KR101689304B1 - Filament composition for 3D printer - Google Patents

Abstract

More particularly, the present invention relates to a filament composition for a 3D printer, which comprises 100 parts by weight of a thermoplastic amorphous resin mixture and 10 to 25 parts by weight of a thermoplastic crystalline resin mixture, wherein the plasticizer, the flame retardant, the antistatic agent, , An inorganic ionic mineral, an antibacterial agent, and an electromagnetic wave shielding agent.
The filament composition for a 3D printer comprising the above components exhibits excellent processability and mechanical properties when applied to a 3D printer, and provides a printed matter exhibiting antistatic, far-infrared radiation and antibacterial effects.

Description

FILAMENT COMPOSITION FOR 3D PRINTER [0002]

The present invention relates to a filament composition for a 3D printer, and more particularly, to a filament composition for a 3D printer, which exhibits excellent workability and mechanical properties when applied to a 3D printer and provides a printed matter exhibiting antistatic, far- .

3D (3-Dimension, 3-D) printers are machines that produce three-dimensional objects by layering layers with fine thickness by sequentially injecting inks of special materials.

3D printer technology is applied to a 3D printer, which is a device for manufacturing three-dimensional objects by stacking materials such as polymer or metal in liquid or powder form by processing and layer-by-layer according to design data. It comes from RP (Rapid Prototyping), which means the technology to rapidly shape the shape to be produced using laser and powder materials.

As opposed to Subtractive Manufacturing, which produces cubic materials by cutting or trimming cubic materials using machining or laser cutting, the official technical term is Additive Fabrication. Additive Fab., Layer Mfg. And Freeform Fab. And the like are mixed.

3D printing technology is spreading in various fields. It is being used by many manufacturers for various models such as development of automobile and aircraft parts, household medical products such as medical human body model, toothbrush and razor. Particularly, the recent trend is that a large number of 3D printers that are widely used for personal use or home use are developed and supplied, and thus, the number of users who manufacture their own designs or ideas, or manufacture and use household products or toys themselves is greatly increased.

3D printing technology is a technology to create 3D shape based on the data obtained through 3D scanning or 3D modeling using the tool path that corresponds to the 3D printer method and 'ASTM international 2012' ', The technical classification of 3D printing is divided into seven categories as follows according to the production method and materials to be used.

1) Material extrusion (technology to produce a three-dimensional shape while selectively feeding a laminated material through a nozzle): using polymer material.

2) Material jetting (technology to produce three-dimensional shape by selectively stacking liquid-phase laminates): Photopolymer and wax materials.

3) Binder jetting Combined injection (technology to selectively combine particles in liquid state using liquid binder and make 3D shape): Use metal, polymer, ceramic material.

4) Sheet lamination (technology to manufacture three-dimensional shape by sticking plate material): Hybrids, metal, ceramic materials.

5) Vat photopolymerization Photocuring (technology to produce three-dimensional shape by selectively curing a liquid polymer by using light energy): Photopolymer and ceramic materials.

6) Powder-bed fusion Powder-bed fusion (3-dimensional shape manufacturing technology by selectively dissolving and coagulating by using high heat energy source in powder chamber): Using metal, polymer, ceramic material.

7) Directed energy deposition: High power thermal energy (3-dimensional lamination technology through melting and coagulation of deposited material by focused thermal energy): using metal material.

In addition, the most widely used material for 3D printing today is photopolymer, which is a photocurable polymer material. The photopolymer is widely used in development and manufacturing plants and has a property of hardening upon receiving light.

The above photopolymer accounts for more than half of the entire market. As the proportion of the photopolymer to the personal and household products has increased recently, a popular material is a solid thermoplastic resin which is free to melt and solidify. It has the largest market share , And it is expected that metal powders and the like will gradually increase in the future.

Dual thermoplastics can have the form of filaments, particles or powders. Filament-type 3D printing is rapidly diffusing because it is faster and more productive than other types in speed.

Polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), HDPE (high density polyethylene) and polycarbonate (PC) are mainly used as the existing filament materials. Firstly, High speed of printing after printing is high, so even if printing speed is fast, it is not deformed, and dimension and shape stability are good.

Second, since the melting point is moderately low, the extrusion is easy and the production efficiency is high when the filament is manufactured. Furthermore, if the melting point is too high, the power consumption is high to melt the filament.

In addition, the material made of the single material can not satisfy various requirements as a 3D printing material requiring a soft feeling with low hardness.

For example, models of toys and infants, work models of schools, and general household items are aesthetically pleasing in 3D printing with soft materials of low hardness.

In addition, these toys, school and household models, household goods, etc. are often touched and users are often infants or adolescents, so that they require versatility, such as practicality in preventing static electricity on the surface, and wellbeing functions such as far infrared radiation and surface antibacterial action. Electronic parts such as housings and related repair parts are required to have additional functions such as functions related to electromagnetic wave shielding and the like.

Therefore, development of new materials having such functions is required.

Korean Patent Registration No. 10-1391293 (Apr. 25, 2014). Korean Patent Registration No. 10-1394119 (2014.05.07).

