JP2019064068A - Three-dimensional shaping apparatus and method for producing three-dimensional shaped object - Google Patents

Abstract

To provide a three-dimensional shaping apparatus that is capable of shaping a three-dimensional shaped object excellent in uniformity and curing characteristics by uniformly mixing a plurality of compositions under simple control.SOLUTION: In a three-dimensional shaping apparatus of the present invention, a plurality of compositions that react by mixing them are used. The three-dimensional shaping apparatus comprises: a plate-like support base that supports a three-dimensional shaped object; a plurality of nozzles that inject droplets of the plurality of compositions respectively; a drive part that relatively displaces the support base and the plurality of nozzles; and a control part that controls droplet-adhering positions so that the droplets of the plurality of compositions are mixed on the support base. Droplet-injecting directions of the plurality of nozzles are in parallel. The droplet-injecting directions of the plurality of nozzles are preferably perpendicular to the surface of the support base.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a three-dimensional modeling apparatus and a method of manufacturing a three-dimensional model.

  In recent years, a three-dimensional modeling apparatus, a so-called 3D printer, has been used in the manufacture of one-item products such as the manufacture of tailor-made products in accordance with the requirements of each customer and the manufacture of trial parts required for designing assembly products. In a 3D printer, for example, a liquid composition is ejected as droplets by a dispenser, laminated on a support base, and repeatedly cured by, for example, applying ultraviolet light to obtain a three-dimensional structure.

  In modeling using such ultraviolet curing, high energy is required to irradiate ultraviolet light. Moreover, in modeling using ultraviolet curing, since the dye which absorbs an ultraviolet-ray and the dye which decomposes | disassembles with an ultraviolet-ray can not be used, coloring of a three-dimensional model is easy to be restrict | limited.

  As modeling without using ultraviolet curing, a method of curing by combining and reacting two types of compositions has been proposed (see JP-A-2003-506228). In this shaping method, the droplets of the first liquid composition containing polyisocyanate and the droplets of the second liquid composition containing polyol are simultaneously ejected so that the angle formed by the ejection direction is 15 ° to 75 °. And collide and mix two kinds of droplets in the air.

  In the modeling in which the two conventional compositions are combined, it is necessary to adjust the conditions for droplet ejection in consideration of the viscosity of the composition and the like so that the droplets of the two compositions collide. For example, in order to cause the above two types of droplets to collide in the air and to deposit the droplets after the collision at a desired position, the ejection angle etc. is made independent for each droplet in consideration of kinetic energy of the droplets and the like. Need to be controlled. In addition, it is necessary to control the collision position in consideration of the fact that the surface of the three-dimensional structure becomes higher as the formation progresses. Thus, in order to mix two types of droplets, the modeling apparatus which performs the above-mentioned conventional modeling needs complicated control for every droplet.

Japanese Patent Publication No. 2003-506228

  The present invention has been made based on the above circumstances, and by mixing a plurality of compositions uniformly by simple control, a three-dimensional object excellent in homogeneity and curing characteristics is formed. An object of the present invention is to provide a three-dimensional modeling apparatus and a method of manufacturing a three-dimensional model.

  The present inventors noticed that the viscosity of the composition used for producing the three-dimensional structure was relatively high, and learned that two compositions can be shaped without simultaneously injecting them. Based on this finding, the present inventors parallelize the droplet ejection directions of the nozzles that eject two types of compositions, and control the droplet deposition positions so that they are mixed on the support table. The inventors have found that the ejection control of the droplets can be dramatically facilitated by ejecting the droplets in order, thus completing the present invention. The present inventors have also found that the same method can be applied to the case where three or more compositions are used.

  That is, the invention made in order to solve the above-mentioned subject is a three-dimensional modeling device using two or more kinds of compositions which react by mixing, and the plate-shaped support stand which supports three-dimensional modeling thing modeled. A plurality of nozzles that respectively eject droplets of the plurality of types of composition, a driving unit that relatively moves the support and the plurality of nozzles, and droplets of the plurality of types of compositions are mixed on the support. Control unit that controls the droplet deposition position so that the droplet ejection directions of the plurality of nozzles are parallel.

  In the three-dimensional structure forming apparatus, a plurality of nozzles can eject droplets of a plurality of compositions in parallel. For this reason, in the three-dimensional modeling apparatus, the positions of the plurality of nozzles in the horizontal plane (plane parallel to the support) are made to coincide, and the droplets are ejected at the same initial velocity to place the respective droplets in the same position. It can be made to drop. That is, since the said three-dimensional modeling apparatus can be made to mix several types of compositions by controlling the horizontal position of a nozzle, and the initial velocity of a droplet, control is easy.

  The droplet ejection directions of the plurality of nozzles may be perpendicular to the surface of the support. As described above, by making the droplet ejection directions of the plurality of nozzles perpendicular to the surface of the support, it is possible to mix a plurality of types of compositions regardless of the initial velocity of the droplets. In addition, since the droplets are ejected from directly above the deposition position, it is not necessary to change the nozzle position even if the surface of the three-dimensional object becomes higher as the formation progresses. Therefore, control of the control unit is further facilitated.

  The driving unit scans the droplet deposition position in the X direction in the XY directions orthogonal to each other in plan view, relatively moves the support and the plurality of nozzles so as to shift in the Y direction, and the plurality of nozzle arrangement directions It is good to be in the X direction. By arranging the nozzles in the scanning direction in this manner, the other nozzles sequentially pass the relative position at which the nozzles first ejected droplets at the time of scanning in the X direction. Therefore, a plurality of compositions can be efficiently mixed by ejecting a droplet each time the relative position is passed.

  A plurality of sets of the plurality of nozzles may be provided, and the plurality of sets of nozzles may be disposed in parallel to the support and in the Y direction. As described above, by providing a plurality of sets of nozzles in parallel in the Y direction with the support table, it is possible to perform multi-row formation processing in one X direction scan. Therefore, the shaping efficiency of the three-dimensional structure can be enhanced.

  Another invention made in order to solve the above-mentioned subject is a manufacturing method of a three-dimensional structure using two or more kinds of composition which react by mixing, and supports a droplet of the 1st composition from the 1st nozzle. Ejecting toward the platform, Ejecting droplets of another liquid composition from the second nozzle toward droplets of the first liquid composition deposited in the first liquid composition ejecting step The droplet ejection direction of the first nozzle is parallel to the droplet ejection direction of the second nozzle.

  In the method of manufacturing a three-dimensional structure, droplets of the composition are ejected in parallel from the first nozzle and the second nozzle. For this reason, in the manufacturing method of the three-dimensional structure, the positions of the first nozzle and the second nozzle in the horizontal plane (plane parallel to the support) are made to coincide, and droplets are ejected at the same initial velocity. Each droplet can be deposited at the same position. That is, by using the method for producing a three-dimensional structure, it is possible to easily mix plural types of compositions by controlling the horizontal position of the nozzle and the initial velocity of the droplets.

  The plurality of types of compositions are two types of a first liquid composition and a second liquid composition, and the first liquid composition is at least one of a urethane prepolymer, a urethane urea prepolymer and a urea prepolymer. The second liquid composition comprises a prepolymer of at least one of a soft segment component of a long chain polyol and a long chain polyamine, and at least one hard chain of a chain extender and a crosslinking agent. It is preferable to include a segment component. Thus, by using the first liquid composition containing the prepolymer and the polyisocyanate, and the second liquid composition containing the soft segment component and the hard segment component, a three-dimensional shaped object using the three-dimensional shaping apparatus Can be manufactured easily and reliably. In addition, when the second liquid composition contains a hard segment component, it becomes easy to adjust the elastic modulus, hardness and the like of the three-dimensional structure to be formed.

  As described above, by using the three-dimensional modeling apparatus and the three-dimensional model manufacturing method of the present invention, a plurality of compositions can be uniformly mixed by simple control, so that uniformity and curing characteristics can be easily achieved. An excellent three-dimensional structure is obtained.

It is a typical perspective view of a three-dimensional modeling device concerning one embodiment of the present invention. It is a schematic cross section explaining the 1st liquid composition injection process of the manufacturing method of the three-dimensional fabrication thing using the three-dimensional fabrication device of FIG. It is a schematic cross section explaining the 2nd liquid composition injection process of the manufacturing method of the three-dimensional fabrication thing using the three-dimensional fabrication device of FIG. It is a schematic enlarged perspective view of the head part of a three-dimensional modeling apparatus different from FIG.

First Embodiment
Hereinafter, the first embodiment of the present invention will be described in detail with reference to the drawings.

[3D modeling device]
The three-dimensional shaping apparatus shown in FIG. 1 is a three-dimensional shaping apparatus using two types of compositions (a first liquid composition and a second liquid composition) that react by mixing. The three-dimensional structure forming apparatus comprises a base 1, a plate-like support 2 disposed on the upper side of the base 1 to support the three-dimensional structure A to be formed, and droplets of the composition A head 3, a drive unit 4 for moving the support 2 and the head 3 relative to each other, and a control unit 5 for controlling the droplet deposition position of droplets ejected from the head 3 are mainly included.

