KR102361558B1 - Coating Composition for Manufacturing Article With Slippery Surfaces - Google Patents

Abstract

The present invention relates to a coating composition capable of producing an article having both an exterior and an interior slippery surface, and a method for preparing the same. The composition for coating according to the present invention makes it possible to manufacture an article having a slippery surface on both the inner surface and the outer surface only by a simple process of molding and curing a polymer resin by a conventional technique. The article manufactured using the composition for coating of the present invention can be used in various industries because it can solve ice removal from the surface of machines such as aircraft and automobiles, biofouling problems in blood vessels, and problems requiring self-cleaning.

Description

Coating Composition for Manufacturing Article With Slippery Surfaces

The present invention relates to a coating composition for manufacturing an article having a slippery surface, and more particularly, to a coating composition capable of manufacturing an article having a slippery surface both on the outside and on the inside by a simple method.

The development of liquid-repellent surfaces is being promoted by the self-cleaning ability of surfaces of animals, insects and plants. The liquid-repellent surface first has a water-repellent surface inspired by the lotus effect. The water-repellent surface is a structure in which water droplets can easily roll off due to the microstructure and low surface energy of the surface. Research has been conducted to continuously improve the performance of water-repellent surfaces in various fields that require self-cleaning, but there are problems such as durability and harmfulness of fluorine-based compounds to the human body during super water-repellent implementation.

After introducing the concept of SLIPS at Havard University in 2011, research on slippery surfaces has been actively conducted. This is a natural imitation of the surface of dung beetle, and there is a lubricating layer on the surface.

The slippery surface has many advantages such as anti-biofouling and low ice adhesion, but most of the research is focused on the coating technique of the two-dimensional surface, which limits its application to the three-dimensional shape. Therefore, the implementation of a slippery surface in various three-dimensional shapes is a necessary part in industries that require self-cleaning.

In Korean Patent Laid-Open Publication No. 10-2014-0004723, a self-healing, scratch-resistant slippery surface prepared by walking a chemically inert, high-density liquid coating on a roughened solid surface characterized by micro- and nanoscale photography is formed. technology is disclosed. However, since this is a two-dimensional surface implementation, it is difficult to implement various complex three-dimensional shapes, and since a slippery surface is formed using coating through immersion, in the case of a shape that is difficult to coat, such as a circular tube with a small inner diameter, the slippery surface inside the cylindrical tube There is a disadvantage in that it is difficult to form uniformly.

In addition, Korean Patent Application Laid-Open No. 10-2011-0048545 relates to the use of a slippery thin film or coating for improving the lubricity of a portion where friction and abrasion are introduced. was produced. However, this is not a three-dimensional shape, but a two-dimensional surface lubricating layer implementation, and has a disadvantage in that it is limited to deposition and coating technologies.

On the other hand, a 3D printer is an equipment that produces a three-dimensional shape as it is based on an input three-dimensional drawing, just like printing type or picture. Recently, 3D printing technology has become a central issue leading the 4th industrial revolution, and is widely used for making various models in the fields of automobiles, medical care, art, and education.

The principle of 3D printer can be largely divided into cutting type and laminate type, and most of the 3D printers that are actually applied are laminate type without material loss.

There are about 20 methods using the layered principle, but the most used methods are SLA (Stereolithography Apparatus), FDM (Fused Deposition Modeling) or FFF (Fused Filament Fabrication) and SLS (Selective Laser Sintering) method.

In the case of SLA, a laser beam is projected into a water tank containing a liquid photocurable resin to form, and an epoxy-type photopolymer, which is a photocurable resin, is mainly used. On the other hand, FDM (or FFF), a method in which the input filament material is discharged in a molten state from the nozzle of the printer moving in the Z, Y, and Z axes, is molded in three dimensions, thermoplastic plastic is used as the main material. On the other hand, SLS implements 3D printing by selectively sintering by firing a laser into a water tank containing powdery materials such as metal, plastic, and ceramic powder.

Among the three methods, the FDM method, which uses a thermoplastic plastic as a filament, is the most popular because the price of a 3D printer is relatively low and the printing speed is faster than other methods. In the FDM method, polylactic acid (PLA), ABS (Acrylonitrile Butadiene Styrene), high density polyethylene (ABS), Materials such as polyethylene; HDPE) and polycarbonate (PC) are usefully used.

Patent documents related to FDM-type 3D printing materials include Korean Patent Application Laid-Open No. 10-2015-0098142 (Composite filament composition for FDM-type 3D printer containing metal powder), Republic of Korea Patent Publication No. 10-1350993 (Method for manufacturing PLA filament for 3D printer having flame-retardant and heat-resistance properties using microcapsules and PLA filament manufactured by the same) and US Patent Application Publication No. 2009/0295032 (method of creating a three-dimensional object using a modified ABS material) has been disclosed.

As a result of research to realize an article having a slippery surface to the inside, the inventors of the present invention manufactured an article having a slippery surface as well as the inside by using a coating composition containing a mixture of a polymer resin and a lubricant with a simple technique found that it can be done and completed the present invention.

