JP6413286B2 - Manufacturing method of three-dimensional structure - Google Patents

Description

The present invention relates to the production how the 3D object.

  Conventionally, for example, a method of forming a three-dimensional structure based on a model of a three-dimensional object generated by three-dimensional CAD software or the like is known.

  As one of methods for forming a three-dimensional structure, a lamination method is known (for example, see Patent Document 1). In the laminating method, generally, after a model of a three-dimensional object is divided into a number of two-dimensional cross-sectional layers, the cross-sectional members corresponding to each two-dimensional cross-sectional layer are sequentially formed, and the cross-sectional members are sequentially laminated to obtain the tertiary Form the original model.

  The lamination method can be formed immediately as long as there is a model of the 3D model to be modeled, and there is no need to create a mold prior to modeling. It is possible to form a shaped object. In addition, since thin plate-like cross-sectional members are laminated one by one, for example, even a complex object having an internal structure can be formed as an integrated shaped object without being divided into a plurality of parts. .

  By the way, in the conventional method, a plane image obtained by dividing the three-dimensional data of the three-dimensional structure is formed by inkjet drawing and laminating, and the model is formed, but the inkjet apparatus draws dots defined by the XY coordinates. While the boundary surface parallel to the feed or scan direction is smooth, the step between dots (jaggy) due to the XY resolution is conspicuous on the oblique boundary surface, especially the acute angle surface with respect to the feed or scan direction. Depending on the shape of the object, there is a problem that the quality is poor.

JP 2000-280354 A

An object of the present invention is relaxed between dots step is a manufacturing method of a three-dimensional shaped object can be produced with high 3D object in quality and provide child.

Such an object is achieved by the present invention described below.
The method for producing a three-dimensional structure of the present invention is a method for producing a three-dimensional structure by producing a three-dimensional structure by laminating layers,
A step of creating the three-dimensional data B of the layer from the three-dimensional data A of the three-dimensional structure;
Converting the three-dimensional data B into bitmap data of a predetermined resolution, further performing a smoothing process, and creating smoothing process data of the layer;
A first gradation dots gradation representation of the smoothing processing data, and contact with the inside of the first gradation dot the layer, and a first adjacent dots present in the interior of the layer, the smoothing processing data Generating data thinned out as main part main data;
Main data is composed of data in which the first gradation dot is arranged at a position where the first adjacent dot is present and data in which the first adjacent dot is arranged as it is at a position where the first adjacent dot is present Generating as sub-sub data;
Reversing the gradation of the first gradation dot and the area on the surface side of the three-dimensional structure in the smoothing processing data, and creating gradation reversal data;
In the gradation inversion data, a second gradation dot obtained by reversing the gradation of the first gradation dot, and a second adjacent dot that is in contact with the second gradation dot on the side opposite to the first adjacent dot , Storing the data thinned out from the gradation inversion data as sacrifice part main data;
Sacrificial data composed of data in which the second gradation dot is arranged at the position where the second adjacent dot is present and data in which the second adjacent dot is arranged as it is at the position where the second adjacent dot is present A step of saving as sub-data;
Forming a main body main data layer using main body forming ink based on the main body main data ;
Forming a sacrificial portion main data layer using a sacrificial portion forming ink based on the sacrificial portion main data ;
A step of discharging the main body forming ink based on the main body sub data;
Based on the sacrificial portion sub data, have a, a step of discharging the sacrificial portion forming ink,
When ejecting the main body forming ink, when the density of the first gradation dot of the main body sub data is 100% when the density of one dot of the main body main data is 100%, The discharge amount of the main body portion forming ink discharged to the first gradation dot portion is controlled to be reduced to X%, and when the sacrifice portion forming ink is discharged, the density of one dot of the sacrifice portion main data When the density of the second gradation dot of the sacrificial portion sub-data when Y is 100% is Y%, the discharge amount of the sacrificial portion forming ink discharged to the second gradation dot portion is Y. It is characterized by controlling to reduce to% .

  Thereby, the manufacturing method of the three-dimensional structure which can relieve the level | step difference between dots and can manufacture a high-quality three-dimensional structure can be provided.

In the three-dimensional structure manufacturing method of the present invention, after forming the main body main data layer and the sacrificial main data layer, the main body main data layer and the sacrificial main data layer are cured, It is preferable that the main body portion forming ink and the sacrificial portion forming ink are ejected to a thinned portion of the main body portion main data layer and the sacrificial portion main data layer.
Thereby, the level | step difference between dots can be relieve | moderated more effectively.

