KR102353553B1 - Coating method using particle alignment and particle coated substrate manufactured by the same - Google Patents

Abstract

The present invention relates to a coating method using particle alignment that can coat a plurality of fine particles at a single layer level at a high density using particle alignment. The coating method using particle alignment according to the present invention comprises the steps of (a) coating a plurality of particles on an upper portion of a first substrate having gas permeability to form a coating film, (b) the surface of the first substrate on which the coating film is formed Applying a coating solution to the, (c) placing a second substrate on the coating solution to cover the coating solution with the second substrate, (d) drying the coating solution to form a coating layer to which the coating film is attached include

Description

Coating method using particle alignment and particle coated substrate manufactured by the same

The present invention relates to a coating method using particle alignment and a particle coating substrate prepared thereby, and more particularly, to a particle alignment using particle alignment capable of coating a plurality of fine particles at a high density at a single layer level using particle alignment. It relates to a coating method and a particle-coated substrate produced thereby.

Techniques for aligning and coating nanometer-level or micrometer-level fine particles on a substrate are required in various fields. For example, these coating technologies include memory devices, linear and non-linear optical devices, optoelectronic devices, photo masks, deposition masks, chemical sensors, biochemical sensors, sensors for detecting medical molecules, dye-sensitized solar cells, thin film solar cells, cell culture, It can be applied to the implant surface and the like.

As a technique for aligning and coating fine particles on a substrate, the Langmuir-Blodgett (LB) method (hereinafter "LB method") is well known. In the LB method, a solution in which fine particles are dispersed in a solvent is floated on the water surface and then compressed by a physical method to form a thin film. A technique using such an LB method is disclosed in Korean Patent Application Laid-Open No. 10-2006-2146 and the like.

However, in the LB method, temperature, humidity, etc. must be precisely controlled so that the particles can self-assemble in the solvent. In addition, particle movement may be affected by surface properties (eg, hydrophobicity, charge properties, surface roughness) of the particles on the substrate. Accordingly, the particles may agglomerate and may not be evenly coated on the substrate. That is, there may be many regions where no particles are applied, and grain boundaries are formed where the aggregated particles meet each other, and many defects may be located.

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

Another object of the present invention is to provide a coating method using particle alignment capable of forming a coating film in which a plurality of particles are aligned in a uniform pattern by a simple method, and a particle coated substrate prepared thereby.

Another object of the present invention is to provide a coating method using particle alignment capable of forming a coating film in which heterogeneous particles are arranged in a uniform pattern, respectively, by a simple method, and a particle coated substrate prepared thereby.

The present invention for achieving the above object
(a) forming a coating film by coating a plurality of particles on a first substrate having gas permeability;
(b) applying a coating solution to the surface of the first substrate on which the coating film is formed;
(c) placing a second substrate on the coating solution and covering the coating solution with the second substrate; and
(d) drying the coating solution to form a coating layer to which the coating film is attached,
When the plurality of particles are non-spherical, the ratio of the average value of the coating film thickness to the average particle diameter of the particles having a particle diameter of the top 10% among the plurality of particles is 1.9 or less.
In addition, after step (d),
(e) separating the coating layer to which the coating film is attached from the first substrate and transferring the coating film to the second substrate through the coating layer as a medium It provides a coating method using particle alignment, characterized in that it further comprises do.
In addition, the method further comprises the step of irradiating light or an active gas toward the first substrate before or after forming the coating film on the first substrate,
It provides a coating method using particle alignment, characterized in that it is possible to control the adhesion force and the area in which the adhesion force of the first substrate is changed according to the irradiation time or irradiation intensity of the light or active gas.
In addition, the method further comprises applying heat to the first substrate before or after forming the coating film on the first substrate,
It provides a coating method using particle alignment, characterized in that the adhesion between the coating film and the first substrate can be adjusted according to the temperature of the heat or the heat application method.
In addition, the first substrate includes a gas-permeable substrate and an adhesive polymer substrate provided on one surface of the gas-permeable substrate,
The coating film provides a coating method using particle alignment, characterized in that provided on the adhesive polymer substrate.
In addition, in step (a), it provides a coating method using particle alignment, characterized in that the coating on the first substrate by applying pressure by rubbing the plurality of particles.
In addition, in the step (a), the plurality of particles provides a coating method using particle alignment, characterized in that in direct contact with the first substrate.
In addition, in step (a), the coating film provides a coating method using particle alignment, characterized in that the plurality of particles are coated in a single layer.
In addition, a plurality of concave portions are provided to be depressed to correspond to the plurality of particles, respectively, on the surface of the first substrate, and a depth ratio of the concave portions to the average particle diameter of the particles is 0.02 to 0.7. A coating method is provided.
In addition, the concave portion provides a coating method using particle alignment, characterized in that the reversible.
In addition, the second substrate provides a coating method using particle alignment, characterized in that the gas impermeable substrate.
In addition, in step (d), the solvent contained in the coating solution passes through the first substrate and is released to the outside, thereby providing a coating method using particle alignment, characterized in that the coating solution is cured into the coating layer in a solid state. do.
The present invention also provides a gas permeable substrate;
an adhesive polymer substrate formed on the gas-permeable substrate and capable of transmitting gas; and
A coating film comprising a plurality of particles coated in a single layer on the surface of the adhesive polymer substrate,
When the plurality of particles are non-spherical, the ratio of the average value of the coating film thickness to the average particle diameter of the particles having a particle diameter of the top 10% among the plurality of particles is 1.9 or less.
In addition, the gas-permeable substrate provides a particle-coated substrate comprising at least one of Korean paper, tissue, corrugated cardboard, hard board paper, and a porous film.
In addition, the adhesive polymer substrate provides a particle-coated substrate comprising at least one of polydimethylsiloxane (PDMS), polyethylene (PE), and polyvinylchloride (PVC).
In addition, it further comprises a coating liquid layer applied to the surface of the adhesive polymer substrate on which the coating film is formed,
The coating liquid layer provides a particle-coated substrate, characterized in that it is cured through drying carried out at room temperature or under the conditions of applying heat.
The present invention also
(a) preparing a gas-permeable substrate;
(b) forming a coating film by coating a plurality of particles on the gas-permeable substrate;
(c) by irradiating light or an active gas toward the gas-permeable substrate with a mask having a mask pattern formed thereon to partially expose or expose the surface of the gas-permeable substrate, so that the light or active gas on the surface of the gas-permeable substrate is irradiated changing the adhesive force of the exposed part;
(d) the non-exposed part or the exposed part in the plurality of particles forming the coating film by using the difference in adhesion between the exposed part and non-exposed part irradiated with light or active gas of the gas-permeable substrate and the particles of the coating film selectively removing the particles disposed on the gas-permeable substrate by using the degree of adhesion to the particle removal member;
(e) applying a coating solution to the surface of the gas-permeable substrate on which the coating film is formed;
(f) covering the coating solution by placing a gas-impermeable substrate on the coating solution; and
(g) by evaporating the solvent contained in the coating solution through the gas-permeable substrate to dry it, the coating film is attached to form a cured coating layer in a solid state,
The particle removal member has an adhesive force greater than that of the non-exposed part and smaller than the adhesive force of the exposed part, and thus provides a coating method using particle alignment, characterized in that the particles disposed on the non-exposed part are removed when the particles are removed after being in contact with the coating film.
The present invention also
(a) preparing a gas-permeable substrate;
(b) forming a primary coating film by coating a plurality of first particles on the gas-permeable substrate;
(c) by irradiating light or an active gas toward the gas-permeable substrate with a mask having a mask pattern formed thereon to partially expose or expose an area on the surface of the gas-permeable substrate in which the primary coating film is formed, the surface of the gas-permeable substrate changing the adhesive force of the exposed portion irradiated with light or active gas;
(d) the plurality of agents forming the primary coating film by using the difference in adhesion between the first particles of the first coating film and the exposed portion and the non-exposed portion that are not irradiated with light or active gas of the gas-permeable substrate selectively removing one particle from the gas-permeable substrate by using the degree of adhesion of the first particles disposed in the non-exposed part or the exposed part to the particle removal member;
(e) forming a secondary coating film by coating a plurality of second particles on the region from which the first particles are removed of the gas-permeable substrate;
(f) applying a coating solution to the surface of the gas-permeable substrate on which the primary coating film and the secondary coating film are formed;
(g) covering the coating solution by placing a gas-impermeable substrate on the coating solution; and
(h) by evaporating the solvent included in the coating solution through the gas-permeable substrate and drying it, at least one of the primary coating film and the secondary coating film is attached to form a cured coating layer in a solid state, and ,
The particle removal member has an adhesive force greater than that of the non-exposed part and smaller than the adhesive force of the exposed part, so that when the first coating film is brought into contact and removed, the first particles disposed on the non-exposed part are removed. provides
The present invention also
(a) preparing a gas-permeable substrate;
(b) Exposing or partially exposing or exposing the surface of the gas-permeable substrate by irradiating light or an active gas toward the gas-permeable substrate with a mask having a mask pattern formed thereon, so that the surface of the gas-permeable substrate is irradiated with light or an active gas changing the adhesive force of the negative;
(c) forming a coating film by coating a plurality of particles on the gas-permeable substrate;
(d) the non-exposed part or the exposed part in the plurality of particles forming the coating film by using the difference in adhesion between the exposed part and non-exposed part irradiated with light or active gas of the gas-permeable substrate and the particles of the coating film selectively removing the particles disposed on the gas-permeable substrate by using the degree of adhesion to the particle removal member;
(e) applying a coating solution to the surface of the gas-permeable substrate on which the coating film is formed;
(f) covering the coating solution by placing a gas-impermeable substrate on the coating solution; and
(g) by evaporating the solvent contained in the coating solution through the gas-permeable substrate to dry it, the coating film is attached to form a cured coating layer in a solid state,
The particle removal member has an adhesive force greater than that of the non-exposed part and smaller than the adhesive force of the exposed part, and thus provides a coating method using particle alignment, characterized in that the particles disposed on the non-exposed part are removed when the particles are removed after being in contact with the coating film.
The present invention also
(a) preparing a gas-permeable substrate;
(b) Exposing or partially exposing or exposing the surface of the gas-permeable substrate by irradiating light or an active gas toward the gas-permeable substrate with a mask having a mask pattern formed thereon, so that the surface of the gas-permeable substrate is irradiated with light or an active gas changing the adhesive force of the negative;
(c) forming a first coating film by coating a plurality of first particles on the gas-permeable substrate;
(d) the plurality of first forming the primary coating film using the difference in adhesion between the exposed portion and the non-exposed portion irradiated with light or active gas of the gas-permeable substrate and the first particles of the primary coating film selectively removing the particles from the gas-permeable substrate by using the degree of adhesion of the particles disposed on the non-exposed part or the exposed part to the particle removal member;
(e) forming a secondary coating film by coating a plurality of second particles on the region from which the first particles are removed of the gas-permeable substrate;
(f) applying a coating solution to the surface of the gas-permeable substrate on which the primary coating film and the secondary coating film are formed;
(g) covering the coating solution by placing a gas-impermeable substrate on the coating solution; and
(h) by evaporating the solvent included in the coating solution through the gas-permeable substrate and drying it, at least one of the primary coating film and the secondary coating film is attached to form a cured coating layer in a solid state, and ,
The particle removal member has an adhesive force greater than that of the non-exposed part and smaller than the adhesive force of the exposed part, so that when the first coating film is brought into contact and removed, the first particles disposed on the non-exposed part are removed. provides