An object of the present invention for solving the above problems is to provide a coating composition capable of manufacturing an article having a slippery surface to the inside by a simple method.

Another object of the present invention is to provide an article having a slippery surface.

In order to achieve the above object, the present invention provides a composition for manufacturing an article having a slippery surface, the composition for coating comprising a mixture of a polymer resin and a lubricating oil.

In the present invention, the coating composition may further include an airgel (aerogel).

In the present invention, the polymer resin is polydimethylsiloxane (PDMS), silicone (silicone), perfluoropolyether (PFPE), polyurethane (polyurethane, PU), polylactic acid (Polylactic acid); PLA), ABS (Acrylonitrile Butadiene Styrene), high density polyethylene (HDPE), polycarbonate (PC), polystyrene (PS), polyester, polyolefin, polyamide ), polyvinyl alcohol, N-vinylpyrrolidone, N-vinylcaprolactam, dimethyl acrylamide, hydroxyethylacrylamide, 2-acryloyloxyethyl isocyanate, isobornyl acrylate, tetrahydro Furfuryl acrylate, phenoxy polyethylene glycol acrylate, lauryl acrylate, benzyl acrylate, ethoxyethyl acrylate, phenoxyethyl acrylate, cyclic trimethylol formal acrylate, 6-hexanediol diacrylate, trimethyl Allpropane triacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, 1,1 (bisacryloyloxymethyl) ethyl isocyanate, polyester acrylate and urethane acrylate It may be one or more selected from the group consisting of.

In the present invention, the lubricating oil is olive oil, fluorinated oil, silicone oil, essential oil, paraffin oil, and petroleum oil (mineral oil) It may be at least one selected from the group consisting of.

In the present invention, the airgel may be at least one selected from silica gel, carbon airgel, and graphene airgel.

The coating composition of the present invention may contain 30 to 100 parts by weight of lubricant based on 100 parts by weight of the polymer resin.

The coating composition of the present invention may further include 1 to 200 parts by weight of airgel based on 100 parts by weight of the lubricant.

The coating composition of the present invention may contain 10 to 30% by weight of essential oil based on the total weight of the lubricating oil.

The coating composition of the present invention further comprises at least one solvent selected from the group consisting of dichloromethane (DCM), tetrahydrofuran, dioxane, methyl ethyl ketone (MEK) and dimethylformamide (DMF) can do.

In the present invention, the solvent may be included so that the concentration of the total composition is 0.05 to 0.30 g/mL.

The present invention also provides an article having a slippery surface formed by curing a composition for coating comprising a blend of a polymeric resin and a lubricating oil.

In the present invention, the coating composition may further include an airgel (aerogel).

An article having a slippery surface of the present invention may have a light transmittance of at least 80%.

The article having a slippery surface of the present invention may comprise between 10 and 100% by weight of the total lubricating oil of essential oil.

The present invention also provides a self-cleaning container formed by curing a coating composition comprising a blend of a polymer resin and a lubricant, the container comprising an oil impermeable material on the outer surface of the container, Provide available containers.

The present invention also provides a medical catheter having a slippery surface, formed by curing a coating composition comprising a blend of a polymer resin and a lubricating oil, comprising 10 to 30% by weight of essential oil of the total lubricating oil , to provide a medical catheter having a slippery surface.

The composition for coating according to the present invention makes it possible to manufacture an article having a slippery surface on both the inner surface and the outer surface only by a simple process of molding and curing a polymer resin by a conventional technique. The article manufactured using the composition for coating of the present invention can be used in various industries because it can solve ice removal from the surface of machines such as aircraft and automobiles, biofouling problems in blood vessels, and problems requiring self-cleaning.

1 shows the state of a mixture of a polymer resin and lubricating oil with or without the addition of airgel.
2 shows an image of a scaffold prepared using PDMS-Slippery Blend.
3(a) shows a conceptual diagram of manufacturing a self-cleaning container with two kinds of foreign substances, slippery blend and PETG, using a two-nozzle DIW printing method.
Figure 3 (b) shows a comparison of the self-cleaning performance when pouring the kettle into the prepared container.
4 is an image of a commercially available medical silicone tube and a silicone tube manufactured by a printing method using PDMS-Slippery Blend.

Hereinafter, specific aspects of the present invention will be described in more detail. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

The present invention relates to a composition for making an article having a slippery surface.

The composition of the present invention comprises a blend of a polymeric resin and a lubricating oil.

In the present invention, the slippery surface means a surface having a self-cleaning ability that easily rolls off even at a small sliding angle without water or ice adhering to the surface of an object containing lubricating oil.

In the present invention, the term “blend” refers to a state in which two or more substances that do not dissolve in each other are uniformly dispersed.

In the present invention, by providing a mixture in which a polymer resin and a lubricating oil are uniformly mixed with each other as a coating composition, the product can have a slippery surface when a desired product is formed by coating the coating composition.

In general, the miscibility of two substances can be calculated as the free energy for mixing as follows.

