particles, and the pitch and spacing of the unevenness of the fine particles. It is considered that the particles became wider and the liquid repellency was lost.

A raw material liquid (parent liquid 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 liquid was measured according to JIS Z 8804: 2012. The surface tension of the raw material liquid was measured by the suspension method (pendant drop method).
In addition, in order to facilitate observation, the raw material liquid contained Blue No. 1 as a dye.
――――――――――――――――――――――――――――――――――――
・ Water 25.05g
・ Glycerin 4.65g
・ Diethylene glycol 3g
・ Orfin (manufactured by Nisshin Chemical Industry Co., Ltd., E1010) 0.03g
・ Blue No. 1 0.27g
――――――――――――――――――――――――――――――――――――

The base material on which the repellent pattern is formed is placed on the support of the film forming portion of the film forming apparatus as shown in FIG. 6 with the repellent pattern forming surface facing up, and the film is formed by aerosol deposition. It was.
As the vibrating device of the film forming section, LW139.141-75 manufactured by Air Brown Co., Ltd. was used. With this vibration exciter, the base material (support) was vibrated at a frequency of 500 Hz and a vibration speed of 2 mm / sec.
After starting the vibration of the base material, the ultrasonic vibrator of the aerosol generation unit was vibrated at 500 kHz to start the aerosolization of the raw material liquid. As the ultrasonic vibrator, IM4-36D manufactured by Seikou Giken Co., Ltd. was used.

The generated aerosol was conveyed from the raw material container to the film forming chamber via an induction pipe using air as a carrier gas. The flow velocity of the carrier gas was 2.8 × 10 ^-3 m ³ / min.
Under such conditions, an aerosol was supplied to the base material for 60 seconds to form a film.
The particle size of the aerosol was calculated by the above formula (D = 0.68 [(π * σ) / (ρ * f ² )] ^{1/2) and found to be 5.5 μm.}

After the film formation was completed, the base material was taken out from the aerosol supply unit, dried, and then the film formation surface was observed with a microscope.
As a result, the adhesion of Blue No. 1 was not confirmed in the liquid-repellent region detected by the confirmation of the above-mentioned repellent pattern, and only the parent-liquid region in which the particles were crushed corresponding to the inclined surface of the pressing plate A. Adhesion of Blue No. 1 was confirmed on the surface, and a good pattern was formed.

[Example 2]
The base material on which the particle layer A was formed was cut out to a size of 50 × 50 mm.
The pressing plate B was pressed against the formed surface of the particle layer A of the cut-out base material with the concave portion forming surface facing. The pressing conditions were the same as in Example 1.

After pressing, it was confirmed by FE-SEM in the same manner as in Example 1. As a result, the particles were completely crushed in the portion corresponding to the convex portion of the pressing plate B. The particles were completely left in the portion of the pressing plate B corresponding to the concave portion.
Further, as in Example 1, when water-based ink was dropped on the surface pressed by the pressing plate B and observed with an optical microscope, there was no ink in the region corresponding to the concave portion of the pressing plate B, and the convex of the pressing plate B. Ink was collectively adhered to the region corresponding to the portion.
From this result, the particles of the particle layer are crushed and made into a liquid in the portion corresponding to the convex portion of the pressing plate B, and the portion corresponding to the concave portion of the pressing plate B is the liquid repellent possessed by the particle layer without being crushed. It was found that the sex was maintained and a repellent 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, the height and roughness of the unevenness of the particles are flattened, and the pitch and spacing of the unevenness of the fine particles are flattened. It is considered that the particles became wider and the liquid repellency was lost.

A film was formed by aerosol deposition on the base material on which the repulsion pattern was formed in this manner in the same manner as in Example 1.
As a result, the adhesion of Blue No. 1 was not confirmed in the liquid-repellent region detected by the above-mentioned confirmation of the repellent pattern, and the particles were crushed parents corresponding to the legs inclined with respect to the concave portion forming surface. Adhesion of Blue No. 1 was confirmed only in the liquid region, and a good pattern could be formed.

