JP5527098B2 - Modeling method - Google Patents

Description

  The present invention relates to a modeling method.

  Conventionally, an additive manufacturing method is frequently used as a method (rapid prototyping) of a prototype quickly. In the additive manufacturing method, after a model of a three-dimensional CAD model is divided into a number of two-dimensional cross-sectional layers, a layered structure corresponding to each two-dimensional cross-sectional layer is sequentially formed and stacked to form a three-dimensional object. To do.

  Specifically, for example, as described in Patent Document 1, first, particles including ceramic, metal, or the like are formed in layers. Next, a binding liquid for binding the particles to each other in a part of the layer made of the particles is discharged to the layer made of the particles by, for example, an ink jet type droplet discharge device. Then, the binding liquid that has permeated into the gaps between the particles binds the particles together with hardening thereof, thereby forming a layered structure corresponding to the two-dimensional cross-sectional layer.

  Thereafter, similarly, the formation of a layer composed of these particles and the discharge of the binding liquid are alternately repeated to form a laminated body in which layers having a layered structure are laminated. Portions other than the layered structure in each layer of the laminated body function as a support portion that mechanically supports the laminated layers. Then, a modeling thing is modeled by removing the above-mentioned support part by pouring a water-based liquid through a layered product.

Japanese Patent No. 2729110

  On the other hand, as a method for removing the support portion, there are a method of applying a liquid to the laminate, a method of immersing the laminate in the liquid, and the like. However, in any method, when the support part is removed at a stretch, the mechanical load accompanying the removal of the support part acts intensively on a specific part of the modeled object, so that the modeled object is deformed. There was something to do.

  This invention is made | formed in view of the said actual condition, The objective is deform | transforming in the process of forming a modeling thing by laminating | stacking the layer containing a granule and removing a part of this layer. It is in providing the modeling method which suppressed that.

  The modeling method of the present invention is a modeling method for modeling a modeled object by binding hydrophobic particles with a binding liquid, and a plurality of layers including the particles are stacked on a part of each layer. Lamination which applies a binding liquid and forms a layered product of the layers partitioned into a binding part where the particles are bound together via the binding liquid and an unbound part other than the binding part A body forming step, and a removal step of removing the unbound portion from the laminate using a liquid. In the laminate forming step, the granules, the aqueous solvent, and the amphiphile dissolved in the aqueous solvent Forming each layer with a slurry containing an ionic polymer, and the amphiphilic polymer in an aqueous system so that the solubility in the liquid is lower than the other part at the end of the unbound portion on the bound portion side. An adjustment solution dissolved in a solvent is applied to the end portion.

  Here, the unbound portion functions as a support portion that mechanically supports the bound portion, and dissolves in the liquid by flowing the liquid through the laminate. The support portion has a lower solubility in the liquid as the amount of the amphiphilic polymer is larger in the slurry layer. Therefore, the portion where the adjustment liquid containing the amphiphilic polymer has permeated contains a lot of amphiphilic polymer as compared to the portion where the adjustment liquid does not penetrate, and the low solubility support portion has relatively low solubility in the liquid. Become.

  In the modeling method of the present invention, the unbound portion is constituted by the low-solubility support portion into which the adjustment liquid has penetrated and the high-solubility support portion into which the adjustment liquid does not penetrate and the liquid has a relatively high solubility. Is done. In the laminate, since the low solubility support portion is formed at the end of the unbound portion on the binding portion side, the binding portion is mechanically supported by the low solubility support portion. Become. If it is such a structure, in a removal process, the low solubility support part which is supporting the binding part will melt | dissolve after a high solubility support part melt | dissolves in a liquid. That is, the support part is removed in stages, and the low dissolution support part is removed in a later stage. Thereby, compared with the case where a support part is removed at a stretch, it can suppress that the load accompanying the removal of a support part acts on the specific site | part of a molded article intensively. Therefore, it is possible to suppress the deformation of the shaped product accompanying the removal of the unbound portion.

In the laminated body forming step of the modeling method, the adjustment liquid is applied to the unbound portion so that the binding portion is surrounded by the adjustment liquid in the layer.
According to this modeling method, the binding portion can be surrounded by the low solubility support portion in the same layer. If it is such a structure, the binding part which comprises a site | part with low mechanical strength like a fine structure, for example can be covered with a low solubility support part. As a result, it is possible to further suppress the deformation of the shaped product due to the removal of the unbound portion.

In the layered body forming step of the modeling method, the binding portion is formed on the portion where the adjustment liquid is applied between the layers.
Here, if the binding liquid applied in the upper layer penetrates to the lower layer, the shape accuracy and mechanical strength of the binding portion in the upper layer are lowered. According to this modeling method, the binding portion in the upper layer is formed so as to overlap the portion where the adjustment liquid is applied in the lower layer. With such a configuration, the binding liquid is less likely to penetrate into a portion containing a large amount of the amphiphilic polymer, so that the binding liquid applied in the upper layer can be prevented from penetrating into the lower layer. Thereby, the fall of the shape precision and mechanical strength of the binding part formed in an upper layer can be suppressed.

In the laminated body forming step of the modeling method, the adjustment liquid is applied to the unbound portion on the bound portion between the layers.
According to this modeling method, not only the fine structure part but also the modeled object itself can be covered with the low solubility support part. Thereby, the deformation | transformation of the molded article accompanying the removal of an unbound part can be suppressed reliably.

