WO2017038985A1 - 立体造形物の製造方法及びこれに用いられるノズル移動経路のデータ作成方法、並びに立体造形物の製造装置及びこれに用いられるノズル移動経路のデータ作成プログラム - Google Patents
立体造形物の製造方法及びこれに用いられるノズル移動経路のデータ作成方法、並びに立体造形物の製造装置及びこれに用いられるノズル移動経路のデータ作成プログラム Download PDFInfo
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- WO2017038985A1 WO2017038985A1 PCT/JP2016/075845 JP2016075845W WO2017038985A1 WO 2017038985 A1 WO2017038985 A1 WO 2017038985A1 JP 2016075845 W JP2016075845 W JP 2016075845W WO 2017038985 A1 WO2017038985 A1 WO 2017038985A1
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
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Definitions
- the present invention is a method for manufacturing a three-dimensional object to be molded by a three-dimensional object material discharged from a nozzle onto a stage, a nozzle moving path data creation method used therefor, a three-dimensional object manufacturing apparatus, and the same.
- the present invention relates to a nozzle creation path data creation program.
- Soft three-dimensional objects such as high-performance gels and soft materials are new organic materials that are expected to be applied to human body organ models, medical equipment parts, artificial skin, artificial blood vessels, automobile parts, and the like.
- an outer shell portion made of a photocurable resin cured body is formed based on tomographic data obtained by MRI or CT scan of the patient himself, and the outer shell is formed. It is described that the inner cavity part located inside the part is filled with a core part made of a fluidizable solid. In this manufacturing method, the outer shell portion is formed by stereolithography.
- the surface of the photocurable resin stored in the liquid tank is scanned with an ultraviolet laser to cure the photocurable resin, and the surface of the liquid tank is raised stepwise to be cured.
- the three-dimensional modeled object is formed by laminating a plurality of photocurable resins.
- a hot melt lamination method is known.
- a long solid resin called a filament is sent to a nozzle part equipped with a heater by a feed part such as a drive roller, and the molten solid resin discharged from the nozzle part is laminated on the stage.
- the three-dimensional model is being modeled.
- the three-dimensional modeling material may flow or deform during modeling. Therefore, when molding a three-dimensional modeled object, it is necessary to select whether to reduce the modeling speed in order to improve the modeling precision or to reduce the modeling precision in order to improve the modeling speed. It was difficult to improve both the modeling speed. In particular, when modeling a three-dimensional model having a soft part, it is particularly difficult to improve both the modeling accuracy and the modeling speed because the three-dimensional model material tends to flow or deform during modeling.
- This invention is made
- One aspect of the first invention is an outer shell that is part of an outer shell of a three-dimensional object to be molded by moving the nozzle and the stage relative to each other while discharging the three-dimensional object material from the nozzle onto the stage. Forming a wall, While discharging the material for three-dimensional modeling from the nozzle to the inner region surrounded by the outer shell wall, the nozzle and the stage are moved relative to each other to form an inner core part that becomes a part of the inner core of the three-dimensional modeled object. And a process for producing a three-dimensional structure.
- One aspect of the second invention is a method of creating nozzle movement path data used in a method of manufacturing a three-dimensional structure, Create or create 3D surface data of the 3D object to be modeled by designing or reading, The solid surface data is sliced at a predetermined interval in a predetermined direction, and processed into linear outer layer data that is stacked in a plurality in the predetermined direction, Based on the outer layer data, create data for the inner core movement path for discharging the inner core molding material from the nozzle, Manufacturing of a three-dimensional structure using the position corrected by a predetermined distance outside the movement path for the inner core section as data of the movement path for the outer shell wall section for discharging the outer shell wall section molding material from the nozzle This is a method for creating nozzle movement path data used in the method.
- Another aspect of the second invention is a method of creating nozzle movement path data used in a method of manufacturing a three-dimensional structure, Create or create 3D surface data of the 3D object to be modeled by designing or reading, The solid surface data is sliced at a predetermined interval in a predetermined direction, and processed into linear outer layer data that is stacked in a plurality in the predetermined direction, Based on the outer layer data, create data of the movement path for the outer shell wall part for discharging the outer shell wall part molding material from the nozzle, In creating the inner core movement path for discharging the inner core molding material from the nozzle, a position corrected by a predetermined distance inside the outer shell wall movement path is moved to the inner core movement. It is in the data creation method of the nozzle movement path used for the manufacturing method of a three-dimensional molded item to be the position of the outer shape in the entire path.
- One aspect of the third aspect of the invention is an apparatus for manufacturing a three-dimensional structure formed by an outer core and an inner core disposed in the outer shell, An outer shell nozzle for discharging the outer shell wall forming material for forming the outer shell; An inner core nozzle that discharges an inner core forming material for forming an inner core; and A stage on which the outer shell wall part forming material discharged from the outer shell nozzle and the inner core part forming material discharged from the inner core nozzle are stacked; A relative movement mechanism for relatively moving the stage, the outer shell nozzle and the inner core nozzle; A control computer for controlling the operation of the outer shell nozzle, the inner core nozzle and the relative movement mechanism, The control computer forms, on the stage, an outer shell wall portion that becomes a part of the outer shell by the outer shell wall portion modeling material discharged from the outer shell nozzle, and from the inner core nozzle, An apparatus for manufacturing a three-dimensional structure, which is configured to form, on the stage, an inner core portion that becomes a part of the inner core by the inner core
- One aspect of the fourth invention is a program of a design computer for creating data of movement paths of the outer shell nozzle and the inner core nozzle used in the three-dimensional structure manufacturing apparatus,
- the design computer When the three-dimensional surface data of the three-dimensional object to be modeled is sliced at a predetermined interval in a predetermined direction, the movement of the inner core nozzle is based on linear outer layer data stacked in a plurality in the predetermined direction. Creating route data; Creating a data of the movement path of the outer shell nozzle at a position corrected by a predetermined distance outside the movement path of the inner core nozzle, and executing the nozzle movement used in the three-dimensional object manufacturing apparatus. In the route data creation program.
- Another aspect of the fourth invention is a design computer program for creating data of movement paths of the outer shell nozzle and the inner core nozzle used in the three-dimensional structure manufacturing apparatus,
- the design computer When the three-dimensional surface data of the three-dimensional object to be modeled is sliced at a predetermined interval in a predetermined direction, the outer shell nozzle is based on linear outer layer data stacked in a plurality in the predetermined direction. Creating travel route data; Creating a data of the movement path of the inner core nozzle at a position corrected by a predetermined distance inside the movement path of the outer shell nozzle, and executing the nozzle movement used in the three-dimensional object manufacturing apparatus. In the route data creation program.
- a three-dimensional structure having an outer shell and an inner core is formed using a three-dimensional structure material discharged from a nozzle.
- the three-dimensional model is formed by an outer shell wall portion that is a part of the outer shell and an inner core portion that is a part of the inner core in the inner region surrounded by the outer shell wall portion.
- the outer shell wall part is preferably formed in an annular shape.
- the outer shell wall portion may not necessarily be formed in a complete ring shape, but may be formed in a ring shape in which a part is released.
- the inner core part can be held by the outer shell wall part by modeling the three-dimensional modeled object using the outer shell wall part and the inner core part. Therefore, it is possible to make the three-dimensional modeling material discharged to the stage difficult to flow or deform when forming the inner core portion, and to improve the modeling accuracy and modeling speed of the inner core portion by the three-dimensional modeling material. Furthermore, even when the inner core portion is a soft three-dimensional modeling material, the modeling accuracy and modeling speed of the inner core portion by the three-dimensional modeling material can be improved.
- the modeling accuracy and the modeling speed of the three-dimensional structure can be improved.
- the nozzle moving path data creation method as one aspect of the second invention, it is possible to create a nozzle moving path suitable for carrying out the manufacturing method of the three-dimensional structure.
- the movement path for the outer shell wall part based on the movement path for the inner core part, it is possible to easily create the movement path for the outer shell wall part.
- nozzle moving path data creation method as another aspect of the second invention, it is possible to create a nozzle moving path suitable for carrying out the manufacturing method of the three-dimensional structure.
- the inner core moving path based on the outer shell wall moving path, it is possible to easily create the inner core moving path.
- the modeling accuracy and the modeling speed of the three-dimensional structure can be improved as in the case of the method for manufacturing a three-dimensional structure.
- nozzle movement path data creation program as one aspect of the fourth invention, it is possible to provide a nozzle movement path data creation program suitable for the control computer of the three-dimensional object manufacturing apparatus.
- nozzle movement path data creation program as another aspect of the fourth invention, it is possible to provide a nozzle movement path data creation program suitable for the control computer of the three-dimensional object manufacturing apparatus.
- FIG. The flowchart which shows the manufacturing method of the three-dimensional molded item concerning Embodiment 1.
- FIG. It is a figure which shows the other manufacturing method of the three-dimensional molded item concerning Embodiment 1, and is explanatory drawing which shows the state which performed the 1st outer shell wall part formation process and the 1st inner core part formation process.
- FIG. Explanatory drawing which shows the three-dimensional molded item concerning Embodiment 2 which removes and manufactures an outer shell.
- the flowchart which shows the manufacturing method of the three-dimensional molded item concerning Embodiment 2.
- FIG. Explanatory drawing which shows the movement path for outer shell walls, and the movement path for inner core parts when moving the outer shell nozzle and the inner core nozzle and the stage relative to each other according to the third embodiment.
- Explanatory drawing which shows the movement path
- Explanatory drawing which shows the movement path
- FIG. Explanatory drawing which shows the movement path
- the manufacturing method of the three-dimensional model is a step of further forming the outer shell wall part by relatively moving the nozzle and the stage while discharging the three-dimensional model material from the nozzle onto the outer shell wall part.
- a step of further forming the inner core part by relatively moving the nozzle and the stage while discharging the three-dimensional modeling material onto the inner core part from the nozzle may be further included.
- the outer shell wall portion and the inner core portion are formed by the three-dimensional material discharged from the nozzle, it is easy to alternately form the outer shell wall portion and the inner core portion.
- a conventional stereolithography method or the like after the entire hard portion of the three-dimensional structure is molded first, the inside of the hard portion is filled with a soft portion.
- the formation speed of the three-dimensional object having the outer shell and the inner core can be improved by repeatedly forming the parts.
- a step of further forming the wall portion 21 (hereinafter referred to as a second outer shell wall portion forming step X2) and a step of further forming the inner core portion 31 (hereinafter referred to as a second inner core portion forming step Y2) are sequentially performed.
- the three-dimensional structure 1 is formed.
- the outer shell wall forming material 20 is discharged from the outer shell nozzle 5A onto the stage 6, while the outer shell nozzle 5A. And the stage 6 are moved relative to each other to form an outer shell wall portion 21 that becomes a part of the outer shell 2 of the three-dimensional structure 1 to be molded.
- the first inner core part forming step Y1 as shown in FIG. 3, while discharging the inner core part forming material 30 from the inner core nozzle 5B to the inner region surrounded by the outer shell wall part 21, The stage 6 is moved relative to each other to form an inner core portion 31 that becomes a part of the inner core 3 of the three-dimensional structure 1 to be molded.
- the outer shell nozzle 5A is discharged while discharging the outer shell wall forming material 20 from the outer shell nozzle 5A onto the outer shell wall 21. And the stage 6 are moved relative to each other to further form the outer shell wall portion 21.
- the inner core nozzle 5B and the stage 6 are relatively moved while discharging the inner core portion forming material 30 from the inner core nozzle 5B onto the inner core portion 31.
- the inner core portion 31 is further formed.
- the second outer shell wall portion forming step X2 and the second inner core portion forming step Y2 are further repeated, as shown in FIG. 6, the outer shell 2 by the outer shell wall portions 21 stacked in a plurality of steps, and a plurality of steps.
- the three-dimensional molded article 1 having the inner core 3 formed by the inner core portions 31 stacked on each other is formed.
- the manufacturing apparatus 10 used for the manufacturing method of the three-dimensional molded item 1 is demonstrated.
- a manufacturing apparatus 10 having an outer shell nozzle 5A, an inner core nozzle 5B, a stage 6, a relative movement mechanism 7 and a control computer 8 is used as shown in FIGS.
- the manufacturing apparatus 10 performs hot melt lamination molding.
- the outer shell nozzle 5 ⁇ / b> A discharges the outer shell wall portion forming material 20 for forming the outer shell 2.
