KR102001850B1 - 3D Printing Composition for Manufacturing Three Dimensional Article With Slippery Surfaces and Method for Preparing Same - Google Patents

Abstract

The present invention relates to a composition for 3D printing capable of producing an article having a three-dimensional shape having both slippery surfaces on the outside and inside, and a method of manufacturing the same.
The 3D printing composition according to the present invention can realize a slippery surface in a complicated three-dimensional shaped article which is difficult to be coated by using a simple process called 3D printing technology. The three-dimensional article manufactured using the 3D printing composition of the present invention can solve various problems such as ice removal on the surface of machines such as airplanes and automobiles, biofouling problems in blood vessels, and problems requiring self-cleaning. Do.

Description

TECHNICAL FIELD [0001] The present invention relates to a 3D printing composition for producing a three-dimensional article having a slippery surface and a method for manufacturing the same,

The present invention relates to a 3D printing composition for producing a three-dimensional article having a slippery surface and a method for producing the same, and more particularly, to a 3D printing composition for forming a three- And a method for producing the same.

The development of liquid-repellent surfaces is inspired by the self-cleaning ability of surfaces of animals, insects and plants. There is a water-repellent surface first inspired by the lotus effect. The water-repellent surface is a structure in which water droplets can be easily rolled off due to the surface microstructure and low surface energy. The water-repellent surface has been studied to improve performance continuously in various fields requiring self-cleaning, but there have been problems such as durability in the implementation of super water-repellent and human harmfulness of fluorine compound.

After the introduction of the concept of SLIPS in 2011 at Havard University, research into slippery surfaces is actively underway. This is a natural simulation of the surface of the insecticidal mulberry, which has a lubricating layer on the surface, which allows the droplet to easily roll down even at small sliding angles.

The slippery surface has many advantages such as anti-biofouling and low ice adhesion. However, most of the studies are focused on the two-dimensional surface coating technique, which limits application to the three-dimensional shape. Thus, the implementation of slippery surfaces in a variety of three-dimensional shapes is a necessary part of the industry in which self-cleaning is required.

Korean Patent Laid-Open Publication No. 10-2014-0004723 discloses a self-recovering scratch resistant slippery surface produced by walking a chemically inert high-density liquid coating on a roughened solid surface characterized by micro and nanoscale photography And the like. However, since this is a two-dimensional surface implementation, it is difficult to implement various complicated three-dimensional shapes, and since a slippery surface is formed by using a coating through immersion, a slippery surface And it is difficult to form uniformly.

 Korean Patent Laid-Open Publication No. 10-2011-0048545 also relates to the use of a slippery thin film or coating for improving the lubricity of a portion to which friction and abrasion is introduced, wherein the coating of the nanoparticles and the coating of the lipophilic layer Respectively. However, this is not a three-dimensional shape but a two-dimensional surface lubricant layer implementation and 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 the input three-dimensional drawing, just as it prints a letter or a picture. Recent 3D printing technology has become a central issue of the fourth industrial revolution and has been used extensively to create various models in the fields of automotive, medical, art, and education.

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

There are about 20 ways to use the stacking principle, but the most commonly used methods are SLA (Stereolithography Apparatus), FDM (Fused Deposition Modeling), FFF (Fused Filament Fabrication) and SLS (Selective Laser Sintering).

In the case of the SLA, an epoxy type photopolymer, which is a photo-curable resin, is mainly used in a method of projecting a laser beam into a water tank containing a liquid photocurable resin. On the other hand, FDM (or FFF), which is a method of forming the three-dimensional shape while injecting the filamentary material in the melted state in 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 laser-selective sintering in a water tank containing powdery materials such as metal, plastic, and ceramic powder.

Among the above three methods, the FDM method in which a thermoplastic plastic is manufactured in a filament form is the most widely used because the price of the 3D printer is comparatively low and the printing speed is faster than other methods. In the FDM method, polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), high density polyethylene (HDPE), and high density polyethylene polyethylene (HDPE), and polycarbonate (PC) are useful materials.

