KR20220103845A - Acrylic-waterbone polyurethane Material for 3D printing - Google Patents

Abstract

The present invention relates to an acrylic-water-based polyurethane composition for 3D printing. The composition is constituted by mixing a water-based polyurethane compound prepared by the reaction of a polyol, diisocyanate, an emulsifier, a neutralizer, and water with an acrylate-based compound.

Description

Acrylic-water-based polyurethane composition for 3D printing {Acrylic-waterbone polyurethane Material for 3D printing}

The present invention relates to an acrylic-polyurethane composition, and more particularly, to an acrylic-water-based polyurethane composition for 3D printing capable of improving physical properties and improving productivity, including the acrylic-water-based polyurethane composition.

In general, photocurable 3D printing is to form a cured layer by irradiating image light corresponding to the cross section of the object to the photocurable resin composition, and to sequentially laminate the formed cured layer to complete the output.

Conventionally, the photocurable resin composition used for the photocurable 3D printing mostly uses an epoxy acrylate, and the epoxy acrylate uses an epoxy resin as a raw material, and in particular, an aromatic composition BPA (bispenol-A) series. Epoxy resin is used.

Since the BPA-based epoxy acrylate follows the basic physical properties of the existing BPA epoxy resin as it is, the curing reaction is fast, inexpensive, and has excellent heat resistance, hardness and chemical resistance.

However, the BPA epoxy acrylate has disadvantages in that it is difficult to handle due to its high molecular weight and viscosity, so a reactive monomer must be used as a diluent, and there is a problem in that yellowing is severe when left outdoors. In addition, when the degree of curing of BPA epoxy acrylate increases, shrinkage increases, adhesion decreases, and brittle properties increase, making the material easy to break or break after curing. In this case, since the shrinkage damages the adhesive surface, a decrease in printing characteristics may occur.

In order to solve the problems of BPA epoxy acrylate as described above, a non-epoxy-based photocurable resin composition has been developed, and a three-dimensional object is formed in a three-dimensional printer in Korean Patent Laid-Open Publication No. 10-2003-0009435 (published on January 19, 2003). A non-aqueous organic monomer compound containing an acrylic monomer including tri(propylene glycol) diacrylate, 1,6 hexanediol dimethacrylate, and the like as a chemical composition.

However, the above-described curable resin compositions for 3D printing have a slow curing rate and difficult uniform curing because the curing mechanism is cured only by photocuring of acrylate or methacrylate double bonds or radical chain polymerization by UV curing. There were problems in that the strength was lowered and the heat resistance was weak.

1 Korea Patent Publication 10-2003-0009435 (20030119) 2 Korea Patent 10-2105493 (20200422)

An object of the present invention is to provide an acrylic-water-based polyurethane composition for 3D printing that can improve mechanical properties (tensile, bending, temperature, time, impact) compared to conventional 3D printing materials and increase production efficiency by reducing photocuring time will provide

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

In order to achieve the above object, the acrylic-water-based polyurethane composition for a 3D printer of the present invention is a mixture of a water-based polyurethane compound and an acrylate-based compound prepared by the reaction of a polyol, a diisocyanate, an emulsifier, a neutralizer, and water characterized.

The polyol includes at least one selected from the group consisting of polytetramethylene glycol, poly-Caprolactone, polypropylene glycol, and polyethylene glycol, and , The diisocyanate is diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (Hexamethylene diisocyanate; HDI), 4'-dicyclohexylmethane diisocyanate (4,4'-Dicyclohexylmethane diisocyanate; H12MDI), Toluene diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI) and isophorone diisocyanate (Isophorone diisocyanate; IPDI) comprising at least one selected from the group consisting of do.

The acrylate-based compound is characterized in that it includes at least one selected from the group consisting of monoacrylate, diacrylate, and triacrylate.

The water-based polyurethane compound is characterized in that it is mixed in a ratio of 10 to 30% by weight.

When mixing the water-based polyurethane compound and the acrylate-based compound, it is characterized in that it further includes a photoinitiator.

The present invention has the following effects in the acrylic-water-based polyurethane composition for 3D printers.

To provide an acrylic-polyurethane composition in which TPU (Thermoplastic polyurethane), which has both a rubber-like soft part and a fiber-like hard part at the same time as a main chain, is introduced into an acrylic-based photocurable resin, it is included in the UV curing solution composition to make it a 3D printing material. When used, the mechanical properties are improved and the photocuring time is shortened.

