KR20170009427A - Filament composition for 3 dimensional print comprising nanocrystalcellulose and red algae fiber - Google Patents
Filament composition for 3 dimensional print comprising nanocrystalcellulose and red algae fiber Download PDFInfo
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- KR20170009427A KR20170009427A KR1020150101455A KR20150101455A KR20170009427A KR 20170009427 A KR20170009427 A KR 20170009427A KR 1020150101455 A KR1020150101455 A KR 1020150101455A KR 20150101455 A KR20150101455 A KR 20150101455A KR 20170009427 A KR20170009427 A KR 20170009427A
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- nanocrystalline cellulose
- filament
- red algae
- cellulose
- fiber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- B29C67/0085—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The present invention relates to a three-dimensional printing filament composition comprising a thermoplastic or photocurable resin mixed with nanocrystalline cellulose and red algae fiber. Since the nanocrystalline cellulose and red algae fibers contained in the three-dimensional printing filament composition are stronger than aluminum or iron in tensile strength, there is an advantage that a three-dimensional printed matter having high strength can be obtained. In addition, nanocrystalline cellulose and red algae fiber Because it is biodegradable, it is also suitable as an environmentally friendly material.
Description
The present invention relates to a three-dimensional printing filament composition comprising a thermoplastic or photocurable resin mixed with nanocrystalline cellulose and red algae fibers.
3D (3 Dimension, 3D) printing is a printing technique that prints the output in a three-dimensional manner by stacking plastics in the Z-axis direction instead of ordinary ink and adjusting the height. 2D printers print pictures or type on a plane consisting of x and y axes, but 3D printers sequentially move inks of special materials and accumulate layers with fine thickness and move in x, y, Dimensional object. Therefore, 3D printing technology is widely used in various fields, so it is a next generation printing method, and it is a technology field with excellent prospect and high possibility of development. An example of a field in which three-dimensional printing technology is utilized is an automobile field composed of a plurality of parts, a medical human body model, a design of a building, and various models of a design product.
3D printers are divided into FDM (Fused Deposition Modeling), SLS (Selective Laser Sintering), SLA (Sereolithography Appartus), DLP (Digital Light Processing) and polyjet depending on the output method. SLS / SLA method is divided into nylon, The DLP (Digital Light Processing) method is a method in which a liquid or powder is sprayed and then light is hardened. In general, the most commonly used FDM Fused deposition modeling method is to heat and extrude thin thermoplastic plastic filaments into a semi-molten state and laminate one by one along a path that is produced by a computer to form a desired shape product.
Currently, most of the materials used in 3D printing are photopolymer, a photocurable polymer that solidifies when exposed to light, accounting for more than 50% of the total market, followed by solid thermoplastics in melting and solidification It occupies about 40% of the market and is still weak, but metal powder is also growing.
Currently, 3D printers for home use mainly filament type plastic materials, and the most commonly used filament materials are polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polyphenylene sulfide (PPS) polyetherimide). They have a high melting point and a high solidification speed after printing, so that even if the printing speed is fast, they are not deformed and their dimensional and shape stability are good. In addition, although the melting point is moderately low, extrusion is easy and production efficiency is high in manufacturing filaments. However, it is not suitable for 3D printing such as infant models requiring a soft touch, a work model of a school, shoes or toys, There is a disadvantage that the diameter is not constant and the thickness to be laminated becomes too thick when extruded by extrusion into a filament form. Further, development of filament materials in various aspects such as durability of filament as well as biodegradability of filament is still required.
One example of a technology relating to a currently known three-dimensional printing filament composition is Korean Patent Laid-Open Publication No. 2015-0039554, which discloses a multi-color ink, a three-dimensional printer and a three-dimensional printer control method for three- -1118095 discloses a curable composition for three-dimensional printing, and Korean Patent No. 1394119 discloses a composition for a three-dimensional printer filament. However, a filament composition for three-dimensional printing including nanocrystal cellulose and red algae fibers Is not known.
The present invention provides a three-dimensional printing filament composition comprising a thermoplastic or photocurable resin mixed with nanocrystalline cellulose and red algae fiber. The present invention relates to a three-dimensional printing filament composition comprising nanocrystal cellulose and red algae fiber, Confirming that the tensile strength is higher than that of aluminum or iron, and fabricating a three-dimensional printing filament composition containing nanocrystal cellulose and red algae fiber and a filament using the same.
In order to accomplish the above object, the present invention provides a three-dimensional printing filament composition comprising a thermoplastic or photocurable resin mixed with nanocrystalline cellulose and red algae fiber.
