KR20200042559A - Coating Composition for Manufacturing Article With Slippery Surfaces - Google Patents

Abstract

The present invention relates to a coating composition capable of manufacturing a product having a slippery surface both inner and outer surfaces, and to a manufacturing method thereof. The coating composition according to the present invention is possible to manufacture a product having a slippery surface on both the inner and outer surfaces with only a simple process of molding and curing a polymer resin with conventional techniques. The product manufactured using the coating composition of the present invention can be used in various industries because of solving problems of ice removal from a surface of machines such as aircraft, automobiles, bio-fouling in blood vessels, and self-cleaning.

Description

Coating composition for manufacturing article with slippery surfaces

The present invention relates to a composition for coating for producing an article having a slippery surface, and more particularly, to a composition for coating that can manufacture an article having a slippery surface both inside and outside in a simple manner.

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

After introducing the concept of SLIPS at Havard University in 2011, studies on slippery surfaces have been actively conducted. This is a natural simulation of the surface of wormweed dung grass, and the presence of a lubricating layer on the surface makes it easy to self-clean even when the droplets roll easily even at small sliding angles.

The slippery surface has many advantages such as anti-biofouling and low ice adhesion, but most studies are mainly focused on the coating technique of the two-dimensional surface, and thus the application to the three-dimensional shape has been limited. Therefore, the realization of slippery surfaces in various three-dimensional shapes is a necessary part in industries requiring self-cleaning.

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

 In addition, Korean Patent Publication No. 10-2011-0048545 relates to the use of a slippery thin film or a coating for improving the lubricity of a portion where friction and abrasion are introduced, through a coating of nanoparticles and a coating of a lipophilic layer. Was produced. However, this is a realization of a lubricating layer of a two-dimensional surface, not a three-dimensional shape, and has a disadvantage that it is limited to deposition and coating techniques.

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

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

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

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

Among the above three methods, the FDM method, which uses thermoplastic plastics in the form of filaments, is the most popular because the 3D printer is relatively inexpensive and has a faster printing speed than other methods. In the FDM method, polylactic acid (PLA), ABS (Acrylonitrile Butadiene Styrene), and high density polyethylene (high density polyethylene) are generally used when forming a 3D structure, because of excellent bed adhesion and layer-to-layer adhesion and good shape stability. Materials such as polyethylene (HDPE) and polycarbonate (PC) are useful.

Korean Patent Publication No. 10-2015-0098142 (FDM-type composite filament composition for 3D printer containing metal powder), Republic of Korea Patent Publication No. 10-1350993 (Pla filament manufacturing method for 3D printers having flame retardant and heat-resistant properties using microcapsules and PLA filament produced thereby) and U.S. Patent Application Publication No. 2009/0295032 (3D object generation method using modified ABS material), etc. It has been disclosed.

The inventors of the present invention have researched to realize an article having a surface slippery to the inside, and, as a result, use a composition for coating comprising a mixture of a polymer resin and a lubricating oil to manufacture an article having a surface slippery to the inside as well as a surface with a simple technique The present invention was completed after discovering that it could be done.

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

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 coating an article having a slippery surface, comprising a blend of a polymer resin and a lubricating oil.

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

In the present invention, the polymer resin is polydimethylsiloxane (polydimethylsiloxane, PDMS), silicone (silicone), perfluoropolyether (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 (Polyamide) ), Polyvinyl alcohol (Poly Vinyl Alcohol), N-vinyl pyrrolidone, N-vinyl caprolactam, dimethylacrylamide, hydroxyethylacrylamide, 2-acryloyloxyethyl isocyanate, isobornyl acrylate, tetrahydro Furfuryl acrylate, phenoxypolyethylene glycol acrylate, lauryl acrylate, benzyl acrylate, ethoxyethyl acrylate, phenoxyethyl acrylate, cycle Trimethylol-formal acrylate, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, 1,1 (bisacryloyl It may be one or more selected from the group consisting of oxymethyl) ethyl isocyanate, polyester acrylate and urethane acrylate.

