JP2006130864A - The molding method of solid molded object by liquid discharge method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding method which can easily form a predetermined solid molded object on a substrate by discharging a liquid object by a liquid discharging method. <P>SOLUTION: The molding method of the solid molded object of this invention comprises: a 1st-layer formation process which discharges a liquid object 12 having a gelatinizer added in a columnar shape from the nozzle 25 of a discharging head 20 and impacts it on a substrate W to form the 1st layer 13; and a laminating process which laminates a 2nd layer 14 and subsequent ones by making the liquid object 12 impact repeatedly in a same way at the position corresponding to the 1st layer 13. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a modeling method for forming a three-dimensional object on a substrate by discharging a liquid material by a liquid discharge method.

  As a modeling method for forming a three-dimensional modeled object, a three-dimensional modeling apparatus disclosed in Patent Document 1 is used to discharge a photocurable uncured resin from a nozzle and irradiate the uncured resin near the nozzle with light. By doing this, a method is known in which the uncured resin is cured to form a three-dimensional shaped object.

  Moreover, the cationic ultraviolet curable composition is dropped from the nozzle of the dispenser, and injected into the mold while irradiating the falling composition with ultraviolet rays from the entire periphery by the ultraviolet rays emitted from the ultraviolet light source lamp. Patent Document 2 discloses a manufacturing method in which a cured product is taken out from a mold to obtain a three-dimensional object.

JP-A-8-230048 JP 2001-96630 A

  The conventional modeling method has a problem that the configuration of the apparatus becomes complicated because a three-dimensional model is formed using a photocurable substance and a light irradiation apparatus for curing the uncured substance is necessary. is doing.

  The present invention has been made in consideration of the above-described problems, and an object thereof is to provide a modeling method capable of easily forming a predetermined three-dimensional modeled object on a substrate by discharging a liquid material by a liquid discharge method. To do.

  The modeling method of the present invention is a modeling method for forming a three-dimensional modeled object on a substrate by discharging a liquid material from a nozzle of a discharge head in a columnar shape toward the substrate, and the liquid material is solidified after being discharged from the nozzle. The first layer forming step of forming the first layer by discharging the liquid material from the nozzles of the discharge head in a columnar shape and landing on the substrate, and the position corresponding to the first layer And a laminating step of repeatedly ejecting a liquid material in a columnar shape from a nozzle of an ejection head and laminating the second and subsequent layers on the first layer.

  According to this method, since the liquid material is prepared such that the liquid material is solidified after being discharged from the nozzle, the liquid material is discharged in a columnar shape from the nozzle of the discharge head in the first layer forming step. The first layer is formed by landing on the first layer, and the liquid material is repeatedly ejected from the nozzle of the ejection head in a columnar shape at a position corresponding to the first layer so that the second and subsequent layers are laminated on the first layer in the laminating step. If it does so, the solid modeling thing solidified on the 1st layer and laminated | stacked in columnar shape can be modeled easily. Compared to the method of forming a three-dimensional model by discharging a liquid material made of a photocurable material from a discharge head and irradiating the discharged liquid material with light from a light irradiation device to cure the photocurable material. A corresponding light irradiation device is not required, and the configuration of the device can be simplified.

  The liquid is characterized in that a gelling agent is added.

  According to this method, since the gelling agent is added to the liquid, gelation is promoted by evaporating the solvent when the liquid is discharged from the nozzle of the discharge head and landed on the substrate. Therefore, even if the second and subsequent layers land on the first layer formed in the first layer forming step, the shape is not easily lost due to gelation, and a columnar three-dimensional object can be easily formed.

  In addition, the molecular weight of the gelling agent and the addition concentration of the gelling agent with respect to the total amount of the liquid are preferably adjusted so that the liquid is gelled when discharged from the nozzle of the discharge head and landed on the substrate. .

  Gelling agents have different molecular weights depending on the type, and even after the same concentration of addition to the total amount of liquid, the elastic modulus and dynamic surface tension after gelation are different. In order to stably discharge a liquid material from a discharge head in a columnar shape, it is necessary to have an appropriate elastic modulus and dynamic surface tension. For example, a liquid material having a higher elastic modulus and a smaller dynamic surface tension is longer in a columnar shape. Can be discharged. By controlling such physical property values, the coating amount after landing of the liquid material is controlled. According to this method, the molecular weight of the gelling agent and the concentration of the gelling agent with respect to the total amount of the liquid are adjusted so that the liquid is gelled when discharged from the nozzle of the discharge head and landed on the substrate. Therefore, the liquid can be discharged in a column shape with a stable length, and the coating amount of the liquid that gels after landing can be stabilized. Therefore, after the first layer is gelled, the second and subsequent layers can be quickly stacked, and in the stacking process, a liquid body is repeatedly discharged from the nozzle of the discharge head into a columnar shape to form a columnar three-dimensional structure that has a stable shape. can do.

  The liquid material is obtained by dissolving or dispersing a functional material in a solvent whose main component is water, and the gelling agent to be added is made of a water-soluble polymer material.

  According to this method, the liquid material is obtained by adding a water-soluble polymer material as a gelling agent to a solution in which a functional material is dissolved or dispersed in a solvent whose main component is water. Compared to the case of using a solvent, a columnar three-dimensional object made of a functional material can be formed using a conventional (known) ink jet head without changing the structure and material of the discharge head so as to correspond to the solvent. Can do.

  The liquid is composed of Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Sb, Ga, and In. It is a fine particle dispersion or solution composed of one or more selected metals, alloys, and metal oxides.

  According to this method, the liquid is Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Sb, Since it is a fine particle dispersion or solution composed of one or more metals, alloys, and metal oxides selected from Ga and In, the liquid material is discharged from the nozzle of the ejection head in the first layer forming step and the laminating step. By heating and firing the columnar three-dimensional object formed on the substrate by discharging it in a columnar shape, a three-dimensional object having conductivity in which the solvent component is removed and the fine particles are sintered can be formed.

