WO2015183008A1 - Coating method using particle alignment - Google Patents

Abstract

The present invention relates to a coating method using particle alignment, capable of coating, at a high density, a plurality of fine particles in a single layer by using particle alignment. The coating method using particle alignment, according to the present invention, comprises the steps of: (a) preparing a tight adhesion-type polymer substrate; (b) forming a coating film by coating while forming, on the surface of the tight adhesion-type substrate, a plurality of concave parts which respectively correspond to each of the plurality of particles, by applying pressure to the plurality of particles; (c) expanding the coating film by extending the tight adhesion-type polymer substrate on which the coating film has been formed to increase the gap between the plurality of particles coated on the tight adhesion-type polymer substrate; and (d) transferring the expanded coating film on a transfer substrate having greater adhesive force than the tight adhesion-type polymer substrate.

Description

Coating Method Using Particle Alignment

The present invention relates to a coating method using particle alignment, and more particularly, to a coating method using particle alignment capable of coating a plurality of fine particles at a single layer level at high density using particle alignment.

There is a need in the art for a technique of arranging and coating nanoparticle-level or micrometer-level fine particles on a substrate. In one example, such coating techniques include memory devices, linear and nonlinear optical devices, photovoltaic devices, photo masks, deposition masks, chemical sensors, biochemical sensors, sensors for medical molecular detection, dye-sensitized solar cells, thin film solar cells, cell culture, It can be applied to the implant surface and the like.

The Langmuir-Blodgett (LB) method (hereinafter referred to as "LB method") is well known as a technique for aligning and coating fine particles on a substrate. In the LB method, a solution in which fine particles are dispersed in a solvent is floated on the surface of the water and then compressed by a physical method to form a thin film. The technique using this LB method is disclosed in Korean Patent Publication No. 10-2006-2146.

However, in the LB method, temperature, humidity, and the like must be precisely controlled so that particles can be self-assembled in a solvent. It may also affect particle migration by the surface properties (eg, hydrophobicity, charge properties, surface roughness) of the particles on the substrate. As a result, the particles may aggregate together and may not be evenly applied on the substrate. That is, there may be many areas where the particles are not applied, and where the aggregated particles meet each other, grain boundaries may be formed and many defects may be located.

The present invention is to solve the problems of the prior art as described above, an object of the present invention is to provide a coating method using a particle alignment that can be evenly applied particles on a substrate by a simple method.

Another object of the present invention is to provide a coating method using particle alignment which can form a coating film in which a plurality of particles are aligned in a predetermined pattern by a simple method.

Still another object of the present invention is to provide a coating method using particle alignment which can form a coating film in which heterogeneous particles are aligned in a predetermined pattern by a simple method.

Coating method using a particle alignment according to an aspect of the present invention for achieving the above object, (a) preparing an adhesive polymer substrate; (b) applying a plurality of particles onto the adhesive polymer substrate to form a coating layer by coating the plurality of recesses corresponding to the plurality of particles on the surface of the adhesive polymer substrate; And (c) extending the coating film by increasing a distance between the particles of the adhesive polymer substrate on which the coating film is formed.

Coating method using a particle alignment in accordance with another aspect of the present invention for achieving the above object, (a) preparing an adhesive polymer substrate; (b) applying a plurality of particles onto the adhesive polymer substrate to form a coating layer by coating the plurality of recesses corresponding to the plurality of particles on the surface of the adhesive polymer substrate; (c) the adhesive force of the exposed part irradiated with the light on the surface of the adhesive polymer substrate by partially irradiating the coating film on the surface of the adhesive polymer substrate by irradiating light toward the adhesive polymer substrate with the mask having the mask pattern formed thereon; Changing the; (d) the degree of impregnation of the particles and the particles disposed in the non-exposed or exposed portions of the plurality of particles forming the coating film using the difference in adhesion between the irradiated and unirradiated portions of the adhesive polymer substrate; Removing from the adhesive polymer substrate by using an adhesive force of the removal member; And (e) extending the coating film by increasing a distance between the particles of the adhesive polymer substrate on which the coating film is formed.

Coating method using a particle alignment according to another aspect of the present invention for achieving the above object, (a) preparing an adhesive polymer substrate; (b) applying a plurality of first particles to the adhesive polymer substrate to apply a pressure to form a first coating layer on the surface of the adhesive polymer substrate while forming a plurality of first recesses corresponding to the plurality of first particles, respectively; step; (c) exposure to which the light on the surface of the adhesive polymer substrate is irradiated by partially exposing a region where the primary coating layer is formed on the surface of the adhesive polymer substrate by irradiating light toward the adhesive polymer substrate with a mask having a mask pattern formed thereon; Changing the adhesion of the negatives; (d) first particles disposed in the non-exposed part or the exposed part of the plurality of first particles forming the coating film by using a difference in adhesion between the irradiated and unirradiated portions of the adhesive polymer substrate; Removing from the adhesive polymer substrate by using the degree of impregnation and the degree of adhesion of the particle removing member; (e) applying a plurality of second particles to a place where the first particles of the adhesive polymer substrate are removed, and coating a plurality of second recesses corresponding to the plurality of second particles to form a second coating layer. Forming; (f) extending the primary coating film and the secondary coating film by increasing a distance between the particles of the adhesive polymer substrate on which the primary coating film and the secondary coating film are formed; And (g) transferring at least one of the extended primary coating layer and the secondary coating layer to the transfer substrate through a difference in adhesion between the non-exposed portion and the exposed portion of the adhesive polymer substrate.

Coating method using a particle alignment according to another aspect of the present invention for achieving the above object, (a) preparing an adhesive polymer substrate; (b) changing the adhesion of the exposed part to which the light on the surface of the adhesive polymer substrate is irradiated by applying light toward the adhesive polymer substrate with the mask on which the mask pattern is formed; (c) forming a primary coating film by coating a plurality of first particles on the adhesive polymer substrate; (d) first particles disposed in the non-exposed portion or the exposed portion of the plurality of first particles forming the primary coating layer by using a difference in adhesion between the irradiated and unirradiated portions of the adhesive polymer substrate; Removing from the adhesive polymer substrate by using the degree of impregnation of the particles and the degree of adhesion of the particle removing member; (e) applying a plurality of second particles to a place where the first particles of the adhesive polymer substrate are removed, and coating a plurality of second recesses corresponding to the plurality of second particles to form a second coating layer. Forming; (f) extending the primary coating layer and the secondary coating layer by increasing the distance between the particles of the adhesive polymer substrate on which the primary coating layer and the secondary coating layer are formed; And (g) transferring at least one of the extended primary coating layer and the secondary coating layer to the transfer substrate through a difference in adhesion between the non-exposed portion and the exposed portion of the adhesive polymer substrate.