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The coating method using particle alignment according to the present invention forms a coating film through the process of applying pressure to the particles in a dry state on an adhesive polymer substrate formed on a gas-permeable substrate without using a solvent or an adhesion aid, and then a thermosetting coating layer is mediated can be stably transferred to another transfer substrate. In the process of coating the particles on the adhesive polymer substrate, when the particles come into contact with the adhesive polymer substrate, the surface of the adhesive polymer substrate with flexibility is transformed into a shape enclosing a part of the particles under the influence of surface tension. Accordingly, concave portions corresponding to particles are formed on the surface of the adhesive polymer substrate, thereby improving bonding properties. The reversible property of the shape deformation of the surface of the adhesive polymer substrate facilitates the two-dimensional movement of the particles in contact with the substrate, so that the distribution of the particles can be easily rearranged.

The improvement of particle adhesion through this shape transformation lowers the dependence on particle surface properties and the type of polymer substrate, so that particles of various surface properties can be coated in a single layer. Therefore, there is no need for detailed environmental control 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 it is possible to easily coat particles with various surface properties in a wide range of environments and conditions. can A single-layer particle coating can be uniformly formed with high density not only when the particles are electrically charged or easily hydrogen-bonded, but also when the particles are non-chargeable and hydrophobic.

As described above, according to the present invention, by a simple method, the particles are evenly distributed on the adhesive polymer substrate to easily form a single-layer coating film having a high density, which is then transferred to another transfer such as a glass substrate, a semiconductor substrate, a polymer substrate, etc. through a thermosetting coating layer. It can be stably transferred to the substrate.

In addition, the coating method using particle alignment according to the present invention partially irradiates light or an active gas on the adhesive polymer substrate using a mask to increase the adhesion of the exposed portion irradiated with light or active gas, and the non-exposed portion with relatively weak adhesion By removing the particles located on the , it is possible to easily form a coating film of various patterns and stably transfer it to another transfer substrate.

1a to 1f show a coating method using particle alignment according to an embodiment of the present invention step by step.
2a to 2f show a coating method using particle alignment according to another embodiment of the present invention step by step.
3 shows another embodiment in which a coating film is formed on a transfer substrate by using the coating method using particle alignment according to the present invention.
4A to 4D are step-by-step views of another embodiment of forming a coating film of a predetermined pattern on an adhesive polymer substrate in a coating method using particle alignment according to the present invention.
FIG. 5A is a step-by-step view of Experimental Example 1 of the present invention, and FIGS. 5B and 5C are SEM images of the particle transfer substrate in Experimental Example 1 of the present invention (in FIG. 5C, LLDPE is a Clean Lab (LLDPE, Linear Low -Density Polyethylene)).
6a, 6b and 6c are photographs showing step by step of Experimental Example 2 of the present invention, and FIG. 6d is an SEM image of the particle transfer substrate in Experimental Example 2 of the present invention (here, the PDMS of FIGS. 6c and 6d is polydimethylsiloxane (meaning polydimethylsiloxane, PDMS).
7a and 7b are images showing comparison according to UV treatment time in Experimental Example 3 of the present invention, FIG. 7c is a graph showing changes in transmittance with respect to wavelength according to UV treatment time, and FIG. 7d is a photograph showing the clarity according to the UV treatment time, FIG. 7e is a graph showing the methylene blue degradation test results, and FIG. 7f is a picture showing the transparency of methylene blue according to the UV treatment time 7g and 7h are graphs of changes in photocatalytic properties according to chemical changes in the substrate, FIG. 7i is a photograph showing the hardness of the substrate according to UV treatment time, and FIG. 7j is a comparison of refractive index according to size change It is a photograph (LBL in FIGS. 7c to 7i is an abbreviation for Langmuir-Blodgett Layer, and refers to a coating film prepared by the Langmuir-Blodgett method used as a control).