In the present invention, the lubricating oil is olive oil, fluorinated oil, silicone oil, essential oil, paraffin oil, and petroleum oil It may be one or more 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 lubricating oil relative to 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 an airgel (aerogel) with respect to 100 parts by weight of the lubricant.

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

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

In the present invention, the solvent may be included so that the total composition concentration 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 polymer resin and a lubricant.

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

Articles having a slippery surface of the present invention may have a light transmission of 80% or more.

Articles having a slippery surface of the present invention may contain 10 to 100% by weight of essential oils of the total lubricant.

The present invention is also a self-cleaning container, formed by curing a composition for coating comprising a blend of a polymer resin and a lubricating oil, comprising a material that is impermeable to the outer surface of the container, self-cleaning. Provide possible containers.

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

The composition for coating according to the present invention is capable of producing an article having a slippery surface on both the inner and outer surfaces with only a simple process of molding and curing the polymer resin by conventional techniques. The article manufactured using the coating composition of the present invention can solve ice removal on the surface of a machine such as an aircraft, an automobile, etc., biofouling problems in blood vessels, and problems requiring self-cleaning, and can be used in various industries.

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

Hereinafter, a specific aspect 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 a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

The present invention relates to a composition for producing a product having a slippery surface.

The composition of the present invention comprises a blend of a polymer resin and a lubricant.

In the present invention, a slippery surface means a surface having a self-cleaning ability because the surface of the object contains lubricant and water or ice does not adhere and easily rolls even at a small sliding angle.

In the present invention, the term "blend (blend)" means a state in which two or more substances that are not dissolved in each other are uniformly dispersed.

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

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 materials are difficult to mix with each other. This means that a large interfacial tension is applied between the two materials, so that the two materials are preferentially separated rather than uniformly mixed.

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

When the 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)

Therefore, the Gibbs energy is changed to less than 0, and the lubricant and the polymer resin can be stably mixed.

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

The lubricant is to use olive oil, fluorinated oil, silicone oil, essential oil, paraffin oil, petroleum oil, etc. desirable.

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

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

If the essential oil, especially clove oil, is included in the lubricating oil, an antibacterial effect can be given to the manufactured product.

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

The airgel may be silica gel, carbon airgel, graphene airgel, or the like. The airgel absorbs the lubricating oil and helps the lubricating oil to stably mix with the polymer resin and prevents the lubricating oil from evaporating easily even after being commercialized.

In addition, the mechanical properties of the airgel can be improved. In one embodiment of the present invention, it was confirmed that mechanical properties such as storage elastic force, tensile strength, and hardness of a product containing an airgel can be greatly improved. Therefore, when preparing a three-dimensional product using the coating composition of the present invention, the airgel is able to maintain a desired shape until the polymer is crosslinked / cured.

The airgel is preferably added in an appropriate amount in consideration of the miscibility 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 (polydimethylsiloxane, PDMS), silicone (silicone), perfluoropolyether (perfluoropolyether, PFPE), polyurethane (polyurethane, PU), polyimide (polyimide, PI) And a liquid polymer such as the like. The liquid polymer may be mixed with the lubricant without a separate solvent, and may be mixed with the lubricant by an airgel if necessary.

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

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

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

To liquefy the solid phase polymer and at the same time select a suitable solvent that can be mixed with the lubricating oil, a Flory-Huggins solution can be applied. The Flory-Huggins constant (χ) is defined as:

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, T is the absolute temperature.

The smaller the χ value, the better the solvent and solute 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, 0.42. Therefore, it can be seen that DCM is more suitable than acetone for dissolving PLA.

In addition, the constant χ between 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 easier to mix with DCM than water (χ = 21.43) or ethylene glycol (χ = 6.08).