In this modeling method, the adjustment liquid is applied after the binding liquid is applied.
As described above, the portion having a larger amount of the amphiphilic polymer in the layer made of slurry is less likely to penetrate the binder solution. For this reason, if the adjustment liquid is applied earlier than the binding liquid, the adjustment liquid may penetrate into the portion that becomes the binding portion, which may reduce the shape accuracy of the binding portion. In this regard, according to this modeling method, the adjustment liquid is applied after the binding liquid has permeated into the portion to be the binding portion. If it is such a structure, it can suppress that the shape precision of a binding part falls by apply | coating adjustment liquid. In addition, since the adjustment liquid is less likely to penetrate into the portion into which the binding liquid has permeated, the penetration of the adjustment liquid can be suppressed at a position along the end of the portion into which the binding liquid has penetrated. Thereby, support of the binding part by a low solubility support part can be made more reliable.

In this modeling method, the amphiphilic polymer is polyvinyl alcohol.
As in this modeling method, polyvinyl alcohol can be used as the amphiphilic polymer having affinity with the hydrophobic particles and the aqueous solvent. Polyvinyl alcohol has a linear hydrocarbon as a main chain and a hydroxyl group which is a hydrophilic functional group as a side chain. Since polyvinyl alcohol contains approximately one hydroxyl group per unit structure, the polyvinyl alcohol maintains affinity with hydrophobic particles by the main chain and has affinity with an aqueous solvent. It will be expensive. Therefore, in the slurry containing polyvinyl alcohol as the amphiphilic polymer, the particles constituting this are more uniformly dispersed.

In this modeling method, the polymerization degree of polyvinyl alcohol contained in the solution is larger than the polymerization degree of polyvinyl alcohol contained in the slurry.
When the amphiphilic polymer is polyvinyl alcohol, the higher the degree of polymerization, which is the polymerization number of the unit structure, the lower the solubility of the structure containing this in an aqueous liquid. That is, when forming the low-solubility support part by applying the adjustment liquid, it can be realized by increasing the polymerization degree of the polyville alcohol contained in the adjustment liquid as in this modeling method.

  In this modeling method, the saponification degree of the polyvinyl alcohol contained in the solution and the slurry is 86 or more, and the saponification degree of the polyvinyl alcohol contained in the solution is higher than the saponification degree of the polyvinyl alcohol contained in the slurry. large.

  When the amphiphilic polymer is polyvinyl alcohol, the solubility in a liquid decreases as the saponification degree increases in the range of approximately 86 or more, which is generally referred to as a partially saponified type. From this, when forming the low-solubility support part by applying the adjustment liquid, as in this modeling method, the saponification degree of the polyvinyl alcohol contained in the slurry is determined as the saponification degree of the polyvinyl alcohol contained in the slurry. It can be realized by making it larger.

The flowchart which shows the procedure of the modeling method which concerns on one embodiment of this invention. (A) (b) The figure which shows typically each process of the modeling method along a procedure. (A) (b) (c) (d) The figure which shows typically each process of the modeling method along a procedure. (A) (b) (c) (d) The figure which shows typically each process of the modeling method along a procedure. The perspective view which shows the perspective structure of a molded article. (A) (b) The figure which shows typically the laminated body formed in a modification. The figure which shows typically the laminated body formed with the application | coating aspect of the PVA solution in a modification.

Hereinafter, an embodiment of a modeling method according to the present invention will be described with reference to FIGS.
First, the procedure of the modeling method in the present embodiment will be described. FIG. 1 is a flowchart showing a procedure of a modeling method according to an embodiment of the present invention. As shown in FIG. 1, in this modeling method, a sacrificial layer forming step (step S10) using a modeling slurry is first performed. Next, the layer formation process (step S21) using the slurry for modeling, the UV curable resin dropping process (step S22), the PVA solution dropping process (step S23), and the ultraviolet irradiation process (step S24) are repeatedly performed. A body formation process (step S20) is implemented. And the support material removal process (step S30) in which a 1st removal process (step S31) and a 2nd removal process (step S32) are implemented continuously is implemented.

  Next, the composition of the molding slurry used in the above-described modeling method will be described. The modeling slurry used in this embodiment is a suspension in which three materials, a hydrophobic particle, an aqueous solvent, and an amphiphilic polymer are kneaded.

  The hydrophobic particles are a main constituent material of a modeled object formed using a modeling slurry. As the hydrophobic particles, hydrophobic resin particles such as acrylic resin powder, silicone resin powder, acrylic silicone resin powder, polyethylene resin powder, and polyethylene acrylic acid copolymer resin powder can be used. In addition, the hydrophobic particle | grains in this Embodiment are the particle | grains which do not melt | dissolve 1g or more with respect to 100g of aqueous solvents.

  With respect to the aqueous solvent, the solubility of the hydrophobic particles constituting the modeled object is low as described above. Therefore, it is difficult for the hydrophobic particles to be modified due to dissolution in the solvent or absorption of the solvent. Therefore, it is preferable as a medium for suppressing scattering of hydrophobic particles. The aqueous solvent includes water and a non-organic solvent such as an aqueous solution of an inorganic salt. Of these, water is preferably used as the aqueous solvent. Further, the aqueous solvent may be one obtained by adding a water-soluble organic solvent to water.

  The amphiphilic polymer is a material that constitutes a shaped object together with the hydrophobic particles. Since this polymer is amphiphilic, it dissolves in the aqueous solvent due to the affinity with the aqueous solvent due to the hydrophilic portion, and the hydrophobic particles due to the affinity with the hydrophobic particle due to the hydrophobic portion. Expresses a dispersing action in a solvent. As the amphiphilic polymer, a material having a hydrocarbon chain as a main chain and a hydrophilic functional group as a side chain can be used.