<Base>
The base 1 is a base which supports each part such as the support 2 and the head 3 of the three-dimensional modeling apparatus. Although the shape of the base 1 is not specifically limited, For example, it can be set as plate shape like FIG. The material of the base 1 is not particularly limited, and may be metal or resin, but metal may be used from the viewpoint of strength. Moreover, the size of the base 1 is appropriately determined by the size of the target three-dimensional structure A.

<Support>
The support 2 is disposed on the upper side of the base 1 via the drive unit 4 and supports the three-dimensional structure A to be formed. The material of the support 2 is not particularly limited, but may be the same material as the base 1. Moreover, the size of the support stand 2 is suitably determined by the size of the target three-dimensional structure A.

  The support 2 is configured to be movable in the X and Y directions by a drive unit 4 described later. The movement of the support 2 can move the support 2 and the head 3 relative to each other.

<Head>
The head 3 is supported by a head support 6. The head support 6 is, for example, a vertical support 6a extending upward (Z direction) from one side edge center of the base 1, and a horizontal support extending from the tip of the vertical support 6a to the center of the base 1. 6b and a height adjustment support 6c connected to the end of the horizontal support 6b and extending in the Z direction. The head 3 is connected to the height adjustment support 6c, and is configured to be able to move up and down the connection position with the height adjustment support 6c by the control unit 5 described later.

  The head 3 includes a head body 30 and two nozzles (a first nozzle 31a and a second nozzle 31b). In addition, the head main body 30 includes a first tank 30a and a second tank 30b, and the first liquid composition and the second liquid composition are stored, respectively.

  The head 3 functions as a dispenser (droplet discharge device), and ejects droplets of the first liquid composition from the first nozzle 31a and ejects droplets of the second liquid composition from the second nozzle 31b. Can. As a droplet discharge method of the head 3, a method used for a known dispenser such as an inkjet method, a needle method, a syringe method or the like can be adopted. Among them, a needle type and a syringe type which can inject accurately even with a composition of high viscosity are preferable.

  The first nozzle 31 a and the second nozzle 31 b protrude from below the first tank 30 a and the second tank 30 b so that the droplet ejection direction is perpendicular to the surface of the support 2. That is, the droplet ejection directions of the first nozzle 31a and the second nozzle 31b are parallel. The nozzle arrangement direction of the first nozzle 31a and the second nozzle 31b is the X direction.

  As a minimum of the nozzle diameter of the 1st nozzle 31a and the 2nd nozzle 31b, 0.001 mm is preferred and 0.05 mm is more preferred. On the other hand, the upper limit of the nozzle diameter is preferably 1 mm, more preferably 0.2 mm, and still more preferably 0.1 mm. If the diameter of the nozzle is less than the above lower limit, the amount of droplets per injection will be small, so that the shaping efficiency may be lowered. On the other hand, when the nozzle diameter exceeds the upper limit, there is a possibility that the modeling accuracy may be reduced, and it may be difficult to uniformly mix the two compositions. The nozzle diameter of the first nozzle 31a and the nozzle diameter of the second nozzle 31b may be the same or different.

  As a minimum of distance (distance between nozzles) between central axes of the 1st nozzle 31a and the 2nd nozzle 31b, 1 mm is preferred and 2 mm is more preferred. On the other hand, as an upper limit of the distance between nozzles, 100 mm is preferable, 70 mm is more preferable, and 3 mm is more preferable. If the distance between the nozzles is less than the lower limit, it may be difficult to make the droplet ejection directions of the first nozzle 31a and the second nozzle 31b parallel. Conversely, when the distance between the nozzles exceeds the upper limit, the droplets of the second liquid composition are deposited by the second nozzle 31b at the droplet deposition positions of the droplets of the first liquid composition deposited by the first nozzle 31a. There is a possibility that the moving distance of the head 3 for depositing droplets may become unnecessarily large.

<Drive part>
The driving unit 4 enables the support 2 to move in the X and Y directions. The configuration of the drive unit 4 is not particularly limited as long as the support base 2 can be moved in the X and Y directions. For example, as shown in FIG. 1, the center axis is in the X direction. The first shaft portion 4a, which is movably supported in the first direction, and a circle that is disposed so that the central axis is in the Y direction and supports the support base 2 and the first shaft portion 4a so as to be movable in the central axis direction It can comprise by the columnar 2nd axial part 4b. By thus configuring, after moving the support 2 and the first shaft 4a to the desired position in the Y direction via the second shaft 4b, the support 2 is moved to the X direction via the first shaft 4a. It can be moved to the desired position in the direction.

<Control unit>
The control unit 5 controls the droplet deposition position so that droplets of the two types of compositions are mixed on the support 2. Further, the control unit 5 controls the height of the head 3 and the droplet diameter of the droplet ejected from the head 3.

  The control unit 5 can be configured by, for example, a microcontroller and a control unit that controls the drive unit 4 and the head 3. The arrangement position of the control unit 5 is not particularly limited as long as it does not hinder the ejection of droplets, for example, the control unit 5 is disposed adjacent to the head support 6 on the side surface of the base 1 in FIG. There is.

  The control unit 5 scans the landing position in the X direction in the XY directions orthogonal to each other in plan view, and controls the drive unit 4 to shift in the Y direction. By thus scanning the deposition position in the X direction, which is the nozzle arrangement direction, it becomes possible to simultaneously perform the ejection of the first liquid composition and the ejection of the second liquid composition, and the shaping efficiency can be improved. .

  The lower limit of the distance in the X direction of the droplet deposition position is preferably 0.1 mm, and more preferably 0.2 mm. On the other hand, 2 mm is preferable as an upper limit of the space | interval of the X direction of a drop application position, and 0.7 mm is more preferable. When the distance in the X direction of the droplet deposition position is less than the above lower limit, the shaping efficiency may be reduced. On the contrary, when the distance in the X direction of the droplet deposition position exceeds the upper limit, the density of the three-dimensional structure A to be formed may be reduced, and unevenness may occur in the mixing of the two types of droplets.

  The interval in the X direction of the droplet deposition position may be determined so as to be 1 / n (n: integer) of the distance between the first nozzle 31a and the second nozzle 31b. As described above, by setting the distance between the droplet positions in the X direction to 1 / n of the distance between nozzles, it becomes possible to simultaneously perform the ejection of the first liquid composition and the ejection of the second liquid composition. Efficiency can be increased. As a minimum of the above-mentioned n, 2 is preferred and 3 is more preferred. On the other hand, as an upper limit of said n, 10 is preferable and 5 is more preferable. If the above n is less than the above lower limit, the distance between the landing positions in the X direction becomes too wide, and the density of the three-dimensional structure A to be formed may be reduced. Conversely, if the above n exceeds the above upper limit, the shaping efficiency may be reduced.

  The lower limit of the distance in the Y direction of the droplet deposition position is preferably 0.1 mm, and more preferably 0.2 mm. On the other hand, 2 mm is preferable and 0.6 mm is more preferable as the upper limit of the distance in the Y direction of the landing position. If the distance between the landing positions in the Y direction is less than the above lower limit, the shaping efficiency may be reduced. On the contrary, when the interval in the Y direction of the landing position exceeds the upper limit, the density of the three-dimensional structure A to be formed may be reduced.

  The lower limit of the moving speed of the head 3 in the X direction is preferably 10 mm / sec, more preferably 20 mm / sec. On the other hand, the upper limit of the moving speed of the head 3 in the X direction is preferably 300 mm / sec, more preferably 100 mm / sec, and still more preferably 35 mm / sec. When the moving speed of the head 3 in the X direction is less than the above lower limit, the shaping efficiency may be reduced. Conversely, when the moving speed of the head 3 in the X direction exceeds the upper limit, shape control of the deposited droplets may be difficult. The moving speed of the head 3 in the Y direction is not particularly limited because it is a shift operation, and is preferably as high as possible.

  The ejection time interval of droplets from the first nozzle 31a and the second nozzle 31b is determined from the interval in the X direction of the landing position and the moving speed of the head 3 in the X direction. The lower limit of the injection time interval is preferably 5 msec, more preferably 10 msec. On the other hand, the upper limit of the injection time interval is preferably 50 msec, and more preferably 30 msec. If the ejection time interval is less than the lower limit, it is necessary to increase the moving speed of the head 3 in the X direction in order to make the deposition interval a desired value, and it is difficult to control the shape of the deposited droplets. May be Conversely, if the injection time interval exceeds the upper limit, the shaping efficiency may be reduced.

  Further, the control unit 5 controls the droplet diameter of the droplets ejected from the first nozzle 31a and the second nozzle 31b. The droplet deposition diameter can be adjusted by the amount of droplets ejected from the first nozzle 31a and the second nozzle 31b and the ejection pressure, in addition to the diameters of the first nozzle 31a and the second nozzle 31b.

