KR102115655B1 - Multilayer build sheet for 3D printers - Google Patents

Abstract

The present invention relates to a build sheet of a multi-layer structure for a 3D printer, the build sheet according to the present invention is easy to attach and detach with a build plate, and ensures that the layers constituting the output structure are fixed securely during the printing process, and the printing process There is an effect that can easily remove the completed output sculpture after completion.
In addition, there is no side reaction with the molten polymer resin in the output process, showing stability, and there is an effect of not causing thermal deformation due to discharged accumulated resin.

Description

Multilayer build sheet for 3D printers

The present invention relates to a build sheet of a multi-layer structure for a 3D printer, and more particularly, to a build sheet mounted on a 3D printer build plate of a Fused Deposition Modeling (FDM) method.

In the 4th industry in the 21st century, 3D printing technology is a promising field for future industrial technology. For 3D printers, material extrusion, photo polymerization, material jetting, binder (binder jetting), powder fusion (powder bed fusion), multilayer lamination, sheet lamination, and directed energy deposition Deposition). The commonality of these various types of 3D printers is the molding of three-dimensional structures with a three-dimensional structure.

The position at which such a three-dimensional object is formed is called a build plate. The build plate is where the object to be printed by the 3D printer is settled. On the build plate, polymer resin is melt extruded at a high temperature and stacked in a layered layer to form an overall structure. It is a principle.

In this process, in order to obtain the desired result with the 3D printer, the output molding must be well attached to the build plate while the molding is being formed by the FDM method, and the output can be easily removed from the build plate after the molding operation is completed. Should be. In addition, in the process of laminating and extruding the polymer resin at a high temperature, deformation of the build plate should not occur due to heat accumulated in the build plate.

If the first layer deviates from the build plate, the next layer formed after the first layer is formed in an undesired position, so that the desired output structure cannot be obtained and the quality of the output structure may deteriorate. Likewise, if deformation of the build plate occurs due to the accumulated heat of the melt-extruded polymer resin, the next layer is formed in the pre-designed direction starting from the direction in which the initial deformation occurred, so that the desired output structure cannot be obtained or the quality of the output structure decreases. Can be.

In addition, it should be easy to remove the completed output sculpture from the build plate after the 3D printer is finished. If the output sculpture formed on the build plate is too tightly attached to the build plate, it is difficult to remove the output sculpture from the build plate. This is because there is a possibility that the 3D printer may be damaged or the output structure may be damaged.

As described above, the factors for improving the quality of the 3D printer output sculpture of the FDM method, that is, the layers constituting the build plate and the output sculpture must be firmly attached, and the deformation of the build plate is not caused in the process of printing the 3D printer. Various methods are currently in use to meet the fact that it should not be and that the finished print sculpture can be easily removed from the build plate after the 3D printer printing process is completed.

One of them is a method in which a polymer material to be used as a layer on a build plate and acetone are diluted and applied to a build plate of a 3D printer to be molded.

However, this method is very bad for health by the user inhaling it during the process of evaporation of acetone, and it is very difficult to remove the finished prints from the build plate after the 3D printer's print process is over. However, there are problems such as being able to damage the 3D printer.

Another frequently used method is surface treatment on the build plate, which is a method of printing after applying a wax, a release agent, or a solid adhesive.

The method of using a solid adhesive is still used, but in the case where the solid adhesive is hardened, the adhesive strength is poor and the output is not attached to the build plate until the printing process of the 3D printer is completed. In addition to the hassle of removing the adhesive applied to the build plate to finish the work and to start work again, during the removal process, the build plate is damaged by using a sharp metal material such as a knife or scraper. There is a problem that the plate smoothness decreases and thus the product completeness decreases.

Another method used is a method in which a reinforcing material such as a build sheet is installed without molding the output molding directly on the build plate, and the output molding is molded on the reinforcing material. This method has the advantage of being able to easily remove the finished output sculpture without damaging the 3D printer, but it has problems such as difficulty in securing thermal stability of the reinforcement material, product peeling force, and uniform flatness.

In addition, most of the commercially available build sheet products have been found to have a problem of poor repeatability due to melting on the surface of the build sheet due to the high temperature nozzle, and because the scraper is used when removing the output, the build sheet is also scratched with damage to the product. A problem that occurred was found.

In particular, most of the build sheet products currently in use correspond to expensive overseas products, and due to the above problems, it is difficult to use for multiple uses, and thus products to replace them are required.

The present invention has been devised to solve the above problems, and an object of the present invention is to provide a stable adhesion with an output during the molding process of a 3D printer and an adhesive force that can satisfy both the ease of removal with the output molding after completion of the molding process. It is to provide a multi-layered build sheet for a 3D printer with a heat-resistant holding power.

In order to achieve the above object, the present invention is an intermediate substrate layer comprising a heat-resistant film; A high-temperature adhesive layer located on one surface of the intermediate substrate layer and including an acrylic adhesive; And it is located on the other side of the intermediate substrate layer, provides a multi-layered build sheet for a 3D printer, characterized in that it comprises a normal temperature adhesive layer containing a silicone-based adhesive.

The heat-resistant film is polyethylene terephthalate (PET) film, polypropylene (PP) film, polystyrene (PS) film, polycarbonate (PC) film, polymethyl methacrylate (PMMA) film, polyethylene naphthalate (PEN) film, Any one or more selected from the group consisting of polyetherimide (PEI) film, polypara phenylene sulfide (PPS) film, polyimide (PI) film, polyether ketone (PEK) film, and polyether ether ketone (PEEK) film It can be characterized as.

The acrylic pressure-sensitive adhesive may be characterized in that it comprises an acrylic prepolymer polymerized with 0.1 to 30 parts by weight of acrylic acid monomer and 1 to 50 parts by weight of acrylamide monomer mixed with respect to 100 parts by weight of acrylate monomer.

The acrylate-based monomer is methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, normal butyl acrylate, It may be characterized by at least one selected from the group consisting of isobutyl acrylate, t -butyl acrylate, glycidyl methacrylate and 2-ethylhexyl acrylate.

The acrylic acid-based monomer may be characterized in that at least one selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylic acid, methyl methacrylic acid, ethyl acrylic acid, ethyl methacrylic acid, butyl acrylic acid and butyl methacrylic acid.

The acrylamide-based monomer is characterized in that at least one selected from the group consisting of acryloyl morpholine, isopropyl acrylamide, N-(2-hydroxyethyl)acrylamide and N,N-diethyl acrylamide. Can be.

The silicone pressure-sensitive adhesive comprises a first binder and a second binder in a weight ratio of 9:1 to 1:9,

The first binder contains 90 to 99% by weight of vinyl polysiloxane,

The second binder may be characterized in that it contains 1 to 5% by weight of an organopolysiloxane and 45 to 60% by weight of an aromatic hydrocarbon solvent.

