WO2015182867A1 - Substrate partially exposing particles and method for manufacturing same - Google Patents

Abstract

A method for manufacturing a particle-coated substrate, according to one embodiment of the present invention, comprises: a preparation step of preparing a tight adhesion-type polymer substrate; a coating step of coating a plurality of particles on top of the tight adhesion-type polymer substrate; and an exposing step of partially exposing the plurality of particles by removing the tight adhesion-type polymer substrate.

Description

Particle partially exposed substrate and its manufacturing method

The present invention relates to a particle coated substrate and a method for producing the same.

BACKGROUND OF THE INVENTION There is a need in the art for a technique of arranging and coating nanometer-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.

In the fine particle alignment coating technique, there is a need for a technique for stably coating a substrate surface without chemical bonding. In this case, the particles may be functional particles having a special function imparted to the surface, and coating a single layer on the surface of the substrate is very advantageous in terms of production cost, side effects (environmental pollution and human exposure), transparency, and the like. However, the technique of producing a single layer of fine diameter particles is performed at the surface or the interface, such as Langmuir-Blodgett (LB) method (see Korean Patent Application Publication No. 10-2006-2146), solution phase There are limitations in terms of commercial use and various applications because they are made through chemical reactions, and temperature, humidity, etc. must be precisely controlled. In addition, the surface properties of the particles (eg, hydrophobicity, charge properties, surface roughness), etc., on the substrate may affect particle migration. As a result, the particles may aggregate together and may not be evenly applied on the substrate. In addition, there may be a limit to materials such as particles coated by the LB method, the substrate on which the particles are coated.

The present invention provides a coating method using a particle alignment that can evenly apply a variety of functional particles on the adhesive polymer substrate, and to provide a method for easily preparing a particle coating substrate utilizing the special features of this coating method.

Through this coating method, even in dry conditions without using a solvent, various functional particles can be aligned on the surface of the adhesive polymer substrate at a monolayer level without additional treatment such as an adhesive. In addition, some of the particles are incorporated into the adhesive polymer in a predetermined ratio during the alignment process. The present invention seeks to provide a particle coated substrate in which particles are transferred to a variety of substrates using these features, while the particle sites embedded in the adhesive polymer are exposed from the substrate.

In addition, to provide a particle coating substrate having good durability and long life characteristics.

Method for producing a particle coating substrate according to the present embodiment, the preparation step of preparing an adhesive polymer substrate; A coating step of coating a plurality of particles on the adhesive polymer substrate; Forming a substrate on the adhesive polymer substrate and the plurality of particles; And coating the plurality of particles by removing the adhesive polymer substrate.

Particle coating substrate according to the present embodiment, the substrate; And a plurality of particles partially embedded in the substrate and partially exposed.

Particle coating method that can be used in the method for producing a particle coating substrate according to the present embodiment may form a coating film by applying a pressure on the adhesive polymer substrate in the dry state without using a solvent or an adhesion aid. In this case, 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. Accordingly, recesses corresponding to the particles may be 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 environmental conditions such as temperature, humidity, and particle concentration required for self-assembly and spin coating when forming a coating film, and can easily coat particles having various surface properties in a wide range of environments and conditions. . The monolayer particle coating can be made uniformly at high density, not only when the particles are chargeable or easy hydrogen bonding, but also non-chargeable (ie, near charge neutral) and hydrophobic materials. As such, it is possible to form a single layer particle coating layer on the adhesive polymer substrate by an easy method.

In addition, it is possible to transfer the particles to various substrates by using a feature in which a part of the particles are incorporated into the adhesive polymer in a predetermined ratio during the alignment process, and a particle coating substrate may be formed in which the particles are partially exposed.

By applying a variety of functional particles can be used as a functional member for a variety of applications. This functional member may have few particles which are not exposed to the outside and cannot exhibit functionality. Thereby, a very efficient function can be exhibited while reducing unnecessary particle loss.

In addition, particle falling from the substrate due to external force is significantly reduced, and a particle coated substrate having good long life characteristics can be produced.

1A to 1F are cross-sectional views illustrating a method of manufacturing a particle coating substrate according to an embodiment of the present invention.

2A and 2B are cross-sectional views illustrating various examples of the adhesive polymer substrate after removing the coating film formed by the coating method using the particle alignment according to the embodiment of the present invention.

3 is electron micrographs of the coating film formed by varying the average particle diameter of the SiO ₂ particles in Experimental Example 1 of 160 nm, 330 nm, 740 nm, 1480 nm, 3020 nm, and 5590 nm.

Figure 4 is an electron micrograph of the coating film formed by varying the average particle diameter of the polystyrene particles to 800nm, 2010mn in Experimental Example 2 of the present invention.

5 is an electron micrograph of the adhesive polymer substrate, SiO ₂ coating film, Ag ₃ PO ₄ coating film, TiO ₂ coating film in Experimental Example 3 of the present invention.

FIG. 6 is a photograph of an adhesive polymer substrate, an adhesive polymer substrate on which an SiO ₂ coating film is formed, an adhesive polymer substrate on which an Ag ₃ PO ₄ coating film is formed, and an adhesive polymer substrate on which a TiO ₂ coating film is formed on a letterpress in Experimental Example 3 of the present invention. .

FIG. 7 is a confocal laser scanning microscope (CLSM) photograph of an enlarged 1000 times and 6000 times SiO ₂ coating film formed on a glass substrate, a polystyrene substrate, and an adhesive polymer substrate in Experimental Example 4 of the present invention.

8 is CLSM photographs of the coating film formed by the particle detachment site and recoating in Experimental Example 5 of the present invention.

9 is a CLSM and electron micrographs of the second SiO ₂ coating film according to the Example and Comparative Example in Experimental Example 6 of the present invention.

FIG. 10 is an atomic force microscope (AFM) image of a region where particles are removed from an SiO ₂ coating layer in Experimental Example 7 of the present invention.

FIG. 11 is a photograph of a SiO ₂ coating film formed on a 15 cm diameter Petri dish substrate in Experimental Example 8 of the present invention. FIG.

12 is an electron microscope photograph of the front surface of the coating film formed in Experimental Example 9 of the present invention.

13 is an electron micrograph photographing the side surface of the coating film formed in Experimental Example 9 of the present invention. FIG. 14 is an AFM image taken after detaching some particles of the coating film using the adhesive tape in Experimental Example 9 of the present invention; Line profile in the coating film.

15 is an average particle height and settlement of a SiO ₂ coating or PS coating film, an amine (+ charge) SiO ₂ coating film formed on a glass substrate, 5% PDMS substrate, 10% PDMS substrate, 20% PDMS substrate in Experimental Example 9 of the present invention A graph showing the rate.

FIG. 16 shows average particle heights and settlement rates of coating films formed using SiO ₂ particles having an average particle diameter of 300 nm on glass substrates, 5% PDMS substrates, 10% PDMS substrates, and 20% PDMS substrates in Experimental Example 9 of the present invention. The graph shown.