1 is a view showing the synthesis process of an acrylic-water-based polyurethane composition for a 3D printer according to the present invention.
Figure 2a is a view showing the UTM (Universal Test Machine) analysis results according to the composition ratio of the aqueous polyurethane constituting the acrylic-water-based polyurethane composition for a 3D printer of the present invention.
Figure 2a is a view showing the analysis result of the particle size according to the composition ratio of the aqueous polyurethane constituting the acrylic-water-based polyurethane composition for a 3D printer of the present invention.
3 is a view showing the mixability according to the mixing ratio of the water-based polyurethane and the acrylate-based composition constituting the acrylic-water-based polyurethane composition for a 3D printer of the present invention.
Figure 4 is a graph showing the viscosity change according to the weight ratio of the water-based polyurethane constituting the acrylic-water-based polyurethane composition for a 3D printer of the present invention.
Figure 5 is a graph showing the change in physical properties according to the weight ratio of the water-based polyurethane constituting the acrylic-water-based polyurethane composition for a 3D printer of the present invention.
Figure 6 is a view showing the result of surface analysis (SEM, Scanning electron microscopy) of the 3D printing output using the acrylic-water-based polyurethane composition of the present invention.

Hereinafter, a preferred embodiment of the acrylic-water-based polyurethane composition for 3D printing according to the present invention will be described in detail with reference to the accompanying drawings.

The acrylic-water-based polyurethane composition for 3D printing according to the present invention may be formed by mixing a polyol and a diisocyanate compound with an emulsifier and a neutralizing agent, and an acrylate-based compound with water.

First, the polyol is one or more selected from the group consisting of polytetramethylene glycol, poly-Caprolactone, polypropylene glycol, and polyethylene glycol. Including, molecular weight of 100 to 20,000 is used.

The diisocyanate-based compound is, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (Hexamethylene diisocyanate; HDI), 4'-dicyclohexylmethane diisocyanate (4,4'-Dicyclohexylmethane diisocyanate; H12MDI) , toluene diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI) and isophorone diisocyanate (Isophorone diisocyanate; IPDI) contains at least one selected from the group consisting of.

The compound of the polyol and the isocyanate constitutes a soft segment in the acrylic-water-based polyurethane composition of the present invention.

In addition, the emulsifier serves to extend the chain and is used for the purpose of introducing an ionic group. The emulsifier uses at least one selected from the group consisting of dimethylol butanoic acid (DMBA) and 2,2-dimethylolpropionic acid (DMPA).

1,4-butanediol, 1,5-pentanediol, dimethylol butanoic acid (DMBA), ethylene glycol, diethylene glycol, propylene At least one selected from the group consisting of glycol, dipropylene glycol, and isosorbide is used.

The compound of the emulsifier and the isocyanate constitutes an ionic group in the acrylic-water-based polyurethane composition of the present invention.

In addition, as the neutralizing agent, a material having a lower acidity than the anionic group may be used without limitation, preferably triethylamine, N-methyl morpholine, dimethyl isopropylamine, diisopropyl aminoethanol, dimethyl ethanolamine and Dimethyl isopropanolamine, more preferably triethylamine (TEA).

Then, water is added to the mixture of the emulsifier and the neutralizer in the polyol and diisocyanate compound. The water is preferably purified water.

Manufactured according to the above-described process is an aqueous polyurethane compound, which is a compound synthesized by sequentially adding diisocyanate, an emulsifier, a neutralizing agent, and water to the polyol, and then adding an acrylate-based compound to react, and a molecular weight of 3,000 to 100,000 to be.

An acrylate-based compound is mixed with the aqueous polyurethane compound.

In addition, the acrylate-based compound includes at least one selected from the group consisting of monoacrylate, diacrylate, and triacrylate, preferably pentaerythritol triacrylate. It is preferable to include (Pentaerythritol triacrylate; PETA).

The water-based polyurethane compound is mixed with the acrylate-based compound in a ratio of 0.2 to 1.0.

A photoinitiator may be further included in the acrylate-based compound in the aqueous polyurethane compound. The photoinitiator is a component that absorbs ultraviolet rays and causes a polymerization reaction, and uses a component having an absorption wavelength band of 320 to 450 nm in the UV absorption spectrum. For example, diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide (IRGACURE® TPO), bis-phenyl phosphine oxide (Bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide (IRGACURE® 819)), 2-Benzyl-2-dimethylamine-1-butanone (2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone (IRGACURE® 369)) and 2-methyl- At least one selected from the group consisting of 1-2-morpholinopropan-1-one (2-Methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907)) includes

The photoinitiator may be used in an amount of 1 to 2 parts by weight based on 100 parts by weight of the acrylic-water-based polyurethane compound.

The acrylate monomer is a diacrylate monomer, for example, 1,6-hexanediol diacrylate (1,6-Hexanediol diacrylate; HDDA), polyethylene glycol diacrylate (Polyethylene glycol diacrylate; PEG-DA) ), dipropylene glycol diacrylate (DPGDA), triethylene glycol dimethacrylate (TEGDMA), and tripropylene glycol diacrylate (TPGDA) includes one or more of the

And, the manufacturing process of the acrylic-water-based polyurethane composition for 3D printing according to the present invention will be described in detail.