Coating method using a particle alignment according to another aspect of the present invention for achieving the above object, (a) preparing an adhesive polymer substrate; (b) applying a plurality of first particles to the adhesive polymer substrate by applying pressure to form a plurality of first recesses respectively corresponding to the plurality of first particles on the surface of the adhesive polymer substrate; (c) extending the coating film by increasing a distance between the first particles of the adhesive polymer substrate on which the coating film is formed; (d) irradiating light to the adhesive polymer substrate to expose the adhesive polymer substrate, thereby increasing the bonding force between the adhesive polymer substrate and the plurality of first particles; (e) applying a plurality of second particles to a region between the plurality of first particles on the surface of the adhesive polymer substrate, wherein the plurality of second recesses respectively correspond to the plurality of second particles on the surface of the adhesive polymer substrate; Coating to form an addition; And (f) transferring at least one of the first particles and the second particles to the transfer substrate through a difference in adhesion and impregnation of the first particles and the second particles of the adhesive polymer substrate.

In the coating method using the particle alignment according to the present invention, a coating film is formed by applying pressure on the adhesive polymer substrate to dry particles without using a solvent or an adhesion aid. In this process, when the particles come into contact with the adhesive polymer substrate, the surface of the flexible adhesive polymer substrate having flexibility is deformed to surround a part of the particles under the influence of the surface tension. As a result, recesses corresponding to the particles are formed on the surface of the adhesive polymer substrate, thereby improving bonding properties. The reversible nature of the shape deformation of the adhesive polymer substrate surface facilitates two-dimensional movement of the particles in contact on the substrate so that the particle distribution can be easily rearranged.

Enhancement of particle adhesion through such shape modification lowers the dependence of the particle surface properties and the type of the polymer substrate so that particles of various surface properties can be coated in a single layer. Therefore, it is not necessary to control the environment such as temperature, humidity, and particle concentration required for self-assembly and spin coating when forming a coating film as in the prior art, and to easily coat particles having various surface properties in a wide range of environments and conditions. Can be. In addition, even when the particles exhibit a charge or easy hydrogen bonding, a single layer particle coating may be uniformly performed at a high density even when the materials are non-chargeable and hydrophobic.

As described above, according to the present exemplary embodiment, the particles are evenly distributed on the adhesive polymer substrate by a simple method, thereby easily forming a coating layer having a high density.

In addition, the coating method using the particle alignment according to the present invention forms a coating film by applying pressure in a state in which dry particles are in direct contact with the adhesive polymer substrate without using a solvent, and the adhesive polymer substrate is stretched to attach to the adhesive polymer substrate. By spreading the gaps between the plurality of particles, it is possible to form an expanded coating film made up of a plurality of particles spaced apart from each other. And the extended coating film can be used by transferring to another transfer substrate.

In addition, the coating method using the particle alignment according to the present invention by using a mask to partially irradiate light on the adhesive polymer substrate to change the adhesion of the exposed portion of the light irradiation, using the degree of impregnation of the particles and the adhesion of the particle removal member By partially removing the particles, coating films of various patterns can be easily formed.

In addition, the coating method using the particle alignment according to the present invention comprises the steps of partially increasing the adhesion of the adhesive polymer substrate by exposing the adhesive polymer substrate using a mask, partially removing the particles of the adhesive polymer substrate, and new particles By repeatedly coating, increasing the adhesive polymer substrate, transferring the particles, and the like, it is possible to easily form various coating films in which various kinds of particles are arranged in a specific pattern on the adhesive polymer substrate.

1A to 1G show step by step a coating method using particle alignment according to an embodiment of the present invention.

2a to 2i show step by step a coating method using particle alignment according to another embodiment of the present invention.

Figure 3 shows another embodiment in which a coating film is formed on a transfer substrate by using a coating method using particle alignment according to the present invention.

Figure 4 shows another embodiment of forming a secondary coating film on the adhesive polymer substrate in the coating method using the particle alignment according to the present invention.

5a to 5d show step by step another embodiment of forming a coating film of a predetermined pattern on the adhesive polymer substrate in the coating method using the particle alignment according to the present invention.

6A-6D illustrate some steps of a coating method using particle alignment according to another embodiment of the present invention.

7 is a photograph schematically showing an apparatus for increasing a PDMS substrate in Experimental Example 1 of the present invention.

8 is a scanning electron microscope (SEM) measurement result for comparing the coating film stretched and the non-stretched coating film in Experimental Example 1 of the present invention.

9 is a SEM photograph for comparing the coating film stretched and the non-stretched coating film in Experimental Example 1 of the present invention.

FIG. 10 is a scanning electron microscope (SEM) measurement result for comparing the increased coating film and the unexpanded coating film in Experimental Example 2 of the present invention.

11 is a SEM photograph for comparing the coating film stretched and the non-stretched coating film in Experimental Example 2 of the present invention.

<Explanation of reference numerals>

10: adhesive polymer substrate 12, 17: first, second recessed portion

14 exposure part 15 non-exposure part

20, 24: particles 22, 25, 27: coating film

30: clamp 32: support

35, 45, 49, 53: transfer substrate 40, 50: mask

Hereinafter, with reference to the accompanying drawings, it will be described in detail with respect to the coating method using the particle alignment according to the present invention.

In describing the present invention, the size or shape of the components shown in the drawings may be exaggerated or simplified for clarity and convenience of description. In addition, terms that are specifically defined in consideration of the configuration and operation of the present invention may vary depending on the intention or custom of the user or operator. These terms should be interpreted as meanings and concepts corresponding to the technical spirit of the present invention based on the contents throughout the specification.

Figure 1a to 1g is a step-by-step showing the coating method using a particle alignment according to an embodiment of the present invention, with reference to Figures 1a to 1g in detail the coating method using a particle alignment according to an embodiment of the present invention. The explanation is as follows.

First, as shown in FIG. 1A, an adhesive polymer substrate 10 having a smooth surface is prepared. The surface of the adhesive polymer substrate 10 may have a state in which a specific pattern or curve is not formed, and does not restrict the movement of the particles 20 (see FIG. 1C) forming the coating layer 22 (see FIG. 1C) thereon. Level of surface roughness and structure. In addition, the adhesive polymer substrate 10 has a property that can be increased by the pulling force or the like.

In this embodiment, the adhesive polymer substrate 10 includes various adhesive polymer materials in which adhesion is present. Adhesive polymers are generally distinguished from adhesives because they do not have commonly used adhesive properties. At least the adhesive polymer has an adhesive force lower than about 0.6 kg / inch of the adhesive force of the Scotch Magic Tape (ASTM D 3330 evaluation). In addition, the adhesive polymer can maintain the shape of a solid state (substrate or film) at room temperature without a separate support.