  The lower limit of the average volume of droplets ejected from the first nozzle 31a and the second nozzle 31b is preferably 1 nL, and more preferably 5 nL. On the other hand, the upper limit of the average volume of the droplets is preferably 20 μL, more preferably 1 μL. If the average volume of the droplets is less than the lower limit, control of the impact position of the droplets becomes difficult due to the influence of static electricity or the like, so that the modeling accuracy of the three-dimensional structure A to be modeled may be reduced. Conversely, if the average volume of the droplets exceeds the upper limit, the shape of the three-dimensional structure A to be formed may be rough.

  As a minimum of injection pressure of a droplet ejected from the 1st nozzle 31a and the 2nd nozzle 31b, 0.02MPa is preferred and 0.05MPa is more preferred. On the other hand, as an upper limit of the above-mentioned injection pressure, 0.5MPa is preferred and 0.2MPa is more preferred. If the injection pressure is less than the lower limit, control of the impact position of the droplets becomes difficult due to the influence of static electricity or the like, and thus the formation accuracy of the three-dimensional object A to be formed may be reduced. On the other hand, when the injection pressure exceeds the upper limit, the droplets are likely to scatter after being deposited, and the shape of the three-dimensional structure A to be formed may be rough.

  As a minimum of a drop diameter of a droplet from the 1st nozzle 31a ejected first, 0.6 mm is preferred and 0.7 mm is more preferred. On the other hand, the upper limit of the droplet diameter of droplets from the first nozzle 31a is preferably 1.2 mm, and more preferably 1.0 mm. When the droplet diameter of the droplets from the first nozzle 31a is less than the above lower limit, the shaping efficiency may be reduced. Conversely, if the droplet diameter of the droplets from the first nozzle 31a exceeds the upper limit, there is a possibility that unevenness occurs in the mixing of the two types of droplets.

  Adjacent droplets ejected and deposited from the first nozzle 31a may be partially overlapped. That is, it is preferable that the droplet deposition diameter of the droplets from the first nozzle 31a be larger than the interval in the X direction of the droplet deposition position. By causing the droplets to be deposited so as to partially overlap, it is possible to suppress the occurrence of uneven density in the three-dimensional structure A to be formed.

  The lower limit of the ratio of the droplet diameter of the droplets from the first nozzle 31a to the distance in the X direction of the droplet positions is preferably 1.2, and more preferably 1.5. On the other hand, 4 is preferable and 3 is more preferable as the upper limit of the ratio of the droplet diameter. When the ratio of the droplet diameter is less than the lower limit, uneven density may occur in the three-dimensional structure A to be formed. On the other hand, when the ratio of the droplet diameter exceeds the upper limit, the shaping efficiency may be reduced.

  The droplet diameter of droplets from the second nozzle 31 b is preferably smaller than the droplet diameter of droplets from the first nozzle 31 a. By making the droplet deposition diameter of the droplets from the second nozzle 31 b smaller than the droplet deposition diameter of the droplets from the first nozzle 31 a, it is possible to easily and surely cover the droplet deposition of the first liquid composition. Droplets of the two-pack composition can be deposited. Therefore, it becomes easy to mix the 1st liquid composition and the 2nd liquid composition uniformly. The droplet diameter of the droplets from the second nozzle 31 b means the diameter of the droplet when it is directly ejected and deposited on the support 2.

  The droplet diameter of droplets from the second nozzle 31b is mainly the droplets of the first liquid composition ejected and dropped from the first nozzle 31a and the second liquid composition ejected from the second nozzle 31b. It is determined by the optimum mixing ratio with the droplet. For this reason, when it is attempted to mix one droplet of the second liquid composition with one droplet of the first liquid composition, the droplet diameter of the second liquid composition is smaller than that of the first liquid composition. It can be larger than the diameter. In such a case, it is effective to mix a plurality of droplets of the second liquid composition with one droplet of the first liquid composition. That is, the control unit 5 adjusts the mixing ratio of the first liquid composition and the second liquid composition based on the number of ejected droplets of the second liquid composition to one droplet of the first liquid composition. By adjusting the mixing ratio in this manner, the droplet diameter of the second liquid composition can be reliably made smaller than the droplet diameter of the first liquid composition, so the droplets of the second liquid composition can be easily made. And it can be surely included in the deposition of the first liquid composition.

  When the control unit 5 adjusts the mixing ratio by the number of droplets of the second liquid composition to one droplet of the first liquid composition, the mixing ratio may be changed in units of droplets. By controlling the mixing ratio in units of droplets, it is possible to partially change the physical properties of the three-dimensional structure A, such as the hardness.

  When the control unit 5 adjusts the mixing ratio according to the number of droplets of the second liquid composition ejected to one droplet of the first liquid composition, the second liquid composition with respect to the droplet diameter of the first liquid composition The ratio of the droplet diameter is preferably 1/3 or more and 4/5 or less. By setting the ratio of the droplet diameter of the second liquid composition to the droplet diameter of the first liquid composition within the above range, the controllability of the mixing ratio can be enhanced while maintaining the shaping efficiency.

  When the number of ejected droplets of the second liquid composition to one droplet of the first liquid composition is two or more, the liquid of the second liquid composition is arranged so that the centers of the respective drop positions do not overlap. You should shoot drops. By injecting the plurality of second liquid composition droplets so that the centers do not overlap in this manner, the uniformity of mixing of the two types of droplets can be enhanced. Conversely, in the case where the number of droplets of the second liquid composition ejected to one droplet of the first liquid composition is 1, the centers of the respective drop positions overlap from the viewpoint of mixing uniformity. It is preferable to eject droplets of the second liquid composition as described above.

  The controller 5 controls the height of the head 3 by changing the position of the head 3 on the height adjustment support 6 c. The three-dimensional structure A increases in height as the formation progresses. Along with this, the landing position also becomes higher, but the control unit 5 holds the distance between the tip of the nozzle and the landing position within a desired range by controlling the height of the head 3.

  The lower limit of the distance (ejection distance) between the first nozzle 31a and the second nozzle 31b and the landing position is preferably 1 mm, and more preferably 2 mm. On the other hand, as an upper limit of the above-mentioned injection distance, 50 mm is preferred, 10 mm is more preferred, and 5 mm is more preferred. There is a possibility that head 3 and three-dimensional modeling thing A under modeling may interfere as the above-mentioned injection distance is less than the above-mentioned minimum. Conversely, if the injection distance exceeds the upper limit, a slight error in the control of the nozzle may expand at the landing position, and the controllability may decrease.

[Manufacturing method of three-dimensional structure]
The method of manufacturing the three-dimensional structure includes a preparation step, a first liquid composition injection step, and a second liquid composition injection step. The manufacturing method of the said three-dimensional structure can be performed using the three-dimensional structure manufacturing apparatus shown in FIG.

<Preparation process>
In the preparation step, the first liquid composition and the second liquid composition are filled in the first tank 30a and the second tank 30b of the head 3 as a modeling material, respectively.

  The first liquid composition and the second liquid composition are different types of compositions that react upon mixing. The first liquid composition and the second liquid composition are not particularly limited as long as they can form a shaped object by mixing, and for example, an isocyanate component such as polyisocyanate as a first liquid composition, a second liquid composition Polyol components such as long chain polyols and / or polyamine components such as long chain polyamines may be used as By mixing these, a polyurethane, polyurethaneurea or polyurea can be obtained by a condensation reaction. These are synthetic resins, are easy to adjust physical properties such as elastic modulus and hardness, and are excellent in wear resistance and moldability.

  As the first liquid composition and the second liquid composition, compositions that react by the pseudo prepolymer method are preferable. Here, in the pseudo prepolymer method, in synthesis of polyurethane and the like, a long chain polyol and / or a part of a long chain polyamine to be used is previously reacted with a polyisocyanate to form a prepolymer, and this prepolymer is combined with the polyisocyanate and isocyanate. It is a method used as an ingredient. In this pseudo prepolymer method, since a long chain polyol and / or a part of a long chain polyamine is used for the synthesis of prepolymer and this prepolymer is used as an isocyanate component, the polyol component and / or polyamine component of the shaping material used The volume with the isocyanate component can be made comparable. Thus, the manufacturing method of the said three-dimensional structure is using the 1st liquid composition and 2nd liquid composition which react by a pseudo | simulation prepolymer method as a modeling material, and 1st liquid composition and 2nd liquid composition Since the volume of the substance can be made the same, the first liquid composition and the second liquid composition can be mixed easily and reliably. As a result, by using the method for producing the three-dimensional structure, it is possible to easily and reliably produce the three-dimensional structure A containing polyurethane, polyurethaneurea or polyurea as a main component. Here, the “main component” is a component with the largest content, and for example, refers to a component with a content of 50% by mass or more.

