KR101980212B1 - Method for producing film of uniform thickness using heterogeneous particle and film produced by the same - Google Patents

Abstract

The present invention can provide a method for producing a complex particle film, comprising the steps of preparing an adhesive polymer substrate; forming an irregular structure on the adhesive polymer substrate using base particles; coating complex particles, wherein heterogeneous particles having different sizes are mixed on the adhesive polymer substrate having the irregular structure; and transferring the complex particles to a highly adhesive substrate.

Description

[0001] The present invention relates to a method for producing a film having uniform thickness using a heterogeneous particle having a uniform size and a film produced thereby,

The present invention relates to a method for producing a composite particle film having uniform thickness using a heterogeneous particle having a uniform size and a composite particle film produced thereby. More specifically, To a coating method for forming a multi-layered film.

Here, background art relating to the present disclosure is provided, and they are not necessarily meant to be known arts.

Pigment is a substance used in a dispersed state having a shape and a size, and is a coloring agent used in all fields such as paints, printing inks, plastics, and cosmetics. The pigment can be synthesized by controlling the size and shape of the pigment in the solvent, and then the pigment is desalted, desolvated and dried. In this process, secondary and tertiary particles of a size larger than the original particles are formed due to intergranular agglomeration. Agglomerates having relatively low cohesive force or Aggregate having a strong cohesive force are used to form non-uniform It appears in one size.

The coating of the pigment is mainly carried out by solvent phase dispersion. When the pigment to be coated is aggregated, it is difficult to individually disperse the particles, thereby forming a coating film having an uneven thickness on the substrate.

Particularly, when coating the pigment particles having a non-uniform size due to agglomeration in the field of paints, since the small particles are first deposited on the substrate and then relatively large particles are deposited, the internal efficiency of the coating is decreased, The thickness and color uniformity of the coating film may be lowered. In the field of cosmetics, the dispersion of pigment particles affects the quality of cosmetics, since the aggregation of pigment particles can affect the color. In addition, since the particles are agglomerated at a random ratio, there is a disadvantage that the color between the manufacturing batches can be changed. Therefore, it is very important to disperse the pigment particles appropriately in the solvent in order to use the pigment in products such as paints, inks, and cosmetics, and then the dispersed solution should be applied to the substrate. Since the agglomerated particles are difficult to be dispersed again, various techniques for dispersion have been introduced and developed.

Most past paints were prepared by dispersing hydrophobic pigments in organic solvents. However, due to the toxicity problem, the necessity of water - based paints has arisen and water has been used as a solvent, which has been detrimental to the wettability and dispersibility of the hydrophobic pigments. As a method for improving the dispersibility, surface modification with a surfactant, a polymer, or the like, or a method such as film formation, plasma, or grinding has been used.

In cosmetics, various particles such as PMMA, TiO ₂ , and Iron Oxide are used. Due to the unique surface characteristics of each particle, it is difficult to uniformly disperse in water or oil phase. Therefore, a uniform dispersion solution was prepared by using additives such as surface modification, wetting agent, stabilizer and sonicator, osterizer and homogenizer.

That is, in order to utilize the pigment as a product, the product should be designed in consideration of the interaction between the surface characteristics of the pigment and the solvent and the additive during solvent dispersion. The pigment must be uniformly dispersed on a solvent to improve the quality of the product, and it is necessary to maintain the dispersed state stably to improve the reproducibility of the product.

Accordingly, the present invention proposes a novel coating method for improving the quality and reproducibility of a product by limiting the use of additives, facilities, etc., thereby reducing the initial cost and facilitating the formation of a coating film.

1. Korean Registered Patent No. 10-1428432 (2014.08.01) 2. Korean Patent No. 10-1224378 (2013.01.15.)

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a coating method capable of forming a composite particle film of uniform thickness without using a dispersion solvent.

However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

The present invention provides a method of manufacturing a semiconductor device, comprising: preparing an adhesive polymer substrate; Forming a concavo-convex structure on the adhesive polymer substrate using the base particles; Coating a composite particle on which an adhesive polymer substrate having the concavo-convex structure is formed, on which a plurality of particles having different sizes are mixed; And transferring the composite particles to a high-adhesion substrate.