- the stage 6 is formed by laminating the outer shell wall part forming material 20 discharged from the outer shell nozzle 5A and the inner core part forming material 30 discharged from the inner core nozzle 5B.
- the relative movement mechanism 7 moves the stage 6, the outer shell nozzle 5 ⁇ / b> A, and the inner core nozzle 5 ⁇ / b> B two-dimensionally relative to the planar directions X and Y of the stage 6 and has a height orthogonal to the planar direction of the stage 6.
- the relative movement is made in the direction Z.
- the control computer 8 is configured to control operations of the outer shell nozzle 5 ⁇ / b> A, the inner core nozzle 5 ⁇ / b> B, and the relative movement mechanism 7.
- the outer shell nozzle 5 ⁇ / b> A is provided in an outer shell discharge device (dispenser) 50 ⁇ / b> A that feeds the linear outer shell wall portion forming material 20 while heating.
- the inner core nozzle 5 ⁇ / b> B is provided in an inner core discharge device (dispenser) 50 ⁇ / b> B that feeds the linear inner core portion forming material 30 while heating.
- Each discharge device 50A, 50B pressurizes and extrudes each modeling material 20, 30 having fluidity.
- each discharge apparatus 50A, 50B can also extrude, heating each filament-shaped modeling material 20,30.
- Each discharge device 50A, 50B is a screw type that extrudes each modeling material 20, 30 using a screw, a piston type that extrudes each modeling material 20, 30 using a screw, and each modeling material 20, using a pump.
- Various configurations such as a pump type for extruding 30 may be adopted.
- one nozzle can be used in common.
- Each nozzle 5A, 5B is provided with an open / close mechanism (not shown) that can open and close the discharge port of each nozzle 5A, 5B in order to control the discharge of each modeling material 20, 30 and the stop of the discharge. It has been.
- the opening / closing mechanism can be configured by an opening / closing portion such as a pin or a valve for opening / closing the discharge port of each nozzle 5A, 5B, and an actuator for moving the opening / closing portion.
- the control computer 8 is configured to control the operation of the opening / closing mechanism of each nozzle 5A, 5B.
- the ejection devices 50A and 50B and the nozzles 5A and 5B are integrally provided in the head unit 51.
- the position of the head unit 51 of this embodiment is fixed, and the relative movement mechanism 7 of this embodiment is configured to move the stage 6 relative to the head unit 51.
- the stage 6 is a table on which the outer shell wall modeling material 20 and the inner core modeling material 30 for forming the three-dimensional model 1 are placed.
- the relative movement mechanism 7 of the present embodiment is configured to move the stage 6 in two directions orthogonal to each other in the horizontal direction as the plane directions X and Y, and to move the stage 6 in the vertical direction as the height direction Z. Has been.
- the relative movement mechanism 7 has three servo motors that move the stage 6 in three directions, respectively.
- the nozzles 5A and 5B and the stage 6 can be relatively moved three-dimensionally so as to form various three-dimensional shapes of the three-dimensional structure 1.
- the control computer 8 forms on the stage 6 an outer shell wall portion 21 that becomes a part of the outer shell 2 by the outer shell wall portion molding material 20 discharged from the outer shell nozzle 5A, and from the inner core nozzle 5B.
- the inner core portion 31 that is a part of the inner core 3 is formed on the stage 6 by the inner core portion forming material 30 that is discharged into the inner region surrounded by the outer shell wall portion 21.
- the control computer 8 is set with movement path data for moving the outer shell nozzle 5A relative to the stage 6 and movement path data for moving the inner core nozzle 5B relative to the stage 6. Is done.
- the data of each movement path set in the control computer 8 can be arbitrarily changed according to the shape of the three-dimensional structure 1 to be molded.
- the modeling speed of the three-dimensional object 1 having the outer shell 2 and the inner core 3 can be easily improved.
- an outer shell nozzle 5A and an inner core nozzle 5B will be described. That is, the outer shell nozzle 5A is used in the first outer shell wall forming step X1 and the second outer shell wall forming step X2, and the inner core is used in the first inner core forming step Y1 and the second inner core forming step Y2.
- Nozzle 5B is used.
- the relative movement mechanism 7 may be configured to move the nozzles 5A and 5B with respect to the stage 6.
- each nozzle 5A, 5B can be moved separately, and can also be moved integrally.
- each nozzle 5A, 5B can also be simultaneously moved separately at the same timing.
- the outer shell wall part forming material 20 and the inner core part forming material 30 have photocurability.
- the outer shell wall portion forming material 20 discharged from the outer shell nozzle 5A and the inner core portion forming material 30 discharged from the inner core nozzle 5B are irradiated with light H such as ultraviolet rays. While the polymerization reaction of the polymerizable monomer in the materials 20 and 30 is performed, the modeling materials 20 and 30 are solidified.
- the manufacturing apparatus 10 for the three-dimensional structure 1 includes a light irradiation apparatus 100 for irradiating the modeling materials 20 and 30 with light H such as ultraviolet rays.
- the light irradiation device 100 is provided integrally with the head unit 51 together with the ejection devices 50A and 50B and the nozzles 5A and 5B.
- the outer shell wall part forming material 20 for forming the outer shell wall part 21 and the inner core part forming material 30 for forming the inner core part 31 contain a polymer, a polymerizable monomer, and a solvent.
- the polymerizable monomer contains at least one selected from a radical polymerizable unsaturated compound and a cationic polymerizable compound.
- the solvent is at least one selected from polar solvents and ionic liquids.
- the outer shell wall modeling material 20 and the inner core modeling material 30 contain at least one selected from a photoradical generator and a photoacid generator in order to promote the polymerization reaction of the polymerizable monomer.
- the three-dimensional modeling material may include at least one selected from a polymer and a polymerizable monomer.
- the polymer is not particularly limited, and examples thereof include vinyl alcohol polymers, acrylic polymers, vinylidene fluoride polymers, acrylonitrile polymers, and polysaccharides.
- acrylic polymers, polyvinyl alcohols, and polysaccharides are used because they have a high strength against the solvent content expressed as M1 / M2 obtained by dividing the solvent mass M1 by the polymer mass M2. It is preferable.
- a polymer having a polymerizable functional group in the case of polymerizing and crosslinking with a polymerizable monomer described later, it is preferable to use a polymer having a polymerizable functional group.
- the polymer having a polymerizable functional group is not particularly limited, and examples thereof include a polymer having a radical polymerizable functional group and a polymer having a cationic polymerizable functional group.
- examples of the radical polymerizable functional group include a (meth) acryloyl group, a vinyl group, an allyl group, a vinyl ether group, and the like, but an acryloyl group is preferable in terms of the rate of the photoinitiated polymerization reaction.
- Examples of the cationic polymerizable functional group include propenyl ether group, vinyl ether group, alicyclic epoxy group, glycidyl group, vinyl group, vinylidene group, and the like. Propenyl ether group, vinyl ether group, alicyclic epoxy group and glycidyl group. Groups are preferred.
- Examples of the polymer having a radical polymerizable functional group include a polymer in which a functional group having reactivity with an isocyanate group has been introduced, modified with a (meth) acrylic acid derivative or vinyl derivative having an isocyanate group. be able to.
- a polymer into which a functional group having reactivity with an isocyanate group is introduced is preferable.
- Examples of such functional groups include a hydroxyl group, a carboxyl group, an amino group, an amide group, a mercapto group, and the like.
- Examples of the polymer include a polymer having a hydroxyl group, a polymer having a carboxyl group, a polymer having an amino group, a polymer having an amide group, and a polymer having a mercapto group.
- Examples of the polymer having a hydroxyl group include vinyl alcohol polymers and polysaccharides.
- Examples of polysaccharides include cellulose derivatives such as methyl cellulose, ethyl cellulose, acetyl cellulose, cellulose acetate, and cellulose triacetate, or acidic cellulose derivatives having a carboxyl group in the side chain, or polyvinyl alcohol, dextran, alkyl cellulose, agarose, pullulan, inulin, Chitosan etc. are mentioned.
- Examples of the vinyl alcohol polymer include poly-2-hydroxypropyl (meth) acrylate and poly-2-hydroxyethyl (meth) acrylate.
- Examples of the polymer having a carboxyl group include (meth) acrylic acid ester and a copolymer having (meth) acrylic acid as a copolymerization component.
- polymers having an amino group examples include polyallylamine, polyethyleneimine, poly-3-aminopropyl (meth) acrylate, poly-3-aminopropyl (meth) acrylamide, chitosan, diallylamine acetate / sulfur dioxide copolymer, acrylamide Examples include diallyldimethylammonium chloride copolymer.
- polystyrene resin examples include polyacrylamide, poly N, N-dimethylacrylamide, polyvinyl pyrrolidone, polyvinyl caprolactam, polyvinyl pyrrolidone / vinyl acetate copolymer, vinyl pyrrolidone / vinyl caprolactam copolymer, vinyl pyrrolidone / vinyl imidazole.
- Copolymer vinylpyrrolidone / acrylic acid copolymer, vinylpyrrolidone / methacrylic acid copolymer, vinylpyrrolidone / 3-methyl-1-vinylimidazolium salt copolymer, N-vinylpyrrolidone, N-vinylpiperidone, N- Examples include vinyl caprolactam, protein, polypeptide, oligopeptide and the like.
- Examples of the polymer having a mercapto group include polysulfide having a thiol group at the terminal.
- Examples of the (meth) acrylic acid derivative or vinyl derivative having an isocyanate group include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 2- (2-methacryloyloxyethyloxy) ethyl isocyanate.
- Examples of the (meth) acrylic acid derivative or vinyl derivative having an isocyanate group include those having a blocked isocyanate group.
- Examples of the blocked isocyanate group include 1,1- (bisacryloyloxymethyl) ethyl isocyanate, 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl 2-[(3 , 5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate.
- an epoxy group-containing vinyl monomer having a polymerizable vinyl group (a group having an ethylenically unsaturated bond) and one or more epoxy groups in one molecule.
- the polymer which has a structural unit derived from a body can be mentioned.
- epoxy group-containing vinyl monomer examples include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, ⁇ - (meth) acryl- ⁇ - Hydroxy group-free (meth) acrylic acid esters such as glycidyl polyethylene glycol, hydroxy group-containing (meth) acrylic acid esters such as glycerin mono (meth) acrylate glycidyl ether, or aromatic monovinyl compounds such as vinylbenzyl glycidyl ether Or allyl glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, and the like.
- epoxy group-containing monovinyl monomer epoxy group-containing (meth) acrylic acid esters and epoxy group-containing aromatic monovinyl compounds are preferable, and epoxy group-containing (meth) acrylic acid esters are more preferable.
- Glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether are more preferable, and glycidyl (meth) acrylate is particularly preferable.
- the polymer having a structural unit derived from an epoxy group-containing vinyl monomer may be a copolymer including a structural unit derived from a monomer other than the epoxy group-containing vinyl monomer.
- monomers other than epoxy group-containing vinyl monomers include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, and the like.
- (Meth) acrylamides such as acrylic acid esters, or (meth) acrylamide, dimethyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone (meth) acrylamide, etc., may be used alone or in combination of two or more. They can be used in combination.
- the weight average molecular weight (Mw) in terms of polystyrene in the polymer measured by gel permeation chromatography (GPC) is preferably 5,000 or more and 200,000 or less, and preferably 10,000 or more and 100,000 or less. It is more preferable. When the weight average molecular weight (Mw) is less than 5,000, the high strength of the three-dimensional structure obtained by molding may not be obtained. If the weight average molecular weight (Mw) is greater than 200,000, molding may be difficult due to an increase in viscosity.
- the radical polymerizable unsaturated compound means a polymerizable unsaturated compound capable of initiating polymerization by a radical species.
- a carboxyl group-containing radical polymerizable unsaturated compound, a hydroxyl group-containing radical polymerizable unsaturated compound, a hydroxyl group-containing radical examples include a reaction product of a polymerizable unsaturated compound and a lactone compound, (meth) acrylic acid esters, (meth) acrylamides, and alkoxysilyl group-containing radical polymerizable unsaturated compounds.
- carboxyl group-containing unsaturated compound examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl ( And (meth) acrylate.
- hydroxyl group-containing radical polymerizable unsaturated compound examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, acrylic acid such as 4-hydroxybutyl (meth) acrylate, and C2-C8 of methacrylic acid. Hydroxyalkyl ester, (poly) ethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, and the like.