In the three-dimensional structure manufacturing method of the present invention, it is preferable that the main body portion forming ink and the sacrificial portion forming ink contain a photocurable resin.
In the three-dimensional structure manufacturing method of the present invention, the viscosity of the main body portion forming ink and the sacrificial portion forming ink is preferably 10 mPa · s or more and 30 mPa · s or less.

It is the elements on larger scale of the bitmap data of the layer which comprises the three-dimensional structure to be formed. It is the elements on larger scale of the smoothing process data of the layer obtained by performing the smoothing process to the bitmap data of FIG. FIG. 3 is a partially enlarged plan view of gradation reversal data obtained by reversing gradation of a first gradation dot and a region on the surface side of a three-dimensional structure in the smoothing processing data of FIG. 2. It is a partial enlarged plan view of main part main data. It is a partial enlarged plan view of sacrifice part main data. It is the elements on larger scale of main part sub data. It is the elements on larger scale of sacrificial part subdata. It is the elements on larger scale of a main-body part main data layer and a sacrifice part main data layer. It is the elements on larger scale of the formed layer.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1. First, a method for creating three-dimensional modeling data will be described.

  The method for creating data for three-dimensional modeling is used in a method for manufacturing a three-dimensional modeled object in which a three-dimensional modeled object is manufactured by stacking layers.

  FIG. 1 is a partially enlarged plan view of bitmap data of a layer constituting a three-dimensional structure to be formed. FIG. 2 is a portion of smoothing processing data of a layer obtained by subjecting the bitmap data of FIG. 1 to smoothing processing. FIG. 3 is an enlarged plan view, FIG. 3 is a partially enlarged plan view of gradation inversion data obtained by gradation inversion of the first gradation dot and the surface side of the three-dimensional structure in the smoothing processing data of FIG. FIG. 5 is a partially enlarged plan view of the sacrifice part main data, FIG. 6 is a partially enlarged plan view of the body part sub data, and FIG. 7 is a partially enlarged plan view of the sacrifice part sub data. 8 is a partially enlarged plan view of the main part main data layer and the sacrifice part main data layer, and FIG. 9 is a partially enlarged plan view of the formed layer. In each figure, the direction perpendicular to the paper surface is the layer thickness direction.

  The method for creating 3D modeling data according to the present embodiment includes a step of creating 3D data B of a layer from 3D data A of a 3D model to be manufactured, and the created 3D data B having a predetermined resolution. Converting to bitmap data 10 and further performing a smoothing process to create layer smoothing process data 11.

  In addition, the method for creating 3D modeling data according to the present embodiment is in contact with the first gradation dot (2A, 2B, 2C) expressed by gradation of the smoothing processing data 11 and the gradation dot inside the layer. In the process of storing the data obtained by thinning out the first adjacent dots 3 from the smoothing processing data 11 as the main body main data 12, the thinned first gradation dots (2A, 2B, 2C) and the first adjacent dots 3 And storing the configured data as the main body sub-data 13.

  In addition, in the method for creating 3D modeling data according to the present embodiment, the first gradation dot (2A, 2B, 2C) and the region on the surface side of the three-dimensional structure in the smoothing processing data 11 are inverted in gradation. , The step of creating the gradation inversion data 41, the second gradation dot (4A, 4B, 4C) obtained by reversing the gradation of the first gradation dot (2A, 2B, 2C), and the second gradation dot (4A). 4B, 4C) and the second adjacent dot 5 that is in contact with the opposite side of the layer, the step of saving the data thinned out from the gradation inversion data 41 as the sacrifice part main data 42, and the thinned second gradation dot ( 4A, 4B, 4C) and the data composed of the second adjacent dots 5 are stored as the sacrifice portion sub-data 43.

  By manufacturing a three-dimensional structure using the three-dimensional structure data created in this way, a step between dots (jaggy) can be relaxed and a high-quality three-dimensional structure can be obtained.

Details will be described below.
[Create bitmap data]
First, a three-dimensional model (three-dimensional data A) of a three-dimensional structure to be manufactured is created with three-dimensional CAD software or the like. The three-dimensional data A is a file generated by three-dimensional CAD or CG software that represents a solid in a predetermined format such as STL, OBJ, or IGES. As an example, when the three-dimensional model data is an STL format file, the three-dimensional data A represents a solid by a set of triangles having three vertices (coordinate values).