The composite particles include titanium dioxide (TiO ₂ ) particles, poly (methylmethacrylate), PMMA particles, iron oxide particles, and silicon dioxide (SiO ₂ ) particles. .

The composite particles may include 20 to 30% by weight of the titanium dioxide particles, 1 to 5% by weight of polymethylmethacrylate particles and iron oxide particles, and 60 to 70% by weight of the silicon dioxide particles. As shown in FIG.

In addition, the high-adhesion substrate is a surface active agent Pluronic ^TM F127 polydimethylsiloxane (polydimethylsiloxane, PDMS) substrate The method of producing a composite film comprising a particle (BASF社).

Further, the highly adhesive substrate is characterized by being a substrate containing 0.005 to 0.3 wt% of the surfactant.

And further forming an adhesive layer by applying and drying an adhesive material onto the composite particles transferred to the high-adhesion substrate.

Further, the adhesive material includes polyacrylate crosspolymer-8.

Further, the adhesive material is characterized by including a solution in which the polyacrylate crosspolymer-8 is diluted with distilled water.

Further, the adhesive material is characterized by including a solution in which distilled water is diluted to 3% or less of the polyacrylate crosspolymer-8.

Further, the adhesive layer is formed by further including boron nitride (BN) as the adhesive material.

Further, the adhesive layer is formed by coating the polyacrylate crosspolymer-8 and then recoating using boron nitride.

Since the dried composite particles can be uniformly applied without being dispersed in a solvent, there is no need to consider the interaction between the solvent and other particles and additives, and titanium dioxide (TiO ₂ ) particles to 25% or more, a coating film having a uniform thickness can be formed.

FIG. 1 shows a base polymer particle adhered to an adhesive polymer substrate according to an embodiment of the present invention to form a concavo-convex structure.
FIG. 2 shows composite particles coated on an adhesive polymer substrate having a concavo-convex structure according to an embodiment of the present invention.
FIG. 3 illustrates transfer of composite particles using a highly adhesive substrate according to an embodiment of the present invention.
Figure 4 illustrates the transfer of composite particles onto a highly adherent substrate according to one embodiment of the present invention.
FIG. 5A shows an optical microscope image of a PDMS substrate coated with silica particles according to an embodiment of the present invention, and FIG. 5B shows an optical microscope image after oven storage.
6 is an optical microscope image of a PDMS substrate filled with composite particles between silica particles according to an embodiment of the present invention.
7 shows an optical microscope image of a highly adhesive substrate onto which composite particles have been transferred according to an embodiment of the present invention.
8 is an image after taping of a composite particle film transferred onto a high-adhesion substrate according to an embodiment of the present invention.
FIG. 9 shows composite particle transition images according to the kind of the adhesive material.
FIG. 10 shows a skin-transferred film image according to an embodiment of the present invention.
11 shows a skin-transferred film image of an adhesive layer according to an embodiment of the present invention.
12 is a colorimetric measurement data of a composite particle film produced according to an embodiment of the present invention.
FIG. 13 shows an image showing uniformity of a composite particle film produced according to an embodiment of the present invention.

Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.

Throughout this specification and claims, the word "comprise", "comprises", "comprising" means including a stated article, step or group of articles, and steps, , Step, or group of objects, or a group of steps.

On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. Any feature that is specifically or advantageously indicated as being advantageous may be combined with any other feature or feature that is indicated as being preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

The method for producing a composite particle film according to an embodiment of the present invention is a method for coating a composite particle in which various kinds of particles having different sizes are mixed in a uniform thickness without being dispersed in a solvent, . The method for producing a composite particle film includes the steps of preparing an adhesive polymer substrate (S10), forming a concavo-convex structure on the adhesive polymer substrate by using base particles (S20), forming a concave-convex structure on the adhesive polymer substrate (S30) of coating a composite particle in which various kinds of particles having a predetermined size are mixed and a step (S40) of transferring the composite particle to a high-adhesion substrate, .

