CN113166291B - Composition for three-dimensional printing - Google Patents
Composition for three-dimensional printing Download PDFInfo
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- CN113166291B CN113166291B CN201980077790.4A CN201980077790A CN113166291B CN 113166291 B CN113166291 B CN 113166291B CN 201980077790 A CN201980077790 A CN 201980077790A CN 113166291 B CN113166291 B CN 113166291B
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- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 238000010146 3D printing Methods 0.000 title claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000007639 printing Methods 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 238000000034 method Methods 0.000 description 24
- 238000001723 curing Methods 0.000 description 22
- 238000013329 compounding Methods 0.000 description 19
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical group C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
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- 230000008569 process Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
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- 238000000016 photochemical curing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 230000004044 response Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical group OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a composition for three-dimensional printing. According to one aspect of the present embodiment, there is provided a composition for three-dimensional printing, which is a composition used as a raw material for a three-dimensional printer, the composition for three-dimensional printing being characterized by comprising a monofunctional monomer, a difunctional monomer, an oligomer, an initiator, and a photosensitizer.
Description
Technical Field
The present invention relates to a photocurable composition for use in three-dimensional printing.
Background
The statements in this section merely provide background information related to one embodiment of the present disclosure and may not constitute prior art.
If the current major trend of global industry technology is counted, 3D printers cannot be excluded. Since 3D printing technology is expected to develop into an industry with high added value in the future, many enterprises in various countries are continually striving to develop hardware (H/W) and software (S/W) themselves. As one of such 3D printing methods, a3D printing method of a type widely used at present is an FDM (Fused Deposition Modeling) method. FDM is a mode in which a3D printer heats and melts filaments of plastic material and extrudes them, and then hardens at normal temperature to stack objects. However, this FDM method has a disadvantage of high failure rate in the actual shape manufacturing process because of a large mechanical movement.
A3D printing technology recently developed to solve such a problem is a technology of printing with photo curing. As representative examples of the photo-curing 3D printing technology, there are SLA (Stereo Lithography Apparatus, stereolithography) mode or DLP (Digital Light Processing ) mode. The SLA method is a method in which a3D printer irradiates a high-density laser beam to cure a resin into a desired shape, and the DLP method is a method in which a3D printer uses a light projector instead of the high-density laser beam to cure the resin. The DLP type 3D printer irradiates light to an area to cure a resin, instead of irradiating light to a specific focus as in the SLA type.
The SLA system 3D printer has an advantage of high precision in the final shape, but has a disadvantage of requiring a long time until the final shape is manufactured, because the resin is cured by irradiating a high-density laser beam to a specific focal point. In contrast, the DLP type 3D printer has an advantage of considerably shortening the manufacturing time of the shape because the resin is cured by irradiating light to the area, but has a disadvantage of decreasing the precision of the final shape, particularly, a disadvantage of decreasing the precision realized on the surface of the shape.
As described above, the existing 3D printing methods using photo curing each have a problem of disadvantages, and thus a new 3D printing method that minimizes the disadvantages is required.
In addition, as a resin used for 3D printing in the past, an opaque plastic material such as ABS resin or urethane is used, and thus, it has an opaque characteristic. Therefore, the conventional resin has a problem that optical characteristics such as aesthetic property and transmission or diffusion are deteriorated. Therefore, there is also a need for a material of transparent material excellent in aesthetic and optical properties and improved in durability for a resin used for 3D printing.
Disclosure of Invention
(problem to be solved by the invention)
It is an object of one embodiment of the present invention to provide a three-dimensional printing composition that is transparent and capable of curing in response to both SLA3D printing and DLP 3D printing.
In addition, it is another object of an embodiment of the present invention to provide a3D printing apparatus that cures the core and shell of the final shape to be manufactured, respectively.