<Preparation of coating liquid B>
285.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was diluted with 175.0 g of methyl isobutyl ketone. Further, 15.0 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) was added, and the mixture was mixed and stirred.
Subsequently, 60.0 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred with an air disper for 120 minutes to completely dissolve the solute.
Further, 240 g of a 60% methyl isobutyl ketone dispersion of solid silica particles (AEROSIL50 manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of 30 nm dispersed by a polytron disperser at 10000 rpm for 20 minutes was added to this solution. Then, 112.5 g of methyl ethyl ketone and 112.5 g of propylene glycol were added, and the mixture was stirred with an air disper for 10 minutes.
The dispersion liquid in which the solid silica particles were dispersed was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating liquid B.

<Formation of particle layer B>
As a base material, 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 liquid B was applied to this substrate using a slot die coater so as to have a concentration of 4.2 g / m ^2, and dried at 30 ° C. for 30 seconds and at 90 ° C. for 40 seconds. After drying, the coating layer was cured by irradiating with ultraviolet rays of 160 W / cm ² under a nitrogen purge to form a particle layer B having a thickness of 1.4 μm on the surface of the base material.
The base material on which the particle layer B was formed had a surface roughness Ra of 0.11 μm and Sm of 1 μm. Further, when water was dropped on the base material on which the particle layer B was formed, it was confirmed that the contact angle was 130 ° and that the particle layer B had liquid repellency. The surface shape was measured by Surfcom manufactured by Tokyo Seimitsu Co., Ltd., and the contact angle was measured by Drop Master 700 manufactured by Kyowa Surface Chemistry Co., Ltd.

[Example 3]
The base material on which the particle layer B was formed was cut out to a size of 50 × 50 mm.
The pressing plate A was pressed against the base material having the cut out particle layer B with the concave portion forming surface facing. The pressing conditions were the same as in Example 1.

The particle layer B on 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 (inclined surface of the recess) inclined with respect to the concave portion forming surface of the pressing plate A, most of the particles were crushed, but there was also a portion where the particles remained without being crushed. It was scattered. Since the fine particles were not hollow, it is probable that some crushing defects occurred. The particles were completely left in the region corresponding to the trapezoidal upper base of the pressing plate A and the legs perpendicular to the concave portion forming surface.
Further, as in Example 1, when water-based ink was dropped and confirmed with an optical microscope, there was no ink in the upper bottom of the trapezoidal cross section of the pressing plate A and the portion corresponding to the leg perpendicular to the concave portion forming surface. Ink was collectively adhered to the portion of the pressing plate A corresponding to the leg inclined with respect to the concave portion forming surface. From this result, it can be determined that the surface of the base material acts as a repellent pattern.

A film was formed by aerosol deposition on the base material on which the repulsion pattern was formed in this manner in the same manner as in Example 1.
As a result, although the film formation pattern was slightly disturbed, the adhesion of Blue No. 1 was not confirmed in the liquid-repellent region detected by the above-mentioned confirmation of the repellent pattern, and it corresponded to the inclined surface of the pressing plate A. Adhesion of Blue No. 1 was confirmed only in the parent liquid region where the particles were crushed, and a good pattern could be formed.

[Example 4]
The base material on which the particle layer B was formed was cut out to a size of 50 × 50 mm.
The pressing plate B was pressed against the base material having the cut out particle layer B with the concave portion forming surface facing. The pressing conditions were the same as in Example 1.

After pressing, it was confirmed by FE-SEM in the same manner as in Example 1. As a result, in the region corresponding to the convex portion of the pressing plate B, most of the particles were crushed, but some parts where the particles were not crushed were found. Since the fine particles were not hollow, it is probable that some crushing defects occurred. The particles were completely left in the portion of the pressing plate B corresponding to the concave portion.
Further, as in Example 1, when water-based ink was dropped and confirmed with an optical microscope, there was no ink in the portion corresponding to the concave portion of the pressing plate B, and the portion corresponding to the convex portion of the pressing plate B was not covered. , Ink was collectively attached. From the result, it can be judged that the surface of the base material acts as a repellent pattern.