First, as shown in Fig. 1, an adhesive polymer substrate 10 having a smooth surface is prepared. The surface of the adhesive polymer substrate 10 may have a state in which a specific pattern or bending is not formed and a surface roughness and a structure having a level not restricting the movement of the base particles 20 forming the concave- have. In addition, the adhesive polymer substrate 10 has characteristics that it can be increased by pulling force or the like.

Examples of the adhesive polymer include a polymer based on a silicone-based polymer such as polydimethylsiloxane (PDMS), a polymer including polyethylene (PE), polyvinylchloride (PVC) A protective film containing a substance, a film having a gloss with which the surface shape can be easily deformed, and the like can be used. In particular, as the adhesive polymer, PDMS which can be easily controlled in hardness and is easy to manufacture in various forms can be used. The adhesive polymer substrate 10 may be prepared by coating a base polymer with an adhesive polymer, or by adhering an adhesive polymer in the form of a sheet or a film.

Herein, the adhesive polymer material generally refers to an organic polymer material containing silicon in a solid state, or adhering property through addition of a plasticizer or surface treatment. Here, the adhesive polymer material is generally characterized in that it is easily deformed by a linear molecular structure and has a low surface tension. The excellent adhesion of such an adhesive polymeric substance is attributed to a soft surface material which is easily deformed in a fine region and a low surface tension. The low surface tension of the adherent macromolecule has the property of spreading widely on the particle to be adhered (similar to the wetting phenomenon of the solution), and the flexible surface makes a tight contact with the particle 20 to be adhered. Thereby having the property of an adherent polymer that is easily removable on a solid surface reversibly without complementary bonding force.

The step (S10) of preparing the adhesive polymer substrate can improve the surface energy of the adhesive polymer substrate 10 by increasing the binding force with the base particle 20 by preparing the adhesive polymer substrate by UV irradiation treatment. When the adhesive polymer substrate is prepared by the UV irradiation treatment, the bonding force is increased, so that the base particles can be adhered to each other under the condition that irregular arrangement is formed without applying pressure for adhering the base particles as described later. It is preferable to irradiate UV with a light output value of at least 28 mW / cm ² and a minimum of 10 mW / cm ² for 2 to 10 minutes.

Subsequently, after the adhesive polymer substrate 10 is prepared as described above, a plurality of base particles 20 are aligned to form a concave-convex structure on the adhesive polymer substrate 10. [ This will be described in more detail as follows.

First, a plurality of dried base particles 20 are coated on the adhesive polymer substrate 10. Unlike the present embodiment, the particles dispersed in the solution are hard to be brought into direct contact with the surface of the adhesive polymer, so that the coating can not be performed well. Therefore, only when a small amount of a solution or a volatile solvent is used that is less than the mass of the particles used, the particles may be dried during the coating operation and the coating operation may be possible. Impregnation of the particles can be induced by applying distilled water, nitrogen blowing or the like after application of the base particles (20).

In this embodiment, the base particles 20 may include various materials for forming the concavo-convex structure. That is, the base particles 20 may include a polymer, an inorganic material, a metal, a magnetic material, a semiconductor, a biomaterial, and the like. In addition, a mixture of particles having different properties can be used as the base particle 20. Preferably, it is an inorganic particle.

Examples of the inorganic substance that can be used as the base particle 20 include silicon oxide (for example, SiO ₂ ), phosphoric acid silver (for example, Ag ₃ PO ₄ ), titanium oxide (for example, TiO ₂ ) to, Fe ₂ O _3), zinc as oxide, are preferably cerium oxide, tin oxide, thallium oxide, barium oxide, aluminum oxide, yttrium oxide, zirconium oxide, copper oxide, nickel oxide, etc. it is recommended to use a silicon oxide .

The base particles 20 may have a symmetrical shape, an asymmetric shape, an amorphous shape, and a porous shape. For example, the base particles 20 may have a spherical shape, an elliptical shape, a hemispherical shape, a cubic shape, a tetrahedron, a goup, a hexahedron, an octahedron, a columnar shape, Of these, the shape of the base particles 20 is preferably spherical or elliptical in comparison with other shapes.

