JP4403384B2 - Three-dimensional additive manufacturing method - Google Patents

Description

  The present invention relates to an inkjet three-dimensional additive manufacturing apparatus.

  The principle of layered modeling is a method in which a three-dimensional object is cut into circles, and the shapes cut into circles are formed by some method and sequentially stacked. This is the same as the method of creating a three-dimensional contour map.

  Laminate modeling methods include optical modeling methods using photocurable resins, powder lamination methods using metal or resin powders, melt deposition methods for melting and depositing resins, and thin plates for laminating paper, plastic sheets, or metal thin plates. Lamination methods have been put into practical use.

  Since these three-dimensional modeling methods can directly obtain a three-dimensional modeled object from three-dimensional CAD data, this technique has rapidly spread with the spread of three-dimensional CAD in recent years, and is also referred to as a rapid prototyping (high-speed prototype) technique. Rapid prototyping is not only used in the field of prototyping, but it has become possible to mold and be used in the manufacturing field. Furthermore, it has come to be used as a three-dimensional copying machine in conjunction with a three-dimensional printer, a digitizer, or a scanner as an output machine of a three-dimensional CAD. In particular, the additive manufacturing method using the ink jet method is expected to be a general-purpose three-dimensional printer or three-dimensional copy machine because the apparatus and handling are simpler than the other additive manufacturing methods described above.

  The additive manufacturing method by the ink jet method is a method in which a binder (binder) is jetted and solidified by an ink jet on a starch or gypsum powder layer developed at the Massachusetts Institute of Technology (this is classified as a powder lamination method). There is a method of directly injecting and laminating a resin for a molded article (this is classified as a molten resin deposition method).

  In the powder lamination method using powder, it is necessary to remove unnecessary powder after completion of modeling, and the powder is scattered. Therefore, the powder lamination method is not suitable for an office environment and is difficult to be a general-purpose 3D printer or 3D copy machine. On the other hand, the method of directly injecting and laminating the resin for modeling objects can be used in an office environment and is suitable as a general-purpose three-dimensional printer or three-dimensional copy machine.

  As a method of directly injecting and laminating this resin for modeling objects, initially an injection nozzle (in principle the same as an inkjet head) is attached to the arm of the robot and moved in three dimensions of XYZ, and modeling is performed. There was a method of modeling by arranging the head in the XY plane and the Z direction. Since these methods do not use a support that supports the object during modeling, when a three-dimensional object is cut into a circle, the floating island shape (when the slice data is stacked and the shape suddenly appears in a layer) ) And long beam shapes such as H-shaped horizontal bars cannot be formed, and shapes that can be formed are limited, and are not suitable for complex shapes such as practical industrial products and medical models.

  As a countermeasure, a method using a support was proposed. This is a method of laminating a resin for a support and a resin for a molded article, and includes a cutting method (for example, see Patent Document 1) for flattening the surface as necessary. This made it possible to form complex shapes. As a method for producing the support, there are a method for producing a shaped article so as to be embedded in the support and a method for producing a columnar or plate-like support at a necessary place. It can be applied to any complex shape, and special data processing (the latter method requires data processing for providing a support) is unnecessary, so that the former model is made to be embedded in the support. The method is good.

  Materials used for ink jet additive manufacturing are classified into materials that are liquid at room temperature and materials that are solid at room temperature. A method using a photocurable resin or a thermosetting resin as a liquid material at room temperature has also been proposed. However, when the viscosity is high, nozzle clogging is likely to occur, and conversely, when the viscosity is low, there is a problem that “sagging” occurs during photocuring or thermal curing after lamination. For this reason, a method has also been proposed in which light is irradiated onto the flight path of the droplet so that the photocurable resin droplet is irradiated with light during the flight (see, for example, Patent Document 2). However, this method has a drawback in that the light leaks to the head side and the reflected light or reflected light easily causes nozzle clogging.

  On the other hand, a material that is solid at room temperature is often a resin that becomes liquid when heated, such as wax or hot melt resin. For example, in a method of making a shaped article so as to be embedded in a support, a method is proposed in which materials having different melting points are used, and the support material is removed using a difference in melting point after formation of the shaped article. (For example, see Patent Document 3). However, these materials are fragile and have a drawback that the modeled material is easily broken. A modeling material in which this defect is improved and toughness is imparted has also been proposed (see, for example, Patent Document 4). Further, the resin that becomes liquid when heated as a solid at room temperature has a disadvantage that warpage deformation due to shrinkage occurs and the dimensional stability of the shaped article is impaired. As an improvement plan, there has been proposed a method of laminating shaped objects while performing a smoothing process with a rotating or high temperature roller, a rotary cutter, or the like (see, for example, Patent Document 5). However, since the smoothing process is performed during the lamination, there is a problem that the lamination time is reduced.

Japanese Patent No. 3179547

Japanese Patent No. 2697138

JP-A-9-123290

JP 2001-214098 A JP 2001-58357 P7-9, FIG.

  In order to use an inkjet additive manufacturing machine as a general-purpose and office-use 3D printer or 3D copy machine, the modeled object is less likely to be broken, and can be modeled with higher accuracy and speed, and at a lower price. It is hoped that there will be. The inkjet type additive manufacturing machine currently on the market has a problem that these user needs are not satisfied.

The present invention aims to provide a three-dimensional layered manufacturing method that can fast shaping the shaped object of a complex three-dimensional structure with high accuracy.

To solve the above problems, the present invention provides a three-dimensional laminate molding method modeled object performs molding by injecting shaped object material and the support-body material so as to be embedded in the support layer by an inkjet method, molding and controlling relative melting point of the support material from (melting point -30) ° C. in the range of (melting point -5) ° C. environmental temperature when. By using an active energy ray-curable compound as a material for a modeled object, and the support material can be melted or deformed by irradiation with active energy rays, the brittleness of the modeled object is improved and the smoothness of each layer during additive manufacturing is achieved. Can be improved.