The adhesive polymer material may be a silicone-based polymer material such as polydimethylsiloxane (PDMS), or a polymer for wrap, adhesion or sealing, including polyethylene (PE) or polyvinyl chloride (PVC). A protective film containing a substance, a film having a gloss easily deformable in surface shape, and the like can be used. In particular, as the adhesive polymer, PDMS, which is easily controlled in hardness and easily manufactured in various forms, may be used. The polymer substrate 10 may be manufactured by coating an adhesive polymer on a base substrate or by attaching an adhesive polymer in a sheet or film form.

In the present embodiment, the surface of the adhesive polymer substrate 10 may be provided with a pattern of a three-dimensional three-dimensional structure.

Here, the adhesive polymer material generally refers to an organic polymer material including silicon in a solid state or endowed with adhesion properties through plasticizer addition or surface treatment. Here, the adhesive polymer material is generally characterized by having a low surface tension and easy deformation of the form by the linear molecular structure. The excellent adhesion of such an adhesive polymer material is due to the soft (flexible) surface material and low surface tension and the like that the surface deformation in the fine region is easy. The low surface tension of the adhesive polymer material has the property of broadly adhering to the particles 20 and 24 to be attached (similar to the solution wetting phenomenon), and the flexible surface is the particles 20 and 24 to be attached. Make sure there is a tight contact with the. This results in an adhesive polymer that is easily removable on a solid surface without complementary bonding strength.

The surface tension of silicon-based polymer materials such as PDMS, a typical adhesive polymer material, is about 20 to 23 dynes / cm, close to Teflon (18 dynes / cm), which is known as the lowest surface tension material. The surface tension of silicon-based polymers such as PDMS is most organic polymers (35-50 dynes / cm), natural materials (綿, 73 dynes / cm), metals (eg silver (Ag, 890 dynes /) cm), aluminum (Al, 500 dynes / cm)), inorganic oxides (eg, glass (1000 dynes / cm), iron oxide (1357 dynes / cm). Even in wraps, a large amount of plasticizer is added to improve adhesion, resulting in low surface tension.

Subsequently, after preparing the adhesive polymer substrate 10 as described above, as shown in FIGS. 1B and 1C, the plurality of particles 20 are aligned to form the coating film 22 on the adhesive polymer substrate 10. do. This will be described in more detail as follows.

First, as shown in FIG. 1B, the plurality of particles 20 dried on the adhesive polymer substrate 10 is placed. Unlike the present embodiment, the particles dispersed in the solution are difficult to make direct contact with the adhesive polymer surface, so that the coating is not well made. Therefore, only a small amount of a solution or a volatile solvent less than the mass of the particles to be used may dry the particles during the coating operation to allow the coating operation.

In the present embodiment, the particles 20 may include various materials for forming the coating layer 22. That is, the particles 20 may include a polymer, an inorganic material, a metal, a magnetic material, a semiconductor, a biological material, and the like. In addition, a mixture of particles having different properties may be used as the particle 20.

Polymers that can be used as the particles 20 include polystyrene (PS), polymethyl methacrylate (PMMA), polyacrylate, polyvinyl chloride (PVC), polyalphastyrene, polybenzyl methacrylate, polyphenylmeta Acrylate, polydiphenyl methacrylate, polycyclohexyl methacrylate, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer and the like.

Inorganic materials that can be used as the particles 20 include silicon oxide (for example, SiO ₂ ), silver phosphate (for example, Ag ₃ PO ₄ ), titanium oxide (for example, TiO ₂ ), iron oxide (for example , Fe ₂ O ₃ ), zinc oxide, cerium oxide, tin oxide, thallium oxide, barium oxide, aluminum oxide, yttrium oxide, zirconium oxide, copper oxide, nickel oxide and the like.

Metals that can be used as the particles 20 include gold, silver, copper, iron, platinum, aluminum, platinum, zinc, cerium, thallium, barium, yttrium, zirconium, tin, titanium, or alloys thereof. .

Semiconductors that can be used as the particles 20 include silicon, germanium, or compound semiconductors (eg, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InP, InAs, InSb, etc.).

Biomaterials that can be used as the particles 20 include coatings on particles or surfaces of proteins, peptides, ribonucleic acid (RNA), deoxyribonucleic acid (DNA), polysaccharides, oligosaccharides, lipids, cells and complex materials thereof. Particles, and particles contained therein. For example, a polymer particle coated with an antibody binding protein called protein A may be used as the particle 20.

Particles 20 may have a symmetrical shape, asymmetrical shape, amorphous, porous shape. For example, the particles 20 may have a spherical shape, an ellipse shape, a hemispherical shape, a cube shape, a tetrahedron, a pentagonal surface, a hexahedron, an octahedron, a columnar shape, a horn shape, and the like. Among these, spherical or elliptical is preferable as the form of the particle 20 compared with other forms.

Such particles 20 preferably have an average particle diameter of 10 nm to 100. When the average particle diameter is less than 10 nm, it may be in the form of being entirely wrapped by the adhesive polymer substrate 10 during coating, it may be difficult to coat the particles 20 to a single layer level. In addition, when the average particle diameter of the particles 20 is less than 10 nm, the particles may agglomerate with each other even in a dry state, and it may be difficult for the particles to individually move only by a rubbing force. If the average particle diameter of the particles 20 exceeds 100, the adhesion of the particles may appear weak.

However, the present invention is not limited thereto, and the average particle diameter of the particles 20 may vary depending on a material constituting the particles 20 or a material constituting the adhesive polymer substrate 10. Here, when the particle 20 is spherical, the diameter of the particle 20 may be used as the particle diameter. On the other hand, when the particle 20 is not spherical, various measurement methods may be used. For example, average values of long and short axes may be used as particle diameters.

Subsequently, as shown in FIG. 1C, a pressure is applied on the plurality of particles 20 to form a coating film 22. As a method of applying pressure to the particles 20, a method of rubbing using a latex, a sponge, a hand, a rubber plate, a plastic plate, a material having a smooth surface, or the like may be used. However, the present invention is not limited thereto, and pressure may be applied to the particles 20 by various methods.

In this embodiment, when the particles 20 are placed on the surface of the adhesive polymer substrate 10 and then pressure is applied, the particles 20 in the pressure-applied portion are attached through the deformation of the adhesive polymer substrate 10. As a result, a plurality of recesses 12 corresponding to the particles 20 are formed in corresponding portions. Therefore, the particles 20 are aligned on the adhesive polymer substrate 10 in a state in which the particles 20 are wrapped in the recess 12.

The recess 12 is reversible as formed by the interaction between the particles and the substrate. That is, it may be extinguished and the position may be moved. For example, when the particles move in the rubbing process, the recesses 12 may disappear due to the elastic restoring force of the adhesive polymer substrate 10, or the positions of the recesses 12 may also be changed according to the movement of the particles 20. have. Due to this reversible action, the particles 20 can be evenly aligned ("reversible" here is a property generated by the flexibility and elastic restoring force of the surface of the adhesive polymer substrate during coating, so that the restoring force of the adhesive polymer substrate is changed over time). Broader meaning also includes weakening or extinction).