It is preferable that the base particles 20 have an average particle diameter of 30 占 퐉 to 100 占 퐉. If the average particle diameter is less than 30 탆, it may be wrapped entirely by the adhesive polymer substrate 10, making it difficult to adhere the base particles 20 at a single layer level. When the average particle size of the base particles 20 is less than 30 占 퐉, it may be difficult to coat the composite particles because the size may be similar to the size of the composite particles to be described later or may be smaller due to the impregnation ratio. If the average particle size of the base particles 20 exceeds 100 탆, the adhesion of the particles may be weak. Preferably, the base particles having an average particle diameter of 40 to 80 탆 are used, and the infiltration rate can be adjusted appropriately, so that the thickness of the multilayer coating film to be finally transferred is easy to control.

The thickness of the composite particle film to be finally transferred can be adjusted by adjusting the particle size of the base particles 20. [ Further, the thickness of the composite particle film to be finally transferred can be controlled by controlling the impregnation rate of the base particles 20 into the adhesive polymer substrate 10.

Subsequently, pressure is applied on the plurality of base particles 20 to form a concavo-convex structure. As a method of applying pressure to the base particles 20, 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 can be applied to the base particles 20 by various methods.

In this embodiment, when the base particles 20 are placed on the surface of the adhesive polymer substrate 10 and then the pressure is applied, the base particles 20 of the applied pressure are adhered through the deformation of the adhesive polymer substrate 10. Thereby, a plurality of concave portions 12 corresponding to the base particles 20 are formed in the corresponding portions. Therefore, in the state that the base particles 20 are enclosed in the concave portion 12, the base particles 20 are adhered to the adhesive polymer substrate 10 It can be aligned in a single layer with hexagonal close packing. Also, as described above, the base particles can be applied to the UV-treated adhesive polymer substrate and then shaken to arrange them in an irregular arrangement.

The concave portion 12 is formed by the interaction between the particle and the substrate and is reversible. That is, it may disappear, and the position may be shifted. For example, when the particles move during the rubbing process, the concave portion 12 disappears due to the elastic restoring force of the adhesive polymer substrate 10, or the concave portion 12 changes in position as the base particle 20 moves . By this reversible action, the base particles 20 can be aligned evenly (here, " reversible " is a property generated by flexibility and elastic restoring force of the surface of the adhesive polymer substrate during coating, And it is broadly meaning that it is weakened or disappears according to.

When the base particles 20 are coated on the adhesive polymer substrate 10 at a low density and are then brought into close contact with each other, the base particles 20 are uniformly adhered to each other with a gap therebetween. As another method of forming the uneven structure, the base particles 20 are coated on the adhesive polymer substrate 10 at a high density and are closely contacted with each other. Thereafter, the adhesive polymer substrate 10 is extended to enlarge the width, Can be generated. As a method of expanding the area of the adhesive polymer substrate 10, a method of clamping the edges of the adhesive polymer substrate 10 with a plurality of clamps and then pulling the adhesive polymer substrate 10 in all directions with uniform force may be used have.

The step S20 of forming the concavo-convex structure may be performed such that the base particles 20 are adhered to the adhesive polymer substrate with a space therebetween at an interval and then stored in an oven after UV irradiation to remove the base particles 20 and the adhesive polymer substrate 10 The bond can be stabilized. At this time, the impregnation rate of the base particles 20 is increased and the adhesive force of the exposed adhesive polymer substrate 10 is lowered. It is preferable to irradiate UV with a light output value of at least 28 mW / cm ² and a minimum light output value of 10 mW / cm ² for 10 to 60 minutes and then store in an oven at 40 to 150 ° C for 2 to 8 hours.

Next, as shown in FIG. 2, the composite particles 30 in which a plurality of particles having different sizes are mixed is applied to the adhesive polymer substrate having the concavo-convex structure formed therein, and then pressure is applied to the composite particles 30, Filling the gap formed between the particles 20. Since the size of the composite particles 30 is smaller than the size of the base particles 20, the composite particles 30 can be filled in multiple layers on the gap, do. The method of applying the pressure may be the same as the method mentioned above.