ΔG _mix =ΔH - TΔS

If the free energy of mixing is greater than zero, the two substances are difficult to mix with each other. This means that a large interfacial tension acts between the two materials, and the two materials prefer to be separated rather than uniformly mixed.

In the present invention, it has been found that the free energy of mixing can cancel the interfacial tension of two materials greater than zero by using a porous aerogel as a compatibilizer. The porous airgel has nano-sized pores providing an extremely large surface area (about 310 m ² /g), and also has excellent oil adsorption properties thanks to its chemical affinity.

When airgel is added to the mixture, the free energy of mixing can be determined as follows.

ΔG _mix = ΔG _PS + ΔG _LS + ΔG _PL

(P: polymer, L: lubricant, S: solid particles)

Accordingly, the Gibbs energy is changed to be smaller than zero, and the lubricating oil and the polymer resin can be mixed stably.

The glass bottle on the left in Figure 1 shows a mixture of polymer resin (PDMS) and lubricant (olive oil) without added airgel. It is confirmed that the two materials were not uniformly mixed and phase separation appeared. On the other hand, in the right glass bottle to which airgel (silica gel) is added, it can be visually confirmed that the three substances maintain a uniform mixture.

The lubricating oil is olive oil, fluorinated oil, silicone oil, essential oil, paraffin oil, petroleum-based oil (mineral oil), etc. to use desirable.

In the present invention, “lubricating oil” may be used in the same sense as “oil” in some cases.

The essential oil may be clove oil, and the paraffinic oil is n-octane, n-decane, n-dodecane, hexadecane. , and may be selected from octadecane and the like, and the petroleum oil may be selected from diesel, gasoline, crude oil, and the like.

If essential oil, particularly clove oil, is included among the lubricating oils, an antibacterial effect can be imparted to the manufactured product.

In the present invention, the lubricant is preferably used by adjusting the desired content according to the degree of slippage of the product to be manufactured, and may be included in an amount of 10 to 200 parts by weight based on 100 parts by weight of the polymer resin. Preferably, it may be included in an amount of 30 to 100 parts by weight based on 100 parts by weight of the polymer resin.

As the airgel, silica gel, carbon airgel, graphene airgel, etc. may be used. The airgel absorbs the lubricating oil so that the lubricating oil is stably mixed with the polymer resin, and the lubricating oil is not easily evaporated even after being commercialized.

In addition, the manufactured mechanical properties of the airgel may be improved. In an embodiment of the present invention, it was confirmed that mechanical properties such as storage elasticity, tensile strength, and hardness of a product including the airgel can be significantly improved. Therefore, when the three-dimensional product is manufactured using the coating composition of the present invention, the airgel can maintain a desired shape until the polymer is crosslinked/cured.

The airgel is preferably added in an appropriate amount in consideration of the compatibility of the polymer resin and the lubricant and the mechanical properties of the product to be manufactured, and may be used in an amount of 1 to 200 parts by weight based on 100 parts by weight of the oil.

In the present invention, the polymer resin is polydimethylsiloxane (PDMS), silicone (silicone), perfluoropolyether (PFPE), polyurethane (PU), polyimide (PI) It may contain a liquid polymer, such as. The liquid polymer may be mixed with lubricating oil without a separate solvent, and may be mixed with lubricating oil by airgel if necessary.

For example, the silicone elastomer and the silicone oil have excellent compatibility even without the addition of airgel, and thus can be used in the coating composition of the present invention, but the silicone elastomer and the olive oil are not mixed without the addition of the airgel.

The polymer resin of the present invention is also polylactic acid (PLA), ABS (Acrylonitrile Butadiene Styrene), high density polyethylene (HDPE), polycarbonate (Polycarbonate; PC), thermoplastic polyurethane (TPU) , polystyrene (PS), polyester (Polyester), polyolefin (polyolefin), polyamide (Polyamide), polyvinyl alcohol (Poly Vinyl Alcohol), and a thermoplastic polymer resin selected from combinations thereof may be used.

When a thermoplastic polymer resin is used as the polymer resin, it is preferable to dissolve the solid polymer in a solvent to liquefy it and mix it with a lubricating oil. As a solvent usable in the present invention, dichloromethane (DCM), tetrahydrofuran (THF), dioxane, methyl ethyl ketone (MEK), dimethylformamide (DMF), etc. can be used.

In order to select a suitable solvent that can be mixed with the lubricant while liquefying the solid polymer at the same time, a Flory-Huggins solution can be applied. The Flory-Huggins constant (χ) is defined as follows.

In the above formula, δ ₁ and δ ₂ represent the solubility constants of the solvent and the solute, V ₁ is the molar volume of the solvent, R is the gas constant, and T is the absolute temperature.

The smaller the χ value, the better the solvent and solutes can be dissolved.

For example, the χ of polylactic acid (PLA) and dichloromethane (DCM) is 0.03, which is much less than the χ of PLA and toluene of 0.42. Therefore, it can be seen that DCM is more suitable than acetone for dissolution of PLA.