- the reaction product of a hydroxyl group-containing radical polymerizable unsaturated compound and a lactone compound includes a hydroxyl group-containing radical polymerizable unsaturated compound, ⁇ -propiolactone, dimethylpropiolactone, butyrolactone, ⁇ -valerolactone, ⁇ Examples thereof include a reaction product with a lactone compound such as caprolactone, ⁇ -caprolactone, ⁇ -lauryllactone, ⁇ -caprolactone, and ⁇ -caprolactone.
- Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, polymethyl methacrylate (meth) acrylate, and polystyrene (meth) acrylate.
- vinyl aromatic compounds include styrene, ⁇ -methyl styrene, vinyl toluene, p-chlorostyrene, vinyl pyridine and the like.
- (Meth) acrylamides include N, N-dimethylacrylamide, diethylacrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (3 -Hydroxypropyl) (meth) acrylamide, N-methyl-N- (2-hydroxyethyl) (meth) acrylamide, N-ethyl-N- (2-hydroxyethyl) (meth) acrylamide, N-methyl-N- ( 2-hydroxypropyl) (meth) acrylamide, N-methyl-N- (3-hydroxypropyl) (meth) acrylamide, N-ethyl-N- (2-hydroxypropyl) (meth) acrylamide, N-ethyl-N- (3-hydroxypropyl) (meth) acrylamide, N, N-di- (2 Hydroxyethyl) (meth) acrylamide, N, N-di - (2-hydroxy
- Examples of the radically polymerizable unsaturated compound containing an alkoxysilyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinyltripropoxysilane, vinyl Examples include methyldipropoxysilane, vinyldimethylpropoxysilane, ⁇ - (meth) acryloyloxypropyltrimethoxysilane, ⁇ - (meth) acryloyloxypropylmethyldimethoxysilane, and ⁇ - (meth) acryloyloxypropyldimethylmethoxysilane. it can.
- examples of the radical polymerizable unsaturated compound include compounds having one radical polymerizable unsaturated bond in one molecule. However, it is not particularly limited to this, and a compound having two or more radically polymerizable unsaturated bonds in one molecule can also be used.
- divinylbenzene ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, 1,3- Butylene glycol di (meth) acrylate, 1,4-butanediol diacrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Erythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, neopentyl glycol diacrylate,
- the cationic polymerizable compound means a polymerizable compound that can initiate polymerization by a cationic species, and examples thereof include an epoxy compound, an oxetane compound, and a vinyl compound. These may be used individually by 1 type and may use 2 or more types together.
- both aliphatic epoxy and alicyclic epoxy can be used.
- an aliphatic epoxy there is no restriction
- the polyglycidyl ether of an aliphatic polyhydric alcohol or its alkylene oxide adduct etc. are mentioned.
- ethylene glycol diglycidyl ether diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6 -Hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, polyethylene glycol diglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether , Hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol G diglycidyl ether, tetramethylbisphenol A diglycidyl ether
- Epolite 100MF trimethylolpropane triglycidyl ether
- EX-411, EX-313, EX-614B manufactured by Nagase ChemteX Corporation
- Epiol E400 manufactured by NOF Corporation. Etc.
- alicyclic epoxy examples include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9 diepoxy limonene, 3,4-epoxycyclohexenylmethyl, 3 ′, 4′- An epoxy cyclohexene carboxylate etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. As a commercial item of alicyclic epoxy, Daicel Chemical Industries Ltd. CEL2000, CEL3000, CEL2021P etc. are mentioned, for example.
- the oxetane compound is a compound having a 4-membered ring ether, that is, an oxetane ring in the molecule.
- the oxetane compound is not particularly limited and may be appropriately selected depending on the intended purpose.
- 3-ethyl-3-hydroxymethyloxetane 1,4-bis [ ⁇ (3-ethyl-3-oxetanyl) methoxy ⁇ Methyl) benzene, 3-ethyl-3- (phenoxymethyl) oxetane, bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane), 3-ethyl- Examples include 3-[ ⁇ (3-triethoxysilyl) propoxy ⁇ methyl] oxetane, oxetanylsilsesquioxane, phenol novolac oxetane, and the like.
- Oxetanylsilsesquioxane is a silane compound having an oxetanyl group, for example, an oxetanyl group obtained by hydrolytic condensation of 3-ethyl-3-[ ⁇ (3-triethoxysilyl) propoxy ⁇ methyl] oxetane. Is a network-like polysiloxane compound having a plurality of.
- the vinyl compound is not particularly limited as long as it can be cationically polymerized, and can be appropriately selected according to the purpose.
- examples thereof include styrene compounds and vinyl ether compounds.
- vinyl ether compounds are particularly preferable from the viewpoint of ease of cationic polymerization.
- the styrene compound means a compound having a structure in which a hydrogen atom of an aromatic ring of styrene or styrene is substituted with an alkyl group, an alkyloxy group or a halogen atom.
- styrene compound examples include p-methylstyrene, m-methylstyrene, p-methoxystyrene, m-methoxystyrene, ⁇ -methyl-p-methoxystyrene, ⁇ -methyl-m-methoxystyrene and the like. These may be used individually by 1 type and may use 2 or more types together.
- vinyl ether compound examples include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, hexyl vinyl ether, cyclohexyl vinyl ether, methyl propenyl ether, ethyl propenyl ether, butyl propenyl ether, methyl butenyl ether, ethyl butenyl.
- the content of the polymerizable monomer in the three-dimensional modeling material is preferably 1% by mass to 95% by mass, more preferably 5% by mass to 90% by mass, and more preferably 10% by mass to 80% by mass. It is more preferable that it is 20 mass% or more and 70 mass% or less. If the content of the polymerizable monomer is less than 1% by mass, a three-dimensional molded article having sufficient flexibility may not be obtained. If the content of the polymerizable monomer exceeds 95% by mass, a three-dimensional molded article having sufficient mechanical strength may not be obtained.
- the content of the polymerizable monomer is preferably 10 parts by mass or more and 10,000 parts by mass or less, more preferably 20 parts by mass or more and 5,000 parts by mass or less, with respect to 100 parts by mass of the polymer.
- the amount is more preferably 50 parts by mass or more and 3,000 parts by mass or less, and particularly preferably 100 parts by mass or more and 2,000 parts by mass or less. If the content of the polymerizable monomer is less than 10 parts by mass, a three-dimensional molded article having sufficient flexibility may not be obtained. If the content of the polymerizable monomer exceeds 10,000 parts by mass, a three-dimensionally shaped article having sufficient mechanical strength may not be obtained.
- the three-dimensional modeling material may contain a solvent.
- the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, alcohols such as ethylene glycol, diethylene glycol, and propylene glycol, cyclic ethers such as tetrahydrofuran and dioxane, or ethylene glycol.
- Monomethyl ether ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol Alkyl ethers of polyhydric alcohols such as monoethyl ether, or alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, or toluene, Aromatic hydrocarbons such as xylene, or ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone
- the ionic liquid is composed of a cation component and an anion component, and preferably has a melting point of 200 ° C. or lower, more preferably 100 ° C. or lower, and even more preferably 50 ° C. or lower.
- the lower limit of the melting point is not limited, but is preferably ⁇ 100 ° C. or higher, and more preferably ⁇ 30 ° C. or higher.
- Specific examples of the cation component include N-methylimidazolium cation, N-ethylimidazolium cation, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, and 1-ethyl-3-methylimidazole.
- anion component examples include halide ions (Cl ⁇ , Br ⁇ , I ⁇ and the like), carboxylate anions (for example, C 2 H 5 CO 2 —, CH 3 CO 2 —, HCO 2 having 1 to 3 carbon atoms in total).
- Pseudohalide ions for example, CN ⁇ , SCN ⁇ , OCN ⁇ , ONC ⁇ , N 3 — etc., which are monovalent and have properties similar to halides
- sulfonate anions for example, CN ⁇ , SCN ⁇ , OCN ⁇ , ONC ⁇ , N 3 — etc., which are monovalent and have properties similar to halides
- sulfonate anions for example, CN ⁇ , SCN ⁇ , OCN ⁇ , ONC ⁇ , N 3 — etc., which are monovalent and have properties similar to halides
- sulfonate anions for example, CN ⁇ , SCN ⁇ , OCN ⁇ , ONC ⁇ , N 3 — etc., which are monovalent and have properties similar to halides
- sulfonate anions for example, CN ⁇ , SCN ⁇ , OCN ⁇
- the solvent contained in the three-dimensional modeling material among the above-mentioned compounds, polarities such as alkyl ethers, alkyl ether acetates, ketones, esters, water, etc. from the viewpoints of handleability, moldability of the three-dimensional modeled object, etc. It is preferable to use a solvent or an ionic liquid.
- the content of the solvent in the three-dimensional modeling material is preferably 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 95% by mass or less with respect to the entire three-dimensional modeling material. More preferably, it is more than 90 mass%, and it is especially preferable that it is 20 mass% or more and 80 mass% or less. If the content of the solvent is less than 1% by mass, a three-dimensional model having sufficient flexibility may not be obtained. When the content of the solvent exceeds 99% by mass, a three-dimensionally shaped object having sufficient mechanical strength may not be obtained.
- the content of the solvent is preferably 1 part by mass or more and 10,000 parts by mass or less, preferably 5 parts by mass or more and 5,000 parts by mass or less with respect to 100 parts by mass of the total mass of the polymer and the polymerizable monomer. Is more preferably 10 parts by mass or more and 1,000 parts by mass or less, and particularly preferably 20 parts by mass or more and 400 parts by mass or less. If the content of the solvent is less than 1 part by mass, a three-dimensionally shaped object having sufficient flexibility may not be obtained. When the content of the solvent exceeds 10,000 parts by mass, a three-dimensional model having sufficient mechanical strength may not be obtained.
- ⁇ Photoradical generator and photoacid generator> As a material for three-dimensional modeling, when a polymerizable monomer such as a radical polymerizable unsaturated compound or a cationic polymerizable compound is included, a photo radical generator and a photoacid are used from the viewpoint of obtaining a three-dimensional model having excellent strength. It is preferable to include at least one selected from generators. In addition, by using a photo radical generator or a photo acid generator, the polymerizable monomer in the three-dimensional modeling material is polymerized when the three-dimensional modeling material is irradiated with light.
- the photo radical generator is a compound that generates a radical capable of initiating polymerization of the above-described polymerizable monomer by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like.
- photo radical generators examples include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, benzoin compounds, benzophenone compounds, ⁇ -diketone compounds, Known compounds such as polynuclear quinone compounds, xanthone compounds, and phosphine compounds can be exemplified.
- thioxanthone compounds include 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like.
- acetophenone compound examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, (1-hydroxycyclohexyl) phenylmeta Non etc. can be mentioned.
- biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′.
- -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like can be mentioned.
- triazine compound examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine and the like can be mentioned.
- O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) And benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime).
- ⁇ -diketone compound examples include ⁇ -ketoglutaric acid.
- phosphine compound examples include diphenyl-2,4,6-trimethylbenzoylphosphine oxide.
- the photoradical generator can be used alone or in admixture of two or more.
- a thioxanthone compound an acetophenone compound, a biimidazole compound, a triazine compound, It is preferable to contain at least one selected from the group consisting of O-acyloxime compounds, ⁇ -diketone compounds, and phosphine compounds.
- the photoacid generator is a compound that generates an acid capable of initiating polymerization of the above-described polymerizable monomer by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.
- a photoacid generator include known compounds such as an onium salt compound, a sulfone compound, a sulfonic acid ester compound, a quinonediazide compound, a sulfonimide compound, and a diazomethane compound.
- the triazine compounds exemplified as the photo radical generator are compounds that also function as a photo acid generator.
- examples of the onium salt compound include diaryl iodonium salts, triarylsulfonium salts, triarylphosphonium salts, and the like.
- Specific examples of the diaryliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyl Examples include iodonium-p-toluenesulfonate.
- triarylsulfonium salt examples include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphonate, Examples thereof include phenylsulfonium trifluoroacetate and triphenylsulfonium-p-toluenesulfonate.
- triarylphosphonium salt examples include triphenylphosphonium tetrafluoroborate, triphenylphosphonium hexafluorophosphonate, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium hexafluoroarsenate, triphenylphosphonium trifluoromethanesulfonate, Examples thereof include phenylphosphonium trifluoroacetate and triphenylphosphonium-p-toluenesulfonate.