The normal temperature adhesive layer may be characterized by having a thickness in the range of 1 to 100 μm.

The multilayer structure build sheet for 3D printer according to the present invention may be characterized in that a release film is attached to each side of the high-temperature adhesive layer and the normal-temperature adhesive layer that are not in contact with the intermediate substrate layer.

In addition, the present invention is a step of applying a silicone-based pressure-sensitive adhesive on one surface of the intermediate substrate layer containing a heat-resistant film and heat-curing and

It provides a method of manufacturing a multi-layered build sheet comprising the step of applying an acrylic adhesive to the other surface of the intermediate substrate layer and photocuring.

The heat curing may be characterized in that it is performed by staying for 30 seconds to 10 minutes in a curing oven or a curing chamber in a temperature range of 100°C to 200°C.

The photocuring may be characterized by proceeding by irradiating with UV for 10 to 200 seconds at an intensity of 5 to 1,000 mW/cm ² .

The multi-layered build sheet for 3D printer according to the present invention is composed of an intermediate base layer containing a heat-resistant film, a high temperature adhesive layer containing an acrylic adhesive, and a normal temperature adhesive layer containing a silicone adhesive, so that attachment and detachment with a build plate is easy And, during the printing process, the layers constituting the output sculpture are firmly fixed, and there is an effect of easily removing the completed output sculpture after the printing process is completed.

In addition, there is no side reaction with the molten polymer resin in the output process, showing stability, and there is an effect of not causing thermal deformation due to discharged accumulated resin.

Figure 1 shows the structure of a multi-layered build sheet according to the present invention.
2 is a result of evaluating the adhesive strength of the acrylic adhesive according to the acrylic acid content.
3 is an FT-IR analysis result of the acrylic adhesive according to the acryloyl morpholine content.
4 is a result of evaluating the adhesive strength of the acrylic adhesive according to the acryloyl morpholine content.
5 is a simplex design plot of a mixture design method for determining the component content of an adhesive.
6 is a result of evaluation of the adhesive strength of the acrylic adhesive according to the content of acrylic acid and acryloyl morpholine.
Figure 7 shows the variation in the adhesive strength according to the temperature of the acrylic adhesive according to the acrylic acid and acryloyl morpholine content.
8 is a result of evaluating the adhesive strength of the acrylic adhesive according to the content of post-added acryloyl morpholine (30min).
9 is a result of evaluating the adhesive strength of the acrylic adhesive according to the content of post-added acryloyl morpholine (24hr).
10 is a result of evaluation of the adhesive strength of the acrylic adhesive according to the content of acryloyl morpholine at a high temperature (80° C.) that is post-added.
11 is a schematic diagram of a method for manufacturing a multi-layered build sheet according to the present invention.
12 is a photograph showing a build sheet performance evaluation result according to Experimental Example 3 of the present invention.

Hereinafter, the present invention will be described in detail. Terms or words used in the present specification and claims should not be interpreted as being limited to a conventional or dictionary meaning, and the inventor may appropriately define the concept of terms to describe his or her invention in the best way. Based on the principle that it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

The present invention relates to a build sheet of a multi-layer structure for a 3D printer, and more particularly, to a build sheet mounted on a 3D printer build plate of a Fused Deposition Modeling (FDM) method.

The FDM method is a method in which a thermoplastic material such as ABS (Acrylonitrile Butadiene Styrene) and polylactic acid (PLA) is melted and sprayed from a nozzle to be stacked.

The build sheet is used to ensure that the output adheres well to the build plate during 3D printing. During the printing process, the material that is sprayed and laminated by the nozzle must be firmly attached, and deformation should not be caused by the high temperature material being sprayed. After the printing process is completed, it should be possible to easily remove the completed output sculpture.

Therefore, the top surface or front surface of the build sheet where the output is sprayed is required to have proper adhesion and heat-resistance at high temperature and room temperature, and the bottom surface or bottom surface of the build sheet is required to have proper adhesion and ease of peeling at room temperature.

The present invention is an intermediate substrate layer comprising a heat-resistant film; A high-temperature adhesive layer located on one surface of the intermediate substrate layer and including an acrylic adhesive; And it is located on the other side of the intermediate substrate layer, provides a multi-layered build sheet for a 3D printer, characterized in that it comprises a normal temperature adhesive layer containing a silicone-based adhesive.

The intermediate substrate layer may include a heat-resistant film, thereby maintaining the strength of the build sheet itself and preventing deformation due to a high temperature material sprayed in the output process.

The heat-resistant film is polyethylene terephthalate (PET) film, polypropylene (PP) film, polystyrene (PS) film, polycarbonate (PC) film, polymethyl methacrylate (PMMA) film, polyethylene naphthalate (PEN) film, Any one or more selected from the group consisting of polyetherimide (PEI) film, polypara phenylene sulfide (PPS) film, polyimide (PI) film, polyether ketone (PEK) film, and polyether ether ketone (PEEK) film It can be characterized as.

The high-temperature adhesive layer includes an acrylic adhesive, has an appropriate adhesive force at high and normal temperatures so that the output moldings can be firmly attached, and a heat-resistant retention force for not being deformed by a high-temperature material can be secured.

The acrylic pressure-sensitive adhesive may be characterized in that it comprises an acrylic prepolymer polymerized with 0.1 to 30 parts by weight of acrylic acid monomer and 1 to 50 parts by weight of acrylamide monomer mixed with respect to 100 parts by weight of acrylate monomer.

More specifically, with respect to 100 parts by weight of the acrylate-based monomer, 0.1 to 30 parts by weight of the acrylic acid-based monomer and 1 to 50 parts by weight of the acrylamide-based monomer may be mixed and include an acrylic prepolymer polymerized, preferably acrylic acid-based It may contain 1 to 20 parts by weight of monomer and 5 to 30 parts by weight of acrylamide-based monomer, and may include an acrylic prepolymer polymerized, more preferably 3 to 10 parts by weight of acrylic acid-based monomer and 10 to 20 parts by weight of acrylamide-based monomer. It may include an acrylic prepolymer mixed and polymerized.

If, when the acrylic acid-based monomer is mixed beyond the above-described range, there is a problem in that the adhesive strength with the ABS resin is lowered, and when mixed below the above-mentioned range, the heat-resistant retention force is lowered, or the sheet of the sheet during 3D printing of the FDM method is reduced. There is a problem that can cause deformation.

In addition, if the acrylamide-based monomer is mixed beyond the above-mentioned range, polymerization becomes impossible due to gelation or there is a problem of product damage when peeling due to adhesion with an ABS resin that is too high, and may be mixed below the above-mentioned range. If there is a problem that the adhesive strength with the ABS resin is lowered.

The acrylic prepolymer may be an acrylic prepolymer in which the monomers are thermally polymerized or photopolymerized, and preferably may be an acrylic prepolymer in which the monomers are photopolymerized.