Japanese Patent Application Laid-Open No. 10-2015-0098142 (composite filament composition for 3D printer using FDM method containing metal powder), Korean Patent Registration No. 10-1350993 (A PLA filament for a 3D printer having flame retardancy and heat resistance using microcapsules and a PLA filament manufactured thereby) and U.S. Patent Application Publication No. 2009/0295032 (a method for producing a three-dimensional object using a modified ABS material) Lt; / RTI >

The inventors of the present invention have studied to realize an article having a three-dimensional shape having a slippery surface up to the interior thereof, and have found that by using an ink composition for 3D printing including oil and a 3D printing technique, The inventors have found that the article can be manufactured with a simple technique and have completed the present invention.

SUMMARY OF THE INVENTION It is an object of the present invention to solve such problems and to provide a composition for 3D printing which can produce a three-dimensional shaped article having a slippery surface up to the inside by a simple method.

It is still another object of the present invention to provide a method for producing a composition for 3D printing having a slippery surface.

In order to achieve the above object, the present invention provides a 3D printing composition for producing a three-dimensional article having a slippery surface, which comprises a polymer resin and an oil.

In the present invention, the 3D printing composition may contain 30 to 100 parts by weight of oil per 100 parts by weight of the polymer resin.

In the present invention, the polymer resin may be selected from the group consisting of polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), high density polyethylene (HDPE), polycarbonate (PC), polyurethane (PU) May be selected from polystyrene (PS), polyester, polyolefin, polyamide, polyvinyl alcohol, and combinations thereof.

Alternatively, in the present invention, the polymer resin may be selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam, dimethyl acrylamide, hydroxyethylacrylamide, 2-acryloyloxyethyl isocyanate, isobornyl acrylate, But are not limited to, acrylic acid, methacrylic acid, maleic anhydride, maleic anhydride, furyl acrylate, phenoxypolyethylene glycol acrylate, lauryl acrylate, benzyl acrylate, ethoxy ethyl acrylate, phenoxy ethyl acrylate, cyclic trimethylol formal acrylate, (Bishy acryloyloxymethyl) ethyl isocyanate, polyester acrylate, and urethane acrylate, which is composed of ethylene glycol diacrylate, propane triacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, 1,1 Lt; RTI ID = 0.0 > photopolymerizable < / RTI >

In the present invention, the oil may be at least one selected from olive oil, silicone oil, paraffin oil and petroleum oil.

In the present invention, the 3D printing composition may further include 1 to 20 parts by weight of an aerogel based on 100 parts by weight of the oil.

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

In the present invention, the 3D printing composition comprises at least one solvent selected from the group consisting of dichloromethane (DCM), tetrahydrofuran, dioxane, methyl ethyl ketone (MEK), and dimethylformamide (DMF) May be further included.

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

The present invention also provides a method of making a 3D printing composition for making a three-dimensional article having a slippery surface, comprising: dissolving a polymer resin in a first solvent to produce a polymer solution; Dissolving the oil in a second solvent to produce an oil solution; And mixing the polymer solution and the oil solution.

In the present invention, in the step of producing the oil solution, an airgel may be added to the second solvent.

In the present invention, the first and second solvents are each independently selected from the group consisting of dichloromethane (DCM), tetrahydrofuran, dioxane, methyl ethyl ketone (MEK), and dimethylformamide It can be more than a species.

In the present invention, the first solvent and the second solvent may be the same solvent.

In the present invention, the concentration of the polymer solution may be 0.03 to 0.30 g / mL.

In the present invention, the concentration of the oil solution may be 10 to 50% (v / v).

The present invention also provides a filament for a 3D printer comprising a 3D printing composition for producing a three-dimensional article having a slippery surface.

In the present invention, the diameter of the filament may be 0.8 to 4.0 mm.

The 3D printing composition according to the present invention can realize a slippery surface in a complicated three-dimensional shaped article which is difficult to be coated by using a simple process called 3D printing technology. The three-dimensional article manufactured using the 3D printing composition of the present invention can solve various problems such as ice removal on the surface of machines such as airplanes and automobiles, biofouling problems in blood vessels, and problems requiring self-cleaning. Do.

Figure 1 (a) shows a polylactic acid solution according to one embodiment of the present invention.
1 (b) shows an olive oil solution according to an embodiment of the present invention.
1 (c) shows a 3D printing composition according to one embodiment of the present invention.
Fig. 2 (a) shows a three-dimensional article in the form of a rectangular parallelepiped having a slippery surface according to an embodiment of the present invention.
Fig. 2 (b) shows a columnar solid article having a slippery surface according to an embodiment of the present invention.
3 (a) shows a droplet movement state of a polylactic acid coating according to a comparative example of the present invention.
Figure 3 (b) illustrates droplet movement of a 3D printing composition coating according to one embodiment of the present invention.
FIG. 3 (c) shows a droplet movement state after the 3D printing composition according to an embodiment of the present invention is melted at high temperature and hardened again.