17 is a graph showing the average particle height and settling rate of the coating film formed using the average particle diameter of 150, 300, 750, 1500 nm particles in Experimental Example 9 of the present invention.

18 is a photograph taken after the SiO ₂ coating film is formed on 7, 10, 20% PDMS substrate in Experimental Example 10 of the present invention.

19 is a photograph taken after the SiO ₂ coating film formed by Experimental Example 10 of the present invention is transferred onto a first substrate (PDMS substrate formed by including 7% by weight of a hardener).

20 is a photograph taken after transferring the SiO ₂ coating film formed by Experimental Example 10 of the present invention to a second substrate (PDMS substrate formed by including 10% by weight of a curing agent).

FIG. 21 is a photograph taken after the SiO ₂ coating film formed by Experimental Example 10 of the present invention is transferred onto a third substrate (PDMS substrate formed by including 20% by weight of a hardener).

FIG. 22 is a photograph of SiO ₂ coating films formed on various adhesive polymer substrates and comparative example substrates in Experimental Example 11 of the present invention. FIG.

FIG. 23 is a photograph of an SiO ₂ coating film formed on an adhesive polymer substrate and a substrate in Example 1. FIG.

24 is a photograph of an SiO ₂ coating film formed on an adhesive polymer substrate and a substrate in Example 2. FIG.

25 is a photograph of a TiO ₂ coating film formed on an adhesive polymer substrate and a substrate in Example 3. FIG.

FIG. 26 is a photograph of a TiO ₂ coating film formed on an adhesive polymer substrate and a substrate in Example 4.

27 is a photograph of a TiO ₂ coating film formed on an adhesive polymer substrate and a substrate in Example 5. FIG.

28 is a photograph of a TiO ₂ coating film formed on an adhesive polymer substrate and a substrate in Example 6. FIG.

29 is an acrylic substrate (Acryl), glass substrate (Glass), particle coating substrate of Example 1 (SiO ₂ -Acryl), particle coating substrate of Example 4 (TiO ₂ -Acryl), particle coating substrate of Example 5 It is a photograph of evaluation of the optical transmittance of (TiO ₂ -Glass).

<Description of Drawing>

10: adhesive polymer substrate

10a: flat

12: recess

20: particle

30: description

Hereinafter, with reference to the accompanying drawings will be described an embodiment of the present invention; However, the present invention is not limited to these embodiments and may be modified in various forms.

In the drawings, illustrations of parts not related to the description are omitted in order to clearly and briefly describe the present invention, and the same reference numerals are used for the same or extremely similar parts throughout the specification. In the drawings, the thickness, the width, and the like are enlarged or reduced in order to clarify the description. The thickness, the width, and the like of the present invention are not limited to those shown in the drawings.

And when any part of the specification "includes" other parts, unless otherwise stated, other parts are not excluded, and may further include other parts. In addition, when a part of a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where the other part is "just above" but also the other part located in the middle. When parts such as layers, films, regions, plates, etc. are "just above" another part, it means that no other part is located in the middle.

Hereinafter, with reference to the accompanying drawings will be described in detail a method for producing a particle coated substrate and a particle coated substrate produced thereby.

Particle coating substrate according to an embodiment of the present invention is a preparation step of preparing an adhesive polymer substrate, a coating step of coating a plurality of particles on the adhesive polymer substrate, the step of forming a substrate on the adhesive polymer substrate and the plurality of particles And an exposure step of partially exposing the plurality of particles by removing the adhesive polymer substrate.

1A to 1F are cross-sectional views illustrating a method of manufacturing a particle coating substrate according to an embodiment of the present invention.

First, as shown in FIG. 1A, in the preparation step ST10, the adhesive polymer substrate 10 is prepared. The adhesive polymer substrate may have a smooth surface 10a. That is, the surface of the adhesive polymer substrate 10 may have a state in which a specific pattern or curvature is not formed, and movement of particles (reference numeral 20 in FIG. 1B) forming a coating film (reference numeral 22 in FIG. 1C) thereon. It can have a level of surface roughness and structure that does not limit.

In this embodiment, the adhesive polymer substrate 10 includes various adhesive polymer materials in which adhesion exists. Adhesive polymers are generally distinguished from adhesives because they do not have commonly used adhesive properties. At least the adhesive polymer has an adhesion of less than about 0.6 kg / inch of the adhesive of the Scotch® Magic ™ Tape (ASTM D 3330 evaluation). In addition, the adhesive polymer may 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), a polymer material for wrap, adhesion or sealing, including polyethylene (PE), polyvinyl chloride (PVC), etc. A protective film containing these can be used. In particular, as the adhesive polymer, it is easy to control the hardness and PDMS can be easily used in various forms. The adhesive polymer substrate 10 may be prepared by coating an adhesive polymer on a base substrate or by attaching an adhesive polymer in a sheet or film form. In addition, the adhesive polymer substrate may further have a permeability through which gas or vapor can pass. One method of imparting air permeability is a method of coating an adhesive polymer on paper, a porous film or a porous structure.

Here, the term "adhesive polymer material" generally refers to an organic polymer material including silicon in a solid state or endowed with adhesive properties through plasticizer addition or surface treatment. The adhesive polymer material is generally easy to be deformed by the linear molecular structure and may have a low surface tension. The excellent adhesion of such an adhesive polymer material is due to the soft (flexible) surface material and low surface tension, etc., which are easy to deform the surface in the fine region. The low surface tension of the adhesive polymer material has the property of broadly adhering to the particles 20 to be attached (similar to the wetting of the solution), and the flexible surface is in seamless contact with the particles 20 to be attached. To lose. Through this, it has the characteristics of the adhesive polymer which is easily detachable to the solid surface without the complementary bonding force. 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 mostly organic polymer (35-50 dynes / cm), natural cotton ( 면, 73 dynes / cm), and metal (eg silver (Ag) is 890 dynes). / cm, aluminum (Al) is less than 500 dynes / cm), inorganic oxide (for example, 1000 dynes / cm for glass, 1357 dynes / cm for iron oxide). In addition, in the case of a wrap including PE, PVC, etc., a large amount of plasticizer is added to improve adhesion, and thus has a low surface tension.

Subsequently, as shown in FIGS. 1B and 1C, in the coating step ST12, the plurality of particles 20 are aligned to form a coating film 22 on the adhesive polymer substrate 10. This is explained in more detail.

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 plurality of particles 20 may include various materials for forming a coating film (reference numeral 22 of FIG. 1C, hereinafter the same). That is, the plurality of particles 20 may include a polymer, an inorganic material, a metal, a magnetic material, a semiconductor, a biological material, and the like. It may be a particle having a special functionality, it may be a composite particle made of a functional coating. In addition, the coating film may be formed by mixing particles having different properties.

 As the polymer, for example, polystyrene (PS), polymethyl methacrylate (PMMA), polyacrylate, polyvinyl chloride (PVC), polyalphastyrene, polybenzyl methacrylate, polyphenyl methacrylate, Polydiphenyl methacrylate, polycyclohexyl methacrylate, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer and the like can be used.

As the inorganic substance, for example, 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 can be used.