When the acrylic prepolymer is formed by photopolymerization, the photoinitiator may be added 0.001 to 10 phr based on the mixture in which the monomers are mixed, preferably 0.01 to 5 phr, and more preferably 0.05 To 0.5 phr can be added.

Photoinitiators that can be used include, but are not limited to, PI-184 (1-Hydroxycyclohexyl phenyl ketone), Irgacure-TPO (Trimethylbenzoyl diphenylphosphine oxide).

When the acrylic prepolymer is formed by photopolymerization, the photopolymerization may be characterized by proceeding with UV irradiation for 10 to 200 seconds at an intensity of 5 to 1,000 mW/cm ² .

More specifically, the photopolymerization may be performed by UV irradiation with an intensity of 5 to 1,000 mW/cm ² , preferably UV irradiation with an intensity of 10 to 800 mW/cm ² , more preferably 100 UV irradiation with an intensity of ~ 500 mW/cm ² may be performed.

If, when irradiated with a strength less than the above-described range, there may be a problem that irradiation is performed in the irradiation range of the lamp (close distance between the lamp and the reactor), resulting in reduced transmittance and broadening of the molecular weight distribution.

Specifically, the range of molecular weight distribution (polydispersity) is not wide due to the stirring process until reaching a certain viscosity during UV irradiation, but as the molecular weight increases, the light transmittance decreases, and the reactor and the UV lamp are hardened on the adjacent surface. The efficiency increases, but does not affect the inside of the reactor, so the range of molecular weight distribution is widened over time.

In addition, when irradiated with a strength exceeding the above-described range, the time required for the polymerization reaction is reduced, but the range of the molecular weight distribution may be widened when a proper processing viscosity is reached in a short time.

Furthermore, the photopolymerization may be performed by UV irradiation for 10 to 200 seconds, preferably UV irradiation for 30 to 150 seconds, and more preferably UV irradiation for 60 to 120 seconds.

If UV irradiation is performed for a time less than the above-described range, the range of molecular weight distribution may be widened, and when UV irradiation is performed for a time exceeding the above-described range, viscosity may be too high, resulting in deterioration of processability.

The acrylate-based monomer is methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, normal butyl acrylate, It may be characterized by at least one selected from the group consisting of isobutyl acrylate, t -butyl acrylate, glycidyl methacrylate and 2-ethylhexyl acrylate.

The acrylate-based monomer imparts surface wettability to the adherend.

The acrylic acid-based monomer may be characterized in that at least one selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylic acid, methyl methacrylic acid, ethyl acrylic acid, ethyl methacrylic acid, butyl acrylic acid and butyl methacrylic acid, Preferably, acrylic acid can be used.

The acrylic acid-based monomer has a polar group and has a high glass transition temperature (T _g ) of the homopolymer to form a hard segment, thereby improving adhesion with an adherend and increasing cohesion after curing the adhesive.

The acrylamide-based monomer is characterized in that at least one selected from the group consisting of acryloyl morpholine, isopropyl acrylamide, N-(2-hydroxyethyl)acrylamide and N,N-diethyl acrylamide. And preferably acryloyl morpholine.

In the acrylamide-based monomer, the glass transition temperature (T _g ) of the homopolymer is higher than that of the acrylate-based monomer homopolymer, thereby improving heat retention.

As an example, the glass transition temperature (T _g ) of the homopolymer of acryloyl morpholine is 147° C., which shows a significantly higher glass transition temperature (T _g ) compared to the acrylate monomer homopolymer.

In addition, as the content of the acrylamide-based monomer is increased, the crosslinking density is increased to increase the adhesion, which is more pronounced in the relationship with the ABS resin.

The viscosity of the acrylic pressure-sensitive adhesive may be characterized in that 10 to 100,000 cps.

More specifically, the viscosity of the acrylic pressure-sensitive adhesive may be 10 to 100,000 cps, preferably 100 to 10,000 cps, and more preferably 1,000 to 5,000 cps.

If the viscosity of the acrylic pressure-sensitive adhesive is less than the stated range, it may not be suitable for casting during molding due to the low viscosity, and there is a problem in that thickness variation of the sheet during sheet production occurs due to a lot of heat generated during the curing process, and it may exceed the stated range. In the case of the curing process, there is a problem in that the movement between the acrylic prepolymers is not smooth and thus unreacted during production of the sheet to generate a gelled portion.

The acrylic pressure-sensitive adhesive comprises a polymer polymerized by mixing 0.1 to 30 parts by weight of acrylic acid or 1 to 50 parts by weight of acryloyl morpholine with respect to 100 parts by weight of acrylic prepolymer,

The acrylic prepolymer may be characterized in that 0.1 to 30 parts by weight of an acrylic acid-based monomer and 1 to 50 parts by weight of an acrylamide-based monomer are mixed and polymerized with respect to 100 parts by weight of an acrylate-based monomer.

More specifically, with respect to 100 parts by weight of the acrylic prepolymer, 0.1 to 30 parts by weight of acrylic acid or 1 to 50 parts by weight of acryloyl morpholine may be mixed to include a polymerized polymer, and preferably 1 to 20 parts by weight of acrylic acid Part or 5 to 30 parts by weight of acryloyl morpholine may be mixed to include a polymerized polymer. More preferably, 3 to 10 parts by weight of acrylic acid or 7 to 20 parts by weight of acryloyl morpholine are mixed to polymerize the polymer. It can contain.

Here, when the acrylic acid or acryloyl morpholine is added below the above-described range, the adhesion strength with the ABS resin at room temperature decreases, and when added above the above-described range, the adhesion strength with the ABS resin at high temperature decreases. There is a problem.

The acrylic prepolymer or polymer may be formed by thermal polymerization or photopolymerization, and preferably may be formed by photopolymerization.

The acrylic prepolymer may be characterized in that the weight average molecular weight is 1,000 g/mol to 1,000,000 g/mol.

More specifically, the weight average molecular weight may be 1,000 g/mol to 1,000,000 g/mol, preferably 3,000 g/mol to 500,000 g/mol, and more preferably 5,000 g/mol to 100,000 g/mol mol.

If the weight-average molecular weight of the acrylic prepolymer is less than the described range, there is a problem in that the sheet thickness variation occurs due to a lot of heat generated during the curing process of the build sheet production, and if it exceeds the stated range, the bonding between the acrylic prepolymers is smooth during the curing process. If not, there is a problem that a gelled portion may occur due to unreacted during sheet production.

The filament that is the raw material of the 3D printer of the FDM method is a thermoplastic resin processed into a thin thread, and is wound around a spool and used as a filament material: ABS, polylactic acid (PLA), high-impact polystyrene (HIPS), Polyamide (PA), thermoplastic urethane (TPU), polyvinylidene fluoride (PVDF), perfluoroalkoxy (PFA), ethylene tetrafluoroethylene (ETFE), and the like.