It is an object of the present invention to provide a filament composition for a 3D printer which, when applied to a 3D printer, exhibits excellent workability and mechanical properties and provides a printed matter exhibiting antistatic, far-infrared radiation and antibacterial effects.

An object of the present invention is achieved by providing a filament composition for a 3D printer, which comprises 100 parts by weight of a thermoplastic amorphous resin mixture and 10 to 25 parts by weight of a thermoplastic crystalline resin mixture.

According to a preferred aspect of the present invention, the thermoplastic amorphous resin mixture comprises 100 parts by weight of a general-purpose polystyrene resin, 60 to 90 parts by weight of a high-impact polystyrene resin and 25 to 50 parts by weight of an acrylonitrile butadiene styrene copolymer.

According to a further preferred feature of the present invention, the thermoplastic crystalline resin mixture is composed of 100 parts by weight of high-density polyethylene and 150 to 250 parts by weight of low-density polyethylene.

According to a further preferred feature of the present invention, the high-density polyethylene has a melt flow rate (190 DEG C, 21.18N) of 1 to 50 g / 10 min and a density of 0.945 to 0.965 g / cm3.

According to a further preferred feature of the present invention, the high-density polyethylene is prepared by copolymerizing 1 to 5.5 parts by weight of a monomer comprising at least one selected from the group consisting of propylene and 1-butene in 100 parts by weight of ethylene.

According to an even more preferred feature of the present invention, the low density polyethylene has a melt flow rate (190 占 폚, 21.18N) of 5 to 70 g / 10 min and a density of 0.915 to 0.930 g / cm3.

According to an even more preferred feature of the present invention, the filament composition for a 3D printer further comprises 1 to 25 parts by weight of an additive comprising plasticizer, flame retardant, antistatic agent, stabilizer and crystal nucleating agent to 100 parts by weight of the thermoplastic amorphous resin mixture .

According to an even more preferred feature of the invention, the plasticizer is dioctyl terephthalate.

According to a further preferred feature of the present invention, the flame retardant is one or more selected from the group consisting of aluminum hydroxide and magnesium hydroxide.

According to a further preferred feature of the present invention, the antistatic agent is at least one selected from the group consisting of polyaniline and polyacetylene.

According to an even more preferred feature of the invention, the stabilizer is selected from the group consisting of tris (2,4-di-t-butylphenyl) and tetrakis [methylene-3- (3 ', 5'- -Hydroxyphenyl) -propionate]. ≪ / RTI >

According to a further preferred feature of the present invention, the nucleating agent is at least one selected from the group consisting of silica, talc and aluminum hydroxide.

According to a further preferred feature of the present invention, the filament composition for 3D printer further comprises 5 to 20 parts by weight of an inorganic ion mineral to 100 parts by weight of the filament composition for 3D printer.

According to an even more preferred feature of the present invention, the inorganic ionic mineral is selected from the group consisting of 100 parts by weight of a first mineral comprising at least one selected from the group consisting of muscovite, sericite and ilite, and a mixture of 100 parts by weight of zeolite, 2 minerals and 30 to 40 parts by weight.

According to an even more preferred feature of the present invention, the inorganic ionic mineral has a particle size of 300 to 500 meshes.

According to a further preferred feature of the present invention, the filament composition for 3D printer further comprises 1 to 2 parts by weight of an antimicrobial agent relative to 100 parts by weight of the filament composition for 3D printer.

According to a further preferred feature of the present invention, the antimicrobial agent is made of an aqueous silver nitrate solution having a mass concentration of 0.1 to 1%.

According to a further preferred feature of the present invention, the filament composition for 3D printer further comprises 1 to 3 parts by weight of an electromagnetic shielding agent relative to 100 parts by weight of the filament composition for 3D printer.

According to a further preferred feature of the present invention, the electromagnetic shielding agent is made of at least one selected from the group consisting of polyacrylonitrile-based carbon fibers and pitch-based carbon fibers.

INDUSTRIAL APPLICABILITY The filament composition for a 3D printer according to the present invention exhibits excellent workability and mechanical properties when applied to a 3D printer, and exhibits an excellent effect of providing a printed matter exhibiting antistatic, far-infrared radiation and antibacterial effects.

Hereinafter, preferred embodiments of the present invention and physical properties of the respective components will be described in detail with reference to the accompanying drawings. However, the present invention is not limited thereto, And this does not mean that the technical idea and scope of the present invention are limited.

The filament composition for a 3D printer according to the present invention comprises 100 parts by weight of a thermoplastic amorphous resin mixture and 10 to 25 parts by weight of a thermoplastic crystalline resin mixture.

The thermoplastic amorphous resin mixture comprises 100 parts by weight of a general-purpose polystyrene resin, 60 to 90 parts by weight of a high-impact polystyrene resin and 25 to 50 parts by weight of an acrylonitrile butadiene styrene copolymer.

Polystyrene (PS) is a thermoplastic plastic that is brittle and rarely used alone. It is often used in combination with other polymers. Typical examples are butadiene rubber (SBR), SBS, HIPS .