  Furthermore, by placing an active energy ray irradiator adjacent to an inkjet head that ejects the support material, the time required for the smoothing process can be saved, and high-speed modeling is possible. Further, if the model material and the support material are different colors, it can be easily determined whether or not the support material remains when the support material is removed. By adding a black dye, a black pigment, or a deep colorant to the support material, the absorption efficiency of active energy rays can be increased, and the smoothness of each layer during layered modeling can be further improved.

According to the present invention, it is possible to provide an inkjet three-dimensional additive manufacturing method that is difficult to break, can be modeled with high accuracy and high speed , and is inexpensive.

  The invention of this application will be described in further detail below.

First, a 3D shape designed by 3D CAD, or 3D surface data or solid data captured by a 3D scanner or digitizer is converted into an STL format and input to an additive manufacturing machine. At this time, the modeling direction of the three-dimensional shape to be modeled is determined based on the input data. The modeling direction is not particularly limited, but usually the direction in which the Z direction (height direction) is the lowest is selected. When the modeling direction is determined, the projected area of the three-dimensional shape on the XY plane, XZ plane, and YZ plane is obtained. In order to reinforce the obtained block shape, the other surfaces are moved outward by an appropriate amount except for the upper surface of the XY plane. The amount to be moved is not particularly limited, and is about 1 to 10 mm, although it varies depending on the shape, size, and material used. With this, the block shape in which the shape to be shaped is confined (the upper surface is opened) is specified.
This block shape is cut into slices (slices) in the Z direction with a single layer thickness. The thickness of one layer depends on the material used, but is usually 20-60 μm. When there is only one model to be modeled, the block shape is arranged so as to be in the middle of the Z stage (a table on which a model is descended one layer at a time for each model). In addition, when a plurality of models are formed simultaneously, the block shape is arranged on the Z stage, but the block shapes can be stacked. These block shaping, circular cut data (slice data: contour data), and arrangement on the Z stage can be automatically created by specifying the material to be used.

  Next, it becomes a modeling process. Based on the outline of the outermost contour of the ring cutting data, the inside / outside determination (determining whether to inject the support material or the shaped article material to the position on the outline), and the position to inject the support material The position for injecting the material for the molded article is controlled. As an order of injection, after the support material forming the support layer is injected, the modeling material is injected. As shown in FIGS. 3 and 4, this can be achieved by arranging the heads having a large number of nozzles (multi-nozzle heads). When spraying in this order, grooves and weirs are first formed in the support, and the material for the molded object is injected into it, and even if a liquid material is used at room temperature as the material for the molded object, "There is no need to worry about" and photo-curing resins and thermosetting resins can be used widely. In order to improve the brittleness of a modeled object, it is preferable to use a material for a modeled object having a molecular weight as large as possible. However, there are restrictions on viscosity for jetting with an ink jet, and the viscosity at the time of jetting is 30 mPa · s or less. Desirably, so high molecular weight materials cannot be used. Therefore, it is possible to improve the brittleness of the molded object by injecting low molecular weight material and polymerizing it later, or by injecting two liquids separately and reacting on the laminated surface to solidify. I can do it. In order to widen the selectivity of the material, it is also an effective means to set the injection temperature of the material for shaped objects to room temperature or higher.

  Further, in order to further shorten the modeling time, a method of laminating the support material and the modeling material on the forward path and the return path of the integrated head is preferable.

  Controlling the environment temperature in the apparatus during modeling to the range of (melting point−30) ° C. to (melting point−5) ° C. with respect to the melting point of the support material is warp deformation due to volume shrinkage accompanying the temperature change of the support material. And the dimensional stability of the modeled object can be improved. Furthermore, it is possible to obtain a smooth surface state without special finishing. When the temperature is lower than (melting point−30) ° C., the dimensional stability is deteriorated due to warp deformation, and the surface state is not smooth. Further, when the temperature is higher than (melting point−5) ° C., the support material is partially deformed depending on the shape of the modeled object, and the dimensional stability of the modeled object is deteriorated. Dimensional stability independent of the shape of the object when the temperature is preferably controlled within the range of (melting point−25) ° C. to (melting point−10) ° C., more preferably within the range of melting point−20) ° C. to (melting point−10) ° C. Can be obtained.

  In addition, by placing an active energy ray irradiator adjacent to the inkjet head that ejects the support material, the time required for the smoothing process can be saved, and high-speed modeling is possible.

  In the three-dimensional modeling method of the present invention, as a head having a large number of nozzles (multi-nozzle head), for example, a head in which a large number of linear heads in which nozzles are arranged in a row is arranged and integrated is used. The configuration of this linear head will be described. FIG. 1 is an exploded perspective view of the linear head, and FIG. 2 is a partial sectional view thereof. In the figure, 1 is a nozzle, 2 is a nozzle plate, 3 is a pressurizing chamber for storing an injection material, 4 is a pressurization chamber plate, 5 is a restrictor serving as a flow path for supplying the injection material to the pressurization chamber 3, A restrictor plate, 7 is a diaphragm forming a part of the wall surface of the pressurizing chamber 3, 8 is a filter unit, 9 is a diaphragm plate, 10 is an injection material supply path for supplying the injection material to the restrictor 5, and 11 is attached A base, 12 is a piezoelectric element, 13 is an adhesive for connecting the diaphragm 7 and the piezoelectric element 12, and 14 is a support substrate to which the piezoelectric element 12 is fixed.

  As materials for these components, the diaphragm plate 9, the restrictor plate 6, the pressurizing chamber plate 4 and the mounting base 11 are made of stainless steel, the nozzle plate 2 is made of nickel, the support substrate 14 is made of an insulator such as ceramics and polyimide. It is made.

  In assembling the components, first, the diaphragm plate 9, the restrictor plate 6, the pressurizing chamber plate 4, and the nozzle plate 2 are pressure-bonded on the mounting base 11 while being positioned. For example, epoxy is used as the adhesive. Next, the piezoelectric element 12 held by the support substrate 14 is inserted into the opening portion of the mounting base 11 and bonded to the diaphragm 7 of the diaphragm plate 9 with, for example, an adhesive made of silicon. The completed linear head is attached to the main body device by means of a mounting base 11 and screws (not shown). Needless to say, the linear head described above is not blocked by the protrusion of the adhesive made of epoxy and is airtight.