(measures taken to solve the problems)
According to one aspect of the present invention, there is provided a composition for a three-dimensional printer, which is used as a raw material for a three-dimensional printer, and is characterized by comprising a monofunctional monomer, a difunctional monomer, an oligomer, an initiator, and a photosensitizer.
According to one aspect of the present invention, the composition for a three-dimensional printer is characterized by comprising 10 to 30 parts by weight of a monofunctional monomer, 20 to 50 parts by weight of a difunctional monomer, 30 to 40 parts by weight of an oligomer, 5 parts by weight or less of an initiator, and 1 part by weight or less of a photosensitizer.
According to one aspect of the present invention, the composition for a three-dimensional printer further comprises a pigment.
According to one aspect of the present invention, the composition for a three-dimensional printer is characterized by containing 1 part by weight or less of pigment.
According to one aspect of the present invention, the monofunctional monomer is an epoxy (epoxy) monomer or an ether monomer.
According to one aspect of the present invention, the composition for a three-dimensional printer is characterized in that the difunctional monomer is an acrylic monomer.
According to one aspect of the present invention, the composition for a three-dimensional printer is characterized in that the difunctional monomer is a bisphenol Z (BPZ) -series monomer.
(effects of the invention)
As described above, according to an aspect of the present invention, the composition for three-dimensional printing is not only transparent, but also has an advantage of being curable in response to both SLA3D printing and DLP 3D printing.
In addition, according to an aspect of the present invention, the 3D printing apparatus cures the core and the shell of the final shape to be manufactured, respectively, thereby having an advantage that both a rapid manufacturing time and excellent precision of the manufactured final shape can be ensured.
Drawings
Fig. 1 is a diagram illustrating a constitution of a3D printing apparatus according to an embodiment of the present invention.
Fig. 2 is a diagram illustrating one specific implementation of a3D printing apparatus according to one embodiment of the present invention.
Fig. 3 is a flowchart illustrating a method of curing a3D printing composition by a3D printing device according to one embodiment of the present invention.
Fig. 4 is a flowchart illustrating a method of curing a3D printing composition by a3D printing device according to another embodiment of the present invention.
Detailed Description
The present invention is capable of many modifications and various embodiments, and thus specific embodiments are illustrated in the drawings and described in detail. It is not intended to limit the invention to the particular embodiments but is to be understood to include all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In describing the drawings, like reference numerals have been used for like components.
The terms first, second, A, B and the like can be used to describe various components, but the components are not limited to the terms. The above terms are used only for the purpose of distinguishing one component from other components. For example, a first component may be named a second component, and similarly, a second component may be named a first component without departing from the scope of the invention. The term "and/or" includes a combination of a plurality of related items or any one of a plurality of related items.
When it is referred to that a certain component is "connected" or "coupled" to another component, it is understood that other components may be present therebetween although it may be directly connected or coupled to the other component. Conversely, when reference is made to one component being "directly connected" or "directly coupled" to another component, it is to be understood that no other component is present between the two.
The terminology used in the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. In this application, the terms "comprises" and "comprising" are to be construed as not excluding in advance the existence or additional possibilities of features, numbers, steps, actions, components, parts or combinations thereof recited in the specification.
Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art.
The terms as defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In addition, each of the components, processes, procedures, methods, and the like included in the embodiments of the present invention may be shared within a range that is not technically contradictory.
Fig. 1 is a diagram illustrating a constitution of a3D printing apparatus according to an embodiment of the present invention.
Referring to fig. 1, a3D printing apparatus 100 according to an embodiment of the present invention includes a first light source 110, a second light source 115, a control part 120, and a motor 130.