Hereinafter, specific embodiments of the present invention will be described in more detail. Unless otherwise defined, 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 well known and commonly used in the art.

The present invention relates to a 3D printing composition for producing an article of three-dimensional shape having a slippery surface.

In the present invention, a slippery surface means a surface that has a self-cleaning ability in which the surface of an object contains lubricating oil so that it does not adhere to water or ice but falls easily even at a small sliding angle.

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

The 3D printing composition of the present invention comprises a polymer resin and an oil.

The polymer resin is not particularly limited as long as it is a polymer resin that can be used in the composition for 3D printing. When applied to a 3D printer of FDM type, the polymer resin may be a polylactic acid (PLA), an acrylonitrile butadiene styrene (ABS), a high density polyethylene (HDPE), polycarbonate (PC), polyurethane (PU), polystyrene (PS), polyester, polyolefin, polyamide, polyvinyl alcohol Polyvinyl alcohol), and a combination thereof, and polylactic acid (PLA) is most preferable in terms of stability.

In addition, when applied to a photocurable 3D printer, it is also possible to use a photocurable polymer resin. Examples of the photo-curable polymer include nitrogen-containing vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, dimethyl acrylamide, hydroxyethyl acrylamide, 2-acryloyloxyethyl isocyanate, isobornyl acrylate Acrylate, phenoxyethyl acrylate, cyclic trimethylol formal acrylate, 6-hexanediol diacrylate, benzyl acrylate, benzyl acrylate, phenoxy ethyl acrylate, phenoxy ethyl acrylate, phenoxy polyethylene glycol acrylate, lauryl acrylate, Acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, 1,1 (bisacryloyloxymethyl) ethyl isocyanate, polyester acrylate, Urethane acrylate, and the like.

In the present invention, the oil is not particularly limited as long as it is a hydrophobic oil that can be dissolved in a solvent, but it is preferable to use olive oil, silicone oil, paraffin oil, petroleum oil or the like. The paraffinic oil may be obtained from n-octane, n-decane, n-dodecane, hexadecane, octadecane, etc. And the petroleum-based oil may be selected from diesel, gasoline, crude oil and the like.

The oil may be contained in an amount of 30 to 100 parts by weight, preferably 50 to 80 parts by weight, based on the weight of the polymer resin. If the amount of the oil is too small, the slip property of the product becomes insufficient. If the amount of the oil is more than the above range, the content of the polymer resin may be insufficient and the lamination may not be performed properly.

The 3D printing composition of the present invention may further comprise an aerogel. The aerogels absorb the oil to help the oil stably mix with the polymer resin and not evaporate easily when made into a three-dimensional article.

As the aerogels usable in the present invention, silica gel, carbon aerogels, graphene aerogels and the like can be used.

The particle size of the aerogels is preferably 20 to 200 mu m. When the particle size of the airgel is less than 20 mu m, it is difficult to sufficiently absorb the oil. When the size of the airgel is 200 mu m or more, it is difficult to inject smoothly by the nozzle of the 3D printer.

The aerogels may be used in an amount of 1 to 20 parts by weight, preferably 5 to 10 parts by weight, based on the weight of the oil.

The polymer resin, the oil and the airgel contained in the 3D printing composition according to the present invention are preferably in a form dissolved in a solvent. The solvent may be a volatile solvent generally used in the composition for 3D printing, and may be selected according to the kind of the polymer used. The solvents according to the exemplary polymer types 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 solvent is preferably added in such a concentration that the concentration of the whole composition is 0.05 to 0.30 g / mL.

The 3D printing composition of the present invention may further comprise at least one additive selected from the group consisting of heat stabilizers, antioxidants, light stabilizers, releasing agents, compatibilizers, dyes, pigments, colorants, plasticizers, impact modifiers, stabilizers, . ≪ / RTI >

When a photocurable polymer resin is used, it is preferable to further include a photoinitiator.

Hereinafter, a method for producing a 3D printing composition for producing a three-dimensional article having a slippery surface according to the present invention will be described in detail.