  In the modeling method of the present invention, the first layer forming step and the laminating step include a gelling step of gelling the liquid material that has landed on the substrate.

  According to this method, since the first layer forming step and the laminating step include a gelling step of gelling the liquid material that has landed on the substrate, it is possible to wait for the natural evaporation of the solvent of the liquid material after landing. By promoting the gelation, a columnar three-dimensional model can be efficiently modeled on the substrate.

  In the gelation step, the liquid material that has landed on the substrate is dried to be gelled. According to this method, by evaporating the solvent by drying the liquid after landing, the liquid can be quickly gelled and a columnar three-dimensional modeled object can be modeled more efficiently on the substrate.

  In the gelation step, it is preferable to dry and gel the liquid material that has landed on the substrate by flowing a gas between the ejection head and the substrate. When a liquid material is ejected in a columnar shape from a plurality of nozzles of a discharge head to attempt to form a plurality of three-dimensional objects at the same time, the evaporation rate of the solvent from the liquid material that has landed around the landing range on the substrate tends to increase. Therefore, according to this method, it is possible to reduce the occurrence of variations in the size between a plurality of three-dimensional objects formed by balancing the evaporation rate of the solvent by flowing a gas between the discharge head and the substrate. be able to.

  In the gelation step, the liquid that has landed on the substrate may be dried and gelled by heating the substrate. According to this method, since the liquid that has landed by heating the substrate is dried and gelled, the liquid that has landed on any surface portion of the substrate is heated and the solvent evaporates to quickly gel. Can be made. In addition, since the liquid that has landed positively by heating the substrate is dried, it can be gelated even with a small concentration of gelling agent.

  Further, in the gel step, the liquid material that has landed on the substrate may be dried and gelled by flowing a gas between the ejection head and the substrate and heating the substrate. According to this method, when a liquid material is ejected in a columnar shape from a plurality of nozzles of a discharge head to attempt to form a plurality of three-dimensional objects at the same time, a gas is allowed to flow between the discharge head and the substrate and the substrate is heated. Thus, since the liquid material that has landed on the substrate is dried and gelled, a plurality of three-dimensional models can be quickly modeled with little variation in size.

  In the modeling method of the present invention, in the stacking step, when the liquid material is landed on the first layer on the substrate and the second and subsequent layers are stacked, the gap between the ejection head and the substrate is gradually increased. Then, the liquid material is ejected from the nozzle of the ejection head in a columnar shape and landed.

  If the gap between the discharge head and the substrate is held at a constant interval and discharged under the same liquid discharge conditions, the gap between the molded object and the discharge head after stacking becomes shorter. The amount of liquid material that lands on the second and subsequent layers increases. In order to avoid this, changing the discharge conditions each time the liquid material is discharged in the stacking process complicates the discharge control. According to this method, in the laminating step, the gap between the ejection head and the substrate is gradually increased so that the liquid material is landed on the first layer on the substrate and the second and subsequent layers are laminated. The second and subsequent layers can be stacked on the first layer in a stable amount of liquid material by discharging in a columnar shape with a fixed length without changing the body discharge conditions. Therefore, it is possible to model a columnar three-dimensional model having a more stable shape.

  Further, in the modeling method of the present invention, the substrate is subjected to a surface treatment so as to have liquid repellency with respect to the liquid material on a surface side on which the liquid material lands.

  According to this method, since the substrate is surface-treated so as to have liquid repellency with respect to the liquid material, the landed liquid material does not wet and spread on the substrate, and the amount and surface tension of the liquid material are reduced. The shape is stable within the range of the corresponding size. Therefore, the liquid material can be landed on the substrate with a smaller landing diameter. That is, it is possible to model a three-dimensional model having a first layer with a smaller diameter in plan view.

  In the modeling method of the present invention, the substrate is subjected to a surface treatment so that the surface on which the liquid material lands is lyophilic with respect to the liquid material.

  According to this method, since the substrate is subjected to surface treatment so as to have lyophilicity with respect to the liquid material, the landed liquid material spreads on the substrate and spreads according to the amount and surface tension of the liquid material. The shape is stable within the range of the size. Therefore, the second and subsequent layers can be stacked on the first layer in a state where the first layer is landed in a wider range. That is, it is possible to model a three-dimensional model having a first layer with a larger diameter in plan view.

(First embodiment)
An embodiment of the present invention is a modeling method for modeling a three-dimensional modeled object on a substrate, and uses a liquid material in which a conductive material as a functional material is dispersed in a solvent and a gelling agent is added, and the substrate is conductive. An example of a modeling method for modeling a three-dimensional modeled object and a liquid discharge apparatus as a modeling apparatus will be described.

  First, a liquid ejection device used when modeling a three-dimensional model will be described. FIG. 1 is a schematic perspective view showing a liquid ejection apparatus. As shown in FIG. 1, a liquid ejection apparatus 10 includes a head unit 1 having a plurality of ejection heads 20 (see FIG. 2) as liquid ejection units that eject a liquid material onto a substrate W, and a stage on which the substrate W is placed. 7. An X-direction guide shaft 4 for driving the head unit 1 in the sub-scanning direction (X direction), a Y-direction guide shaft 5 for driving the stage 7 in the main scanning direction (Y direction), and an X-direction guide shaft. An X-direction drive motor 2 that rotates 4 and a Y-direction drive motor 3 that rotates a Y-direction guide shaft 5 are provided. The X-direction guide shaft 4 and the Y-direction guide shaft 5 are disposed on the upper portion of the base 9, and a control unit 6 is provided on the lower portion of the base 9. Further, the liquid ejection device 10 includes a cleaning mechanism 8 for cleaning the head unit 1 and a heater 11 for heating the ejected liquid material to evaporate and dry the solvent, and to fire it.