As the metal, for example, gold, silver, copper, iron, platinum, aluminum, platinum, zinc, cerium, thallium, barium, yttrium, zirconium, tin, titanium, or an alloy thereof may be used.

As the semiconductor, for example, silicon, germanium, or a compound semiconductor (for example, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InP, InAs, InSb, etc.) may be used.

Biomaterials include, for example, particles coated on, or particles of, proteins, peptides, ribonucleic acid (RNA), deoxyribonucleic acid (DNA), polysaccharides, oligosaccharides, lipids, cells, and complex materials thereof. Included particles and the like can be used. For example, a polymer particle coated with an antibody binding protein called protein A may be used.

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. At this time, the particles 20 preferably have a spherical or elliptical shape.

Such particles 20 may have an average particle diameter of 10 nm to 100 μm. If the average particle diameter is less than 10 nm it may be a form that is entirely wrapped by the adhesive polymer substrate 10 may be difficult to coat the particle 20 to a single layer level. In addition, when it is less than 10nm it may be difficult for the particles to move individually by the force that the particles aggregate and rub together even in a dry state. If the average particle diameter exceeds 100 mu m, the adhesion of particles may appear weak. In this case, the average particle diameter may be more preferably 50 nm to 10 ㎛. However, the present invention is not limited thereto, and the average particle diameter may vary depending on the material of the particles or the material of the adhesive polymer substrate 10. At this time, when the particle 20 is spherical, the diameter of the particle 20 can be used as the particle diameter. When the particle 20 is not spherical, various measuring methods may be used. For example, average values of the long axis and the short axis may be used as the particle diameter.

Subsequently, as illustrated 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, a method of rubbing 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 20 by various methods.

In the present embodiment, when the particles 20 are raised on the plane 10a of the adhesive polymer substrate 10 and then pressure is applied, the particles 20 in the pressurized portion are in close contact with each other by deformation of the adhesive polymer substrate 10. . As a result, recesses 12 corresponding to the particles 20 are formed in corresponding portions. Therefore, the particles 20 are aligned with the adhesive polymer substrate 10 while the recesses 12 surround the particles 20. 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 recess 12 may disappear due to the elastic restoring force of the substrate, or the position of the recess 12 may also be changed according to the movement of the particles. Due to this reversible action, the particles 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 becomes weak over time or Broad meaning also includes cases that are extinguished and no longer reversible). Particles 20 that are not bonded to the substrate is moved to the area of the adhesive polymer substrate 10 is not coated with the particle 20 by the rubbing force, etc., by the particle 20 in the uncoated portion The concave portion 12 is formed and the adhesive polymer substrate 10 and the particle 20 are bonded while the concave portion 12 surrounds the particles 20. Through this process, a single layer particle coating film 22 is formed on the adhesive polymer substrate 10 at a high density.

The concave portion 12 may have a shape corresponding to the shape of the particle 20 to surround a portion of the particle 20. For example, when the particles 20 are spherical, the recesses 12 may also have a rounded shape so that the recesses 12 may be in close contact with a part of the particles 20. 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.

At this time, the ratio (sedimentation rate) L1 / D of the depth L1 of the recess 12 to the average particle diameter D of the particles 20 may be 0.02 to 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 the degree of particle exposure of the finally obtained particle coating substrate may be weak.

In this 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 more coupled. 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 attached to an empty space on the surface of the adhesive polymer substrate 10. do. According to such rearrangement characteristics, the coating layer 22 may be coated at a single layer level to have a high density. For example, the centers of the particles 20 may be arranged to form a hexagonal shape. On the other hand, when the particle 20 is non-spherical (eg, Ag ₃ PO ₄ ) it can be defined by a variety of methods monolayer level. 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% particles 20 (that is, the particles 20 having a larger particle size within 10%) of the particles 20 is 1.9 or less. Can be seen to be coated at a monolayer level. However, the present invention is not limited thereto, and the coating film 22 may have a multilayer structure according to the type and particle diameter of the particles 20. This also belongs to the scope of the present invention.

In this embodiment, the coating film 22 is formed 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. Accordingly, when the coating film 22 is formed, self-assembly of the particles 20 in the solvent is not required, so it is not necessary to precisely control the temperature, humidity, and the like, and is not greatly influenced by the surface characteristics of the particles 20. . That is, even when the particle 20 is a chargeable material as well as a non-chargeable (ie, charge-neutral) material, the coating may be uniformly performed at a high density. In addition, not only hydrophilic particles but also hydrophobic particles can be uniformly coated. As described above, according to the present exemplary embodiment, the coating layer 22 having a single density may be formed by uniformly distributing the particles on the adhesive polymer substrate 10 by a simple method.

On the other hand, the particle coating film 22 may be formed in a predetermined pattern by removing a part of the particles after the coating step. Particles coated as described above on the adhesive polymer substrate are characterized by being easily transferred to a substrate having a higher adhesion or adhesion. By using this property, a portion of the particles of the particle coating film may be transferred and removed to form a predetermined pattern. In conclusion, it is possible to obtain a particle coating substrate in which particles are arranged and exposed in a predetermined pattern. The shape of the pattern is not limited.

In the present embodiment, since the recess 12 is formed in the adhesive polymer substrate 10 by elastic deformation, in the portion where the coating film 22 is removed thereafter, as shown in FIG. 2A, the adhesive polymer substrate 10 is formed. The recessed portion 12 is reversibly removed and returned to the smooth surface 10a. However, when the coating film 22 is removed after a long time after the coating film 22 is formed, as shown in FIG. 2B, the traces of the shape of the recesses 12 are formed on the surface of the adhesive polymer substrate 10. May remain.

Subsequently, a substrate is formed on an adhesive polymer substrate and a coating film composed of a plurality of particles. Forming the substrate may preferably include placing a substrate composition on the adhesive polymer substrate and the plurality of particles, and curing the substrate composition to form a substrate. As an example, what is shown in FIG. 1D and FIG. 1E is mentioned. The material of the substrate is not limited. It may be an organic substrate such as a polymer, may be an inorganic substrate such as silicate, may be silica glass, or may be a substrate made of other composite materials. In addition, the substrate may be made of a multilayer. As an example, the method of contact | adhering with the board | substrate with sufficient strength after apply | coating on a particle | grain with an organic or inorganic coating material is mentioned.

Various methods may be used as a method of placing the composition for forming the substrate 30 on the coating film 22 composed of the adhesive polymer substrate 10 and the plurality of particles 20. In one example, the substrate composition may be applied onto the adhesive polymer substrate 10 and the plurality of particles 20. Alternatively, as shown in FIGS. 1D and 1E, a method of placing the adhesive polymer substrate 10 on the substrate composition such that the plurality of particles 20 are positioned is also possible.

As the organic substrate such as a polymer, various polymers capable of stably fixing and supporting the plurality of particles 20 may be used. And the polymer substrate can be cured under specific conditions, including cured resin. For example, in the present embodiment, the polymer substrate may be cured by ultraviolet (UV) or the like including an ultraviolet curable resin. When using an ultraviolet curable resin, it can be easily hardened by irradiating light, such as an ultraviolet-ray.