In addition, polystyrene is a low-cost and hard-hard plastic that is commonly found in everyday life after polyethylene. Polystyrene includes HIPS polystyrene, which partially compensates for the disadvantages of pure polystyrene and pure polystyrene, and acrylic and biotin in styrene. And ABS resin which has good properties by mixing.

Pure polystyrene has good moldability compared to ABS resin, but it is mainly used for large black household appliances such as TV, because it has low durability and wears white. It is also widely used for remote control, general purpose electronic calculator, yogurt container and weighing cup .

Therefore, in order to compensate for the disadvantages of the polystyrene resin, the present invention is characterized by mixing 100 parts by weight of a general-purpose polystyrene resin, 60 to 90 parts by weight of a high-impact polystyrene resin, and 25 to 50 parts by weight of an acrylonitrile butadiene- Amorphous mixture was prepared.

Wherein the thermoplastic crystalline resin mixture comprises 100 parts by weight of high density polyethylene and 150 to 250 parts by weight of low density polyethylene having a melt flow rate (190 占 폚, 21.18 N) of from 1 to 50 g / 10 minutes and a melt flow rate of from 0.945 to 0.965 g / Or 1 to 5.5 parts by weight of a monomer comprising at least one selected from the group consisting of propylene and 1-butene in 100 parts by weight of ethylene.

Polyethylene (PE) is a type of thermoplastic, a general plastic that is light and flexible and feels like a wax. It is also used as a material for commonly used plastic bags, shampoo bottles, children's toys, and even bulletproof vests. Polyethylene consists of carbon and hydrogen, and it is the simplest type of polymer.

Polyethylene is a low-density polyethylene (LDPE) with a large amount of branches and a high-density polyethylene (HDPE) with a small amount of branches and a relatively linear shape depending on the amount of branches connected to the chain. . Linear polyethylene (HDPE) is stronger than nonlinear polyethylene (LDPE), but nonlinear polyethylene is cheaper and easier to mold. The molecular weight of polyethylene sold on the market is usually between 200,000 and 500,000. Polyethylene with higher molecular weight is used for special applications. Polyethylene with a molecular weight between 3,000,000 and 6,000,000 is called Ultra-High Molecular Weight Polyethylene (UHMWPE). UHMWPE can be made into a very strong fiber form and used as a bulletproof vest instead of Kevlar. It can be extruded in plate form and used as a skating link instead of ice. Polyethylene is produced by polymerizing ethylene monomers. Low density polyethylene (LDPE) is produced by free radical polymerization under high temperature and high pressure, but high density polyethylene (HDPE) is produced by a more complex process called Ziegler-Natta polymerization. UHMWPE is prepared by metallocene catalytic polymerization. The characteristics are as follows. There are four types of low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) and ultra high molecular weight polyethylene (UHMW-PE). Polyethylene is milky white translucent soft resin, crystalline plastic, but transparency is not good.

The specific gravity of the low density polyethylene is 0.925 or less, the specific gravity of the medium density polyethylene is about 0.926 to 0.94, and the specific gravity of 0.941 or more is high density polyethylene. Polyethylene is light in weight and floats in water. High-density polyethylene is mainly used for injection molding because it is resistant to impact and does not break well and maintains its strength even at -40 ° C. It has good electrical properties and low moisture absorption, so preliminary drying is not required.

However, it is prone to stress cracking and does not dissolve in solvents at room temperature. Acid, alkali, solvent, alcohol, gasoline, water resistant.

It is flammable, burns brightly with paraffin-like odor, and blue at the center of the flame. Water resistance, chemical resistance, tasteless, nontoxic, and odorless. Adhesiveness and printability are poor. And printing is performed while performing the surface treatment. Heat welding ultrasonic welding or the like. Coloring is easy, but Pearl effect is lower than PS. The high-density polyethylene and the low-density polyethylene can be mixed at an arbitrary ratio and molded. Impact resistance, and weather resistance, while the heat resistance is very bad, and there is no polarity, so the adhesion is also very bad.

 Considering the problem of adhesion of the polyethylene, the experience value for the composition of the poly (ethylene terephthalate) mixed resin suitable for the filament for the 3D printer of the composite resin composition and the powder used is as follows. The high-density polyethylene resin based on the polyethylene polymer has a melt flow rate (190 占 폚, 21.18 N) of 1 to 50 g / 10 min and a density of 0.945 to 0.965 g / cm3.

The low-density polyethylene resin preferably exhibits a melt flow rate (190 占 폚, 21.18N) of from 5 to 70 g / 10 min and a density of from 0.915 to 0.930 g / cm3.

The filament composition for a 3D printer may further contain 1 to 25 parts by weight of an additive composed of a plasticizer, a flame retardant, an antistatic agent, a stabilizer, and a crystal nucleating agent to 100 parts by weight of the thermoplastic amorphous resin mixture.

The additive preferably comprises 100 parts by weight of a plasticizer, 65 to 85 parts by weight of an antistatic agent, 55 to 75 parts by weight of a flame retardant, 15 to 25 parts by weight of a stabilizer, and 35 to 45 parts by weight of a nucleating agent.