The first light source 110 irradiates a certain area of light to a3D printing composition (hereinafter, simply referred to as "composition"). The first light source 110 irradiates light of an area corresponding to a shape of a core portion of a shape (hereinafter, simply referred to as a "final shape") finally manufactured by the 3D printing apparatus, instead of irradiating light focused into one point. The first light source 110 irradiates a certain area of light to the composition while curing the composition corresponding to the certain area. The area of the light irradiated by the first light source 110 varies with the area of the core portion in each layer (layer) of the final shape. The first light source 110 irradiates light corresponding to the area of the core portion in each layer of the final shape to the composition so that the composition can be cured into a shape like the core portion of the final shape. The first light source 110 enables the 3D printing apparatus 100 to operate in a DLP 3D printing mode.
The second light source 115 irradiates a focal point of laser light to the container containing the composition. The second light source 115 irradiates a laser focused to one focal point and moves the focal point to cure the composition to become a Shell (Shell) portion of the final shape. The second light source 115 further cures the final shaped shell portion after the first light source 110 cures the composition or simultaneously with the first light source 110. The SLA3D printing apparatus cures the composition by irradiating a laser focused to one focal point like the second light source, and thus takes a considerable time to cure the composition into a final shape. However, since the second light source 115 is only required to cure the shell portion of the composition in which the curing of the core portion has been completed using the first light source, the 3D printing apparatus 100 does not require a lengthy curing time unlike the conventional SLA3D printing apparatus, and can show high precision on the surface of the final shape. The second light source 115 enables the 3D printing apparatus 100 to operate in an SLA3D printing mode.
The area or volume of the core portion of the final shape cured by the first light source 110 and the shell portion of the final shape cured by the second light source 115 may vary according to the setting of the control part 120. For example, depending on the setting of the control portion 120, the shell portion may refer to a portion from the outermost peripheral surface to 10% of the total volume of the final shape.
As an example of the wavelength band for curing the composition, the first light source 110 and the second light source 115 may irradiate light or laser light having a wavelength of 405nm, but is not necessarily limited thereto.
The control part 120 causes the first light source 110 and the second light source 115 to be alternately operated or simultaneously operated to cure the composition into a final shape.
The control part 120 may set an area or volume of the core portion of the final shape cured by the first light source 110 and an area or volume of the shell portion of the final shape cured by the second light source 115.
The control section 120 alternately operates the first light source 110 and the second light source 115. As previously described, the first light source 110 first cures the final shaped core portion in each layer, and thereafter, the second light source 115 cures the final shaped shell portion in each layer. The control part 120 controls the motor 130 to move the first light source 110, the second light source 115, or the container containing the composition so that the first light source 110 and the second light source 115 can be alternately operated to cure the composition. In the case where the first light source 110 and the second light source 115 are both located on the same optical axis or a certain region of the optical axis in order to cure the composition by the first light source 110 and the second light source 115, respectively, light or laser light irradiated from one light source may be disturbed by the other light source. In order to prevent such a problem, the control section 120 controls the motor 130 to move the first light source 110 or the second light source 115, thereby moving the other light source located on the optical axis when one light source irradiates light. Alternatively, the control unit 120 controls the motor 130 to move the container containing the composition, and thereby moves the container containing the composition onto the optical axis of each of the light sources arranged to have different optical axes. Thus, the first light source 110 and the second light source 115 do not interfere with each other, and each can completely irradiate light to the composition.
The control section 120 causes the first light source 110 and the second light source 115 to operate simultaneously. Unlike the foregoing, each of the first light source 110 and the second light source 115 may be disposed within a range that does not affect the optical axis of each other or move within the range. In this case, in order to increase the curing speed of the composition, the control part 120 causes the first light source 110 and the second light source 115 to simultaneously operate so that the curing of the composition corresponding to the shape of the core and the shell of the final shape is simultaneously performed.
The control unit 120 may control the motor 130 to control the respective light sources 110, 115 to be close to the container containing the composition or to control the container containing the composition to be close to the respective light sources 110, 115. Depending on the kind or nature of the light source used, there are cases where curing is performed only if the light source and the composition are in close proximity or even in a state where the light source is immersed in the composition. In this case, each light source 110, 115 and the container containing the composition must be either close to or remote from each other. The control unit 120 may control the motor 130 to control the respective light sources 110, 115 to approach or separate from the container. Instead, the control section 120 may control the motor 130 to control the container toward or away from each of the light sources 110, 115.