  Explaining the injection operation of the injection material from the nozzle, the injection material flows from the injection material tank (not shown) in the order of the injection material supply path 10, the filter unit 8, the restrictor 5, the pressurizing chamber 3, and the nozzle 1. By applying and cutting the electrical signal to the piezoelectric element 12, the diaphragm 7 of the diaphragm plate 9 repeatedly bends and restores, ejecting a spray material droplet from an arbitrary nozzle 1, and spraying the spray material into the pressurizing chamber 3 The supply is repeated.

  As the injection material used for the linear head described above, there are a support material for forming a support layer, and a shaped article material to be injected after the support material injection.

As the support material, one to multiple components selected from fatty acid amide, polyester, polyvinyl acetate, silicone resin, coumarone resin, fatty acid ester, glyceride, wax and the like are used. Since these support materials have a melting point of about 70 to 90 ° C., the linear head composed of the above components and the support material tank (not shown) need to be stably maintained at a high temperature of at least 100 ° C. or more by heater control or the like. There is. Further, it is important that the support material is excellent in heat resistance.
Since these support materials are solidified as soon as they adhere to the recording medium after being ejected from the nozzles, high-speed recording is possible. Furthermore, not only is drying after recording unnecessary, but the solvent is not evaporated and the environment is excellent.

  Examples of the fatty acid amide include monoamide, bisamide, tetraamide, polyamide, and ester amide. The monoamide is used by mixing at least one selected from lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, palmitic acid amide, behenic acid amide, brassic acid amide and the like. be able to. N-substituted fatty acid amides may be used, N, N′-2-hydroxtearic acid amide, N, N′-ethylenebisoleic acid amide, N, N′-xylene bisstearic acid amide, stearic acid monomethylolamide N-oleyl stearic acid amide, N-stearyl stearic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide , N, N'-distearylisophthalic acid amide, 2-stearamide ethyl stearate, or the like can be used in combination.

  As the bisamide, N, N′-ethylenebisoleic acid amide, N, N′-xylene bisstearic acid amide, or the like is selected. As tetraamide, UNIREZ 2224, UNIREZ 2970 (manufactured by Union Camp) and the like can be used. Polyamide is SYLVAMID E-5 (manufactured by Arizona Chemical), DPX 335-10, DPX H-415, DPX 335-11, DPX 830, DPX 850, DPX 925, DPX 927, DPX 1160, DPX 1163, DPX 1175, DPX 1196, DPX 1358, Versamide 711, Versamide 725, Versamide 930, Versamide 940, Bar Salon 1117, Bar Salon 1138, Bar Salon 1300 (manufactured by Henkel), Tomide 391, Tomide 393, Tomide 394, Tomide 395, Tomide 397, Tomide 509, tomide 535, tomide 558, tomide 560, tomide 1310, tomide 1396, tomide 90, tomide 92 (above, wealth Chemical Industry Co., Ltd.), and the like can be used. The ester amide is typically a fatty acid ester amide such as stearic acid ester amide, and CPH-380N (manufactured by CP Hall), Kawaslip SA (manufactured by Kawaken Fine Chemical) and the like can be used.

  Moreover, KTR2150 (made by Kao) as polyester, AC401, AC540, AC580 (above, made by Allied Chemical) as polyvinyl acetate, silicone SH6018 (made by Toray Silicone) as silicone resin, silicone KR215, silicone KR216, silicone KR220 (above, Shinetsu) Silicone) and Escron G-90 (manufactured by Nippon Steel Chemical Co., Ltd.) can be used as a coumarone resin.

  As the fatty acid ester, a monohydric or polyhydric alcohol fatty acid ester is desirable. For example, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, polyethylene glycol monostearate, polyethylene glycol distearate, propylene glycol monostearate, ethylene glycol distearate and the like are selected. Specifically, rheodol SP-S10, rheodol SP-S30, rheodol SA10, emazole P-10, emazole S-10, emazole S-20, emazole B, rheodol super SP-S10, emmanon 3299, emmanon 3299, exepar PE-MS (above, manufactured by Kao Corporation), UNISTAR M9766, UNISTA-M2222SL (above, made by NOF Corporation) and the like can be used.

  Furthermore, higher alcohol esters of higher fatty acids such as myricyl serotate, ceryl serotic acid, ceryl montanate, myricyl palmitate, myricyl stearate, cetyl palmitate, cetyl stearate and the like are selected.

  As the glyceride, stearic acid monoglyceride, palmitic monoglyceride, oleic acid monoglyceride, behenic acid monoglyceride and the like are selected. Specifically, rheodol MS-50, rheodol MS-60, rheodol MS-165, rheodol Mo-60, and exepal G-MB (above, manufactured by Kao) are selected.

  As the wax, petroleum wax such as paraffin wax, microcrystalline wax and Fischer-Tropsch wax, plant wax such as candelilla wax and carnauba wax, special ester wax, polyethylene wax and the like are selected. Specifically, deodorized and purified carnauba wax No. 1 is used. 1. Refined candelilla wax No. 1 1 (above, made by Celerica Noda), synchrowax ERL-C, synchrowax HR-C (above, made by Croda) can be used. Exepearl DS-C2 (manufactured by Kao) is selected as the special ester wax.

  High molecular weight resins such as alicyclic saturated hydrocarbon resins, rosin resins, hydrocarbon resins, amide resins, acrylic and methacrylic polymers, styrene polymers, ethylene vinyl acetate copolymers, polyketones, etc. Can also be added.

  In order to further develop functionality, various surface treatment agents, surfactants, viscosity modifiers, adhesion promoters, antioxidants, anti-aging agents, crosslinking accelerators, ultraviolet absorbers, plasticizers, preservatives, dispersions It is good to mix agents.