The plasticizer serves to improve the processability of the thermoplastic amorphous resin mixture and the thermoplastic crystalline resin mixture and is preferably made of a nonphthalate type plasticizer. Examples thereof include dimethyl phthalate, diethyl phthalate, dibutyl phthalate , Dicyclohexyl phthalate, dihexyl phthalate, 2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate and butyl octyl phthalate, Dicyclohexyl adipate, di-n-octyl adipate and didecyl adipate; dicarboxylic acid ester plasticizers such as dibutyl sebacate , Di-2-ethylhexyl sebacate, diisooctyl sebacate and Sebacate ester plasticizers such as butyl benzyl sebacate, azela phosphate ester plasticizers such as di-2-ethylhexyl azelate, dihexyl azelate and diisooctyl azelate, triethyl citric acid, triethyl acetyl citric acid, tri Citric acid ester plasticizers such as butyl citric acid and tributyl acetyl citric acid, glycolate plasticizers such as methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate, tributyl trimethyl citrate, tri- Trimethylate plasticizers such as hexyl trimethylate, tri-2-ethylhexyl trimethylate and tri-n-octyl trimethylate, phthalic acid isomer esters such as di-2-ethylhexyl isophthalate and di- A plasticizer, methyl acetyl ricinolate, and butyl acetyl ricinoleate. (2-ethylhexyl) stearate, epoxy and amylin, and 2-ethylhexyl methacrylate, as well as epoxy plasticizers such as polyvinyl chloride, polyvinyl chloride, -Ethylhexyl epoxytrate and the like can be used, and there are many problems of harmfulness of the plasticizer, and it is necessary to simplify the process by using commercially available environmentally friendly plasticizer. Among non-phthalate plasticizers, it is most preferable to use DOTP (Dioctyl terephthalate, dioctyl terephthalate), which is an environmentally friendly plasticizer.

DOTP has been confirmed to have no effects on carcinogenicity and human toxicity in various toxicity test data published so far. DOP (Dioctyl Phthalate), which is similar to DOP (Dioctyl Phthalate), is superior in terms of volatility and electrical insulation because it has boiling point, freezing point and density. DOTP is 80 ~ 90% in terms of processability and physical properties compared with phthalate plasticizers such as DOP and DINP. It is used for soft PVC products including toys for toys.

The antistatic agent is composed of at least one member selected from the group consisting of polyaniline and polyacetylene. When 3D printing is performed using a material composed of the thermoplastic amorphous resin mixture and the thermoplastic crystalline resin mixture, Thereby reducing the occurrence of defects.

As the antistatic agent used for the material composed of the thermoplastic amorphous resin mixture and the thermoplastic crystalline resin mixture as described above, the polar polymer is the most convenient and preferable, and the polymer polymer containing the polarity is a polyaniline (PANI ) Or polyacetylene (polyacetylene). Polyaniline (PANI) has developed a conductive polymer of new 'polyaniline' using a method of mixing water and oil together in Korea. The resulting polyaniline has much higher electrical conductivity than polyacetylene. Polyacetylenes are pi-conjugated polymers. These polymers provide the source of electrons, which is called doping. Doping is the addition of one or more other electrons as impurities. Therefore, when a polymer is doped with a substance such as iodine, iodine takes one of the loose bonds, the polymer becomes less electrons (soliton, positive soliton state), and the electrons move accordingly (hopping). Polyaniline, on the other hand, is easier to handle and mass-producible than polyacetylene, and as a conductive polymer, it exhibits a characteristic of lowering electrical resistance as temperature is lowered for the first time.

The flame retardant imparts flame retardancy to the material composed of the thermoplastic amorphous resin mixture and the thermoplastic crystalline resin mixture, and plays a role of exhibiting excellent flame retardancy after the 3D printing process or printing.

At this time, the flame retardant is composed of at least one selected from the group consisting of aluminum hydroxide and magnesium hydroxide. As the flame retardant of the thermoplastic resin as described above, a known phosphate ester flame retardant may be blended in addition to the non-halogen flame retardant, . Examples of the non-halogen flame retardant include inorganic flame retardants such as aluminum hydroxide and the like. Halogen flame retardants with excellent flame retardant effect change the chemical structure and stop the radical chain reaction, so that the combustion cycle is broken and the fire is easily digested.

The stabilizer serves to prevent and stabilize oxidation of a material composed of the thermoplastic amorphous resin mixture and the thermoplastic crystalline resin mixture. The stabilizer acts to prevent and stabilize oxidation of tris (2,4-di-t-butylphenyl) and tetrakis [methylene- - (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate].

As the stabilizer, a primary antioxidant or a secondary antioxidant may be used. A primary antioxidant is to stabilize a polymer by making a radical instead of a polymer, and a secondary antioxidant is an oxygen atom The antioxidant used as a stabilizer is required to use a product which is non-toxic, low in cost, and does not adversely affect the processability and physical properties of the polymer. Therefore, The secondary antioxidants listed are preferably used as stabilizers.