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

Table 1 below shows the types of suitable solvents according to the exemplary solid polymer resin.

polymer menstruum Polylactic acid (PLA) Dichloromethane (DCM)
Tetrahydrofuran
Dioxane Acrylonitrile Butadiene Styrene (ABS) DCM
Methyl ethyl ketone (MEK) Polyurethane (PU) Dimethyl formamide (DMF) Polystyrene (PS) DCM Acrylic MEK Polycarbonate (PC) DCM
MEK

A method for preparing the coating composition of the present invention using a solid polymer resin comprises dissolving the polymer resin in a first solvent to prepare a polymer solution; And mixing the polymer solution and a lubricant.

In the above method, mixing the lubricating oil may include mixing a lubricating oil solution in which the lubricating oil is dissolved in a second solvent.

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

According to the present invention, the polymer is dissolved in a solvent to form a liquid phase at room temperature, and after dissolving the lubricant in a separate solvent, the polymer and the lubricant in the liquid phase are mixed so that the polymer is well mixed with the lubricant, and the polymer is easily cured. Or prevent the lubricant from evaporating easily 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 little by little to the lubricant solution.

The polymer resin may also use a photocurable polymer resin depending on the application. Examples of the photocurable polymer include nitrogen-containing vinyl compounds such as N-vinylpyrrolidone and N-vinyl caprolactam, dimethylacrylamide, hydroxyethylacrylamide, 2-acryloyloxyethyl isocyanate, and isobornyl acrylic Rate, tetrahydrofurfuryl acrylate, phenoxypolyethylene 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, And urethane acrylates.

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

Moreover, when using a photocurable polymer resin, it is preferable to further contain a photoinitiator.

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

The molding may use various known molding techniques such as coating, molding, and 3D printing.

The composition for coating comprising a thermosetting polymer resin can be molded into a shape of a product using molding and then crosslinked by heat to produce a product having a slippery surface. Similarly, when a photocurable polymer resin is included, a product having a slippery surface can be prepared by photocuring.

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

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

In the present invention, a three-dimensional article having a slippery surface means having a slippery surface not only on the outside but also on the inside of the article having a three-dimensional shape.

The airgel usable for the 3D printing composition of the present invention preferably has a particle size of 20 to 200 μm. If the particle size of the airgel is less than 20 μm, it is difficult to sufficiently absorb oil, and if it is 200 μm or more, there is a problem that it is difficult to smoothly spray the nozzle by the 3D printer.

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

Moreover, when using a photocurable polymer resin, it is preferable to further contain a photoinitiator.

The 3D printing composition according to the present invention prepared by the above method may be made of filaments for 3D printers.

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

It is preferable that the filament for the 3D printer has a standard that can be used in a commercially available 3D printer.

The filament for the 3D printer of the present invention preferably has a diameter of 0.8 to 4.0 mm, and more preferably 1.5 to 3 mm. If the diameter of the filament is less than 0.8 mm, it is too thin, so that the printer device cannot easily supply the filament or the filament may be pressed, so that the filament may not be ejected and the printing speed may be slowed down. In addition, if the filament diameter is more than 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 realize a three-dimensionally shaped article having a slippery surface through a simple 3D printing technique. When the 3D printing ink composition containing oil is output, the output is cured by the liquefaction lamination method while the solvent evaporates, and the output has a slippery surface to the inside as well as the outside due to the characteristics of the ink. Through this, it is possible to easily provide a slippery surface to a three-dimensional shape that was difficult to form a slippery surface using a conventional coating technique.

In one preferred embodiment of the present invention, the composition for coating of the present invention can be used in the production of zero-residue containers.

The remaining container is a self-cleanable container, and the coating composition of the present invention and an oil impermeable material are printed at once 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. It is possible to make the outer surface formed by a material that does not penetrate.

As a material applicable to the outer surface of the remaining container, PETG (glycolmodified polyethylene terephthalate) may be used, 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 remaining container, for example, it is preferable to use silicone oil.

