KR101720665B1 - Method for Preparation of Polymer Layer with Micro Patterns on Different Substrates - Google Patents

Abstract

The present invention relates to a method for producing micro-polymer patterns on a variety of substrates. More specifically, there is provided a method for producing a polymer solution, comprising: (a) dissolving a polymer resin in a solvent to prepare a polymer solution; (b) coating the polymer solution on the substrate and drying; (c) diluting the solvent in the non-solvent to prepare a mixed solvent; And (d) treating the mixed solvent on a substrate coated with the polymer solution and drying the mixed solvent; Lt; RTI ID = 0.0 > micro-polymer < / RTI >

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of laminating a polymer layer of a micropattern on a substrate,

The present invention relates to a method for producing micro-polymer patterns on a variety of substrates.

Patterned and functionalized polymer surface preparation is increasingly of interest due to the potential for microfluidics, microelectromechanical systems, polymer electronics, multifunctional coatings and biotechnology. The patterned polymer surface can be easily machined to provide a method of manufacturing by reducing the cost used when patterning other types of surfaces such as metals or ceramics.

Micropatterning, which is essential for typical semiconductor and display fabrication, is usually micropatterned by photolithography. However, non-photolithographic techniques such as micro contact printing (μCP), inkjet printing and screen printing techniques are used to fabricate micropatterns because photolithography is expensive and consumes a large amount of energy and materials. Inkjet printing or screen printing methods are not suitable for making micropatterns below 10 μm. The microcontact printing (μCP) method is a technique that can directly obtain a micropattern of 10 μm or less without etching with a minimum material. Microcontact printing (μCP) technology has been applied mainly for patterning self-assembled monolayers (SAMs).

Known imprint lithography techniques include the formation of layer-relief patterns possible with polymers and transfer of patterns corresponding to relief patterns on the base substrate.

Block copolymers (BCPs) consist of two or more chemically different polymer chains at the end of one polymer. The non-favored action of the fragments in the block creates a periodic array of spherical, cylindrical or layered microdomains of several tens of nanometers in size, depending on the volume fraction of the blocks in the microphase separation of the BCP. BCP templates are used in polarizers, templates for microelectronic integrated circuits, magnetic media, and optical waveguides. The key to the use of block copolymers (BCPs) is to control the lattice order and orientation of the microdomains on thin films. In recent years, there has been a growing interest in the field of optical devices, such as external fields, shear, temperature gradients, graphoepitaxy, chemically patterned materials, limited interfacial interaction, zone casting, optical alignment, Many approaches have been developed by enhancing the lattice order and process control of the microdomain applied to the store, but most of these methods are time consuming and expensive.

U.S.A. Patent No. 2004-0065976, WO 2011-049283 A1

Accordingly, the present inventor intends to manufacture a micropattern on various substrates in a short time by using a solvent and a non-solvent system.

The present invention relates to a method of producing a micro polymer pattern on various substrates, and more particularly, to a method of manufacturing a micro polymer pattern on a substrate, comprising the steps of: (a) dissolving a polymer resin in a solvent to prepare a polymer solution; (b) coating and drying the polymer solution onto a substrate; (c) diluting the solvent in the non-solvent to prepare a mixed solvent; And (d) treating the mixed solvent on a substrate coated with the polymer solution and drying the mixed solvent; Lt; RTI ID = 0.0 > micro-polymer < / RTI >

The polymer pattern of the present invention can be adjusted according to the appropriate ratio of solvent to non-solvent based on the solubility parameter of the polymer and can be prepared at low cost.

Further, the present invention is applicable to semiconductor and display fabrication, and it is possible to prepare a biomaterial interface.

Figs. 1 to 3 show scanning electron microscope (SEM) photographs of a polymer film fine pattern on a substrate.

The present invention relates to a method for producing large area micro-polymer patterns on various substrates. More specifically,

(a) dissolving a polymer resin in a solvent to prepare a polymer solution; (b) coating and drying the polymer solution onto a substrate; (c) diluting the solvent in the non-solvent to prepare a mixed solvent; And (d) treating the mixed solvent on a substrate coated with the polymer solution and drying the mixed solvent;

Lt; RTI ID = 0.0 > micro-polymer < / RTI >

The polymer resin includes, but is not limited to, polystyrene (PS), polypropylene PP, polyethylene (PE), polymethyl methacrylate (PMMA), polylactic acid ), Polyethylene terephthalate (PET), polyvinyl chloride (PVC), polycarbonate (PC), or polyvinylidene fluoride (PVDF).