Next, the created three-dimensional data A is divided into a plurality of two-dimensional cross-sectional layer three-dimensional data B.
Next, as shown in FIG. 1, each obtained three-dimensional data B is converted into bitmap data 10 having a predetermined resolution. The bitmap data 10 is composed of a plurality of dots (normal dots) 1.

  Here, the predetermined resolution is determined by a resolution that can be drawn by an apparatus used for manufacturing a three-dimensional structure.

[Create smoothing processing data and gradation inversion data]
Next, smoothing processing is performed on the formed bitmap data 10. As a result, smoothing processing data 11 composed of the first gradation dots (2A, 2B, 2C) and the normal dots 1 as shown in FIG.

  In the present embodiment, the smoothing processing data 11 is expressed by four gray scale gradations. The normal dot 1 has a 100% density, the first gradation dot 2A has a 75% density, and the first gradation dot 2B. Is expressed at 50% density, and the first gradation dot 2C is expressed at 25% density.

  Furthermore, the first smoothing dot (2A, 2B, 2C) of the obtained smoothing processing data 11 and the area on the surface side of the three-dimensional structure (the white area on the upper side in FIG. 2) are inverted in gradation. Then, gradation inversion data 41 as shown in FIG. 3 is obtained. As shown in FIG. 3, the gradation inversion data 41 includes second gradation dots (4A, 4B, 4C) and normal dots. The second gradation dot 4A is expressed with 75% density, the second gradation dot 4B is expressed with 50% density, and the second gradation dot 4C is expressed with 25% density.

[Create main unit main data and main unit sub data]
Next, data obtained by thinning out the first gradation dots (2A, 2B, 2C) of the formed smoothing processing data 11 and the first adjacent dots 3 adjacent to the gradation dots inside the layer (see FIG. 4). ) And is stored as main body main data 12. Here, the main body refers to a substance part of the three-dimensional structure.

  On the other hand, the data (see FIG. 6) composed of the first gradation dots (2A, 2B, 2C) and the first adjacent dots 3 thinned out from the smoothing processing data 11 is stored as the main body sub data 13. In the present embodiment, the data in which the first gradation dots (2A, 2B, 2C) are arranged at the position where the first adjacent dot 3 was present is used as the first adjacency at the position where the sub data 13A and the first adjacent dot 3 were present. Data in which the dots 3 are arranged is stored as sub data 13B.

[Creation of sacrifice part main data and sacrifice part sub-data]
On the other hand, the second gradation dot (4A, 4B, 4C) of the formed gradation inversion data 41, and the gradation dot and the second gradation dot (4A, 4B, 4C) are in contact with the layer on the opposite side. Data (refer to FIG. 5) in which two adjacent dots 5 are thinned out is created and saved as the sacrifice part main data 42. Here, a sacrificial part refers to what is provided in the area | region of the surface side of the three-dimensional structure to form, assists modeling of a three-dimensional structure, and is finally removed.

  On the other hand, the data (see FIG. 7) composed of the second gradation dots (4A, 4B, 4C) and the second adjacent dots 5 thinned out from the gradation inversion data 41 is stored as the sacrifice portion sub-data 43. . In the present embodiment, the data in which the second gradation dots (4A, 4B, 4C) are arranged at the position where the second adjacent dot 5 was present is used as it is at the position where the sub data 43A and the second adjacent dot 5 were present. Data in which the dots 5 are arranged is stored as sub data 43B.

  Based on the 3D modeling data composed of the main body main data 12, the main body sub data 13, the sacrificial main data 42, and the sacrificial sub data 43, the three-dimensional structure is manufactured. Do. By using such three-dimensional modeling data, the step between dots (jaggy) can be relaxed, and a high-quality three-dimensional model can be manufactured.

2. Next, a method for manufacturing a three-dimensional structure will be described.

  The manufacturing method of the three-dimensional structure according to the present embodiment includes the main body main data 12, the main body sub data 13, the sacrificial main data 42, and the sacrificial sub data obtained by the above-described three-dimensional modeling data creation method. A three-dimensional structure is manufactured by stacking the layers formed using the data 43.

  Specifically, the manufacturing method of the three-dimensional structure according to the present embodiment uses the main body portion forming data and the sacrificial portion forming ink based on the main body portion main data 12 and the sacrificial portion main data 42, and the main body portion main data. A first ejection step for forming the data layer 15 and the sacrifice portion main data layer 45 (see FIG. 8), a first curing step for hardening the main portion main data layer 15 and the sacrifice portion main data layer 45, and main portion main data. In the layer 15 and the sacrificial part main data layer 45, a portion (a recessed part 151 and a part between the main part main data layer 15 and the sacrificial part main data layer 45) that is thinned based on the main body sub data 13 and the sacrificial part sub data 43. A second ejection step of ejecting the body portion forming ink and the sacrificial portion forming ink to the recessed portion 451), and curing the body portion forming ink and the sacrificial portion forming ink ejected to the recessed portion 151 and the recessed portion 451; A second curing step of forming a (unit layer), the.