In addition, the constant χ of DCM and lubricant is also important for mixing. It can be seen that olive oil (χ = 0.47) and petroleum oil (χ = 0.91) are more easily miscible with DCM than water (χ = 21.43) or ethylene glycol (χ = 6.08).

The solvent is preferably added in an amount such that the concentration of the entire composition is 0.05 to 0.30 g/mL, and more preferably, 0.05 to 0.15 g/mL.

The types of suitable solvents according to exemplary solid polymer resins are shown in Table 1 below.

polymer menstruum Polylactic acid (PLA) Dichloromethane (DCM)
tetrahydrofuran
dioxane Acrylonitrile Butadiene Styrene (ABS) DCM
Methyl ethyl ketone (MEK) Polyurethane (PU) Dimethylformamide (DMF) Polystyrene (PS) DCM acrylic MEK Polycarbonate (PC) DCM
MEK

The method for preparing the coating composition of the present invention using a solid polymer resin comprises the steps of: preparing a polymer solution by dissolving the polymer resin in a first solvent; and mixing the polymer solution and the lubricant oil. In the method, the step of mixing the lubricant oil may include mixing the lubricant oil solution in which the lubricant oil is dissolved in a second solvent.

In a preferred embodiment of the present invention, in the step of mixing the lubricating oil, it is preferable to further mix the airgel, and after adding the airgel to the lubricating oil solution, it is most preferable to mix the polymer resin solution and the lubricating oil solution.

According to the present invention, the polymer is dissolved in a solvent to form a liquid phase at room temperature, the lubricating oil is dissolved in a separate solvent, and then the liquid polymer and the lubricating oil are mixed so that the polymer can be mixed well with the lubricating oil, and the polymer is easily cured or to prevent the lubricating oil from easily evaporating at high temperatures.

The first solvent and the second solvent are preferably the same solvent.

The lubricating oil solution preferably has a concentration of 10 to 50% (v/v), more preferably 15 to 30% (v/v).

In the present invention, the mixing of the two solutions is preferably continuously stirred while adding the polymer solution to the lubricating oil solution little by little.

It is also possible to use a photocurable polymer resin according to the application as the polymer resin. Examples of the photocurable polymer include nitrogen-containing vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, dimethyl acrylamide, hydroxyethyl acrylamide, 2-acryloyloxyethyl isocyanate, isobornyl acryl Late, tetrahydrofurfuryl acrylate, phenoxy polyethylene glycol acrylate, lauryl acrylate, benzyl acrylate, ethoxyethyl acrylate, phenoxyethyl acrylate, cyclic trimethylolformal acrylate, 6-hexanedioldi Acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, 1,1 (bisacryloyloxymethyl) ethyl isocyanate, polyester acrylate, Urethane acrylate etc. are mentioned.

In addition, the coating composition of the present invention, if necessary, one or more additives selected from the group consisting of heat stabilizers, antioxidants, light stabilizers, release agents, compatibilizers, dyes, pigments, colorants, plasticizers, impact modifiers, stabilizers and lubricants may further include.

In addition, when using a photocurable polymer resin, it is preferable to further include a photoinitiator.

The composition for coating of the present invention may be commercialized by a known method. For example, when a film having a slippery surface is to be manufactured, the coating composition may be molded using a known molding technique, and then a product may be manufactured by curing the used polymer resin.

For the molding, various known molding techniques such as coating, molding, and 3D printing may be used.

The coating composition including the thermosetting polymer resin can be crosslinked by heat after forming the shape of the product using molding to manufacture a product having a slippery surface. Similarly, when a photocurable polymer resin is included, an article having a slippery surface can be produced by photocuring.

Depending on the type of polymer resin and lubricating oil, the coating composition of the present invention may produce a product having characteristics such as optical transparency, stretchability, flexibility, ice non-adhesion (icephobicity), and antibacterial/sterilizing properties. can In particular, in one embodiment of the present invention, it was confirmed that the PDMS-based lubricating product exhibits a light transmittance of 88% or more at a wavelength of 300 to 800 nm.

In a preferred embodiment of the present invention, the coating composition may be a 3D printing composition for manufacturing a three-dimensional article having a slippery surface.

In the present invention, a three-dimensional article having a slippery surface means that an article having a three-dimensional three-dimensional shape has a slippery surface as well as the inside thereof.

The airgel usable in the 3D printing composition of the present invention preferably has a particle size of 20 to 200 μm. When the particle size of the airgel is less than 20 μm, it is difficult to sufficiently absorb oil, and when it is 200 μm or more, it is caught in the nozzle of the 3D printer and it is difficult to achieve smooth injection.

The 3D printing composition of the present invention may also optionally include one or more additives selected from the group consisting of heat stabilizers, antioxidants, light stabilizers, release agents, compatibilizers, dyes, pigments, colorants, plasticizers, impact modifiers, stabilizers and lubricants. may further include.

In addition, when using a photocurable polymer resin, it is preferable to further include a photoinitiator.

The 3D printing composition according to the present invention prepared by the above method may be prepared as a filament for a 3D printer.