  As the colorant, dyes and pigments that are dissolved or stably dispersed in the above-mentioned support material and are excellent in thermal stability are suitable. Soluble dyes are desirable, but are not particularly limited. Also, two or more kinds of colorants can be mixed in a timely manner by adjusting the color.

Specifically, there are the following dyes.
<Magenta dye>
MS Magenta VP, MS Magenta HM-1450, MS Magenta Hso-147 (Mitsui Toatsu), AIZEN SOT Red series, SPIRON Red GEHSSPECIAL (Hodogaya Chemical), MACROLEX ROT 5B (Bayer Japan) REDASET KAYASET Red 802 (Nippon Kayaku), ROSE Bengal (Daiwa Kasei), DIARESIN Red K (Mitsubishi Kasei), Oil Red (BASF Japan), Oil Pink 330 (Central Synthetic Chemistry).
<Cyan dye>
MS Cyan HM-1238, MS Cyan VPG (Mitsui Toatsu), AIZEN SOT Blue-4 (Hodogaya Chemical), MACROLEX Blue RR (Bayer Japan), KAYASET Blue N, KAYASET Blue 814 (Nippon Kayaku), DAIWA 7000 , Oleosol Fast Blue GL (Daiwa Kasei), DIARESINBlue P (Mitsubishi Kasei), SUDAN Blue 670, NEOPEN Blue 808, ZAPON Blue 806 (BASF Japan).
<Black dye>
MS BLACK VPC (Mitsui Toatsu), AIZEN SOT BLACK-1, AIZEN SOT BLACK-5 (Hodogaya Chemical), RESOLIN BLACK BS (Bayer Japan), KAYASET BLACK A-N (Nippon Kayaku), DAIWA BLACK MSC (Daiwa) Kasei), HSB-202 (Mitsubishi Kasei), NEPTUNE BLACK X60, NEOPEN BLACK X58 (BASF Japan), Oleosol Fast BLACK RL (Taoka Chemical Industries), Chuo BLACK80, Chuo BLACK80-15 (Central Synthetic Chemistry).

  As the pigment, various organic and inorganic pigments can be used. Specific product names include, for example, Chromo Fine Magenta 6880, 6891N, 6790, 6887, Chromo Fine Red 6830, Chromo Fine Blue HS-3, 5187, 5197, 5085N, SR-4937, 4933GN-EP, 5214, 5221, 5000P, Chromo Fine Black A-1103, Seika Fast Red 8040, CA120, LR-116, 1531B, 8060R, ZAW-262, 1537B, 4R-4016, ZA-215, Seikalite Violet B800, 7805, Seikalite Blue C718, A612, cyanine blue 4933M, 4933GN-EP, 4940, 4973 (manufactured by Dainichi Chemical Industries), KET Red 301, 302, 303, 304, 305, 306, 30 7, 308, 309, 310, 336, 337, 338, 346, KET Blue 101, 102, 103, 104, 105, 106, 111, 118, 124 (manufactured by Dainippon Ink and Chemicals, Inc.), Colortex Red 115, 116, D3B, H-1024, Colortex Violet 600, Pigment Red 122, Colortex Blue 516, 517, 518, 519, A818, P-908, Colortex Black 702, U905 (manufactured by Sanyo Dye), Lionol Blue FG350F, G7530G, 05G (Manufactured by Toyo Ink), carbon black # 2600, # 2400, # 2350, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 850, MCF88, # 750, # 650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, # 52, # 50, # 47, # 45, # 45L, # 40, # 33, # 32, # 30, # 25, # 20, # 10, # 44, CF9 (manufactured by Mitsubishi Chemical) and the like.

  The material for the modeled object is not particularly limited as long as the melting point of the modeled material = [(the melting point of the support material) − (5 to 30)] ° C. or less, but the active energy ray irradiation, Examples include active energy ray-curable or thermosetting compounds that are cured by heating or the like.

  An active energy ray-curable compound is a compound that undergoes radical polymerization or cationic polymerization upon irradiation with active energy rays. As a compound that undergoes radical polymerization, a compound having an ethylenically unsaturated group, a compound that undergoes cationic polymerization, A compound having an alicyclic epoxy group or an oxetane ring is preferably used.

  The photo-curable resin monomer in the molding material is a resin monomer having a relatively low viscosity having an unsaturated double bond capable of radical polymerization in the molecular structure, for example, a monofunctional 2-ethylhexyl (meth) Acrylate (EHA), 2-hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl (meth) acrylate (HPA), caprolactone modified tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, caprolactone ( Acrylate), ethoxylated nonylphenol (meth) acrylate, bifunctional tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Neopentyl glycol hydroxypivalate ester di (meth) acrylate (MANDA) and hydroxypivalate neopentyl glycol ester di (meth) acrylate (HPNDA), 1,3-butanediol di (meth) acrylate (BGDA), 1,4 -Butanediol di (meth) acrylate (BUDA), 1,6-hexanediol di (meth) acrylate (HDDA), 1,9-nonanediol di (meth) acrylate , Diethylene glycol di (meth) acrylate (DEGDA), neopentyl glycol di (meth) acrylate (NPGDA), tripropylene glycol di (meth) acrylate (TPGDA), caprolactone-modified hydroxypivalic acid neopentyl glycol ester di (meth) acrylate, Propoxylated opentyl glycol di (meth) acrylate, ethoxy modified bisphenol A di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, multifunctional trimethylolpropane tri (meth) Acrylate (TMPTA), pentaerythritol tri (meth) acrylate (PETA), dipentaerythritol hexa (meth) acrylate ( DPHA), triallyl isocyanate, ε-caprolactone modified dipentaerythritol (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylol Propane tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ethoxylated pentaerythritol tetra (meth) ) Acrylate, penta (meth) acrylate ester and the like are preferable.