Hereinafter, each step will be described in detail.
[First discharge process]
First, based on the main body main data 12 and the sacrificial part main data 42, the main body forming ink and the sacrificial part forming ink are ejected by the ink jet method, and the main body main body including the recessed portion 151 as shown in FIG. A sacrificial portion main data layer 45 including the data layer 15 and the recessed portion 451 is formed (first ejection step).

  As the ink jet method, a piezo method or a method in which ink is ejected by bubbles generated by heating the ink can be used. However, from the viewpoint of difficulty in changing the constituent components of the ink, the piezo method is used. The method is preferred.

[First curing step]
Next, the curing component contained in the main body main data layer 15 and the sacrifice main data layer 45 is cured. By curing the main body main data layer 15 and the sacrificial main data layer 45 before the second ejection step, the main body forming ink for the main body sub data 13 is wetted along the wall surface inside the recessed portion 151. It becomes easy to spread, and the sacrificial portion forming ink for the sacrificial portion sub-data 43 easily spreads along the wall surface inside the recessed portion 451.

  This step varies depending on the type of curable component (curable resin). For example, when the curable component (curable resin) is a thermosetting resin, it can be performed by heating, and the curable component (curable resin) is light. In the case of a curable resin, it can be performed by irradiation with the corresponding light (for example, when the curable component (curable resin) is an ultraviolet curable resin, it can be performed by irradiation with ultraviolet rays).

[Second discharge process]
Next, on the basis of the main body sub-data 13, the main body portion is formed with the total amount of the discharge amount of the gradation dots and the discharge amount of the adjacent dots at the coordinates of the adjacent dots 3 inside the recessed portion 151 of the main body main data layer 15. Ink is ejected by the ink jet method, and based on the sacrifice portion sub-data 43, the total amount of the discharge amount of the gradation dot and the discharge amount of the adjacent dot at the coordinates of the adjacent dot 5 inside the recessed portion 451 of the sacrifice portion main data layer 45 The sacrificial portion forming ink is ejected by an ink jet method.

  In this step, the main body forming ink and the sacrificial forming ink are ejected almost simultaneously. As a result, it is possible to fill the region surrounded by the recessed portion 151 and the recessed portion 451 while forming an interface between the main body portion forming ink and the sacrificial portion forming ink. As a result, the dot step can be more easily mitigated.

  Further, in this step, the discharge amount of the main body forming ink and the sacrificial portion forming ink discharged to each concave portion 151 and each concave portion 451 is set to the gradation of the gradation of the main body sub data 13 and the sacrifice portion sub data 43. Control by degree. Thereby, the interface between the main body portion forming ink and the sacrificial portion forming ink is formed so as to relieve the dot level difference, and as a result, a high-quality three-dimensional structure can be manufactured. Further, it is possible to prevent the discharged main body portion forming ink and sacrificial portion forming ink from overflowing from the region surrounded by the recessed portion 151 and the recessed portion 451.

  The control of the discharge amount of the main body forming ink by the density of the first gradation dot in the main body sub-data 13 is that the density of the first gradation dot is X% when the density of the normal dot 1 is 100%. In this case, control is performed so that the discharge amount of the main body forming ink discharged to the first gradation dot portion is reduced to X%.

  Further, the control of the ejection amount of the sacrifice portion forming ink by the density of the second gradation dot of the sacrifice portion sub-data 43 is the second gradation when the density of one dot of the sacrifice portion main data 42 is 100%. When the dot density is Y%, control is performed to reduce the discharge amount of the sacrifice portion forming ink discharged to the second gradation dot portion to Y%.

  More specifically, the discharge amount in the case of the first gradation dot 2A (density 75%) and the second gradation dot 4A (density 75%) is 75, which is the amount discharged to the normal dot 1 (density 100%). %, The discharge amount in the case of the first gradation dot 2B (density 50%) and the second gradation dot 4B (density 50%) is 50% of the amount discharged to the normal dot 1, and the first gradation dot The discharge amount in the case of 2C (density 25%) and the second gradation dot 4C (density 25%) is controlled to be 25% of the amount discharged to the normal dot 1. In addition, in the case of the 1st adjacent dot 3 and the 2nd adjacent dot 5, the same amount as the amount discharged to the normal dot 1 is discharged.