- sulfonimide compound examples include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trimethyl).
- diazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyl.
- diazomethane 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, and the like.
- the photoacid generators can be used alone or in admixture of two or more.
- the photoacid generator in the present invention preferably contains at least one selected from the group of onium salt compounds, sulfonimide compounds and diazomethane compounds, and particularly preferably contains an onium salt compound.
- the content of the photo radical generator is not particularly limited, but is usually 0.01% by mass or more and 10% by weight or less, preferably 0%, based on the total mass of the polymer and the polymerizable monomer. 0.05% by weight or more and 5% by weight or less.
- the content of the photoacid generator is not particularly limited, but is usually 0.01% by mass or more and 10% by mass or less, and preferably 0%, based on the total mass of the polymer and the polymerizable monomer. 0.05% by weight or more and 5% by weight or less.
- the material for three-dimensional modeling used in the present invention is a colorant, a filler, a plasticizer, a stabilizer, a colorant, and an anti-aging agent within a range that does not impair the effects of the present invention for the purpose of imparting a function corresponding to the application.
- blend additives such as an agent, a foaming agent, and a rust preventive agent.
- the content of the additive varies depending on the type in order to impart the desired function, but it is desirable that the content be capable of maintaining the fluidity of the material for three-dimensional modeling.
- the content of the additive is preferably 0.01% by mass or more and 50% by mass or less, more preferably 0.1% by mass or more and 40% by mass or less, with respect to 100% by mass of the material for three-dimensional modeling. It is particularly preferably 1% by mass or more and 30% by mass or less. From the viewpoint of imparting a desired function to the three-dimensional modeling material, 1% by mass or more is particularly preferable. From the viewpoint of maintaining fluidity and maintaining the moldability of the three-dimensional modeling material, 30% by mass or less is preferable. Particularly preferred.
- the viscosity of the three-dimensional modeling material when discharged from the nozzle is not particularly limited, but is preferably 1000 poise or less, and more preferably 100 poise or less.
- the outer shell wall part forming material 20 and the inner core part forming material 30 may be different in the content ratio of the polymer and the polymerizable monomer.
- the hardness of the outer shell 2 formed by solidifying the outer shell wall 21 by the outer shell wall modeling material 20 is that of the inner core 3 formed by solidifying the inner core 31 by the inner core modeling material 30. It can be higher than the hardness.
- the content of the polymer and the polymerizable monomer in the entire outer shell wall modeling material 20 is changed to the entire inner core modeling material 30.
- the content of the polymer and the polymerizable monomer in can be increased.
- the content of the solvent in the entire outer shell wall modeling material 20 is changed to the content of the solvent in the entire inner core modeling material 30. Can be less.
- the positions of the outer shell nozzle 5A and the inner core nozzle 5B in the manufacturing apparatus 10 of the present embodiment are fixed, and the stage 6 is moved in the plane directions X and Y with respect to the nozzles 5A and 5B, and then on the stage 6
- the planar shape of the outer shell wall portion 21 and the inner core portion 31 for one layer is formed, and the stage 6 is further lowered by one layer in the height direction Z, and the outer shell wall portion for another layer is placed on the stage 6.
- the planar shape of 21 and the inner core part 31 is formed, and the outer shell 2 and the inner core 3 are formed.
- the three-dimensional structure 1 having a quadrangular prism shape is formed.
- the shape of the three-dimensional structure 1 can be various shapes having the inner core 3 in the inner region of the outer shell 2.
- a hard outer shell wall forming material 20 is discharged onto the stage 6 from the outer shell nozzle 5A.
- the stage 6 is moved in a plane with respect to the outer shell nozzle 5A, and the outer shell wall portion 21A of the first layer, which is a part of the outer shell 2 and the bottom portion 211 of the three-dimensional structure 1 to be molded, is formed.
- the outer shell wall part forming material 20 discharged from the outer shell nozzle 5A is irradiated with light H from the light irradiation device 100, and the outer shell wall part forming material 20 is solidified.
- irradiation of the light H by the light irradiation apparatus 100 is performed on the entire outer core wall forming material 20 discharged from the outer shell nozzle 5A and the inner core forming material 30 discharged from the inner core nozzle 5B. This is continued while the three-dimensional structure 1 is formed.
- the outer shell wall forming material 20 is continuously discharged from the outer shell nozzle 5A while the outer shell nozzle 21A is being discharged.
- the stage 6 is moved in a plane with respect to 5A.
- a second-layer outer shell wall portion 21B made of the outer-shell wall-forming material 20 is formed on the entire circumference of the outer edge on the first-layer outer shell wall portion 21A.
- the outer shell wall forming material 20 is also solidified.
- step S2 of FIGS. 3 and 9 as the first inner core portion forming step Y1, the soft inner core portion forming material 30 is surrounded by the second outer shell wall portion 21B from the inner core nozzle 5B.
- the stage 6 is moved in a plane with respect to the inner core nozzle 5B while being discharged into the inner region.
- the inner core part forming material 30 is discharged so as to fill the entire inner region surrounded by the outer shell wall part 21B of the second layer.
- molding material 30 is formed in the inner area
- the outer shell wall portion forming material 20 is transferred from the outer shell nozzle 5A to the second outer shell wall portion. While discharging onto 21B, the stage 6 is moved in a plane with respect to the outer shell nozzle 5A. Then, a third-layer outer shell wall portion 21 ⁇ / b> C made of the outer shell wall portion shaping material 20 is formed on the second-layer outer shell wall portion 21 ⁇ / b> B, and is irradiated with the light H from the light irradiation device 100. Thus, the outer shell wall part forming material 20 is also solidified.
- the inner core portion forming material 30 is surrounded by the third outer shell wall portion 21C from the inner core nozzle 5B. While discharging to the inner region, the stage 6 is moved in a plane with respect to the inner core nozzle 5B. At this time, the inner core part shaping material 30 is discharged so as to fill the entire inner region surrounded by the outer shell wall part 21C of the third layer. Then, the inner core portion 31B of the second layer made of the inner core part three-dimensional material 30 is formed in the inner region of the outer shell wall portion 21C of the third layer, and is irradiated with the light H from the light irradiation device 100. The inner core part forming material 30 is also solidified.
- step S5 of FIG. 9 the second outer shell wall portion forming step X2 and the second inner core portion forming step Y2 are repeatedly performed at the number of times corresponding to the height of the three-dimensional structure 1.
- a three-dimensional structure 1 having an outer shell 2 formed by outer shell wall portions 21 stacked in a plurality of stages and an inner core 3 formed by inner core portions 31 stacked in a plurality of stages is formed.
- step S6 of FIGS. 6 and 9 after the three-dimensional structure 1 having the outer shell 2 and the inner core 3 is formed and the entire outer shell 2 and the inner core 3 are solidified, A step of removing the outer shell 2 in the three-dimensional structure 1 is performed.
- the outer shell 2 to be removed is indicated by a two-dot chain line.
- the removal of the outer shell 2 can be performed by various methods such as a peeling method and a shaving method.
- the three-dimensional molded item 1 as the final product is constituted only by the inner core 3 formed from the inner core part forming material 30.
- the outer shell wall portion 21 that becomes the ceiling portion is formed. It can be formed so that the entire inner core 3 is encased in the outer shell 2.
- the case where the second outer shell wall forming step X2 and the second inner core forming step Y2 are sequentially repeated is shown.
- the first outer shell wall portion forming step X1 and the first inner core portion forming step Y1 are performed, and as shown in FIG. 10 (b), the second outer shell portion forming step X1 is performed.
- the second inner core portion forming step Y2 can be performed only once.
- the three-dimensional structure 1 having the outer shell 2 formed by the outer shell wall portion 21 and the inner core 3 formed by the inner core portion 31 can be formed.
- the first outer shell wall portion forming step X1 is performed, and as shown in FIG. 11B, the second outer shell wall portion forming step X2 is performed.
- the first inner core part forming step Y1 is performed, and the inner core surrounded by the outer shell wall part 21 stacked in a plurality of stages
- the part 31 can also be formed.
- the inner core portion 31 is not only formed at the same height as the outer shell wall portion 21 (indicated by a two-dot chain line in FIG. 11 (c)), but the height of one step of the outer shell wall portion 21. Within this range, it can be formed lower than the outer shell wall portion 21.
- the formation height of the inner core portion 31 (upper surface position 312 of the inner core portion 31) is lower than the formation height of the outer shell wall portion 21 (upper surface position 212 of the outer shell wall portion 21). In particular, it becomes easy to remove the outer shell 2 from the molded three-dimensional structure 1.
- the idea of making the formation height of the inner core portion 31 lower than the formation height of the outer shell wall portion 21 can be similarly adopted in the above-described embodiment.
- the second outer shell wall portion forming step X2 and the second inner core portion forming step Y2 can be alternately performed a plurality of times.
- the inner core portions 31 can be sequentially stacked so that the formation height of the inner core portion 31 is slightly lower than the formation height of the outer shell wall portion 21.
- the resulting three-dimensional model 1 is excellent in flexibility and mechanical strength, and is a human or animal biological organ model used for medical simulations, medical equipment parts such as mouse inhalation pads and joint fixing devices, biological materials such as artificial joints, cells, etc. It can be suitably used as medical materials such as culture sheets, soft contact lenses, drug delivery systems and wound dressings, flexible parts for interiors of rooms and automobiles, and various shock absorbing / damping materials.
- the hardness of the three-dimensional structure 1 is not particularly limited.
- the hardness (Duro-00) may be 0 or more and 100 or less. This hardness is measured by the measuring method shown in the following examples.
- the breaking strength of the three-dimensional structure 1 is not particularly limited, and may be, for example, 0.01 MPa or more and 20.0 MPa or less. In addition, this breaking strength is measured by the measuring method shown in the following Example.
- the elongation at break of the three-dimensional structure 1 is not particularly limited, and may be, for example, 10% or more and 2,000% or less. In addition, this breaking elongation is measured by the measuring method shown in the following Example.
- the tensile modulus of the three-dimensional object 1 is not limited in particular, for example, it may be 0.01 N / m 2 or more 10 N / m 2 or less.
- this tensile elasticity modulus is measured by the measuring method shown in the following Example.
- the modeling speed of the three-dimensional molded item 1 which has the outer shell 2 and the inner core 3 can be improved by forming the outer shell wall part 21 and the inner core part 31 repeatedly sequentially.
- the outer shell 2 is removed as an unnecessary portion.
- the modeling accuracy and the modeling speed can be improved even when the three-dimensional structure 1 has a soft portion.
- the outer shell 2 composed of outer shell wall portions 21 stacked in a plurality of stages, the core material 4 composed of core members 41 stacked in a plurality of stages, and a plurality of stages.
- the three-dimensional structure 1 having the inner core 3 composed of the laminated inner core portions 31 is formed.
- the core material 4 is a bone portion embedded in the inner core 3, and in this embodiment, is formed in a lattice shape that opens in the stacking direction L of the plurality of core material portions 41.
- the core material 4 can be formed into a honeycomb shape having openings in the stacking direction L of the plurality of core material portions 41 or various polygonal shapes in addition to the lattice shape.
- the step of forming the core material portion 41 is performed after the step of forming the outer shell wall portion 21 and before the step of forming the inner core portion 31.
- the manufacturing apparatus 10 of this embodiment has a core material nozzle 5C that discharges the core material modeling material 40. And as shown in the flowchart of FIG. 14, after the first outer shell wall forming step X1 (step S11) shown in the first embodiment and before the first inner core portion forming step Y1 (S13), while performing the first core material portion forming step Z1 (S12), the core material material 40 is discharged from the core material nozzle 5C onto the bottom portion 211 formed by the first outer shell wall portion 21A. The stage 6 is moved relative to the nozzle 5C in a plane.
- the first layer core portion 41 made of the core portion shaping material 40 is formed, and the light H from the light irradiation device 100 is emitted.
- the core part modeling material 40 is solidified.
- the stage 6 is relatively moved in a plane relative to the core material nozzle 5C while discharging the core material modeling material 40 from the core material nozzle 5C onto the core material portion 41. And on the core material part 41 of the 1st layer, the core material part 41 of the 2nd layer by the material for core material part modeling 40 is formed, receiving irradiation of light H from the light irradiation device 100, This core part modeling material 40 is solidified.