A film was formed by aerosol deposition on the base material on which the repulsion pattern was formed in this manner in the same manner as in Example 1.
As a result, although the film formation pattern was slightly disturbed, the adhesion of Blue No. 1 was not confirmed in the liquid-repellent region detected by the above-mentioned confirmation of the repellent pattern, and it corresponded to the inclined surface of the pressing plate B. Adhesion of Blue No. 1 was confirmed only in the parent liquid region where the particles were crushed, and a good pattern could be formed.
The results are shown in the table below.

As shown in Table 1, according to the present invention, the desired repellent pattern can be formed and the desired pattern can be formed by the unevenness of the pressing plate.
In Examples 3 and 4 in which solid particles were used in the particle layer, some irregularities were observed in the film formation pattern, but there was no problem in terms of quality.

For example, it can be suitably used for manufacturing optical elements, semiconductor devices, electric devices, solar cells, and the like.

10 Base material 10a Liquid repellent area 10b Parent liquid area 12 Particle layer 12a Particles 14, 18, 20 Press plate 14a, 18a Concave 14b Convex part 14R Roller press plate 50, 78 Film forming device 52 Aerosol generation part 54, 54A 56 Induction pipe 58 Raw material container 60 Container 62 Ultrasonic transducer 64 Gas supply means 64a Gas supply pipe 70, 70A Casing 72 Support 74 Vibration device 80, 82 Conveyor roller 86 Particle layer forming means A Aerosol L Raw material liquid W Water

Claims (13)

A particle layer containing particles having a particle size of 10 to 200 nm is formed on the surface of the base material, a pressing plate having irregularities is pressed against the particle layer, and a part of the particles in the particle layer is pressed by the pressing plate. A pattern forming method characterized by forming a liquid-repellent region that is lipophilic to a target liquid and a liquid-repellent region that is liquid-repellent to the target liquid by crushing. The pattern forming method according to claim 1, wherein the particles are hollow particles. The pattern forming method according to claim 1 or 2, wherein the particle layer is molded into irregularities by pressing with the pressing plate. Claims 1 to 3 wherein the pressing plate has a plurality of recesses arranged in at least one direction, and the recesses have an inclined surface inclined in the arrangement direction with respect to the concave portion forming surface of the pressing plate. The pattern forming method according to any one item. The pattern forming method according to claim 4, wherein the recesses of the pressing plate have a quadrangular shape in a cross section in the arrangement direction of the recesses. The pattern forming method according to claim 5, wherein the recesses of the pressing plate are trapezoidal in a cross section in the arrangement direction of the recesses. The pattern forming method according to any one of claims 1 to 6, wherein the surface of the base material is liquefied before the particle layer is formed on the surface of the base material. The pattern formation according to any one of claims 1 to 7, wherein the base material is in the form of a sheet, and the parent liquid region and the liquid repellent region are formed on at least one surface of the sheet-like base material. Method. The raw material liquid containing the film-forming material is made into an aerosol,
A film forming method for supplying the aerosol to the parent liquid region and the liquid repellent region formed by the pattern forming method according to any one of claims 1 to 8. The film forming method according to claim 9, wherein the aerosol is supplied to the parent liquid region and the liquid repellent region while vibrating the base material. The film forming method according to claim 9 or 10, wherein the aerosol is supplied to the parent liquid region and the liquid repellent region while heating the base material. It has a plurality of protrusions arranged in at least one direction on at least one surface, and has a plurality of protrusions.
The convex portion has a plane inclined with respect to the arrangement direction and a plane continuous with the plane.
The plane of the convex portion is liquid-friendly with respect to the target liquid, and the surface of the convex portion continuous with the plane has liquid repellency due to unevenness due to particles having a particle size of 10 to 200 nm. A sheet-like material characterized by this. The sheet-like material according to claim 12, further comprising a film on the surface of the liquid-forming surface.

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