The solvent includes, but is not limited to, acetone, acetic acid, aniline, allylamine, benzene, bromobenzene, chloroform, chloroethane the solvent is preferably selected from the group consisting of chloroethane, chlorobenzene, cyclohexanol, ethylbenzene, ethoxyethane, hexane, methyl acetate, It may be N-methyl-2-pyrrolidone, 2-pyrrolidone, pyridine, p-dioxane, tetrahydrofuran or toluene. have.

The non-solvent may include, but is not limited to, butanol, 1-butoxybutane, 1,3-butanediol, cyclohexanol, ethanol, Butylene glycol, ethylene glycol, formamide, 1-pentanol, 2-isopropoxypropane, isopropyl alcohol, methanol or water .

 In the step (a), the polymer resin may be dissolved in 1 to 10 kinds of solvents to prepare a 0.01 to 50 wt% polymer solution. It can also be prepared in suitable proportions of solvent and non-solvent based on 0.01 to 50 wt% of the polymer solution and the solubility parameter of the polymer.

The solubility constant value can be used as an index indicating how well the polymer resin is dissolved in the solvent, that is, a half power of the aggregate energy density. The solubility constant value in the present invention is the solubility constant is hildeo brand (Hildebrand) define, when the absolute value of the separated solvent and non-solvent ^{5 J 1/2 / cm 3} /2 may not be the permanent application, , The relative energy difference between solvent and polymer solute is calculated using Hansen's three-dimensional solubility constant value. If this is within the interaction radius, it is a solvent, and if it exceeds this range, Can be defined.

The solvent may be used as a solvent or non-solvent depending on the kind of the polymer resin. If the absolute value of the solubility constant value difference of the solubility constant of the selected polymer resins of the selected solvent is difficult to dissolve the polymeric resin selected exceeding ^{5 J 1/2 / cm 3} /2 , the said selected solvent is used as a non-solvent, On the other hand, when the absolute value of the solubility constant of the selected solvent and the solubility constant of the selected polymer resin is less than 5 J ^1/2 / cm ^{3/2, the} polymer resin selected can be easily dissolved and used as a solvent. As an example, when the solubility constant of the polymer resin 15 J of ^{1/2 /} cm ^3/2, the solubility constant value of ^{17 J 1/2 / cm 3} /2 in the solvent is the absolute of the difference between the polymer resin and the solubility constant value is ^{5 J 1/2 / cm 3} /2 or less because it can be used as a solvent, the solubility constant value of ^{21 J 1/2 / cm 3} /2 in the case of the solvent include the absolute value of the difference of the polymer resin and the solubility constant 5 is greater than the ^{J 1/2 / cm 3/} 2 , so may be used as a non-solvent.

The substrate may be, but is not limited to, an aluminum sheet, a ceramic, a common glass, a copper, a polymer sheet, an FTO glass, a silicon wafer ), A silver sheet or a zinc substrate.

In the step (b), when the polymer pattern is formed as the coating and drying process progresses sequentially, a doctor blade, a bar coating, a dip coating, Or may be spin coating.

When the doctor blade method is used, the coating can be performed at a rate of 0.5 to 200 mm / sec. In the case of the bar coating, the relationship between the thickness of the coating layer and the coating bar is shown in Table 1. In the case of the immersion coating, coating may be performed at a speed of 0.1 μm / sec to 200 mm / sec and for 1 second to 30 minutes. The spin coating may be performed at a rate of 50 to 5000 rpm.

The depth and size of the micro polymer pattern well according to the present invention may become deeper and larger from the upper layer to the bottom layer, and the thickness of the polymer resin may become thicker as the coating bar number becomes larger.

NO . ㎛ NO . ㎛ 3 # 6.86 12 # 27.4 4# 9.14 14 # 32.0 5 # 11.4 16 # 36.6 6 # 13.7 18 # 41.1 7 # 16.0 20 # 45.7 8# 18.3 22 # 50.3 9 # 20.6 24 # 54.8 10 # 22.9 26 # 59.4

The drying in the step (b) may be performed at 0 to 100 ° C for 1 to 48 hours.

In the step (c), 1 to 10 kinds of solvents may be diluted with 1 to 10 kinds of non-solvent to prepare a mixed solvent of 1 to 100 vol%, and the volume ratio of the solvent and non-solvent may be 1 to 100: 100 < / RTI >

The drying in step (d) may be performed at 0 to 100 ° C for 1 to 48 hours.