ABS resin is easy to manufacture filament, has excellent physical properties of output, has relatively high strength and easy post-processing compared to PLA, but has low floor adhesion, so the adhesive layer on the top or front side of the build sheet is different from ABS. It is required to adjust the appropriate adhesive force.

In addition, the ABS resin has a melting point of 230°C to 238°C, and it has a characteristic of being easily contracted, so it is important to control the temperature of the output plate, and is generally set to 80°C to 100°C.

The high-temperature adhesive layer of the present invention includes an acrylic prepolymer obtained by polymerizing acrylate-based monomers, acrylic acid-based monomers, and acrylamide-based monomers at a certain content ratio, and thus can not only have adequate adhesion with ABS resin, but also have high temperature (80°C) and room temperature. The change in adhesive strength at (25°C) is small, and thus, when using ABS resin, there is a characteristic that can exhibit an optimized effect.

The normal temperature adhesive layer includes a silicone adhesive, and has an appropriate adhesive force to secure a seating performance on a build plate and prevent residues and lifting during desorption.

The silicone pressure-sensitive adhesive comprises a first binder and a second binder in a weight ratio of 9:1 to 1:9,

The first binder contains 90 to 99% by weight of vinyl polysiloxane,

The second binder may be characterized in that it contains 1 to 5% by weight of an organopolysiloxane and 45 to 60% by weight of an aromatic hydrocarbon solvent.

More specifically, the first binder and the second binder may include a weight ratio of 9:1 to 1:9, preferably a weight ratio of 6:1 to 1:9, and more preferably It may be included in a weight ratio of 4:1 to 1:9.

If, when the weight ratio of the first binder and the second binder is out of the above-described range, there is a problem in that the adhesion is too high or too low to secure the seating performance on the build plate and the residue and lift-off prevention function during desorption.

The first binder may include 90 to 99% by weight of vinyl polysiloxane.

The vinyl polysiloxane is a siloxane containing a vinyl group at the terminal, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 2,4,6,8-tetramethyl-2,4,6, Any one or more selected from the group consisting of 8-tetravinylcyclotetrasiloxane and 1,1,1,3,5,5,5-heptamethyl-3-vinyltrisiloxane may be used, preferably 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane can be used.

In addition, the first binder is 1-ethynylcyclohexanol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol and 3,5-dimethyl-1-hexine-3 -Any one or more additives selected from the group consisting of all may further include 0.01 to 1% by weight.

The second binder may include 1 to 5% by weight of an organopolysiloxane and 45 to 60% by weight of an aromatic hydrocarbon solvent.

The organopolysiloxane includes tetrakis(trimethylsiloxy)silane, methyltris(trimethylsiloxy)silane, ethyltris(trimethylsiloxy)silane, propyltris(trimethylsiloxy)silane and phenyltris(trimethylsiloxy)silane. Any one or more selected from the group consisting of can be used, and preferably tetrakis(trimethylsiloxy)silane.

The aromatic hydrocarbon solvent is used as a diluent, may be used any one or more selected from the group consisting of xylene, ethylbenzene, toluene, pyridine, quinoline, anisole and mesitylene, preferably xylene 35 to 40 weight % And 10 to 15% by weight of ethylbenzene can be used in combination.

The normal temperature adhesive layer may be characterized by having a thickness in the range of 1 to 100 μm.

More specifically, the room temperature adhesive layer may have a thickness in the range of 1 to 100 μm, preferably a thickness in the range of 5 to 60 μm, and more preferably a thickness in the range of 10 to 50 μm. Can be.

If, when the normal temperature adhesive layer has a thickness less than the above-described range, there is a problem in that the adhesion properties are not secured and the heat-resistance retention force is lowered, and when it has a thickness exceeding the described range, it is often used as a build plate material or glass or SUS. There is a problem that the wettability is deteriorated.

The multilayer structure build sheet for 3D printer according to the present invention may be characterized in that a release film is attached to each side of the high-temperature adhesive layer and the normal-temperature adhesive layer that are not in contact with the intermediate substrate layer.

The release film is attached to one surface of the high temperature adhesive layer not in contact with the intermediate substrate layer and one surface of the normal temperature adhesive layer not in contact with the intermediate substrate layer to protect the adhesive layer, and is removed when used in a 3D printer.

As the release film, those known in the art may be used, and preferably a silicone release film may be used.

In addition, the present invention is a step of applying a silicone-based pressure-sensitive adhesive on one surface of the intermediate substrate layer containing a heat-resistant film and heat-curing and

It provides a method of manufacturing a multi-layered build sheet comprising the step of applying an acrylic adhesive to the other surface of the intermediate substrate layer and photocuring.

Here, the silicone-based adhesive or acrylic-based adhesive may be applied by a bar coater, using methods such as comma coating, slot die coating, roll-to-roll coating, gravure coating, micro gravure coating, and flexographic coating. Can be applied.

In addition, the silicone-based adhesive or acrylic-based adhesive may be applied in a thickness in the range of 1 to 100 μm, preferably in the range of 5 to 60 μm, and more preferably in the range of 10 to 50 μm. .

The coated silicone adhesive may form a normal temperature adhesive layer through thermal curing, and the thermal curing proceeds by staying in a curing oven or a curing chamber in a temperature range of 100°C to 200°C for 30 seconds to 10 minutes. It can be characterized as.

The applied acrylic adhesive may form a high temperature adhesive layer through photocuring, and the photocuring may be characterized by proceeding by irradiating with UV at a strength of 5 to 1,000 mW/cm ² for 10 to 200 seconds.

Hereinafter, examples and experimental examples will be described in detail to specifically describe the present invention. However, the embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Experimental Example 1. Evaluation of physical properties of the acrylic adhesive contained in the high temperature adhesive layer

1-1. Evaluation of physical properties of acrylic adhesives according to acrylic acid content

(1) Preparation of acrylic pressure-sensitive adhesive through photopolymerization

In order to control the physical properties of the adhesive, the glass transition temperature (T _g ) and the degree of crosslinking were controlled by varying the type and content ratio of the monomer, and through this, the wettability with the adherend, the secondary bonding properties with the adherend after wetting and the adhesive The monomer was selected considering the cohesive force inside.

2-ethylhexyl acrylate (2-EHA,2-Ethylhexyl acrylate) is used as a basic monomer for imparting surface wettability to the adherend, while having a polar group to give adhesion with the adherend and increase cohesion after curing the adhesive Acrylic acid, which can form a hard segment, was used because the glass transition temperature (T _g ) was high.