(First liquid composition)
The first liquid composition preferably contains at least one prepolymer of urethane prepolymer, urethane urea prepolymer and urea prepolymer, and polyisocyanate. Polyol component and / or polyamine of second liquid composition by using prepolymer such as urethane prepolymer in which condensation reaction between isocyanate component and polyol component and / or polyamine component has partially progressed in first liquid composition The components can be reduced to reduce their volume, and the volumes of the first liquid composition and the second liquid composition can be made closer. In addition, by using the above prepolymer in the first liquid composition, it is possible to partially complete the condensation reaction of the isocyanate component with the polyol component and / or the polyamine component. Thereby, the curing speed after mixing the first liquid composition and the second liquid composition can be improved. Furthermore, when the first liquid composition contains a polyisocyanate having a molecular weight smaller than that of the above-mentioned prepolymer, the increase in viscosity due to prepolymerization can be suppressed, so when mixing the first liquid composition and the second liquid composition It can suppress the diffusion of

  The upper limit of the viscosity at 80 ° C. of the first liquid composition is preferably 400 mPa · s, more preferably 300 mPa · s. If the viscosity at 80 ° C. of the first liquid composition exceeds the above upper limit, mixing with the second liquid composition becomes difficult, and as a result, the curing of the three-dimensional structure A to be formed may become insufficient, or desired Physical properties of may not be obtained. On the other hand, the lower limit of the viscosity at 80 ° C. of the first liquid composition is not particularly limited, and is, for example, 50 mPa · s.

  The urethane prepolymer used in the first liquid composition is an oligomer having a urethane bond (-NHCOO-) in the main chain, and can be obtained, for example, by reacting polyisocyanate and a long chain polyol. The urethane prepolymer usually has an isocyanate group (-N = C = O) at both ends.

  As a lower limit of the number average molecular weight of the above-mentioned urethane prepolymer, 800 is preferred and 1,000 is more preferred. On the other hand, as an upper limit of the number average molecular weight of the above-mentioned urethane prepolymer, 5,000 are preferred and 2,000 is more preferred. If the number average molecular weight of the urethane prepolymer is less than the above lower limit, the curing speed after mixing of the first liquid composition and the second liquid composition may be reduced, and the shaping efficiency may be reduced. Conversely, if the number average molecular weight of the urethane prepolymer exceeds the above upper limit, the viscosity of the first liquid composition may increase, which may make it difficult to mix with the second liquid composition. Here, “number average molecular weight” means gel permeation chromatography according to JIS-K7252-1: 2008 “Plastics — Determination of average molecular weight and molecular weight distribution of polymer by size exclusion chromatography-part 1: general rules” It refers to the value measured using chromatography (GPC).

  The polyisocyanate is a compound having two or more isocyanate groups in the molecule. Examples of the polyisocyanate include aliphatic polyisocyanate (including alicyclic polyisocyanate), aromatic polyisocyanate and the like. The above-mentioned polyisocyanate usually does not have a urethane bond and a urea bond in the main chain.

  Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, isopropylidene bis (4-cyclohexylisocyanate), norbornane diisocyanate, modified products and multimers thereof, and the like. Examples of the aromatic isocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, modified products and multimers thereof, and the like. As said polyisocyanate, aliphatic polyisocyanate is preferable and diphenylmethane diisocyanate is more preferable.

  The long chain polyol is a compound having a molecular weight of 300 or more and having two or more hydroxyl groups (-OH) in the molecule. Examples of the long chain polyol include polyether polyol, polycarbonate polyol, polyester polyol and the like.

  Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, polytetramethylene ether glycol, polytetramethylene ether triol, polyoxyalkylene glycols such as co-condensates of these, and side chains thereof And derivatives in which a branched structure is introduced, modified products, and the like.

  Examples of the polycarbonate polyol include a reaction product of a dialkyl carbonate and a diol, a reaction product of a diaryl carbonate and a diol, a reaction product of an alkylene carbonate and a diol, and the like. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate and the like. As said diaryl carbonate, a diphenyl carbonate etc. are mentioned. Ethylene carbonate etc. are mentioned as said alkylene carbonate. As said diol, the short chain diol etc. which are mentioned later are mentioned, for example.

  Examples of the polycarbonate polyol include a reaction product of a dialkyl carbonate and a diol, a reaction product of a diaryl carbonate and a diol, a reaction product of an alkylene carbonate and a diol, and the like. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate and the like. As said diaryl carbonate, a diphenyl carbonate etc. are mentioned. Ethylene carbonate etc. are mentioned as said alkylene carbonate. As said diol, the short chain diol etc. which are mentioned later are mentioned, for example.

  As said polyester polyol, the dehydration condensation product of dicarboxylic acid and the glycol of molecular weight less than 300 etc. are mentioned, for example. Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like Family dicarboxylic acids and the like. Examples of the glycol include ethylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,9-nonanediol, triethylene glycol Aliphatic glycols, alicyclic glycols such as 1,4-cyclohexanedimethanol, aromatic diols such as p-xylene diol, polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol Be Moreover, as said polyester polyol, polycaprolactone polyols, such as polycaprolactone glycol, polycaprolactone triol, polycaprolactone tetraol, etc. are mentioned, for example. The polyester polyols described above usually have a linear structure, but derivatives, modified products and the like in which side chains or branched structures are introduced into these can also be used. Moreover, as said polyester polyol, what has a branched structure obtained by the dehydration condensation reaction of the said dicarboxylic acid, the said glycol, and the trivalent or more carboxylic acid and / or the trivalent or more polyol can also be used. In addition, as conditions for the dehydration condensation reaction of the dicarboxylic acid and the glycol, for example, the molar ratio of glycol to dicarboxylic acid can be 1.1 or more and 1.3 or less, and the temperature can be 150 ° C. or more and 300 ° C. or less.

  As the above long chain polyol, polyether polyol is preferable, and polytetramethylene ether glycol is more preferable.

  The lower limit of the number average molecular weight of the long chain polyol can be appropriately changed depending on the use of the three-dimensional structure A to be formed, etc., but 500 is preferable and 800 is more preferable. On the other hand, the upper limit of the number average molecular weight of the long chain polyol is preferably 5,000, more preferably 2,500. As described above, by setting the number average molecular weight of the long chain polyol in the above range, the moldability is balanced with physical properties such as elastic modulus, hardness, abrasion resistance, and moldability of the three-dimensional structure A to be shaped. It can be improved well.

  The urethane urea prepolymer used in the first liquid composition is an oligomer having a urethane bond and a urea bond (-NHCONH-) in the main chain, and for example, by reacting polyisocyanate with a long chain polyol and a long chain polyamine. can get. The above urethane urea prepolymer usually has isocyanate groups at both ends. The polyisocyanate and long chain polyol used for the synthesis of the urethane urea prepolymer can be the same as those used for the synthesis of the urethane prepolymer.

  As a lower limit of the number average molecular weight of the above-mentioned urethane urea prepolymer, 1,000 is preferred and 1,500 is more preferred. On the other hand, as an upper limit of the number average molecular weight of the above-mentioned urethane urea prepolymer, 15,000 are preferred and 10,000 are more preferred. If the number average molecular weight of the urethane urea prepolymer is less than the above lower limit, the curing speed after mixing of the first liquid composition and the second liquid composition may be reduced, and the shaping efficiency may be reduced. Conversely, if the number average molecular weight of the urethane urea prepolymer exceeds the above upper limit, the viscosity of the first liquid composition may increase and it may be difficult to mix with the second liquid composition.

  The long chain polyamine used in the first liquid composition is a compound having a molecular weight of 300 or more having two or more amino groups in the molecule. The above amino group includes an alkylamino group, a dialkylamino group and an imino group.

  Examples of the long chain polyamine include long chains such as poly (ethylene glycol) diamine, poly (propylene glycol) diamine, poly (tetramethylene ether glycol) diamine, and diamine of a cocondensate of polytetramethylene ether glycol and polypropylene glycol. Examples thereof include diamines and long chain triamines such as poly (ethylene glycol) triamine and poly (propylene glycol) triamine.

  The long chain polyamine is preferably a long chain diamine, more preferably a diamine of a copolymer of polytetramethylene ether glycol and polypropylene glycol and polypropylene glycol diamine.

  The number average molecular weight of the long chain polyamine can be suitably changed according to the application etc. of the three-dimensional structure A to be formed, but the lower limit of the number average molecular weight of the long chain polyamine is preferably 500, more preferably 800. On the other hand, the upper limit of the number average molecular weight of the long chain polyamine is preferably 5,000, more preferably 2,500. As described above, by setting the number average molecular weight of the long chain polyamine to the above range, the moldability is balanced with the physical properties such as the elastic modulus, hardness, wear resistance, and moldability of the three-dimensional structure A to be shaped. It can be improved well.