The solvent / non-solvent treated polymer film according to the present invention can form a large area micro-single crystal layer used in template-assisted synthesis of recent one-dimensional microarchitecture arrays. Compared to other types of templates, the polymer monolayer can be easily formed and controlled on a substrate, and in the process, the polymer pattern is prepared in an appropriate ratio of solvent to non-solvent based on the solubility parameter of the polymer. The polymer can be easily adjusted to form a hexagonal or round patterned polymer.

The micropatterned surface according to the present invention provides an intelligent surface that can selectively affect various functions applied to biomaterials, surface engineering, photomagnetism and sensor systems, rather than merely providing unique properties Can play a role.

1 shows a scanning electron microscope (SEM) photograph of a polymer film micropattern on a substrate according to an embodiment of the present invention. The final texture of the polymer surface was determined by phase separation of the polymer plate and selective solvent treatment.

In one embodiment of the present invention, the micro-polymer pattern may be a large-area micro-polymer pattern. Large area is 1 mm ² To be can be a large area of ² m.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are intended to illustrate the contents of the present invention, but the scope of the present invention is not limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

< Example >

Example  One

As a process for preparing a micro polymer pattern on a glass plate, more specifically, a PS resin was dissolved in four kinds of solvents to prepare a 10 wt% PS solution. The PS solution was spin-coated on the glass at 1000 rpm and then dried at 50 ° C for 24 hours. Four kinds of solvents were diluted with two kinds of non - solvent to prepare a mixed solvent of 30 vol%. The glass coated with PS in the mixed solvent was treated with 9 # bar and dried at 25 ° C for 12 hours.

At this time, tetrahydrofuran, alumin, benzene and toluene were used as solvents, and ethanol and formamide were used as non-solvent. Here, the ratio of the solvent was 1: 1: 1: 1, and the ratio of the non-solvent was 1: 2.

Example  2

As a process for producing a micro polymer pattern on a silicon wafer, more specifically, a PLA resin was dissolved in two kinds of solvents to prepare a 25 wt% PLA solution. The PLA solution was coated on the silicon wafer by 22 # bar and dried at 40 ° C for 8 hours. Three kinds of solvents were diluted with two kinds of non - solvent to prepare a mixed solvent of 50 vol%. A silicon wafer coated with PS for 5 minutes in the mixed solvent was vertically immersed. Then, the silicon wafer was taken out at a speed of 10 mm / sec and dried at 35 DEG C for 10 hours.

At this time, tetrahydrofuran, bromobenzene and chloroform were used as a solvent, and cyclohexanol and water were used as non-solvent.

At this time, the PLA resin was dissolved in bromobenzene and chloroform (volume ratio = 2: 3). The 50 vol% mixed solvent was made by diluting tetrahydrofuran, bromobenzene and chloroform (volume ratio = 2: 2: 3) with cyclohexanol and water-chloroform (volume ratio = 3: 5).

Example  3

More specifically, PMMA resin was dissolved in THF to prepare a 5 wt% PMMA solution on a copper foil. The copper plate was immersed in the PMMA solution at 5 mm / sec and dried at 70 ° C for 1 hour. Five kinds of solvents were diluted with four kinds of non-solvent to prepare a mixed solvent of 10 vol%. The mixed solvent was dropped onto the PMMA-coated copper for 3 minutes, spin-coated at 2000 rpm, and then dried at 30 ° C for 5 hours.

At this time, N-methyl-2-pyrrolidone, 2-pyrrolidone, pyridine, benzene and toluene were used as solvents, and ethanol, water, ethylene glycol and formamide were used as non-solvent. Here, the ratio of the solvent was 1: 2: 3: 4: 5, and the ratio of the non-solvent was 5: 1: 3: 1.

Example  4

More specifically, PVDF resin was dissolved in N-methyl-2-pyrrolidone to prepare a 30 wt% PVDF solution on a ceramic plate. PVDF solution was coated on the ceramic by a doctor blade coating at 50 mm / sec and dried at 100 ° C for 5 hours. Six kinds of solvents were diluted with five kinds of non-solvent to prepare a mixed solvent of 70 vol%. The ceramic coated with PVDF was immersed in the mixed solvent for 30 minutes, the specimen was taken at 100 mm / sec, And dried at 100 DEG C for 48 hours.

In this case, N-methyl-2-pyrrolidone, 2-pyrrolidone, pyridine, p-dioxane, tetrahydrofuran and toluene were used as a solvent, And ethanol were used as non-solvent. Here, the ratio of solvent was 1: 2: 3: 4: 5: 6, and the ratio of non-solvent was 3: 2: 3: 7: 5.