The ultraviolet curable resin may include various materials to receive the ultraviolet rays and cause crosslinking and curing. For example, the ultraviolet curable resin may include oligomers (base resins), monomers (reactive diluents), photopolymerization initiators, and various additives. can do.

The oligomer is an important component that influences the physical properties of the resin, and forms a polymer bond by a polymerization reaction to cause curing. Depending on the structure of the skeleton molecule, it may be made of an acrylate such as polyester, epoxy, urethane, polyether, polyacrylic, and the like. The monomer can serve as a diluent of the oligomer and can participate in the reaction. A crosslinking agent may be further included for crosslinking. The photopolymerization initiator absorbs ultraviolet rays to generate radicals or cations to initiate polymerization, and may include one or more materials. The additive is additionally added depending on the use, and there may be a photosensitizer, a colorant, a thickener, a polymerization inhibitor, and the like depending on the use.

Subsequently, as shown in FIG. 1F, the substrate composition is cured and the adhesive polymer substrate (reference numeral 10 of FIG. 1E) is removed to partially expose the plurality of particles to prepare a particle coated substrate.

A portion of the plurality of particles 20 that is wrapped in the adhesive polymer substrate 10 may be exposed on the substrate 30. Thereby, the ratio (L2 / D) of the height L2 of the exposed part with respect to the average particle diameter D of the some particle 20 is 0.02-0. 98 may be. When the ratio (L2 / D) is less than 0.02, the bonding force between the particles 20 and the adhesive polymer substrate 10 is not sufficient, so that the coating film 22 may be formed on the adhesive polymer substrate 10 by the plurality of particles 20. This may not be stably formed and the exposure of the particles may be insufficient. When the ratio L2 / D exceeds 0.50, the particles 20 may not be stably fixed by the substrate 30.

The particle coated substrate according to this embodiment can be arranged and exposed at a monolayer level. Particles that are not exposed from the substrate by being prepared by the method described above may be 10% or less of the total particles on a number basis. In particular, it may be 5% or less and may be rarely present. In addition, the particles may be present in close proximity to acceptable theoretical densities. For example, when the average particle diameter of the particles is referred to as D, and the average distance between the exposed particles (distance between particle centers) is P, it may be exposed while satisfying D ≦ P ≦ 1.5D. In addition, the particles can be precisely aligned by the particle coating method described above, and in particular can be exposed in alignment in the form of hexagonal.

In addition, when the plurality of particles are non-spherical, the ratio of the average value of the thickness of the coating layer consisting of the plurality of particles to the average particle diameter of the top 10% particles of the plurality of particles is formed to be 1.9 or less to be partially exposed have.

In addition, the substrate may be formed of a single material, or may be formed of multiple layers. As an example of the multilayer, it may be configured to include a coating layer in contact with the particles and a support substrate in contact with the coating layer. This structure can be obtained by coating a substrate composition on an adhesive substrate and a coating film composed of a plurality of particles, attaching a supporting substrate thereon, and then curing. As another example of the multilayer, it may include a coating layer in contact with the particles, a pressure-sensitive adhesive layer applied on the coating layer and a release film that can be attached to the adhesive layer and released. It may be prepared in the form of a functional adhesive sheet and may be prepared in a form that can be attached to the skin complex while removing the release film.

As such, according to the present exemplary embodiment, the particles 20 for various functions may be partially exposed from the substrate 30 fairly uniformly, thereby realizing the functions more efficiently. For example, if the particle 20 includes a photocatalytic material and there is a material covering the particles 20, the light may not be transmitted or distorted due to the transmittance of the material. As a result, the amount of light used in the photocatalytic reaction may be reduced compared to the actual light, thereby reducing the photocatalytic efficiency. In contrast, in the present embodiment, a part of the particles 20 may be exposed to the outside to use all of the light, thereby maximizing the photocatalytic efficiency.

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 was prepared, consisting of PDMS, formed of 10% by weight of a curing agent based on Silgard 184 (Dow Corning, USA).

Adhesion to the SiO ₂ coating film by using a sponge enclosed in a latex film combines the SiO ₂ particles and adhesion to a polymer substrate, forming a concave portion on the adhesion surface of the polymer substrate by rubbing while applying a pressure by hand and then placed the SiO ₂ particles on a polymer substrate Formed.

At this time, the electron micrographs of the coating film formed by varying the average particle diameter of the SiO ₂ particles to 160 nm, 330 nm, 740 nm, 1480 nm, 3020 nm, and 5590 nm are shown in FIGS. 3A, 3B, 3C, 3D, (e) and (f) are shown, respectively. Referring to FIG. 3, it can be seen that the centers are arranged in an arrangement of hexagonal blades such that SiO ₂ particle diameters have a high density. That is, according to the present invention it can be seen that the particles can be evenly coated with a single layer of high density.

Experimental Example 2

An adhesive polymer substrate was prepared, consisting of PDMS formed with 10% by weight of a curing agent based on Sylgard 184 product.

The polystyrene particles were placed on the adhesive polymer substrate and rubbed while applying pressure by hand using a sponge wrapped with a latex film to form a recess on the surface of the adhesive polymer substrate, thereby combining the polystyrene particles and the adhesive polymer substrate to form a polystyrene coating film.

At this time, the electron micrographs of the coating film formed by varying the average particle diameter of the polystyrene particles to 800 nm and 2010 mn are shown in FIGS. 4A and 4B, respectively. Referring to FIG. 4, it can be seen that the centers of the particles are arranged in a hexagonal arrangement so that the polystyrene particle diameters have a high density. That is, according to the present invention it can be seen that the particles having a non-charge property can be evenly coated with a high density.

Experimental Example 3

A plurality of adhesive polymer substrates including PDMS formed by including 10% by weight of a curing agent based on Sylgard 184 product were prepared.

SiO ₂ particles with an average particle diameter of 750 nm were placed on the adhesive polymer substrate, and then rubbed under pressure by hand using a sponge wrapped with a latex film to form recesses on the surface of the adhesive polymer substrate to bond the SiO ₂ particles with the adhesive polymer substrate. To form a SiO ₂ coating.

Ag ₃ PO ₄ particles are placed on another adhesive polymer substrate, and then rubbed under pressure by hand using a sponge wrapped with a latex film to bond the Ag ₃ PO ₄ particles with the adhesive polymer substrate while forming a recess in the surface of the adhesive polymer substrate. To form an Ag ₃ PO ₄ coating.

The TiO ₂ particles having an average particle diameter of 40 nm were placed on another adhesive polymer substrate, and then rubbed while applying pressure by hand using a sponge wrapped with a latex film to form recesses on the surface of the adhesive polymer substrate, thereby adhering the TiO ₂ particles to the adhesive polymer substrate. Were combined to form a TiO ₂ coating film. At this time, the TiO ₂ particles were formed with a multi-layered structure even under the pressure of rubbing and washing with ethanol and distilled water due to the small diameters.