Particles 20 that are not bonded to the adhesive polymer substrate 10 are moved to an area where the particles 20 of the adhesive polymer substrate 10 are not coated by a rubbing force, and the like. The recessed part 12 is formed by the 20. In addition, the adhesive polymer substrate 10 and the particle 20 are bonded in the state in which the particle 20 is wrapped in the newly formed recess 12. Through this process, the coating film 22 having a single layer level is formed on the adhesive polymer substrate 10 at a high density.

Here, the concave portion 12 may have a shape corresponding to the outer shape of the particle 20 to surround a part of the particle 20. For example, when the particles 20 are spherical, the recesses 12 may also have a spherical shape, and a portion of the particles 20 may be in close contact with the recesses 12. The depth L1 of the recess 12 may vary depending on the hardness of the adhesive polymer substrate 10, the shape of the particles 20, the hardness, and environmental factors (eg, temperature). That is, as the hardness of the adhesive polymer substrate 10 increases, the depth L1 of the concave portion 12 may decrease, and as the temperature increases, the depth L1 of the concave portion 12 may increase.

It is preferable that the ratio (sedimentation rate) (L1 / D) of the depth L1 of the recessed part 12 with respect to the average particle diameter D of the particle | grain 20 is 0.02-0.98. When the ratio L1 / D is less than 0.02, the binding force between the particles 20 and the adhesive polymer substrate 10 may not be sufficient, and when the ratio L1 / D exceeds 0.98, the particles 20 may be coated at a monolayer level. It can be difficult. In consideration of the bonding force and coating properties, etc., the ratio (L1 / D) is more preferably 0.05 to 0.6, more specifically, 0.08 to 0.4.

As in the present embodiment, when a part of each particle 20 is wrapped by the concave portion 12 generated by the elastic deformation, the particle 20 and the adhesive polymer substrate 10 may be better bonded. . In addition, the particles 20 bonded to the adhesive polymer substrate 10 may also move to an uncoated portion of the surrounding, so that the new particles 20 may be partially disposed in the hollow recesses 12 on the surface of the adhesive polymer substrate 10. Can be accommodated. According to such rearrangement characteristics, the coating layer 22 may be coated at a single layer level at a high density. In one example, the particles 20 may be disposed such that each center has a hexagonal shape.

On the other hand, when the particle 20 is non-spherical (for example, Ag ₃ PO ₄ ) it can be determined whether the level is a monolayer by a variety of methods. For example, when the ratio of the average value of the thickness of the coating film 22 to the average particle diameter of the top 10% of the particles 20 (that is, particles having a particle diameter of less than 10%) is 1.9 or less, the coating is performed at a single layer level. You can see that.

After the coating film 22 is formed on the adhesive polymer substrate 10, as shown in FIGS. 1D and 1E, the adhesive polymer substrate 10 having the coating film 22 formed thereon is extended to extend its width. As shown in the drawing, the edges of the adhesive polymer substrate 10 are clamped by a plurality of clamps 30, and then the adhesive polymer substrate 10 is uniformly applied. Pulling in all directions can be used.

In the figure, the two clamps 30 are shown to extend by holding both edges of the adhesive polymer substrate 10. However, when the rectangular adhesive polymer substrate 10 is used, the adhesive polymer substrate 10 may be formed by four clamps 30. By holding the four edges of the), the adhesive polymer substrate 10 can be stretched. Of course, the shape of the adhesive polymer substrate 10 or the shape of increasing the adhesive polymer substrate 10 may vary depending on the spacing or alignment pattern between the plurality of particles 20 as a final target. For example, the adhesive polymer substrate 10 may be uniformly expanded in all directions, the adhesive polymer substrate 10 may be extended only in the longitudinal direction, or the adhesive polymer substrate 10 may be extended only in the width direction.

When the adhesive polymer substrate 10 on which the coating film 22 is formed is extended to expand the width thereof, as shown in FIG. 1E, as the gap between the plurality of particles 20 forming the coating film 22 increases, An expanded coating film 22 composed of a plurality of gaps 20 formed therebetween is formed. In this state, as illustrated in FIG. 1F, when the transfer substrate 35 having an adhesion greater than that of the adhesive polymer substrate 10 is brought into contact with the extended coating film 22 and detached, as shown in FIG. 1G, The expanded coating film 22 made up of the plurality of particles 20 which are separated from each other may be transferred to the transfer substrate 35.

As described above, in the coating method using the particle alignment according to the present invention, the coating film 22 is applied by applying pressure in a state in which the dry particles 20 are in direct contact with the adhesive polymer substrate 10 without using a solvent. And forming an adhesive polymer substrate 10 to expand the interval between the plurality of particles 20 attached to the adhesive polymer substrate 10, thereby expanding the coating film composed of the plurality of particles 20 which are spaced apart from each other. (22) can be formed. The extended coating film 22 may be transferred to another transfer substrate 35 and used.

Meanwhile, after transferring the plurality of particles 20 coated on the adhesive polymer substrate 10 to the transfer substrate 35, for example, the resin, the O ₂ plasma is irradiated to etch the remaining space except for the portion where the particles are transferred. As illustrated in FIG. 1H, a film (transfer film) of a Moth-Eye type may be manufactured.

In the coating method using the particle alignment according to the present invention, since the self-assembly of the particles in the solvent is not required when forming the coating film, it is not necessary to precisely control the temperature, humidity and the like and have a great influence on the surface properties of the particles. Do not receive. That is, the coating can be uniformly made at a high density not only when the particles are chargeable materials, but also when they are non-chargeable (ie, near charge neutral) materials. In addition, not only hydrophilic particles but also hydrophobic particles can be uniformly coated. As described above, according to the present invention, the particles 20 may be evenly distributed on the adhesive polymer substrate 10 by a simple method to form a coating layer 22 and an expanded coating layer 22 ′ having a high density. .

On the other hand, Figures 2a to 2i shows step by step the coating method using the particle alignment according to another embodiment of the present invention.

In the coating method using particle alignment according to another embodiment of the present invention, the adhesive polymer substrate 10 is prepared to form a primary coating layer 22 including a plurality of first particles 20 on the adhesive polymer substrate 10. The process of forming the primary coating film 22 is the same as the process of forming the coating film 22 made of a plurality of particles 20 on the adhesive polymer substrate 10 in a coating method using particle alignment.

