TW201927519A - 3D printing material with ceramic powder additive - Google Patents

Abstract

A 3D printing material with a ceramic powder additive contains from about 11% to about 40% matrix materials by volume; from about 60% to about 89% ceramic powder by volume; from about 3 to 5 phr of a flexibilizer; and from about 0.25 to 1.5 phr of a lubricant. The matrix materials are selected from the group consisting of aliphatic polyester, polyamide, thermoplastic elastic solid and water-soluble material. The ceramic powder is selected from the group consisting of zirconium oxide, silicon dioxide and alumina. The exterior surface of the 3D printing product made of disclosed 3D printing material presents ceramic-like color and gloss and renders texture and touch of a ceramic object.

Description

Adding a layered printing material of ceramic powder

The present invention relates to a composition ratio of a laminate printing material which can directly produce a ceramic color, texture and feel on a 3D printed product.

The 3D printing technology currently used is an emerging technology. Due to its wide range of products, from small to small components to mechanical models, it can be achieved through 3D printing technology. Due to the 3D printing technology, a 3D printing machine is used to melt the laminated printing material, and then the layer printing is performed to produce a 3D object. However, when the above-mentioned 3D printed laminated printed material structure is used, it has only a change in color, and does not have a special texture and a change in touch.

Therefore, there is a patent for the invention of the method of manufacturing a three-dimensional printed article and a method for manufacturing a three-dimensional printed wire, disclosed in the publication No. 201643034 of the Republic of China on December 16, 105, which discloses: providing a ceramic powder and a first Polymer materials are used as a raw material. The weight percentage of the ceramic powder in the raw material is between about 60% and 85%, and the weight percentage of the first polymer material in the raw material is between about 15% and 40%. The raw material is ejected into a three-dimensional printing wire by injection molding. The ceramic powder comprises alumina, zirconia or a mixture of the two. The material of the first polymer material includes acrylonitrile-butadiene-styrene terpolymer (ABS), polylactic acid (PLA), polypropylene (PP), and high density. High density polyethylene (HDPE), nylon (nylon), polyvinyl alcohol (PVA) or a mixture of at least two of the above materials. The ceramic powder and the first polymer material are heated to a temperature higher than a melting temperature of the first polymer material (for example, about 180 ° C to 220 ° C) and kneaded to obtain a fluid material. The kneading method is carried out, for example, using a kneader equipped with an injection machine or a plastic injection machine. Next, the fluid material is extruded into a three-dimensional printing line. The method of extrusion is carried out, for example, using a device such as a plastic injection machine.

However, the patent does not disclose the addition of tougheners and lubricants. Therefore, the material produced is too brittle and fragile, and it is impossible to produce the color, touch and texture of the ceramic material.

There is also a patent of the "Three-Dimensional Printed Wire" of Invention No. 201711830 published by the Republic of China on April 1, 106, which discloses that it is suitable for forming a three-dimensional printed object through a fused deposition technique. The three-dimensional printing wire material includes a polymer material and a nano ceramic powder mixed in the polymer material. The weight percentage of the nano ceramic powder in the three-dimensional printing wire is between about 0.2% and 10%. The material of the above nano ceramic powder includes ceria, zirconia or alumina. The above three-dimensional printing wire further comprises a lubricant mixed in the polymer material, wherein the weight percentage of the lubricant in the three-dimensional printing wire is between about 0.1% and 1%. The lubricant includes paraffin wax, potassium stearate, zinc stearate or calcium stearate.

However, the patent application does not disclose the addition of a toughening agent to solve the disadvantage that the material produced is too brittle and fragile, and the proportion of the ceramic powder added is too low, so the strength of the ceramic material cannot be fully exhibited. , color choice, touch and texture. Further, when the content of the ceramic powder is too low, the hardness of the finished product after sintering is insufficient and the abrasion resistance is poor, and thus it is significantly different from the technical features of the present invention.

Therefore, in view of the fact that the surface of the laminate printing material currently used for 3D printing does not have ceramic color, texture and touch. Therefore, the present invention provides a laminated printing material for adding ceramic powder, comprising: a matrix material, which is 11% to 40% by volume, and the matrix material is an aliphatic polyester, a polyamide, a thermoplastic elastomer. Or one of the water-soluble materials or any combination thereof; a ceramic powder, which is 60% to 89% by volume, the ceramic powder is zirconia, ceria or alumina; a toughening agent, which accounts for 3 A portion to 5 phr; a slip agent, which is a portion of 0.25 to 1.5 phr.