  The urea prepolymer used in the first liquid composition is an oligomer having a urea bond in the main chain, and can be obtained, for example, by reacting polyisocyanate and a long chain polyamine. The above urea prepolymer usually has isocyanate groups at both ends. The polyisocyanate and long chain polyamine used for the synthesis of the above-mentioned urea prepolymer can be similar to those used for the synthesis of the above-mentioned urethane urea prepolymer.

  As a minimum of the number average molecular weight of the above-mentioned urea prepolymer, 1,000 are preferred, and 1,500 are more preferred. On the other hand, as an upper limit of the number average molecular weight of the above-mentioned urea prepolymer, 15,000 are preferred and 10,000 are more preferred. When the number average molecular weight of the above-mentioned urea prepolymer is less than the above-mentioned lower limit, the curing rate after mixing of the first liquid composition and the second liquid composition may be reduced, and the shaping efficiency may be reduced. On the contrary, when the number average molecular weight of the above-mentioned urea prepolymer exceeds the above-mentioned upper limit, the viscosity of the first liquid composition may increase and it may be difficult to mix it with the second liquid composition.

  The lower limit of the content of the prepolymer (total content of urethane prepolymer, urethane urea prepolymer and urea prepolymer) in the first liquid composition is preferably 10% by mass, more preferably 20% by mass, and 40% by mass. Is more preferred. On the other hand, as an upper limit of content of the said prepolymer, 80 mass% is preferable, 70 mass% is more preferable, and 60 mass% is more preferable. When the content of the prepolymer is less than the above lower limit, the volume of the second liquid composition increases because the amount of the polyol component and / or the polyamine component necessary for curing the first liquid composition increases. It may be difficult to mix with the one-component composition. Conversely, when the content of the prepolymer exceeds the upper limit, the viscosity of the first liquid composition increases due to the relative decrease of the polyisocyanate content, and the first liquid composition and the second liquid composition It may be difficult to mix things.

  The polyisocyanate used in the first liquid composition can be the same as that described above for the urethane prepolymer. However, the polyisocyanate used for the synthesis of the urethane prepolymer, the urethane urea prepolymer and / or the urea prepolymer contained in the first liquid composition may be the same as or different from the polyisocyanate.

  The lower limit of the content of the polyisocyanate in the first liquid composition is preferably 20% by mass, more preferably 30% by mass, and still more preferably 40% by mass. On the other hand, as an upper limit of content of the said polyisocyanate, 90 mass% is preferable, 80 mass% is more preferable, and 60 mass% is more preferable. If the content of the polyisocyanate is less than the lower limit, the viscosity of the first liquid composition may be increased, which may make it difficult to mix the first liquid composition and the second liquid composition. Conversely, when the content of the polyisocyanate exceeds the upper limit, the volume of the second liquid composition increases because the polyol component and / or the polyamine component necessary for curing the first liquid composition increases. There is a possibility that mixing with the first liquid composition may be difficult.

(Second liquid composition)
The second liquid composition preferably includes at least one soft segment component of long chain polyol and long chain polyamine, and at least one hard segment component of a chain extender and a crosslinking agent.

  The upper limit of the viscosity at 80 ° C. of the second liquid composition is preferably 400 mPa · s, more preferably 300 mPa · s. When the viscosity at 80 ° C. of the second liquid composition exceeds the above upper limit, mixing with the first liquid composition may be difficult. On the other hand, the lower limit of the viscosity at 80 ° C. of the second liquid composition is not particularly limited, and is, for example, 50 mPa · s.

  The long chain polyol used in the second liquid composition may be the same as that used in the synthesis of the above urethane prepolymer. Moreover, as a long chain polyamine used for a 2nd liquid composition, it can be made to be the same as that used for the synthesis | combination of the said urethane urea prepolymer. The long chain polyol and the long chain polyamine contained in the second liquid composition are used to synthesize the urethane prepolymer, the urethane urea prepolymer and / or the urea prepolymer contained in the first liquid composition. It may be the same as or different from the long chain polyol.

  The lower limit of the total content of the long chain polyol and the long chain polyamine in the second liquid composition is preferably 70% by mass, and more preferably 80% by mass. On the other hand, as an upper limit of the above-mentioned total content, 95 mass% is preferred, and 90 mass% is more preferred. If the total content is less than the above lower limit, the volume of the second liquid composition necessary for curing the first liquid composition is increased, so the first liquid composition and the second liquid composition are mixed. May be difficult. Conversely, if the total content exceeds the above upper limit, the content of the chain extender, crosslinking agent, etc. in the second liquid composition relatively decreases, and the physical properties of the three-dimensional model A to be shaped are adjusted. It may be difficult.

  The chain extender used for the second liquid composition improves the toughness and the like of the three-dimensional structure A to be formed. As said chain extender, short chain diol, short chain diamine etc. can be used, for example.

  The short chain diol is a compound having a molecular weight of less than 300 and having two hydroxyl groups in the molecule. Examples of the short chain diol include 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol and 2-methyl-1 , 8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1, Aliphatic diols such as 5-pentanediol and neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) -propane Etc. can be mentioned. In addition, as the short chain diol, a copolycarbonate diol obtained by the reaction of an aliphatic diol and an alicyclic diol with a dialkyl carbonate or the like can also be used. Examples of the copolycarbonate diol include polycarbonate glycol, derivatives in which a side chain and a branched structure are introduced thereto, modified products, and the like. Among them, aliphatic diols are preferable, and 1,4-butanediol is more preferable.

  The short chain diamine is a compound having a molecular weight of less than 300 and having two amino groups in the molecule. Examples of the short chain diamine include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophorone diamine, trimethylhexamethylene diamine (2,2,2,3 4-isomer and 2,4,4-isomer isomer mixture), 2-methylpentamethylenediamine, 1,3-xylylenediamine, 1,4-xylylenediamine, α, α, α ′, α′- Tetramethyl-1,3-xylylenediamine, α, α, α ′, α′-tetramethyl-1,4-xylylenediamine, 4,4′-diaminodicyclohexylmethane, diethylmethylbenzenediamine (DETDA), 4 4,4'-Diamino-3,3'-dichlorodiphenylmethane (MOCA), dimethylethylenediamine, 1,4-bis (amino) Methyl, cyclohexane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,5-diethyl-3 ', 5'-diisopropyldicyclohexylmethane and the like can be mentioned. Among them, diethyl methyl benzene diamine (DETDA) is preferable.

  As a minimum of content of the above-mentioned chain extender in the 2nd liquid constituent, 1 mass% is preferred and 5 mass% is more preferred. On the other hand, as a maximum of content of the above-mentioned chain extender, 20 mass% is preferred, and 15 mass% is more preferred. If the content of the chain extender is less than the above lower limit, it may be difficult to adjust the physical properties of the three-dimensional structure A to be formed. Conversely, when the content of the chain extender exceeds the above upper limit, the flexibility of the three-dimensional structure A to be formed may be reduced.

  The crosslinking agent used for the second liquid composition improves the elastic modulus and the like of the three-dimensional structure A to be formed. As said crosslinking agent, short chain triol, short chain tetraol, short chain triamine etc. can be used, for example.

  The short chain triol is a compound having a molecular weight of less than 300 and having three hydroxyl groups in the molecule. Examples of the short chain triol include trimethylol propane, trimethylol ethane, glycerin and hexane triol. Among these, trimethylolpropane is preferred.

  The short chain tetraol is a compound having a molecular weight of less than 300 and having four hydroxyl groups in the molecule. As said short chain tetraol, a pentaerythritol etc. are mentioned, for example.

  The short chain triamine is a compound having a molecular weight of less than 300 and having three amino groups in the molecule. Examples of the short chain triamine include diethylenetriamine, iminobispropylamine, bishexamethylenetriamine and the like.

  As a minimum of content of the above-mentioned crosslinking agent in the 2nd liquid constituent, 0.5 mass% is preferred and 3 mass% is more preferred. On the other hand, as an upper limit of content of the said crosslinking agent, 15 mass% is preferable, and 5 mass% is more preferable. If the content of the crosslinking agent is less than the above lower limit, it may be difficult to adjust the physical properties of the three-dimensional structure A to be formed. On the contrary, when content of the above-mentioned crosslinking agent exceeds the above-mentioned maximum, there is a possibility that the pliability of three-dimensional modeling thing A modeled may fall.

  The second liquid composition preferably further contains a plasticizer, a catalyst or a combination thereof. The second liquid composition may further contain optional components such as a colorant, a light stabilizer, a heat stabilizer, an antioxidant, a mildew proofing agent, and a flame retardant. The above optional components are generally contained in the second liquid composition from the viewpoint of storage stability of the isocyanate component, but may be contained in the first liquid composition.

  The plasticizer used for the second liquid composition reduces the viscosity of the second liquid composition and facilitates mixing with the first liquid composition. Moreover, the said plasticizer adjusts the elastic modulus of the three-dimensional model A to be modeled.