  Then, the main body forming ink of the total amount of the ejection amount of the first gradation dot and the ejection amount of the first adjacent dot is ejected into each recess portion 121, and the second gradation dot is ejected into each recess portion 451. The sacrificial part forming ink is ejected in the total amount of the ejection amount of the second adjacent dots and the ejection amount of the second adjacent dots.

[Second curing step]
Next, the body portion forming ink and the sacrificial portion forming ink discharged to the recessed portion 121 and the recessed portion 451 are cured to obtain the layer 14.

  And by repeating the said process, after laminating | stacking the layer 14, the three-dimensional molded item is obtained by removing the part which the sacrificial part 44 laminated | stacked.

3. Main body forming ink The main body forming ink contains at least a curable resin (curing component).

(Curable resin)
Examples of the curable resin (curing component) include a thermosetting resin; a visible light curable resin (narrowly defined photocurable resin) that is cured by light in the visible light region, an ultraviolet curable resin, an infrared curable resin, and the like. Various photo-curable resins; X-ray curable resins and the like can be mentioned, and one or two or more selected from these can be used in combination.

  Among these, UV curable resins (polymerizable compounds) are particularly preferable from the viewpoints of mechanical strength of the obtained three-dimensional structure, productivity of the three-dimensional structure, storage stability of the ink for forming the main body, and the like.

  As the ultraviolet curable resin (polymerizable compound), a resin in which addition polymerization or ring-opening polymerization is initiated by irradiation with ultraviolet rays by radical species or cationic species generated from a photopolymerization initiator, and a polymer is preferably used. . Examples of the polymerization mode of addition polymerization include radical, cation, anion, metathesis, and coordination polymerization. Examples of the ring-opening polymerization method include cation, anion, radical, metathesis, and coordination polymerization.

  Examples of the addition polymerizable compound include compounds having at least one ethylenically unsaturated double bond. As the addition polymerizable compound, a compound having at least one, preferably two or more terminal ethylenically unsaturated bonds can be preferably used.

  The ethylenically unsaturated polymerizable compound has a chemical form of a monofunctional polymerizable compound and a polyfunctional polymerizable compound, or a mixture thereof.

  Examples of the monofunctional polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like.

  As the polyfunctional polymerizable compound, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic amine compound is used.

  In addition, unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl group, amino group, mercapto group and the like, addition products of isocyanates and epoxies, dehydration condensation products of carboxylic acids, etc. Can be used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with alcohols, amines and thiols, as well as removal of halogen groups, tosyloxy groups, etc. A substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasing substituent and an alcohol, amine or thiol can also be used.

  Specific examples of the radical polymerizable compound that is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound include, for example, (meth) acrylic acid ester, which is either monofunctional or polyfunctional. Can also be used.

  Specific examples of the monofunctional (meth) acrylate include, for example, tolyloxyethyl (meth) acrylate, phenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, isobornyl (Meth) acrylate, dipropylene glycol di (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2-hydroxy- Examples include 3-phenoxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

  Specific examples of the bifunctional (meth) acrylate include, for example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, penta Examples include erythritol di (meth) acrylate and dipentaerythritol di (meth) acrylate.

  Specific examples of the trifunctional (meth) acrylate include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((Meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri ( Data) acrylate, and the like.

  Specific examples of the tetrafunctional (meth) acrylate include, for example, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, Examples include ethoxylated pentaerythritol tetra (meth) acrylate.

  Specific examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Specific examples of the hexafunctional (meth) acrylate include, for example, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, captolactone-modified dipentaerythritol hexa ( And (meth) acrylate.

  Examples of the polymerizable compound other than (meth) acrylate include itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester and the like.

  Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diesterate. Examples include itaconate and sorbitol tetritaconate.

  Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

  Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5240, Japanese Patent Application Laid-Open No. 59-5241, Japanese Patent Application Laid-Open No. 2-226149, and those containing an amino group described in Japanese Patent Application Laid-Open No. 1-165613 are also used. be able to.

  Specific examples of the amide monomer of unsaturated carboxylic acid and aliphatic amine compound include, for example, methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, (meth) acryloylmorpholine and the like.

  Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, a urethane-based addition polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable. As such a specific example, for example, one molecule described in JP-B-48-41708 A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (1) to a polyisocyanate compound having two or more isocyanate groups. Etc.