  The plurality of ejection heads 20 of the head unit 1 can eject the liquid material individually for each nozzle according to the ejection voltage supplied from the control unit 6. The discharge head 20 will be described later.

  The X direction drive motor 2 is not limited to this, but is, for example, a stepping motor. When a drive pulse signal in the X axis direction is supplied from the control unit 6, the X direction guide shaft 4 is rotated to The head unit 1 engaged with the direction guide shaft 4 is moved in the X direction.

  Similarly, the Y-direction drive motors 3 and 18 are not limited to this, but are stepping motors, for example. When a drive pulse signal in the Y-axis direction is supplied from the control unit 6, the Y-direction guide shaft 5 is moved. The stage 7 and the cleaning mechanism 8 that are rotated and engaged with the Y-direction guide shaft 5 are moved in the Y-axis direction.

  When cleaning the head unit 1, the cleaning mechanism 8 moves to a position facing the head unit 1, and adheres to the nozzle surface of the ejection head 20 so that an unnecessary liquid material is sucked and a liquid material is attached. A wiping operation for wiping the nozzle surface 26 (see FIG. 2) is performed. Details of the cleaning mechanism 8 are omitted.

  The heater 11 is means for heat-treating the substrate W by, for example, lamp annealing, and performs heat treatment for evaporating and drying the liquid material discharged onto the substrate W to solidify it. The controller 6 also controls the turning on and off of the heater 11. In addition, a heater 19 (see FIG. 8B) made of a heating element capable of heating the substrate W is also provided inside the stage 7. The configuration of the heaters 11 and 19 is not limited to this.

  The operation of the liquid ejection apparatus 10 is performed by sending a predetermined drive pulse signal from the control unit 6 to the X direction drive motor 2 and the Y direction drive motor 3, moving the head unit 1 in the sub-scanning direction (X direction), and moving the stage 7 to the main. Relative movement in the scanning direction (Y direction). Then, a discharge voltage is supplied from the control unit 6 to discharge the liquid material from the head unit 1 to a predetermined position of the substrate W. The plurality of ejection heads 20 are supported by the head unit 1 so that the arrangement direction of the plurality of nozzles 25 (see FIG. 2) is arranged in parallel at a constant interval in the Y-axis direction that is the main scanning direction. The angle of the head unit 1 may be adjusted so that the arrangement direction of the plurality of nozzles 25 intersects the Y axis direction (main scanning direction). In this way, the pitch between the nozzles of the ejection head 20 can be adjusted relative to the substrate W. Further, the head unit 1 includes an actuator 27 (see FIG. 2) for moving the ejection head 20 up and down in the Z direction, and the distance between the substrate W and the nozzle surface 26 can be arbitrarily set within a predetermined range.

  FIG. 2 is a schematic view showing a liquid material discharge mechanism including a discharge head. As shown in FIG. 2, the ejection head 20 includes a liquid chamber 21 that communicates with the nozzle 25 and a piezo element 22 that pressurizes the liquid 12 filled in the liquid chamber 21. The liquid material 12 is supplied to the liquid chamber 21 from a liquid material supply system 23 including a material tank that stores the liquid material 12. The piezo element 22 is electrically connected to a drive circuit 24 provided in the control unit 6, and a drive voltage (discharge voltage) is applied from the drive circuit 24 to the piezo element 22 to deform the piezo element 22. The liquid chamber 21 is deformed and the liquid material 12 is discharged from the nozzle 25. In this case, the amount of distortion of the piezo element 22 is controlled by changing the value of the drive voltage. Further, the distortion speed of the piezo element 22 is controlled by changing the frequency of the drive voltage. The discharge amount and length of the liquid material 12 discharged from the discharge head 20 in a columnar shape can be adjusted by the drive voltage (discharge voltage) and the frequency supplied from the drive circuit 24 to the piezo element 22. Since ejection by the piezo method does not apply heat to the material, it has an advantage of hardly affecting the composition of the material.

  FIG. 3 is a graph showing the waveform of the drive voltage applied to the piezo element of the ejection head. As shown in FIG. 3, the waveform of the drive voltage in this case is a trapezoidal wave having a gradient, the application time is about 8 μsec, the maximum voltage is 30 V, and the frequency is 1 kHz.

  Next, a method for forming a three-dimensional object that is one embodiment of the present invention using the liquid ejection device 10 will be described with reference to the drawings.

  FIG. 4 is a flowchart showing a method for modeling a three-dimensional model. As shown in the flowchart of FIG. 4, the modeling method of the present embodiment includes a first layer forming step of forming the first layer by discharging the liquid material 12 in a columnar shape from the nozzles 25 of the discharge head 20 and landing on the substrate W. The liquid material 12 is repeatedly ejected in a columnar shape from the nozzle 25 of the ejection head 20 at a position corresponding to the first layer, and the second and subsequent layers are laminated on the first layer, and the laminated liquid material 12 And a baking step of heating and baking the layer made of In addition, a gelation step is included in which the liquid 12 that has landed on the substrate W is gelled. In the flowchart of FIG. 4, the gelation process is shown separately, but is basically included in the first layer formation process and the lamination process.

  The liquid 12 is prepared by mixing raw materials so as to be gelled (solidified) after being discharged from the nozzle 25, and is composed of water as a main solvent and ATO (Antimony Tin Oxide) as a functional material. ) Was dispersed in about 1 wt%, and a water-soluble polymer material polydimethylacrylamide was added as a gelling agent so as to have an addition concentration of 0.7 wt% with respect to the total amount of the liquid material 12. The molecular weight of polydimethylacrylamide is about 380000, and preferably about 200000 to 500000. As a result, the liquid 12 has an appropriate elastic modulus and dynamic surface tension, and when a predetermined drive voltage (discharge voltage) is applied to the discharge head 20, the liquid 12 is discharged in a columnar shape from the nozzle 25 and gels when landed on the substrate W. . The mechanism of gelation is due to the fact that the long-molecule gelling agent present in the solvent grows in such a way that the long molecules are entangled or networked by evaporation or heating of the solvent.