  Examples of the plasticizer include diethylhexyl phthalate, diisononyl phthalate (DINP), dibutyl phthalate, trischloroethyl phosphate, trischloropropyl phosphate (TCPP), 1,2-cyclohexanedicarboxylic acid diisononyl ester and the like. Among these, 1,2-cyclohexanedicarboxylic acid diisononyl ester is preferable.

  When the second liquid composition contains the plasticizer, the lower limit of the content of the plasticizer in the second liquid composition is preferably 5% by mass, and more preferably 10% by mass. On the other hand, as an upper limit of content of the above-mentioned plasticizer, 30 mass% is preferred and 20 mass% is more preferred. If the content of the plasticizer is less than the lower limit, it may be difficult to adjust the elastic modulus of the three-dimensional structure A to be formed. Conversely, if the content of the plasticizer exceeds the upper limit, the content of the long chain polyol and / or the long chain polyamine relatively decreases, and thus it is necessary to cure the first liquid composition. The volume of the second liquid composition may increase, which may make it difficult to mix the first liquid composition and the second liquid composition.

  The catalyst used for the second liquid composition promotes the curing reaction between the polyisocyanate component of the first liquid composition and the polyol component of the second liquid composition. Examples of the catalyst include organic tin compounds such as di-n-butyl tin dilaurate, dimethyl tin dilaurate, dibutyl tin oxide, octane tin, organic titanium compounds, organic zirconium compounds, carboxylic acid tin salts, carboxylic acid bismuth salts, Examples include amine catalysts such as ethylene diamine. Among them, from the viewpoint of suppressing the color change of the three-dimensional structure A to be formed, a catalyst other than an amine catalyst is preferable, an organic tin compound is more preferable, and dimethyltin dilaurate is more preferable.

  As a minimum of content of the above-mentioned catalyst in the 2nd liquid constituent, 0.005 mass% is preferred, and 0.02 mass% is more preferred. On the other hand, the upper limit of the content of the catalyst in the second liquid composition is preferably 0.1% by mass, and more preferably 0.05% by mass. If the content of the catalyst is less than the above lower limit, the curing rate after mixing of the first liquid composition and the second liquid composition may be reduced, and the shaping efficiency may be reduced. Conversely, if the content of the catalyst exceeds the upper limit, the curing rate after mixing of the first liquid composition and the second liquid composition may be too fast, and the production of the three-dimensional structure A may be difficult. is there.

  This preparation process is performed at least once before performing the first liquid composition injection process and the second liquid composition injection process. In addition, even at the stage where the three-dimensional structure A is shaped by the first liquid composition injection step and the second liquid composition injection step, along with the decrease in the liquid amount of the first liquid composition and the second liquid composition, The first liquid composition injection step and the second liquid composition injection step are interrupted and appropriately performed. In the case where the three-dimensional structure A is subjected to the preparation step during modeling, both the first liquid composition and the second liquid composition may be filled, but only the insufficient liquid may be filled.

<First liquid composition injection step>
In the first liquid composition injection step, droplets of the first liquid composition are ejected from the first nozzle 31 a toward the support 2. As shown in FIG. 2, the droplet B1 from the first nozzle 31a is three-dimensional corresponding to the landing height on the support 2 or on the uppermost surface of the three-dimensional structure A when the three-dimensional object A is in the process of being shaped. A first liquid layer A1 having a planar shape that matches the cross-sectional shape of the object A is formed. The first liquid layer A1 may be configured such that a plurality of droplets of the first liquid composition deposited as shown in FIG. 2 partially overlap the adjacent droplets.

  The shape of the first liquid layer A1 to be formed is based on, for example, cross-sectional shape data of the three-dimensional structure A created based on CAD (Computer Aided Design) data or the like. Further, the position of the first nozzle 31a and the ejection condition of the droplet B1 are controlled by the control unit 5 as described above.

  As liquid temperature of the 1st liquid composition to inject, 20 ° C or more and 60 ° C or less are preferred. Moreover, as temperature of the support stand 2, 15 degreeC or more and 150 degrees C or less are preferable. If the liquid temperature of the first liquid composition or the temperature of the temperature of the support table 2 is less than the above lower limit, the viscosity of the first liquid composition becomes too high, and in the second liquid composition injection step described later, the first liquid It may be difficult to uniformly mix the composition and the second liquid composition. Conversely, if the liquid temperature of the first liquid composition or the temperature of the temperature of the support table 2 exceeds the above upper limit, the viscosity of the first liquid composition becomes too low, making it difficult to control the shape of the deposited droplets. There is a fear.

<Second liquid composition injection step>
In the second liquid composition injection step, droplets of the second liquid composition are ejected from the second nozzle 31 b toward the droplets of the first liquid composition deposited in the first liquid composition injection step. The droplet ejection direction of the second nozzle 31b is parallel to the droplet ejection direction of the first nozzle 31a.

  The second liquid composition injection step may be performed after one row or the entire plane of the first liquid layer A1 in the X direction is formed in the first liquid composition injection step, but as shown in FIG. It is preferable from the viewpoint of shaping efficiency to carry out simultaneously with the composition injection step. The interval (P in FIG. 3) of the droplet deposition position in the X direction is 1 / n (n: integer) of the inter-nozzle distance (D in FIG. 3) between the first nozzle 31a and the second nozzle 31b; n = 2 in FIG. It can carry out simultaneously with a 1st liquid composition injection process by controlling the space | interval of the X direction of a drop application position so that it may become. For example, in FIG. 3, when the droplet B1 is ejected from the first nozzle 31a, by simultaneously ejecting the droplet B2 from the second nozzle 31b, the droplet B1 of the first liquid composition ejected two droplets earlier The droplet B2 of the second liquid composition can be deposited at the central position. In the first row of ejection in the X direction, there is no corresponding droplet B1 of the dropped first liquid composition, so ejection of the second liquid composition droplet B2 is performed. Absent. On the contrary, since the last n drops are out of the range of the cross-sectional shape to be formed by the first nozzle 31a, the ejection of the droplet B1 of the first liquid composition is not performed.

  Droplets B2 of the second liquid composition ejected from the second nozzle 31b are ejected in the first liquid composition injection step, mixed with the droplets B1 of the dropped first liquid composition, and cured. The hardened layer A2 is formed.

  The lower limit of the mass ratio of the first liquid composition and the second liquid composition to be mixed (first liquid composition: second liquid composition) is preferably 100: 250, more preferably 100: 180, and 100: 120. Is more preferred. On the other hand, the upper limit of the mass ratio is preferably 100: 40, and more preferably 100: 70. Thus, by setting the mass ratio to the above range, it becomes easy to adjust the volume ratio of the injection amounts of the first liquid composition and the second liquid composition to a range relatively close to 1: 1, the first liquid The composition and the second liquid composition can be more easily mixed uniformly.

  As a minimum of gelation time at 80 ° C after mixing of the 1st liquid composition and the 2nd liquid composition, 3 seconds are preferred and 5 seconds are more preferred. On the other hand, as a maximum of the above-mentioned gelation time, 10 seconds are preferred and 8 seconds are more preferred. If the gelation time is less than the above lower limit, curing may start before the first liquid composition and the second liquid composition are sufficiently mixed, and the uniformity of the mixing may be reduced. On the contrary, when the above-mentioned gelation time exceeds the above-mentioned upper limit, there is a possibility that modeling efficiency may fall.

  As a minimum of average thickness per one layer of hardening layer A2 formed, 0.05 mm is preferred and 0.1 mm is more preferred. On the other hand, as a maximum of average thickness per one layer of hardened layer A2, 2 mm is preferred and 1 mm is more preferred. When the average thickness per one layer of the hardened layer A2 is less than the above lower limit, the shaping efficiency may be reduced. On the contrary, when the average thickness per one layer of the hardened layer A2 exceeds the above upper limit, there is a possibility that the modeling accuracy may be lowered.

  The liquid temperature of the second liquid composition to be injected is the same as the liquid temperature of the first liquid composition.

  In the method of manufacturing the three-dimensional structure, the three-dimensional structure A is obtained by repeatedly performing the first liquid composition injection step and the second liquid composition injection step layer by layer.

〔advantage〕
In the three-dimensional modeling apparatus and the method of manufacturing the three-dimensional model, droplets of the first liquid composition and the second liquid composition are respectively ejected perpendicularly from the first nozzle 31a and the second nozzle 31b. Therefore, in the three-dimensional modeling apparatus and the method of manufacturing the three-dimensional model, the positions of the first nozzle 31a and the second nozzle 31b in the horizontal plane (plane parallel to the support 2) are made to coincide with each other By ejection, each droplet can be deposited at the same position. That is, by using the three-dimensional modeling apparatus and the three-dimensional model manufacturing method, two types of compositions can be easily mixed by controlling the horizontal position of the nozzle.