After the primary coating layer 22 is formed on the adhesive polymer substrate 10, the surface of the adhesive polymer substrate 10 may be irradiated with light by applying a mask 40 on which the mask pattern 41 is formed, as shown in FIG. 2A. The region in which the primary coating film 22 is formed is partially exposed. Although the surface of the adhesive polymer substrate 10 is covered with the primary coating film 22 composed of the plurality of first particles 20, the irradiated light is exposed through the gap between the plurality of first particles 20. (10) can be reached and the adhesive polymer substrate 10 can be exposed. When the first particles 20 are made of a material that can transmit light, the irradiated light may pass through the first particles 20 to reach the adhesive polymer substrate 10. In this embodiment, the light includes visible light, ultraviolet light, and the like.

As such, when the mask 40 is disposed on the adhesive polymer substrate 10, light is irradiated onto the adhesive polymer substrate 10. As shown in FIG. 2B, the light on the surface of the adhesive polymer substrate 10 is irradiated. The adhesion of the exposed exposure portion 14 is greater than that of the non-exposed portion 15 that is not irradiated with light. This is because the solubility is poor and the thermal properties and the chemical resistance are significantly increased while the molecular weight is greatly increased by a reaction such as crosslinking or photodimerization by exposure upon exposure to the site. Therefore, the first particles 20 positioned in the exposed portion 14 may maintain a state of being attached to the adhesive polymer substrate 10 with a stronger bonding force than the first particles 20 disposed in the non-exposed portion 15.

For example, PDMS is known to damage the methyl portion of the chemical structure when exposed to UV light, and thus, reactive groups are temporarily formed in the polymer. Such functional groups have improved properties that can have adhesion with particles such as hydrogen bonds, compared to methyl groups, and chemical covalent bonds can be formed through dehydration condensation bonds.

Subsequently, as shown in FIG. 2C, the particle removing member 43 having the adhesion greater than the adhesion of the non-exposed portion 15 of the adhesive polymer substrate 10 and smaller than the adhesion of the exposed portion 14 may be formed using a primary coating film ( 22) Touch above and remove. In this case, as illustrated in FIG. 2D, the first particles 20 disposed in the non-exposed part 15 among the plurality of first particles 20 forming the primary coating layer 22 may have a particle removal member 43. Attached to and removed from the adhesive polymer substrate 10. As the particle removal member 43, a difference between polymer materials and adhesive strength, such as polydimethylsiloxane (PDMS), polyethylene (PE, PE), polyvinyl chloride (PVC), etc. Various kinds of materials such as scotch tapes having the same may be used. In addition, the particle removing member 43 may be a general adhesive tape having an adhesive force that does not damage the substrate coated with particles, or a rubber-like material such as PDMS having a lower hardness. Do.

On the other hand, in addition to the adhesion of the particle removal member 43, depending on the degree of impregnation of the particles to the adhesive polymer substrate 10 can also be partially removed.

As such, when the first particles 20 positioned in the non-exposed part 15 of the adhesive polymer substrate 10 are removed using the particle removing member 43, the exposed part 14 may be exposed to the adhesive polymer substrate 10. Only the first particles 20 positioned at are left, so that the first coating film 22 having a predetermined pattern is formed on the adhesive polymer substrate 10.

Subsequently, as shown in FIG. 2E, the first particles 20 and the other second particles 24 are coated on the surface of the adhesive polymer substrate 10 coated with the plurality of first particles 20. The method of coating the plurality of second particles 24 is the same as the method of coating the plurality of first particles 20 on the adhesive polymer substrate 10, and the specific method thereof is as follows.

First, a plurality of dried second particles 24 are placed on the adhesive polymer substrate 10 on which the primary coating layer 22 is formed. As the second particles 24, a polymer, an inorganic material, a metal, a magnetic material, a semiconductor, a biological material, or the like may be used, and the specific types thereof are the same as described above. Then, pressure is applied on the plurality of second particles 24 to coat the second particles 24 on the non-exposed part 15 where the first particles 20 are not disposed. The method of applying pressure to the second particles 24 is the same as the method used to coat the first particles 20 as described above, and includes latex, sponges, hands, rubber plates, plastic plates, materials having a smooth surface, and the like. A method of rubbing using may be used. The mechanism in which the plurality of second particles 24 are coated on the adhesive polymer substrate 10 is the same as that of the aforementioned first particles 20 is coated on the adhesive polymer substrate 10.

That is, when the second particles 24 are placed on the adhesive polymer substrate 10 and then pressure is applied, the second particles 24 in the portion to which the pressure is applied are attached through the deformation of the adhesive polymer substrate 10. A plurality of second recesses 17 corresponding to the second particles 24 are formed in corresponding portions of the polymer substrate 10. Accordingly, while the second particles 24 are aligned with the non-exposed portions 15 of the adhesive polymer substrate 10 while the second particles 24 are wrapped in the second recessed portions 17, the non-exposed portions 15 A secondary coating film 25 composed of a plurality of second particles 24 is formed. Of course, the second particles 24 may be aligned and coated on the adhesive polymer substrate 10 while the second particles 24 are partially accommodated in the empty first recesses 12 from which the first particles 20 are removed. have.

After the primary coating film 22 and the secondary coating film 25 are formed on the adhesive polymer substrate 10, as shown in FIGS. 2F and 2G, the primary coating film 22 and the secondary coating film 25 are formed. The adhesive polymer substrate 10 is formed to extend its width. The method of extending the width of the adhesive polymer substrate 10 is as described above.

When the adhesive polymer substrate 10 on which the primary coating film 22 is formed is extended to expand its width, the gap between the plurality of first particles 20 forming the primary coating film 22 as shown in FIG. 2G. And a plurality of second particles 24 forming the secondary coating film 25. On the adhesive polymer substrate 10, an expanded primary coating film 22 ′ composed of a plurality of first particles 20 spaced apart from each other, and an expansion made up of a plurality of second particles 24 spaced apart from each other. Secondary coating film 25 'is formed. In this state, as illustrated in FIG. 2H, the transfer substrate 45 having the adhesion greater than the adhesion of the non-exposed portion 15 of the adhesive polymer substrate 10 and less than the adhesion of the exposed portion 14 is expanded. When contacted and removed on the coating film 22 'and the expanded secondary coating film 25', the expanded coating film 25 'consisting of a plurality of second particles 24 spaced at regular intervals, as shown in FIG. 2I. ) Can be transferred to the transfer substrate 45.

As described above, in the coating method using the particle alignment according to another embodiment of the present invention, the adhesive polymer substrate 10 having the primary coating layer 22 formed through partial exposure and partial particle removal may be applied to the secondary coating layer 25. Can be used as a mold to form a. That is, as described above, after transferring the plurality of second particles 24 coated on the adhesive polymer substrate 10 to another transfer substrate 45, the external force on the adhesive polymer substrate 10 is removed to remove the adhesive polymer substrate. Restoring (10) to the original state in which only the primary coating layer 22 of a predetermined pattern is formed, coating the second particles 24 on the adhesive polymer substrate 10, and increasing the adhesive polymer substrate 10; By repeating the step of transferring the secondary coating film 25 made of the second particles 24 to the other transfer substrate 45, the expanded secondary made of the plurality of second particles 24 having a gap therebetween. The coating film 25 'may be repeatedly formed.