A method for producing a 3D printing composition of the present invention comprises: dissolving a polymer resin in a first solvent to prepare a polymer solution; Dissolving the oil in a second solvent to produce an oil solution; And mixing the polymer solution and the oil solution.

In a preferred embodiment of the present invention, the oil solution preferably comprises an aerogel. The aerogels are preferably contained in an amount of 1 to 20 parts by weight based on the weight of the oil.

According to the present invention, the polymer is dissolved in a solvent to form a liquid phase at room temperature, the oil is dissolved in a separate solvent, and then the polymer is mixed with the oil by mixing the liquid phase polymer and the oil, So as to prevent the oil from easily evaporating at high temperature.

The first and second solvents may each independently be selected from dichloromethane (DCM), tetrahydrofuran, dioxane, methyl ethyl ketone (MEK), dimethylformamide (DMF) It is preferable to use a solvent suitable for the kind.

In a preferred embodiment of the present invention, the first solvent is preferably the same solvent as the second solvent.

The polymer solution preferably has a concentration of 0.03 to 0.30 g / mL, more preferably 0.05 to 0.15 g / mL.

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

In the present invention, it is preferable that the two solutions are continuously mixed while gradually adding the polymer solution to the oil solution.

The 3D printing composition in which the two solutions are mixed preferably has a concentration of the entire composition of 0.05 to 0.30 g / mL.

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

Specifically, the 3D printing composition of the present invention can exhibit similar performance even when melted by heating at a later time by curing the solvent by evaporating the solvent at room temperature. Therefore, it is possible to realize the shape of a filament for a desired 3D printer by forming or curing a filament using an extrusion or molding process in the process of curing the 3D printing composition of the present invention, and then performing additional cutting .

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

The diameter of the filament for the 3D printer of the present invention may preferably be 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 apparatus can not easily supply the filament, or the filament may be pushed out, and the printing speed may be slowed down. Also, if the filament diameter is more than 4 mm, the solidification speed is slow and it is difficult to melt the filament, and the precision of the printed molding may be lowered.

The 3D printing composition according to the present invention can realize a three-dimensional shaped article having a slippery surface through a simple 3D printing technique. When the ink composition capable of 3D printing containing oil is output, the output is hardened by the liquefied lamination method while the solvent evaporates, and the output has a slippery surface not only on the outer surface but also on the inner surface due to the characteristics of the ink. This makes it possible to easily provide a slippery surface to a three-dimensional shape that was difficult to form a slippery surface with conventional coating techniques.

A three-dimensional article having a slippery surface that can be produced using the 3D printing composition of the present invention is useful for a field requiring anti-biofouling as well as a field requiring low ice adhesion such as an airplane, a ship, an automobile, It can be used in various industries by benefiting from an efficient aspect.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. It should be noted, however, that these examples are illustrative of some experimental methods and compositions in order to illustrate the present invention, and the scope of the present invention is not limited to these examples.

Example 1: Preparation of 3D printing composition

5 g of polylactic acid was added to 80 ml of dichloromethane at room temperature and stirred until completely dissolved in the solvent to prepare a polylactic acid solution (Fig. 1 (a)).

5 ml of olive oil and 1 g of silica airgel were added to 20 ml of dichloromethane and stirred to prepare an olive oil solution (Fig. 1 (b)).

The polylactic acid solution was slowly added dropwise to the olive solution while stirring to prepare a 3D printing composition (Fig. 1 (c)).

Example 2: Fabrication of filament for 3D printer

The 3D printing composition prepared in Example 1 was fed to the extruder through a hopper. The composition was melted and kneaded in an extruder and spun through a spinneret. The screw temperature of the extruder was set at 200 ° C. The spun filaments were cooled in air to remove filaments for 3D printers having an average diameter of 1.75 mm.

Example 3: Production of a three-dimensional shape having a slippery surface

The filament produced in Example 2 was put into an FDM type 3D printer having a nozzle diameter of 400 mu m and was output through a nozzle at a speed of 60 mm / s at an operating temperature of 200 DEG C.

As shown in Fig. 2, solid articles in the shape of a rectangular parallelepiped (a) and a cylinder (b) were produced, and it was confirmed that the 3D printer composition of the present invention containing oil can be applied to a commercially available 3D printer.