  Specifically, KAYARAD TC-110S, KAYARAD R-128H, KAYARAD R-526, KAYARAD NPGDA, KAYARAD PEG400DA, KAYARAD MANDA, KAYARAD R-167, KAYAARAD HX-220, AD R-712, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD TPA-320, KAYARAD TPA-330, KAYARAD PET-30, KAYARAD RPAR-40, KAYARAD RPAR-40 KAYARAD DPHA, KAYARAD DPHA -2C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYAARAD DPCA-120, KAYARAD DN-0075, KAYARAMAD DN-2475, KAYAMER AM -21, KS series HDDA, TPGDA, TMPTA, SR series 256, 257, 285, 335, 339A, 395, 440, 495, 504, 111, 212, 213, 230, 259, 268, 272, 344, 349, 601 602,610,9003,368,415,444,454,492,499,502,9020,9035,295,355,399E494,9041203 208, 242, 313, 604, 205, 206, 209, 210, 214, 231E239, 248, 252, 297, 348, 365C, 480, 9036, 350 (above, manufactured by Nippon Kayaku), Beam set 770 (Arakawa Chemical) Can be used.

  Moreover, as a photopolymerizable prepolymer, the photopolymerizable prepolymer used for manufacture of an ultraviolet curable resin can be used. Examples of the prepolymer include polyester resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, ether resins, acrylates such as polyhydric alcohols, and methacrylates without limitation. Moreover, it can be used also about water-soluble resin and emulsion type photocurable resin. Specifically, polyester (meth) acrylate, bisphenol epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, propylene oxide modified bisphenol A epoxy (meth) acrylate, alkali-soluble epoxy (meth) acrylate, acrylic Modified epoxy (meth) acrylate, phosphoric acid modified epoxy (meth) acrylate, polycarbonate urethane (meth) acrylate, polyester urethane (meth) acrylate, alicyclic urethane (meth) acrylate, aliphatic urethane (meth) acrylate, polybutadiene (Meth) acrylate, polystyryl (meth) acrylate, etc. can be mentioned.

  For example, diamond beam UK6105, diamond beam UK6038, diamond beam UK6055, diamond beam UK6063, diamond beam UK4203 (manufactured by Mitsubishi Rayon), Olester Ra1574 (manufactured by Mitsui Chemicals), KAYARAD UX series 2201, 2301, 3204, 3301, 4101, 6101 , 7101, 8101, KAYARAD R & EX series, 011, 300, 130, 190, 2320, 205, 131, 146, 280, KAYARAD MAX series, 1100, 2100, 2101, 1022, 2203, 2104, 3100, 3101, 3510, 3661 (Nippon Kayaku), Beam Set 700, 710, 720, 750, 502H, 504H, 505A-6, 510, 550B, 551B, 75, 261, 265, 267, 259, 255, 271, 243, 101, 102, 115, 207TS, 575CB, AQ-7, AQ-9, AQ-11, EM-90, EM-92 (above, Arakawa Chemical) Manufactured by Kogyo), 0304TB, 0401TA, 0403KA, 0404EA, 0404TB, 0502TI0502TC, 102A, 103A, 103B, 104A, 1312MA, 1403EA, 1422TM, 1428TA, 1438MG, 1551MB, IBR-305, 1FC-507, 1SM-012, 1AN- 202, 1ST-307, 1AP-201, 1PA-202, 1XV-003, 1KW-430, 1KW-501, 4501TA, 4502MA, 4503MX, 4517MB, 4512MA, 4523TI, 4537M 4557MB, 6501MA, 6508MG, 6513MG, 6416MA, 6421MA, 6560MA, 6614MA, 717-1, 856-5, QT701-45, 6522MA, 6479MA, 6519MB, 6535MA, 724-65A, 824-65, 6540MA, 6RI-350 6TH-419, 6HB-601, 6543MB, 6AZ-162, 6AZ-309, 6AZ-215, 6544MA, 6AT-203B, 6BF-203, 6AT-113, 6HY316, 6RL-505, 7408MA, 7501TE, 7511MA, 7505TC , 7529MA, MT408-13, MT408-15, MT408-42, 7CJ-601, 7PN-302, 7541MB, 7RZ-011, 7613MA, 8DL -100, 8AZ-103, 5YD-420, 9504MNS, ACRITT WEM-202U, 030U, 321U, 306U, 162, WBR-183U, 601U, 401U, 3DR-057, 829, 828 (manufactured by Taisei Kako) .

  Furthermore, as the photopolymerization initiator, any substance that generates radicals upon irradiation with light (particularly, ultraviolet light having a wavelength of 220 nm to 400 nm) can be used. Specifically, acetophenone, 2,2-diethoxy can be used. Acetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin-n-propyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzylmethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy-2-methyl- -Phenyl-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, methylbenzoyl formate, 1-hydroxycyclohexyl phenyl ketone, azobisisobutyronitrile, benzoyl peroxide, Examples include di-tert-butyl peroxide. These photopolymerization initiators can be used alone or in combination.

  When irradiating light (especially ultraviolet light), the pigment in the ink composition according to the present invention is increased for the purpose of preventing the curing rate from being lowered due to absorption or concealment of light (especially ultraviolet light). Sensitizers can also be used. Sensitizers include aliphatic amines, aromatic amines, or cyclic amine compounds such as piperidine, urea compounds such as o-tolylthiourea, soluble salts of sodium diethylthiophosphate or aromatic sulfinic acid, etc. Sulfur compounds, nitrile compounds such as N, N′-disubstituted-p-aminobenzonitrile, phosphorus compounds such as tri-n-butylphosphine or sodium diethyldithiophosphide, Michler's ketone, N-nitrosohydroxylamine derivatives, oxazolidine compounds, Examples include nitrogen compounds such as tetrahydro-1,3-oxazine compounds, formaldehyde or a condensate of acetaldehyde and diamine. These sensitizers can be used alone or in combination.

  As the colorant, dyes and pigments that are dissolved or stably dispersed in the material for shaped articles are suitable. Although it does not specifically limit, what was described in the material for supports can be used. Also, two or more kinds of colorants can be mixed in a timely manner by adjusting the color.