  In the slurry in which the above three materials are kneaded, the hydrophobic particles are cross-linked with each other by the hydrophobic portion of the amphiphilic polymer. Therefore, even when vibrations are applied to the slurry during formation of the shaped object, the hydrophobic particles are retained in the structure formed by cross-linking between the particles, so that the scattering of the particles is suppressed. Will come to be.

  In addition, the hydrophobic particles are uniformly dispersed in the aqueous solvent through the hydrophilic portion of the amphiphilic polymer that interacts in the hydrophobic portion. Therefore, in the molded object formed using such a slurry, the hydrophobic particles as the forming material are present uniformly. In addition, since such an amphiphilic polymer itself is a forming material of a modeled object, an operation of removing the amphiphilic polymer during or after the formation is not required when the modeled object is formed. .

Below, the specific example of an amphiphilic polymer is described.
Preferable examples of the amphiphilic polymer include polyvinyl alcohol (PVA). The structure of polyvinyl alcohol is shown below.

ポリビニルアルコールは、主鎖として直鎖状の炭化水素を有するとともに、側鎖として親水性の官能基であるヒドロキシル基を有する。ポリビニルアルコールには、その単位構造当りにおよそ一つのヒドロキシル基が含まれることから、該ポリビニルアルコールは、疎水性の粒体との親和性を主鎖によって維持しつつ、水系溶媒との親和性が高いものとなる。なお、ポリビニルアルコールの単量体であるビニルアルコール（Ｈ_２Ｃ＝ＣＨＯＨ）はケト−エノール互変異性による平衡がケト体であるアセトアルデヒド（ＣＨ_３ＣＨＯ）側に大きく偏っていて不安定であることから、ポリビニルアルコールは一般に以下の手順で生成される。

Polyvinyl alcohol has a linear hydrocarbon as a main chain and a hydroxyl group which is a hydrophilic functional group as a side chain. Since polyvinyl alcohol contains approximately one hydroxyl group per unit structure, the polyvinyl alcohol maintains affinity with hydrophobic particles by the main chain and has affinity with an aqueous solvent. It will be expensive. In addition, vinyl alcohol (H ₂ C═CHOH), which is a monomer of polyvinyl alcohol, is unstable because the equilibrium due to keto-enol tautomerism is largely biased toward the keto acetaldehyde (CH ₃ CHO) side. Thus, polyvinyl alcohol is generally produced by the following procedure.

(A) First, polyvinyl acetate is produced by polymerizing acetic acid (CH ₃ COOH) and vinyl acetate having a structure esterified (CH ₃ COOCH═CH ₂ ).
(B) Hydrolyze (saponify) the ester bond of polyvinyl acetate to replace —C═OCH ₃ with —H.

Therefore, as shown in the chemical formula (1), polyvinyl alcohol has a part of —OC═OCH ₃ group in addition to a hydroxyl group (—OH) as a functional group in the side chain. Substances collectively referred to as polyvinyl alcohol include substances having different ratios of the number of hydroxyl groups to the degree of polymerization of polyvinyl acetate due to the difference in the degree of hydrolysis. The percentage of the ratio of the number of hydroxyl groups to the degree of polymerization is called the degree of saponification and is used as an indicator of the characteristics of polyvinyl alcohol.

Further, as an index indicating the characteristics of polyvinyl alcohol, the degree of polymerization, which is the number of polymerizations of the unit structure represented by the chemical formula (1), is also used.
These saponification degrees and polymerization degrees have the following tendencies.

(A) Since the hydrophilicity increases as the degree of saponification increases, the solubility in an aqueous solvent increases.
(A) However, in the range of saponification degree 86 or more, which is generally referred to as a partially saponified type, crystallization becomes easier as the saponification degree approaches 100%, so that the solubility in an aqueous solvent decreases.

(C) Since the hydrophobicity increases as the degree of saponification decreases, the solubility in aqueous solvents decreases.
(D) The greater the degree of polymerization, the greater the mechanical strength of the structure containing polyvinyl alcohol.

(E) The smaller the degree of polymerization, the greater the solubility in aqueous solvents, particularly cold water.
Next, the PVA solution as the adjustment liquid used in the above-described modeling method will be described.

The PVA solution is a solution in which polyvinyl alcohol (PVA) that is an amphiphilic polymer is dissolved in an aqueous solvent. As described above, the hydrophobic particles are connected to each other by the amphiphilic polymer in the slurry. Therefore, when such a PVA solution is partially contained in the slurry, the density of polyvinyl alcohol at that portion is increased, and the crosslinked structure between the hydrophobic particles becomes stronger. That is, the solubility with respect to an aqueous liquid falls in the part containing the PVA solution. And when this slurry is dissolved with an aqueous liquid, the part not containing the PVA solution is first dissolved, and then the part containing the PVA solution is dissolved. That is, the slurry can be removed stepwise by partially including the PVA solution in the slurry.

  In addition, what has the same physical property as what was used for the said slurry for modeling can be used for the polyvinyl alcohol dissolved in this PVA solution. However, in order to reduce the solubility of the slurry containing the PVA solution in an aqueous liquid, those having a higher saponification degree than the polyvinyl alcohol used in the slurry are preferable based on the above (a). Similarly, based on the above (e) (e), those having a degree of polymerization greater than the polyvinyl alcohol used in the slurry are preferred. By using such a PVA solution containing polyvinyl alcohol, the solubility of the slurry containing the PVA solution in an aqueous liquid can be efficiently reduced.