The composite particles include titanium dioxide (TiO ₂ ) particles, polymethylmethacrylate (PMMA) particles, iron oxide particles, and silicon dioxide (SiO ₂ ) particles . Titanium dioxide particles may be included to cover UV protection and skin imperfections, and polymethylmethacrylate particles may be included to enhance feel, and iron oxide particles may be included for color and saturation control.

At this time, the titanium dioxide particles include silicon dioxide particles in order to lower the content of the titanium dioxide particles, since the particles are intense particles. In general, silicon dioxide particles are treated with an anti-caking agent such as Highly Polymerized Methyl Polysiloxane (Methicone) in order to improve the dispersibility of the solvent phase and the feeling of use of cosmetic formulations. However, It is possible to uniformly coat dried composite particles Therefore, untreated silicon dioxide particles may be used.

Wherein the composite particles comprise 20 to 30% by weight of the titanium dioxide particles, 1 to 5% by weight of polymethylmethacrylate particles and iron oxide particles, respectively, and 60 to 70% by weight of the silicon dioxide particles do. According to the coating method of the present invention, it is possible to form a coating film having a uniform thickness even if the content of TiO _{2 having} a high degree of particle aggregation is increased to 25% or more.

The titanium dioxide particles have an average particle diameter of 1 to 3 占 퐉, polymethylmethacrylate particles have an average particle diameter of 10 to 20 占 퐉, iron oxide particles of 0.5 to 2 占 퐉, and silicon dioxide particles having an average particle diameter of 10 to 20 占 퐉 do.

The composite particles 30 coated on the adhesive polymer substrate on which the concavo-convex structure has been formed can be transferred to the high-adhesion substrate 40 having a higher adhesive force as shown in Fig.

The highly adhesive substrate 40 uses a substrate made of a silicon-based polymer material such as polydimethylsiloxane (PDMS) containing a surfactant. More specifically, use the Pluronic ^TM F127 (BASF社) as the surfactant.

The highly adhesive substrate 40 uses a PDMS substrate containing 0.005 to 0.3 wt% of the surfactant. The adhesion between the composite particles and the adhesive polymer substrate 10 may be lost in the heat treatment process after the composite particles are transferred in the highly adhesive substrate 40 containing the surfactant, And can be easily separated from the highly adhesive substrate when coated on the substrate through the material. In the case of the PDMS substrate not including the surfactant or containing more than 0.3 wt% of the surfactant, the transition of the composite particles from the adhesive polymer substrate to the highly adhesive substrate is performed well, but the adhesive force of the PDMS itself . In addition, in the case of a PDMS substrate containing less than 0.005 wt% of the surfactant, there is a problem that the composite particles are not easily transferred. Preferably, a PDMS substrate containing the surfactant in an amount of 0.005 to 0.2 wt% is used, and more preferably, the PDMS substrate containing the surfactant in an amount of 0.005 to 0.01 wt% is used.

The method for producing a composite particle film according to the present invention further comprises a step (S50) of forming an adhesive layer by applying and drying an adhesive material onto the composite particle transferred to the high-adhesion substrate. The adhesive layer 50 (not shown) can adhere the composite particles to an individual such as a skin. According to the practical use example, the composite particle film having the adhesive layer formed thereon may be attached to the release film and stored, and the release film may be removed during use (when the skin is attached) to adhere to the skin.

The adhesive material may be selected from the group consisting of Pullulan, Acrylates / Polytrimethylsiloxymethacrylate copolymer, MQ resin, Polyacrylate crosspolymer-8, Etc., and it is preferable to use Polyacrylate crosspolymer-8 in view of the ability to transfer a composite particle and adhesion to a highly adhesive substrate. Also, when polyacrylate crosspolymer-8 is used, the adhesive force can be applied to the skin even after drying.

Preferably, the polyacrylate crosspolymer-8 is diluted to not more than 3% in the distilled water, so that the adhesive force of the polyacrylate crosspolymer-8 is low. More preferably, polyacrylate crosspolymer-8 is diluted to not more than 0.6% in distilled water.

It is also preferable to use a film produced by further including boron nitride (BN) as an adhesive material. In the case of the adhesive coating film formed by using the polyacrylate crosspolymer-8, even after adhering to the skin, the adhesive force is liable to be contaminated with dust or the like. However, in the case of using the film prepared by further containing boron nitride, Adhesion is mostly lost.