  In addition, the liquid 12 is a fine particle dispersion or a functional material made of a metal such as Au, Ag, Cu, Ni, Mn, alloys of these metals, or ATO or ITO (Indium Tin Oxide) as a metal oxide. A solution is preferred.

  FIGS. 5A to 5C are schematic views showing the state of the first layer forming step. As shown in FIG. 5A, in the first layer forming process of step S1, the ejection head 20 is disposed to face the substrate W placed on the stage 7 at a predetermined interval L0 (in this example, approximately 200 μm). ing. When the drive voltage shown in FIG. 3 is applied to the piezo element 22, the piezo element 22 contracts and the liquid chamber 21 expands when the drive voltage is in a positive gradient, so that the liquid 12 is supplied from the liquid supply system 23 to the liquid chamber. 21. Subsequently, when the driving voltage has a negative gradient, the liquid element 12 is discharged from the nozzle 25 by pressurizing the liquid chamber 21 so that the piezo element 22 returns to the original state. The liquid 12 has an appropriate viscosity and is discharged in a columnar shape by the added polymer material as a gelling agent.

  As shown in FIG. 4B, the liquid material 12 ejected in a columnar shape has its tip landed on the substrate W and spreads in a wet state according to the surface treatment state of the substrate W.

  As shown in FIG. 3C, when the application of the driving voltage to the piezo element 22 is completed, the liquid material 12 tries to return into the nozzle 25 by its elastic force. At this time, the columnar liquid body 12 is torn and cut by a Rayleigh wave node whose wavelength depends on the dynamic surface tension, density, viscosity, diameter of the nozzle 25 and the like. One of the torn liquids 12 returns into the nozzle 25, and the other reaches the substrate W and spreads wet.

  Next, in the gelation process of step S2, the liquid material 12 which has landed and wetted and spread on the substrate W is solidified by evaporating the solvent component and promoting gelation, as shown in FIG. 5C. 13 is formed. Details of the gelation step will be described later. Then, the process proceeds to step S3.

  FIGS. 6A to 6C are schematic views showing the state of the lamination process. As shown in FIG. 6A, in the stacking process of step S3, the ejection head 20 is disposed to face the substrate W at a distance L1 that is slightly larger than the distance L0. The liquid material 12 is discharged in a column shape from the nozzle 25 of the discharge head 20 at a position corresponding to the first layer 13 and is landed on the first layer 13. The landed liquid material 12 is torn off in the same manner as in step S1. One of the torn liquid bodies 12 returns into the nozzle 25, and the other is laminated on the first layer 13. Then, the process proceeds to step S4.

  In the gelation process of step S4, the laminated liquid body 12 is gelled to form the second layer. Then, the process proceeds to step S5.

  Step S5 is a step of determining whether or not the liquid material 12 has been laminated by a predetermined number of ejections. If it is not laminated by the predetermined number of discharges, the process returns to step S3 again and the lamination is repeated.

  When returning to step S3 again and repeating the lamination, as shown in FIG. 6B, the liquid material 12 is transferred from the nozzle 25 to the second layer 14 with the discharge head 20 and the substrate W being set at an interval L2 (L2> L1). Discharge in a columnar shape. The liquid body 12 that has landed on the second layer 14 is torn and gelled to form a three-dimensional structure 15a in which the third layer 15 is laminated.

  Furthermore, when repeating the lamination process of step S3-step S4, as shown in FIG.6 (c), the liquid body 12 is made into the 3rd layer from the nozzle 25 by making the discharge head 20 and the board | substrate W into the space | interval L3 (L3> L2). It is discharged in a columnar shape toward the three-dimensional structure 15a on which 15 is laminated. The liquid body 12 that has landed on the three-dimensional structure 15a is torn and gelled to form a three-dimensional structure 16a in which the fourth layer 16 is laminated. As described above, in the laminating process, the gap (interval) between the ejection head 20 and the substrate W is gradually increased, and the liquid material 12 is repeatedly landed on the first layer 13 so that the layers after the second layer 14 are formed. Laminate. The number of discharges of the liquid material 12 in the stacking process is counted and controlled by the control unit 6.

  Next, when the control unit 6 determines that the liquid body 12 has been laminated at a predetermined number of discharges in step S5, the three-dimensional structure 16a formed in this way is provided in the liquid discharge device 10 in the firing step of step S6. When the heat treatment is performed by the heater 11, the solvent is evaporated and baked to obtain a three-dimensional structure 16 a having conductivity. Alternatively, the heater 11 may be used as another apparatus such as a firing furnace, and the substrate W on which the three-dimensional structure 16a is formed may be charged and fired.

  FIG. 7 is a schematic view showing a landing state according to the surface treatment state of the substrate. FIG. 4A is a schematic diagram showing a landing state when the substrate surface is subjected to a liquid repellent treatment, and FIG. 4B is a schematic diagram showing a landing state when the substrate surface is subjected to a lyophilic treatment.

  As shown in FIG. 7A, in this embodiment, the substrate W is subjected to a liquid repellent treatment on the surface 17 to form a liquid repellent treatment surface 17a. Examples of the liquid repellent treatment include a method of forming an organic thin film such as a fluorine-containing alkylsilane compound on the surface 17 of the substrate W, a plasma treatment using a fluorocarbon compound as a treatment gas, and a liquid repellent polymer compound. The method etc. which apply | coat (for example, fluorine-containing polyimide resin etc.) are mentioned.

  Thus, by performing the liquid repellent treatment on the surface 17 of the substrate W, the landed liquid body 12 is difficult to spread on the surface 17 of the substrate W, and the landing diameter can be made smaller. Therefore, when it is intended to form a columnar three-dimensionally shaped object on the substrate W at a high density, it is desirable to perform a surface treatment so that the surface 17 has liquid repellency with respect to the liquid body 12.