The control part 120 controls the first light source 110 and the second light source 115 to cure the composition in layers. The control part 120 divides the final shape into horizontal layers that each light source can cure in one operation. Thereafter, the control unit 120 controls the light sources 110 and 115 so that the composition can be cured in the same manner as the layers of the final shape. First, the control unit 120 controls the first light source 110 to cure the composition into the same shape as the core in the specific layer of the final shape. At the same time or thereafter, the control section 120 controls the second light source 115 to solidify the composition into the same shape as the shell in the specific layer of the final shape. After curing is completed for a specific layer, the control section 120 determines whether the layer after curing is completed is a final layer. If the cured layer is the final layer, the control unit 120 ends the curing because the entire curing is completed by the light sources 110 and 115. In contrast, in the case where the cured layer is not the final layer, the control section 120 controls each light source 110, 115 so that each light source 110, 115 cures the composition in accordance with the next layer.
The motor 130 moves each of the light sources 110, 115 or the container containing the composition under the control of the control section 120. The motor 130 moves each light source 110, 115 or the container containing the composition to enable each light source 110, 115 to alternately cure the composition and moves each light source 110, 115 or the container containing the composition to enable each light source 110, 115 to cure the composition in close proximity to the composition.
Fig. 2 is a diagram illustrating one specific implementation of a3D printing apparatus according to one embodiment of the present invention.
First, the first light source 110 irradiates light to the composition 220 in the container 210 to simultaneously cure the composition corresponding to the area 230 of the core in the specific layer of the final shape. At this time, the control part (not shown) can control the second light source 115 to be away from the optical axis of the first light source 110 such that the light irradiated from the first light source 110 can be completely irradiated to the composition 220 without being disturbed by the second light source 115. At this time, the control unit (not shown) can control the motor (not shown) to move the container 210 so as to bring the first light source 110 and the container 210 closer together.
Thereafter, the second light source 120 irradiates light to the composition 220 to cure the composition corresponding to the shell 240 in the specific layer of the final shape. The control unit (not shown) controls the motor (not shown) to move the second light source 120 again to a position where the laser light irradiated from the second light source 120 can be incident on the composition so that the second light source 120 can cure the composition. The control unit (not shown) can control the motor (not shown) to move the container 210 so that the second light source 115 and the container 210 come close to each other.
In this way, the 3D printing apparatus 100 alternately cures the composition by the first light source 110 and the second light source 115, thereby enabling to secure a level of both excellent curing speed and quality.
Although fig. 2 illustrates only an example in which the first light source 110 and the second light source 115 are alternately operated, the present invention is not necessarily limited thereto, and the second light source 115 is disposed in a range that does not affect or move within an optical axis to which the first light source 110 irradiates, so that the first light source 110 and the second light source 115 can be operated simultaneously. Although the second light source 115 and the container 210 are illustrated as moving, this is not necessarily the case.
Fig. 3 is a flowchart illustrating a method of curing a3D printing composition by a3D printing device according to one embodiment of the present invention.
The control part 120 controls the first light source 110 to irradiate light to cure the core part (S310). The control part 120 controls the first light source 110 to irradiate a certain area of light to the composition. The first light source 110 irradiates a certain area of light to the composition, thereby simultaneously curing the composition corresponding to the area of the core in a specific layer of the final shape.
The control part 120 controls the motor 130 such that the second light source 115 is put on the optical axis of the first light source 110 (S320).
The control part 120 controls the second light source 115 to irradiate light to cure the shell portion (S330). The control unit 120 controls the second light source 115 to irradiate the composition with laser light having one focal point from the second light source 115. The second light source 115 irradiates laser light focused to one focal point, and moves the focal point under the control of the control part 120 to cure the composition to the shape of the shell part of the final shape.