First, polycaprolactone diol (PCL) and 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) and dimethylolbutanoic acid (DMBA) were vacuumed for 6 hours. dry in condition.

Using acetone (Acetone), the polycaprolactone diol (PCL) and 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) and dimethylol butanoic acid (Dimethylolbutanoic acid, DMBA) ) to dissolve the mixture.

More specifically, first, polycaprolactone diol (PCL) and 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with 200rpm stirring speed under N2 atmosphere. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours.

Then, 0.5 g of dimethylol butanoic acid (0.01 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane. / Agitate to form a hard structure.

After cooling to 50° C., 1.02447 g of triethylamine (TEA) was sequentially added to make the same molar ratio (0.01 mol) as that of dimethylol butanoic acid.

The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes.

After mixing the acrylate-based compound with the water-based polyurethane compound, the mixture is stirred at 50° C. for 3 hours.

Next, the present invention, an acrylic for a 3D printer - a manufacturing experiment of the water-based polyurethane composition will be described in detail.

[Example 1]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0293 mol of polycaprolactone diol (PCL) and 0.0393 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. After mixing the water-based polyurethane compound with triacrylate in a weight ratio of 1:0.3, the mixture is stirred at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

[Example 2]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0310 mol of polycaprolactone diol (PCL) and 0.0360 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. After mixing the water-based polyurethane compound with triacrylate in a weight ratio of 1:0.3, the mixture is stirred at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

[Example 3]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0316 mol of polycaprolactone diol (PCL) and 0.0346 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. After mixing the water-based polyurethane compound with triacrylate in a weight ratio of 1:0.3, the mixture is stirred at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

[Example 4]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0323 mol of polycaprolactone diol (PCL) and 0.0333 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. After mixing the water-based polyurethane compound with triacrylate in a weight ratio of 1:0.3, the mixture is stirred at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

MWpre Series soft segment Ionic group TEA PCL H ₁₂ MDI DMBA H ₁₂ MDI #One 3000 Example 1 0.0293 0.0393 0.0101 0.0101 0.0101 #2 6000 Example 2 0.0310 0.0360 0.0101 0.0101 0.0101 #3 10000 Example 3 0.0316 0.0346 0.0101 0.0101 0.0101 #4 30000 Example 4 0.0323 0.0333 0.0101 0.0101 0.0101

(Solid: 30 g, Ionic group: 5 wt.%).1. PCL = Mn = 530 g/mol, Sigma-Aldrich

2. H ₁₂ MDI = Tokyo Chemical Industry Co., Ltd

3. DMBA = Sigma-Aldrich

4. TEA = Sigma-Aldrich

As shown in FIGS. 2A and 2B , it was confirmed that the physical properties improved as the amount of the aqueous polyurethane increased.

Next, the acrylic-water-based polyurethane composition of the present invention will be described in detail with reference to the experiment of mixing properties according to the type and amount of the aqueous polyurethane and the acrylate-based compound.

[Example 5]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0323 mol of polycaprolactone diol (PCL) and 0.0333 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. After mixing the diacrylate with the water-based polyurethane compound in a weight ratio of 1:1, the mixture is stirred at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

[Example 6]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0323 mol of polycaprolactone diol (PCL) and 0.0333 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. The water-based polyurethane compound is mixed with diacrylate in a weight ratio of 1:0.2 and then stirred at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

[Example 7]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0323 mol of polycaprolactone diol (PCL) and 0.0333 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. After mixing the water-based polyurethane compound with triacrylate in a weight ratio of 1:0.3, the mixture is stirred at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

[Example 8]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0323 mol of polycaprolactone diol (PCL) and 0.0333 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. After mixing the water-based polyurethane compound with triacrylate in a weight ratio of 1:0.2, the mixture is stirred at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

As shown in FIG. 3 , when the diacrylate was mixed with the aqueous polyurethane, dispersion was not performed well, but when the triacrylate was mixed with the aqueous polyurethane, it was confirmed that the dispersion was made well.

Next, an experimental process for producing a material having a viscosity that can be used in a DLP method in a 3D printer by adjusting the amount of water-based polyurethane in the acrylic-water-based polyurethane composition of the present invention will be described in detail.