First, nitrogen was purged for 30 minutes (N ₂ purging) to block the oxygen inside to form a polymerization reaction atmosphere, and then mixed with 2-ethylhexyl acrylate, acrylic acid, and a photoinitiator (PI-184) and stirred while mercury UV UV light was irradiated (black light) for 90 seconds using a lamp (40W) to obtain a photopolymerized acrylic prepolymer.

Next, after adding a photocuring agent (1,6-Hexanediol diacrylate) to the acrylic prepolymer, UV irradiation was performed again with a mercury UV lamp (40W) to obtain a photopolymerizable adhesive.

Table 1 shows the content ratios of 2-ethylhexyl acrylate (2-EHA), acrylic acid (AA), and photoinitiator used.

division 2-EHA
(Parts by weight) AA
(Parts by weight) PI-184
(phr) FDM_T1-1 100 - 0.05 FDM_T1-2 100 One 0.05 FDM_T1-3 100 3 0.05 FDM_T1-4 100 5 0.05 FDM_T1-5 100 8 0.05 FDM_T1-6 100 10 0.05 FDM_T1-7 100 15 0.05 FDM_T1-8 100 20 0.05

(2) Evaluation of heat-resistance and adhesive strength of the adhesive

The basic physical properties of viscosity and photopolymerization reactivity (FT-IR) were measured using the pressure-sensitive adhesive, and an adhesive sheet sample having a thickness of 400 μm was prepared based on the measured data to evaluate heat-resistant retention and adhesion.

First, in order to evaluate the heat-resistance retention force, the adhesive sheet prepared with a width of 25.4 mm (1 inch) was attached to the SUS-304 specimen and the ABS specimen with a width of 25.4 × 25.4 mm (1 inch), and with a 2 kg rubber roller. It adhered by reciprocating once.

Next, a weight of 1 kg was hung on one end of the pressure sensitive adhesive sheet to maintain it at 80° C., and the holding time and the sliding of the sheet were observed for 72 hours. The adhesive sheet that did not reach the retention time was measured when it fell.

To evaluate the adhesive strength, cut the adhesive sheet to a width of 25.4 mm (1 inch), pass the 2 kg rubber roller twice through the washed SUS-304 specimen and the ABS resin specimen for 30 minutes at room temperature, and then install the UTM equipment. It was determined by using an adhesive force measurement angle of 180°, peeling rate of 300 mm/min and an average value.

As a result of the evaluation, in the case of a product using only 2-ethylhexyl acrylate (2-EHA) or adding a low proportion of acrylic acid (AA), the heat-resistance retention power did not reach the target set reference value, and when the adhesive strength was measured, the adhesive layer was pushed or residue. The back was observed. Conversely, when the experiment was carried out by filling too much acrylic acid (AA), the heat-resistance retention evaluation showed stable results and increased adhesion with stainless steel (SUS), but the adhesion with ABS resin was confirmed to be low. Could (see Figure 2).

Accordingly, in order to prepare a pressure-sensitive adhesive having physical properties suitable for the reference value, it was determined that 5 to 10 parts by weight of acrylic acid having little correlation between SUS and ABS was added and it was necessary to examine additional monomers. Accordingly, additional monomer addition experiments were conducted.

1-2. Evaluation of physical properties of adhesives according to acryloyl morpholine content

The proportion of 8 parts by weight of acrylic acid (AA) with respect to 100 parts by weight of 2-ethylhexyl acrylate (2-EHA) is fixed, and an adhesive is added in the same manner as in Experimental Example 1-1 by adding acryloyl morpholine (ACMO). It was prepared and each content ratio is shown in Table 2.

During the synthesis process, as the content of acryloyl morpholine (ACMO) increased, the reaction rate increased, and polymerization was impossible due to gelation at a content above a certain level.

division 2-EHA
(Parts by weight) AA
(Parts by weight) ACMO
(Parts by weight) PI-184
(phr) FDM_T2-1 100 8 0 0.05 FDM_T2-2 100 8 3 0.05 FDM_T2-3 100 8 5 0.05 FDM_T2-4 100 8 12 0.05 FDM_T2-5 100 8 20 0.05

First, as a result of analyzing the polymer polymerized through FT-IR, it was confirmed that the content of acryloyl morpholine (ACMO) increased through an increase in the CN peak at 1640 cm ^-1 and 1615 cm ^-1 (see FIG. 3). . In addition, as a result of evaluating the adhesive strength in the same manner as in Experimental Example 1-1, as the acryloyl morpholine (ACMO) content increased, the adhesive strength with the ABS resin increased but the adhesive strength with the SUS was confirmed to decrease. Particularly, when the content of acryloyl morpholine (ACMO) was added in an amount of 10 parts by weight or more, it was confirmed that the adhesion properties with SUS rapidly decreased (see FIG. 4).

1-3. Evaluation of physical properties according to the content ratio of adhesive

Based on the results of Experimental Examples 1-1 and 1-2, the mixture design method was applied to determine the content of each monomer to be used in the preparation of the adhesive (see FIG. 5).

Specifically, in consideration of the adhesive strength, heat-resistance, and release workability of the pressure-sensitive adhesive, the content of acrylic acid (AA) is 5 to 10 parts by weight, acrylic to 100 parts by weight of 2-ethylhexyl acrylate (2-EHA) The content of daily morpholine (ACMO) was determined to be the most ideal to use 10 to 20 parts by weight.

In particular, as the content of acryloyl morpholine (ACMO) increases, the adhesion with ABS resin increases, but considering that it is an adhesive to be applied to 3D printers in FDM, too high adhesion can cause damage to the product and deterioration of workability when peeling off. So, it was determined that 10 to 20 parts by weight of acryloyl morpholine (ACMO) is ideal.

Based on the results, the content ratio of 2-ethylhexyl acrylate (2-EHA), acrylic acid (AA), and acryloyl morpholine (ACMO) was varied to prepare an adhesive in the same manner as in Experimental Example 1-1. It was prepared and each content ratio is shown in Table 3.

division 2-EHA
(Parts by weight) AA
(Parts by weight) ACMO
(Parts by weight) PI-184
(phr) FDM_T3-1 100 5 12 0.05 FDM_T3-2 100 5 15 0.05 FDM_T3-3 100 6 12 0.05 FDM_T3-4 100 6 15 0.05 FDM_T3-5 100 7 12 0.05 FDM_T3-6 100 7 15 0.05 FDM_T3-7 100 8 12 0.05 FDM_T3-8 100 8 15 0.05

In order to analyze the correlation according to each content at the normal temperature (25 °C) and high temperature (80 °C) conditions of the prepared pressure-sensitive adhesive, room temperature (25 °C) and high temperature (80 °C) in the same manner as in Experimental Example 1-1. In the evaluation of the adhesion with ABS resin was conducted. As a result of analysis, it was confirmed that as the content of acrylic acid (AA) decreased and the content of acryloyl morpholine (ACMO) increased, the ABS resin exhibited somewhat higher adhesion (FIG. 6). Reference).