The control unit 120 determines whether or not the cured layer is a final layer (S340). The control part 120 determines whether the layer cured by the first and second light sources 110 and 115 is a final layer of a final shape. If the cured layer is the final layer, the control unit 120 ends the curing because all curing is completed by the light sources 110 and 115.
If the cured layer is not the final layer, the control unit 120 controls the motor to move the light source or the container so that the next layer of the cured layer can be cured (S350). In the case where the cured layer is not the final layer, the next layer must be cured. Accordingly, the control part 120 controls the motor to move the light source or the container so that the curing process of S310 to S330 can be performed on the next layer.
Fig. 4 is a flowchart illustrating a method of curing a3D printing composition by a3D printing device according to another embodiment of the present invention.
The control part 120 controls the first and second light sources 110 and 115 to irradiate light to cure the core and shell parts (S410). The control part 120 controls the first light source 110 and the second light source 115 to simultaneously operate to simultaneously cure the compositions corresponding to the core part and the shell part.
The control unit 120 determines whether or not the cured layer is a final layer (S420).
If the cured layer is not the final layer, the control unit 120 controls the motor to move the light source or the container so that the next layer of the cured layer can be cured (S430). In the case where the cured layer is not the final layer, the next layer must be cured. Accordingly, the control part 120 controls the motor to move the light source or the container so that the curing process of S410 can be performed on the next layer.
The composition 220 according to an embodiment of the present invention, which is cured by the 3D printing apparatus 100 to be formed into a final shape, has transparent characteristics and has characteristics of being cured by both the light source of the DLP 3D printing mode and the light source of the SLA3D printing mode.
Composition 220 comprises monofunctional monomers (Monomers), difunctional monomers, oligomers (Oligomers), initiators, photosensitizers, and other additives.
The monofunctional monomer uses an epoxy-based or ether-based monomer and contains 10 to 20 parts by weight. The monofunctional monomer is added to the composition 220 in order to adjust the viscosity of the composition. In the case where the viscosity of the composition is too high, it is difficult to handle the composition when the 3D printing device performs 3D printing using the composition. To prevent this problem, a monofunctional monomer is additionally contained independently of the difunctional monomer in order to prevent the viscosity of the composition from becoming excessively high. However, the monofunctional monomer contains only 10 to 20 parts by weight to prevent the strength of the composition from decreasing and yellowing.
The difunctional monomer uses an acrylic monomer and contains 20 to 50 parts by weight.
Difunctional monomers are the components that are the largest in content in the composition and form the backbone (Main Chain), which corresponds to the Main component that affects the overall reactivity and clarity of the composition. If it is said that the existing composition includes only specific components without distinguishing the monofunctional monomer and the difunctional monomer, the composition 220 includes the monofunctional monomer and the difunctional monomer and includes only a certain part by weight, respectively. Since different kinds of monomers are contained in the composition 220, the viscosity and reactivity of the composition can be controlled separately.
The acrylic monomer used as the difunctional monomer consists of the newly synthesized bisphenol Z (BPZ) series, rather than the existing bisphenol a (BPA) series. Monomers of the bisphenol Z series to be used as difunctional monomers were prepared by the following procedure.
The second bisphenol Z (BPZ (EO), a post-reaction substance, was synthesized by adding Ethylene Oxide (EO) to the existing bisphenol Z (pre-reaction substance).
To both end (-OH) groups of the synthesized second bisphenol Z, acrylate (Acrylate) functional groups capable of Polymerization (Polymerization) were added to synthesize a third bisphenol Z (BPZ (EO) Ac).
Since the thus newly synthesized acrylic monomer (third bisphenol Z) is used as a difunctional monomer, the composition 220 has advantages of high transparency, strength and abrasion resistance.