  In the material for modeling objects according to the present invention, it is preferable that the ink composition of the present invention contains a low boiling point organic solvent (particularly a low boiling point alcohol) for the purpose of increasing the drying speed. Examples of the low boiling point alcohol include aliphatic alcohols having 1 to 4 carbon atoms, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, or isobutyl alcohol. Etc.

  These low boiling point organic solvents can be used alone or in combination. The content of the low-boiling organic solvent (particularly low-boiling alcohol) is preferably 1 to 30% by weight, more preferably 10 to 20% by weight, based on the total weight of the ink composition. If it exceeds 30% by weight, there may be a problem in dischargeability, and if it is less than 1% by weight, the drying rate may be lowered.

  Examples of means for curing the modeling material include an ultraviolet (UV) irradiation lamp and an electron beam. It is preferable that a mechanism for removing ozone is provided. Examples of the lamp include high pressure mercury lamp, ultra high pressure mercury lamp, and metal halide. The ultra-high pressure mercury lamp is a point light source, but the Deep UV type, which has high light utilization efficiency in combination with an optical system, can irradiate in a short wavelength region. Metal halide is effective for colored materials because of its wide wavelength range. Metal halides such as Pb, Sn, and Fe are used and can be selected according to the absorption spectrum of the photoinitiator. Any lamp that is effective for curing can be used without particular limitation. For example, a commercially available product such as an H lamp, D lamp, or V lamp manufactured by Fusion System can also be used.

  Next, an example in which a large number of the linear heads are arranged and integrated will be described with reference to FIG. First, the arrangement method of the linear heads will be described. The pitch between the five nozzles 1 provided on the nozzle plate 2 is set to four times the predetermined resolution pitch. Reference numeral 15 denotes a multi-head unit in which four linear heads composed of the nozzle plate 2 are fixed to the fixed plate 16 while being shifted stepwise by a predetermined resolution pitch in the vertical direction of the arrows A and B. Here, the direction of arrow A is the forward path when the linear head composed of the nozzle plate 2 is moved, and the direction of arrow B is the return path, which is operated by a uniaxial drive mechanism (not shown). Reference numerals 17 and 18 denote multi-head units having the same configuration as the multi-head unit 15 and are fixed to the fixed plate 16 so that predetermined resolution pitches in the vertical direction in the directions of arrows A and B are connected. Further, 19 and 20 are fixed plates having a multi-head unit configuration similar to the fixed plate 16 to which the multi-head units 15, 17 and 18 are fixed. The multi-head units 21, 22 and 23 and the multi-head units 24, 25 and 26 are The fixing plates 16, 19, and 20 are fixed with screws (not shown) so as to be integrated. The nozzle arrangement heights in the vertical direction in the directions of arrows A and B between the multi-head units 15, 21, 24, between the multi-head units 17, 22, 25, and between the multi-head units 18, 23, 26 are all the same.

  The injection operation of the injection material from each linear head will be described. The multi-head units 15, 17, and 18 of the fixed plate 16 and the multi-head units 24, 25, and 26 of the fixed plate 20 are room temperature that is a support material. Thus, the solid ink is configured to be ejected from the multi-head units 21, 22, and 23 of the fixed plate 19 by the photocurable resin ink that is the material for the modeled article. Here, when the integrated fixed plates 16, 19, 20 move in the direction of the arrow A as the forward path, the multi-head units 15, 17, 18 are used, and when they move in the direction of the arrow B as the return path, the multi-plates Solid ink that forms a support is ejected from the head units 24, 25, and 26. Here, when moving in the directions of arrows A and B, the multi-head units 15, 17, and 18 and the multi-head units 24, 25, and 26 control the ejection timing of the solid ink so that a predetermined resolution is obtained at a predetermined position.

  The support is laminated by ejecting ink while repeating the above operations. Into the grooves and weirs of the support thus completed, the photocurable resin ink, which is the material for the molded article, is jetted from the multi-head units 21, 22, and 23 as necessary, and is polymerized and cured by an ultraviolet irradiator (not shown). Therefore, even if this photocurable resin ink is liquid at room temperature, there is no concern about “sagging”. Further, even if it is necessary to eject the photocurable resin ink every time when the integrated fixed plates 16, 19, and 20 are moved forward and backward, the multi-head unit 21 that ejects the photocurable resin ink is required. , 22, 23 are located at both sides of the multi-head units 15, 17, 18 and the multi-head units 24, 25, 26 that eject solid ink at room temperature. After the jetting, the photocurable resin ink can be jetted, and the lamination speed can be increased. Further, even if the nozzles of the multi-head units 15, 17, and 18 that eject solid ink at room temperature are ejected, that corresponds to the ejection of the other multi-head units 24, 25, and 26. It is also possible to perform alternative injection with the nozzle at the position. In this case, there is a need for a control device that detects injection, that is, nozzles, and performs alternative injection with other nozzles.

  FIG. 4 shows another example in which the arrangement method of the linear heads is changed. Reference numeral 27 denotes a plurality of nozzle plates 2 which are inclined so that the pitch between the nozzles 1 has a predetermined resolution in the vertical direction of the arrow A direction which is the forward path when moving the linear head and the arrow B direction which is the return path. It is a fixed plate. 28 and 29 are fixed plates having the same arrangement of the nozzle plates 2 as the fixed plate 27. The fixed plate 27 and the fixed plate 27 are arranged so that the nozzle arrangement heights of the nozzle plates 2 between the fixed plates 27, 28 and 29 are all the same. It is integrated.

  The fixing plates 27 and 29 are configured to eject ink that is solid at room temperature, which is a support material, and the photocurable resin ink, which is a material for a model, from the fixing plate 28. In addition, about the injection operation | movement from each linear head, since it is the same as the description in FIG. 3, it abbreviate | omits.