^{_{CH 2 = C (R 1)}} COOCH 2 CH (R 2) OH (1)
(However, in formula (1), R ¹ and R ² each independently represent H or CH ^3. )

  In the present invention, a cationic ring-opening polymerizable compound having at least one cyclic ether group such as an epoxy group or an oxetane group in the molecule can be suitably used as the ultraviolet curable resin (polymerizable compound).

  Examples of the cationic polymerizable compound include a curable compound containing a ring-opening polymerizable group, and among them, a heterocyclic group-containing curable compound is particularly preferable. Such curable compounds include, for example, epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, cyclic imino ethers such as oxazoline derivatives, vinyl ethers, etc. Among them, epoxy derivatives, oxetanes, etc. Derivatives and vinyl ethers are preferred.

  Examples of preferred epoxy derivatives include monofunctional glycidyl ethers, polyfunctional glycidyl ethers, monofunctional alicyclic epoxies, polyfunctional alicyclic epoxies, and the like.

  Specific examples of glycidyl ethers include, for example, diglycidyl ethers (for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, etc.), tri- or more functional glycidyl ethers (for example, trimethylolethane triglycidyl). Ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.), tetra- or higher functional glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, poly of cresol novolac resin) Glycidyl ether, polyglycidyl ether of phenol novolac resin, etc.), alicyclic epoxies (eg, Celoxide 2) 21P, Celoxide 2081, Epolide GT-301, Epolide GT-401 (manufactured by Daicel Chemical Industries, Ltd.), EHPE (manufactured by Daicel Chemical Industries, Ltd.), polycyclohexyl epoxy methyl ether of phenol novolac resin, etc. Oxetanes (for example, OX-SQ, PNOX-1009 (above, manufactured by Toagosei Co., Ltd.)) and the like.

  As the polymerizable compound, an alicyclic epoxy derivative can be preferably used. The “alicyclic epoxy group” refers to a partial structure obtained by epoxidizing a double bond of a cycloalkene ring such as a cyclopentene group or a cyclohexene group with an appropriate oxidizing agent such as hydrogen peroxide or peracid.

  The alicyclic epoxy compound is preferably a polyfunctional alicyclic epoxy having two or more cyclohexene oxide groups or cyclopentene oxide groups in one molecule. Specific examples of the alicyclic epoxy compound include, for example, 4-vinylcyclohexylene dioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, di (3,4-epoxycyclohexyl) adipate, Examples include di (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, di (2,3-epoxy-6-methylcyclohexylmethyl) adipate, and dicyclopentadiene dioxide.

  The glycidyl compound which has a normal epoxy group which does not have an alicyclic structure in a molecule | numerator can be used independently, or can also be used together with the said alicyclic epoxy compound.

  Examples of such normal glycidyl compounds include glycidyl ether compounds and glycidyl ester compounds, but it is preferable to use glycidyl ether compounds in combination.

  Specific examples of the glycidyl ether compound include 1,3-bis (2,3-epoxypropyloxy) benzene, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac. Glycidyl ether compounds such as epoxy resin, trisphenol methane epoxy resin, aliphatic glycidyl ethers such as 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane tritriglycidyl ether Compounds and the like. Examples of the glycidyl ester include a glycidyl ester of linolenic acid dimer.

  As the polymerizable compound, a compound having an oxetanyl group which is a 4-membered cyclic ether (hereinafter, also simply referred to as “oxetane compound”) can be used. An oxetanyl group-containing compound is a compound having one or more oxetanyl groups in one molecule.

  Among the above-mentioned curing components, the ink for forming the main body part is, in particular, (meth) acrylic acid 2- (2-vinyloxyethoxy) ethyl, polyether aliphatic urethane (meth) acrylate oligomer, 2-hydroxy-3- It is preferable to include one or more selected from the group consisting of phenoxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. As a result, the ink for forming the main body portion can be cured at a more appropriate curing rate, and the productivity of the three-dimensional structure can be made particularly excellent.

Further, the strength, durability, and reliability of the three-dimensional structure can be made particularly excellent.
Further, by including these curing components, the solubility and swelling property of the cured product of the main body forming ink in various solvents (for example, water) can be made particularly low. As a result, when removing the sacrificial part, the sacrificial part can be more reliably removed with high selectivity, and unintentional deformation caused by a defect in the three-dimensional structure can be prevented. it can. As a result, the dimensional accuracy of the three-dimensional structure can be increased more reliably.