- the second outer shell wall portion forming step X2, the second core portion forming step Z2, and the second inner core are performed at the number of times corresponding to the height of the three-dimensional structure 1.
- the part forming step Y2 is repeatedly performed, and the outer shell 2 by the outer shell wall portion 21 stacked in a plurality of stages, the core material 4 by the core member 41 stacked in a plurality of stages, and the inner core section stacked in a plurality of stages.
- the three-dimensional structure 1 having the inner core 3 by 31 is formed.
- the three-dimensional structure 1 having the outer shell 2, the core material 4, and the inner core 3 is molded, and the entire outer shell 2, the core material 4 and the inner core 3 are formed.
- the process of removing the outer shell 2 in the three-dimensional structure 1 is performed.
- the three-dimensional model 1 as the final product is composed of the inner core 3 molded from the inner core part molding material 30 and the core material 4 molded from the core part molding material 40 and embedded in the inner core 3. Composed.
- the composition of the core part modeling material 40 that molds the core material 4 is different from the composition of the outer shell wall part modeling material 20 that molds the outer shell 2.
- the core part modeling material 40 for molding the core material 4 can be either softer or harder than the outer shell wall part modeling material 20 for molding the outer shell 2.
- the hardness of the core material 4 formed by solidifying the core material portion 41 is higher than the hardness of the inner core 3 formed by solidifying the inner core portion 31.
- the core material forming material 40 for forming the core material 4 can be discharged by the outer shell nozzle 5A without using the core material nozzle 5C.
- the inner core portion forming material 30 discharged from the inner core nozzle 5 ⁇ / b> B to the stage 6 is used as the outer shell wall portion forming material 20. Further, the outer shell wall portion 21 and the core material portion 41 formed from the core material modeling material 40 can be held. Therefore, the inner core part modeling material 30 discharged to the stage 6 can be made difficult to flow or deform, and the modeling accuracy and modeling speed of the inner core 3 by the inner core part modeling material 30 can be improved. In addition, the molding speed of the three-dimensional structure 1 having the outer shell 2, the core material 4, and the inner core 3 can be improved by sequentially forming the outer shell wall portion 21, the core material portion 41, and the inner core portion 31. .
- the three-dimensional structure 1 having the outer shell 2, the core material 4 and the inner core 3 is once molded, and then the outer shell 2 is removed as an unnecessary portion. Then, in the three-dimensional structure 1 as the final product, the contour shape of the inner core 3 made of the inner core portion forming material 30 can be held by the core material 4 made of the core material portion forming material 40. Accordingly, when the three-dimensional structure 1 is too soft due to the inner core 3 made of the inner core portion modeling material 30 being a soft material, the hard core material 4 gives the three-dimensional structure 1 an appropriate hardness. Can do.
- the modeling accuracy and the modeling speed of the three-dimensional structure 1 formed from the inner core part forming material 30 and the core part forming material 40 can be improved.
- the other components and the components indicated by the reference numerals in the drawings are the same as those in the first embodiment, and the same effects as those in the first embodiment can be obtained.
- a route data creation method and a data creation program will be described.
- the nozzle movement path data is generated by the design computer 80 and then transmitted to the control computer 8, and is used when the three-dimensional object 1 is formed by the control computer 8.
- the nozzle movement path data is set in the control computer 8. Specifically, the movement when the outer shell nozzle 5 ⁇ / b> A and the inner core nozzle 5 ⁇ / b> B are moved relative to the stage 6. Created as route data.
- This movement path data is created as a control code (G code) used by the control computer 8 in the design computer 80.
- the nozzle movement path data of the present embodiment includes the data of the outer wall wall movement path K1 used when the outer shell nozzle 5A is moved relative to the stage 6 and the inner core nozzle relative to the stage 6. It is created as data of the movement path K2 for the inner core part used when the 5B is relatively moved.
- the data on the outer shell wall moving path K1 indicates data on the moving path of the outer shell nozzle 5A
- the data on the inner core moving path K2 indicates data on the moving path of the inner core nozzle 5B.
- the three-dimensional surface data D1 of the three-dimensional object 1 to be modeled is designed or read and created.
- the three-dimensional shape of the three-dimensional object 1 formed by various three-dimensional material such as resin can be a three-dimensional shape that is artificially designed in the design computer 80, for example.
- the three-dimensional shape of the three-dimensional structure 1 may be a natural object such as a living body or a three-dimensional shape of various master models read by the design computer 80 using a camera, a scanner, or the like.
- the three-dimensional surface data D1 is read into 3D-CAD software called a slicer in the design computer 80, and the three-dimensional surface data D1 is processed by the software.
- the three-dimensional surface data D1 is sliced at regular intervals in the height direction Z and processed into a linear outer layer data D2 stacked in a plurality in the height direction Z.
- the height direction Z refers to a direction in which the outer wall wall modeling material 20 and the inner core modeling material 30 are stacked on the stage 6.
- the outer layer data D2 is data of a two-dimensional shape on each cut surface when the three-dimensional surface data D1 is cut into a plurality of pieces in the height direction Z.
- the outer shape layer data D2 of this embodiment is stacked in the height direction Z as a predetermined direction.
- the predetermined direction in which the outer layer data D2 is stacked may be a direction inclined in the height direction Z.
- the data of the inner core part movement path K2 is for moving the inner core nozzle 5B relative to the stage 6 when the inner core portion 31 is formed.
- the outer position of the inner core part 31 to be formed is set to the position indicated by the outer layer data D2.
- the inner core part shaping material 30 is not necessarily discharged from the inner core nozzle 5B in a circular cross section, and may be discharged in various cross sectional shapes. The same applies to the outer shell wall part forming material 20.
- the created data for the inner core moving path K2 is used as data for position control of the control code in the control computer 8.
- the data of the inner core moving path K2 is obtained from the inner core forming material 30 from the inner core nozzle 5B that moves relative to the stage 6 when the control computer 8 controls the operation of the inner core nozzle 5B and the relative moving mechanism 7. This is data for determining the position at which ink is discharged.
- a plurality of pieces of data of the inner core moving path K2 are created corresponding to each of the plurality of outer layer data D2.
- the outer shell wall moving path K1 for discharging the outer shell wall forming material 20 from the outer nozzle 5A.
- the data of the movement path K1 for the outer shell wall part is for moving the outer shell nozzle 5A relative to the stage 6 when the outer shell wall part 21 is formed.
- the outer shell wall moving path K1 is created as a position corrected by a predetermined distance outside the inner core moving path K2.
- the outer side means the side opposite to the inner side indicating the center side of the inner core moving path K2.
- the predetermined distance for correcting the outer shell wall moving path K1 to the outside of the inner core moving path K2 takes into account the diameter or cross-sectional outer shape of the outer shell wall forming material 20 discharged from the outer shell nozzle 5A.
- the outer shell wall portion 21 and the outer core portion 31 are determined so as to be adjacent to each other. It should be noted that the distance corrected outside the inner core moving path K ⁇ b> 2 may be set to a different value as appropriate according to each location where the inner core portion 31 is formed.
- the created data of the outer shell wall moving path K1 is used as data for position control of the control code in the control computer 8.
- the data of the movement path K1 for the outer shell wall is obtained from the outer shell nozzle 5A that moves relative to the stage 6 when the control computer 8 controls the operation of the outer shell nozzle 5A and the relative movement mechanism 7. This is data for determining the position at which the wall forming material 20 is discharged. Further, a plurality of data of the outer shell wall moving path K1 are created corresponding to each of the plurality of outer layer data D2.
- a control code including data of the inner core moving path K2 and the outer shell wall moving path K1 used by the control computer 8 is constructed.
- the control code only needs to include data on each position of the inner core moving path K2 and the outer shell wall moving path K1, and the order in which the outer shell wall 21 and the inner core 31 are formed is determined by modeling. It can determine suitably according to the three-dimensional molded item 1 to be performed.
- the outer shell wall moving path K1 is created based on the inner core moving path K2, and the outer shell wall moving path K1 can be easily created.
- Each data of the inner core moving path K2 and the outer shell wall moving path K1 can be automatically created in the design computer 80 by a data creating program operating as software.
- the data creation program operating in the design computer 80 creates the data for the inner core moving path K2 of the inner core nozzle 5B and the data for the outer shell wall moving path K1 of the outer nozzle 5A. Execute the step to create.
- the creation of the data for the movement path K1 for the outer shell wall portion of the outer shell nozzle 5A can be performed using a position correction function provided in the data creation program.
- the other components and the components indicated by the reference numerals in the drawings are the same as those in the first embodiment, and the same effects as those in the first embodiment can be obtained.
- the thickness for forming the outer shell 2 in the three-dimensional structure 1 of this embodiment is the thickness of one layer of the outer shell wall portion forming material 20 discharged from the outer shell nozzle 5A.
- the thickness for forming the outer shell 2 may be equal to or more than two layers of the outer shell wall portion forming material 20 discharged from the outer shell nozzle 5A.
- the outer shell wall portion forming material 20 is discharged from the outer shell nozzle 5 ⁇ / b> A so as to overlap two or more layers in the planar directions X and Y of the stage 6.
- the inner core 3 of this embodiment is formed in a solid shape so as to fill the interior of the three-dimensional structure 1. Further, the inner core 3 can be formed in a hollow shape so as to form a cavity inside the three-dimensional structure 1.
- the inner core portion moving path K2 by the inner core nozzle 5B can have any pattern as long as the outer shape position path K20 adjacent to the inner side of the outer shell wall section moving path K1 is determined. For example, as shown in FIG. 17, the inner core moving path K2 can be formed in a state in which the entire outer position path K20 adjacent to the inner side of the outer shell wall moving path K1 is continuously included. Further, as shown in FIG.
- the inner core moving path K2 may be formed in a state in which the outer position path K20 adjacent to the inner side of the outer shell wall moving path K1 is intermittently included. In creating the inner core moving path K2, it is only necessary to determine the outer position path K20 based on the outer layer data D2, and the inner core moving path K2 other than the outer position path K20 is arbitrarily determined. Can do.
- the creation of the three-dimensional surface data D1 of the three-dimensional structure 1 and the processing of the linear outer layer data D2 are the same as in the third embodiment.
- the outer shell wall forming material 20 is discharged from the outer shell nozzle 5A that moves relative to the stage 6 when forming the outer shell wall portion 21 based on the outer layer data D2.
- Data of the shell wall moving path K1 is created.
- the data of the generated outer shell wall moving path K1 is used as position control data for the control code in the control computer 8. Further, a plurality of data of the outer shell wall moving path K1 are created corresponding to each of the plurality of outer layer data D2.
- the position corrected by a predetermined distance inside the outer shell wall moving path K1 is defined as an outer position path K20 as the position of the outer shape of the entire inner core moving path K2.
- the inner side means the inner side as the annular center side of the movement path K1 for the outer shell wall portion formed in an annular shape.
- the predetermined distance for correcting the inner core moving path K2 to the inner side of the outer shell wall moving path K1 takes into account the diameter or cross-sectional outer shape of the inner core forming material 30 discharged from the inner core nozzle 5B. It determines so that the wall part 21 and the external shape part of the inner core part 31 may adjoin. It should be noted that the distance corrected to the inside of the outer shell wall portion movement path K ⁇ b> 1 can be set to a different value as appropriate depending on each location where the outer shell wall portion 21 is formed.
- the created data of the inner core moving path K2 is used as position control data for the control code in the control computer 8.
- a plurality of pieces of data of the inner core moving path K2 are created corresponding to each of the plurality of outer layer data D2.
- the inner core moving path K2 is created based on the outer shell wall moving path K1, and the inner core moving path K2 can be easily created.
- Each data of the movement path K1 for the outer shell wall part and the movement path K2 for the inner core part can be automatically created in the design computer 80 by a data creation program operating as software.
- the data creation program operating in the design computer 80 creates the data of the outer shell wall moving path K1 of the outer shell nozzle 5A and the data of the inner core moving path K2 of the inner core nozzle 5B. Execute the step to create.
- the creation of the data for the inner core moving path K2 of the inner core nozzle 5B can be performed using the position correction function provided in the data creation program.
- the other components and the components indicated by the reference numerals in the drawings are the same as those in the third embodiment, and the same effects as those in the third embodiment can be obtained.