As another example, the expanded primary coating layer 22 ′ and the expanded secondary coating layer 25 ′ formed on the adhesive polymer substrate 10 may be transferred together to another substrate. That is, after the adhesive polymer substrate 10 is stretched to form the expanded primary coating film 22 and the expanded secondary coating film 25, the adhesive polymer substrate 10 has a larger adhesion than the exposed portion 14 of the adhesive polymer substrate 10. When the transfer substrate 49 is brought into contact with the extended primary coating layer 22 and the expanded secondary coating layer 25 and removed, as shown in FIG. 3, the expanded primary coating layer 22 and the expanded secondary layer are shown. The coating film in which the coating film 25 is combined in a specific pattern may be transferred to another transfer substrate 49.

In addition, the coating method using the particle alignment according to another embodiment of the present invention is carried out by repeatedly performing the exposure step, partial particle removal step, new particle coating step, coating film expansion step, transfer step and the like as described above, Various types of particles may be formed on the polymer substrate 10 with various coating layers each arranged in a specific pattern. The alignment pattern of each particle can be varied by varying the mask pattern 41 of the mask 40 used in the exposure step.

In addition, in the coating method using the particle alignment according to another embodiment of the present invention, the first coating film 22 is formed on the adhesive polymer substrate 10, and the plurality of first coating films 22 constituting the first coating film 22 after exposure. After removing the first particles 20 located in the non-exposure portion 15 among the particles 20, the adhesive polymer substrate 10 is stretched in a state in which the secondary coating layer 25 is not formed thereon, thereby expanding the expanded primary. The coating film 22 'may be formed. In addition, the expanded primary coating film 22 ′ may be transferred to another transfer substrate having an adhesive force greater than that of the exposure part 14.

Meanwhile, FIG. 4 shows another embodiment in which the second particles 24 are coated on the adhesive polymer substrate 10 in the coating method using the particle alignment according to the present invention. In the present invention, since the concave portion is formed in the adhesive polymer substrate 10 by elastic deformation, when the particles accommodated in the concave portion are removed, the surface of the adhesive polymer substrate 10 as shown in (a) of FIG. 4. This recess may disappear and return to the smooth surface. In such a state that the first concave portion 12 (see FIG. 2D) in which the first particles 20 are accommodated is reversibly dissipated, the plurality of second particles 24 are placed on the adhesive polymer substrate 10 and pressure is applied thereto. The second particles 24 may be coated while the second recesses 17 (see FIG. 2E) corresponding to the second particles 24 are formed in the non-exposed parts 15.

Of course, as described above, when the first particle 20 is removed from the first recess 12 after a long time after the primary coating film 22 is formed, as shown in FIG. Traces of the first recesses 12 or the first recesses 12 may remain on the surface of the adhesive polymer substrate 10. In this case, the newly coated second particles 24 are partially wrapped in the first recesses 12, or the adhesive polymer substrates are penetrated by digging into the adhesive polymer substrate 10 at a position corresponding to the first recesses 12. 10 may be attached.

On the other hand, Figure 5a to 5d is a step showing another embodiment of forming a coating film of a predetermined pattern on the adhesive polymer substrate in the coating method using the particle alignment according to the present invention, to form a coating film of a predetermined pattern on the adhesive polymer substrate The specific method of another embodiment is as follows.

First, as shown in FIG. 5A, an adhesive polymer substrate 10 having a smooth surface is prepared, and the surface of the adhesive polymer substrate 10 is irradiated by applying light to the mask 50 on which the mask pattern 51 is formed. Partially exposed. The adhesive polymer substrate 10 is the same as described above, and the light exposing the adhesive polymer substrate 10 is also the same as described above.

As such, when the mask 50 is disposed on the adhesive polymer substrate 10, light is irradiated onto the adhesive polymer substrate 10, and as shown in FIG. 5B, light is emitted on the surface of the adhesive polymer substrate 10. The adhesion of the exposed exposure portion 14 is greater than the adhesion of the non-exposed portion 15 that is not irradiated with light. After exposing the adhesive polymer substrate 10 to light to form the exposed portion 14, as shown in FIG. 5C, the plurality of particles 20 are aligned to form a coating film 22 on the adhesive polymer substrate 10. To form.

Here, the kind of particle 20 and the specific method of forming the coating film 22 from the some particle 20 are as having mentioned above. However, in the present exemplary embodiment, when the plurality of particles 20 are placed on the adhesive polymer substrate 10 having the exposed portion 14 and are applied to the adhesive polymer substrate 10 by applying pressure thereto, the particles 20 are positioned on the exposed portion 14. The binding force of the particles 20 to the adhesive polymer substrate 10 is greater than the bonding force of the particles 20 positioned on the non-exposed part 15 to the adhesive polymer substrate 10, and thus the particles positioned on the exposed part 14. 20 is more firmly bonded to the adhesive polymer substrate 10 than the particles 20 located in the non-exposed part 15.

Subsequently, as shown in FIG. 5D, the particle removing member 43 (see FIG. 2C) having an adhesion force greater than that of the non-exposed portion 15 of the adhesive polymer substrate 10 and smaller than that of the exposure portion 14 is provided. If the particles 20 disposed on the non-exposed part 15 are removed from the plurality of particles 20 forming the coating film 22 by using the coating film 22, the coating film 22 having a pattern corresponding to the exposure pattern may be formed.

Subsequently, when the secondary coating film formation, coating film expansion, coating film transfer, and the like are further performed as described above (FIGS. 2E to 2I), various kinds of particles are arranged on the adhesive polymer substrate 10 in a specific pattern. A coating film may be formed, or the coating film made of various particles or formed in various patterns may be transferred to another substrate. For example, after forming the secondary coating film 25 (see FIG. 2E), stretching the adhesive polymer substrate 10, only the expanded secondary coating film 25 '(see FIG. 2G) is transferred to another substrate, or the expanded primary Both the coating film 22 '(see FIG. 2G) and the expanded secondary coating film 25' (see FIG. 2G) can be transferred to another substrate.

On the other hand, Figures 6a to 6d shows some steps of the coating method using a particle alignment according to another embodiment of the present invention.

In the coating method using particle alignment shown in FIGS. 6A to 6D, a primary coating layer 22 including a plurality of first particles 20 is formed on the adhesive polymer substrate 10, and the adhesive polymer substrate 10 is stretched to increase adhesion. A process of forming the expanded primary coating layer 22 ′ consisting of a plurality of first particles 20 having a spaced apart from each other on the polymer substrate 10 is as shown in FIGS. 1A to 1E.