  In addition, since the swellability (solvent absorbability) of the cured product of the main body portion forming ink can be reduced, for example, the drying process as a post-treatment after removing the sacrificial part can be omitted or simplified. it can. Moreover, since the solvent resistance of the finally obtained three-dimensional structure is improved, the reliability of the three-dimensional structure is particularly high.

  In particular, when the main body forming ink contains 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, it is difficult to be inhibited by oxygen and can be cured at low energy, and other monomers are included. The effect of accelerating copolymerization and increasing the strength of the shaped article can be obtained.

  Moreover, the effect that the high intensity | strength and high toughness of a molded article are made compatible is acquired as the main body part formation ink contains a polyether aliphatic urethane (meth) acrylate oligomer.

  Further, when the main body portion forming ink contains 2-hydroxy-3-phenoxypropyl (meth) acrylate, an effect of improving flexibility and elongation at break can be obtained.

  In addition, if the ink for forming the main body part contains 4-hydroxybutyl (meth) acrylate, the effect of increasing the strength of the molded article by improving the adhesion to PMMA, PEMA particles, silica particles, metal particles, and the like. Is obtained.

  The ink for forming the main body is the specific curing component described above (2- (2-vinyloxyethoxy) ethyl (meth) acrylate, polyether aliphatic urethane (meth) acrylate oligomer), 2-hydroxy-3-phenoxypropyl ( (1) or two or more selected from the group consisting of (meth) acrylate and 4-hydroxybutyl (meth) acrylate), the specific curing component for all curing components constituting the main body forming ink The ratio is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass. Thereby, the effects as described above are more remarkably exhibited.

  The content of the curing component in the main body forming ink is preferably 80% by mass or more and 97% by mass or less, and more preferably 85% by mass or more and 95% by mass or less.

  Thereby, the mechanical strength of the finally obtained three-dimensional structure can be made particularly excellent. In addition, the productivity of the three-dimensional structure can be made particularly excellent.

(Polymerization initiator)
The main body forming ink preferably contains a polymerization initiator.

  Thereby, the cure rate of the ink for forming the main body part at the time of manufacturing the three-dimensional structure can be increased, and the productivity of the three-dimensional structure can be made particularly excellent.

  Examples of the polymerization initiator include photo radical polymerization initiators (aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds), hexaary, and the like. A rubiimidazole compound, a ketoxime ester compound, a borate compound, an azinium compound, a metallocene compound, an active ester compound, a compound having a carbon halogen bond, an alkylamine compound, etc.), a photocationic polymerization initiator, etc. Are acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethyl And azoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like. One kind or a combination of two or more kinds can be used.

  Among them, the polymerization initiator constituting the main body forming ink includes bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Is preferred.

  By including such a polymerization initiator, the ink for forming the main body can be cured at a more appropriate curing rate, and the productivity of the three-dimensional structure can be made particularly excellent. Further, the strength, durability, and reliability of the three-dimensional structure can be made particularly excellent.

  In particular, when the ink for forming the main body part contains bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide as a polymerization initiator together with the ink for forming the sacrificial part described in detail later, With respect to the ink and the sacrificial portion forming ink, the curing rate can be controlled more suitably, and the productivity of the three-dimensional structure can be further improved.

  In the case where the main body portion forming ink contains bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide as a polymerization initiator together with the sacrificial portion forming ink described in detail later, The content of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide in the ink is more than the content of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide in the sacrificial part forming ink. It is preferably high.

  Thereby, the main body portion forming ink and the sacrificial portion forming ink can be cured at a more suitable speed.

  The content of the polymerization initiator in the main body forming ink is not particularly limited, but is preferably higher than the content of the polymerization initiator in the sacrificial portion forming ink.

  Thereby, the main body portion forming ink and the sacrificial portion forming ink can be cured at a more suitable speed.

  In addition, for example, by adjusting the processing conditions of the curing process, the degree of polymerization of the sacrificial portion may be relatively low after the curing process is completed, while the degree of curing of the three-dimensional structure is sufficiently high. it can. As a result, the sacrificial part can be removed more easily, and the productivity of the three-dimensional structure can be made particularly excellent.

  Moreover, since it is not necessary to raise the energy dose irradiated more than necessary, it is preferable also from a viewpoint of energy saving.

In particular, when the content of the polymerization initiator in the main body portion forming ink is X ₁ [mass%] and the content of the polymerization initiator in the sacrificial portion forming ink is X ₂ [mass%], 1.05 It is preferable to satisfy the relationship of ≦ X ₁ / X ₂ ≦ 2.0, and it is more preferable to satisfy the relationship of 1.1 ≦ X ₁ / X ₂ ≦ 1.5. Thereby, the main body portion forming ink and the sacrificial portion forming ink can be cured at a more suitable speed, respectively, and the productivity of the three-dimensional structure can be further improved.