When the boron nitride is further used, it may be coated with the polyacrylate crosspolymer-8 and then coated again with boron nitride to form an adhesive coating film. In the case of secondary coating, as compared with the case where the polyacrylate crosslinker-8 and boron nitride are mixed to perform the primary coating, the adhesion is lost and the contamination problem can be reduced, There is an effect that the boron nitride is not easily removed by the external stimulus.

Examples and Experimental Examples

A PDMS substrate (hereinafter referred to as a '4% PDMS substrate') containing 4 wt% of solution B relative to the solution A was dissolved in 5 * 5% by using a Sylgard 184 product composed of a solution of silicon jane A and a solution B as a curing agent (Unit: cm). After irradiation of UV for 5 min on the 4% PDMS substrate, 0.3 g (12 mg / cm ² ) of silica particles having a size of 60 μm was evenly applied. Thereafter, silica particles were coated on the surface of the 4% PDMS substrate with an irregular arrangement of a single layer by shaking uniformly on a 4% PDMS substrate. After impregnation of the particles with distilled water was conducted, the substrate was irradiated with UV for 20 minutes and left in an oven for 4 hours to prepare a substrate having a concave-convex structure (hereinafter referred to as Si-PDMS substrate). FIG. 5A shows an optical microscope image of a PDMS substrate coated with silica particles, and FIG. 5B shows an optical microscope image after oven storage.

On the Si-PDMS substrate having the concavo-convex structure formed by the silica particles, 25 wt% TiO ₂ particles of 1 to 3 μm size, 4 wt% of PMMA particles of 10 to 20 μm size, 4 wt% of FeO particles of 1 to 2 μm size, And 0.3 g of a composite particle in which SiO ₂ particles of ~ 20 μm size were mixed in 67 wt% were evenly coated. Thereafter, the composite particles were sandwiched between the silica particles by hand using a sponge wrapped with a latex film. Fig. 6 shows an optical microscope image of a PDMS substrate filled with composite particles between silica particles.

Thereafter, the composite particles were transferred from the PDMS substrate filled with the composite particles between the silica particles to the high-adhesion substrate using a PDMS substrate containing the components shown in Table 1 as a high-adhesion substrate. FIG. 7 shows an image of a highly adhesive substrate on which composite particles have been transferred.

F127 (wt%) Curing agent (wt%) Silicone Example 1 0.01 20 remain Example 2 0.4 20 remain Example 3 0.2 20 remain Example 4 0.1 20 remain Example 5 - 3 remain Example 6 0.004 20 remain

An adhesive material (MQ resin) was applied on the PDMS substrate on which the composite particles were transferred, and a nitrogen gas was blown thereon to thinly coat the PDMS substrate, followed by drying in an oven at 80 ° C for 1 hour. Thereafter, the state of the composite particle film transferred by taping was confirmed and is shown in FIG.

As shown in Fig. 8, in the case of Example 5 (3% PDMS), the transition was well performed, but the adhesive force of PDMS itself was present and it was difficult to peel off with tape. There was an untransferred hole in a portion of the transferred particle film. It is expected that the structure of MQ resin is similar to that of PDMS, and MQ resin penetrated inside.

In case of Example 2 (F127 0.4% PDMS), the PDMS-resin strongly adhered at the time of taping and did not fall well. The pattern appears crisp in the direction of removal and can be seen to be stiffly peeled off.

Also in the case of Example 3 (F127 0.2% PDMS) and Example 4 (F127 0.1% PDMS), the transition occurred partially due to the decreased adhesion of the PDMS-resin during taping. It was relatively easy to remove the tape.

Also, in Example 1 (F127 0.01% PDMS), the transition occurred in a neat film form due to the decrease in adhesion of the PDMS-resin at tapping. It was very easy to peel off with tape.

In addition, in the case of Example 5 (3% PDMS), composite particles were difficult to transfer to the skin due to the 3% PDMS self-adhesive force when the composite particles were transferred to form a composite particle film, whereas Examples 1 to 4 (F127 PDMS ), It is easy to transfer the composite particles onto the skin by drying in an oven because the adhesive force disappears when heat is applied.