Electron micrographs of the uncoated adhesive polymer substrate, the SiO ₂ coating film, the Ag ₃ PO ₄ coating film, and the TiO ₂ coating film are shown in FIGS. 5 (a), (b), (c) and (d), respectively. Referring to (b) to (d) of Figure 5, it can be seen that each coating film is uniformly and evenly distributed.

After the adhesive polymer substrate, the adhesive polymer substrate with the SiO ₂ coating film, the adhesive polymer substrate with the Ag ₃ PO ₄ coating film, and the adhesive polymer substrate with the TiO ₂ coating film were placed on the letterpress, the photographs are shown in FIGS. 6A and 6B. , (c) and (d) are shown, respectively. Referring to Figure 6 (b) ~ (d), it can be seen that each coating film has excellent transparency. That is, it can be seen that the coating film is coated at a single layer level.

Experimental Example 4

Experiments were conducted to explain the difference in particle coating properties between the adhesive polymer substrate and other substrates. A washed general glass substrate, a polystyrene (PS) substrate, and an adhesive polymer substrate were prepared. At this time, the adhesive polymer substrate is made of PDMS formed by including 10% by weight of a curing agent based on the Sylgard 184 product. SiO ₂ particles having an average particle diameter of 750 nm were placed on the substrate, and then rubbed under pressure by hand using a sponge wrapped with a latex film to form an SiO ₂ coating film.

Confocal laser scanning microscopy (CLSM) photographs of the SiO ₂ coating film formed on the glass substrate, the PS substrate and the adhesive polymer substrate at 1000 and 6000 times magnification are shown in FIGS. 7A, 7B, and 7C, respectively. .

In the case of using a glass substrate or a PS substrate as shown in (a) and (b) of FIG. 7, the particles are irregularly coated with a low density, while in the PDMS substrate as shown in (c) of FIG. It can be seen that an aligned monolayer coating film is formed.

Experimental Example 5

In order to show reversible adhesion between the adhesive polymer substrate and the particles, the following experiment was conducted. An adhesive polymer substrate was prepared, consisting of PDMS formed with 10% by weight of a curing agent based on Sylgard 184 product. SiO ₂ particles with an average particle diameter of 750 nm were placed on the adhesive polymer substrate, and then rubbed under pressure by hand using a sponge wrapped with a latex film to form recesses on the surface of the adhesive polymer substrate to bond the SiO ₂ particles with the adhesive polymer substrate. To form a SiO ₂ coating.

A portion of the particle coating film was removed as shown in FIGS. 8A and 8B by attaching and detaching an adhesive tape (3M Magic Tape, USA) to a part of the area where the particles were coated. And then placed the after SiO ₂ particles having an average particle diameter of 750nm on the adhesion polymer substrate again wrapped in a latex film with a sponge to form a rubbed while applying a pressure with hands concave on the surface of adhesion between the polymer substrate SiO ₂ particles and the adhesion between a polymer substrate To combine to form a SiO ₂ coating. As a result, as shown in (c) of FIG. 8, it was confirmed that a coating layer having a single layer level in which particles were aligned at a high density was formed in a portion where the adhesive tape was detached.

Experimental Example 6

In order to show the difference between the method of coating the particles on the adhesive polymer substrate and the use of particle alignment through general self-assembly, the following experiment was conducted. An adhesive polymer substrate was prepared, consisting of PDMS formed with 10% by weight of a curing agent based on Sylgard 184 product. SiO ₂ particles with an average particle diameter of 750 nm were placed on the adhesive polymer substrate, and then rubbed under pressure by hand using a sponge wrapped with a latex film to form recesses on the surface of the adhesive polymer substrate to bond the SiO ₂ particles with the adhesive polymer substrate. To form a first SiO ₂ coating film. After removing a portion of the first SiO ₂ coating film using an adhesive tape, the SiO ₂ particles were formed by rubbing while applying pressure by hand using a sponge wrapped with a latex film without placing additional particles on the surface of the adhesive polymer substrate. And an adhesive polymer substrate were combined to form a second SiO ₂ coating film according to the embodiment.

CLSM photograph of the second SiO ₂ coating film is shown in Figure 9 (a). As a comparative example, an electron micrograph of a coating film formed using a general LB method is illustrated in FIG. 9B.

Referring to FIG. 9 (a), it can be seen that in the rearrangement of the particles for forming the second SiO ₂ coating film, the gap between the particles is widened due to the insufficient number of particles for forming a coating layer having a seamless monolayer level. On the other hand, referring to Figure 9 (b), in the case of the LB method it can be seen that the particles are agglomerated with each other to form a large empty space while forming a domain. This is because the particle coating on the adhesive polymer substrate is caused by the interaction between the substrate surface and the particles, not the attraction between particles and particles used in self-assembly, and the bonding between the particles and the substrate is reversible in plane. This is because the particles are free to move in the plane.

Experimental Example 7

In order to coat the particles on the adhesive polymer substrate, the following experiment was conducted to explain the deformation and restoring force (elasticity) of the adhesive polymer. An adhesive polymer substrate (PDMS substrate) consisting of PDMS formed containing 10% by weight of a curing agent based on Sylgard 184 product was prepared. SiO ₂ particles with an average particle diameter of 750 nm were placed on the adhesive polymer substrate, and then rubbed under pressure by hand using a sponge wrapped with a latex film to form recesses on the surface of the adhesive polymer substrate to bond the SiO ₂ particles with the adhesive polymer substrate. To form a SiO ₂ coating. After the substrate on which the SiO ₂ coating film was formed was stored at room temperature for 3 days, a portion of the coating film was removed using an adhesive tape. The area from which the particles were removed was observed in three dimensions using an atomic force microscope (AFM). An AFM image of a region where particles are removed from the SiO ₂ coating film is shown in FIG. 10.

As shown in FIG. 10, the concave portion of the surface of the PDMS substrate was formed in the same manner as the aligned state of the particles. The maximum depth of the recess was very low, within 10 nm. By separate measurement, it was found that a 110 nm height reduction (impregnation depth of particles) occurs when the particles are coated on the PDMS substrate. That is, the maximum depth of the concave portion was a value within 10% of the impregnation depth of the particles. It is interpreted that the surface of the PDMS substrate was deformed by the particles, but restored to its original form by more than 90%.

Experimental Example 8

In order to demonstrate that the method of coating the particles on the adhesive polymer substrate is possible on a large area, the experiment was carried out on a 15 cm diameter Petri dish as follows. An adhesive polymer substrate consisting of PDMS formed containing 10% by weight of a curing agent based on Sylgard 184 product was prepared on a dish. SiO ₂ particles with an average particle diameter of 750 nm were placed on the adhesive polymer substrate, and then rubbed under pressure by hand using a sponge wrapped with a latex film to form recesses on the surface of the adhesive polymer substrate to bond the SiO ₂ particles with the adhesive polymer substrate. To form a SiO ₂ coating. A photograph of a SiO ₂ coating film formed on a 15 cm diameter Petri dish substrate is shown in FIG. 11.