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

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 explanation. In addition, terms 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 consistent with the technical spirit of the present invention based on the contents throughout this specification.

1a to 1f show the coating method using particle alignment according to an embodiment of the present invention step by step. The explanation is as follows.

First, as shown in FIG. 1A , a gas-permeable substrate 10 is prepared, a liquid adhesive polymer is applied on the gas-permeable substrate 10 , and then dried to form an adhesive polymer substrate 20 . Here, the gas-permeable substrate 10 has a gas-permeable property, for example, Korean paper, tissue, corrugated cardboard, hard board paper, porous film, etc. may be used, but is not limited thereto. In addition, like the gas-permeable substrate 10 , the adhesive polymer substrate 20 also has a gas-permeable characteristic.

In an embodiment of the present invention, the adhesive polymer substrate 20 includes at least one polymer material such as polydimethylsiloxane (PDMS), linear low-density polyethylene (LLPDE), or polyvinyl chloride (PVC). On the other hand, a flexible polymer material that is not dense in tissue structure has gas permeation properties, and the flexible polymer material can be applied as an adhesive polymer usable for the gas permeable substrate 10 .

The surface of the adhesive polymer substrate 20 formed on the gas-permeable substrate 10 may have a state in which a specific pattern or curve is not formed, and particles 30 (FIG. 1C) forming a coating film 32 (see FIG. 1C) thereon ) can have a level of surface roughness and structure that does not limit the movement of In this embodiment, including the gas-permeable substrate 10 and the adhesive polymer substrate 20 provided on one surface of the gas-permeable substrate, it is called a first substrate.

In this embodiment, the adhesive polymer substrate 20 includes various adhesive polymer materials having adhesive properties. Adhesive polymers are distinguished from pressure-sensitive adhesives because they do not have commonly used tackiness. At least the adhesive polymer has an adhesive force of less than about 0.6 kg/inch (ASTM D 3330 evaluation) of the adhesive force of the 'Scotch Magic™ Tape'. In addition, the adhesive polymer can maintain the shape of a solid state (such as a substrate or film) at room temperature without a separate support.

Here, the adhesive polymer material generally refers to an organic polymer material that contains solid state silicone or has adhesion properties through the addition of a plasticizer or surface treatment. Here, the adhesive polymer material is characterized in that it is generally easily deformable in shape due to a linear molecular structure and has a low surface tension. The excellent adhesion of the adhesive polymer material is due to a soft (flexible) surface material that is easy to deform in a microscopic area, and low surface tension. The low surface tension of the adhesive polymer material brings the characteristic of being widely adhered to the particle 30 to be attached (similar to the wetting of a solution), and the flexible surface is in tight contact with the particle 30 to be attached. let it go Through this, it has the characteristics of an adhesive polymer that can be reversibly attached to and detached from a solid surface without a complementary bonding force.

The surface tension of a silicone-based polymer material such as PDMS, a representative 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. And the surface tension of the adhesive polymer, for example, a silicone-based polymer material, is found in most organic polymers (35 to 50 dynes/cm), natural materials such as cotton (綿, 73 dynes/cm), and metals (eg, silver (Ag, 890 dynes/cm), aluminum (Al, 500 dynes/cm), inorganic oxides (eg, glass (1000 dynes/cm), and iron oxide (1357 dynes/cm).

Subsequently, after forming the adhesive polymer substrate 20 as described above, as shown in FIGS. 1b and 1c , a plurality of particles 30 are aligned to form a coating film 32 on the adhesive polymer substrate 20 . to form This will be described in more detail as follows.

First, as shown in FIG. 1b , a plurality of dried particles 30 are placed on the adhesive polymer substrate 20 . Unlike this embodiment, the particles dispersed in the solution are difficult to make direct contact with the surface of the adhesive polymer, so that the coating is not performed well. Therefore, only when a small amount of a solution or a volatile solvent less than the mass of the particles used is used, the particles are dried during the coating operation, so that the coating operation may be possible.

In this embodiment, the particles 30 may include various materials for forming the coating film 32 . That is, the particles 30 may include a polymer, an inorganic material, a metal, a magnetic material, a semiconductor, a biological material, and the like. Also, a mixture of particles having different properties may be used as the particles 30 .

Polymers that can be used as the particles 30 include polystyrene (PS), polymethyl methacrylate (PMMA), polyacrylate, polyvinyl chloride (PVC), polyalphastyrene, polybenzyl methacrylate, polyphenylmethacrylate acrylate, polydiphenyl methacrylate, polycyclohexyl methacrylate, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, and the like.

As an inorganic material that can be used as the particle 30 , silicon oxide (eg, SiO ₂ ), silver phosphate (eg, Ag ₃ PO ₄ ), titanium oxide (eg, TiO ₂ ), iron oxide (eg, , 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 30 include gold, silver, copper, iron, platinum, aluminum, platinum, zinc, cerium, thallium, barium, yttrium, zirconium, tin, titanium, or an alloy thereof. .

A semiconductor that can be used as the particle 30 includes silicon, germanium, or a compound semiconductor (eg, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InP, InAs, InSb, etc.).

Biomaterials that can be used as the particles 30 include proteins, peptides, ribonucleic acid (RNA), deoxyribonucleic acid (DNA), polysaccharides, oligosaccharides, lipids, cells, and coatings on particles or surfaces of complex materials thereof There are particles that have been formed, and particles that are contained within. For example, a polymer particle coated with an antibody-binding protein called protein A may be used as the particle 30 .

The particle 30 may have a symmetrical shape, an asymmetrical shape, an amorphous shape, or a porous shape. As an example, the particles 30 may have a spherical shape, an elliptical shape, a hemispherical shape, a cube shape, a tetrahedron, a pentahedron, a hexahedron, an octahedron, a columnar shape, a cone shape, and the like. Among them, as the shape of the particles 30, a spherical or oval shape is preferable compared to other shapes.

The particles 30 may have an average particle diameter of 10 nm to 100 μm, and more specifically, preferably 10 nm to 50 μm. When the average particle diameter is less than 10 nm, it may be in a form that is entirely covered by the adhesive polymer substrate 20 during coating, so it may be difficult to coat the particles 30 at a single layer level. In addition, when the average particle diameter of the particles 30 is less than 10 nm, the particles may agglomerate with each other even in a dry state, so it may be difficult to individually move the particles only by rubbing force. When the average particle diameter of the particles 30 exceeds 100 μm, adhesion of the particles may be weak. Here, the average particle diameter of the particles 30 may be more preferably 50nm to 10㎛.

However, the present invention is not limited thereto, and the average particle diameter of the particles 30 may vary depending on the material constituting the particle 30 or the material constituting the adhesive polymer substrate 20 . Here, when the particle 30 is spherical, the diameter of the particle 30 may be used as the particle diameter. On the other hand, when the particle 30 is not spherical, various measurement methods may be used. For example, the average value of the major axis and the minor axis may be used as the particle diameter.