The above aliphatic polyester contains one of polylactic acid, polycaprolactone, butane succinate copolymer, biodegradable polyester or polyhydroxybutyrate or any combination thereof.

The above polyamine contains one of nylon 6, nylon 66 or nylon 12 or any combination thereof.

The above thermoplastic elastomer comprises one of thermoplastic elastomers, thermoplastic polyurethanes, thermoplastic rubbers or thermoplastic polyester elastomers, or any combination thereof.

The above water soluble material comprises polyvinyl alcohol.

The toughening agent is composed of acrylic, ethylene propylene rubber, polybutadiene rubber, butyl rubber, nitrile rubber, styrene butadiene rubber, styrene-butadiene thermoplastic elastomer, methyl methacrylate. One of butadiene-styrene terpolymer, acrylonitrile-butadiene-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, polyamine resin or any combination thereof.

The components of the above slip agent are fatty acid esters or alcohols.

The above-mentioned matrix material, the ceramic powder, the toughening agent and the slip agent are mixed according to the above ratio, and then placed in a kneader and kneaded at a processing temperature of 160 ° C to 280 ° C, and the processing time is It is 10 minutes to 15 minutes.

The above technical features have the following advantages:

1. The laminated printing material produced can form a ceramic color on the surface of the product which has been printed by 3D, thereby producing a texture and a touch which are made of real ceramics.

2. Since the 3D column product can fully display the ceramic color which can be found in real ceramics, it can enhance the value of 3D printing products to attract more consumers to purchase, so as to increase sales.

3. It can further replace the use of real ceramic materials to reduce ceramic consumption and protect the earth's resources.

4. It can be stored for a long time without corrosion, and there is no disadvantage that ceramic materials are afraid of moisture and easy oxidation.

Referring to the first figure, the embodiment of the present invention is a multi-layer printing material (1), and the laminated printing material (1) is described by a wire. The system comprises: a matrix material (11), a ceramic powder (12), a toughening agent (13) and a lubricant (14), wherein:

The matrix material (11) is in a percentage by volume of 11% to 40%. The matrix material (11) may be one of aliphatic polyester, polyamine, thermoplastic elastomer or water soluble material or any combination thereof. Wherein the aliphatic polyester comprises polylactic acid (PLA), polycaprolactone (PCL), butyl succinate copolymer (PBS), biodegradable polyester (PBAT) or polyhydroxybutyrate ( PHB) one or any combination thereof (the combination of two or more is also called gelatin). Among them, the polylactic acid is widely used and convenient to use, and the 3D printing material is listed as a preset material by a plurality of 3D printing machines. The advantage of the polylactic acid is that it can be widely used in various fields because it has no odor when printed, and even emits a light sweet taste, and is not easy to curl. There is no need to heat the plate during manufacture, and the finished product is hard. In particular, the polylactic acid is one of biodegradable and environmentally friendly materials, which is derived from mixed corn starch and sugar cane, meets food grade and biodegradable standards, and can fully meet the high environmental protection requirements. And a variety of colors to choose from for 3D printing. Further, the polyamine comprises one of nylon 6 (PA6), nylon 66 (PA66) or nylon 12 (PA12) or any combination thereof. Further, the thermoplastic elastomer comprises one of thermoplastic elastomer (TPE), thermoplastic polyurethane (TPU), thermoplastic rubber (TPR) or thermoplastic polyester elastomer (TPEE), or any combination thereof. Further, the water soluble material comprises polyvinyl alcohol (PVA).

The ceramic powder (12) is 60% to 89% by volume. The ceramic powder (12) may be zirconia, ceria or alumina.

The toughening agent (13) is a fraction of 3 to 5 phr (parts per hundred of resin; that is, phr = the number of parts added per 100 parts by volume of the matrix material and the ceramic powder, so 3 to 5 phr = for each 100 parts by volume of the matrix material and ceramic powder are added with 3 to 5 parts of toughening agent]. The effect of adding the toughening agent (13) is to prevent the wire to be easily broken. The toughening agent (13) is composed of: acrylic oxime, ethylene propylene rubber (EPR), polybutadiene rubber (BB), butyl rubber, nitrile rubber, styrene butadiene rubber, styrene-butyl Ether thermoplastic elastomer (SBS), methyl methacrylate-butadiene-styrene terpolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS), chlorinated polyethylene (CPE) And one of ethylene-vinyl acetate copolymer (EVA), polyamine resin or any combination thereof.