Referring to FIG. 11, it was observed that the SiO ₂ coating film was evenly coated with particles over the entire dish of 15 cm diameter so that an interference color (only observed in a uniform thin film) appeared.

Experimental Example 9

In order to demonstrate that the method of coating the particles on the adhesive polymer substrate is possible in the particles of various surface properties, the experiment was carried out as follows. A plurality of adhesive polymer substrates (5% PDMS substrates) including PDMS formed of 5 parts by weight of a curing agent based on Sylgard 184 product were prepared. A plurality of adhesion polymer substrate respectively on negative adult average particle diameter of 750nm in claim 1 SiO ₂ particles, hydrophobic average particle diameter of 800 nm in the claim 2 SiO ₂ particles PS particles, positively charged adult average particle diameter of 750nm (amine-modified SiO ₂₎ After placing each of them by using a sponge wrapped with a latex film by rubbing while applying pressure by hand to form a recess on the surface of the adhesive polymer substrate to form a SiO ₂ coating film or PS coating film by bonding the particles and the adhesive polymer substrate.

In the same manner as described above, a SiO ₂ coating film or a PS coating film was formed on an adhesive polymer substrate (10% PDMS substrate) made of PDMS formed by including 10 parts by weight of a curing agent. SiO ₂ coating film or PS coating film was formed on the adhesive polymer substrate (20% PDMS substrate) consisting of PDMS formed by including the 20 parts by weight of the curing agent in the same manner as described above.

An electron micrograph of the front surface of the particles of the coating film formed by using the first SiO ₂ particles, the PS particles, and the second SiO ₂ particles is shown in FIGS. 12A, 12B, and 12C, respectively. At this time, the top row is a photograph of the coating film formed on the 5% PDMS, the middle row is a photograph of the coating film formed on the 10% PDMS substrate, the bottom row is a photograph of the coating film formed on the 20% PDMS substrate.

Electron micrographs photographing side surfaces of the particles of the coating film formed using the first SiO ₂ particles, the PS particles, and the second SiO ₂ particles are shown in FIGS. 13A, 13B, and 13C, respectively. At this time, the top row is a photograph of the coating film formed on the 5% PDMS, the middle row is a photograph of the coating film formed on the 10% PDMS substrate, the bottom row is a photograph of the coating film formed on the 20% PDMS substrate.

Referring to FIG. 12, the SiO ₂ coating layer or the PS coating layer appeared as a single-layer particle thin film aligned at a high density regardless of the degree of curing of the PDMS substrate and the charge characteristics of the particles. Referring to FIG. 13, it can be seen that the SiO ₂ coating layer or the PS coating layer has a difference in the degree of settlement according to the degree of curing of the PDMS substrate. The PDMS substrate, which is easily deformed due to a low curing degree of 5 parts by weight of the curing agent, has a large particle settling degree and the PDMS substrate comes to the bottom of the particle like a capillary phenomenon. This phenomenon was found that the weight part of the degree of cure increased to 10, 20, which was not easy to deform and gradually decreased on the high elasticity PDMS substrate. As such, the phenomenon that the PDMS substrate comes with particles like a capillary phenomenon is a feature that appears because the adhesive polymers in the micro area have fluidity.

In order to quantify that the settling phenomenon of the particles is changed by the degree of curing (elastic force) of the substrate, an AFM image photographed after desorption of some particles of the coating film using an adhesive tape and a line profile in the portion where the coating film is formed are shown in FIG. 14. Indicated. The average particle height and settling rate of the SiO ₂ coated film or PS coated film formed on the glass substrate, the 5% PDMS substrate, the 10% PDMS substrate, the 20% PDMS substrate were measured using AFM, and the results are shown in FIGS. 15A and 15B. Respectively. Referring to FIG. 15, particles having different surface properties (charges, polarities) commonly exhibited lower particle heights in PDMS substrates than glass substrates without surface deformation. The settling rate was 12% on the high hardness 20% PDMS substrate and increased with decreasing hardness. The surface characteristics of the particles are judged to have a smaller effect than the hardness difference of the substrate.

In addition, the results obtained by coating SiO ₂ particles having an average particle diameter of 300 nm by the same method as described above are shown in FIG. 16. In this case, the height of the PDMS substrate was lower than that of the glass substrate. The settling rate was 15% on 20% PDMS substrate with high hardness, and increased with decreasing hardness.

In order to confirm the influence of the particle size, particles having an average particle diameter of 150 and 1500 nm were also formed on the 10% PDMS substrate. The average particle height and settling rate in the coating film formed using the particles having an average particle diameter of 150 nm, 300 nm, 750 nm, and 1500 nm are shown in FIGS. 17A and 17B, respectively. Referring to FIG. 17, it was confirmed that a trend similar to that of the results of FIGS. 15 and 16 appeared. No particular trend was observed with the size of the particles, and the settlement rate compared to the particle diameter of 10-20% was observed.

Experimental Example 10

Sylgard 184 product based on the adhesive polymer substrate (7% PDMS substrate, 10% PDMS substrate, 20% PDMS substrate) formed of 7, 10, 20 parts by weight of each of the curing agent, each of the SiO ₂ particles having an average particle diameter of 750nm After placing it, a sponge wrapped with a latex film was rubbed while applying pressure by hand to form a recess on the surface of the adhesive polymer substrate, and the SiO ₂ particles and the adhesive polymer substrate were bonded to form an SiO ₂ coating film. The photographs are shown in Figs. 18A, 18B and 18C, respectively. In this case, (a) is a photograph of the SiO ₂ coating film formed on the 7% PDMS substrate (denoted by 0.7), (b) is a photograph of the SiO ₂ coating film formed on the 10% PDMS substrate (denoted by 1.0), (c) is A photograph of a SiO ₂ coating film formed on a 20% PDMS substrate (denoted 2.0). The same is true in FIGS. 19 to 21 below.

The photographs obtained by transferring the SiO ₂ coating film formed on the adhesive polymer substrate described above to the first substrate (PDMS substrate formed by including 7% by weight of a curing agent) are shown in FIGS. 19A, 19B and 19C, respectively. .

The photographs of the SiO ₂ coating film formed on the adhesive polymer substrate described above to the second substrate (PDMS substrate formed by including 10% by weight of a hardener) are shown in FIGS. 20A, 20B and 20C, respectively. .

The photograph of the transfer of the SiO ₂ coating film formed on the adhesive polymer substrate described above to the third substrate (PDMS substrate formed with 20% by weight of a curing agent) is shown in FIGS. 21A, 21B and 21C, respectively. .

Referring to FIG. 19, it can be seen that the SiO ₂ coating film formed on the 7% PDMS substrate from (a) is not transferred to the first substrate well, and formed on the 10% and 20% PDMS substrates from (b) and (c). It can be seen that it is well transferred to the first substrate. Referring to FIG. 20, it can be seen that the SiO ₂ coating film formed on the 7% and 10% PDMS substrates from (a) and (b) does not easily transfer to the second substrate, and from (c) the 20% PDMS substrate It can be seen that the formed SiO ₂ coating film transfers well to the second substrate. Referring to FIG. 21, it can be seen that the SiO ₂ coating film formed on the 7%, 10%, and 20% PDMS substrates from (a), (b), and (c) does not easily transfer to the third substrate.