Subsequently, as shown in FIG. 1c , a coating film 32 is formed by applying pressure on the plurality of particles 30 . As a method of applying pressure to the particles 30, a rubbing method using 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 30 by various methods.

In this embodiment, when the pressure is applied after putting the particles 30 on the surface of the adhesive polymer substrate 20 , the particles 30 in the portion to which the pressure is applied are attached through deformation of the adhesive polymer substrate 20 . Accordingly, a plurality of concave portions 22 respectively corresponding to the particles 30 are formed in the corresponding portion. Accordingly, the particles 30 are aligned on the adhesive polymer substrate 20 in a state in which the particles 30 are wrapped in the recess 22 .

The concave portion 22 is formed by the interaction between the particles and the substrate and is reversible. That is, it may be destroyed and the position may be moved. For example, if the particles move during the rubbing process, the concave portion 22 disappears due to the elastic restoring force of the adhesive polymer substrate 20, or the concave portion 22 may change position according to the movement of the particles 30. have. The particles 30 can be evenly aligned by this reversible action (herein, "reversible" 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 changes over time. It has a broad meaning that includes cases where it weakens or disappears according to it).

The particles 30 that are not bonded to the adhesive polymer substrate 20 move to the area where the particles 30 of the adhesive polymer substrate 20 are not coated by a rubbing force, etc., and the particles in the uncoated portion The concave portion 22 is formed by (30). And in a state in which the particles 30 are wrapped in the newly formed concave portion 22 , the adhesive polymer substrate 20 and the particles 30 are combined. Through this process, a single-layer coating film 32 is formed at a high density on the adhesive polymer substrate 20 .

Here, the concave portion 22 may have a shape corresponding to the outer shape of the particle 30 so as to surround a portion of the particle 30 . For example, when the particle 30 is spherical, the concave portion 22 may also have a spherical shape so that a portion of the particle 30 may be in close contact with the concave portion 22 . In addition, the depth L1 of the concave portion 22 may vary depending on the hardness of the adhesive polymer substrate 20 , the shape of the particles 30 , hardness, environmental factors (eg, temperature), and the like. That is, as the hardness of the adhesive polymer substrate 20 increases, the depth L1 of the concave portion 22 may decrease, and as the temperature increases, the depth L1 of the concave portion 22 may increase.

It is preferable that the ratio (settlement rate) (L1/D) of the depth L1 of the concave portion 22 to the average particle diameter D of the particles 30 is 0.02 to 0.7. When the ratio (L1/D) is less than 0.02, the bonding force between the particles 30 and the adhesive polymer substrate 20 may not be sufficient, and when it exceeds 0.7, the particles 30 are coated at a single layer level. It can be difficult. In consideration of the bonding force and coating properties, 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 portion of each particle 30 is surrounded by the concave portion 22 generated by elastic deformation, the particle 30 and the adhesive polymer substrate 20 can be better combined. . In addition, the particles 30 bonded to the adhesive polymer substrate 20 can also move to the surrounding uncoated portion, so that the new particles 30 are partially in the hollow concave portion 22 of the surface of the adhesive polymer substrate 20 . can be accepted as According to this rearrangement characteristic, the coating layer 32 may be coated at a single layer level with a high density. For example, the particles 30 may be arranged so that each center forms a hexagonal shape.

On the other hand, when the particles 30 are non-spherical (eg, Ag ₃ PO ₄ ), it can be determined whether the particles are at a monolayer level by various methods. As an example, when the ratio of the average value of the thickness of the coating film 32 to the average particle diameter of the top 10% of the particles 30 (that is, particles having a large particle size within 10%) is 1.9 or less, the coating is coated at a single layer level you can see

After forming the coating film 32 on the adhesive polymer substrate 20, as shown in FIG. 1D, the coating solution 40 is applied to the surface of the adhesive polymer substrate 20 on which the coating film 32 is formed. Here, as the coating solution 40, any coating solution having a property of being cured by drying at room temperature or in a state in which heat is applied (hereinafter referred to as 'thermosetting coating solution') may be used.

Subsequently, after applying the thermosetting coating solution 40 to the adhesive polymer substrate 20, as shown in FIG. 1e, the gas impermeable transfer substrate 45 is placed on the thermosetting coating solution 40 and the thermosetting coating solution 40 is covered with the transfer substrate 45, and the thermosetting coating solution 40 is dried. Here, as the gas-impermeable transfer substrate 45 , various types of substrates, such as a glass substrate, a semiconductor substrate, and a polymer substrate, may be used. In this embodiment, the gas-impermeable transfer substrate 45 is referred to as a second substrate corresponding to the first substrate described above.

In drying the thermosetting coating solution 40, the transfer substrate 45 is naturally dried while pressing toward the adhesive polymer substrate 20, or heat is applied while pressing the transfer substrate 45 toward the PDMS substrate 20. can be used

Specifically, in order to dry the thermosetting coating solution 40 , it is necessary to dry slowly without bubbles in the solvent in the thermosetting coating solution 40 . For example, these drying conditions may require a temperature condition at room temperature and a drying time for approximately 12 to 24 hours, in addition, the thickness of the adhesive polymer substrate 20 is thinner than a certain amount or the gas-permeable substrate 10 is porous. When used as a support, the drying time can be further shortened. In addition, when heat is applied, the drying time can also be shortened.

When the thermosetting coating solution 40 is dried in this way, the solvent in the thermosetting coating solution 40 passes through the adhesive polymer substrate 20 and the gas-permeable substrate 10 in sequence and is discharged to the outside. When drying is performed while the gas-permeable substrate 10 is placed on the bottom surface of another base substrate, etc., since gas cannot pass through the lower portion of the gas-permeable substrate 10, the evaporated solvent is applied to the gas-permeable substrate ( 10) is emitted toward the side of the edge.

In this way, when the solvent in the thermosetting coating solution 40 is evaporated, a solid thermosetting coating layer 42 in which the thermosetting coating solution 40 is dried is formed. This thermosetting coating layer 42 is firmly attached to the transfer substrate 45 and is thermosetting The coating film 32 formed on the coating layer 42 is firmly attached to the thermosetting coating layer 42 with a greater bonding force than the bonding strength with the adhesive polymer substrate 20 .

In this embodiment, the thermosetting coating liquid 40, that is, the coating liquid layer preferably includes a material that prevents the shape change of the adhesive polymer substrate 20 and the coating film 32 from occurring during the drying process.

Subsequently, as shown in FIG. 1f , when the thermosetting coating layer 42 is separated from the adhesive polymer substrate 20 together with the transfer substrate 45 , the coating film 32 is also attached to the thermosetting coating layer 42 . By separating from the polymer substrate 20 , it is possible to obtain a particle-coated substrate 46 comprising the transfer substrate 45 , the thermosetting coating layer 42 , and the coating film 32 .

On the other hand, a plurality of concave portions 22 remain on the surface of the adhesive polymer substrate 20 from which the plurality of particles 30 forming the coating film 32 have escaped, and the concave portions 22 may disappear over time. have. Therefore, after transferring the coating film 32 to the transfer substrate 45, by repeatedly performing the steps of applying the thermosetting coating solution and bonding the transfer substrate, drying the thermosetting coating solution, transferring the coating layer, etc., one formed on the gas-permeable substrate 10 The particle-coated substrate can be repeatedly made with the adhesive polymer substrate 20 .