[Example 9]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0323 mol of polycaprolactone diol (PCL) and 0.0333 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. Triacrylate is mixed with the water-based polyurethane compound, and the mixture is mixed so that the water-based polyurethane compound is 5% by weight, followed by stirring at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

[Example 10]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0323 mol of polycaprolactone diol (PCL) and 0.0333 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. A triacrylate is mixed with the water-based polyurethane compound and mixed so that the water-based polyurethane compound is 10% by weight, followed by stirring at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

[Example 11]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0323 mol of polycaprolactone diol (PCL) and 0.0333 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. Triacrylate is mixed with the water-based polyurethane compound and mixed so that the water-based polyurethane compound is 20% by weight, followed by stirring at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

[Example 12]

Total weight of polycaprolactone diol (PCL), 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI), dimethylol butanoic acid and triethylamine (TEA) With respect to 30 g, 0.0323 mol of polycaprolactone diol (PCL) and 0.0333 mol of 4,4'-methylene dicyclohexyl diisocyanate (4,4'-dicyclohexyl diisocyanate, H12MDI) were mixed with N2 at a stirring speed of 200 rpm. A prepolymer was prepared by mechanically stirring at 80° C. for 7 hours under an atmosphere. 0.5 g of dimethylolbutanoic acid (0.0101 mol) and 2.6261 g of 4,4'-methylene dicyclohexyl diisocyanate (0.0101 mol) were mixed in 5 ml of acetone and stirred at 80° C. for 1 hour to form a soft part of the polyurethane ( Agitate to form a soft/hard structure. After cooling to 50° C., 1.02447 g of triethylamine (TEA) (0.0101 mol) was sequentially added and added in the same molar ratio as the dimethylol butanoic acid. The polyurethane compound was added to 70 ml of purified water and dispersed by stirring at 30° C. at 600 rpm. After removing the remaining acetone, the aqueous polyurethane is heated at 60° C. for 30 minutes. A triacrylate is mixed with the water-based polyurethane compound, and the mixture is mixed so that the water-based polyurethane compound is 30% by weight, followed by stirring at 50° C. for 3 hours. Here, 2 g of a photoinitiator was mixed and outputted with a 3D printer of the DLP method.

4, when the water-based polyurethane compound is less than 10% by weight, the viscosity is low for use in the DLP method, and when it exceeds 30% by weight, the viscosity is too high and cannot be used in the DLP method, 10 to 30% by weight It can be seen that the viscosity suitable for use in the DLP method is made within the range of %, and the best viscosity is formed when it is 20% by weight.

In addition, as shown in FIG. 5 , it can be seen that the amount of water-based polyurethane in the acrylic-water-based polyurethane compound of the present invention affects bending properties and flowability.

In Fig. 6, (a) and (b) are SEM cross-sectional images, (c) (d) (e) are SEM plane images, the left is the water-based polyurethane compound 5% by weight, the middle is the water-based polyurethane compound 20% by weight, the right side is 30% by weight of a water-based polyurethane compound.

As shown in FIG. 6, when 20 wt% of the water-based polyurethane compound is used in the acrylic-water-based polyurethane composition of the present invention, the strength is 95 and the flexural strength is 23.0 MPa, showing higher physical properties than the conventional UV curing elastomer.

All technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art, unless otherwise stated. Also throughout this specification and claims, unless otherwise indicated, the term comprise, comprises, comprising is meant to include the recited object, step or group of objects, and steps, and any other It is not used in the sense of excluding an object, step, or group of objects or groups of steps.

Prior to describing the present invention in detail below, it is to be understood that the terminology used herein is for the purpose of describing specific embodiments and is not intended to limit the scope of the present invention, which is limited only by the appended claims. shall.

On the other hand, various embodiments of the present invention may be combined with any other embodiments unless clearly indicated to the contrary. Any feature indicated as particularly preferred or advantageous may be combined with any other feature and features indicated as preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

Claims (5)

An acrylic-water-based polyurethane composition for 3D printing, characterized in that a water-based polyurethane compound prepared by reaction of a polyol, a diisocyanate, an emulsifier, a neutralizer, and water and an acrylate-based compound are mixed. The method of claim 1,
The polyol is
It contains at least one selected from the group consisting of polytetramethylene glycol, poly-Caprolactone, polypropylene glycol and polyethylene glycol,
The diisocyanate is
Diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), 4'-dicyclohexylmethane diisocyanate (4,4'-Dicyclohexylmethane diisocyanate; H12MDI), toluene diisocyanate (Toluene diisocyanate) ; TDI), dicyclohexylmethane diisocyanate (HMDI) and isophorone diisocyanate (Isophorone diisocyanate; IPDI), characterized in that it contains at least one selected from the group consisting of 3D printing acrylic- A water-based polyurethane composition. The method of claim 1,
The acrylate-based compound is
Acrylic-water-based polyurethane composition for 3D printing, comprising at least one selected from the group consisting of monoacrylate, diacrylate, and triacrylate. The method of claim 1,
The acryl-water-based polyurethane composition for 3D printing, characterized in that the water-based polyurethane compound is mixed in a ratio of 10 wt% to 30 wt%. The method of claim 1,
Acryl-water-based polyurethane composition for 3D printing, characterized in that the mixture further includes a photoinitiator when mixing the water-based polyurethane compound and the acrylate-based compound.

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