In one preferred embodiment of the present invention, the composition for coating of the present invention can be used in the manufacture of an antibacterial catheter.

In the medical field, catheters are widely used as carriers for body fluids, drugs, and medical equipment. However, the biofilm was easily formed on the surface of the tube, and the possibility of clogging of the tube or contamination by bacteria was high.

For medical catheters, slippery surfaces and antibacterial properties are essential. The conventional catheter was used after impregnating the rubber catheter with oil for a certain period of time for a slippery surface. However, in the case of an oil-impregnated catheter, there is a problem that the inner diameter decreases due to the oil, and there is a problem in that the slipperiness does not last for a long time due to the oil slipping out even with a little use.

If a catheter having a slippery surface is prepared using the composition for coating according to the present invention, a catheter having a slippery surface can be used immediately without a separate oil impregnation process, and the slippery surface may last for a long time because oil does not escape even when used 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 suit the application.

It is preferable that the composition for coating for preparing the catheter includes mineral oil, for example, clove oil. When the clove oil is included, the manufactured product exhibits antibacterial properties, and thus is preferable for medical use.

As a polymer resin for producing a catheter, it is preferable to use a silicone resin or a polyurethane resin from the viewpoint of flexibility.

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

Articles having a slippery surface that can be produced using the coating composition of the present invention are economical and energy efficient in areas requiring low ice adhesion, such as aircraft, ships, and automobiles, as well as areas requiring anti-biofouling and areas requiring self-cleaning. In terms of benefits, it can be used in various industries.

Example

The present invention will be described in more detail through the following examples. However, these examples show some experimental methods and compositions to illustrate the present invention by way of example, and the scope of the present invention is not limited to these examples.

Preparation for the experiment

Slippery Blend ink manufacturing

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

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% by weight of Darocure 1173, a photoinitiator of Fluorolink MD700, was mixed.

PDMS was mixed with a 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, the composition for coating for manufacturing a three-dimensional article is referred to as Slippery Blend or Slippery Blend ink.

3D printing of Slippery Blend items

Preparation of the Slippery Blend article using Slippery Blend was performed by inserting 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

Analysis of the rheological properties of the Slippery Blend ink prepared based on PFPE, PDMS and PLA polymer resins was performed.

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

The storage elastic modulus (G ') and loss elastic modulus (G' ') for shear stress of PFPE and PFPE-based slippery blends 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 elastic modulus and the loss modulus of PFPE were not changed and exhibited a parallel profile despite the increase in vibration stress.

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

The storage modulus (G ') and loss modulus (G' ') of the 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 in a mixing ratio of PDMS: mineral oil: silica gel = (70: 25: 5).

In Table 3, the shear yield stress of the PDSM-Slippery Blend containing the airgel was higher than that of the PDMS + oil mixture without the airgel.

This means that the ink can maintain the shape of the filament even at higher shear stress, and printing is possible with a narrower nozzle.

The storage elastic modulus and loss elastic modulus according to the evaporation time of the 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 in a mixing ratio of PLA: mineral oil: silica gel = (70:20:10).

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

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

Experimental Example 2: Preparation of 3D article

To confirm the possibility of 3D printing 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, by shearing mint and non-Newtonian fluid properties, Slippery Blend ink was easily extruded from the micro-sized nozzle to maintain the filament shape. The scaffold produced was composed of a filament of about 250 μm diameter and a space of about 800 μm.

This means that a micro-dimensional three-dimensional object can be produced 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. Samples for hardness measurement were prepared with a thickness of 2 cm. Shore A hardness was measured using a Shore A durometer.

The mechanical properties of the Slippery Blend material according to different polymer, lubricant and aerosol content are shown in Table 5 below.

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

As the content of the silica airgel increased, the ultimate strength increased, and the Slippery Blend containing 11.9% by weight of the silica airgel showed about 8.1 Mpa, showing a higher strength compared to the PDMS alone showing about 6.0 Mpa.