As described above, in the coating method using particle alignment according to the present invention, the particles 30 in a dry state without using a solvent on the adhesive polymer substrate 20 formed on the gas-permeable substrate 10 are formed on the adhesive polymer substrate ( 20) It is possible to form a coating film 32 by applying pressure in a state in which it is in direct contact with the top, and to stably transfer it to various transfer substrates 45 such as a glass substrate, a semiconductor substrate, a polymer substrate, and the like. Accordingly, when forming a coating film compared to the prior art, since self-assembly of the particles in the solvent is not required, it is not necessary to precisely control temperature, humidity, etc., and the surface properties of the particles are not greatly affected. That is, the coating can be made uniformly with high density not only when the particles are charged materials, but also when the particles are non-charged (ie, electrically neutral) materials. In addition, it is possible to uniformly coat not only the hydrophilic particles, but also the hydrophobic particles. As described above, according to the present invention, the particles 30 are evenly distributed on the adhesive polymer substrate 20 by a simple method to form a single layer-level coating film 32 having a high density, and this is stably transferred to another transfer substrate 45 . can be fought with

On the other hand, Figures 2a to 2f is a step-by-step representation of a coating method using particle alignment according to another embodiment of the present invention. A coating method using particle alignment according to another embodiment of the present invention will be described with reference to FIGS. 2A to 2F as follows.

First, a gas-permeable substrate 10 is prepared and an adhesive polymer substrate 20 is formed thereon, and then a primary coating film 32 composed of a plurality of first particles 30 is formed on the adhesive polymer substrate 20 . . The specific method of forming the adhesive polymer substrate 20 and forming the primary coating film 32 is the same as described above.

After forming the first coating film 32 on the adhesive polymer substrate 20, as shown in FIG. 2A, the mask 47 on which the mask pattern 48 is formed is irradiated with light or an active gas to irradiate the adhesive polymer substrate ( 20) The area on the surface where the primary coating film 32 is formed is partially exposed. The surface of the adhesive polymer substrate 20 is covered with a primary coating film 32 composed of a plurality of first particles 30 , but the irradiated light or active gas is transmitted through the gap between the plurality of first particles 30 . It can reach the adhesive polymer substrate 20 and expose the adhesive polymer substrate 20 . And when the first particle 30 is made of a material that can transmit light or active gas, the irradiated light or active gas can pass through the first particle 30 to reach the adhesive polymer substrate 20 . .

In this embodiment, for example, when the adhesive polymer substrate 10 is made of a PDMS material, the above-described light can be specifically applied as ultraviolet light, but is not limited thereto, and visible light or infrared light depending on the material of the adhesive polymer substrate 10 . Of course, it is also applicable.

In this way, when light or an active gas is irradiated to the adhesive polymer substrate 20 in a state where the mask 47 is placed on the adhesive polymer substrate 20, as shown in FIG. 2B, the surface of the adhesive polymer substrate 20 is The adhesive force of the exposed portion 24 irradiated with light or active gas is greater than that of the non-exposed portion 25 that has not been irradiated with light or active gas. This is because the molecular weight is greatly increased due to reactions such as crosslinking and photodimerization by irradiation with the light or active gas, and solubility is reduced, and thermal properties and chemical resistance are remarkably improved. In addition, the hardness of the adhesive polymer substrate 20 is changed by irradiation with light or an active gas, or bonding with functional groups on the particle surface is made. Therefore, the first particles 30 located in the exposed portion 24 can maintain a state attached to the adhesive polymer substrate 20 with a stronger bonding force compared to the first particles 30 located in the non-exposed portion 25 .

In addition, in an embodiment of the present invention, it is possible to adjust the adhesion force of the adhesive polymer substrate 20 and the area in which the adhesion force is changed according to the irradiation time or irradiation intensity of light or active gas.

Also, in the present invention, before or after forming the coating film 32 on the adhesive polymer substrate 20 or after forming the coating film 32, the step of applying heat to the adhesive polymer substrate 20 may be further provided. This heating can also adjust the adhesion of the coating film 32 and the adhesive polymer substrate 20 similarly to the above-described irradiation of light or active gas, and specifically, the above-described adhesion can be adjusted according to the temperature or heat application method of heat. .

Subsequently, as shown in FIG. 2c, the particle removal member 50 having an adhesive force greater than the adhesion force of the non-exposed part 25 of the adhesive polymer substrate 20 and smaller than the adhesion force of the exposed part 24 was applied to the primary coating film ( 32) Touch on top and peel off. At this time, as shown in FIG. 2D , the first particles 30 disposed in the non-exposed part 25 among the plurality of first particles 30 forming the primary coating film 32 are the particle removing member 50 . It is attached to and removed from the adhesive polymer substrate 20 . As the particle removal member 50, a polymer material such as polydimethylsiloxane (PDMS), polyethylene (PE), polyvinylchloride (PVC), etc. having a difference in adhesion and relative adhesion on one surface and a difference in adhesive strength Various types of eggplants, such as scotch tape, may be used. For example, the particle removal member 50 may be applied with a low hardness 2 to 7% PDMS adhesive tape in order to utilize the removed particles.

In this way, when the first particles 30 positioned on the non-exposed portion 25 of the adhesive polymer substrate 20 are removed using the particle removal member 50, the adhesive polymer substrate 20 has the exposed portion 24. A first coating film 32 of a predetermined pattern made of the first particles 30 positioned on is provided.

Subsequently, as shown in FIG. 2e, the first particles 30 and other second particles 34 are coated on the surface of the adhesive polymer substrate 20 coated with a plurality of first particles 30 to form an adhesive polymer A secondary coating film 35 is formed on the substrate 20 . The method of coating the plurality of second particles 34 is the same as the method of coating the plurality of first particles 30 described above on the adhesive polymer substrate 20, and the specific method is as follows.

First, a plurality of dried second particles 34 are placed on the adhesive polymer substrate 20 on which the primary coating film 32 is formed. As the second particle 34, a polymer, an inorganic material, a metal, a magnetic material, a semiconductor, a biological material, etc. may be used, and specific types of each are the same as described above. And by applying pressure on the plurality of second particles 34, the second particles 34 are coated on the non-exposed portion 25 in which the first particles 30 are not disposed. The method of applying pressure to the second particles 34 is the same as the method used when coating the first particles 30 as described above, such as latex, a sponge, a hand, a rubber plate, a plastic plate, a material having a smooth surface, etc. A method of rubbing using The mechanism in which the plurality of second particles 34 are coated on the adhesive polymer substrate 20 and 20 is the same as the principle in which the first particles 30 are coated on the adhesive polymer substrate 20 .

That is, when the pressure is applied after putting the second particles 34 on the adhesive polymer substrate 20 , the second particles 34 in the portion to which the pressure is applied are attached through deformation of the adhesive polymer substrate 20 , and the adhesiveness A plurality of second concave portions 27 respectively corresponding to the second particles 34 are formed in the corresponding portion of the polymer substrate 20 . Therefore, while the second particles 34 are aligned in the non-exposed portion 25 of the adhesive polymer substrate 20 in a state in which the second particles 34 are wrapped in the second concave portion 27, the non-exposed portion 25 is A secondary coating film 25 made of a plurality of second particles 34 is formed. Of course, while the second particles 34 are partially accommodated in the empty first concave portions 22 from which the first particles 30 have escaped, the second particles 34 may be aligned and coated on the adhesive polymer substrate 20 . have.