The oligomer uses epoxy acrylate and urethane acrylate and contains 30 to 50 parts by weight.
Oligomers are components that affect the mechanical physical properties of the composition, such as strength. However, yellowing may occur in the case where an excessive amount of the oligomer is contained, and thus the oligomer is contained in an amount of 30 to 50 parts by weight.
Epoxy acrylates and urethane acrylates are used as the oligomer. Since urethane acrylates are mainly affected by light sources of the DLP 3D printing system, it is not possible to use only urethane acrylates as oligomers in order to cure the composition also by light sources of the SLA3D printing system. Therefore, the oligomer includes not only urethane acrylate but also epoxy acrylate reactive to both the DLP 3D printing light source and the SLA3D printing light source.
The initiator contains both a radical initiator component and a cationic initiator component and is contained in an amount of 5 parts by weight or less.
An initiator is a substance that initiates a reaction in a specific wavelength band. The polymerization reaction is a chain reaction, and the initiator initiates a reaction by a light reaction of a specific wavelength band.
As the initiator, an initiator containing both a radical initiator component and a cationic initiator component is used. Because both components are contained, the initiator can initiate reaction under the action of the light source of the DLP 3D printing mode and the light source of the SLA3D printing mode.
The pigment is contained in an amount of 1 part by weight. The pigment has an effect of improving color, although there is a possibility that transmittance and reaction speed of light in a visible light band are reduced by a certain level. Thus, small amounts of pigments may be included in the composition.
As the photosensitizer, a silane coupling agent may be used and contained within 1 part by weight. The photosensitizer absorbs light of a specific wavelength, thereby enabling to minimize the phenomenon of light divergence at the time of 3D printout. Thus, the photosensitizer improves the accuracy of the final shape. In addition, the photosensitizer suppresses the reaction rate, and thus can prevent excessive reaction. Since the photosensitizer suppresses the reaction rate, it is preferably contained in an amount of 1 part by weight or less as described above.
Further, other additives may be further included depending on the desired properties.
The following description will be made by comparing examples of the present invention and comparative examples in which the blending ratios of the respective components are different from each other.
Example 1
Compositions were prepared according to the compounding ratios disclosed in the following table.
Example 2
Compositions were prepared according to the compounding ratios disclosed in the following table.
Example 3
Compositions were prepared according to the compounding ratios disclosed in the following table.
Example 4
Compositions were prepared according to the compounding ratios disclosed in the following table.
Example 5
Compositions were prepared according to the compounding ratios disclosed in the following table.
Example 6
Compositions were prepared according to the compounding ratios disclosed in the following table.
Example 7
Compositions were prepared according to the compounding ratios disclosed in the following table.
In contrast, the blending ratio of each comparative example is as follows.
Comparative example 1
Compositions were prepared according to the compounding ratios disclosed in the following table.
Comparative example 2
Compositions were prepared according to the compounding ratios disclosed in the following table.
Comparative example 3
Compositions were prepared according to the compounding ratios disclosed in the following table.
Comparative example 4
Compositions were prepared according to the compounding ratios disclosed in the following table.
Comparative example 5
Compositions were prepared according to the compounding ratios disclosed in the following table.
Experiments were performed on physical properties of the compositions prepared in the compounding ratios of examples 1 to 7 and the compositions prepared in the compounding ratios of comparative examples 1 to 5. The experimental results are shown in the tables disclosed below. The case where no additional description is given in the remarks corresponds to the case where post-curing for 30 minutes is performed.
It was confirmed that the tensile strength of the compositions cured by blending in the proportions of examples 1 to 6 was 46 to 53MPa, whereas the tensile strength of the compositions cured by blending in the proportions of comparative examples was 7 to 41MPa, which had a considerably low tensile strength. The reason why the cured compositions prepared by blending in the proportions of examples 1 to 6 have excellent tensile strength is considered to be that the oligomer is contained in an appropriate weight part and the bifunctional monomer is contained in an appropriate weight part.