Specifically, if the 3D printing composition of the present invention is cured by evaporating the solvent at room temperature, it can exhibit similar performance even if it is melted by applying heat later. Therefore, in the process of curing the 3D printing composition of the present invention, it is possible to implement the desired shape of the filament for a 3D printer through an additional cutting process after forming it in the shape of a filament or curing it using an extrusion or molding process. .

The filament for the 3D printer preferably has a standard that can be used in a commercially available 3D printer.

The filament for the 3D printer of the present invention may have a diameter of preferably 0.8 to 4.0 mm, more preferably 1.5 to 3 mm. If the diameter of the filament is less than 0.8 mm, the printer device may not easily supply the filament because it is too thin, or the filament may not be ejected because the filament is pressed, and the printing speed may be slow. In addition, if the diameter of the filament exceeds 4mm, the solidification rate is slow, it is difficult to melt the filament, and the precision of the printed sculpture may be deteriorated.

The 3D printing composition according to the present invention can implement a three-dimensional article having a slippery surface through a simple 3D printing technology. When an ink composition capable of 3D printing containing oil is printed, the output is hardened by the liquefaction lamination method as the solvent evaporates. Through this, it is possible to easily impart a slippery surface to a three-dimensional shape in which it is difficult to form a slippery surface by a conventional coating technique.

In a preferred embodiment of the present invention, the coating composition of the present invention can be used in the manufacture of zero-residue containers.

The no-residue container is a self-cleaning container, and the coating composition of the present invention and an oil-impermeable material are printed at one time to form an inner surface having a slippery surface on the inner surface of the container, and the outer surface of the container is oil-free It is possible to form an outer surface by a non-permeable material.

PETG (glycolmodified polyethylene terephthalate) may be used as a material applicable to the outer surface of the non-residual container, but is not limited thereto.

It is preferable to use an edible oil for the coating composition for use on the inner surface of the non-residual container, for example, it is preferable to use a silicone oil.

In a preferred embodiment of the present invention, the coating composition of the present invention can be used in the manufacture of an antibacterial catheter (catheter).

In the medical world, catheters are used in various ways as a transport route for body fluids, drugs, medical equipment, and the like. However, a biofilm is easy to form on the surface of the tube, and there is a high possibility of clogging the tube or contamination by bacteria.

For medical catheters, a slippery surface and antibacterial properties are essential. In the conventional catheter, a rubber catheter was immersed in oil for a certain period of time for a slippery surface, and then taken out and used. However, in the case of the oil-impregnated catheter, there is a problem in that the inner diameter is reduced by the oil, and the oil escapes even if used a little, and the slippery property does not last for a long time.

If a catheter having a slippery surface is manufactured using the coating composition according to the present invention, a catheter having a slippery surface can be used immediately without a separate oil impregnation process, and the oil does not escape even after long-term use, so that the slippery surface can last for a long time have. In addition, since the catheter can be manufactured with desired mechanical properties and specifications, it can be suitably used to fit the intended use.

The coating composition for manufacturing the catheter preferably includes mineral oil, for example, clove oil. When clove oil is included, the manufactured product exhibits antibacterial properties, so it is preferable to use it for medical purposes.

It is preferable from a viewpoint of flexibility to use a silicone resin or a polyurethane resin as a polymer resin for manufacturing a catheter.

When using a silicone resin, it is excellent in compatibility to use silicone oil as a lubricant. However, clove oil may interfere with crosslinking of the silicone resin when used in large amounts. Therefore, the clove oil is preferably used in an amount of 5 to 30% by weight based on the total weight of the oil.

An article having a slippery surface that can be manufactured using the coating composition of the present invention is economical and energy-efficient in fields requiring low ice adhesion, such as aircraft, ships, and automobiles, as well as fields requiring anti-biofouling and self-cleaning. It can be used in various industries by bringing benefits in terms of aspects.

Example

The present invention will be described in more detail with reference to the following examples. However, these Examples show some experimental methods and compositions for illustrative purposes of the present invention, and the scope of the present invention is not limited to these Examples.

Experiment preparation

Slippery Blend Ink Manufacturing

Silica gel was purchased from REM-tech with a particle size of 2 to 20 μm and was used.

PDMS was purchased from Dow Corning and used.

Polylactic acid (PLA) was dissolved in dichloromethane (DCM) at a ratio of 1:6 (w/w) and stirred for 24 hours.

In the composition used for the UV curing method, 5 wt% of Darocure 1173, a photoinitiator of Fluorolink MD700, was mixed.

PDMS was mixed with the curing agent in a weight ratio of 10:1.

The coating compositions mixed in the composition ratio described in each experimental example were used by stirring at 2000 rpm for 3 minutes using a centrifugal mixer (Thinky, ARE-310).

Hereinafter, a coating composition for manufacturing a three-dimensional article is called Slippery Blend or Slippery Blend ink.

3D Printing of Slippery Blend Items

The manufacture of Slippery Blend articles using Slippery Blend was prepared by putting Slippery Blend ink into a syringe barrel, removing air, and then 3D printing using a 200 μm gauge tapered tip as a spray nozzle. Printing using solvent casting was performed with a direct ink-writing system using motor-action.