  On the other hand, as shown in FIG. 7B, it is also effective to form a lyophilic treatment surface 17b by subjecting the surface 17 of the substrate W to lyophilic treatment. By subjecting the surface 17 of the substrate W to lyophilic treatment, the landed liquid 12 is wetted and spreads on the surface 17 of the substrate W so that the landing diameter can be made larger. For example, when trying to model a plurality of three-dimensional objects with the second and subsequent layers formed in a state where the first layers are connected, the surface 17 is lyophilic with respect to the liquid body 12. Surface treatment is desirable.

As a method of lyophilic treatment, for example, a method of applying a photocatalyst such as titanium oxide to the surface 17 and then irradiating with ultraviolet rays to make it lyophilic, a method of performing plasma treatment using oxygen (O ₂ ) as a treatment gas, etc. Is mentioned.

  Next, the gelation step included in the first layer formation step and the lamination step will be described. FIG. 8 is a schematic view showing the state of the gelation process. FIG. 4A is a schematic diagram showing a state of gelation by natural drying, and FIG. 4B is a schematic diagram showing a state of gelation by aggressive drying.

  As shown in FIG. 8A, the liquid material 12 is ejected from the plurality of nozzles 25 of the ejection head 20 in the first layer forming process and landed on the substrate W to form the first layer 13, and the same process is performed in the laminating process. When the liquid material 12 is discharged from the plurality of nozzles 25 and the second layer is stacked and naturally dried, the evaporation rate of water that is the solvent of the liquid material 12 varies depending on the landing position. In particular, since the evaporation speed in the peripheral area of the landing area of the plurality of liquid bodies 12 is increased, the gelation speed is similarly increased, and the height of the inner second layer 14a is lower than that of the second layer 14b in the peripheral area. That is, the modeling speed of the columnar three-dimensional model becomes slower as it goes to the center of the landing area.

  In the present embodiment, in order to improve such a variation in modeling speed, air as a gas is about 1 m / sec between the discharge head 20 and the substrate W using the blower 28 as shown in FIG. 8B. To make it flow in a certain direction. Further, the substrate W is heated to approximately 100 ° C. by the heater 19 provided on the stage 7. In addition, since it is considered that the evaporation rate and gelation rate of the solvent change depending on the material configuration of the liquid material 12, in the gelation step of gelling the landed liquid material 12, one of the above drying methods is selected. It may be adopted. In addition to the blower 28, the air may be exhausted at a position corresponding to between the ejection head 20 and the substrate W so that air flows in a certain direction.

  In this embodiment, when the liquid material 12 is landed on the first layer 13 and laminated and gelled approximately 10,000 times in the laminating step, a columnar shape made of ATO having a height of approximately 100 μm and a diameter of approximately 25 to 40 μm. A three-dimensional model was created.

  The effects of the first embodiment are as follows.

  (1) In the method for modeling a three-dimensional object according to the present embodiment, polydimethylacrylamide, which is a water-soluble polymer material, is added to the liquid 12 as a gelling agent. The liquid body 12 is ejected in a columnar shape from the nozzle 25 and landed on the substrate W to form the first layer 13. In the laminating step, the first layer is so formed that the second layer 14 and subsequent layers are laminated on the first layer 13. The liquid material 12 is repeatedly discharged in a columnar shape at a position corresponding to 13. Therefore, it is possible to easily form the three-dimensional structure 16a that is gelled on the first layer 13 and stacked in a columnar shape on the substrate W. Compared to a method of forming a three-dimensional structure by discharging a liquid material made of a photocurable material from the discharge head 20 and irradiating the discharged liquid material with light from a light irradiation device to cure the photocurable material. The light irradiation device corresponding to the above is not required, and the configuration of the device can be simplified.

  (2) Since the liquid 12 has ATO as a functional material dispersed in water as a main solvent and polydimethylacrylamide is added as a gelling agent, the solvent evaporates when landing on the substrate W. Promotes gelation. Therefore, after the 1st layer 13 gelatinizes, the 2nd layer 14 or later can be laminated | stacked quickly, a shape does not collapse easily in a lamination | stacking process, and the columnar three-dimensional molded item 16a can be modeled easily.

  (3) Since the liquid 12 has a molecular weight of about 380000 polydimethylacrylamide as a gelling agent and is adjusted to an addition concentration of about 0.7 wt% so that the liquid 12 gels upon landing on the substrate W. The liquid body 12 is discharged in a column shape with a stable length, and can stabilize the coating amount of the liquid body 12 that gels after landing. Further, since gelation occurs immediately after landing, a higher columnar three-dimensional structure 16a can be formed with a small number of discharges.

  (4) When an organic solvent is used as the solvent, the liquid body 12 needs to be changed in structure and material so that the material and surface treatment of the discharge head 20 are not eroded by the organic solvent. In this case, since ATO as a functional material is dispersed in a solvent whose main component is water and polydimethylacrylamide, which is a water-soluble polymer material, is added as a gelling agent, the material constituting the discharge head 20 and Even if the surface treatment or the like is not changed, the columnar three-dimensional structure 16a made of ATO can be formed using an ink jet head that discharges recording ink.

  (5) In the gelation step included in the first layer forming step and the laminating step, air as a gas is allowed to flow between the ejection head 20 and the substrate W in a certain direction and the substrate W is heated to approximately 100 ° C. Since the liquid material 12 that has landed on the substrate W is dried and gelled by the above, even if a plurality of liquid materials 12 are landed on the substrate W at once, the variation in size between the landing positions can be reduced quickly. A plurality of three-dimensional models 16a can be modeled.