It was confirmed that the compositions cured by compounding in the compounding ratios of examples 1 to 6 all had excellent elongation at a level of 3 to 8, whereas the compositions cured by compounding in the compounding ratios of comparative examples had low elongation at a level of approximately 1 to 2. Although it was confirmed that the composition cured by blending in the compounding ratio of comparative example 5 had a high elongation of 34.65, this was a result of extremely low tensile strength, and therefore was excluded from the elongation judgment.
In addition, it was confirmed that each of the compositions cured by blending in the proportions of examples 1 to 5 had flexural strengths of 117 to 134MPa, whereas each of the compositions cured by blending in the proportions of comparative examples did not have flexural strengths.
Referring to the results of such experiments, it is apparent that the composition according to the present embodiment has transparent characteristics and has quite excellent physical properties even without performing an additional post-treatment process.
In fig. 3 and 4, each process is described as being performed in sequence, but this is merely illustrative of the technical idea of one embodiment of the present invention. In other words, the order described in fig. 3 and 4 or the order in which one or more of the processes are executed in parallel can be modified and modified variously by a person skilled in the art without departing from the essential characteristics of one embodiment of the present invention, and thus fig. 3 and 4 are not limited to the time-series order.
On the other hand, each of the processes illustrated in fig. 3 and 4 may be embodied by computer readable codes in a computer readable recording medium. The computer-readable recording medium includes all types of recording devices that store data that can be read by a computer system. That is, the computer-readable recording medium includes storage media such as magnetic storage media (e.g., ROM, floppy disks, hard disks, etc.) and optical read-out media (e.g., CD-ROMs, DVDs, etc.). In addition, the computer-readable recording medium may store and execute codes which are distributed in computer systems connected through a network and are readable by computers in a distributed manner.
The above description is merely illustrative of the technical idea of the present embodiment, and a person of ordinary skill in the art can make various modifications and variations within a range that does not escape from the essential characteristics of the present embodiment. Accordingly, the embodiments of the present invention are intended to illustrate the technical idea of the present invention, and not to limit the technical idea of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of the present invention should be construed by the appended claims, and all technical ideas falling within the scope equivalent thereto should be construed to be included in the scope of the claims.
Cross Reference to Related Applications
If the present patent application claims priority for korean application No. 10-2018-0172241 on 12 months of 2018 according to U.S. patent law, item 119 (a) (35 u.s.c. ≡119 (a)), the entire contents thereof are incorporated herein by reference. And, if the present patent application also claims priority to countries other than the united states for the same reasons as described above, all of the contents thereof are incorporated by reference into the present patent application.
Claims (2)
1. A three-dimensional printing composition used as a raw material for SLA3D printing and DLP 3D printing, characterized in that,
the composition for three-dimensional printing contains 10 to 20 parts by weight of a monofunctional monomer as an epoxy monomer or an ether monomer, 20 to 50 parts by weight of a difunctional monomer as a bisphenol Z-series monomer, 30 to 50 parts by weight of an oligomer as an epoxy acrylate and a urethane acrylate, 5 parts by weight or less of an initiator containing a radical initiator component and a cationic initiator component, and 1 part by weight or less of a photosensitizer as a silane coupling agent.