Experimental Example 1: Measurement of rheological properties of ink

The rheological properties of Slippery Blend inks prepared based on PFPE, PDMS and PLA polymer resins were analyzed.

For the measurement, a 40 mm plate geometer and a DHR-3 Rheometer (TA Instruments) having a gap of 1000 μm were used. The vibration test for measuring the storage modulus and loss modulus at different stress changes was performed while changing the stress from 0.1 to 1000 Pa at a fixed frequency of 1 Hz. The yield stress was set as the value when the storage modulus dropped to 90% of the initial value.

The storage modulus (G') and loss modulus (G'') of the PFPE and PFPE-based slippery blends with respect to shear stress are shown in Table 2 below. In Table 2, the unit is Pa, and PFPE-Slipery Blend was prepared by mixing in a weight ratio of PFPE: fluorine-based oil: silica gel = (65:25:10).

In Table 2, the storage modulus and loss modulus of PFPE did not change despite the increase in vibrational stress and showed parallel profiles.

However, the Slippery Blend with silica airgel particles added had a higher storage modulus (G'>G'') at low shear yield stress (τ _y < 10 Pa), but was stored with an increase in shear stress (τ _y > 10 Pa). The elastic modulus decreased rapidly, so that the loss modulus became more dominant.

The storage modulus (G') and loss modulus (G'') with respect to vibration stress of PDMS and PDMS-Slippery Blend are shown in Table 3 below. In Table 3, the unit is Pa, and PDMS-Slipery Blend was prepared by mixing at a mixing ratio of PDMS:mineral oil:silica gel=(70:25:5).

In Table 3, the shear yield stress of PDSM-Slippery Blend containing airgel was higher than that of PDMS+oil mixture containing no airgel.

This means that the ink can retain the shape of the filaments even at higher shear stresses, and can be printed with a narrower nozzle.

The storage modulus and loss modulus according to evaporation time of PLA and PLA-Slippery Blend solvent dissolved in DCM are shown in Table 4 below. In Table 4, the unit is Pa, and PLA-Slipery Blend was prepared by mixing at a mixing ratio of PLA:mineral oil:silica gel = (70:20:10).

In Table 4, the storage modulus and the loss modulus were confirmed immediately after the solvent was removed. Solidification of PLA-Slippery Blend was possible immediately after coming out of the nozzle by rapid solvent evaporation.

The above result is significant in that it means that even a polymer-lubricating oil mixture having physical properties that cannot maintain the shape of a three-dimensional product can maintain the three-dimensional shape by the addition of airgel.

Experimental Example 2: Manufacture of a three-dimensional article

In order to confirm the 3D printing possibility of Slippery Blend, a scaffold was prepared using a micro nozzle (200 μm diameter) using PDMS-Slippery Blend.

As can be seen in FIG. 2 , due to the shear mint and non-Newtonian fluid properties, the Slippery Blend ink was easily extruded from the micro-size nozzle to maintain the filament shape. The prepared scaffold consisted of a filament of about 250 μm in diameter and a space of about 800 μm.

This means that a micro-scale three-dimensional object can be manufactured using the coating composition of the present invention.

Experimental Example 3: Measurement of mechanical properties

To test the mechanical properties of Slippery Blend, tensile strength and shore hardness were measured.

Dumbbell-shaped samples for tensile testing were prepared according to standard DIN 53504. The test was performed at a speed of 500 mm/min using a 1 kN loading cell. A sample for hardness measurement was prepared with a thickness of 2 cm. Shore A hardness was measured using a Shore A durometer.

The mechanical properties of the Slippery Blend materials for different polymers, lubricants and aerosol contents are shown in Table 5 below.

In Table 5 above, the ultimate strength of PDMS-Slippery Blend containing 30% by weight of oil-airgel mixture was reduced by 48.6% compared to PDMS without oil.

As the content of silica airgel increased, the ultimate strength increased, so that the slippery blend containing 11.9 wt% of silica airgel showed about 8.1 Mpa, which was higher than that of PDMS alone, which showed about 6.0 Mpa.

In Table 5, although the hardness was greatly reduced according to the addition of lubricating oil, it can be seen that the addition of silica airgel shows higher hardness despite the addition of the lubricating oil.

From these results, it can be seen that the addition of airgel can greatly improve the mechanical properties of the mixture of polymer resin and lubricating oil.

Experimental Example 4: Analysis of lubrication performance of Slippery Blend

Critical sliding angle measurements were performed for various polar and non-polar liquid droplets to analyze the lubrication performance of Slippery Blend articles.

Wettability with respect to liquids having various surface tensions shown in Table 6 below was measured using a contact angle measurement stage. A droplet of 10 μl was dropped at 10 different locations on the PDSM and PFPE-based samples having the composition of Experimental Example 1. The sliding angle was measured by dropping 10 μl of a droplet on a tilt stage using a high-speed camera.