Next, the modeling method using the slurry having the above composition will be described in more detail with reference to FIGS. 2, 3, and 4 schematically show processing performed in each of the above steps.
As shown in FIG. 1, in this modeling method, first, in the sacrificial layer forming step (step S10: FIG. 2 (a)), for example, on a substrate 1 (base) such as a glass substrate or a plastic sheet, The sacrificial layer 2 is formed as the lowermost layer of the slurry layer by applying the slurry so that the thickness is 200 μm. For applying the slurry, a known method such as a squeegee method, a screen printing method, a doctor blade method, and a spin coating method can form a slurry layer having a substantially uniform thickness on the substrate 1. Can be used.

  Subsequently, a laminated body formation process (step S20) is implemented. This laminated body formation process (step S20) is a slurry layer shaping | molding process (step S21), an ultraviolet curable resin dripping process (step S22), a PVA solution dripping process (step S23), and an ultraviolet irradiation process, as shown in FIG. (Step S24) is a process in which the stacked body 60 (see FIG. 4C) is formed in the sacrificial layer 2 by being repeatedly performed in order. In the present embodiment, a case where the model 70 shown in FIG. 5 is modeled will be described. The modeled object 70 is obtained by sequentially stacking five modeled parts 12, 22, 32, 42, and 52 described later. In the modeled part 32, the modeled part 22 in the lower layer and the modeled part 42 in the upper layer are formed. In contrast, a projecting portion 32a projecting in a direction perpendicular to the stacking direction is provided.

  First, in the slurry layer forming step (step S21: FIG. 2B), the slurry is applied to form a first slurry layer 11 so as to have a thickness of 100 μm. In addition, when forming the slurry layer 11, the above-described known method can be used as in the formation of the sacrificial layer 2.

Then, in the ultraviolet curable resin dropping step (step S22: FIG. 3A), a droplet discharge device is formed on the modeling portion 12 for forming a part of the modeling object 70 (see FIG. 5) in the slurry layer 11. 3 and the UV ink I containing an ultraviolet curable resin as a binding liquid is ejected by an ink jet method. Here, in the slurry layer 11, the hydrophobic particles are crosslinked with the polyvinyl alcohol so that the hydrophobic particles are arranged with a predetermined space between each other, and the space Inside is filled with water. Therefore, the UV ink I ejected from above the slurry layer 11 toward the surface of the slurry layer 11 reaches the back surface of the slurry layer 11 through the above-described space. That is, UV is applied to the entire modeling unit 12.
Since the ink I penetrates, the strength of the modeling portion 12 is improved.

  Thus, the modeling part 12 to which the UV ink I is dropped becomes a binding part that is cured by irradiation with ultraviolet rays L (see FIG. 3C) and constitutes a part of the modeled object 70. On the other hand, the unbound portion that is a region other than the modeling portion 12 in the slurry layer 11 is the modeling portion 12 formed in the slurry layer 11 or the second slurry layer 21 that is the next layer of the slurry layer 11. It functions as a support part that mechanically supports the modeling part 22 and the like formed on the like. Thereby, even if it is a case where the molded article 70 which has the overhang | projection part 32a as shown in FIG. 5 is formed, it is not necessary to form the support part which supports the overhang | projection part 32a separately. In addition, since the modeled object 70 is formed in a state where the slurry layer exists immediately below the projecting part 32 a, it is possible to suppress the projecting part 32 a from being lost during the formation of the modeled object 70.

  The UV ink I includes a cationic polymerization type ultraviolet curable resin that cures by a polymerization reaction using a cation as an active species, and a radical polymerization type ultraviolet curable resin that cures by a polymerization reaction using a radical as an active species. There is a thing. In the present embodiment, any of these UV inks I can be used. However, the UV ink I is dropped onto the modeling part 12 of the slurry layer 11 and then cured together with the hydrophobic particles contained in the modeling part 12. Therefore, it is preferable to select compatible materials for the UV ink I, particularly the ultraviolet curable resin and the hydrophobic particles. That is, it is preferable to use the same material for the UV ink I and the hydrophobic particles, for example, the acrylic UV ink I and the acrylic resin powder. Alternatively, it is preferable to use UV ink I and hydrophobic particles having a material similar to UV ink I introduced on the surface, for example, acrylic UV ink I and acrylic silicone resin powder. That is, here, the same system means that the main skeleton of the repeating unit structure constituting the hydrophobic particles and the main skeleton of the unit structure of the resin contained in the UV ink I are the same. In addition, the same system is different in the side chain functional group in the unit structure and part of the main skeleton in the unit structure, but the interaction between the hydrophobic liquid and the resin is substantially the same as the interaction between the hydrophobic particles. This means that the main skeletons of the unit structure partially overlap each other. Therefore, when each of the hydrophobic particles and the resin is a copolymer, those in which the composition ratios of the atoms contained in these particles are not the same are assumed to be the same system.