In Table 5, although the hardness was significantly decreased with the addition of the lubricant, it can be seen that adding silica airgel showed a higher hardness despite the addition of the lubricant.

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

Experimental Example 4: Analysis of lubrication performance of slippery blend

To analyze the lubricating performance of Slippery Blend articles, critical sliding angle measurements were performed on various polar and non-polar liquid droplets.

Wetting properties for liquids with various surface tensions shown in Table 6 below were measured using a contact angle measurement stage. Droplets of 10 µl were dropped at 10 different positions on PDSM and PFPE-based samples having the composition of Experimental Example 1. The sliding angle was measured by dropping 10 μl of droplets onto the tilt stage using a high-speed camera.

In Table 6, PDMS-Slippery Blend showed a low critical sliding angle of 10 ° or less for water, ethylene glycol, and olive oil. However, PDMS-Slippery Blend did not exhibit lubricating properties for volatile solvents such as chloroform and petroleum ether, which PDMS easily swells against volatile solvents, and mineral oils are easily dissolved in such solutions and thus cannot maintain the lubricating layer. It is because.

On the other hand, PFPE-based Slippery Blend using fluorine-based lubricants exhibited a very low sliding angle of about 5 ° or less for all target liquids.

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

Experimental Example 5: Preparation of self-cleanable containers

We tried to produce functional products by printing different types of materials at once using the Slippery Blend platform.

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

PDMS-Slippery Blend ink was used to manufacture the inner surface of the container, and PETG filament was used on the outer surface of the container to maintain the lubrication surface while preventing the lubricant from spreading through the outer surface.

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

Experimental Example 6: Optical transmittance measurement

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. PDMS-based samples were drop-cast onto a slide glass at 500 μm, and samples were separated from the glass to minimize the effect of the slides. The results are shown in Table 7 below. In Table 7, PDMS + Silicagel was mixed at a weight ratio of 93: 7, and Slippery Blend was prepared with the composition of Experimental Example 1.

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

On the other hand, the PDMS-aerogel substrate had a slightly reduced permeability to 83.5 to 86.2%, because the airgel scattered light. On the other hand, the PDMS-Slippery Blend showed better transparency than the PDMS substrate because the lubricant had a refractive index similar to that of PDMS, further reducing light reflection.

Therefore, the coating composition of the present invention can manufacture an optically transparent 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 having various lubricating oil contents were prepared by drop casting on a flat glass to a thickness of 500 μm. Load cells were used with a sensitivity of 5 mN.

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

In Table 8, it can be seen that the PDMS-Slippery Blend containing 15% of the silicone oil and airgel mixture has a 44.6% reduction in ice adhesion compared to the case of not containing the 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 the same in the PFPE-based slippery blend. PFPD-Slippery Blend containing 30% of fluorinated oil showed a significantly reduced ice adhesion to 96.2% compared to samples without oil.

Experimental Example 8: Antibacterial test

The bacterial adhesion test was performed according to JIS Z2801.

E. coli EG1655 was used as the strain. The sample was dropped cast 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 on the sample. The medium was covered with 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 sample was carefully washed with PBS solution to remove non-adherent bacteria.

After removing the bacterial film 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 times. Thereafter, 200 μl of the solution was incubated in an LB agar plate for 24 hours.

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

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

When the clove oil was added, it was confirmed that the number of strains decreased to 99.9% (PLA) and 98.2% (PDMS), thereby exhibiting 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 spread of bacteria.

Experimental Example 9: Preparation of antibacterial catheter

To confirm the practical applicability of the antibacterial Slippery Blend, an antibacterial Slippery Blend catheter tube was prepared.

FIG. 4 is an image of a 6 cm long, 7 mm inner diameter, 0.8 mm thick tube and commercially available medical silicone tube prepared by printing using PDMS-Slippery Blend. The tubes were prepared using FDA-approved non-reactive mineral oil and silicone elastomer for biocompatibility.