In addition, as a result, as the contents of acrylic acid (AA) and acryloyl morpholine (ACMO) increased, it was confirmed that a large variation in physical property changes with temperature (see FIG. 7 ).

As a result, based on 100 parts by weight of 2-ethylhexyl acrylate (2-EHA), 5% by weight of acrylic acid (AA) and 12 to 15 parts by weight of acryloyl morpholine (ACMO) have excellent physical properties. Room temperature and high temperature, especially when the content of acrylic acid (AA) is 5 parts by weight and the content of acryloyl morpholine (ACMO) is 15 parts by weight, based on 100 parts by weight of 2-ethylhexyl acrylate (2-EHA) It was confirmed that the composition was optimized for the build sheet for 3D printers of the FDM method with the smallest difference in adhesive force of.

1-4. Evaluation of adhesive strength according to the content of post-added acryloyl morpholine

(1) Preparation of adhesive through photopolymerization

First, nitrogen was purged for 30 minutes (N ₂ purging) to block the oxygen inside to form a polymerization reaction atmosphere, and then mixed with 2-ethylhexyl acrylate, acrylic acid, acryloyl morpholine, and a photoinitiator (PI-184). While stirring, a UV light was irradiated (black light) for 90 seconds using a mercury UV lamp (40W) to obtain a photopolymerized acrylic prepolymer.

Next, based on 100 parts by weight of the acrylic prepolymer, the content of acryloyl morpholine is added differently, and after adding a photoinitiator (PI-184) and a photocuring agent (1,6-hexanediol diacrylate), mercury is added. UV irradiation was performed with a UV lamp (40W) to obtain a photopolymerizable polymer.

Table 2 shows the content ratio of 2-ethylhexyl acrylate (2-EHA), acrylic acid (AA), acryloyl morpholine (ACMO), photoinitiator and photocuring agent used.

division FDM_11-01 FDM_11-02 FDM_11-03 FDM_11-04 prepolymer 2-EHA (parts by weight) 100 100 100 100 AA (parts by weight) 5.0 5.0 5.0 5.0 ACMO (parts by weight) 15.0 15.0 15.0 15.0 PI-184(phr) 0.1 0.1 0.1 0.1 polymer prepolymer
(Parts by weight) 100 100 100 100 ACMO (parts by weight) 7.0 10.0 15.0 20 PI-184(phr) 0.5 0.5 0.5 0.5 HDDA(phr) 0.3 0.3 0.3 0.3

(2) Evaluation of the adhesive strength of the adhesive at room temperature and high temperature Using the prepared photopolymerization polymer, a sample of 400 μm thick adhesive sheet was prepared, and after cutting the adhesive sheet to a width of 25.4 mm (1 inch), washed SUS-304, 2 kg of rubber rollers were passed through the GLASS and ABS specimens twice, and allowed to stand at room temperature for 30 minutes. Using the UTM equipment, the adhesive force was measured at an angle of 180° and a peeling rate of 300 mm/min to determine the average value, and the adhesive force was measured in the same manner after 24 hours, and the results are shown in FIGS. 8 and 9.

As shown, with respect to 100 parts by weight of the prepolymer, the adhesive strength of the SUS was reduced when the acryloyl morpholine was added at least 10 parts by weight, and when it was 20 parts by weight, the adhesive strength was less than 10 N/in. Even in the case of GLASS, it was confirmed that the adhesive strength of 10 N/in or less was exhibited when 20 parts by weight of acryloyl morpholine was added to 100 parts by weight of the prepolymer.

In the ABS resin, as the content of acryloyl morpholine increased, the adhesive strength showed a tendency to decrease, but compared to SUS and GLASS, the adhesive strength gradually increased, and especially with respect to 100 parts by weight of the prepolymer, acryloyl mortar Even when 20 parts by weight of polyline was included, it exhibited an adhesive strength of 10 N/in or more.

In addition, after leaving for 30 minutes at a high temperature (80 ℃) in the same manner, the adhesive strength was evaluated and the results are shown in FIG. 10.

As shown, the adhesive strength increased as the content of acryloyl morpholine added to both SUS and ABS increased, and showed an adhesive strength of 10 N/in or more.

As a result, it was confirmed that the adhesive having a post-addition of acryloyl morpholine has suitable physical properties in ABS resin.

1-5. Evaluation of adhesive strength according to the amount of acrylic acid added after

(1) Preparation of adhesive through photopolymerization

First, nitrogen was purged for 30 minutes (N ₂ purging) to block the oxygen inside to form a polymerization reaction atmosphere, and then mixed with 2-ethylhexyl acrylate, acryloyl morpholine, acrylic acid, and a photoinitiator (PI-184). While stirring, a UV light was irradiated (black light) for 90 seconds using a mercury UV lamp (40W) to obtain a photopolymerized acrylic prepolymer.

Next, based on 100 parts by weight of the acrylic prepolymer, the content of acrylic acid is added differently, and after adding acryloyl morpholine, photoinitiator (PI-184) and photocuring agent (1,6-hexanediol diacrylate) , UV irradiation with a mercury UV lamp (40W) to obtain a photopolymerizable polymer.

Table 2 shows the content ratio of 2-ethylhexyl acrylate (2-EHA), acrylic acid (AA), acryloyl morpholine (ACMO), photoinitiator and photocuring agent used.

division FDM_12-01 FDM_12-04 prepolymer 2-EHA (parts by weight) 100 100 AA (parts by weight) 5.0 5.0 ACMO (parts by weight) 15.0 15.0 PI-184(phr) 0.1 0.1 polymer prepolymer
(Parts by weight) 100 100 ACMO (parts by weight) 5.0 5.0 AA (parts by weight) 3.0 10.0 PI-184(phr) 0.5 0.5 HDDA(phr) 0.3 0.3

(2) Evaluation of adhesive strength of the adhesive at room temperature and high temperature

Using the prepared photopolymerization polymer, a sample of 400 μm thick adhesive sheet was prepared, and after cutting the adhesive sheet to a width of 25.4 mm (1 inch), 2 kg of rubber roller was applied to the washed SUS-304, GLASS, ABS specimens. Passed twice and left for 30 minutes at room temperature. Using the UTM equipment, the adhesive force was measured at an angle of 180° and the peeling rate at 300 mm/min, and determined as an average value. After 24 hours, the adhesive force was measured in the same manner and the results are shown in Table 6.

FDM_12-01
(N/in) FDM_12-04
(N/in) 18O degree Peel test
(30 min)
SUS 12.30 8.02 GLASS 16.09 7.40 ABS 31.44 12.82 18O degree Peel test
(24 hr)
SUS 12.30 8.02 GLASS 16.09 7.40 ABS 31.44 12.82

As shown in Table 6, in the case of SUS or GLASS, when the content of acrylic acid was 10 parts by weight, the adhesive strength was reduced to less than 10 N/in, but in ABS, it was confirmed that the adhesive strength was maintained above 10 N/in. After standing at high temperature (80° C.) for 30 minutes in the same manner, the adhesive strength was evaluated and the results are shown in Table 7 below.