That is, the SiO ₂ coating film formed on the adhesive polymer substrate can be seen that most of the particles can be transferred to a new substrate having a smaller hardness (higher flexibility) than the adhesive polymer substrate. This phenomenon shows that the adhesion of the particles to the substrate is due to flexibility (elasticity) and shows the tendency of the particles to bond with the substrate. In addition, the high flexibility (low hardness) shows that there is a property that can be easily transferred to a high adhesion substrate.

Experimental Example 11

In order to demonstrate that it is possible to coat the particles on a variety of adhesive polymer substrate was carried out as follows. Adhesive polymer substrates, PDMS substrates containing 10% by weight of a curing agent based on Sylgard 184, silicone-based sealing tape for research, linear low-density polyethylene (LLDPE) wraps for home use, substrate gloss protection A protective film, poly vinyl chloride (PVC) wrap was prepared. As a comparative example, a non-adhesive polymethylmethacrylate (PMMA) substrate and 3M magic tape were prepared. On each of the adhesive polymer substrates, the comparative PMMA substrate and the 3M magic tape, SiO ₂ particles having an average particle diameter of 750 nm were placed on the adhesive polymer substrate and rubbed while applying pressure by hand using a sponge wrapped with a latex film to concave on the surface of the adhesive polymer substrate. While forming the portion, the SiO ₂ particles and the adhesive polymer substrate were bonded to form an SiO ₂ coating film.

A photo of the SiO ₂ coating film formed on the PDMS substrate is shown in Figure 22 (a), Figure 22 (b) is a photograph of the SiO ₂ coating film formed on the silicon-based sealing tape for research, Figure 22 (c) the SiO ₂ formed on the PVC wrap showed a picture of the SiO ₂ coating film formed exhibited a picture of the SiO ₂ coating, in Fig. 22 (d) substrate glossy protective protective film formed on the LLDPE wrap, as shown in FIG. 22 (e) The photograph of the coating film is shown. 22 (f) shows a picture of the SiO ₂ coating film formed on the PMMA substrate, and FIG. 22 (g) shows a picture of the SiO ₂ coating film formed with the 3M magic tape.

Referring to (a) to (e) of FIG. 22, the adhesive polymer substrates exhibit the color of light interference due to uniform coating of particles. However, referring to (f) and (g), the substrate of the comparative example showed a turbid white color. .

As described above, it can be seen that the bonding properties can be improved by directly contacting and bonding the dry particles on the adhesive polymer substrate without using a separate adhesion assistant layer, a solvent, or the like.

Example: Preparation of Particle Coated Substrate

<Example 1>

An adhesive polymer substrate (10% PDMS substrate) consisting of PDMS formed containing 10 parts by weight of a curing agent based on Sylgard 184 product was prepared.

SiO ₂ particles with an average particle diameter of 750 nm were placed on the adhesive polymer substrate, and then rubbed under pressure by hand using a sponge wrapped with a latex film to form recesses on the surface of the adhesive polymer substrate to bond the particles and the adhesive polymer substrate to each other. ₂ coating film was formed.

After the polymer substrate composition including the acrylic UV curable resin was applied onto the adhesive polymer substrate and the SiO ₂ coating layer, ultraviolet rays were irradiated for 10 minutes to cure the polymer substrate. The adhesive polymer substrate was removed to complete the preparation of the particle coated substrate.

A photograph of the SiO ₂ coating film formed on the adhesive polymer substrate is shown in FIG. 23A, and a photograph of SiO ₂ exposed on the polymer substrate is shown in FIG. 23B.

Referring to (a) of FIG. 23, in the SiO ₂ coating film formed on the adhesive polymer substrate, the centers of the particles are arranged in a dense structure having a hexagonal shape, and the particles are uniformly coated. In addition, referring to FIG. 23B, it can be seen that the SiO ₂ coating layer was well transferred to the polymer substrate and the particles were partially exposed.

<Example 2>

Preparation of the particle coating substrate was completed in the same manner as in Example 1 except that the adhesive polymer substrate contained 20 parts by weight of the curing agent.

A photograph of the SiO ₂ coating film formed on the adhesive polymer substrate is shown in FIG. 24A, and a photograph of the SiO ₂ coating film formed on the polymer substrate is shown in FIG. 24B.

Referring to (a) of FIG. 24, in the SiO ₂ coating film formed on the adhesive polymer substrate, the centers of the particles are arranged in a dense structure having a hexagonal shape, and thus the particles are uniformly coated. And (b) of Figure 24, it can be seen that the SiO ₂ coating film is well transferred to the polymer substrate and the particles are partially exposed.

23 to 24 (a), it can be seen that as the hardness of the adhesive polymer substrate increases, the portion of the particles covered by the adhesive polymer substrate decreases. Accordingly, as shown in the lower photo of FIGS. 23 to 24 (b), it can be seen that as the hardness of the adhesive polymer substrate increases, the height of the portion exposed to the outside on the polymer substrate decreases.

<Example 3>

An adhesive polymer substrate (5% PDMS substrate) consisting of PDMS formed containing 5 parts by weight of a curing agent based on Sylgard 184 product was prepared.

Adhesion to form a TiO ₂ coating film by combining the TiO ₂ particles and the adhesion between a polymer substrate, forming rubbing while applying a pressure with hands concave on the surface of adhesion between the polymer substrate portions after placed the TiO ₂ particles having a mean particle diameter of 750nm on a polymer substrate.

The polymer substrate including the ultraviolet curable resin is placed on the adhesive polymer substrate and the TiO ₂ coating layer and then irradiated with ultraviolet rays for 10 minutes to cure the polymer substrate. The adhesive polymer substrate was removed to complete the preparation of the particle coated substrate.

A photo of the TiO ₂ coating film formed on the adhesive polymer substrate is shown in FIG. 25 (a), and a photo of the TiO ₂ coating film formed on the polymer substrate is shown in FIG. 25 (b).

Referring to FIG. 25 (a), it can be seen that particles of the particles are uniformly applied in the TiO ₂ coating film formed on the adhesive polymer substrate. And (b) of Figure 25, it can be seen that the TiO ₂ coating film is well transferred to the polymer substrate and the particles are partially exposed. However, due to the nonuniform particle size and shape of the TiO ₂ particles, it can be seen that a multilayer structure exists in some parts.

<Example 4>

Preparation of the particle coating substrate was completed in the same manner as in Example 1 except that the adhesive polymer substrate contained 10 parts by weight of the curing agent.

A photo of the TiO ₂ coating film formed on the adhesive polymer substrate is shown in FIG. 26A, and a photo of the TiO ₂ coating film formed on the polymer substrate is shown in FIG. 26B.