The nucleating agent serves to shorten the curing time of the material composed of the thermoplastic amorphous resin mixture and the thermoplastic crystalline resin mixture, and is preferably composed of at least one selected from the group consisting of silica, talc, and aluminum hydroxide.

The crystalline resin, such as the thermoplastic crystalline resin mixture, is molded in a molten state (molten state), and then cooled to solidify into a solid state. When the polymer resin that has been melted and dissolved melts and crystallizes, Is very fast or becomes crystal clear. Crystalline nucleating agents are used to improve transparency and mechanical properties by promoting the crystallization rate of polymers and reducing the size of crystals. They are generally used for packaging films or thin containers requiring transparency. Examples of inorganic additives include talc, silica, and kaolin. Organic compounds include mono or polymer carboxilic acid salt and pigment. Examples of the polymer include ethylene acrylic ester Copolymer (Ethylene Acrylic ester copolymer). Examples of organic nucleating agents include organic phosphorus compounds and metal salts thereof, fatty acids and fatty acid metal salts, aldehyde compounds and high melting point polymers such as polyvinylcycloalkane, poly (3-methyl-1-butene), and polyalkenylsilane, benzylidene sorbitol, And sorbitol-based ones are widely used in the United States, Japan and the like. Examples thereof include 1,3: 2,4-dibenzylidene sorbitol, 1,3: 2,4-bis (p-methylbenzylidene) sorbitol, 3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, and 1,3: 2,4-bis (p-ethylbenzylidene) sorbitol.

Talc is a magnesium hydrate mineral. Talc is a mineral that develops during the process of degeneration and is made by denaturation of the parental rocks involved in magnesium. Talc products are sold in a variety of grades with physical or functional characteristics to suit their intended use. It is used in the organic and paper industries. It is also used as excipients such as medicines, cosmetics, insecticides, fillers, diluents, active agents, thermal insulation materials and refractories. Its main destinations are North America, Northeast China, France, Italy and Norway. Talc as a pure mineral consists of SiO ₂ (63.5%), MgO (31.7%) and H ₂ O (4.8%), and mineral talc generally has a flat plate-like structure but also exists as asbestiform fibers. The main cause of asbestos in the talc is the mining process of talc. The center of the ore is composed of serpentinite, talc carbonate and stearate. When talc is mixed with talc, the main cause of asbestos is detected in talc . Therefore, silica may be a more preferable nucleating agent than talc due to the problems of such extraction and use of talc.

Silica (silicon dioxide (二酸化硅素), Slica) is an oxide of silicon, it has the formula SiO _2. It is found in sand and quartz, and is distributed in the cell walls of diatoms. 59% of the crustal mass and 95% of the rocks. It has three main crystal forms: quartz (the most abundant form), tridymite, and cristobalite. Other variants include Coesite, Kiatite, Ricardialite and others. Silica sand is used in the form of gravel, Portland cement, concrete, mortar when building buildings and road pavement. Silica is also used as grinding glass, grinding glass, rotating grindstone, grinding stone, casting mold, glass, ceramics, silicon carbide, ferro silicon and silicon. It is also used as refractory and gemstones.

In addition, the filament composition for a 3D printer may further contain 5 to 20 parts by weight of an inorganic ion mineral to 100 parts by weight of the thermoplastic amorphous resin mixture. The inorganic ion mineral may be one selected from the group consisting of muscovite, 100 parts by weight of the first mineral and 30 to 40 parts by weight of the second mineral selected from the group consisting of zeolite, amphibole and tourmaline.

Inorganic ionic minerals composed of the above components emit far-infrared rays. Far infrared rays have the longest wavelength, that is, the longest wavelength and the lowest frequency, of electromagnetic waves when the infrared region is subdivided according to wavelength. The distances between 15 and 1 millimeter (frequencies between 20 and 300 gigahertz) are usually divided into far infrared rays, but in astronomy, far infrared rays can be seen between 25 and 350 micrometers.

It is known that the far infrared ray, which is a type of electromagnetic wave, is deeply absorbed into the human body and reaches the depth of skin (4-5 cm) which is 80 times as deep as the normal heat, resonating with minute vibration about 2000 times per minute. In this case, anion refers to an atom or an atomic group that has a negative charge in a dictionary concept. According to a study by Dr. Ertege, a German medical scientist, the average life span of anion - rich areas is 85 years and the mean life span of anion - poor areas is 50 years. To maintain a healthy life, there should be 400 to 1000 negative ions per cubic centimeter. Although the efficacy of the anion has the effect of air purification, antioxidation, relaxation of the autonomic nervous system, and promotion of metabolism, the exact medical basis is unknown, so the efficacy of the inorganic ion mineral mixture in this patent focuses more on the efficacy of the raw outer Let's fit it.