Example 4: Confirmation of slippery properties

The slip properties of the 3D printing composition prepared in Example 1 were confirmed.

Only the 3D printing composition prepared in Example 1 and polylactic acid as a comparative example were coated on a slide glass by a dip coating method, and the solvent was allowed to evaporate at room temperature to naturally cure.

Fig. 3 is a view showing the movement of the droplet for 6 seconds in a state in which the polylactic acid (a) and the composition (b) of Example 1 are coated on a slide glass and the glass is inclined at 10 deg.

In the case of FIG. 3 (a), there was almost no movement of the droplet for 6 seconds, but in the case of FIG. 3 (b), the droplet slipped down after 6 seconds.

The composition of Example 1 was melted at 200 캜 and cooled again at room temperature to confirm that the composition of the present invention can maintain a slippery property even when the composition is output to a 3D printer.

As can be seen in FIG. 3 (c), it can be seen that the composition of the present invention, which is hardened again after high-temperature melting, still has a slippery surface, and the droplet slips down.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (17)

A 3D printing composition for producing a three-dimensional article having a slippery surface,
And 30 to 100 parts by weight of oil relative to 100 parts by weight of the polymer resin,
A 3D printing composition, further comprising an aerogel.
delete The method according to claim 1,
The polymer resin is selected from the group consisting of polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), high density polyethylene (HDPE), polycarbonate (PC), polyurethane (PU), polystyrene PS), a polyester, a polyolefin, a polyamide, a polyvinyl alcohol, and a combination thereof.
The method according to claim 1,
Wherein the polymer resin is selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam, dimethyl acrylamide, hydroxyethyl acrylamide, 2-acryloyloxyethyl isocyanate, isobornyl acrylate, tetrahydrofurfuryl acrylate, But are not limited to, polyethylene glycol acrylate, lauryl acrylate, benzyl acrylate, ethoxy ethyl acrylate, phenoxy ethyl acrylate, cyclic trimethylol formal acrylate, 6-hexanediol diacrylate, trimethylol propane triacrylate, A photopolymerizable polymer selected from the group consisting of ethylene glycol diacrylate, 1,1 (bisacryloyloxymethyl) ethyl isocyanate, polyester acrylate and urethane acrylate, . ≪ / RTI >
The method according to claim 1,
Wherein the oil is at least one selected from olive oil, silicone oil, paraffin oil and petroleum oil.
The method according to claim 1,
A 3D printing composition comprising 1 to 20 parts by weight of an aerogel based on 100 parts by weight of oil.
The method according to claim 1,
Wherein the aerogels are at least one selected from silica gel, carbon aerogels and graphene airgel.
The method according to claim 1,
A 3D printing composition further comprising at least one solvent selected from the group consisting of dichloromethane (DCM), tetrahydrofuran, dioxane, methyl ethyl ketone (MEK) and dimethylformamide (DMF).
9. The method of claim 8,
Wherein the solvent is included such that the concentration of the total composition is 0.05 to 0.30 g / mL.
10. A method for producing a 3D printing composition for producing a three-dimensional article having a slippery surface according to any one of claims 1 and 3 to 9,
Dissolving the polymer resin in a first solvent to prepare a polymer solution;
Dissolving the oil in a second solvent to produce an oil solution; And
Mixing the polymer solution and the oil solution, the method comprising:
30 to 100 parts by weight of oil are mixed with 100 parts by weight of the polymer resin,
Wherein the step of preparing the oil solution comprises adding an aerogel to the second solvent.
delete 11. The method of claim 10,
The first and second solvents are each independently at least one selected from the group consisting of dichloromethane (DCM), tetrahydrofuran, dioxane, methyl ethyl ketone (MEK), and dimethylformamide (DMF) ≪ RTI ID = 0.0 >
13. The method of claim 12,
Wherein the first solvent and the second solvent are the same solvent.
11. The method of claim 10,
Wherein the concentration of the polymer solution is from 0.03 to 0.30 g / mL.
11. The method of claim 10,
Wherein the concentration of the oil solution is 10 to 50% (v / v).
A filament for a 3D printer for producing a three-dimensional article having a slippery surface, which is produced by curing a 3D printing composition according to any one of claims 1 to 9.
17. The method of claim 16,
And the diameter of the filament is 0.8 to 4.0 mm.

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