  (6) In the stacking step, the gap (interval) between the ejection head 20 and the substrate W is gradually increased, and the liquid material 12 is landed on the first layer 13 on the substrate W, and the layers after the second layer 14. Therefore, the second and subsequent layers 14 are stacked on the first layer 13 with a stable coating amount of the liquid material 12 without changing the discharge conditions of the liquid material 12. be able to. Therefore, the columnar three-dimensional model 16a having a more stable shape can be modeled. Further, it is possible to prevent the discharged liquid material 12 from being gelled while being connected to the nozzle 25 of the discharge head 20 without being broken.

  (7) When the surface 17 of the substrate W is subjected to a liquid repellent treatment so as to have liquid repellency with respect to the liquid 12, the landed liquid 12 does not wet and spread on the substrate W, and the amount of the liquid 12 The shape is stable in the range of the size according to the surface tension. Therefore, the liquid 12 can be landed on the substrate W with a smaller landing diameter. That is, the three-dimensional structure 16a having the first layer 13 having a smaller diameter in plan view can be formed.

  (8) When the surface 17 of the substrate W is subjected to a lyophilic treatment so as to have lyophilicity with respect to the liquid material 12, the landed liquid material 12 spreads wet on the substrate W and the amount and surface of the liquid material 12 The shape is stable in the range of the size according to the tension. Therefore, the liquid 12 can be landed on the substrate W with a larger landing diameter. That is, it is possible to model the three-dimensional model 16a having the first layer 13 having a larger diameter in plan view.

(Second Embodiment)
The present embodiment is a multilayer wiring board in which a plurality of layers of metal wiring are formed on a substrate W, and an interlayer conductive portion that conducts between the plurality of layers of metal wiring is formed using the modeling method shown in the first embodiment. A manufacturing method is shown.

  In this case, as the liquid, a conductive liquid 30 is used in which Ag particles are dispersed as a functional material in water as a main solvent and polydimethylacrylamide is added as a gelling agent at an addition concentration of 0.7 wt%.

  In addition, a glass substrate is used as the substrate W, and a portion where the metal wiring is formed as a surface treatment is subjected to a lyophilic treatment and another portion is subjected to a liquid repellent treatment. For the lyophilic treatment and the liquid repellent treatment, the methods described above in the first embodiment are used.

  9A to 9G are schematic cross-sectional views illustrating a method for manufacturing a multilayer wiring board. First, as shown in FIG. 2A, the conductive liquid 30 is ejected in a columnar shape from the nozzles 25 of the ejection head 20 and landed on the portion where the metal wiring on the substrate W is formed.

  As shown in FIG. 4B, the landed conductive liquid 30 is torn and spreads and gels along the lyophilic portion to form the first layer 31. As a matter of course, the landing position of the conductive liquid 30 is a position along the wiring direction of the metal wiring.

  Alternatively, the surface of the substrate W may be subjected to a liquid repellent treatment, and the first layer 31 may be formed by landing again at a position where the conductive liquid bodies 30 landed on a small diameter are joined. If the drying speed of the landed conductive liquid 30 is adjusted to reduce the gelation speed, the first layer 31 having a predetermined film thickness can be formed by leveling the previous landing and the subsequent landing.

  Next, as shown in FIG. 3C, the conductive liquid 30 is repeatedly landed on the portion where the metal wiring is to be formed, thereby forming the first layer 31, thereby completing the metal wiring layer 32.

Next, as shown in FIG. 4D, the conductive liquid 30 is deposited at positions where conduction is required corresponding to the metal wiring layers to be formed later, and laminated so as to have the required height. Thereby, interlayer conductive portions 33, 34, and 35 are formed on the metal wiring layer 32. These interlayer conductive portions 33, 34, 35 and the metal wiring layer 32 are baked by heating the substrate W to a predetermined temperature in order to provide conductivity. Then, after forming the interlayer conductive portions 33, 34, 35, the entire surface is treated with O ₂ plasma to make it lyophilic, and an insulating material such as a polyimide resin is applied to the entire surface as the interlayer insulating layer 40. As a coating method, a method such as spray coating or spin coating may be used. In this case, the thickness of the interlayer insulating layer 40 is set such that the interlayer conductive portions 33 and 34 penetrate the interlayer insulating layer 40 slightly. The interlayer insulating layer 40 applied by drying the substrate W is formed by removing the solvent component.

  Next, a second metal wiring layer 36 is formed on the interlayer insulating layer 40 as shown in FIG. In this case, since the surface of the interlayer insulating layer 40 has liquid repellency, the metal wiring layer 36 is formed by landing so as to join the conductive liquid 30 as described above. The metal wiring layer 36 is formed so as to be electrically connected to the first metal wiring layer 32 at the interlayer conductive portions 33 and 34.

  Next, as shown in FIG. 6F, an interlayer insulating layer 41 is formed in the same manner as the interlayer insulating layer 40 previously formed on the surface on which the metal wiring layer 36 is formed. At this time, an insulating material is applied and dried so that the interlayer conductive portion 35 penetrates slightly from the interlayer insulating layer 41, and the interlayer insulating layer 41 is formed.

  Next, a third metal wiring layer 37 is formed on the interlayer insulating layer 41 in the same manner as the second metal wiring layer 36 as shown in FIG. The metal wiring layer 37 is formed so as to be electrically connected to the first metal wiring layer 32 at the interlayer conductive portion 35.

  As described above, a multilayer wiring substrate is completed in which the first metal wiring layer 32 is electrically connected to the second metal wiring layer 36 and the third metal wiring layer 37 at a predetermined position. Furthermore, it is possible to form a multilayer wiring board having four or more layers by laminating metal wiring layers.

  The effects of the second embodiment are as follows.

  (1) In the method of manufacturing the multilayer wiring board according to the second embodiment, the interlayer conduction portions 33, 34, 35 that connect the metal wiring layers 32, 36, 37 are disposed on the first metal wiring layer 32. Since the conductive liquid material 30 is ejected from the 20 nozzles 25 in a columnar shape and stacked, for example, each time the interlayer insulating layers 40 and 41 are formed, the portion where the interlayer conductive portion is formed is masked or drilled. It is possible to reduce a manufacturing process in which the opening is made and the conductive material is disposed in the opening.