In the coating method using the particle alignment according to another embodiment of the present invention, the adhesive polymer substrate 10 is stretched to form an expanded primary coating film 22 ′ on the adhesive polymer substrate 10, and then shown in FIG. 6A. As shown, light is directed toward the expanded primary coating layer 22 ′ on the adhesive polymer substrate 10. At this time, the adhesive force of the exposed portion 14 irradiated with light on the surface of the adhesive polymer substrate 10 is increased to increase the bonding force of the plurality of first particles 20 in the adhesive polymer substrate 10. In this state, as shown in FIG. 6B, when the plurality of second particles 24 are placed on the adhesive polymer substrate 10 and rubbed with the pressure applying the plurality of second particles 24 in the same manner as described above, A plurality of second particles 24 are drilled into the absence of the first particles 20 and coated. Subsequently, as shown in FIGS. 6C and 6D, the expanded primary coating layer 22 ′ and the plurality of second particles 24 disposed between the plurality of first particles 20 are disposed on the secondary coating layer 27. When the transfer substrate 53 having a larger adhesion than the adhesion of the exposed portion 14 of the adhesive polymer substrate 10 is brought into contact with and removed, the primary coating film 22 and the secondary coating film 27 are attached to the transfer substrate 53. The mixed coating film can be transferred.

Hereinafter, the present invention will be described in more detail with reference to experimental examples of the present invention. These experimental examples are only illustrated to explain the present invention in detail, but the present invention is not limited thereto.

Experimental Example 1

An adhesive polymer substrate made of PDMS formed from Sylgard 184 (Dow Corning, USA) containing 20 wt% of a curing agent was prepared in a 15 cm diameter Petri dish.

UV was applied under an air atmosphere for 30 minutes to improve the surface hardness of the adhesive polymer substrate for uniform coating of the particles.

120 nm SiO ₂ particles were placed on the adhesive polymer substrate, and then the particles were coated on the surface of the adhesive polymer substrate by a single layer using a sponge wrapped with a latex film. For monolayer coating, a 120 nm SiO ₂ coating film was blown with nitrogen gas to remove particles in a portion where a multi layer was formed.

The adhesive polymer substrate is removed in a petri dish, and then fixed between the devices 1 and 2 of FIG. 7 and then coupled with the device 3 and 4 of FIG. 7 to increase the substrate.

The resin containing the ultraviolet curable resin was placed on the adhesive polymer substrate and the SiO ₂ coating layer, and then the resin was cured by covering the OHP film and curing in an oven for 5 minutes and then irradiating with UV for 60 minutes.

Thereafter, the adhesive polymer substrate was removed to complete the manufacture of an embossed coating substrate in which SiO ₂ particles on an OHP film were transferred while the SiO ₂ coating layer coated on the substrate and the substrate were elongated.

FIG. 8 is a result of measuring a scanning electron microscope (SEM) to compare the coating film and the uncoated coating film. As can be seen from the results of FIG. 8, in the case of the present invention, the adhesive polymer substrate is coated after the particles are coated on the adhesive polymer substrate. It can be seen that it is possible to produce coated substrates which are stretched and then transferred. In addition, the SEM image on the right side of FIG. 9, in which the substrate is stretched and transferred, may be compared with the SEM image on the left side of FIG.

Experimental Example 2

An adhesive polymer substrate made of PDMS formed from Sylgard 184 (Dow Corning, USA) containing 3 wt% of a curing agent was prepared in a 15 cm diameter Petri dish.

UV was applied under an air atmosphere for 30 minutes to improve the surface hardness of the adhesive polymer substrate for uniform coating of the particles.

After placing 1200 nm SiO ₂ particles on the adhesive polymer substrate, using a sponge wrapped with a latex film, using a sponge and rubbed to coat the particles with a single layer on the surface of the adhesive polymer substrate. For monolayer coating, a 1200 nm SiO ₂ coating film was blown with nitrogen gas to remove particles in a portion where a multi layer was formed.

The adhesive polymer substrate was removed in a petri dish, and then fixed between the devices 1 and 2 of FIG. 7 and then combined with the device 3 and 4 of FIG. 7 to increase the substrate.

The resin containing the ultraviolet curable resin was placed on the adhesive polymer substrate and the SiO ₂ coating layer, and then the resin was cured by covering the OHP film and curing in an oven for 5 minutes and then irradiating with UV for 60 minutes.

Thereafter, the adhesive polymer substrate was removed to complete the manufacture of an embossed coating substrate in which SiO ₂ particles on an OHP film were transferred while the SiO ₂ coating layer coated on the substrate and the substrate were elongated.

10 is a result of measuring a scanning electron microscope (SEM) to compare the coating film and the coating film not stretched, and as shown in the results of FIG. 10, in the case of the present invention, after the particles are coated on the adhesive polymer substrate, It was confirmed that the coated substrate which was transferred after being stretched could be prepared. In addition, the SEM image on the right side of FIG. 11, which was extended by transferring the substrate, was increased compared to the SEM image on the left side of FIG.

Embodiments of the present invention described above and illustrated in the drawings should not be construed as limiting the technical spirit of the present invention. The protection scope of the present invention is limited only by the matters described in the claims, and those skilled in the art can improve and change the technical idea of the present invention in various forms. Accordingly, such improvements and modifications will fall within the protection scope of the present invention as long as it will be apparent to those skilled in the art.

In the coating method using particle alignment according to the present invention, a coating layer composed of a plurality of particles is patterned, an adhesive polymer substrate is exposed using a mask, the patterned coating layer is firmly attached onto the adhesive polymer substrate, and then new particles are patterned coating layer. By coating in between, the various types of particles can be easily formed on the adhesive polymer substrate, each of which is arranged in a specific pattern, and the various coating films formed can be transferred to another transfer substrate, which is industrially useful.