FDM_12-01
(N/in) FDM_12-04
(N/in) 18O degree Peel test
(30 min)
SUS 12.5 15.88 ABS 11.94 15.56

As shown, both the SUS and ABS increased the adhesive strength when the content of the acrylic acid post-added increased, and showed an adhesive strength of 10 N/in or more. As a result, it was confirmed that the adhesive having post-addition of acryloyl morpholine and acrylic acid has suitable properties, especially in ABS resin.

Experimental Example 2. Evaluation of physical properties of the silicone-based adhesive contained in the normal temperature adhesive layer

2-1. Evaluation of adhesive strength of silicone adhesive

(1) Preparation of silicone adhesive through thermal curing

In order to prepare a silicone-based adhesive, the mixture was designed using silicone resin of Dow Corning from overseas. After using Dow Corning's 7646 silicone resin as the first binder and Dow Corning's 7657 resin as the second binder, diluting it in toluene with different mixing ratios of the first binder and the second binder, diluting it in toluene, and then using the same amount of catalyst (DOW CORINING 4000), a curing agent ((DOW CORINING SYL-OFF 7689) was added to prepare a mixture. After coating the prepared mixture to a thickness of 10 µm and 30 µm on PET substrates, the mixture was cured for 2 minutes in a dry oven at 160° C. An adhesive sheet was prepared The content ratio of the prepared mixture is shown in Table 8.

division FDM
BA2-1 FDM
BA2-2 FDM
BA2-3 FDM
BA2-4 FDM
BA2-5 1st Binder
(Parts by weight) 60 30 20 15 10 Second Binder
(Parts by weight) 40 70 80 85 90 additive
(Parts by weight) 1.0 1.0 1.0 1.0 1.0 Pt-catalyst
(Parts by weight) 1.2 1.2 1.2 1.2 1.2 Hardener
(Parts by weight) 1.0 1.0 1.0 1.0 1.0 toluene
(Parts by weight) 30 30 30 30 30

(2) Evaluation of adhesion

After cutting the prepared silicone-based adhesive sheet to a width of 25.4 mm, the washed SUS and GLASS specimens were passed twice using a 2 kg rubber roller.

After standing for 24 hours in an 80° C. dry oven, the taken-out specimen was cooled at 25° C. and checked for occurrence of excitation and peeling, then peeled at a rate of 180°, 300 mm/min using UTM to measure adhesion Table 9 shows the results.

FDM BA2-1
(gf/25.4 mm) FDM BA2-2
(gf/25.4 mm) FDM BA2-3
(gf/25.4 mm) FDM BA2-4
(gf/25.4 mm) FDM BA2-5
(gf/25.4 mm) 10 μm SUS 8 to 10 17-20 52-53 110 ~ 120 230 ~ 250 GLASS 8 to 10 16 ~ 18 48-50 95 ~ 105 210 ~ 230 30 μm SUS 12-15 22-27 56 ~ 59 151 ~ 157 352 ~ 375 GLASS 11-13 21 to 24 58-60 148 ~ 155 340 ~ 350

As shown, as the coating thickness of the adhesive layer increased, it was confirmed that the adhesive strength increased, and when the adhesive strength was low, it was confirmed that the change according to the coating thickness appeared less.

In addition, it was confirmed that no lifting or air bubbles were generated in all the adhesive sheets.

2-2. Transfer confirmation according to composition and coating thickness of silicone adhesive

The appearance was analyzed to confirm the occurrence of transfer according to the coating thickness of the silicone-based adhesive sheet prepared in Experimental Example 2-1.

First, the silicone-based adhesive sheet prepared in Experimental Example 2-1 was cut to a width of 25.4 mm (1 inch) and attached to SUS-304, Glass, ABS specimens, and was bonded by reciprocating once with a 2 kg rubber roller. The adhesive-attached specimen was left for 24 hours at 85°C and 85% humidity, and then the adhesive was removed, and the presence or absence of the adhesive residue on the specimen was visually analyzed using a microscope and the results are shown in Table 10. .

FDM BA2-1 FDM BA2-2 FDM BA2-3 FDM BA2-4 FDM BA2-5 10 μm Good Good Good Good Good 30 μm Good Good Good Good Partial observation

As shown, no transfer was observed in most silicone-based adhesive sheets, and only partially observed in 30 μm thick FDM BA2-5.

2-3. Check wettability according to composition and coating thickness of silicone adhesive

Using the silicone-based adhesive sheet prepared in Experimental Example 2-1, the wettability with tempered glass, SUS, which is frequently used in build plates, was evaluated, and the results are shown in Table 11.

FDM BA2-1 FDM BA2-2 FDM BA2-3 FDM BA2-4 FDM BA2-5 10 μm Very good Very good Good Good Good 30 μm Very good Very good Very good Good Process improvement required

As shown, it was found that the wettability with tempered glass and SUS was good in most silicone-based adhesive sheets, and it was determined that process improvement was necessary in 30 μm thick FDM BA2-5.

2-4. Evaluation of heat-resistant retention power according to composition and coating thickness of silicone adhesive

Using the silicone-based pressure-sensitive adhesive sheet prepared in Experimental Example 2-1, heat-resistance retention was evaluated.

First, the adhesive sheet prepared with a width of 25.4 mm (1 inch) was attached to the SUS-304 test piece with a width of 25.4 × 25.4 mm (1 inch) and adhered by reciprocating once with a 2 kg rubber roller. 1 kg of weight was suspended at one end of the adhered adhesive film and maintained at 80° C., and the holding time and sheet slipping were observed for 24 hr. The adhesive sheet that did not reach the retention time was measured when it fell, and the results are shown in Table 12.

FDM BA2-1 FDM BA2-2 FDM BA2-3 FDM BA2-4 FDM BA2-5 10 μm Bad Bad Good Good Good 30 μm Good Good Good Good Good

As shown, it was confirmed that the heat-resistance retention power had good characteristics except for 10 μm-thick FDM BA2-1 and FDM BA2-2.

As a result, it was judged in consideration of adhesion, transfer generation, ease of application (wetting), and high temperature retention in consideration of adhesion characteristics with the build plate of the 3D printer. It was confirmed to have.

Example 1. Preparation of a multi-layered build sheet for 3D printers

In order to manufacture a multi-layered build sheet for 3D printers, KOLON's 75 µm PET was used as the intermediate substrate layer, and SKC haas' 50 µm silicone release film was used as the release film.