As a result, it can be understood that the composite particles are most preferably transferred to the skin when the composite particles are transferred using the F127 0.01% PDMS substrate of Example 1.

Acrylates / Polytrimethylsiloxymethacrylate copolymer, MQ resin, and Polyacrylate crosspolymer-8 were also tested for their ability to transfer composite particles. FIG. 9 shows a composite particle transition image according to the kind of the adhesive material.

As shown in FIG. 9, in the case of Pullulan, Acrylates / Polytrimethylsiloxymethacrylate copolymer and MQ resin, the adhesive was lost after drying, and it was dried in a film form and easily broken because it was not flexible. In the case of Polyacrylate Crosspolymer-8, it was able to transfer to the skin due to the adhesive force after drying, and it had good skin adhesion and thin thickness. However, there was a problem that the adhesive force remained after the skin metastasis and thus it was easily contaminated.

Thus, the polyacrylate crosspolymer-8 solution was diluted under the conditions shown in Table 2 below, and the composite particles were applied to the transferred film, dried at 80 ° C in an oven, and then adhered. FIG. 10 shows images of the skin-phase transferred films of Example 6 and Examples 12-15. As shown in the following Table 2 and FIG. 10, it was confirmed that the residual adhesive strength of the polycrylate crosspolymer was similar at or below a certain concentration (0.6%).

Polyacrylate
Crosspolymer Composition (%)
/ (Volume of solution) EtOH (ml) DW Total capacity (ml) Residual adhesive strength Example 7 0.6
(0.3 mL) 2 Balance 10 △ Example 8 2
(1 mL) 2 Balance 10 △ Example 9 3
(1.5 mL) 2 Balance 10 △ Example 10 4
(2 mL) 2 Balance 10 ○ Example 11 7
(3.5 mL) 2 Balance 10 ◎ Example 12 0.3
(150 μl) 2 Balance 10 △ Example 13 0.15
(75 [mu] l) 2 Balance 10 △ Example 14 0.06
(30 [mu] l) 2 Balance 10 △ Example 15 0.02
(10 [mu] l) 2 Balance 10 △

(A), polycrylate crosspolymer, and boron nitride (BN) were coated after polycrylate crosspolymer coating in order to solve the problem that the adhesive force of the polycrylate crosspolymer at the concentration of 0.6% Fig. 11 shows a comparison of (B) in the case of mixing and coating.

In the case of coating with boron nitride (BN) after coating polycrylate crosspolymer (A), adhesion was lost and BN was not removed by stimulation, and when polycrylate crosspolymer and boron nitride were mixed and coated (B) The film was thicker than the film of the case of using only the coating.

According to the above results, it can be seen that BN (Boron Nitride) having a plate-like structure can effectively reduce the adhesion of polyacrylate crosspolymer in comparison with spherical particles. In case of boron nitride (BN) coating after polycrylate crosspolymer coating It can be seen that it exhibits the optimum effect.

In order to confirm the reproducibility and uniformity of the composite particle film produced according to Example 1 and Example 6 of the present invention, a Konica Minolta color CR-400 machine was used The colorimetric data was measured and shown in FIG. 12, and the shot image of the composite particle film is shown in FIG. Five samples were prepared according to Example 1 and Example 6, respectively. K / S St. (Max) means a relative value when the color density of Sample 1 (Data No. 1) was taken as 100, (sample 1) were measured for the remaining four samples.

As shown in FIG. 12, the composite particle film produced according to Example 6 has a K / S St (max) value of 110 or less, . Value of from 198.67 to 119.01 appeared unevenly coated, whereas the composite particle film prepared according to Example 1 of the present invention exhibited a K / S < RTI ID = 0.0 > The value is less than 110, so that there is little color difference, and the reproducibility of the product is maintained.

13, the composite particle film (a) prepared in Example 1 was uniformly coated, whereas the composite particle film (b) prepared in Example 6 was non-uniformly coated, .

The features, structures, effects, and the like illustrated in the above-described embodiments can be combined and modified in other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.