In the present invention, since a recess is formed in the adhesive polymer substrate 20 by elastic deformation, when the particles accommodated in the recess are removed, the surface of the adhesive polymer substrate 20 disappears and the recess is returned to a smooth surface. have. In a state in which the first concave portion 22 in which the first particle 30 was accommodated is reversibly extinguished, a plurality of second particles 34 are placed on the adhesive polymer substrate 20 and pressure is applied to the non-exposed portion 25 ) may be coated with the second particle 34 while forming the second concave portion 27 corresponding to the second particle 34 .

Of course, when the first particles 30 are removed from the first concave portion 22 after a long time has elapsed after the primary coating film 32 is formed, as described above, the first concave portion 22 or the second 1 Traces of the concave portion 22 may remain on the surface of the adhesive polymer substrate 20 . In this case, the newly coated second particles 34 are partially wrapped in the first concave portion 22 or dig into the adhesive polymer substrate 20 at a position corresponding to the first concave portion 22 to form an adhesive polymer substrate. (20) can be attached.

After forming the primary coating film 32 and the secondary coating film 35 on the adhesive polymer substrate 20 in this way, the steps of applying the thermosetting coating solution and bonding the transfer substrate as described above, and separating the thermosetting coating layer (FIG. 1D) ~ 1f), as shown in Figure 2f, the primary coating film 32 and the secondary coating film 35 formed on the adhesive polymer substrate 20 through the thermosetting coating layer 42 through the transfer substrate 45 ) can be transcribed.

In transferring the coating film formed on the adhesive polymer substrate 20 to another transfer substrate 45 , the adhesive polymer substrate 20 of the secondary coating film 35 formed on the non-exposed portion 25 of the adhesive polymer substrate 20 and Since the bonding force is smaller than the bonding strength of the primary coating film 32 formed on the exposure part 24 with the adhesive polymer substrate 20 , it is also possible to transfer only the secondary coating film 35 to the other transfer substrate 45 . That is, when the bonding force of the adhesive polymer substrate 20 and the particles through exposure and the bonding strength of the thermosetting coating solution 40 and the particles are appropriately adjusted, as shown in FIG. 3, the non-exposed portion of the adhesive polymer substrate 20 ( Only the secondary coating film 35 formed on the 25 ) may be transferred to another transfer substrate 45 via the thermosetting coating layer 42 .

In addition, the coating method using particle alignment according to the present invention includes the exposure step, partial particle removal step, new particle coating step, thermosetting coating solution application and transfer substrate bonding step, thermosetting coating solution drying step, transfer step, etc. as described above. By repeatedly performing, various types of particles may be formed on the adhesive polymer substrate 20 to form various coating films arranged in a specific pattern, respectively, and this may be transferred to another transfer substrate. The alignment pattern of each particle can be variously changed by diversifying the mask pattern 48 of the mask 47 used in the exposure step.

In this way, the coating method using particle alignment according to another embodiment of the present invention is a furnace irradiated with light or active gas by partially irradiating light or active gas on the adhesive polymer substrate 20 using a mask 47 . Increase the adhesion of the light part 24 or apply heat to the adhesive polymer substrate 20 to increase the adhesion of the exposed part 24, and the particles 30 located in the non-exposed part 25 with relatively weak adhesive force By removing the coating film, it is possible to form a coating film of various patterns and transfer it to the transfer substrate 45 .

For example, after forming a plurality of coating films patterned in various forms on the adhesive polymer substrate 20 as described above, it may be transferred to another transfer substrate 45, and only the patterned secondary coating film 35 is transferred to another transfer substrate. It may be transferred to the substrate 45 , and only the patterned primary coating film 32 may be transferred to another transfer substrate 45 . When only the patterned primary coating film 32 is transferred to another transfer substrate 45, after forming the patterned primary coating film 32 on the adhesive polymer substrate 20 as shown in FIG. 2d, the secondary In a state in which the coating film 35 is not formed, by performing steps such as applying a thermosetting coating solution and bonding the electronic substrate, drying the thermosetting coating solution, and separating the thermosetting coating layer, only the patterned primary coating layer 32 is transferred to the substrate 45 can be fought with

On the other hand, Figure 4a to Figure 4d is a step-by-step view of 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. A specific method of forming a coating film of a predetermined pattern on an adhesive polymer substrate will be described in detail with reference to FIGS. 4A to 4D .

First, as shown in FIG. 4A, an adhesive polymer substrate 20 is formed on a gas-permeable substrate 10, and a mask 52 on which a mask pattern 53 is formed is irradiated with light or an active gas to irradiate an adhesive polymer substrate. The surface of (20) is partially exposed. The method of forming the adhesive polymer substrate 20 and the principle of exposure are the same as described above. In addition, by applying heat to the adhesive polymer substrate 20, it is also possible to adjust the adhesion between the particles and the adhesive polymer substrate 20 to be described later.

In this way, when light or an active gas is irradiated to the adhesive polymer substrate 20 in a state where the mask 52 is placed on the adhesive polymer substrate 20, as shown in FIG. 4B, the surface of the adhesive polymer substrate 20 is The adhesive force of the exposed portion 24 irradiated with light or active gas is greater than that of the non-exposed portion 25 not irradiated with light or active gas. After irradiating light or an active gas to the adhesive polymer substrate 20 to form the exposed portion 24, as shown in FIG. 4c, a plurality of particles 30 are aligned to form a coating film on the adhesive polymer substrate 20 (32) is formed.

Here, the specific method of forming the coating film 32 with the kind or the plurality of particles 30 of the particles 30 is the same as described above. However, in this embodiment, when the plurality of particles 30 are placed on the adhesive polymer substrate 20 on which the exposure part 24 is formed and attached to the adhesive polymer substrate 20 by applying pressure thereto, it is located on the exposure part 24 . The binding force of the particles 30 to the adhesive polymer substrate 20 is greater than the binding force of the particles 30 positioned in the non-exposed part 25 to the adhesive polymer substrate 20, and the particles positioned in the exposed part 24 (30) is more tightly coupled to the adhesive polymer substrate (20) than the particles (30) located in the non-exposed portion (25).

Subsequently, as shown in Fig. 4d, the particle removal member 50 (see Fig. 2c) having an adhesion greater than the adhesion force of the non-exposed portion 25 of the adhesive polymer substrate 20 and smaller than the adhesion force of the exposed portion 24; When the particles 30 disposed on the non-exposed portion 25 are removed from among the plurality of particles 30 forming the coating film 32 by using the coating film 32 , the coating film 32 having a pattern corresponding to the exposure pattern can be formed.

Subsequently, by further performing the secondary coating film formation step, the thermosetting coating solution application and transfer substrate bonding step, the thermosetting coating solution drying step, the thermosetting coating layer separation step, etc. as described above, the coating film made of various particles or formed in various patterns is different It can be transferred to a substrate.

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

<Experimental Example 1>

FIG. 5A is a view showing in stages of Experimental Example 1 of the present invention, and FIGS. 5B and 5C are SEM images of the particle transfer substrate in Experimental Example 1 of the present invention. For reference, the image on the right in FIG. 5C is an enlarged image of the image on the left.

Referring to FIG. 5a, first, a clean lab (LLDPE, Linear Low-Density Polyethylene) was prepared (S100). Thereafter, in order to remove the adhesion properties of the LLDPE film, TiO ₂ particles are lightly rubbed on one side of the coating (S200). The particle-coated surface of the LLDPE wrap is covered with a perforated Petri dish and fixed using a fixing rubber band (S300).