First, in order to prepare an acrylic adhesive used for a high temperature adhesive layer, nitrogen is purged for 30 minutes (N ₂ purging) to block the oxygen inside to form a polymerization reaction atmosphere, and then 100 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, 15 parts by weight of acryloyl morpholine and 0.05 phr of photoinitiator (PI-184) were mixed and irradiated with UV for 90 seconds using a mercury UV lamp (40W) to obtain a photopolymerizable acrylic prepolymer. .

Next, in order to prepare a silicone-based adhesive used for the normal temperature adhesive layer, 30 parts by weight of toluene as an organic solvent based on 100 parts by weight of the mixture is used for the mixture in which the first binder and the second binder are mixed at a weight ratio of 3:7 The mixture was diluted.

With respect to 100 parts by weight of the diluted mixture, 1 part by weight of an additive, 1.2 parts by weight of a Pt-catalyst, and 1.0 part by weight of a curing agent were added to prepare a silicone adhesive.

In order to manufacture a multi-layered build sheet, a silicone-based adhesive prepared using a bar coater is applied to a 75 μm thick PET substrate to a thickness of 30 μm, followed by curing for 2 minutes in a 160° C. dry oven to adhere to room temperature. A layer was formed.

Subsequently, a release film was laminated on one surface of the normal temperature adhesive layer that was not in contact with the PET substrate.

Next, the acrylic prepolymer prepared above was applied to the other surface of the PET substrate on which the normal temperature adhesive layer was not laminated using a bar coater.

Subsequently, a photocuring agent (1,6-hexanediol diacrylate) and an additive were applied to the acrylic prepolymer, and a release film was laminated on the acrylic prepolymer coating layer.

Thereafter, UV-irradiated with a mercury UV lamp (40W) for 90 seconds to form an acrylic adhesive layer to obtain a final build sheet (see FIG. 11).

Experimental Example 3. Performance evaluation of 3D printer multi-layered build sheet

When the multi-layered structured build sheet prepared in Example 1 was applied to a 3D printer build plate, seating performance, residue and desorption during detachment were observed.

Specifically, after manufacturing a cuboid of 10.0 cm in width, 10.0 cm in height, and 1.5 cm in height based on the FDM 3D printer's bottom temperature of 80℃ and the filament to be output as ABS, build it after cooling to room temperature for 30 minutes in the printer. The sheet was removed to evaluate the appearance of the output.

In addition, when a commercially available adhesive sheet was used, peeling of the adhesive layer was observed upon desorption, and the lifting between the plate and the sheet, the warping of the molded object, and the separation between the sheet and the molded object occurred before the ABS output formed a cuboid.

In comparison, in the case of Example 1, it was confirmed that distortion of the output did not occur and residue or excitation did not occur during desorption (see FIG. 12 ).

Claims (12)

An intermediate base layer comprising a heat resistant film;
A high-temperature adhesive layer located on one surface of the intermediate substrate layer and including an acrylic adhesive; And
Located on the other side of the intermediate substrate layer, and includes a room temperature adhesive layer containing a silicone-based adhesive,
The acrylic pressure-sensitive adhesive comprises a photopolymerized polymer by mixing 0.1 to 30 parts by weight of acrylic acid or 1 to 50 parts by weight of acryloyl morpholine with respect to 100 parts by weight of acrylic prepolymer,
The acrylic prepolymer is photopolymerized by mixing 0.1 to 30 parts by weight of acrylic acid monomer and 1 to 50 parts by weight of acrylamide monomer based on 100 parts by weight of acrylate monomer.
The silicone pressure-sensitive adhesive comprises a first binder and a second binder in a weight ratio of 4:1 to 1:9, the first binder includes vinylpolysiloxane, and the second binder comprises organopolysiloxane Multi-layer build sheet for 3D printers.
According to claim 1,
The heat-resistant film is polyethylene terephthalate (PET) film, polypropylene (PP) film, polystyrene (PS) film, polycarbonate (PC) film, polymethyl methacrylate (PMMA) film, polyethylene naphthalate (PEN) film, Any one or more selected from the group consisting of polyetherimide (PEI) film, polypara phenylene sulfide (PPS) film, polyimide (PI) film, polyether ketone (PEK) film, and polyether ether ketone (PEEK) film Multi-layered build sheet for 3D printers.
delete According to claim 1,
The acrylate-based monomer is methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, normal butyl acrylate, Multi-layer structure build sheet for 3D printers, characterized in that at least one selected from the group consisting of isobutyl acrylate, t -butyl acrylate, glycidyl methacrylate and 2-ethylhexyl acrylate.
According to claim 1,
The acrylic acid-based monomer is for 3D printer, characterized in that at least one selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylic acid, methyl methacrylic acid, ethyl acrylic acid, ethyl methacrylic acid, butyl acrylic acid and butyl methacrylic acid Multilayer structure build sheet.
According to claim 1,
The acrylamide-based monomer is at least one selected from the group consisting of acryloyl morpholine, isopropyl acrylamide, N-(2-hydroxyethyl)acrylamide and N,N-diethyl acrylamide. Multi-layer build sheet for 3D printers.
delete According to claim 1,
The normal temperature adhesive layer is a multi-layer structure build sheet for a 3D printer, characterized in that having a thickness in the range of 1 to 100 ㎛.
According to claim 1,
A multi-layered build sheet for a 3D printer, characterized in that a release film is attached to each side of the high-temperature adhesive layer and the normal-temperature adhesive layer that are not in contact with the intermediate substrate layer.
Applying a silicone-based pressure-sensitive adhesive on one surface of the intermediate substrate layer containing a heat-resistant film and heat-curing
And applying an acrylic pressure-sensitive adhesive to the other surface of the intermediate substrate layer and photocuring the same;
The acrylic pressure-sensitive adhesive contains 0.1 to 30 parts by weight of acrylic acid or 1 to 50 parts by weight of acryloyl morpholine, based on 100 parts by weight of acrylic prepolymer,
The acrylic prepolymer is photopolymerized by mixing 0.1 to 30 parts by weight of acrylic acid monomer and 1 to 50 parts by weight of acrylamide monomer based on 100 parts by weight of acrylate monomer.
The silicone pressure-sensitive adhesive comprises a first binder and a second binder in a weight ratio of 4:1 to 1:9, the first binder includes vinylpolysiloxane, and the second binder comprises organopolysiloxane Method of manufacturing a multi-layered build sheet for 3D printers.
The method of claim 10,
The method of manufacturing a multi-layered build sheet for a 3D printer, characterized in that the thermal curing proceeds by staying in a curing oven or a curing chamber in a temperature range of 100°C to 200°C for 30 seconds to 10 minutes.
The method of claim 10,
The photo-curing method of manufacturing a multi-layer structure for 3D printer, characterized in that proceeds by UV irradiation for 10 to 200 seconds at an intensity of 5 to 1,000 mW/cm ² .

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