10: Adhesive polymer substrate
20: Base particles
30: Composite particle
40: high adhesion substrate
50: Adhesive layer

Claims (20)

Preparing an adhesive polymer substrate;
Forming a concavo-convex structure on the adhesive polymer substrate using the base particles;
Coating a composite particle on which a plurality of particles having different sizes are mixed on an adhesive polymer substrate having the concavo-convex structure formed by a method of applying pressure; And
And transferring the composite particles mixed with the plurality of particles having the non-uniform size to a high-adhesion substrate.
The method according to claim 1,
The composite particles include titanium dioxide (TiO ₂ ) particles, poly (methylmethacrylate), PMMA particles, iron oxide particles, and silicon dioxide (SiO ₂ ) particles. A method for producing a composite particle film.
3. The method of claim 2,
Wherein the composite particles comprise 20 to 30% by weight of the titanium dioxide particles, 1 to 5% by weight of each of polymethyl methacrylate particles and iron oxide particles, 60 to 70% by weight of the silicon dioxide particles ≪ / RTI >
The method according to claim 1,
The high adhesion substrate is a surface active agent Pluronic ^TM F127 polydimethylsiloxane (polydimethylsiloxane, PDMS) substrate The method of producing a composite film comprising a particle (BASF社).
5. The method of claim 4,
Wherein the highly adhesive substrate is a substrate containing 0.005 to 0.3 wt% of the surfactant.
The method according to claim 1,
Applying the adhesive material onto the composite particle transferred to the high-adhesion substrate and drying the composite particle to form an adhesive layer.
The method according to claim 6,
Wherein the adhesive material comprises polyacrylate crosspolymer-8.
8. The method of claim 7,
Wherein the adhesive material comprises a solution diluted with the polyacrylate crosspolymer-8 in distilled water.
8. The method of claim 7,
Wherein the adhesive material comprises a solution obtained by diluting the polyacrylate crosspolymer-8 to 3% or less with distilled water.
8. The method of claim 7,
Wherein the adhesive layer is formed by further including boron nitride (BN) as the adhesive material.
11. The method of claim 10,
Wherein the adhesive layer is formed by coating the polyacrylate crosspolymer-8 followed by recoating using boron nitride.
A high adhesion substrate; And
And a composite particle layer provided on the high-adhesion substrate,
Wherein the composite particle layer includes composite particles in which a plurality of particles having different sizes are mixed,
Wherein the composite particle film has a color difference value (K / S St.) value of 110 or less as measured using a Konica Minolta colorimeter CR-400 equipment.
13. The method of claim 12,
The composite particles include titanium dioxide (TiO ₂ ) particles, poly (methylmethacrylate), PMMA particles, iron oxide particles, and silicon dioxide (SiO ₂ ) particles. Composite particle film.
14. The method of claim 13,
Wherein the composite particles comprise 20 to 30% by weight of the titanium dioxide particles, 1 to 5% by weight of each of polymethyl methacrylate particles and iron oxide particles, 60 to 70% by weight of the silicon dioxide particles Containing composite particle film.
14. The method of claim 13,
Wherein the titanium dioxide particles have an average particle diameter of 1 to 3 占 퐉, the polymethylmethacrylate particles have an average particle diameter of 10 to 20 占 퐉, the iron oxide particles have a diameter of 0.5 to 2 占 퐉, and the silicon dioxide particles have an average particle diameter of 10 to 20 占 퐉. film.
13. The method of claim 12,
The high adhesion substrate is a surface active agent Pluronic ^TM F127 (BASF社) polydimethylsiloxane (polydimethylsiloxane, PDMS) substrate a composite film comprising a particle.
17. The method of claim 16,
Wherein the highly adhesive substrate is a substrate containing 0.005 to 0.3 wt% of the surfactant.
13. The method of claim 12,
And an adhesive layer formed on the composite particle layer,
Wherein the adhesive layer is a layer formed by including a polyacrylate crosspolymer-8.
19. The method of claim 18,
The adhesive layer is a layer formed by further including boron nitride (BN) having a color difference value (K / S St.) value of 110 or less as measured using a Konica Minolta color system CR-400 equipment of the boron composite particle film Composite particle film. delete

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