In Table 6, PDMS-Slippery Blend exhibited a low critical sliding angle of 10° or less with respect to water, ethylene glycol, and olive oil. However, PDMS-Slippery Blend did not show lubricating properties against volatile solvents such as chloroform and petroleum ether, which means that PDMS swells easily with volatile solvents, and mineral oil is easily dissolved in such solutions, which makes it difficult to maintain a lubricating layer. because it does

On the other hand, the PFPE-based slippery blend using a fluorine-based lubricant showed a very low sliding angle of about 5° or less for all target liquids.

This means that the coating composition of the present invention can be used to prepare an omniphobicity product.

Experimental Example 5: Preparation of self-cleaning containers

Using the Slippery Blend platform, different types of materials were printed at once to produce functional products.

As shown in Fig. 3(a), a self-cleaning container was prepared using a two nozzle DIW printing method.

In order to prevent the lubricating oil from diffusing through the outer surface while maintaining the lubricating surface of the inner surface of the container, PDMS-Slippery Blend ink was used to manufacture the inner surface of the container, and PETG filament was used for the outer surface of the container.

As shown in Fig. 3(b), the prepared container was able to easily remove the sticky contents without special measures.

Experimental Example 6: Optical transmittance measurement

In order to measure the optical transmittance of the PDMS-based lubricating product, a UV-Visible Spectrophotometer (Lambda 650S, Perkin Elmer) was used.

Measurements were performed at wavelengths of 400, 600 and 800 nm, respectively. A PDMS-based sample was drop-casted to 500 μm on a slide glass, and the sample was separated from the glass to minimize the influence of the slide. The results are shown in Table 7 below. In Table 7, PDMS + silicagel was mixed in a weight ratio of 93:7, and slippery blend was prepared according to the composition of Experimental Example 1.

In Table 7, transmittance at 400 to 800 nm of PDMS and PDMS-Slippery Blend was 85.7 to 92.4% for PDMS, and 86.8 to 91.1% for PDMS-Slippery Blend. This means that both PDMS and PDMS-Slippery Blend substrates show transparency.

On the other hand, the PDMS-airgel substrate had a slight decrease in transmittance to 83.5 to 86.2%, because the airgel scattered light. On the other hand, the reason that PDMS-Slippery Blend showed better transparency than the PDMS substrate was because the lubricant had a refractive index similar to that of PDMS and further reduced light reflection.

Accordingly, the coating composition of the present invention can be optically transparent and can produce a product having slippery properties.

Experimental Example 7: Ice adhesion test

An experiment was performed to check the ice adhesion according to the lubricant content.

Samples with various lubricating oil contents were prepared by drop casting on flat glass to a thickness of 500 μm. A load cell was used with a sensitivity of 5 mN.

After fixing the sample on the stage, a plastic cylinder with a diameter of 0.75 cm and a height of 1 cm was placed vertically and 200 μl of demineralized water was sprayed. After maintaining the ambient temperature at -15°C for 1 hour, the tip of the force probe was positioned 1 mm away from the sample surface, and the force required to remove the ice was measured by pushing the sample at a speed of 0.05 mm/s. The results are shown in Table 8.

In Table 8, it can be seen that the PDMS-Slippery Blend containing 15% of the silicone oil and airgel mixture reduced ice adhesion by 44.6% compared to the case without oil. In addition, the sample containing 30% of the silicone oil and airgel mixture showed an ice adhesion of 60.3 kPa, which was reduced by 62.3% compared to PDMS alone.

This tendency was also found in the PFPE-based slippery blend. The PFPD-Slippery Blend containing 30% of fluorinated oil showed a significantly reduced ice adhesion to 96.2% compared to the sample without oil.

Experimental Example 8: Antimicrobial test

Bacterial adhesion test was performed according to JIS Z2801.

E. coli EG1655 was used as the strain. The sample was drop-casted to a thickness of 1 mm, cut into 5 x 5 cm ² size, placed in an autoclave, and sterilized at 100 °C. The sterilized sample was placed in a Petri dish and 400 μl of E. coli medium (˜10 ⁸ CFU/mL) was placed over the sample. The medium was covered with a sterile polyester film (4 x 4 cm ² ) to control the contact area. Samples were incubated at 36° C. for 24 hours. After incubation, the samples were carefully washed with PBS solution to remove non-adherent bacteria.

After the bacterial film was removed from the sample surface using a cotton swab, the sample and the cotton swab were placed in a conical tube containing 20 mL of PBS solution. The conical tube was sonicated for 10 minutes and diluted 1000-fold. Then, 200 μl of the solution was incubated on an LB agar plate for 24 hours.

In PLA and PDMS-based 3D-LUBIRC, the number of strains when no oil was added, when only olive oil was added, and when olive oil and clove oil were added in a weight ratio of 5:1 are shown in Table 9 below.

In PLA and PDMS-based 3D LUBRIC, it was confirmed that some antibacterial activity occurred even when only olive oil was added (83.2% and 85.7%, respectively).

When clove oil was added, the number of strains decreased to 99.9% (PLA) and 98.2% (PDMS), confirming that it exhibited very excellent antibacterial activity.