  (2) Since the interlayer conductive portions 33, 34, and 35 are formed by laminating the conductive liquid 30 from the nozzles 25 of the discharge head 20 in a columnar shape, the interlayer conductive portions 33, 34, and 35 are formed as interlayer conductive portions of the interlayer insulating layers 40 and 41. Interlayer conduction parts 33, 34, and 35 can be easily formed on the fine metal wiring layer 32 as compared with the case where it is formed by a method such as masking or drilling.

  (3) Since the conductive liquid 30 is adjusted in molecular weight and addition amount of the gelling agent so as to be gelled when landed on the substrate W, the interlayer conduction part as a three-dimensional structure having a stable shape 33, 34, 35 can be formed.

(Third embodiment)
This embodiment shows a manufacturing method of an electron emission part of a Spindt type FED (Field Emission Display).

  First, the Spindt type FED will be briefly described. FIG. 10 is a schematic cross-sectional view showing the structure of a typical Spindt type FED.

  As shown in FIG. 10A, the Spindt-type FED 50 is formed on the phosphor 52 and the glass substrate 51 having the anode 53 formed so as to cover the phosphor 52, the cathode 55, and the cathode 55. A glass substrate 54 having an emitter electrode 58 as an electron emitting portion and a gate electrode 57 is formed. The glass substrate 51 and the glass substrate 54 are disposed to face each other and are sealed in a vacuum state.

  FIG. 10B is an enlarged schematic cross-sectional view of a portion A in FIG. As shown in FIG. 4B, the emitter electrode 58 as an electron emission portion is formed of a minute conical metal or semiconductor. The gate electrode 57 is formed on the insulating layer 56 formed on the cathode electrode 55, and is formed so as to surround the tip of the emitter electrode 58 from which electrons are emitted.

The Spindt-type FED 50 operates by applying a gate voltage Vd between the cathode electrode 55 and the gate electrode 57 and applying an accelerating voltage Va between the gate electrode 57 and the anode electrode 53. Electrons (e ⁻ ) emitted into the vacuum by the tunnel phenomenon are accelerated toward the anode electrode 53. The electrons collide with the phosphor 52 to excite and emit light. By arranging the phosphor 52 as a pixel on the glass substrate 51, it functions as a self-luminous display.

  11A to 11D are schematic cross-sectional views illustrating a method for manufacturing an electron emission portion. First, as shown in FIG. 3A, a cathode electrode 55, an insulating layer 56, and a gate electrode 57 are sequentially formed on a glass substrate 54 by using a known material corresponding to each other by vacuum deposition or sputtering. .

  Next, as shown in FIG. 5B, the gate electrode 57 is etched at a position corresponding to the emitter electrode 58 to form an opening 57a. Thereby, the surface 56a of the insulating layer 56 is exposed to the opening 57a.

  Next, as shown in FIG. 5C, the insulating layer 56 is etched from the surface 56a while covering the portions other than the opening 57a of the gate electrode 57 with a resist. Thereby, the surface 55a of the cathode electrode 55 is exposed.

  Next, as shown in FIG. 4D, the liquid metal 60 is ejected from the nozzles 25 of the ejection head 20 in a columnar shape and landed on the surface 55a of the cathode electrode 55 to form the first layer 61. Subsequently, the metal liquid body 60 is repeatedly ejected in a columnar shape on the first layer 61 and laminated to form a three-dimensional shaped object 62 having a substantially conical tip. In this case, the metal liquid 60 is obtained by dispersing Mo (molybdenum) fine particles as a metal material in water as a main solvent and adding a gelling agent. By heating the glass substrate 54 to a predetermined temperature and firing the first layer 61 and the three-dimensional model 62 to impart conductivity, the emitter electrode 58 as an electron emission portion can be obtained.

  The effects of the third embodiment are as follows.

  (1) In the method of manufacturing the electron emission portion according to the third embodiment, the metal liquid 60 is ejected in a columnar shape from the nozzle 25 of the ejection head 20 and landed on the surface 55a of the cathode electrode 55 and stacked. In order to form the three-dimensional structure 62, the steps such as the vacuum deposition process and the etching process are omitted as compared with the method in which the emitter electrode 58 is formed by the oblique deposition method and then the sacrificial film formed on the gate electrode 57 is peeled off. An electron emission portion can be formed.

  Modifications other than the above embodiment are as follows.

  (Modification 1) The means for pressurizing the liquid 12 in the ejection head 20 is not limited to the piezo element 22. For example, one surface of the liquid chamber 21 that communicates with the nozzle 25 is used as a vibration plate portion, and a voltage is applied between the electrodes disposed opposite to the vibration plate portion to displace the vibration plate portion by electrostatic force, so that the liquid material 12 is formed. It is good also as an electrostatic system to pressurize. According to this, similarly to the piezoelectric element 22, the liquid 12 can be discharged from the nozzle 25 without heating.

  (Modification 2) The gelling agent made of a water-soluble polymer material is not limited to polydimethylacrylamide. For example, organic substances such as synthetic polymer polyacrylamide, carboxyvinyl polymer, and natural polymer such as agar, gelatin, carrageenan, pectin, and glucomannan are used. Then, the molecular weight and the added concentration may be determined so that the gel is formed before the columnar shape collapses after the liquid 12 has landed.

  (Modification 3) In the first embodiment, the liquid 12 may be gelated after a while after landing. If the surface 17 of the substrate W has been subjected to a liquid repellent treatment, the landed liquid body 12 can be made spherical and have a height, and the previous layer is gelled when the liquid body 12 to be laminated on the next layer is discharged. The next layer can be laminated immediately without drying.