  In addition, since the droplets are ejected from directly above the deposition position, it is not necessary to change the nozzle position even if the surface of the three-dimensional structure A becomes high as the formation progresses. Therefore, control of the control unit 5 is further facilitated.

Second Embodiment
Hereinafter, a second embodiment of the present invention will be described in detail with reference to the drawings.

  The head 7 of FIG. 4 is used in place of the head 3 of the three-dimensional modeling apparatus of FIG. The head 7 includes a head body 70 and four sets of two nozzles (a first nozzle 71a and a second nozzle 71b). One set of the first nozzle 71a and the second nozzle 71b are arranged in the X direction. Further, four sets of nozzles are arranged in parallel to the support 2 in the Y direction.

  The head main body 70 includes a first tank 70a and a second tank 70b, and the first liquid composition and the second liquid composition are stored, respectively. The first liquid composition and the second liquid composition are respectively supplied from the first tank 70a and the second tank 70b to the four sets of the first nozzle 71a and the second nozzle 71b. The first tank 70 a and the second tank 70 b may be provided one by one for the four first nozzles 71 a and the second nozzles 71 b in common, or one for each of the nozzles.

  One set of the first nozzle 71a and the second nozzle 71b can be configured in the same manner as the first nozzle 31a and the second nozzle 31b of the three-dimensional modeling apparatus of FIG.

  The four sets of nozzles may be arranged at equal intervals in the Y direction. As a minimum of adjacent two sets of nozzle intervals, 0.1 mm is preferred and 0.2 mm is more preferred. On the other hand, 2 mm is preferable as an upper limit of adjacent two sets of nozzle intervals, and 0.6 mm is more preferable. If the distance between the adjacent two sets of nozzles is less than the above lower limit, the shaping efficiency may be reduced. Conversely, if the upper limit of the adjacent two sets of nozzle intervals is exceeded, the density of the three-dimensional structure A to be formed may be reduced.

  Further, it is preferable that the distance between the adjacent two sets of nozzles be the same as or an integral multiple of the distance in the Y direction of the landing position. By setting the distance between the adjacent two sets of nozzles in the Y direction to the same value as the distance in the Y direction of the drop positions or an integral multiple thereof, it is possible to perform forming processing for four rows at one time. The upper limit of the multiple is preferably 5 times, more preferably 3 times, and even more preferably 2 times, when the interval between two adjacent sets of nozzles is an integral multiple of the distance in the Y direction of the landing position. When the above-mentioned multiple exceeds the above-mentioned upper limit, processing which fills up between the columns becomes difficult, and there is a possibility that modeling accuracy may fall. On the other hand, the lower limit of the multiple is 1 which is equal to the interval in the Y direction.

  The method of manufacturing a three-dimensional structure using the three-dimensional structure forming apparatus including the head 7 includes a preparation process, a first liquid composition injection process, and a second liquid composition injection process. The manufacturing method of the three-dimensional structure is the three-dimensional structure of FIG. 1 except that processing of four rows is possible in one injection in the first liquid composition injection step and the second liquid composition injection step. Since it is the same as that of the manufacturing method of the three-dimensional modeling thing using a modeling device, detailed explanation is omitted.

<Advantage>
The three-dimensional modeling apparatus includes four sets of nozzles, and can be parallel to the support and arranged in the Y direction to perform four lines of modeling processing with one scan in the X direction. Therefore, the three-dimensional structure forming apparatus can increase the formation efficiency of the three-dimensional structure A.

Other Embodiments
The present invention is not limited to the above embodiment, and can be implemented in various modifications and improvements in addition to the above embodiment.

  Although the said embodiment demonstrated the case where two types of compositions, a 1st liquid composition and a 2nd liquid composition, were used, three or more types of compositions may be sufficient. The said three-dimensional shaping apparatus is equipped with the nozzle corresponding to the each kind, when a composition is 3 or more types.

  Although the case where the droplet ejection direction of the first nozzle and the second nozzle is perpendicular to the surface of the support table has been described in the above embodiment, the droplet ejection direction is not limited to this, and the first nozzle and the second nozzle As long as the droplet ejection directions of the two nozzles are parallel, they may not be perpendicular to the surface of the support. The angle between the first nozzle and the second nozzle with respect to the surface of the support in the droplet ejection direction is preferably 60 ° or more and 90 ° or less from the viewpoint of controllability of droplet deposition. Also, if the first nozzle and the second nozzle with respect to the droplet ejection direction have an angle of 90 ° with respect to the surface of the support, the droplet adheres while forming a parabola under the influence of gravity. It is good to control so that the injection speed of each droplet from 1 nozzle and the 2nd nozzle becomes the same. As a result, it is possible to easily make the positions where the droplets of the first liquid composition and the droplets of the second liquid composition adhere to coincide with each other.

  In the above embodiment, the drive unit moves the support in the X and Y directions. However, the head may be movable in the X and Y directions instead of the support.

  In the above embodiment, the control unit adjusts the height of the head. However, the height of the support may be adjusted instead of the head.

  In the above embodiment, the driving unit scans the droplet deposition position in the X direction in the X and Y directions orthogonal to one another in plan view, and moves the support and the nozzle relative to shift in the Y direction. The method of scanning the position is not limited to this, and it is also possible to scan concentrically, for example.

  Although the case where the 1st nozzle and the 2nd nozzle were arranged in the X direction was explained in the above-mentioned embodiment, the arrangement direction of the 1st nozzle and the 2nd nozzle is not limited to this, for example, even if arranged in the Y direction Good.

  Although the said 3rd embodiment demonstrated the case where the said three-dimensional modeling apparatus was equipped with four sets of nozzles, the number of sets of a nozzle is not limited to four, Even if it is two sets, three sets, or five sets or more Good. As a maximum of the number of sets of nozzles, 50 sets are preferable, 30 sets are more preferable, and 10 sets are more preferable. If the number of sets of nozzles exceeds the above upper limit, the number of nozzles not used increases depending on the cross-sectional shape of the three-dimensional structure to be formed (the shape of one hardened layer), and the improvement effect of the formation efficiency may not be sufficiently obtained is there.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples.

[Composition]
First, the following materials were prepared.
Urethane prepolymer: Urethane prepolymer contained in "L5299" of Mitsui Chemicals, Inc. (reaction product of polytetramethylene ether glycol (PTMG) and 4,4'-diphenylmethane diisocyanate (4,4'-MDI))
Polyisocyanate: 4,4'-MDI contained in "L5299" of Mitsui Chemicals, Inc.
Long-chain polyol: "TERATHANE (registered trademark) 1000" of INVISTA, polytetramethylene ether glycol (PTMG) polyol, number average molecular weight 1,000
Chain extender (short chain diol): Mitsubishi Chemical's "1,4 butanediol", 1,4 butanediol Crosslinking agent (short chain triol): Mitsubishi Gas Chemical's "trimethylolpropane", trimethylolpropane (TMP )
Catalyst: "Fomrez catalyst UL-28" from Momentive, Dimethyltin dilaurate Colorant: "UT BLUE 4867" from Sanyo Dye Co., Ltd., phthalocyanine-based blue pigment (CI Pigment Blue 15 (5.4% by mass) Oil-based processed pigment mixed with di-2-ethylhexyl adipate (94.6% by mass)

  Mitsui Chemicals, Inc. “L5299” containing urethane prepolymer and polyisocyanate was used as a first liquid composition. In addition, 73.97 parts by mass of a long chain polyol, 8.93 parts by mass of a chain extender, 3.8 parts by mass of a crosslinking agent, and 0.037 parts by mass of a catalyst. Stirring and mixing were performed for 1 minute and 30 seconds with a stirrer “Azita (registered trademark)”, and the obtained mixture was used as a second liquid composition. In addition, an appropriate amount of coloring agent was added to both the first liquid composition and the second liquid composition.

“L5299” is a product in which PTMG with a number average molecular weight of 1,000 and 4,4′-MDI with a molecular weight of 250 are reacted to adjust the isocyanate group content (NCO content) to 20 mass%. is there. Since the urethane prepolymer contained in this “L5299” is considered to consist mainly of 4,4′-MDI bonded to both ends of PTMG, the number average molecular weight is estimated to be about 1,500. Ru. Here, the isocyanate group content of “L5299” can be represented by the following formula (1). Assuming that the molecular weight of the isocyanate group in the following formula (1) is 42 and the number average molecular weight of the urethane prepolymer is 1,500, “L5299” has a content of urethane prepolymer of about 49% by mass, 4 The content of 4,4′-MDI is estimated to be about 51% by mass.
(Content of urethane prepolymer [mass%] × molecular weight of two isocyanate groups / number average molecular weight of urethane prepolymer) + (content of MDI [mass%] × molecular weight of two isocyanate groups / molecular weight of MDI ) = Isocyanate group content [mass%] (1)

Example 1
A forming process was performed according to the method for producing a three-dimensional structure using the three-dimensional structure shown in FIG. 1 to obtain a sheet-like three-dimensional structure. The diameters of the first and second nozzles of the three-dimensional modeling apparatus used are both 0.15 mm, and the distance between the nozzles (X direction) is 68 mm.