Referring to FIG. 26A, it can be seen that the particles of the particles are uniformly coated in the TiO ₂ coating film formed on the adhesive polymer substrate. And (b) of Figure 26, it can be seen that the TiO ₂ coating film is well transferred to the polymer substrate and the particles are partially exposed. However, due to the nonuniform particle size and shape of the TiO ₂ particles, it can be seen that a multilayer structure exists in some parts.

Example 5

Preparation of the particle coating substrate was completed in the same manner as in Example 1 except that the adhesive polymer substrate contained 20 parts by weight of the curing agent.

A photo of the TiO ₂ coating film formed on the adhesive polymer substrate is shown in FIG. 27A, and a photo of the TiO ₂ coating film formed on the polymer substrate is shown in FIG. 27B.

Referring to FIG. 27A, it can be seen that the particles of the particles are uniformly coated in the TiO ₂ coating film formed on the adhesive polymer substrate. And referring to FIG. 27 (b), it can be seen that the TiO ₂ coating film is well transferred to the polymer substrate and the particles are partially exposed. However, due to the nonuniform particle size and shape of the TiO ₂ particles, it can be seen that a multilayer structure exists in some parts.

25 to 27 (a), it can be seen that as the hardness of the adhesive polymer substrate increases, the portion of the particles covered by the adhesive polymer substrate decreases. Accordingly, as shown in the lower photo of FIGS. 25 to 27 (b), it can be seen that as the hardness of the adhesive polymer substrate increases, the height of the portion exposed to the outside on the polymer substrate decreases.

<Example 6>

By using LLDPE wrap the adhesion polymer substrate having an average particle diameter of combining the TiO ₂ particles and the adhesion between the polymer substrate and rubbed while applying a pressure with hands, forming a concave portion on the surface of adhesion between the polymer substrate and then placed the TiO ₂ particles of 750nm TiO ₂ A coating film was formed.

The polymer substrate including the ultraviolet curable resin is placed on the adhesive polymer substrate and the TiO ₂ coating layer, and then the acrylic substrate is covered, and the polymer substrate is cured by irradiating ultraviolet rays for 30 minutes. The adhesive polymer substrate was removed to complete the preparation of the particle coated substrate. The photo is shown in FIG.

Referring to FIG. 28, it can be seen that the TiO ₂ coating film was well transferred to the acrylic substrate and the particles were partially exposed.

<Optical transmittance evaluation>

Optical transmittance evaluation of an acrylic substrate (Acryl particle coating substrate of Example 1 (SiO 2 -Acryl) and Example 4 particle coating substrate (TiO 2 -Acryl) was performed. The results are shown in Fig. 29. Light transmittance loss compared to the substrate We can confirm that there is little.

In general, SiO2 showed less than 10% light loss at 500nm wavelength. The loss rate was excellent at tio2 with high refractive index below 20%.

Features, structures, effects, and the like as described above are included in at least one embodiment of the present invention, and are not necessarily limited to only one embodiment. In addition, the features, structures, effects, and the like illustrated in the embodiments may be combined or modified with respect to other embodiments by those skilled in the art to which the embodiments belong. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.

Particle-exposed type substrate and a method for manufacturing the same according to the present embodiment can form a single-layer particle coating layer on the adhesive polymer substrate by an easy method, and a part of the particles are embedded in the adhesive polymer at a predetermined ratio during the alignment process. The particles can be transferred to various substrates, and a particle coated substrate can be formed with the particles partially exposed evenly. By applying a variety of functional particles can be used as a functional member for a variety of applications is industrially useful.

Claims (24)

A preparation step of preparing an adhesive polymer substrate; A coating step of coating a plurality of particles on the adhesive polymer substrate; Forming a substrate on the adhesive polymer substrate and the plurality of particles; And An exposure step of partially exposing the plurality of particles by removing the adhesive polymer substrate; Method for producing a particle coating substrate comprising a. The method of claim 1, Forming the substrate, Positioning a substrate composition on the adhesive polymer substrate and the plurality of particles; And Curing step of forming the substrate by curing the substrate composition; Method of manufacturing a particle-coated substrate comprising a. The method of claim 1, And removing a part of the particles selectively after the coating step to form a pattern. The method of claim 1, The coating step is a method for producing a particle coating substrate is coated on the adhesive polymer substrate to form a plurality of reversible concave portions respectively corresponding to the plurality of particles. The method of claim 1, In the coating step, the method of producing a particle coating substrate to rub the plurality of particles evenly aligned. The method of claim 1, The method of producing a particle coating substrate using a particle alignment in which the plurality of particles in the coating step is in direct contact with the adhesive polymer substrate in a single layer. The method of claim 1, 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 top 10% particles of the plurality of particles is 1.9 or less, the method of producing a particle coating substrate using a particle alignment. The method of claim 1, The substrate is a method for producing a particle coating substrate formed by curing the ultraviolet curable resin. The method of claim 1, The substrate is a method for producing a particle coated substrate comprising an inorganic material. The method of claim 1, The average height of the plurality of particles exposed from the substrate is 0.02 ~ 0.98 times the particle average particle diameter manufacturing method of the particle coated substrate. The method of claim 1, Method for producing a particle coating substrate having an average particle diameter of the plurality of particles is 10nm to 100㎛. The method of claim 1, Method for producing a particle coating substrate having a plurality of particles having a spherical or hemispherical shape. The method of claim 1, The plurality of particles are photocatalyst particles, a method for producing a particle coating substrate. The method of claim 1, The adhesive polymer substrate is a method of manufacturing a particle coating substrate comprising one of a polymer material, such as polydimethylsiloxane (PDMS), polyethylene (PE, PE) and polyvinyl chloride (PVC), a wrap, a surface protection film . The method of claim 1, The support of the adhesive polymer substrate is a method for producing a particle coating substrate comprising a permeable material such as Hanji, tissue, corrugated cardboard, hardboard, or a porous film. materials; And A plurality of particles partially embedded in the substrate and partially exposed; Particle coating substrate comprising a. The method of claim 16, The average height of the plurality of particles exposed from the substrate is 0.02 ~ 0.50 times the particle average particle diameter of the particle coating substrate. The method of claim 16, A particle coating substrate satisfying D ≦ P ≦ 1.5D when an average particle diameter of the particles is D, and an average interval (distance between particle centers) between the exposed particles is P. The method of claim 16, And said plurality of particles are arranged at a monolayer level. The method of claim 16, When the plurality of particles is non-spherical, the particle coating substrate having a ratio of the average value of the thickness of the coating layer consisting of the plurality of particles to the average particle diameter of the particles of the top 10% of the plurality of particles is 1.9 or less. The method of claim 16, Particle coating substrate exposed by sorting the particles in the form of hexagonal. The method of claim 16, The substrate is a particle coating substrate comprising at least one of an inorganic material, silica glass, and an organic material, respectively. The method of claim 16, The substrate is a particle coating substrate comprising a coating layer and a support substrate in contact with the particles. The method of claim 16, The substrate is a particle coating substrate comprising a coating layer in contact with the particles, a pressure-sensitive adhesive layer applied on the coating layer and a release film attached to the adhesive layer and can be released.

Images