 Muscovite is a layered silicate mineral of aluminum and potassium. It is an economically important mineral because it can make electrical insulators and thermal insulators with low iron content. Muscovites are typically found in metamorphic rocks, and are produced in crystals or plate form. It also occurs in granitic and fine-grained sedimentary rocks, and is also present in some siliceous cancers. At this time, fine-grained muscovite is also called sericite or white mica. Sericite is a variant of silicate minerals, white mica and paragenite. It is widely used in various fields of ceramics industry. Its main reason is that it is produced in clay phase and has high plasticity, high dry strength and high ginger strength, and high viscosity of glassy phase produced by melting, so that softening temperature under load. We use only fine particles such as clay for weaving, and we use it as an abrasion preventing agent for machine parts by using its lubricity. In addition, fine particles and pure whiteness can also be used as an extender for cosmetics and medicines, and can be used in various forms such as rubber filler, abrasive powder, lubricant, and paint.

 The Illite is a fine particulate mineral having a hardness of 1 to 2 and a specific gravity of 2.6 to 2.9, and usually has a size of 2 to 4 μm or less. It is a clay mineral with a plate - like structure similar to general muscovite. Its chemical composition is less potassium and aluminum compared to muscovite, but silicon and water are slightly larger. The structure is similar to muscovite but the crystallinity is slightly lower than that of muscovite and the binding force of potassium ions between layers is weaker. However, in the environment where the temperature is increased and potassium is supplied well, when the ailite reacts for a long time, it gradually changes to muscovite. On the contrary, when the muscovite is weathered or altered, potassium is released and an illite is formed. It is difficult to accurately distinguish between muscovite and ilite, and it is not wrong to say that mineral is a clay-like fine particulate matter and its charge (or potassium content per unit) is 0.9 or less and its crystallinity is rather low.

Quartzite is a rock belonging to quartz porphyry among igneous rocks. Huhjun's Donguibogam and China's main river gangmyeon is called 石 石 ((药 石). There is a record that it is used as an anti-inflammatory agent for various skin diseases such as larynx, boils and the like because it is warm and has no toxicity. It is mainly composed of anhydrous silicic acid and aluminum oxide, and is characterized by containing ferric oxide necessary for human and living cells. It has 45 kinds of minerals to regulate the development and physiological function of the living body to maintain the vitality of the cells and to have 3,000 to 150,000 lots of pores per 1 cm 3, , It emits far infrared rays and maintains freshness. Its appearance is reddish and white spots in yellowish white, light tan or lightly colored stone, and its shape looks like a "barley rice".

The zeolite is a term generally referred to as a mineral in which an anion generated by the bonding of aluminum oxide and silicate oxide is combined with an alkali metal and an alkaline earth metal. That is, crystalline aluminum silicate minerals. Zeolite is a kind of natural minerals. It is widely used as catalyst, adsorbent, detergent additive, feed additive, soil improving agent and so on because of its unique adsorption property and ion exchange ability. It is known that there are about 200 species in nature and synthesis. The zeolite has excellent heat insulation effect because it has many air-filled pores with low thermal conductivity, and it has a humidity control function that absorbs moisture when wet and releases moisture when dried. Using these characteristics, gemstones are also used as building bricks. Good deodorization powders are coated on non-woven fabric and used as a pasteboard, and also used as an additive for functional paints.

The amphibole (Actinolitum) is a silicate mineral bianchi or its heterotrophic asbestos. It is irregular columnar or lumpy and uneven in size. Outer surface is grayish white, dark gray to light green, light yellowish brown pattern or floral pattern and glossy. The vagina is heavy and brittle, and the cut side is uneven, and when cut vertically, it looks like a thread.

The tourmaline (tourmaline, tourmaline) is a borosilicate having hexagonal columnar crystals and is a natural mineral belonging to the hexagonal system. The tourmaline crystal itself has the characteristic of generating electricity and has a nickname called tourmaline. When we apply about 100 degrees of heat to tourmaline, we get pyroelectricity to attract dust. It is lower than quartz, but it also has piezoelectricity caused by pressure. It is anticipated to have various effects on the human body due to the antioxidant effect and the effect of anion and far-infrared ray synergy generated by a small electric current of 0.06A.

If the content of the inorganic ionic mineral composed of the above components is less than 5 parts by weight, the effect of far-infrared radiation is insignificant. If the content of the inorganic ionic mineral exceeds 20 parts by weight, the mechanical properties of the filament composition for 3D printer may be deteriorated.

The inorganic ionic mineral preferably exhibits a particle size of 300 to 500 meshes in consideration of the mixing property with the thermoplastic amorphous resin mixture and the thermoplastic crystalline resin mixture.

In addition, the filament composition for 3D printer may further contain 1 to 2 parts by weight of an antimicrobial agent relative to 100 parts by weight of the thermoplastic amorphous resin mixture. The antibacterial agent has a role of imparting antimicrobial properties to the filament composition for 3D printer according to the present invention do.

As described above, the filament composition to which the antimicrobial agent is added and the product made of the composition exhibit excellent antibacterial properties, and the antimicrobial agent preferably comprises an aqueous solution of silver nitrate (AgNO ₃ ) having a mass concentration of 0.1 to 1%.