  Subsequently, in the PVA solution dropping step (step S23: FIG. 3B), the PVA solution F is applied to the slurry layer 11 from the droplet discharge device 3 so as to surround the modeling portion 12 in the slurry layer 11. To discharge. The discharge of the PVA solution F by the droplet discharge device 3 is performed based on discharge data that defines information related to the discharge of the PVA solution F in the slurry layer 11. The discharge data is data that is generated in advance based on the cross-sectional data of the model 70, for example, and is data that defines the discharge position of the PVA solution F, the number of discharges at that position, and the like. Like the UV ink I, the PVA solution discharged from above the slurry layer 11 onto the surface of the slurry layer 11 penetrates the slurry layer 11 through the space formed by the hydrophobic particles, and eventually enters the back surface and the modeling portion 12. Reach the continuous position. And the site | part which the PVA solution F osmose | permeated becomes stronger than the site | part which the PVA solution F did not osmose | permeate, the cross-linking structure of a particle | grain is strengthened, and the solubility with respect to an aqueous liquid is improved. Lower. That is, parts other than the modeling part 12 in the slurry layer 11 are constituted by the low solubility support part 13 into which the PVA solution F has penetrated and the high solubility support part 14 into which the PVA solution F has not penetrated. That is, when removing the support part, the low-solubility support part 13 supporting the shaped article 70 is removed after the high-solubility support part 14 is removed. By removing the support part in stages as described above, the mechanical load accompanying the removal of the support part is concentrated on a specific part of the molded article 70 as compared with the case where the support part is removed at once. It can suppress acting. Therefore, it is possible to suppress deformation of the modeled object 70 due to the removal of the support part.

  In addition, it is also possible to implement a PVA solution dripping process (step S23) before an ultraviolet curable resin dripping process (step S22). However, since the UV ink I is less likely to penetrate into the portion of the slurry layer 11 where the PVA solution F has permeated, if the PVA solution F penetrates into the portion that becomes the modeling portion 12, it will be part of the modeling portion 12. However, the UV ink I does not penetrate, and the shape accuracy of the modeling part 12 may be reduced. In this regard, as in the present embodiment, the UV ink I is infiltrated into the modeling portion 12 and then the PVA solution F is discharged to the slurry layer 11, thereby reducing the shape accuracy of the modeling portion 12 and consequently the modeling object 70. Can be suppressed. On the other hand, since the PVA solution F is less likely to penetrate into the modeling portion 12 into which the UV ink I has penetrated, the penetration of the PVA solution F at the position along the end of the modeling portion 12 is suppressed. Thereby, the modeling part 12 can be reliably supported by the low solubility support part 13. Then, by discharging the PVA solution F so as to surround the modeling part 12, it is possible to cover the periphery of the modeling part 12 in the slurry layer 11 with the low solubility support part 13.

  The PVA solution F is obtained by dissolving PVA in an aqueous solvent. Therefore, in the part where the PVA solution F is discharged, a part of the slurry layer 11 is dissolved in the aqueous solvent contained in the PVA solution F. If this is excessively dissolved, the surface of the slurry layer 11 is dissolved. Concavities and convexities may be formed on the surface. Since the support parts 13 and 14 are more easily dissolved in the liquid as the temperature of the aqueous liquid to be dissolved becomes higher, the support parts 13 and 14 are discharged in order to suppress excessive dissolution of the slurry layer 11 due to the discharge of the PVA solution F described above. In the PVA solution F, it is preferable to generate the molding slurry and the PVA solution F so that the slurry layer 11 is hardly dissolved in the aqueous solvent of the PVA solution F.

  Then, the modeling part 12 is hardened | cured by irradiating the ultraviolet-ray L to the said slurry layer 11 whole at an ultraviolet irradiation process (step S24: FIG.3 (c)). Note that the ultraviolet light L does not have to be applied to the entire slurry layer 11, and at least the modeling part 12 in the slurry layer 11 may be applied. Further, the irradiation with the ultraviolet light L can be performed alternately with the dropping of the UV ink I onto the modeling unit 12 by, for example, the ultraviolet irradiation device mounted on the droplet discharging device 3. 3 can be carried out for each slurry layer by an ultraviolet irradiation device provided separately from 3.

  The four steps from the slurry layer forming step (step S21) to the ultraviolet irradiation step (step S24) described above are repeated until all of the modeling parts 12, 22, 32, 42, and 52 constituting the modeled object 70 are formed. To be implemented. Thus, since the laminated body 60 (refer FIG.4 (c)) comprised from a some layer can be formed by repeating 4 processes from a layer formation process to an ultraviolet irradiation process in order, the said modeling method The degree of freedom related to the shape of the shaped object 70 formed by the above becomes higher.

  Here, the modeled object 70 has an overhang part 32a in the modeled part 32 of the third layer. Therefore, in the PVA solution dropping step (step S23) related to the second slurry layer 21, as shown in FIG. 3D, in addition to the periphery of the modeling portion 22, the portion overlapping the overhanging portion 32a. The PVA solution F is discharged over the entire area. In other words, the overhanging portion 32a is formed so as to overlap the low solubility support portion 23 to which the PVA solution F is applied.

With such a configuration, since the UV ink I hardly permeates into the portion into which the PVA solution F has permeated, as shown in FIG. 4A, the entire slurry layer 31 is formed to form the overhanging portion 32a. Even if the UV ink I is ejected, the penetration of the UV ink I into the slurry layer 21 can be suppressed. Thereby, it can suppress that the shape accuracy of the overhang | projection part 32a falls by penetration | infiltration to the slurry layer 21 of UV ink I. FIG. Further, when the UV ink I penetrates into the slurry layer 21, the density of the UV ink I in the slurry layer 31 is lowered, so that the mechanical strength of the overhanging portion 32a is lowered.
However, with the configuration described above, since the penetration of the UV ink I into the slurry layer 21 is suppressed, it is possible to suppress a decrease in the mechanical strength of the overhanging portion 32a.

  Also in the PVA solution dropping step (step S23) related to the fourth slurry layer 41, as shown in FIG. 4B, the PVA solution F is discharged to a portion overlapping the projecting portion 32a of the slurry layer 31. The With such a configuration, the overhanging portion 32 a is sandwiched between the low solubility support portion 23 in the slurry layer 21 and the low solubility support portion 43 in the slurry layer 41. That is, in the stacking direction, the overhanging portion 32a can be covered with the low solubility support portion.