In order to confirm the anti-adherence activity of the prepared tube, a flow bacterial adhesion test was performed.

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

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

Biofilm formation was checked at 8, 16, and 24 hours, and the results of performance comparison are shown in Table 10 below.

In Table 10, the Slippery Blend tube showed reduced optical density from 16 hours to 87.6%, and 71.4% after 24 hours, when biofilms began to form, compared to a commercially available medical silicone tube, confirming that antibacterial activity occurred. Became.

As described above, specific parts of the present invention have been described in detail. For those skilled in the art, this specific technique is only a preferred embodiment, and the scope of the present invention is not limited thereby. It will be obvious. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (16)

A composition for producing an article having a slippery surface,
A composition for coating comprising a blend of a polymer resin and a lubricant.
According to claim 1,
A composition for coating, further comprising an aerogel.
According to claim 1,
The polymer resin is polydimethylsiloxane (PDMS), silicone (silicone), perfluoropolyether (perfluoropolyether, PFPE), polyurethane (polyurethane, PU), thermoplastic polyurethane (thermoplastic polyurethane, TPU), polyyi Polyimide (PI), Polylactic acid (PLA), Acrylonitrile Butadiene Styrene (ABS), high density polyethylene (HDPE), polycarbonate (PC), polystyrene (PS), polyester (Polyester), polyolefin, polyamide, polyvinyl alcohol, N-vinylpyrrolidone, N-vinyl caprolactam, dimethylacrylamide, hydroxyethylacrylamide, 2-acrylic Royloxyethyl isocyanate, isobornyl acrylate, tetrahydrofurfuryl acrylate, phenoxypolyethylene glycol acrylate, lauryl acrylate, benzyl acrylate, ethoxy Tyl acrylate, phenoxyethyl acrylate, cyclic trimethylol formal acrylate, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, tetraethylene glycol Diacrylate, 1,1 (bisacryloyloxymethyl) ethyl isocyanate, characterized in that at least one selected from the group consisting of polyester acrylate and urethane acrylate, coating composition.
According to 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 coating composition.
According to claim 2,
The airgel is a composition for coating, characterized in that at least one selected from silica gel, carbon airgel and graphene airgel.
According to claim 1,
It characterized in that it contains 30 to 100 parts by weight of lubricating oil relative to 100 parts by weight of the polymer resin, the coating composition.
According to claim 2,
The coating composition further comprises 1 to 200 parts by weight of an airgel (aerogel) based on 100 parts by weight of the lubricant.
The method of claim 4,
It characterized in that it contains 10 to 100% by weight of essential oils (essential oil) based on the total weight of the lubricant, the coating composition.
According to claim 1,
A composition for coating further comprising at least one solvent selected from the group consisting of dichloromethane (DCM), tetrahydrofuran, dioxane, methylethylketone (MEK) and dimethylformamide (DMF).
The method of claim 9,
The solvent is characterized in that it is included so that the concentration of the total composition is 0.05 to 0.30g / mL, coating composition.
An article having a slippery surface formed by curing a composition for coating comprising a blend of a polymer resin and a lubricant.
The method of claim 11,
An article having a slippery surface, characterized in that the coating composition further comprises an aerogel.
The method of claim 11,
An article having a slippery surface, having a light transmission of 80% or more.
The method of claim 11,
An article having a slippery surface comprising 10-100% by weight of essential oil of the total lubricant.
A self-cleanable container formed by curing a composition for coating comprising a blend of a polymer resin and a lubricant,
A self-cleanable container comprising a material impermeable to oil on the outer surface of the container.
A medical catheter having a slippery surface formed by curing a coating composition comprising a blend of a polymer resin and a lubricant,
A medical catheter having a slippery surface comprising 10 to 30% by weight of essential oil of the total lubricant.

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