The above-mentioned silver nitrate is a caustic compound which is importantly used for the industrial manufacture and preservative of reagents or silver salts of analytical chemistry. When silver nitrate is used for skin and mucous membranes, a silver nitrate rod or a 0.01 to 10% silver nitrate aqueous solution Lt; / RTI > Silver nitrate rods are used to remove warts and parenchyma tissue and to cure wounds and ulcers. Very dilute solutions are used as astringent and weak disinfectant. The 1 to 2% silver nitrate solution is effective against gonorrhea, so the newborn's eyes are infected with gonorrhea and this solution is added to prevent the snow from staying on. Pure silver nitrate is used as an intermediate in the manufacture of silver salts such as silver halide, which is used in medicine for colloidal silver compounds and photographic emulsions. Analytical chemistry is used for the determination of cations of various acids (acids) forming a reducing agent and an insoluble silver salt by using an aqueous silver nitrate solution to analyze the capacity of halide, cyanide, thiocyanate and the like.

If the content of the antibacterial agent is less than 1 part by weight, the antibacterial effect is insignificant. If the content of the antibacterial agent exceeds 2 parts by weight, the antibacterial effect is not greatly improved but the manufacturing cost is increased.

The filament composition for a 3D printer may further contain 1 to 3 parts by weight of an electromagnetic shielding agent relative to 100 parts by weight of the thermoplastic amorphous resin mixture. The electromagnetic shielding agent imparts an electromagnetic wave shielding function to the filament composition for a 3D printer according to the present invention .

The electromagnetic shielding agent is preferably composed of at least one selected from the group consisting of polyacrylonitrile-based carbon fibers and pitch-based carbon fibers. When the content of the electromagnetic shielding agent is less than 1 part by weight, the electromagnetic shielding effect is insignificant. When the content of the electromagnetic shielding agent exceeds 3 parts by weight, the electromagnetic shielding effect is not greatly improved but the manufacturing cost is increased.

The filament composition for a 3D printer composed of the above components may be prepared as a filament type having a diameter of 0.7 to 2.5 or a powder type having a particle size of 50 to 300 meshes. The composition is supplied to a print head of a 3D printer and then heated. The heated filament composition is melt-extruded to form a print layer, and a plurality of print layers formed through the above process are laminated to form a three-dimensional structure .

In addition, in the case of a powdery composition, mixing the powdery composition with a liquid binder, heating the mixture prepared by mixing with the liquid binder, melting the mixture, and injecting the mixed mixture with a nozzle, A step of forming a layer, and a method of laminating a print layer.

In addition, in the case of a powdery composition, a powdery composition is applied to a bed in a chamber, a powdery composition applied to the bed is selectively irradiated with a laser to sinter the powdery composition, A method of laminating the print layer by repeating the process of applying the powdery composition to the upper surface again and irradiating the laser may be commercialized.

Hereinafter, the method and properties of the filament composition for a 3D printer according to the present invention will be described with reference to examples.

≪ Example 1 >

100 parts by weight of a thermoplastic amorphous resin mixture (100 parts by weight of a general-purpose polystyrene resin, 75 parts by weight of a high-impact polystyrene resin and 40 parts by weight of an acrylonitrile butadiene styrene copolymer) and 100 parts by weight of a thermoplastic crystalline resin mixture (100 parts by weight of high- 12 parts by weight of an additive (100 parts by weight of a plasticizer, 65 parts by weight of an antistatic agent consisting of polyaniline, 65 parts by weight of a flame retardant, 20 parts by weight of a stabilizer and 40 parts by weight of a crystal nucleating agent) 13 parts by weight of inorganic ionic mineral (100 parts by weight of sericite, 12.5 parts by weight of elvan, and 12.5 parts by weight of zeolite) having a size of 400 meshes, 1.5 parts by weight of an antibacterial agent composed of an aqueous silver nitrate solution having a mass concentration of 0.5% And 2 parts by weight of an electromagnetic wave shielding agent made of carbon fiber were mixed to prepare a filament composition for 3D printer Joe was.

≪ Example 2 >

The procedure of Example 1 was followed except that 85 parts by weight of an antistatic agent was mixed to prepare a filament composition for a 3D printer.

≪ Example 3 >

The procedure of Example 1 was followed except that a filament composition for a 3D printer was prepared using an antistatic agent consisting of polyacetylene instead of polyaniline.

<Example 4>

The procedure of Example 3 was followed except that 85 parts by weight of an antistatic agent was mixed to prepare a filament composition for a 3D printer.

&Lt; Comparative Example 1 &

The procedure of Example 1 was followed except that the filament composition for 3D printer was prepared without mixing the antistatic agent.

&Lt; Comparative Example 2 &

The procedure of Example 1 was followed except that a filament composition for a 3D printer was prepared without mixing an antimicrobial agent.

The electrostatic tests of the filament compositions for 3D printer prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were conducted and are shown in Table 2 below.