The present invention also provides a filament comprising the filament composition for three-dimensional printing.
The present invention also provides a method for producing a three-dimensional object, comprising the steps of: (1) producing a three-dimensional object using a three-dimensional printing machine using a filament containing nanocrystalline cellulose and red algae fiber; And
(2) irradiating the three-dimensional object generated in the step (1) with light selected from ultraviolet light and electron beam, or curing the object in a temperature condition of 50 to 300 ° C or less, The method comprising the steps of:
The present invention relates to a three-dimensional printing filament composition comprising a thermoplastic or photocurable resin mixed with nanocrystalline cellulose and red algae fibers. The filament manufactured using the three-dimensional printing filament composition according to the present invention uses natural materials of nanocrystal cellulose and red algae fiber, so that it is possible to print a three-dimensional printed material that is not only environmentally friendly but also strong.
The present invention relates to a three-dimensional printing filament composition comprising a thermoplastic or photocurable resin mixed with nanocrystalline cellulose and red algae fibers.
The filament composition for three-dimensional printing according to an embodiment of the present invention preferably has 1 to 30 parts by weight of nanocrystalline cellulose and 1 to 30 parts by weight of algae fiber based on 100 parts by weight of the resin, The resin can be selected from the group consisting of acrylonitrile butadiene styrene (ABS), nylon, polylactic acid (PLA), polycarbonate (PC), polyphenylene sulfide (PPS), polyetherimide, polyvinyl chloride, polyethylene, polystyrene polystyrene, and acrylic resin, but is not limited thereto.
The three-dimensional printing filament composition according to an embodiment of the present invention may further include at least one selected from a photo initiator, a reactive wax, and a gelling agent in addition to the thermoplastic or photocurable resin mixed with the nanocrystalline cellulose and red algae fiber .
In the present invention, photoinitiator refers to a substance that initiates polymerization reaction by absorbing light energy such as ultraviolet rays or a laser. The photoinitiator may vary depending on the type of resin, but the photoinitiator may be contained in an amount of 0.1 to 5 wt% Preferred examples of the photoinitiator include alpha-hydroxy ketone, alpha-amino ketone, benzophene, thioxanthone, phenylglycine, Phenyl glyoxylate, acryl phosphine oxide and benzyl dimethyl ketal (BDK), more preferably 1-phenyl-2-hydroxy-2-methylpropane Hydroxy-2-methyl propane-1-one, Darocure 1173, HMPP, 1-hydroxycyclohexyl phenyl ketone, Irgacure 184, HCPK, alpha -amino acetophenone (2-ETAQ, 2-Ethylthraquinone) selected from the group consisting of benzoic acid, ophenone, Irgacure-907, Benzyl Dimethyl Ketal, Irgacure-651, BenzoPhenone, Thioxanthone and 2- One or more photoinitiators may be selected and used, but are not limited thereto.
The reactive wax is a curable wax component which can be mixed with other components contained in the 3D printing filament composition of the present invention and can be polymerized with a curable monomer to form a polymer. Examples of the reactive wax include acrylate, methacrylate, alkene, allyl ether, but not limited thereto. The reactive wax may contain 1 to 25% by weight of the filament composition, preferably 2 to 20% % Of reactive wax, and more preferably 2.5 to 15% by weight of the composition.
The gelling agent is a material that causes the 3D printing filament composition of the present invention to form an anti-solid gel at a temperature lower than a specific temperature. Preferable examples of the gelling agent include a curable amide, a curable polyamide-epoxy acrylate component, and a poly A curable gelling agent composed of an amide component; A curable composite gelling agent composed of a curable epoxy resin and a polyamide resin; Mixtures thereof, but are not limited thereto.
The light is preferably ultraviolet light or electron beam, and heat is preferably applied at a temperature of 50 to 300 ° C, but is not limited thereto.
The nanocrystalline cellulose used in the present invention is a cellulose fiber having acyl hydrolyzed to form needle-like high-strength nanocrystalline cellulose having a width of 5 to 200 nm, a length of 1 탆 or less, and 95% But it is not limited to the nanocrystalline cellulose of crystal form to be measured.