The slip agent (14), also known as a dispersant, is present in an amount of from 0.25 to 1.5 phr. The addition of the slip agent (14) serves to increase the surface smoothness of the 3D printed product. The components of the slip agent (14) are: fatty acid esters or alcohols.

As shown in the first figure, when the laminated printing material (1) is manufactured, the matrix material (11), the ceramic powder (12), the toughening agent (13) and the lubricant (14) are respectively According to the above appropriate ratio, they are mixed and placed in a kneader for kneading. The processing temperature is preferably between 160 ° C and 280 ° C. The processing time is preferably between 10 minutes and 15 minutes. After the above materials are mixed, they form a dough, which is then pelletized by a granulating device, or extruded through a twin-screw extruder to form a strand and then pelletized. As shown in the second figure, it is finally placed in a wire drawing machine to form a disk-shaped laminated printing material (1) for use in 3D printing. The laminated printing material (1) can be changed in accordance with the temperature and speed of the printing of the nozzle of the 3D printing machine. However, the above-described methods for producing and producing the laminated printing material (1) are all conventional manufacturing methods and will not be described again.

Therefore, the laminated printing material produced according to the above embodiment of the present invention has ceramic powder in the composition of the laminated printing material, so that the ceramic color can be formed on the surface of the product which has been printed by 3D printing. In order to produce the texture and touch that is made of real ceramics, it can fully display the ceramic color that real ceramics can have, so as to enhance the value of 3D printing products.

In view of the foregoing description of the embodiments, the operation and the use of the present invention and the effects of the present invention are fully understood, but the above described embodiments are merely preferred embodiments of the present invention, and the invention may not be limited thereto. Included within the scope of the present invention are the scope of the present invention.

(1)‧‧‧Multilayer printing materials

(11)‧‧‧Material materials

(12)‧‧‧Ceramic powder

(13)‧‧‧Toughener

(14) ‧‧ ‧ slip agent

[First Image] is a schematic view showing the composition of a laminate printing material according to an embodiment of the present invention.

[Second diagram] is a schematic view of a laminate printing material produced by an embodiment of the present invention.

Claims (8)

A laminated printing material for adding ceramic powder, comprising: a matrix material, which is 11% to 40% by volume, and the matrix material is an aliphatic polyester, a polyamide, a thermoplastic elastomer or a water-soluble material. One or any combination thereof; a ceramic powder, which is 60% to 89% by volume, the ceramic powder is zirconia, ceria or alumina; and a toughening agent, which is 3 to 5 phr. A slip agent, which is a portion of 0.25 to 1.5 phr. A laminate printing material for adding a ceramic powder according to the first aspect of the invention, wherein the aliphatic polyester comprises polylactic acid, polycaprolactone, butane succinate copolymer, biodegradable polyester or One of polyhydroxybutyrate or any combination thereof. A laminate printing material for adding a ceramic powder according to the first aspect of the invention, wherein the polyamide comprises one of nylon 6, nylon 66 or nylon 12 or any combination thereof. A laminated printing material for adding a ceramic powder according to the first aspect of the invention, wherein the thermoplastic elastomer comprises one of a thermoplastic elastomer, a thermoplastic polyurethane, a thermoplastic rubber or a thermoplastic polyester elastomer or random combination. A laminate printing material for adding a ceramic powder according to the first aspect of the invention, wherein the water-soluble material comprises polyvinyl alcohol. The laminated printing material for adding ceramic powder according to the first aspect of the patent application, wherein the toughening agent is made of acrylic, ethylene propylene rubber, polybutadiene rubber, butyl rubber, nitrile rubber, Styrene-butadiene rubber, styrene-butadiene thermoplastic elastomer, methyl methacrylate-butadiene-styrene terpolymer, acrylonitrile-butadiene-styrene copolymer, chlorinated polyethylene, ethylene- One of vinyl acetate copolymer, polyamine resin or any combination thereof. A laminate printing material in which a ceramic powder is added as described in the first aspect of the invention, wherein the component of the lubricant is a fatty acid ester or an alcohol. The laminated printing material of the ceramic powder according to the first aspect of the invention, wherein the matrix material, the ceramic powder, the toughening agent and the slip agent are mixed according to the above ratio, and then placed It is kneaded in a kneading machine, and its processing temperature is 160 ° C to 280 ° C, and the processing time is 10 minutes to 15 minutes.