(The human body capacitance is 90 pF, and the intensity of the electric shock according to the charging unit is as shown in Table 1 below. The electrostatic test was conducted at an ambient temperature of 15 to 35 DEG C, a relative humidity of 30 to 60%, an atmospheric pressure of 86 kPa (860 mbar) to 106 kPa (1060 mbar), an electrostatic tester MZ-15EC Single Corp) (Discharge ± 1 to 25 kV, Single-Short, and Repetitive) (Interval: 10s, 3s, 1s, 0.5s)

<Table 1>

<Table 2>

As shown in Table 2 above, the filament composition for a 3D printer in which the antistatic agent was mixed through Examples 1 to 4 of the present invention exhibited an excellent antistatic effect compared with the filament composition for 3D printer manufactured in Comparative Example 1 Able to know.

The far infrared ray emissivity and the radiant energy of the filament composition for 3D printer manufactured through Example 1 were measured and shown in Table 3 below.

(However, the far-infrared emissivity and radiant energy were measured at 40 ° C, and the measurement was made by measuring the results of the comparison with the black body using an ultraviolet spectrophotometer, FT-IR Spectrometer.

<Table 3>

As shown in Table 3 above, it can be seen that the filament composition for a 3D printer manufactured through Example 1 of the present invention shows significantly higher emissivity and radiant energy of far-infrared rays, have.

The antibacterial properties of the filament compositions for 3D printer prepared in Example 1 and Comparative Example 2 were measured and are shown in Table 4 below.

(However, the antibacterial activity was measured with KICM-FIR 1002 (SHAKE FLASH METHOD) for Escherichia coli and Pseudomonas aeruginosa.

<Table 4>

As shown in Table 4 above, it can be seen that the filament composition for 3D printer produced through Example 1 of the present invention exhibits excellent antibacterial properties.

Claims (19)

100 parts by weight of a thermoplastic amorphous resin mixture and 10 to 25 parts by weight of a thermoplastic crystalline resin mixture,
Wherein the thermoplastic amorphous resin mixture comprises 100 parts by weight of a general-purpose polystyrene resin, 60 to 90 parts by weight of a high-impact polystyrene resin, and 25 to 50 parts by weight of an acrylonitrile butadiene styrene copolymer.
delete The method according to claim 1,
Wherein the thermoplastic crystalline resin mixture comprises 100 parts by weight of high-density polyethylene and 150 to 250 parts by weight of low-density polyethylene.
The method of claim 3,
Wherein the high-density polyethylene has a melt flow rate (190 占 폚, 21.18 N) of 1 to 50 g / 10 minutes and a density of 0.945 to 0.965 g / cm3.
The method of claim 3,
Wherein the high-density polyethylene is prepared by copolymerizing 1 to 5.5 parts by weight of a monomer comprising at least one selected from the group consisting of propylene and 1-butene in 100 parts by weight of ethylene.
The method of claim 3,
Wherein the low density polyethylene has a melt flow rate (190 占 폚, 21.18N) of 5 to 70 g / 10 minutes and a density of 0.915 to 0.930 g / cm3.
The method according to claim 1,
Wherein the filament composition for a 3D printer further comprises 1 to 25 parts by weight of an additive composed of a plasticizer, a flame retardant, an antistatic agent, a stabilizer and a crystal nucleating agent to 100 parts by weight of the thermoplastic amorphous resin mixture.
The method of claim 7,
Wherein the plasticizer is dioctyl terephthalate.
The method of claim 7,
Wherein the flame retardant is at least one selected from the group consisting of aluminum hydroxide and magnesium hydroxide.
The method of claim 7,
Wherein the antistatic agent is at least one selected from the group consisting of polyaniline and polyacetylene.
The method of claim 7,
Butylphenyl) and tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate] Wherein the filament composition is at least one selected from the group consisting of polypropylene and polypropylene.
The method of claim 7,
Wherein the crystal nucleating agent is at least one selected from the group consisting of silica, talc, and aluminum hydroxide.
The method according to claim 1,
Wherein the filament composition for a 3D printer further contains 5 to 20 parts by weight of an inorganic ion mineral to 100 parts by weight of the filament composition for a 3D printer.
14. The method of claim 13,
The inorganic ionic mineral is composed of 100 parts by weight of a first mineral composed of at least one selected from the group consisting of muscovite, sericite and ilite, and 30 to 40 parts by weight of a second mineral composed of two selected from the group consisting of zeolite, By weight based on the weight of the filament.
14. The method according to claim 13 or 14,
Wherein the inorganic ionic mineral has a particle size of 300 to 500 meshes.
The method according to claim 1,
Wherein the filament composition for a 3D printer further comprises 1 to 2 parts by weight of an antimicrobial agent based on 100 parts by weight of the filament composition for 3D printer.
18. The method of claim 16,
Wherein the antimicrobial agent comprises an aqueous silver nitrate solution having a mass concentration of 0.1 to 1%.
The method according to claim 1,
Wherein the filament composition for a 3D printer further comprises 1 to 3 parts by weight of an electromagnetic wave shielding agent relative to 100 parts by weight of the filament composition for a 3D printer.
19. The method of claim 18,
Wherein the electromagnetic wave shielding agent is at least one selected from the group consisting of polyacrylonitrile-based carbon fibers and pitch-based carbon fibers.