In the filament composition for three-dimensional printing according to an embodiment of the present invention,
The nanocrystalline cellulose comprises: (1) adding a strong acid to a cellulosic fiber from which lignin is removed and reacting;
(2) repeating centrifugation and dialysis after the reaction of step (1) to purify nanocrystalline cellulose;
(3) adjusting the mixed solution of nanocrystalline cellulose to pH 7.0 in step (2);
(4) vacuum drying the nanocrystal cellulose contained in the supernatant liquid having the pH adjusted to 7.0 in the step (3) so that the concentration of the nanocrystal cellulose is 2% (w / v) or more; And
(5) lyophilizing the solution containing the vacuum-dried nanocrystalline cellulose; and
In step (1), the reaction is preferably carried out at 50 ° C. for 40 to 50 minutes. However, the reaction is not limited thereto, and the strong acid is preferably sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or a mixture thereof, more preferably 65 % Sulfuric acid, but is not limited thereto.
In the above step (3), it is preferable, but not limited, to take the supernatant which has been pulverized by the formation of nanocrystalline cellulose and treat the caustic soda to pH 7.0. The nanocrystalline cellulose is very small in size and has no problems in the production of a three-dimensional printing filament including a synthetic resin. The strength is superior to that of stainless steel and exhibits a strength close to that of carbon nanotubes. Because of its biodegradability, It is advantageous for the construction of the structure.
In the three-dimensional printing filament composition according to one embodiment of the present invention, the length of the red algae fiber is preferably 50 to 800 탆, the width is 1 to 3 탆, more preferably the length of the red algae fiber is 50 to 300 탆 And the width is 1 to 3 탆, but the present invention is not limited thereto, and the length of the red algae fiber is measured by drying.
The kind of the red algae fiber is preferably extracted from at least one member selected from the group consisting of Kim, Ugukgasari, Kwangwoo, Kwangwoo, Koiwara, Kashiwumu, , And more preferably, it is extracted from Mugwort.
The mixture of the nanocrystalline cellulose and the red algae fiber has a very high strength, is biodegradable, and is a mixture of materials having different sizes. The nanocrystalline cellulose improves the strength and the red algae fiber increases the elongation, .
The present invention also relates to a filament containing the filament composition for three-dimensional printing. The filament is preferably a FDM (Fused Deposition Modeling) method or a Polyjet type 3D printer, but is not limited thereto.
The present invention also provides a method for producing a three-dimensional object, comprising the steps of: (1) producing a three-dimensional object using a three-dimensional printing machine using a filament containing nanocrystalline cellulose and red algae fiber; And
(2) irradiating the three-dimensional object generated in the step (1) with light selected from ultraviolet light and electron beam, or curing the object in a temperature condition of 50 to 300 ° C or less, And a method for manufacturing the same.
Claims (8)
(2) repeating centrifugation and dialysis after the reaction of step (1) to purify nanocrystalline cellulose;
(3) adjusting the mixed solution of nanocrystalline cellulose to pH 7.0 in step (2);
(4) vacuum drying the nanocrystal cellulose contained in the supernatant liquid having a pH adjusted to 7.0 in the step (3) so that the concentration of the nanocrystal cellulose is 2% (w / v) or more; And
(5) lyophilizing the solution containing the vacuum-dried nanocrystalline cellulose.
(2) irradiating the three-dimensional object generated in the step (1) with light selected from ultraviolet light and electron beam, or curing the object in a temperature condition of 50 to 300 ° C or less, .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150101455A KR20170009427A (en) | 2015-07-17 | 2015-07-17 | Filament composition for 3 dimensional print comprising nanocrystalcellulose and red algae fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150101455A KR20170009427A (en) | 2015-07-17 | 2015-07-17 | Filament composition for 3 dimensional print comprising nanocrystalcellulose and red algae fiber |
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| Publication Number | Publication Date |
|---|---|
| KR20170009427A true KR20170009427A (en) | 2017-01-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020150101455A KR20170009427A (en) | 2015-07-17 | 2015-07-17 | Filament composition for 3 dimensional print comprising nanocrystalcellulose and red algae fiber |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822511A (en) * | 2018-04-17 | 2018-11-16 | 广州科苑新型材料有限公司 | A kind of preparation method of the full biomass 3D printing nano combined wire rod of PLA |
| CN114304553A (en) * | 2022-01-17 | 2022-04-12 | 郑州轻工业大学 | Preparation method of pitaya dietary fiber 3D printing powder |
-
2015
- 2015-07-17 KR KR1020150101455A patent/KR20170009427A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822511A (en) * | 2018-04-17 | 2018-11-16 | 广州科苑新型材料有限公司 | A kind of preparation method of the full biomass 3D printing nano combined wire rod of PLA |
| CN114304553A (en) * | 2022-01-17 | 2022-04-12 | 郑州轻工业大学 | Preparation method of pitaya dietary fiber 3D printing powder |
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