_{100nm ~ 200nm TiO 2} particles are rubbed on the top of the LLDPE wrap tightly covered in the Petri dish and coated evenly (S400).

The glass film coating agent of HiCNP, in which silicate is applied on EtOH, is sufficiently sprayed on the single-layer coating surface coated with _{TiO 2 (S500).}

The washed glass substrate is covered on the solution, and after drying at room temperature for 48 hours, primary heating is performed at 60° C. for 3 hours (S600).

After removing the rubber band for fixing and separating the LLDPE wrap from the Petri dish, the glass substrate and the LLDPE wrap on which the particles are transferred are separated, and secondary heating is performed at 150° C. for 20 minutes (S700).

Referring to FIGS. 5B and 5C , it was clearly confirmed that the surface of the particles transferred through intentional damage was not exposed but was impregnated in LLDPE in order to clearly confirm whether the particles were exposed after the particle transition process.

<Experimental Example 2>

6a, 6b, and 6c are photographs showing step by step of Experimental Example 2 of the present invention, and FIG. 6d is an SEM image of the particle transfer substrate in Experimental Example 2 of the present invention. For reference, the image on the right in FIG. 6D is an enlarged image of the image on the left.

Referring to FIGS. 6A, 6B and 6C, first, paper is cut to fit the size of the Petri dish, and then uncured Sylgard 184 (Dow Corning, USA) on the Petri dish 20% by weight based on the product After pouring the formed PDMS solution containing the negative curing agent, the paper was covered. Then, it was cured by drying at room temperature for 10 hours and heating at 60° C. for 3 hours.

In order to coat the particles with strong cohesiveness on PDMS Paper as a single layer, it was heated at 200°C for 3 hours.

_{After evenly coating 100nm ~ 200nm TiO 2} particles by rubbing on the heat-treated PDMS Paper, HiCNP's glass film coating agent coated with silicate on EtOH _{was sufficiently sprayed on the TiO 2} coated single-layer coating surface.

Put PDMS Paper on the porous plate, cover the washed glass on the surface of PDMS Paper coated with glass film coating, dry at room temperature for 10 hours, and apply 3 hours of primary heating at 60°C to evaporate EtOH solution. Thereafter, after separating the PDMS Paper from the glass, the glass substrate to which the particles were transferred was heated a second time at 200° C. for 1 hour to improve the durability of the substrate.

Thereafter, the surface of the particles transferred through intentional damage was observed to clearly confirm whether the particles were exposed after the particle transfer process. Looking at the SEM image of FIG. 6d , it was confirmed that the surface of the particles was exposed when using PDMS, unlike that coated with LLDPE.

<Experimental Example 3>

First, the paper is cut to fit the size of the Petri dish, and then the PDMS solution formed including 20% by weight of the curing agent based on the uncured Sylgard 184 (Dow Corning, USA) product is poured on the Petri dish, and then the paper covered the

Then, it was cured by drying at room temperature for 10 hours and heating at 60° C. for 3 hours. The cured PDMS Paper was treated with UV of 185 nm for 0 minutes, 15 minutes, 30 minutes, and 60 minutes, respectively.

In this way, 50 nm ~ 150 nm TiO ₂ particles were rubbed onto the UV-treated PDMS Paper to evenly coat, and then the glass film coating agent of HiCNP, in which silicate was applied on EtOH _{, was sufficiently sprayed on the TiO 2} coated single-layer coating surface.

The PDMS Paper was placed on the porous plate, the washed glass was covered on the surface of the PDMS Paper coated with the glass film coating agent, and the EtOH solution was evaporated by drying at room temperature for 10 hours and heating at 60°C for 3 hours.

Thereafter, after separating the PDMS Paper from the glass, the glass substrate to which the particles were transferred was heated a second time at 200° C. for 1 hour to improve the durability of the substrate.

_{It can be seen from FIG. 7a that the impregnation degree of TiO 2} particles varies according to the UV treatment time, and it can be seen that the surface hardness of the PDMS substrate increases with the UV treatment time and is proportional to the time.

In addition, in FIG. 7b , it can be seen that the uniformity _{of the TiO 2} particle size coated on the substrate varies according to the time of UV treatment for 0 min, 15 min, 30 min, and 60 min. The reason for this is that the surface hardness of the PDMS substrate is increased by the UV/0 treatment time, and the adhesion between large particles and the substrate is reduced, so that relatively small particles are preferentially attached.

In FIG. 7c , it is shown through a graph that the transmittance of light increases as the UV treatment time increases. In addition, it can be seen from FIG. 7d that the characters are clearly seen as the UV treatment time is longer.

7e is a graph showing the results of a methylene blue decomposition experiment to find out the photocatalytic properties. Methylene blue takes advantage of the property of losing its initial blue color and becoming transparent as bonds are broken by the photocatalytic effect. Through the graph of FIG. 7e and FIG. 7f , as the UV treatment time increases, Methylene blue becomes transparent, and it can be seen that _{TiO 2 has a photocatalytic effect.}

7g and 7h show changes in photocatalytic properties according to chemical changes on the substrate. can be checked

7i shows the hardness of the substrate. In the LBL method, the surface of the substrate was damaged even at low pencil hardness, but in the case of the substrate made through the above experimental method, there was no damage even in the case of pencil hardness 9H regardless of the UV treatment time. can be checked

7j shows that coating is possible not only in a small area but also in a size of 40 cm×40 cm, and it can be confirmed that there is no difference in refractive index with the naked eye when viewing the actually coated glass.

The embodiments of the present invention described above and shown 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 it is possible for those of ordinary skill in the art to 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 is apparent to those of ordinary skill in the art.

10: gas permeable substrate 20: PDMS substrate
22, 27: concave part 24: exposure part
25: non-exposed part 30, 34: particle
32, 35: coating film 40: thermosetting coating solution
42: thermosetting coating layer 45: transfer substrate
47, 52: mask 50: particle removing member

Claims (21)