  And as shown in FIG.4 (c), in order to form the modeling part 52 of the 5th layer, from the said slurry layer formation process (step S21) to the said ultraviolet irradiation process (step S24) is implemented again. Thus, the stacked body 60 is formed on the sacrificial layer 2.

  When the stacked body 60 is thus formed on the sacrificial layer 2, a support portion removing step (step S30) is then performed. The support part removing step (step S30) of the present embodiment uses water as the aqueous liquid, and the first removing step (step S31) mainly for dissolving the high solubility support parts 14 and 54, and the low solubility support. And a second removal step (step S32) for dissolving the parts 13, 23, 43, 53.

  In the first removal step (step S31), the laminated body 60 is immersed in a first liquid which is water having a temperature at which the low solubility support portions 13, 23, 43, 53 are difficult to dissolve, and the first liquid is laminated. This is performed by spraying the body 60 with a predetermined pressure. As a result, as shown in FIG. 4D, the sacrificial layer 2 is dissolved and the substrate 1 is detached, and the high-solubility support portions 14 and 54 are dissolved, and the low-solubility support portions 13, 23, and 43 are dissolved. , 53 to form a laminate 61 in a state in which the low-solubility support portion 63 is attached to the model 70.

  In the subsequent second removal step (step S32), the laminate 61 is immersed in a second liquid that is water having a temperature higher than that of the first liquid and in which the low-solubility support part 63 is easy to dissolve, the second liquid For example, by spraying the laminated body 61 with a predetermined pressure. Thereby, as FIG. 5 shows, the low solubility support part 63 melt | dissolves and the molded article 70 appears.

  Here, it is also possible to dissolve the low-solubility support part 63 using the first liquid. However, it takes a long time to dissolve the low-solubility support part 63, and the productivity of the shaped article 70 is greatly reduced. On the other hand, in the second removal step of the present embodiment, the low solubility support portion 63 is dissolved using the second liquid that is water having a temperature higher than that of the first liquid. With such a configuration, the dissolution time of the low solubility support part 63 can be shortened while removing the support part in stages.

  Thus, by comprising a support part by the high solubility support parts 14 and 54 and the low solubility support part 63, the 1st removal process (step S31) and the 2nd removal process (step S32) from which conditions differ mutually. Thus, the support part removing step (step S30) can be configured.

  For example, in the first removal step (step S31), the molded article 70 is continuously supported by the low solubility support portion 63, so that the molded article 70 is removed along with the removal of the high solubility support portions 14 and 54. The mechanical load is distributed to the low solubility support part 63. For this reason, even if the first removal step is performed under a condition in which the mechanical load on the modeled object 70 is large, such as increasing the pressure of the aqueous liquid sprayed on the laminate 61, the deformation of the modeled object 70 is suppressed. Can do.

  Further, for example, in the second removal step (step S32), an aqueous liquid having a condition in which the low-solubility support part 63 is more difficult to dissolve than the first liquid is used, and it takes less time than the first liquid to dissolve less. It is also possible to remove the sex support part 63. With such a configuration, it is possible to reliably suppress the deformation of the shaped article 70 accompanying the removal of the support portion, particularly the deformation in the fine structure portion.

  If the polymerization degree of polyvinyl alcohol, which is a constituent material of the molding slurry, is 300 or more and 1000 or less and the saponification degree is 85 or more and 90 or less, the solubility of the high solubility support parts 14 and 54 in the aqueous liquid is reduced. Can be suppressed. Therefore, in the molding slurry composed of polyvinyl alcohol having the above-described polymerization degree and saponification degree, only the highly soluble support parts 14 and 54 are easily removed from the laminate 60 in the support part removing step (step S30). It is preferable in that it can be removed.

In addition, the water used in the support portion removing step includes hydrophobic particles that constitute each support portion. As described above, since the hydrophobic particles constituting the support portion are difficult to dissolve in water, the hydrophobic particles can be extracted by filtering the water. That is, you may make it perform the extraction process of a hydrophobic particle following the said support part removal process. The hydrophobic particles extracted in this way can be reused as a constituent material of the slurry.
-Slurry for modeling (A) Hydrophobic granules Charine R-170S (particle size 30 μm) (manufactured by Nissin Chemical Industry Co., Ltd.) (Charine: registered trademark)
(B) Aqueous solvent Water (C) Amphiphilic polymer Poval JP-03 (manufactured by Nippon Vinegar Poval Co., Ltd., polymerization degree 300, saponification degree 86.0-90.0 (88))
Composition ratio (A) :( B) :( C) = 7: 3.1: 0.22 (unit: g)
・ Thickness of each slurry layer 100μm
UV ink Acrylic UV ink PVA solution (D) Aqueous solvent Water (E) Amphiphilic polymer Poval JT-05 (Nippon Vinegar-Poval Co., Ltd., polymerization degree 500, saponification degree 93.5 to 95) .5 (94.5))
Composition ratio (D) :( E) = 3.1: 0.22 (unit: g)
As described above, according to the modeling method according to the present embodiment, the effects listed below can be obtained.

  (1) The laminated body forming step (step S20) includes a PVA solution dropping step (step S23) in which the PVA solution F is discharged to the slurry layer and penetrated so that the discharged PVA solution F is continuous with the modeling portion. It was. With such a configuration, the support portion is composed of the high solubility support portions 14 and 54 having a relatively high solubility in the aqueous liquid and the low solubility support portions 13, 23, 43, and 53 having a relatively low solubility. According to such a configuration, since the support portion is removed step by step, the mechanical load accompanying the removal of the support portion is applied to a specific part of the shaped article 70 as compared with the case where the support portion is removed at a stretch. It can suppress acting intensively. Therefore, it is possible to suppress deformation of the modeled object 70 in the support part removing step (step S30).