2. The three-dimensional printing composition according to claim 1, wherein,
the three-dimensional printing composition further comprises a pigment.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2018-0172241 | 2018-12-28 | ||
| KR1020180172241A KR102152043B1 (en) | 2018-12-28 | 2018-12-28 | Composition for 3D Printer |
| PCT/KR2019/009447 WO2020138621A1 (en) | 2018-12-28 | 2019-07-29 | Three-dimensional printing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113166291A CN113166291A (en) | 2021-07-23 |
| CN113166291B true CN113166291B (en) | 2023-05-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980077790.4A Active CN113166291B (en) | 2018-12-28 | 2019-07-29 | Composition for three-dimensional printing |
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| Country | Link |
|---|---|
| JP (1) | JP7249694B2 (en) |
| KR (1) | KR102152043B1 (en) |
| CN (1) | CN113166291B (en) |
| WO (1) | WO2020138621A1 (en) |
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| CN101384959A (en) * | 2006-05-01 | 2009-03-11 | Dsmip财产有限公司 | Radiation curable resin composition and rapid three dimensional imaging process using the same |
| CN101755238A (en) * | 2007-04-13 | 2010-06-23 | 亨斯迈先进材料美国有限责任公司 | Dual photoinitiator, photo curable composition, their purposes and the method for preparing three-dimensional article |
| KR20160058595A (en) * | 2014-11-17 | 2016-05-25 | 대한잉크 주식회사 | The 3D Full Color Ink Composition and 3D soft sculpture formed by using the same |
| WO2016199611A1 (en) * | 2015-06-08 | 2016-12-15 | 富士フイルム株式会社 | Active light-curable inkjet ink set for three-dimensional printing, three-dimensional printing method and three-dimensional printing system |
| EP3321002A1 (en) * | 2016-11-15 | 2018-05-16 | Höganäs AB | Feedstock for an additive manufacturing method, additive manufacturing method using the same, and article obtained therefrom |
| WO2018105463A1 (en) * | 2016-12-05 | 2018-06-14 | Dic株式会社 | Photocurable resin composition for optical stereolithography |
| JP2018130883A (en) * | 2017-02-15 | 2018-08-23 | セイコーエプソン株式会社 | Inkjet method |
-
2018
- 2018-12-28 KR KR1020180172241A patent/KR102152043B1/en active IP Right Grant
-
2019
- 2019-07-29 JP JP2021534320A patent/JP7249694B2/en active Active
- 2019-07-29 CN CN201980077790.4A patent/CN113166291B/en active Active
- 2019-07-29 WO PCT/KR2019/009447 patent/WO2020138621A1/en active Application Filing
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|---|---|---|---|---|
| CN101384959A (en) * | 2006-05-01 | 2009-03-11 | Dsmip财产有限公司 | Radiation curable resin composition and rapid three dimensional imaging process using the same |
| CN101755238A (en) * | 2007-04-13 | 2010-06-23 | 亨斯迈先进材料美国有限责任公司 | Dual photoinitiator, photo curable composition, their purposes and the method for preparing three-dimensional article |
| KR20160058595A (en) * | 2014-11-17 | 2016-05-25 | 대한잉크 주식회사 | The 3D Full Color Ink Composition and 3D soft sculpture formed by using the same |
| WO2016199611A1 (en) * | 2015-06-08 | 2016-12-15 | 富士フイルム株式会社 | Active light-curable inkjet ink set for three-dimensional printing, three-dimensional printing method and three-dimensional printing system |
| EP3321002A1 (en) * | 2016-11-15 | 2018-05-16 | Höganäs AB | Feedstock for an additive manufacturing method, additive manufacturing method using the same, and article obtained therefrom |
| WO2018091517A1 (en) * | 2016-11-15 | 2018-05-24 | Höganäs Ab | Feedstock for an additive manufacturing method, additive manufacturing method using the same, and article obtained therefrom |
| WO2018105463A1 (en) * | 2016-12-05 | 2018-06-14 | Dic株式会社 | Photocurable resin composition for optical stereolithography |
| JP2018130883A (en) * | 2017-02-15 | 2018-08-23 | セイコーエプソン株式会社 | Inkjet method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102152043B1 (en) | 2020-09-04 |
| WO2020138621A1 (en) | 2020-07-02 |
| JP2022513909A (en) | 2022-02-09 |
| KR20200087314A (en) | 2020-07-21 |
| JP7249694B2 (en) | 2023-03-31 |
| CN113166291A (en) | 2021-07-23 |
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