  (Modification 4) In the first embodiment, the drive voltage waveform applied to the piezo element 22 of the ejection head 20 is not limited to a positive trapezoidal wave. For example, a combination of waveforms having different polarities may be used. According to this, the residual vibration of the piezoelectric element 22 can be suppressed by applying a negative voltage to the piezoelectric element 22 with respect to the positive voltage. According to this, when a voltage in the negative direction is applied, the piezo element 22 expands, so that the liquid material 12 ejected in a columnar shape can be forcibly drawn without causing excessive vibration and can be efficiently torn off.

  (Modification 5) In the first embodiment, the ejection head 20 and the substrate W are arranged to face each other at a predetermined interval. However, the ejection head 20 and the substrate W are inclined with respect to one of them in the stacking process. If arranged in this manner, the liquid material 12 can be ejected in a columnar shape from the nozzle 25 and landed on the first layer 13 so that the second layer 14 and subsequent layers are inclined and stacked.

  (Modification 6) In the first embodiment, the surface of the substrate W on which the liquid material 12 lands is subjected to liquid repellency. However, when the material used as the substrate W has liquid repellency, the liquid repellency treatment is performed. It does not have to be applied.

  (Modification 7) In the second embodiment, the functional material of the conductive liquid 30 is not limited to Ag. For example, metals such as Au, Al, Cu, Ni, and alloys thereof can be used.

  (Modification 8) In the second embodiment, the substrate W is not limited to a glass substrate. For example, a ceramic substrate, a resin substrate such as glass epoxy, or a heat resistant resin film such as polyimide may be used.

  (Modification 9) In the third embodiment, the functional material of the metal liquid 60 is not limited to Mo (molybdenum). For example, a refractory metal such as Si, Ti, or W can be used.

  (Modification 10) In addition to the gelling agent, another resin may be added in order to give the liquid 12 a viscosity for enabling columnar discharge.

  (Modification 11) It is not always necessary to add a gelling agent to the liquid 12. For example, if an anaerobic curable resin component is included as the composition of the liquid body 12, the liquid body 12 discharged from the nozzle 25 can be cured by touching air.

FIG. 2 is a schematic perspective view showing a liquid ejection device. Schematic which shows the discharge mechanism of the liquid body containing a discharge head. The graph which shows the waveform of the drive voltage given to the piezo element of an ejection head. The flowchart which shows the modeling method of a three-dimensional molded item. (A)-(c) Schematic which shows the state of a 1st layer formation process. (A)-(c) Schematic which shows the state of a lamination process. Schematic which shows the landing state by the surface treatment state of a board | substrate. Schematic which shows the state of a gelatinization process. (A)-(g) The schematic sectional drawing which shows the manufacturing method of a multilayer wiring board. 1 is a schematic cross-sectional view showing a structure of a typical Spindt type FED. (A)-(d) The schematic sectional drawing which shows the manufacturing method of an electron emission part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Liquid discharge apparatus, 12 ... Liquid body, 13 ... 1st layer, 14 ... 2nd layer, 17 ... Surface as a surface which a liquid body lands, 20 ... Discharge head, 25 ... Nozzle, 30 ... As liquid body Conductive liquid, 60 ... metal liquid as liquid, L0 to L3 ... interval as gap, W ... substrate.

Claims (13)

A modeling method for forming a three-dimensional object on the substrate by discharging a liquid material from a nozzle of an ejection head toward a substrate in a columnar shape,
The liquid material is prepared by mixing raw materials so as to solidify after being discharged from the nozzle,
A first layer forming step of forming the first layer by discharging the liquid from the nozzle of the discharge head in a columnar shape and landing on the substrate;
And a laminating step of repeatedly ejecting the liquid material from the nozzles of the ejection head in a columnar shape at a position corresponding to the first layer, and laminating the second and subsequent layers on the first layer. Modeling method.   The modeling method according to claim 1, wherein the liquid is a gel to which a gelling agent is added.   The molecular weight of the gelling agent and the concentration of the gelling agent with respect to the total amount of the liquid are adjusted so that the liquid is gelled when discharged from the nozzle of the discharge head and landed on the substrate. The modeling method according to claim 2, wherein:   The liquid material is obtained by dissolving or dispersing a functional material in a solvent whose main component is water, and the gelling agent to be added is made of a water-soluble polymer material. The modeling method according to 2 or 3.   The liquid is selected from Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Sb, Ga, and In. The modeling method according to any one of claims 1 to 4, wherein the molding method is a fine particle dispersion or solution composed of one or more kinds of metals, alloys, and metal oxides.   The modeling method according to claim 1, wherein the first layer forming step and the laminating step include a gelling step of gelling the liquid material that has landed on the substrate. .   The modeling method according to claim 6, wherein in the gelation step, the liquid material that has landed on the substrate is dried to be gelled.   The modeling method according to claim 7, wherein, in the gelling step, the liquid material that has landed on the substrate is dried and gelled by flowing a gas between the discharge head and the substrate. .   The modeling method according to claim 7, wherein in the gelation step, the liquid material that has landed on the substrate is dried to be gelled by heating the substrate.   The gelling step is characterized in that the liquid material landed on the substrate is dried and gelled by flowing a gas between the discharge head and the substrate and heating the substrate. Item 8. The modeling method according to Item 7.   In the stacking step, when the liquid material is landed on the first layer on the substrate to stack the second and subsequent layers, the gap between the ejection head and the substrate is gradually increased. The modeling method according to claim 1, wherein the liquid material is ejected in a columnar shape from the nozzle of the ejection head and landed.   12. The substrate according to any one of claims 1 to 11, wherein the substrate is subjected to a surface treatment so that the surface on which the liquid material lands has liquid repellency with respect to the liquid material. The modeling method described. 12. The substrate according to any one of claims 1 to 11, wherein the substrate is surface-treated so that the surface on which the liquid material lands is lyophilic with respect to the liquid material. The modeling method described.

Images