(2) In the PVA solution dropping step (step S23), the PVA solution F was discharged so as to surround the shaped portion of each slurry layer. With such a configuration, it is possible to surround the modeling part with the low solubility support part. Therefore, it becomes possible to cover the modeling part which comprises a site | part with low mechanical strength like a fine structure with a low solubility support part in the direction orthogonal to the lamination direction. As a result, it is possible to further suppress deformation of the modeled object 70 in the support part removing step (step S30).

  (3) In the PVA solution dropping step (step S23) in the slurry layer 21, the PVA solution F was also discharged to a portion overlapping the overhanging portion 32a of the modeling portion 32 of the slurry layer 31 that is the next layer. With such a configuration, it is possible to suppress the UV ink I discharged to the slurry layer 31 from penetrating into the slurry layer 21. Thereby, the fall of the shape precision regarding the overhang | projection part 32a and mechanical strength can be suppressed.

  (4) In the PVA solution dropping step (step S23) in the slurry layer 41, the PVA solution F was also discharged to a portion overlapping with the overhanging portion 32a of the modeling portion 32 of the slurry layer 31 as the previous layer. Thereby, the overhang | projection part 32a can be covered with the low solubility support parts 23 and 43 in the lamination direction. As a result, in the support part removing step (step S30), the deformation of the projecting part 32a can be reliably suppressed.

  (5) The PVA solution dropping step (step S23) was performed after the ultraviolet curable resin dropping step (step S22). With such a configuration, the PVA solution F is discharged after the UV ink I has permeated the modeling portion. Thereby, it can suppress that the shape accuracy of a modeling part and by extension, the shape accuracy of the molded article 70 fall.

(6) Moreover, since the penetration of the PVA solution F is suppressed at a position along the end of the modeling part, the support of the modeling part by the low-solubility support part becomes more reliable.
(7) The support part was comprised by the high solubility support part 14 and 54 with relatively high solubility with respect to an aqueous liquid, and the low solubility support part 13, 23, 43, and 53 with comparatively low solubility. According to such a configuration, the first removal step (step S31) for removing the high solubility support portions 14, 54 and the second removal step (step S31) for removing the low solubility support portions 13, 23, 43, 53 (step S31). Step S32) can be carried out under different conditions. Since the degree of freedom related to the removal method of the support part is increased in this way, it is possible to flexibly meet the demands related to the shaped object, such as the shape and productivity of the shaped object, while suppressing the deformation of the shaped object due to the removal of the support part. It is also possible to correspond to.

  (8) A slurry was formed from water as an aqueous solvent, resin particles as hydrophobic particles, and polyvinyl alcohol as an amphiphilic polymer. Thereby, the resin granule which forms the molded article 70 is mixed with water and polyvinyl alcohol, and exists in the slurry which is a suspension. Moreover, in the said slurry, since the hydrocarbon chain | strand in polyvinyl alcohol has affinity with a resin particle, it exists in the state with which the particle | grains were connected via polyvinyl alcohol. That is, the resin particles are not in an independent state, but are in a state of being cross-linked with each other through the intervention of polyvinyl alcohol. Therefore, even when vibration or the like is given to the slurry during formation of the shaped object 70, the resin particles are held in the structure formed by the cross-linking between the particles, so that the scattering of the particles is suppressed. Become so.

  (9) The PVA solution F was applied using an inkjet method. In the ink jet method, the discharge position and the discharge amount can be changed in units of droplets. Therefore, regarding the application of the PVA solution F, the position and amount of application can be changed in units of droplets. Therefore, the freedom degree regarding the formation position and mechanical strength of a low solubility support part can be improved.

It should be noted that the above embodiment can be implemented with appropriate modifications as follows.
-The amphiphilic polymer is not limited to polyvinyl alcohol, and may be any amphiphilic polymer that intervenes between the hydrophobic particles and connects them, and can uniformly disperse the hydrophobic particles in the aqueous solvent. .

  ・ Amphiphilic polymers are not limited to those having a hydrocarbon chain as a main chain and a hydrophilic functional group as a side chain, and have a hydrophobic part and a hydrophilic part, and are hydrophobic. As long as it is intervened between the hydrophobic particles by the part, and can be dispersed in the aqueous solvent by the hydrophilic part.

  A PVA solution dropping step (Step S23) was provided between the ultraviolet curable resin dropping step (Step S22) and the ultraviolet irradiation step (Step S24). Not only this but a PVA solution dropping process may be provided before an ultraviolet curable resin dropping process as mentioned above, and a PVA solution dropping process may be provided after an ultraviolet irradiation process.

  In the slurry layers 21 and 41, the PVA solution F was also applied to a portion of the slurry layer 31 that overlaps the overhang portion 32 a in the modeling portion 32. Not only this but in the slurry layers 21 and 41, you may make it apply | coat the PVA solution F only so that the modeling parts 22 and 42 may be enclosed.

  In the above embodiment, the laminate 60 is formed so that a part of the outer shape of the shaped object 70 is exposed. By changing this, a laminate may be formed as shown in FIG. 6A and 6B are diagrams schematically illustrating a laminate formed in the modification, in which FIG. 6A is a front view and a rear view of the laminate 80, and FIG. 6B is a side view of the laminate 80. FIG. . That is, as shown in FIG. 6, the laminate 80 may be formed so that the modeled product 70 is completely covered by the low solubility support portion 83. According to such a configuration, in the support part removing step (step S30), it is possible to surely suppress the deformation of the modeling part and consequently the modeled object. In addition, such an aspect is very effective with respect to the molded article which has a fine structure.