- An outer shell wall forming material 20 for forming the outer shell 2 is obtained by dissolving 20 g of polymethyl methacrylate macromonomer in 100 g of tetraethylene glycol diacrylate, and adding 1 g of (1-hydroxycyclohexyl) phenylmethanone to this. It was obtained by further dissolving.
- the inner core part shaping material 30 for constituting the inner core 3 was obtained as follows. First, 4.284 g of a cellulose derivative (hydroxypropylcellulose, HPC, viscosity in water at 20 ° C./25° C .: 150 to 400 mPa ⁇ s) is added to 77 g of N, N-dimethylacrylamide and stirred until the cellulose derivative is dissolved. .
- the outer shell wall modeling material 20 is discharged from the outer shell nozzle 5A to form the outer shell wall portion 21, and the inner core modeling material 30 is removed from the inner core nozzle 5B.
- the three-dimensional shaped object 1 having the outer shell 2 and the inner core 3 was formed by discharging and forming the inner core portion 31.
- the outer shell 2 was removed from this three-dimensional molded item 1, and the three-dimensional molded item 1 which consists only of the inner core 3 by the inner core part modeling material 30 was obtained.
- evaluation of the obtained three-dimensional molded item 1 was performed as follows.
- Hardness measurement According to ASTM D 2240 standard, the sample piece of the molded three-dimensional structure 1 was measured with a durometer (Duro-00 type) manufactured by Teclock Co. As a result, the hardness was 20.
- Strength measurement Results of performing a tensile strength test using a material strength tester (EZ Graph) manufactured by Shimadzu Corporation after punching a sample piece of the molded three-dimensional structure 1 into a dumbbell shape (No. 6 size) in accordance with JIS K625 standard The breaking strength was 0.23 MPa, the breaking elongation was 300%, and the tensile modulus was 0.06 N / m 2 .
- the three-dimensional model 1 obtained by the manufacturing method of the three-dimensional model 1 of the present invention is excellent in flexibility and mechanical strength, and is used for medical simulations of human and animal biological organ models and biological tissue models, mouse inhalation pads and joints.
- Medical device parts such as fixed devices, biomaterials such as artificial joints, cell culture sheets, soft contact lenses, medical materials such as drug delivery systems and wound dressings, flexible parts for interiors of rooms and automobiles, various types of shock absorption and vibration control Use in various fields such as materials can be expected.
- biological organ models include models of digestive organs such as the stomach, small intestine, large intestine, liver and pancreas, circulatory organs such as the heart and blood vessels, reproductive organs such as the prostate, and urinary organs such as the kidney.
- Examples of the model include a model of a living tissue constituting these living organs.
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Abstract
Description
例えば、特許文献1の人体患部実体モデル及びその製造方法においては、患者本人のMRI又はCTスキャンで得た断層データに基づいて光硬化性樹脂硬化体からなる外殻部分を形成するとともに、外殻部分の内部に位置する内部空洞部分に、流動化可能な固体からなる心材部分を充填することが記載されている。この製造方法においては、光造形法によって外殻部分を形成している。光造形法においては、液槽内に貯留された光硬化性樹脂の表面に紫外線レーザーを走査して、この光硬化性樹脂を硬化させ、液槽の表面を段階的に上昇させて、硬化された光硬化性樹脂を複数積層することによって、立体造形物を成形している。
立体造形用材料をノズルから前記外殻壁部に囲まれた内側領域に吐出しながら、前記ノズルと前記ステージとを相対移動させて、前記立体造形物の内核の一部となる内核部を形成する工程と、を含む、立体造形物の製造方法にある。
造形しようとする前記立体造形物の立体表面データを、設計又は読取りを行って作成し、
前記立体表面データを、所定の方向に一定の間隔でスライスして、前記所定の方向に複数に積み重なる線状の外形層データに加工し、
前記外形層データに基づき、前記ノズルから内核部造形用材料を吐出させるための内核部用移動経路のデータを作成し、
前記内核部用移動経路の外側に所定の距離だけ補正した位置を、前記ノズルから外殻壁部造形用材料を吐出させるための外殻壁部用移動経路のデータとする、立体造形物の製造方法に用いられるノズル移動経路のデータ作成方法にある。
造形しようとする前記立体造形物の立体表面データを、設計又は読取りを行って作成し、
前記立体表面データを、所定の方向に一定の間隔でスライスして、前記所定の方向に複数に積み重なる線状の外形層データに加工し、
前記外形層データに基づき、前記ノズルから外殻壁部造形用材料を吐出させるための外殻壁部用移動経路のデータを作成し、
前記ノズルから内核部造形用材料を吐出させるための内核部用移動経路のデータを作成するに当たり、前記外殻壁部用移動経路の内側に所定の距離だけ補正した位置を、前記内核部用移動経路の全体における外形の位置とする、立体造形物の製造方法に用いられるノズル移動経路のデータ作成方法にある。
外殻を形成するための外殻壁部造形用材料を吐出する外殻用ノズルと、
内核を形成するための内核部造形用材料を吐出する内核用ノズルと、
前記外殻用ノズルから吐出される前記外殻壁部造形用材料及び前記内核用ノズルから吐出される前記内核部造形用材料が積層されるステージと、
前記ステージと前記外殻用ノズル及び前記内核用ノズルとを相対移動させる相対移動機構と、
前記外殻用ノズル、前記内核用ノズル及び前記相対移動機構の動作を制御する制御コンピュータと、を備え、
前記制御コンピュータは、前記外殻用ノズルから吐出される前記外殻壁部造形用材料によって前記外殻の一部となる外殻壁部を前記ステージ上に形成するとともに、前記内核用ノズルから、前記外殻壁部に囲まれた内側領域に吐出される前記内核部造形用材料によって前記内核の一部となる内核部を前記ステージ上に形成するよう構成されている、立体造形物の製造装置にある。
前記設計コンピュータに、
造形しようとする前記立体造形物の立体表面データを所定の方向に一定の間隔でスライスしたときに、前記所定の方向に複数に積み重なる線状の外形層データに基づいて、前記内核用ノズルの移動経路のデータを作成するステップと、
前記内核用ノズルの移動経路の外側に所定の距離だけ補正した位置に、前記外殻用ノズルの移動経路のデータを作成するステップと、を実行させる、立体造形物の製造装置に用いられるノズル移動経路のデータ作成プログラムにある。
前記設計コンピュータに、
造形しようとする前記立体造形物の立体表面データを所定の方向に一定の間隔でスライスしたときに、前記所定の方向に複数に積み重なる線状の外形層データに基づいて、前記外殻用ノズルの移動経路のデータを作成するステップと、
前記外殻用ノズルの移動経路の内側に所定の距離だけ補正した位置に、前記内核用ノズルの移動経路のデータを作成するステップと、を実行させる、立体造形物の製造装置に用いられるノズル移動経路のデータ作成プログラムにある。
ここで、外殻壁部は、環形状に形成されていることが好ましい。また、外殻壁部は、必ずしも完全な環形状に形成されていなくても、一部が解放された環形状に形成されていてもよい。
立体造形物の製造方法は、立体造形用材料をノズルから前記外殻壁部上に吐出しながら、前記ノズルと前記ステージとを相対移動させて、前記外殻壁部を更に形成する工程と、立体造形用材料をノズルから前記内核部上に吐出しながら、前記ノズルと前記ステージとを相対移動させて、前記内核部を更に形成する工程と、をさらに含んでいてもよい。
立体造形物1の製造方法においては、図6に示すように、複数段に積層された外殻壁部21からなる外殻2と、複数段に積層された内核部31からなる内核3とを有する立体造形物1を成形する。そして、外殻壁部21を形成する工程(以下、第1外殻壁部形成工程X1という。)、内核部31を形成する工程(以下、第1内核部形成工程Y1という。)、外殻壁部21を更に形成する工程(以下、第2外殻壁部形成工程X2という。)、内核部31を更に形成する工程(以下、第2内核部形成工程Y2という。)を順次行って、立体造形物1を成形する。
そして、第2外殻壁部形成工程X2及び第2内核部形成工程Y2を更に繰り返して、図6に示すように、複数段に積層された外殻壁部21による外殻2と、複数段に積層された内核部31による内核3とを有する立体造形物1を成形する。
まず、立体造形物1の製造方法に用いる製造装置10について説明する。
立体造形物1の製造方法においては、図1~図8に示すように、外殻用ノズル5A、内核用ノズル5B、ステージ6、相対移動機構7及び制御コンピュータ8を有する製造装置10を用いる。製造装置10は、熱溶解積層成形を行うものである。
外殻用ノズル5Aは、外殻2を形成するための外殻壁部造形用材料20を吐出するものである。内核用ノズル5Bは、内核3を形成するための内核部造形用材料30を吐出するものである。ステージ6は、外殻用ノズル5Aから吐出される外殻壁部造形用材料20及び内核用ノズル5Bから吐出される内核部造形用材料30が積層されるものである。相対移動機構7は、ステージ6と外殻用ノズル5A及び内核用ノズル5Bとを、ステージ6の平面方向X,Yに二次元的に相対移動させるとともに、ステージ6の平面方向に直交する高さ方向Zに相対移動させるものである。制御コンピュータ8は、外殻用ノズル5A、内核用ノズル5B及び相対移動機構7の動作を制御するよう構成されている。
なお、外殻用ノズル5A及び内核用ノズル5Bには、別々のノズルを用いる以外にも、1つのノズルを共通して用いることもできる。
実施形態1においては、外殻用ノズル5A及び内核用ノズル5Bの2つのノズルを用いた例について説明する。すなわち、第1外殻壁部形成工程X1及び第2外殻壁部形成工程X2においては外殻用ノズル5Aを用い、第1内核部形成工程Y1及び第2内核部形成工程Y2においては内核用ノズル5Bを用いる。
次に、立体造形用材料(外殻壁部造形用材料20及び内核部造形用材料30)について説明する。