  As described above, when the plurality of nozzle plates 2 are arranged to be inclined with respect to the directions of the arrows A and B when the linear head is moved, not only the mounting density of the nozzle plate with respect to the fixed plate can be increased, but also the nozzle plate is added. Since the injection width in the vertical direction of the arrows A and B can be increased by that amount, there is an advantage that the specified injection width can be efficiently set using a minimum number of nozzle plates.

  FIG. 5 is a schematic diagram illustrating an example of a molded article manufacturing process according to the present invention. The modeling apparatus 39 uses the multi-head unit in which the linear heads shown in FIGS. 3 to 4 are arranged, and supplies the modeling object material from the modeling object ink ejection head unit 30, and the support ink ejection head units 31, 32. Then, the support material is sprayed and laminated while the molded material is cured by the adjacent ultraviolet irradiators 33 and 34.

  When the multi-head unit moves in the direction of the arrow A, the support 36 and the model 35 are basically moved using the ink jet head unit 31 for the support, the ink jet head unit 30 for the model, and the ultraviolet irradiator 34. It forms on the molded article support substrate 37. The support ink jet head unit 32 and the ultraviolet irradiator 33 may be used supplementarily. The surface of the laminated support material is smoothed by the heat generated by the ultraviolet irradiation, and as a result, the dimensional stability of the shaped article can be improved.

  Moreover, this structure arrange | positions the ink jet head unit for support bodies between the ink jet head unit for model objects (UV curable ink) and a UV irradiator, so that leakage light and reflected light can be generated from ink for model objects ( UV curable ink) It is difficult to hit the ejection head unit, and it is difficult to cause clogging due to thickening or curing of ink in the nozzle portion.

  When the multi-head unit moves in the direction of arrow B, the support 36, the modeled object is basically used by using the ink jet head unit 32 for the support, the ink jet head unit 30 for the modeled object, and the ultraviolet irradiator 33. 35 is formed on the molded article support substrate 37. The support ink jet head unit 31 and the ultraviolet irradiator 34 may be used supplementarily. The surface of the laminated support material is smoothed by the heat generated by the ultraviolet irradiation, and as a result, the dimensional stability of the shaped article can be improved.

  Further, in order to keep the gap between the ink jet head units 30, 31, 32 and the ultraviolet irradiators 33, 34, the modeled object 35, and the support 36, the layers are stacked while lowering the stage 36 according to the number of times of stacking. The environmental temperature sensor 41 measures the environmental temperature of the modeling apparatus 39 as a whole, or the environmental temperature in the vicinity of the layered surface of the modeled object and the support, and controls the temperature by a temperature control unit (not shown). The environmental temperature sensor 41 is installed at a height as shown in the figure.

  FIG. 6 is a schematic diagram illustrating an example of a molded article manufacturing process that can improve the smoothness of each layer as compared with FIG. 5. The basic steps are the same as those in FIG. 5 except that the ultraviolet irradiators 33 and 34 are arranged between the molded material injection head 30 and the support material injection heads 31 and 32. In the apparatus of this system, the ultraviolet irradiators 33 and 34 are used when moving in the directions of arrows A and B, and the surface of the laminated support material is smoothed by the heat generated by the ultraviolet irradiation. As a result, the dimensional stability of the shaped article can be improved.

  The environmental temperature sensor 41 measures the environmental temperature of the modeling apparatus 39 as a whole, or the environmental temperature in the vicinity of the layered surface of the modeled object and the support, and controls the temperature by a temperature control unit (not shown). The environmental temperature sensor 41 is preferably installed at a height as shown in the figure.

  As an apparatus, it is possible to add an ink recovery and recycling mechanism. A blade for removing ink adhering to the nozzle surface and a non-ejection nozzle detection mechanism may be provided.

  FIG. 7 is a schematic view of the three-dimensional additive manufacturing apparatus configuration of FIG. 6 as viewed from above. The environmental temperature sensor 41 is located slightly away from the model support substrate 37 and the stage 38 so as not to collide with the model ink jet head unit 30, the support ink jet head units 31 and 32, and the UV irradiators 33 and 34. It is good to install in.

  EXAMPLES Next, although an Example demonstrates this invention concretely, it is not limited to a description example.

  10 parts by weight of urethane acrylate (Mitsubishi Rayon, trade name: Diabeam UK6038) and 90 weights of neopentyl glycol hydroxypivalate ester di (meth) acrylate (Nippon Kayaku, trade name: KAYARAD MANDA) as materials for modeling Homogenizer (Hitachi) 3 parts by weight and photopolymerization initiator (product name: Irgacure 1700, manufactured by Ciba Specialty Chemicals) and 2 parts by weight of blue pigment (product name: Lionol Blue 7400G, manufactured by Toyo Ink) as a colorant Using a machine tool HG30), dispersion was performed at a rotational speed of 2,000 rpm until a homogeneous mixture was obtained, followed by filtration to remove impurities and the like to obtain a uniform ink composition for a modeled article. The viscosity of the ink was measured with a rotational viscometer (ELD model manufactured by Tokimec), and the surface tension was measured with an automatic surface tension meter (CVBP-Z model manufactured by Kyowa Interface Science). In either case, the measurement temperature is 25 ° C. The viscosity was 9.5 mPa · s, and the surface tension was 32.5 mN / m.

  As the material for the support, 50 parts by weight of carnauba wax (manufactured by Celalica Noda, trade name: deodorized and purified carbauba wax No. 1), 50 parts by weight of ester amide (manufactured by Kawaken Fine Chemicals, Kawaslip SA), colorant As a black pigment (Mitsubishi Chemical Co., Ltd., trade name: MA77) 3 parts by weight are dispersed using a homogenizer (Hitachi Koki HG30) at a rotational speed of 2,000 rpm until a homogeneous mixture is obtained, followed by filtration. Then, impurities and the like were removed to obtain a homogeneous ink composition for a support. The viscosity of the ink was 11.0 mPa · s, and the surface tension was 20.0 mN / m. All are measured values at 130 ° C. of the injection temperature. The melting point was measured with a micro melting point apparatus MP-S3 manufactured by Yanagimoto Seisakusho. About 3 mg of ink was placed on the sample stage and heated at a rate of temperature increase of about 2 ° C./min. In general, the melting point is the temperature from the beginning of the ink to the end of melting. The melting point in the present invention refers to the temperature at which the ink starts to melt. The melting point of the ink of this example was 75 ° C.