The mass ratio of the injection amount of the first liquid composition and the second liquid composition (first liquid composition: second liquid composition) was 100 parts by mass: 86.73 parts by mass. The injection condition is
Injection pressure: 0.1MPa
Liquid temperature: 25 ° C (normal temperature)
Support stand temperature: 25 ° C (normal temperature)
Injection time interval: 10 msec
Droplet mean volume: ~ 10 ⁴ pL
Distance between drop positions: X direction = 0.5 mm, Y direction = 0.25 mm
The drop diameter was 0.5 mm.

Example 2
The forming process is performed in the same manner as in Example 1 except that a head including four sets of two nozzles (first and second nozzles 71a and 71b) shown in FIG. 4 is used as a three-dimensional forming apparatus. I got a three-dimensional object. The interval between adjacent two sets of nozzles (Y direction) is 32 mm.

[Example 3]
A forming process was performed in the same manner as in Example 2 except that the nozzle diameters of the first and second nozzles of the three-dimensional modeling apparatus were both set to 0.08 mm, and a sheet-like three-dimensional model was obtained.

Comparative Example 1
As a three-dimensional modeling apparatus, a three-dimensional modeling apparatus in which the first nozzle and the second nozzle are not parallel was used. Specifically, in the three-dimensional shaping apparatus of Comparative Example 1, the angles of the first nozzle and the second nozzle with respect to the surface of the support in the droplet ejection direction are both 70 °, and the first nozzle and the second nozzle The angle of the droplet ejection direction of is 40 °. That is, the droplets are simultaneously ejected from the first nozzle and the second nozzle, and they are set so as to draw a V-shape and to collide at the landing position. A modeling process was performed in the same manner as in Example 1 except that this three-dimensional modeling apparatus was used, and a sheet-like three-dimensional model was obtained.

[Evaluation]
The following evaluation was performed on the obtained three-dimensional structure. The results are shown in Table 1.

<Specific gravity>
The specific gravity was calculated by dividing the mass (g) of the obtained three-dimensional structure by the volume (cm ³ ).

<Tensile characteristics>
Tensile properties are in accordance with JIS-K7312: 1996 “Physical test method for thermosetting polyurethane elastomer moldings”, and elongation modulus (M50) at 50% elongation of a three-dimensional structure, tensile strength (TB) and Elongation at break (EB) was measured.

<Appearance>
The appearance was visually evaluated for homogeneity, delamination and bleed out. Evaluation criteria are as follows.

(Homogeneity)
The homogeneity refers to the mixed state of the dropped first liquid composition and the second liquid composition. If not sufficiently mixed, a part of the three-dimensional structure is not sufficiently cured and becomes gelled. Therefore, it was judged that the homogeneity was inferior if part of the three-dimensional structure was gel-like.
A: Excellent in homogeneity.
B: Poor in homogeneity.

(Peeling)
Delamination refers to the presence or absence of delamination between the cured layers in the height direction of the three-dimensional structure. Delamination is less likely to occur if the upper layer is formed before the lower layer is sufficiently cured. From this, it can be seen that the shaping efficiency is high as no delamination is observed.
A: No delamination was observed.
B: Although slight delamination is observed, there is no problem in practical use. C: Delamination is observed.

(Bleed out)
The bleed-out refers to the presence or absence of the phenomenon in which the coloring agent floats on the surface of the three-dimensional structure. Bleed-out is less likely to occur when a colorant is incorporated in the three-dimensional network structure in the three-dimensional structure after curing. From this, when bleed-out has occurred, it can be judged that the coloring agent is not properly taken in at the time of curing, and curing failure occurs.
A: There is no bleed-out.
B: Bleeding out is permitted.

  From Table 1, the three-dimensional objects of Examples 1 to 3 modeled using the three-dimensional modeling apparatus in which the droplet ejection direction of the first nozzle and the second nozzle is perpendicular to the surface of the support table are: The tensile strength and the appearance are excellent as compared with the three-dimensional structure of Comparative Example 1 formed by using the three-dimensional structure forming device in which the first nozzle and the second nozzle are arranged to cause droplets to collide with each other.

  In more detail, the three-dimensional structures of Examples 1 to 3 have excellent tensile strength, particularly elongation at break (EB), and no bleeding is observed, so that curing defects do not occur. I understand. Moreover, since the three-dimensional structure of Example 1 to Example 3 is excellent in the homogeneity of the appearance, the first liquid composition and the second liquid composition on which the droplets are dropped are sufficiently mixed. I understand. Furthermore, since the three-dimensional structure of Examples 1 to 3 is in a range in which the occurrence of delamination is not observed or in the range in which there is no problem in practical use, it can be seen that the shaping efficiency is high.

  On the other hand, the three-dimensional structure of Comparative Example 1 mixes the first liquid composition and the second liquid composition by V-shaped collision, so it is difficult to uniformly mix them, and bleeding out and curing failure occur. it seems to do.

  From the above, by using the three-dimensional modeling apparatus and the three-dimensional model manufacturing method in which the droplet ejection direction of the first nozzle and the second nozzle is perpendicular to the surface of the support table, mixing of the two types of compositions It can be seen that a three-dimensional object is obtained which is easy to control and is excellent in homogeneity and curing characteristics.

  Moreover, when Example 1 and Example 2 are compared, the direction of the three-dimensional structure of Example 2 can suppress generation | occurrence | production of delamination. From this, it can be seen that, by providing a plurality of sets of nozzles, it is possible to perform multi-row formation processing in one X-direction scan, and therefore the formation efficiency of the three-dimensional object can be enhanced.

  Furthermore, when Example 2 and Example 3 which performed modeling by the three-dimensional modeling apparatus provided with several sets of nozzles are compared, the direction of the three-dimensional model of Example 3 is excellent in tensile strength. From this, it is understood that by setting the nozzle diameter to 0.1 mm or less, the modeling accuracy is improved and the tensile strength is excellent.

  As described above, by using the three-dimensional modeling apparatus and the three-dimensional model manufacturing method of the present invention, a plurality of compositions can be uniformly mixed by simple control, so that uniformity and curing characteristics can be easily achieved. An excellent three-dimensional structure is obtained.

DESCRIPTION OF SYMBOLS 1 base 2 support stand 3, 7 head 30, 70 head main body 30a, 70a 1st tank 30b, 70b 2nd tank 31a, 71a 1st nozzle 31b, 71b 2nd nozzle 4 drive part 4a 1st axial part 4b 2nd Shaft part 5 Control part 6 Head support part 6a Vertical support part 6b Horizontal support part 6c Height adjustment support part A Three-dimensional model A1 First liquid layer A2 Hardened layer B1, B2 Droplet

Claims (6)

A three-dimensional modeling apparatus using a plurality of compositions that react by mixing,
A plate-like support for supporting a three-dimensional object to be formed;
A plurality of nozzles that respectively eject droplets of the plurality of types of compositions;
A driving unit for relatively moving the support and the plurality of nozzles;
A control unit that controls the droplet deposition position so that droplets of the plurality of types of compositions are mixed on the support table;
The three-dimensional modeling apparatus in which the droplet ejection directions of the plurality of nozzles are parallel.   The three-dimensional shaping apparatus according to claim 1, wherein the droplet ejection direction of the plurality of nozzles is perpendicular to the surface of the support table. The driving unit scans the droplet deposition position in the X direction in the XY directions orthogonal to each other in plan view, and relatively moves the support and the plurality of nozzles so as to shift in the Y direction.
The three-dimensional shaping apparatus according to claim 1 or 2, wherein the plurality of nozzle arrangement directions are X directions. Equipped with multiple sets of the above multiple nozzles,
The three-dimensional shaping apparatus according to claim 3, wherein the plurality of sets of nozzles are disposed in parallel to the support and in the Y direction. A method for producing a three-dimensional structure using a plurality of compositions that react by mixing,
Ejecting droplets of the first composition from the first nozzle toward the support;
Ejecting droplets of the other composition from the second nozzle toward the droplets of the first liquid composition deposited in the first liquid composition injecting step;
The manufacturing method of the three-dimensional molded article whose droplet ejection direction of said 1st nozzle and the droplet ejection direction of said 2nd nozzle are parallel. The plurality of types of compositions are two types of a first liquid composition and a second liquid composition,
The first liquid composition comprises a prepolymer of at least one of a urethane prepolymer, a urethane urea prepolymer and a urea prepolymer, and a polyisocyanate.
The second liquid composition according to claim 5, comprising at least one soft segment component of long chain polyol and long chain polyamine and at least one hard segment component of a chain extender and a crosslinking agent. A method of manufacturing a three-dimensional object.

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