外殻壁部21を形成するための外殻壁部造形用材料20、及び内核部31を形成するための内核部造形用材料30は、重合体、重合性モノマー及び溶媒を含有している。また、重合性モノマーは、ラジカル重合性不飽和化合物及びカチオン重合性化合物から選ばれる少なくとも一種を含んでいる。溶媒は、極性溶媒及びイオン液体から選ばれる少なくとも一種である。外殻壁部造形用材料20及び内核部造形用材料30は、重合性モノマーの重合反応を促進するために、光ラジカル発生剤及び光酸発生剤から選ばれる少なくとも一種を含んでいる。
立体造形用材料は、重合体及び重合性モノマーから選ばれる少なくとも一種を含んでいてもよい。
重合体としては、特に限定されるものではないが、ビニルアルコール系重合体、アクリル系重合体、フッ化ビニリデン系重合体、アクリロニトリル系重合体、多糖類などが挙げられる。前記重合体の中でも、特に、溶媒の質量M1を重合体の質量M2で除したM1/M2として表される含溶媒率に対する強度が高い点で、アクリル系重合体、ポリビニルアルコール、多糖類を用いることが好ましい。
ここで、ラジカル重合性官能基としては、(メタ)アクリロイル基、ビニル基、アリル基、ビニルエーテル基等が挙げられるが、光開始重合反応速度の点で好ましいのはアクリロイル基である。
また、カチオン重合性官能基としては、プロペニルエーテル基、ビニルエーテル基、脂環式エポキシ基、グリシジル基、ビニル基、ビニリデン基等が挙げられ、プロペニルエーテル基、ビニルエーテル基、脂環式エポキシ基及びグリシジル基が好ましい。
イソシアネート基と反応性を有する重合体としては、イソシアネート基と反応性を有する官能基が導入されているポリマーが好ましい。このような官能基の例としては、例えば、水酸基、カルボキシル基、アミノ基、アミド基、メルカプト基等が挙げられる。ポリマーとしては、水酸基を有するポリマー、カルボキシル基を有するポリマー、アミノ基を有するポリマー、アミド基を有するポリマー、メルカプト基を有するポリマー等が挙げられる。
エポキシ基含有ビニル単量体としては、例えば、グリシジル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートグリシジルエーテル、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート、α-(メタ)アクリル-ω-グリシジルポリエチレングリコール等のヒドロキシ基非含有(メタ)アクリル酸エステル類、あるいはグリセリンモノ(メタ)アクリレートグリシジルエーテル等のヒドロキシ基含有(メタ)アクリル酸エステル類、あるいはビニルベンジルグリシジルエーテル等の芳香族モノビニル化合物、あるいはアリルグリシジルエーテル、3,4-エポキシ-1-ブテン、3,4-エポキシ-3-メチル-1-ブテン等が挙げられる。
次に、重合性モノマーについて説明する。重合性モノマーとしては、特に限定されるものではないが、ラジカル重合性不飽和化合物とカチオン重合性化合物を挙げることができる。
ラジカル重合性不飽和化合物としては、ラジカル種により重合を開始し得る重合性不飽和化合物を意味し、例えば、カルボキシル基含有ラジカル重合性不飽和化合物、水酸基含有ラジカル重合性不飽和化合物、水酸基含有ラジカル重合性不飽和化合物とラクトン類化合物との反応物、(メタ)アクリル酸エステル類、(メタ)アクリルアミド類、アルコキシシリル基含有ラジカル重合性不飽和化合物等を挙げることができる。
カチオン重合性化合物は、カチオン種により重合を開始し得る重合性化合物を意味し、例えば、エポキシ化合物、オキセタン化合物、ビニル化合物などが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
脂肪族エポキシの市販品としては、例えば共栄社化学株式会社製エポライト100MF(トリメチロールプロパントリグリシジルエーテル)、ナガセケムテックス社製EX-411、EX-313、EX-614B、日油株式会社製エピオールE400などが挙げられる。
脂環式エポキシの市販品としては、例えばダイセル化学工業株式会社製CEL2000、CEL3000、CEL2021Pなどが挙げられる。
オキセタン化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス〔{(3-エチル-3-オキセタニル)メトキシ}メチル〕ベンゼン、3-エチル-3-(フェノキシメチル)オキセタン、ビス(3-エチル-3-オキセタニルメチル)エーテル、3-エチル-3-(2-エチルヘキシロキシメチル)オキセタン)、3-エチル-3-[{(3-トリエトキシシリル)プロポキシ}メチル]オキセタン、オキセタニルシルセスキオキサン、フェノールノボラックオキセタンなどが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
オキセタニルシルセスキオキサンは、オキセタニル基を有するシラン化合物であり、例えば、3-エチル-3-〔{(3-トリエトキシシリル)プロポキシ}メチル〕オキセタンを加水分解縮合させることにより得られる、オキセタニル基を複数有するネットワーク状ポリシロキサン化合物である。
立体造形用材料における重合性モノマーの含有量は、1質量%以上95質量%以下であることが好ましく、5質量%以上90質量%以下であることがより好ましく、10質量%以上80質量%以下であることがさらに好ましく、20質量%以上70質量%以下であることが特に好ましい。重合性モノマーの含有量が1質量%未満であると、十分な柔軟性を有する立体造形物が得られないことがある。重合性モノマーの含有量が95質量%を超えると、十分な機械的強度を有する立体造形物が得られないことがある。
また、立体造形用材料は、溶媒を含んでいてもよい。
溶媒としては、例えばメタノール、エタノール、1-プロパノール、2-プロパノール、1-ブタノール、2-ブタノール、エチレングリコール、ジエチレングリコール、プロピレングリコールなどのアルコール類、あるいはテトラヒドロフラン、ジオキサンなどの環状エーテル類、あるいはエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルなどの多価アルコールのアルキルエーテル類、あるいはエチレングリコールエチルエーテルアセテート、ジエチレングリコールエチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなどの多価アルコールのアルキルエーテルアセテート類、あるいはトルエン、キシレンなどの芳香族炭化水素類、あるいはアセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、4-ヒドロキシ-4-メチル-2-ペンタノン、ジアセトンアルコールなどのケトン類、あるいは酢酸エチル、酢酸ブチル、2-ヒドロキシプロピオン酸エチル、2-ヒドロキシ-2-メチルプロピオン酸エチル、2-ヒドロキシ-2-メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、2-ヒドロキシ-3-メチルブタン酸メチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、酢酸エチル、酢酸ブチルなどのエステル類、ジメチルスルホキシド、ジエチルスルホキシド、アセトニトリル、N-メチル-2-ピロリドン、γ-ブチロラクトン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド(DMAc)、1,3-ジメチル-2-イミダゾリジノン、スルホラン、ジメチルスルホン、ジエチルスルホン、ジイソプロピルスルホン、ジフェニルスルホン、ジフェニルエーテル、ベンゾフェノン、ジアルコキシベンゼン(アルコキシ基の炭素数1~4)及びトリアルコキシベンゼン(アルコキシ基の炭素数1~4)等の非プロトン性極性溶媒、水、イオン性液体が挙げられる。
カチオン成分としては、具体的には、N-メチルイミダゾリウムカチオン、N-エチルイミダゾリウムカチオン、1,3-ジメチルイミダゾリウムカチオン、1,3-ジエチルイミダゾリウムカチオン、1-エチル-3-メチルイミダゾリウムカチオン、1-プロピル-3-メチルイミダゾリウムカチオン、1-ブチル-3-メチルイミダゾリウムカチオン、1-ヘキシル-3-メチルイミダゾリウムカチオン、1,2,3-トリメチルイミダゾリウムカチオン及び1,2,3,4-テトラメチルイミダゾリウムカチオン、1-アリル-3-メチルイミダゾリウムカチオン、N-プロピルピリジニウムカチオン、N-ブチルピリジニウムカチオン、1,4-ジメチルピリジニウムカチオン、1-ブチル-4-メチルピリジニウムカチオン及び1-ブチル-2,4-ジメチルピリジニウムカチオン、トリメチルアンモニウムカチオン、エチルジメチルアンモニウムカチオン、ジエチルメチルアンモニウムカチオン、トリエチルアンモニウムカチオン、テトラメチルアンモニウムカチオン、トリエチルメチルアンモニウムカチオン、テトラエチルアンモニウムカチオン等が挙げられる。
また、溶媒の含有量は、重合体及び重合性モノマーの合計質量100質量部に対して、1質量部以上10,000質量部以下であることが好ましく、5質量部以上5,000質量部以下であることがより好ましく、10質量部以上1,000質量部以下であることがさらに好ましく、20質量部以上400質量部以下であることが特に好ましい。溶媒の含有量が1質量部未満であると、十分な柔軟性を有する立体造形物が得られないことがある。溶媒の含有量が10,000質量部を超えると、十分な機械的強度を有する立体造形物が得られないことがある。
また、立体造形用材料としては、ラジカル重合性不飽和化合物やカチオン重合性化合物等の重合性モノマーを含む場合には、強度に優れた立体造形物を得る観点から、光ラジカル発生剤及び光酸発生剤から選ばれる少なくとも一つ以上を含むことが好ましい。なお、光ラジカル発生剤又は光酸発生剤を用いることにより、立体造形用材料に光が照射されたときに、立体造形用材料における重合性モノマーが重合することとなる。
また、ホスフィン系化合物としてはジフェニル-2,4,6-トリメチルベンゾイルホスフィンオキサイド等を挙げることができる。
このような光酸発生剤としては、例えば、オニウム塩化合物、スルホン化合物、スルホン酸エステル化合物、キノンジアジド化合物、スルホンイミド化合物、ジアゾメタン化合物等の公知の化合物を挙げることができる。また、前記光ラジカル発生剤として例示したトリアジン系化合物は、光酸発生剤としても機能する化合物である。
前記ジアリールヨードニウム塩の具体例としては、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムヘキサフルオロホスホネート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムヘキサフルオロアルセネート、ジフェニルヨードニウムトリフルオロメタンスルホナート、ジフェニルヨードニウムトリフルオロアセテート、ジフェニルヨードニウム-p-トルエンスルホナート等を挙げることができる。
光酸発生剤の含有量としては、特に限定されるものではないが、通常、重合体及び重合性モノマーの合計質量に対して、0.01質量%以上10重量%以下であり、好ましくは0.05質量%以上5重量%以下である。
本発明で用いられる立体造形用材料は、用途に応じた機能を付与する目的で、本発明の効果を損なわない範囲で、着色剤、充填剤、可塑剤、安定剤、着色剤、老化防止剤、酸化防止剤、帯電防止剤、耐候剤、紫外線吸収剤、ブロッキング防止剤、結晶核剤、難燃化剤、加硫剤、加硫助剤、防菌・防カビ剤、分散剤、着色防止剤、発泡剤、防錆剤などの添加剤を配合してもよい。
本発明の立体造形物を生体器官模型用に用いる場合には、生体器官模型と近似させるために、立体造形物を所望の色に着色剤で着色することが好ましい。
また、ノズルから吐出する際の立体造形用材料の粘度は、特に限定されるものではないが、1000Poise以下であることが好ましく、100Poise以下であることがより好ましい。
次に、立体造形物1の製造方法について、図1~図8を参照して詳説する。
本形態の製造装置10における外殻用ノズル5A及び内核用ノズル5Bの位置は固定されており、各ノズル5A,5Bに対してステージ6を平面方向X,Yに移動させて、ステージ6上に1層分の外殻壁部21及び内核部31の平面形状を形成し、さらにステージ6を高さ方向Zに1層分下降させて、ステージ6上に他の1層分の外殻壁部21及び内核部31の平面形状を形成して、外殻2及び内核3を形成していく。
本形態においては、説明を簡単にするため、四角柱の形状を有する立体造形物1を形成する。これ以外にも、立体造形物1の形状は、外殻2の内側領域に内核3を有する種々の形状とすることができる。
また、特に、最終的な製品としての立体造形物1が外殻2及び内核3を有する場合には、最後の外殻壁部21を形成する工程において、天井部分となる外殻壁部21を形成して、内核3の全体が外殻2に包まれるようにすることができる。
また、立体造形物1の破断強度は、特に限定されるものではなく、例えば、0.01MPa以上20.0MPa以下であってもよい。なお、この破断強度は、下記の実施例に示す測定方法で測定されるものである。
また、立体造形物1の破断伸びは、特に限定されるものではなく、例えば、10%以上2,000%以下であってもよい。なお、この破断伸びは、下記の実施例に示す測定方法で測定されるものである。
また、立体造形物1の引張弾性率は、特に限定されるものではなく、例えば、0.01N/m2以上10N/m2以下であってもよい。なお、この引張弾性率は、下記の実施例に示す測定方法で測定されるものである。
次に、立体造形物1の製造方法による作用効果について説明する。
立体造形物1の製造方法において、各内核部形成工程Y1,Y2を行う際には、内核用ノズル5Bからステージ6へ吐出された内核部造形用材料30を、外殻壁部造形用材料20から形成された外殻壁部21によって保持することができる。そのため、ステージ6へ吐出された内核部造形用材料30が流動又は変形しにくくすることができ、内核部造形用材料30による内核3の造形精度及び造形速度を向上させることができる。