This phenomenon is thought to be because eugenol, the main component of clove oil, damages the cell membrane of bacteria and negatively affects the metabolism and proliferation of bacteria.

Experimental Example 9: Preparation of an antibacterial catheter

In order to confirm the practical applicability of the antimicrobial Slippery Blend, an antimicrobial Slippery Blend catheter tube was prepared.

4 is an image of a commercially available medical silicone tube and a tube having a length of 6 cm, an inner diameter of 7 mm, and a thickness of 0.8 mm manufactured by a printing method using PDMS-Slippery Blend. The tube was manufactured using an FDA-approved, non-reactive mineral oil and silicone elastomer for biocompatibility.

In order to confirm the bioadhesion prevention activity of the prepared tube, a flow bacterial adhesion test was performed.

P. aeruginosa cultured overnight was mixed with LB Broth at a ratio of 1:100dml and continuously rotated using a Peristaltic pump.

A sterile silicone tube (I.O: 6.4 mm, Cole Parmer, Masterflex L/S 17) was connected to the pump, and the inlet was immersed in the medium, and the outlet was placed on the medium by connecting a Slippery Blend tube.

The results of comparing the performance by checking the biofilm formation at 8, 16 and 24 hours are shown in Table 10 below.

In Table 10, the Slippery Blend tube showed a reduced optical density of 87.6% at 16 hours when the biofilm started to form, and 71.4% even after 24 hours compared to commercially available medical silicone tubes, confirming that antibacterial activity occurred. became

As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. It will be obvious. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

Claims (13)

A composition for making an article having a slippery surface, the composition comprising:
30 to 100 parts by weight of lubricating oil is mixed with respect to 100 parts by weight of the polymer resin,
A coating composition further comprising an airgel (aerogel) having a particle size of 20 to 200㎛.
The method of claim 1,
The polymer resin is polydimethylsiloxane (PDMS), silicone (silicone), perfluoropolyether (PFPE), polyurethane (polyurethane, PU), thermoplastic polyurethane (TPU), poly E Mid (polyimide, PI), polylactic acid (PLA), ABS (Acrylonitrile Butadiene Styrene), high density polyethylene (HDPE), polycarbonate (PC), polystyrene (PS), polyester (Polyester), polyolefin, polyamide, polyvinyl alcohol, N-vinylpyrrolidone, N-vinylcaprolactam, dimethylacrylamide, hydroxyethylacrylamide, 2-acryl Royloxyethyl isocyanate, isobornyl acrylate, tetrahydrofurfuryl acrylate, phenoxy polyethylene glycol acrylate, lauryl acrylate, benzyl acrylate, ethoxyethyl acrylate, phenoxyethyl acrylate, cyclic trimethylol Formal acrylate, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, 1,1 (bisacryloyloxymethyl ) A composition for coating, characterized in that at least one selected from the group consisting of ethyl isocyanate, polyester acrylate and urethane acrylate.
The method of claim 1,
The lubricating oil is at least one selected from olive oil, fluorinated oil, silicone oil, essential oil, paraffin oil, and mineral oil. Characterized in that, the composition for coating.
The method of claim 1,
The airgel is at least one selected from silica gel, carbon airgel and graphene airgel, the coating composition.
The method of claim 1,
The coating composition further comprising 1 to 200 parts by weight of airgel (aerogel) based on 100 parts by weight of the lubricating oil.
4. The method of claim 3,
Based on the total weight of the lubricating oil, 10 to 100% by weight of essential oil (essential oil), characterized in that it comprises a coating composition.
The method of claim 1,
Dichloromethane (DCM), tetrahydrofuran, dioxane (dioxane), methyl ethyl ketone (MEK), and further comprising one or more solvents selected from the group consisting of dimethylformamide (DMF), coating composition.
8. The method of claim 7,
The composition for coating, characterized in that the solvent is included so that the concentration of the total composition is 0.05 to 0.30 g/mL.
Formed by curing a coating composition comprising a mixture (blend) in which 30 to 100 parts by weight of lubricating oil is mixed with respect to 100 parts by weight of the polymer resin, and further comprising an airgel having a particle size of 20 to 200 μm, Articles having a slippery surface.
10. The method of claim 9,
An article having a slippery surface having a light transmittance of at least 80%.
10. The method of claim 9,
An article having a slippery surface comprising 10 to 100% by weight of the essential oil of the total lubricating oil.
Formed by curing a coating composition comprising a mixture (blend) in which 30 to 100 parts by weight of lubricating oil is mixed with respect to 100 parts by weight of the polymer resin, and further comprising an airgel having a particle size of 20 to 200 μm, A self-cleaning container comprising:
and an oil impermeable material on the outer surface of the container.
Formed by curing a coating composition comprising a mixture (blend) in which 30 to 100 parts by weight of lubricating oil is mixed with respect to 100 parts by weight of the polymer resin, and further comprising an airgel having a particle size of 20 to 200 μm, A medical catheter having a slippery surface, comprising:
A medical catheter having a slippery surface comprising 10 to 30% by weight of essential oil of total lubricating oil.

Images