(a) forming a coating film by coating a plurality of particles on a first substrate having gas permeability;
(b) applying a coating solution to the surface of the first substrate on which the coating film is formed;
(c) placing a second substrate on the coating solution and covering the coating solution with the second substrate; and
(d) drying the coating solution to form a coating layer to which the coating film is attached,
When the plurality of particles are non-spherical, the ratio of the average value of the coating film thickness to the average particle diameter of the particles having the top 10% particle diameter among the plurality of particles is 1.9 or less.
According to claim 1,
After step (d),
(e) separating the coating layer to which the coating film is attached from the first substrate and transferring the coating film to the second substrate via the coating layer. According to claim 1,
Further comprising the step of irradiating light or an active gas toward the first substrate before or after forming the coating film on the first substrate,
A coating method using particle alignment, characterized in that it is possible to control the adhesion force of the first substrate and the area in which the adhesion force is changed according to the irradiation time or irradiation intensity of the light or active gas. According to claim 1,
Further comprising the step of applying heat to the first substrate before or after forming the coating film on the first substrate,
A coating method using particle alignment, characterized in that the adhesion between the coating film and the first substrate can be adjusted according to the temperature of the heat or the heat application method. According to claim 1,
The first substrate includes a gas-permeable substrate and an adhesive polymer substrate provided on one surface of the gas-permeable substrate,
The coating film is a coating method using particle alignment, characterized in that provided on the adhesive polymer substrate. According to claim 1,
In the step (a), the coating method using particle alignment, characterized in that the coating on the first substrate by applying pressure by rubbing the plurality of particles. According to claim 1,
In the step (a), the plurality of particles is a coating method using particle alignment, characterized in that in direct contact with the first substrate. According to claim 1,
In the step (a), the coating film is a coating method using particle alignment, characterized in that the plurality of particles are coated in a single layer. delete According to claim 1,
Coating using particle alignment, characterized in that a plurality of concave portions are provided to be depressed on the surface of the first substrate to respectively correspond to the plurality of particles, and a depth ratio of the concave portions to the average particle diameter of the particles is 0.02 to 0.7 Way. 11. The method of claim 10,
Coating method using particle alignment, characterized in that the concave portion is reversible. According to claim 1,
The second substrate is a coating method using particle alignment, characterized in that the gas impermeable substrate. According to claim 1,
In the step (d), the coating method using particle alignment, characterized in that the solvent contained in the coating solution is discharged to the outside through the first substrate, whereby the coating solution is cured into the coating layer in a solid state. gas permeable substrate;
an adhesive polymer substrate formed on the gas-permeable substrate and capable of transmitting gas; and
A coating film comprising a plurality of particles coated in a single layer on the surface of the adhesive polymer substrate,
When the plurality of particles are non-spherical, the ratio of the average value of the coating film thickness to the average particle diameter of the top 10% particles among the plurality of particles is 1.9 or less.
15. The method of claim 14,
The gas-permeable substrate is a particle-coated substrate, characterized in that it comprises at least one of Korean paper, tissue, corrugated cardboard, hard board paper, and a porous film. 15. The method of claim 14,
The adhesive polymer substrate is a particle-coated substrate comprising at least one of polydimethylsiloxane (PDMS), polyethylene (PE), and polyvinylchloride (PVC). 15. The method of claim 14,
Further comprising a coating solution layer applied to the surface of the adhesive polymer substrate on which the coating film is formed,
The coating liquid layer is a particle-coated substrate, characterized in that it is cured through drying carried out at room temperature or heat applied conditions. (a) preparing a gas-permeable substrate;
(b) forming a coating film by coating a plurality of particles on the gas-permeable substrate;
(c) by irradiating light or an active gas toward the gas-permeable substrate with a mask having a mask pattern formed thereon to partially expose or expose the surface of the gas-permeable substrate, so that the light or active gas on the surface of the gas-permeable substrate is irradiated changing the adhesive force of the exposed part;
(d) an unexposed portion or an exposed portion in the plurality of particles forming the coating film by using the difference in adhesion between the exposed portion and non-exposed portion irradiated with light or active gas of the gas-permeable substrate and the particles of the coating film selectively removing the particles disposed on the gas-permeable substrate by using the degree of adhesion to the particle removal member;
(e) applying a coating solution to the surface of the gas-permeable substrate on which the coating film is formed;
(f) covering the coating solution by placing a gas-impermeable substrate on the coating solution; and
(g) by evaporating the solvent contained in the coating solution through the gas-permeable substrate to dry it, the coating film is attached to form a cured coating layer in a solid state,
The particle removal member has an adhesive force greater than the adhesion force of the non-exposed part and smaller than the adhesion force of the exposed part, so that the particles disposed on the non-exposed part are removed when the particle removing member is brought into contact with the coating film and peeled off.
(a) preparing a gas-permeable substrate;
(b) forming a primary coating film by coating a plurality of first particles on the gas-permeable substrate;
(c) by irradiating light or an active gas toward the gas-permeable substrate with a mask having a mask pattern formed thereon to partially expose or expose an area on the surface of the gas-permeable substrate in which the primary coating film is formed, the surface of the gas-permeable substrate changing the adhesive force of the exposed portion irradiated with light or active gas;
(d) the plurality of agents forming the primary coating film by using the difference in adhesion between the first particles of the primary coating film and the exposed part and non-exposed part irradiated with light or active gas of the gas-permeable substrate selectively removing one particle from the gas-permeable substrate by using the degree of adhesion of the first particles disposed in the non-exposed part or the exposed part to the particle removal member;
(e) forming a secondary coating film by coating a plurality of second particles on the region from which the first particles are removed of the gas-permeable substrate;
(f) applying a coating solution to the surface of the gas-permeable substrate on which the primary coating film and the secondary coating film are formed;
(g) covering the coating solution by placing a gas-impermeable substrate on the coating solution; and
(h) by evaporating the solvent included in the coating solution through the gas-permeable substrate and drying it, at least one of the primary coating film and the secondary coating film is attached to form a cured coating layer in a solid state, and ,
The particle removal member has an adhesive force greater than that of the non-exposed part and smaller than the adhesive force of the exposed part, so that when the first coating film is brought into contact and removed, the first particles disposed on the non-exposed part are removed. .
(a) preparing a gas-permeable substrate;
(b) exposure to light or active gas on the gas-permeable substrate surface by partially exposing or exposing the surface of the gas-permeable substrate by irradiating light or an active gas toward the gas-permeable substrate with a mask having a mask pattern formed thereon changing the adhesive force of the negative;
(c) forming a coating film by coating a plurality of particles on the gas-permeable substrate;
(d) an unexposed portion or an exposed portion in the plurality of particles forming the coating film by using the difference in adhesion between the exposed portion and non-exposed portion irradiated with light or active gas of the gas-permeable substrate and the particles of the coating film selectively removing the particles disposed on the gas-permeable substrate by using the degree of adhesion to the particle removal member;
(e) applying a coating solution to the surface of the gas-permeable substrate on which the coating film is formed;
(f) covering the coating solution by placing a gas-impermeable substrate on the coating solution; and
(g) by evaporating the solvent contained in the coating solution through the gas-permeable substrate to dry it, the coating film is attached to form a cured coating layer in a solid state,
The particle removal member has an adhesive force greater than the adhesion force of the non-exposed part and smaller than the adhesion force of the exposed part, so that the particles disposed on the non-exposed part are removed when the particle removing member is brought into contact with the coating film and peeled off.
(a) preparing a gas-permeable substrate;
(b) exposure to light or active gas on the gas-permeable substrate surface by partially exposing or exposing the surface of the gas-permeable substrate by irradiating light or an active gas toward the gas-permeable substrate with a mask having a mask pattern formed thereon changing the adhesive force of the negative;
(c) forming a first coating film by coating a plurality of first particles on the gas-permeable substrate;
(d) the plurality of first forming the primary coating film using the difference in adhesion between the exposed portion and non-exposed portion irradiated with light or active gas of the gas-permeable substrate and the first particles of the primary coating film selectively removing the particles from the gas-permeable substrate by using the degree of adhesion of the particles disposed on the non-exposed part or the exposed part to the particle removal member;
(e) forming a secondary coating film by coating a plurality of second particles on the region from which the first particles are removed of the gas-permeable substrate;
(f) applying a coating solution to the surface of the gas-permeable substrate on which the primary coating film and the secondary coating film are formed;
(g) covering the coating solution by placing a gas-impermeable substrate on the coating solution; and
(h) by evaporating the solvent included in the coating solution through the gas-permeable substrate and drying it, at least one of the primary coating film and the secondary coating film is attached to form a cured coating layer in a solid state, and ,
The particle removal member has an adhesive force greater than that of the non-exposed part and smaller than the adhesive force of the exposed part, so that when the first coating film is brought into contact and removed, the first particles disposed on the non-exposed part are removed. .

Images