6, the environmental temperature in the modeling apparatus 39 is controlled to 50 ° C., and the molded article material is cured by irradiating a light amount of 350 mJ / cm ² with an ultraviolet irradiation apparatus (USHIO, SP5-250DB). The model was formed while letting it go. The formed object had a smoother surface state without warping or partial deformation.

Using the same modeling material and support material as in Example 1, the environment temperature in the modeling apparatus 39 is controlled to 70 ° C. with the apparatus having the configuration shown in FIG. 6, and an ultraviolet irradiation device (USHIO, SP5- The molded object was formed while irradiating a light amount of 250 mJ / cm ² at 250 DB) to cure the molded object material. The formed object had a smoother surface state without warping or partial deformation.

Using the same modeling material and support material as in Example 1, the environment temperature in the modeling apparatus 39 is controlled at 45 ° C. with the apparatus having the configuration shown in FIG. 6, and an ultraviolet irradiation device (USHIO, SP5- 250DB), a molded object was formed while irradiating a light quantity of 350 mJ / cm ² to cure the molded object material. The formed object was not warped or partially deformed. The surface condition was slightly lacking in smoothness.

Using the same modeling material and support material as in Example 1, the environment temperature in the modeling apparatus 39 is controlled to 55 ° C. with the apparatus having the configuration shown in FIG. 6, and an ultraviolet irradiation device (USHIO, SP5- 250DB), a molded object was formed while irradiating a light amount of 300 mJ / cm ² to cure the molded object material. The formed object had a smoother surface state without warping or partial deformation.

Using the same modeling material and support material as in Example 1, the environment temperature in the modeling apparatus 39 is controlled to 60 ° C. with the apparatus having the configuration shown in FIG. 250DB), a molded object was formed while irradiating a light amount of 300 mJ / cm ² to cure the molded object material. The formed object had a smoother surface state without warping or partial deformation.

By using the same modeling material and support material as in Example 1, the environment temperature in the modeling apparatus 39 is controlled to 65 ° C. with the apparatus having the configuration shown in FIG. 250DB), a molded object was formed while irradiating a light amount of 300 mJ / cm ² to cure the molded object material. The formed object had a smoother surface state without warping or partial deformation.
<Comparative Example 1>

Using the same modeling material and support material as in Example 1, the environment temperature in the modeling apparatus 39 is controlled to 71 ° C. with the apparatus having the configuration shown in FIG. 6, and an ultraviolet irradiation device (USHIO, SP5- 250DB), a molded object was formed while irradiating a light amount of 300 mJ / cm ² to cure the molded object material. Depending on the shape of the modeled object, the formed model may partially deform the support material, resulting in poor dimensional stability of the modeled object.
<Comparative example 2>

Using the same modeling material and support material as in Example 1, the environment temperature in the modeling apparatus 39 is controlled to 44 ° C. with the apparatus having the configuration shown in FIG. 250DB), a molded object was formed while irradiating a light amount of 300 mJ / cm ² to cure the molded object material. The formed object was slightly deformed or misaligned at the end or elongated part. The surface condition was not smooth.

It is a disassembled perspective view of a linear head. It is a fragmentary sectional view of a linear head. It is a schematic diagram which shows the nozzle arrangement state of a linear head. It is a schematic diagram which shows the nozzle arrangement state of a linear head. It is the schematic which shows the structure of the three-dimensional layered modeling apparatus which becomes an example of this invention. It is the schematic which shows the structure of the three-dimensional layered modeling apparatus which becomes another example of this invention. It is the schematic which looked at the three-dimensional additive manufacturing apparatus structure of FIG. 6 of this invention from upper direction.

Explanation of symbols

1 is a nozzle, 2 is a nozzle plate, 3 is a pressurizing chamber, 4 is a pressurizing chamber plate, 5 is a restrictor, 6 is a restrictor plate, 7 is a diaphragm, 8 is a filter section, 9 is a diaphragm plate, 10 is Injection material supply path, 11 is a mounting base, 12 is a piezoelectric element, 13 is an adhesive, 14 is a support substrate, 15, 17, 18, 21, 22, 23, 24, 25, 26 are multi-head units, 16, 19 , 20, 27, 28, 29 are fixed plates. Further, 30 is an ink jet head unit for a model, 31 and 32 are ink jet head units for a support, 33 and 34 are UV irradiators, 35 is a model, 36 is a support, 37 is a model support substrate, 38 Is a stage, 39 is a modeling apparatus, and 41 is an environmental temperature sensor.

Claims (7)

In the three-dimensional layered manufacturing method of molded object to perform molding by injecting shaped object material and the support-body material so as to be embedded in the support layer by an inkjet method, shaping at environmental temperature of the support material of A three-dimensional additive manufacturing method characterized by controlling the melting point within a range from (melting point-30) ° C. to (melting point-5) ° C. The three-dimensional additive manufacturing method according to claim 1, wherein an active energy ray-curable compound is used as the material for the modeled article. 3. The three-dimensional additive manufacturing method according to claim 2, wherein the support material is meltable or deformable by active energy ray irradiation. An active energy ray irradiator is arranged adjacent to an inkjet head that ejects a support material, and modeling is performed while the support material is cured by irradiating the active energy ray irradiator. The three-dimensional additive manufacturing method according to claim 3. Three dimensional laminate molding method according to claim 1, any one of 4, wherein the molded material and the support material is shaped in a different color. Three-dimensional layered manufacturing method of 請 Motomeko 5 wherein you, characterized in that the support-body material comprises a colorant. 7. The three-dimensional additive manufacturing method according to claim 6, wherein a support material to which at least one black dye, black pigment, dark dye or pigment is added is used.

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