  -The low solubility support part was formed so that the circumference | surroundings of the modeling part might be enclosed in each slurry layer. By changing this, a low-solubility support part may be formed as shown in FIG. FIG. 7 is a diagram schematically showing a laminate formed by a PVA solution application mode in a modified example. The low-solubility support portion only needs to be formed at the end of the unbound portion on the binding portion side. For example, the low-solubility support portion has overhang portions 85 and 86 that face each other like a laminate 84 shown in FIG. You may apply | coat PVA solution F with respect to the molded article 87 so that the low solubility support part 88 may be formed like the pillar pinched | interposed into this overhang | projection part 85,86.

  -In a laminated body formation process (step S20), the process introduced suitably according to the shape etc. of a molded article may be sufficient as a PVA solution dripping process (step S23), for example. That is, in the laminated body forming step (step S20), for example, a configuration introduced in a laminating process related to a portion having a low mechanical strength such as a fine structure or an overhang portion may be used.

The hydrophobic particles are not limited to particles made of resin, but may be other hydrophobic particles, for example, particles of silicone oxide having hydrophobicity on the surface.
-As the hydrophobic particles, those having a hydrophilic group on the surface thereof may be used.

The aqueous slurry of the modeling slurry and the PVA solution F is not limited to water, and may be other non-organic aqueous solvents such as an aqueous solution of an inorganic salt.
The water-based solvent of the modeling slurry and the PVA solution F may be a water-soluble organic solvent added to water.

-The aqueous slurry of the slurry for modeling and the PVA solution F is not limited to a non-organic solvent, and if the shape of the model 70 can be controlled, alcohols such as ethanol and n-propanol, polyvalents such as diethylene glycol and glycerin You may make it use the solvent which has organic solvents, such as alcohols and a pyrrolidone-type solvent, as a main component. In this case, it is preferable to use a fluid having low solubility in an organic solvent such as the above-mentioned silicone oxide as the hydrophobic fluid constituting the modeled object 70.

  In the above embodiment, the unbound region is configured by the high solubility support portion and the low solubility support portion. That is, the unbound region is removed in two steps. In addition to this, in removing the unbound region stepwise, for example, by using two or more adjustment liquids having different amphiphilic polymers dissolved in the adjustment liquid, the unbound region has three or more stages. It may be a configuration that is removed by.

  UV ink I and PVA solution F were applied to the slurry layers 11, 21, 31, 41, 51 by an ink jet method using the droplet discharge device 3. Not limited to this, for example, the UV ink I and the PVA are applied to the slurry layers 11, 21, 31, 41, 51 using other methods such as a method using a mask in which the application position of the UV ink I or the PVA solution F is defined. Solution F may be applied.

  F ... PVA solution, I ... UV ink, L ... UV, 1 ... substrate, 2 ... sacrificial layer, 3 ... droplet ejection device, 11,21,31,41,51 ... slurry layer, 12,22,32,42 , 52 ... modeling part, 13, 23, 43, 53, 63 ... low solubility support part, 14, 54 ... high solubility support part, 32a ... overhang part, 60, 61 ... laminate, 70 ... modeled object, 80 DESCRIPTION OF SYMBOLS ... Laminated body, 83 ... Low solubility support part, 84 ... Laminate body, 85, 86 ... Overhang | projection part, 87 ... Modeling thing, 88 ... Low solubility support part.

Claims (8)

A modeling method for modeling a molded article by binding hydrophobic particles with a binding liquid,
The binding liquid is applied to a part of each layer while stacking a plurality of layers including the particles, and the particles are bonded to each other via the binding liquid and the remaining portions other than the binding parts. A laminate forming step of forming a laminate of the layers partitioned into a binding portion;
Removing the unbound portion from the laminate using a liquid,
In the laminate forming step,
Forming each layer with a slurry containing the granules, an aqueous solvent and an amphiphilic polymer dissolved in the aqueous solvent;
An adjustment liquid in which an amphiphilic polymer is dissolved in an aqueous solvent is used as the end portion so that the solubility in the liquid at the end of the unbound portion on the binding portion side is lower than other portions. A modeling method characterized by applying. In the laminate forming step,
The modeling method according to claim 1, wherein the adjustment liquid is applied to the unbound portion so that the binding portion is surrounded by the adjustment liquid in the layer. The laminate forming step includes
The modeling method according to claim 1, wherein the binding portion is formed on a portion where the adjustment liquid is applied between the layers. In the laminate forming step,
The modeling method according to any one of claims 1 to 3, wherein the adjustment liquid is applied to the unbound portion on the bound portion in the interlayer. The modeling method according to claim 1, wherein the adjustment liquid is applied after the binding liquid is applied. The modeling method according to any one of claims 1 to 5, wherein the amphiphilic polymer is polyvinyl alcohol. The modeling method according to claim 6, wherein a polymerization degree of polyvinyl alcohol contained in the adjustment liquid is larger than a polymerization degree of polyvinyl alcohol contained in the slurry. The saponification degree of polyvinyl alcohol contained in the adjustment liquid and the slurry is 86 or more, and the saponification degree of polyvinyl alcohol contained in the adjustment liquid is larger than the saponification degree of polyvinyl alcohol contained in the slurry. The modeling method according to 6 or 7.

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