Example  5

More specifically, a 2 wt% PS solution was prepared by dissolving PS resin in benzene. PS solution was coated on PET by doctor blade coating at 10 mm / sec and dried at 80 ° C for 24 hours. Four kinds of solvents were diluted with two kinds of non-solvent to prepare a mixed solvent of 40 vol%. PS-coated PET was immersed in the mixed solvent for 10 minutes, and the specimen was taken at 50 mm / sec and dried at 50 ° C for 48 hours.

At this time, benzene, p-dioxane, tetrahydrofuran and toluene were used as solvents, and methanol and water were used as non-solvent. Here, the ratio of the solvent was 1: 2: 4: 6, and the ratio of the non-solvent was 3: 7.

Example  6

More specifically, PLA resin was dissolved in chloroform to prepare a 3 wt% PLA solution. A 3 # bar of PLA solution was coated on the copper foil and then dried at 25 ° C for 1 hour. Chloroform

Methanol was mixed with a magnetic bar at a volume ratio of 17: 3 for 24 hours to prepare a solution. The mixed solvent was vertically immersed in a copper foil coated with PLA for 5 seconds. The copper foil was taken out at a speed of 30 mm / sec and then dried at 25 DEG C for 1 hour.

The results of the above embodiment are shown in Fig. The polymer formed a polygonal pattern, and the bottom showed that 100% copper was exposed as a result of EDS (Energy Dispersive Spectrometry) analysis. These patterns can be useful for structural control and synthesis of various electrode materials through additional deposition, sputtering or plating processes.

Example  7

In the process of fabricating the micro polymer pattern on the copper foil, the bottom well was not exposed to copper when the coating bar number was 5 #. In the process of preparing a micro polymer pattern on a copper foil using a PLA resin, 3 wt% of PLA is coated with 3 # bars and then immersed for 5 seconds. When the time is further shortened, etching is not performed, It was not.

The results of the above embodiment are shown in FIG. 2 and FIG.

Claims (11)

(a) dissolving a polymer resin in a solvent to prepare a polymer solution;
(b) coating the polymer solution on the substrate and drying;
(c) diluting the solvent in the non-solvent to prepare a mixed solvent; And
(d) treating the mixed solvent with a substrate coated with the polymer solution and drying the mixed solvent;
&Lt; / RTI &gt; wherein the polymer layer of the micro pattern is laminated on the substrate. The substrate according to claim 1, wherein the polymer resin is polystyrene, polypropylene, polyethylene, polymethylmethacrylate, polylactic acid, polyethylene terephthalate, polyvinyl chloride, polycarbonate or polyvinylidene fluoride A method for laminating a polymer layer of a micro pattern. The method of claim 1, wherein the solvent is selected from the group consisting of acetone, acetic acid, aniline, allylamine, benzene, bromobenzene, chloroform, chloroethane, chlorobenzene, chlorohexanol, ethylbenzene, ethoxyethane, hexane, Methyl-2-pyrrolidone, 2-pyrrolidone, pyridine, p-dioxane, tetrahydrofuran or toluene. The method according to claim 1, wherein in the step (a), the polymer resin is dissolved in 1 to 10 kinds of solvents to prepare a 0.01 to 50 wt% polymer solution. . The method of claim 1, wherein the substrate is an aluminum substrate, ceramic, glass, copper, polymer substrate, FTO glass, silicon wafer, silver or zinc substrate. The method of claim 1, wherein the coating of step (b) is a doctor blade, a bar coating, a dip coating, or a spin coating. &Lt; / RTI &gt; wherein the polymer layer of the pattern is laminated. The method according to claim 1, wherein the drying in step (b) is performed at 0 to 100 ° C for 1 to 48 hours. 2. The process of claim 1, wherein the non-solvent is selected from the group consisting of butanol, 1-butoxybutane, 1,3-butanediol, cyclohexanol, ethanol, ethylene glycol, formamide, 1-pentanol, 2-isopropoxypropane, , Methanol or water. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 1, wherein the step (c) comprises diluting 1 to 10 kinds of solvents with 1 to 10 kinds of non-solvent to prepare a mixed solvent having a solvent of 1 vol% or more and less than 100 vol% A method for laminating a polymer layer of a micro pattern. The method of claim 1, wherein the volume ratio of solvent to non-solvent is from 1 to 100: 1 to 100. The method of claim 1, wherein the drying in step (d) is performed at 0 to 100 ° C for 1 to 48 hours.

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