Claims (19)

1. (a) preparing an adhesive polymer substrate;

   (b) applying a plurality of particles onto the adhesive polymer substrate to form a coating layer by coating the plurality of recesses corresponding to the plurality of particles on the surface of the adhesive polymer substrate; And

   (c) expanding the coating film by increasing the spacing between the particles of the adhesive polymer substrate on which the coating film is formed.
2. The method of claim 1,

   After the step (c),

   (d) transferring the expanded coating film to a transfer substrate having an adhesive force different from that of the adhesive polymer substrate.
3. The method of claim 1,

   The adhesive polymer substrate is a coating method using a particle alignment, characterized in that selected from a silicon-based polymer material, wraps, a film for protecting the surface, a film having a gloss easy to change the surface shape.
4. The method of claim 1,

   The adhesive polymer substrate is a coating method using particle alignment, characterized in that it comprises at least one of polydimethylsiloxane (PDMS), polyethylene (PE, PE), polyvinyl chloride (PVC).
5. The method of claim 1,

   The coating method using the particle alignment, characterized in that in the step (b) the plurality of particles are in direct contact with the adhesive polymer substrate.
6. The method of claim 1,

   The coating method in the step (b) is the coating method using a particle alignment, characterized in that the plurality of particles are made of a single layer coating.
7. The method of claim 1,

   In the step (b), when the plurality of particles are non-spherical, the ratio of the average value of the thickness of the coating film to the average particle diameter of the upper 10% particles of the plurality of particles is 1.9 or less, using the particle alignment, Coating method.
8. The method of claim 1,

   The coating method using the particle alignment, characterized in that the depth ratio of the concave portion to the average particle diameter of the particles in step (b) is 0.02 ~ 0.98.
9. The method of claim 1,

   The coating method using a particle alignment, characterized in that the average particle diameter of the plurality of particles in step (b) is 10nm to 100.
10. The method of claim 1,

    In the step (b), the adhesive polymer substrate is provided with a plurality of recesses recessed to correspond to the plurality of particles by deformation of the adhesive polymer substrate, and the plurality of recesses are provided in a reversible state. Coating method using the particle alignment to be.
11. The method of claim 1,

    Wherein each of the plurality of particles comprises at least one of a chargeable material and a non-chargeable material, a hydrophobic material, and a hydrophilic material.
12. The method of claim 1,

    Coating method using a particle alignment, characterized in that the surface of the adhesive polymer substrate is provided with a pattern of three-dimensional three-dimensional structure.
13. The method of claim 1,

    After the step (c), after transferring the plurality of particles coated on the adhesive polymer substrate to the resin, by irradiating O ₂ plasma to etch the remaining space except the portion where the particles are transferred to produce a Moth-Eye type film Coating method using a particle alignment, characterized in that.
14. The method of claim 1,

    In the step (c),

    The adhesive polymer substrate is uniformly expanded in all directions, only in the longitudinal direction, or the coating method using a particle alignment, characterized in that only extend in the width direction.
15. (a) preparing an adhesive polymer substrate;

    (b) applying a plurality of particles onto the adhesive polymer substrate to form a coating layer by coating the plurality of recesses corresponding to the plurality of particles on the surface of the adhesive polymer substrate;

    (c) the adhesive force of the exposed part irradiated with the light on the surface of the adhesive polymer substrate by partially irradiating the coating film on the surface of the adhesive polymer substrate by irradiating light toward the adhesive polymer substrate with the mask having the mask pattern formed thereon; Changing the;

    (d) the degree of impregnation of the particles and the particles disposed in the non-exposed or exposed portions of the plurality of particles forming the coating film using the difference in adhesion between the irradiated and unirradiated portions of the adhesive polymer substrate; Removing from the adhesive polymer substrate by using an adhesive force of the removal member; And

    (e) expanding the coating film by increasing the spacing between the particles of the adhesive polymer substrate on which the coating film is formed.
16. (a) preparing an adhesive polymer substrate;

    (b) applying a plurality of first particles to the adhesive polymer substrate to apply a pressure to form a first coating layer on the surface of the adhesive polymer substrate while forming a plurality of first recesses corresponding to the plurality of first particles, respectively; step;

    (c) exposure to which the light on the surface of the adhesive polymer substrate is irradiated by partially exposing a region where the primary coating layer is formed on the surface of the adhesive polymer substrate by irradiating light toward the adhesive polymer substrate with a mask having a mask pattern formed thereon; Changing the adhesion of the negatives;

    (d) first particles disposed in the non-exposed part or the exposed part of the plurality of first particles forming the coating film by using a difference in adhesion between the irradiated and unirradiated portions of the adhesive polymer substrate; Removing from the adhesive polymer substrate by using the degree of impregnation and the degree of adhesion of the particle removing member;

    (e) applying a plurality of second particles to a place where the first particles of the adhesive polymer substrate are removed, and coating a plurality of second recesses corresponding to the plurality of second particles to form a second coating layer. Forming;

    (f) extending the primary coating film and the secondary coating film by increasing a distance between the particles of the adhesive polymer substrate on which the primary coating film and the secondary coating film are formed; And

    (g) transferring at least one of the extended primary coating film and the secondary coating film to a transfer substrate through a difference in adhesion between the non-exposed part and the exposed part of the adhesive polymer substrate.
17. (a) preparing an adhesive polymer substrate;

    (b) changing the adhesion of the exposed part to which the light on the surface of the adhesive polymer substrate is irradiated by applying light toward the adhesive polymer substrate with the mask on which the mask pattern is formed;

    (c) forming a primary coating film by coating a plurality of first particles on the adhesive polymer substrate;

    (d) first particles disposed in the non-exposed portion or the exposed portion of the plurality of first particles forming the primary coating layer by using a difference in adhesion between the irradiated and unirradiated portions of the adhesive polymer substrate; Removing from the adhesive polymer substrate by using the degree of impregnation of the particles and the degree of adhesion of the particle removing member;

    (e) applying a plurality of second particles to a place where the first particles of the adhesive polymer substrate are removed, and coating a plurality of second recesses corresponding to the plurality of second particles to form a second coating layer. Forming;

    (f) extending the primary coating layer and the secondary coating layer by increasing the distance between the particles of the adhesive polymer substrate on which the primary coating layer and the secondary coating layer are formed; And

    (g) transferring at least one of the extended primary coating film and the secondary coating film to a transfer substrate through a difference in adhesion between the non-exposed part and the exposed part of the adhesive polymer substrate.
18. (a) preparing an adhesive polymer substrate;

    (b) applying a plurality of first particles to the adhesive polymer substrate by applying pressure to form a plurality of first recesses respectively corresponding to the plurality of first particles on the surface of the adhesive polymer substrate;

    (c) extending the coating film by increasing a distance between the first particles of the adhesive polymer substrate on which the coating film is formed;

    (d) irradiating light to the adhesive polymer substrate to expose the adhesive polymer substrate, thereby increasing the bonding force between the adhesive polymer substrate and the plurality of first particles;

    (e) applying a plurality of second particles to a region between the plurality of first particles on the surface of the adhesive polymer substrate, wherein the plurality of second recesses respectively correspond to the plurality of second particles on the surface of the adhesive polymer substrate; Coating to form an addition; And

    (f) transferring at least one of the first particles and the second particles to the transfer substrate through a difference in adhesion and impregnation degree between the first particles and the second particles of the adhesive polymer substrate. Coating method using.
19. The method of claim 18,

    And transferring the first particles and the second particles to the transfer substrate through a difference in adhesion and impregnation degree between the first particles and the second particles of the adhesive polymer substrate in the step (f). Coating method using the particle alignment to be.

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