それ故、本形態の立体造形物1の製造方法によれば、立体造形物1が軟質部分を有する場合においても造形精度及び造形速度を向上させることができる。
本形態においては、図13に示すように、複数段に積層された外殻壁部21からなる外殻2と、複数段に積層された芯材部41からなる芯材4と、複数段に積層された内核部31からなる内核3とを有する立体造形物1を成形する。芯材4は、内核3に埋め込まれる骨部分であり、本形態においては、複数の芯材部41の積層方向Lに開口する格子状に形成される。芯材4は、格子状とする以外にも、複数の芯材部41の積層方向Lに開口を有するハニカム状、又は種々の多角形状とすることもできる。
そして、図14のフローチャートに示すように、実施形態1に示した第1外殻壁部形成工程X1(ステップS11)の後であって第1内核部形成工程Y1(S13)の前には、第1芯材部形成工程Z1(S12)を行い、芯材部造形用材料40を芯材用ノズル5Cから第1層目の外殻壁部21Aによる底部分211上に吐出しながら、芯材用ノズル5Cに対してステージ6を平面的に相対移動させる。そして、第1層目の外殻壁部21Aの底部分211の上に、芯材部造形用材料40による第1層目の芯材部41が形成され、光照射装置100からの光Hの照射を受けて、この芯材部造形用材料40が固化する。
また、芯材4を成形する芯材部造形用材料40の組成と、外殻2を成形する立体造形用材料20の組成とを同じにする場合には、各芯材部形成工程Z1,Z2においては、芯材用ノズル5Cを用いずに、外殻用ノズル5Aによって芯材4を成形するための芯材部造形用材料40を吐出させることができる。
また、外殻壁部21と芯材部41と内核部31とを順次繰り返し形成することにより、外殻2、芯材4及び内核3を有する立体造形物1の造形速度を向上させることができる。
本形態は、実施形態1,2に示した立体造形物1の製造方法及び製造装置10において、ステージ6に対して外殻用ノズル5A及び内核用ノズル5Bを相対移動させる際に用いられるノズル移動経路のデータ作成方法及びデータ作成プログラムについて示す。ノズル移動経路のデータは、図7に示すように、設計コンピュータ80において作成された後、制御コンピュータ8に送信され、制御コンピュータ8によって立体造形物1が造形される際に利用される。
本形態においては、外殻壁部用移動経路K1を内核部用移動経路K2に基づいて作成しており、外殻壁部用移動経路K1の作成を容易にすることができる。
また、本形態においても、その他の構成及び図中の符号が示す構成要素は実施形態1と同様であり、実施形態1と同様の作用効果を得ることができる。
内核部用移動経路K2の作成においては、外形層データD2に基づいて外形位置経路K20が決定されればよく、外形位置経路K20を除く内核部用移動経路K2の部分は、任意に決定することができる。
本形態も、実施形態1,2に示した立体造形物1の製造方法及び製造装置10において、ステージ6に対して外殻用ノズル5A及び内核用ノズル5Bを相対移動させる際に用いられるノズル移動経路のデータ作成方法及びデータ作成プログラムについて示す。本形態のノズル移動経路のデータ作成方法及びデータ作成プログラムは、実施形態3に示した場合と比較して、外殻壁部用移動経路K1と内核部用移動経路K2とを作成する順序が異なるものである。
本形態においては、外形層データD2に基づき、外殻壁部21を形成する際にステージ6に対して相対移動する外殻用ノズル5Aから外殻壁部造形用材料20を吐出させるための外殻壁部用移動経路K1のデータを作成する。作成された外殻壁部用移動経路K1のデータは、制御コンピュータ8における制御コードの位置制御用のデータとして用いられる。また、外殻壁部用移動経路K1のデータは、複数の外形層データD2のそれぞれに対応して複数作成される。
本形態においては、内核部用移動経路K2を外殻壁部用移動経路K1に基づいて作成しており、内核部用移動経路K2の作成を容易にすることができる。
また、本形態においても、その他の構成及び図中の符号が示す構成要素は実施形態3と同様であり、実施形態3と同様の作用効果を得ることができる。
内核3を構成するための内核部造形用材料30は、次のようにして得た。まず、N,N-ジメチルアクリルアミド77gに、セルロース誘導体(ヒドロキシプロピルセルロース、HPC、水中20g/L・25℃における粘度:150~400mPa・s)4.284gを加え、セルロース誘導体が溶解するまで撹拌する。次いで、2-(2-メタクリロイルオキシエチルオキシ)エチルイソシアナートを、セルロース誘導体の構成単位モノマーであるピラノース環1モルに対し、0.3モル量を加え、60℃の温度で1時間撹拌する。次いで、純水140mLを加え、さらに光ラジカル開始剤であるα-ケトグルタル酸0.22gを加えて攪拌することによって、内核部造形用材料30を得た。
(硬度測定)
ASTM D 2240規格に準拠し、成形した立体造形物1のサンプル片をテクロック社製デュロメータ(Duro-00タイプ)で測定した結果、硬度は20であった。
(強度測定)
JIS K625規格に準拠し、成形した立体造形物1のサンプル片をダンベル形状(6号サイズ)に打ち抜いた後、島津製作所製材料強度試験機(EZ Graph)を用いて引張強度試験を実施した結果、破断強度が0.23MPa、破断伸びが300%、引張弾性率が0.06N/m2であった。
外殻壁部造形用材料20を使用せず、内核部造形用材料30のみを内核用ノズル5Bから吐出させて内核部31を形成して、内核3を有する立体造形物を成形した。しかし、この立体造形物は、柔らかくて形状が不安定であり、きれいに造形することができなかった。
Claims (23)
- 立体造形用材料を、ノズルからステージ上に吐出しながら、前記ノズルと前記ステージとを相対移動させて、成形する立体造形物の外殻の一部となる外殻壁部を形成する工程と、
立体造形用材料をノズルから前記外殻壁部に囲まれた内側領域に吐出しながら、前記ノズルと前記ステージとを相対移動させて、前記立体造形物の内核の一部となる内核部を形成する工程と、を含む、立体造形物の製造方法。 - 立体造形用材料をノズルから前記外殻壁部上に吐出しながら、前記ノズルと前記ステージとを相対移動させて、前記外殻壁部を更に形成する工程と、
立体造形用材料をノズルから前記内核部上に吐出しながら、前記ノズルと前記ステージとを相対移動させて、前記内核部を更に形成する工程と、をさらに含む、請求項1に記載の立体造形物の製造方法。 - 前記外殻壁部を形成するための立体造形用材料と、前記内核部を形成するための立体造形用材料とは互いに異なる、請求項2に記載の立体造形物の製造方法。
- 前記外殻壁部が固化して形成される前記外殻の硬度は、前記内核部が固化して形成される前記内核の硬度よりも高い、請求項2又は3に記載の立体造形物の製造方法。
- 前記外殻壁部を形成するための立体造形用材料は、光硬化性を有するものであり、
前記外殻壁部を形成する工程及び前記外殻壁部を更に形成する工程においては、ノズルから吐出される立体造形用材料に光を照射して前記立体造形用材料を固化させる、請求項2~4のいずれか一項に記載の立体造形物の製造方法。 - 前記内核部を形成するための立体造形用材料は、光硬化性を有するものであり、
前記内核部を形成する工程及び前記内核部を更に形成する工程においては、ノズルから吐出される立体造形用材料に光を照射して前記立体造形用材料を固化させる、請求項2~5のいずれか一項に記載の立体造形物の製造方法。 - 前記外殻壁部を形成する工程の後であって前記内核部を形成する工程の前には、立体造形用材料をノズルから前記外殻壁部による底部分上に吐出しながら、前記ノズルと前記ステージとを相対移動させて、前記内核に埋め込まれる芯材の一部となる芯材部を形成する工程を行い、
前記内核部を形成する工程においては、立体造形用材料をノズルから前記外殻壁部と前記芯材部とに囲まれた内側領域に吐出し、
前記外殻壁部を更に形成する工程の後であって前記内核部を更に形成する工程の前には、立体造形用材料をノズルから前記芯材部上に更に吐出しながら、前記ノズルと前記ステージとを相対移動させて、前記芯材部を更に形成する工程を行う、請求項2~6のいずれか一項に記載の立体造形物の製造方法。 - 前記芯材部を形成する工程及び前記芯材部を更に形成する工程においては、立体造形用材料によって格子状又はハニカム状の前記芯材を形成する、請求項7に記載の立体造形物の製造方法。
- 前記芯材部が固化して形成される前記芯材の硬度は、前記内核部が固化して形成される前記内核の硬度よりも高い、請求項7又は8に記載の立体造形物の製造方法。
- 立体造形物を成形した後には、前記立体造形物における前記外殻を除去する工程を行う、請求項1~9のいずれか一項に記載の立体造形物の製造方法。
- 立体造形用材料が、重合体及び重合性モノマーから選ばれる少なくとも一種を含む、請求項1~10のいずれか一項に記載の立体造形物の製造方法。
- 立体造形用材料が、光ラジカル発生剤及び光酸発生剤から選ばれる少なくとも一種を含む、請求項11に記載の立体造形物の製造方法。
- 前記重合性モノマーは、ラジカル重合性不飽和化合物及びカチオン重合性化合物から選ばれる少なくとも一種を含む、請求項11又は12に記載の立体造形物の製造方法。
- 立体造形用材料が、溶媒を含む、請求項11~13のいずれか一項に記載の立体造形物の製造方法。
- 立体造形用材料全体における溶媒の含有量は、1質量%以上99質量%以下である、請求項14に記載の立体造形物の製造方法。
- 立体造形用材料全体における溶媒の含有量は、20質量%以上80質量%以下である、請求項14に記載の立体造形物の製造方法。
- 前記溶媒が、極性溶媒及びイオン液体から選ばれる少なくとも一種である、請求項14~16のいずれか一項に記載の立体造形物の製造方法。
- 前記極性溶媒は、水、アルコール類、多価アルコールのアルキルエーテル類及び非プロトン性極性溶媒から選ばれる少なくとも一種である、請求項17に記載の立体造形物の製造方法。
- 請求項1~18のいずれか一項に記載の立体造形物の製造方法に用いられるノズル移動経路のデータを作成する方法であって、
造形しようとする前記立体造形物の立体表面データを、設計又は読取りを行って作成し、
前記立体表面データを、所定の方向に一定の間隔でスライスして、前記所定の方向に複数に積み重なる線状の外形層データに加工し、
前記外形層データに基づき、前記ノズルから内核部造形用材料を吐出させるための内核部用移動経路のデータを作成し、
前記内核部用移動経路の外側に所定の距離だけ補正した位置を、前記ノズルから外殻壁部造形用材料を吐出させるための外殻壁部用移動経路のデータとする、立体造形物の製造方法に用いられるノズル移動経路のデータ作成方法。 - 請求項1~18のいずれか一項に記載の立体造形物の製造方法に用いられるノズル移動経路のデータを作成する方法であって、
造形しようとする前記立体造形物の立体表面データを、設計又は読取りを行って作成し、
前記立体表面データを、所定の方向に一定の間隔でスライスして、前記所定の方向に複数に積み重なる線状の外形層データに加工し、
前記外形層データに基づき、前記ノズルから外殻壁部造形用材料を吐出させるための外殻壁部用移動経路のデータを作成し、
前記ノズルから内核部造形用材料を吐出させるための内核部用移動経路のデータを作成するに当たり、前記外殻壁部用移動経路の内側に所定の距離だけ補正した位置を、前記内核部用移動経路の全体における外形の位置とする、立体造形物の製造方法に用いられるノズル移動経路のデータ作成方法。 - 外殻及び前記外殻内に配置される内核による立体造形物を製造する装置であって、
外殻を形成するための外殻壁部造形用材料を吐出する外殻用ノズルと、
内核を形成するための内核部造形用材料を吐出する内核用ノズルと、
前記外殻用ノズルから吐出される前記外殻壁部造形用材料及び前記内核用ノズルから吐出される前記内核部造形用材料が積層されるステージと、
前記ステージと前記外殻用ノズル及び前記内核用ノズルとを相対移動させる相対移動機構と、
前記外殻用ノズル、前記内核用ノズル及び前記相対移動機構の動作を制御する制御コンピュータと、を備え、
前記制御コンピュータは、前記外殻用ノズルから吐出される前記外殻壁部造形用材料によって前記外殻の一部となる外殻壁部を前記ステージ上に形成するとともに、前記内核用ノズルから、前記外殻壁部に囲まれた内側領域に吐出される前記内核部造形用材料によって前記内核の一部となる内核部を前記ステージ上に形成するよう構成されている、立体造形物の製造装置。 - 請求項21に記載の立体造形物の製造装置に用いられる前記外殻用ノズル及び前記内核用ノズルの移動経路のデータを作成するための設計コンピュータのプログラムであって、
前記設計コンピュータに、
造形しようとする前記立体造形物の立体表面データを所定の方向に一定の間隔でスライスしたときに、前記所定の方向に複数に積み重なる線状の外形層データに基づいて、前記内核用ノズルの移動経路のデータを作成するステップと、
前記内核用ノズルの移動経路の外側に所定の距離だけ補正した位置に、前記外殻用ノズルの移動経路のデータを作成するステップと、を実行させる、立体造形物の製造装置に用いられるノズル移動経路のデータ作成プログラム。 - 請求項21に記載の立体造形物の製造装置に用いられる前記外殻用ノズル及び前記内核用ノズルの移動経路のデータを作成するための設計コンピュータのプログラムであって、
前記設計コンピュータに、
造形しようとする前記立体造形物の立体表面データを所定の方向に一定の間隔でスライスしたときに、前記所定の方向に複数に積み重なる線状の外形層データに基づいて、前記外殻用ノズルの移動経路のデータを作成するステップと、
前記外殻用ノズルの移動経路の内側に所定の距離だけ補正した位置に、前記内核用ノズルの移動経路のデータを作成するステップと、を実行させる、立体造形物の製造装置に用いられるノズル移動経路のデータ作成プログラム。
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