  The specific value of the content of the polymerization initiator in the main body forming ink is preferably 3.0% by mass or more and 18% by mass or less, and more preferably 5.0% by mass or more and 15% by mass or less. Is more preferable. Thereby, the ink for forming the main body portion can be cured at a more appropriate curing rate, and the productivity of the three-dimensional structure can be made particularly excellent. Further, the mechanical strength and shape stability of the three-dimensional structure formed by curing the main body forming ink can be made particularly excellent. As a result, the strength, durability, and reliability of the three-dimensional structure can be made particularly excellent.

  Preferred examples of the mixing ratio of the curable resin and the polymerization initiator in the main body forming ink (ink composition excluding “other components” described below) are shown below. It goes without saying that the composition of is not limited to those described below.

"Example of blending ratio"
-2- (2-vinyloxyethoxy) ethyl acrylate: 32 parts by mass-Polyether aliphatic urethane acrylate oligomer: 10 parts by mass-2-hydroxy-3-phenoxypropyl acrylate: 13.75 parts by mass-Dipropylene glycol Diacrylate: 15 parts by mass, 4-hydroxybutyl acrylate: 20 parts by mass, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: 5 parts by mass, 2,4,6-trimethylbenzoyl-diphenyl-phos Fin oxide: 4 parts by mass In the case of the above blending, the effects as described above are more remarkably exhibited.

(Other ingredients)
Further, the main body forming ink may contain components other than those described above.

  Examples of such components include various colorants such as pigments and dyes, dispersants, surfactants, sensitizers, polymerization accelerators, solvents, penetration accelerators, wetting agents (humectants), fixing agents, and prevention agents. Examples include glazes; antiseptics; antioxidants; ultraviolet absorbers; chelating agents; pH adjusters; thickeners; fillers;

  In particular, when the main body forming ink contains a colorant, a three-dimensional structure colored in a color corresponding to the color of the colorant can be obtained.

  In particular, by including a pigment as the colorant, the light resistance of the main body forming ink and the three-dimensional structure can be improved. As the pigment, either an inorganic pigment or an organic pigment can be used.

Examples of the inorganic pigment include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, iron oxide, titanium oxide, and the like, and one kind selected from these. Alternatively, two or more kinds can be used in combination.
Among the inorganic pigments, titanium oxide is preferable in order to exhibit a preferable white color.

  Examples of the organic pigment include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, Daylight fluorescent pigments and the like can be mentioned, and one or more selected from these can be used in combination.

  More specifically, as carbon black used as a black (black) pigment, for example, No. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B and the like (manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (and above, manufactured by Columbia Columbia), Regal 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (above, manufactured by CABOT JAPAN K. C. Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6S Degussa)).

  Examples of white pigments include C.I. I. Pigment white 6, 18, 21 and the like.

  Examples of yellow (yellow) pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, 180 and the like.

  Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

  Examples of the violet (cyan) pigment include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, C.I. I. Bat Blue 4, 60 and the like.

  Examples of other pigments include C.I. I. Pigment green 7,10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, and the like.

  When the main body forming ink contains a pigment, the average particle diameter of the pigment is preferably 300 nm or less, and more preferably 50 nm or more and 250 nm or less.

  Thereby, the discharge stability of the ink for forming the main body part and the dispersion stability of the pigment in the ink for forming the main body part can be made particularly excellent, and an image with better image quality can be formed.

  Examples of the dye include acid dyes, direct dyes, reactive dyes, basic dyes, and the like, and one or more selected from these can be used in combination.

  Specific examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive black 3, 4, 35 etc. are mentioned.

  When the main body forming ink contains a colorant, the content of the coloring agent in the main body forming ink is preferably 1% by mass or more and 20% by mass or less. Thereby, particularly excellent concealability and color reproducibility can be obtained.

  In particular, when the main body forming ink contains titanium oxide as a colorant, the content of titanium oxide in the main body forming ink is preferably 12% by mass or more and 18% by mass or less, and 14% by mass. More preferably, it is 16 mass% or less. Thereby, a particularly excellent concealing property is obtained.

  When the main body portion forming ink contains a pigment, the dispersibility of the pigment can be further improved by further containing a dispersant.

  Although it does not specifically limit as a dispersing agent, For example, the dispersing agent currently used in preparing pigment dispersion liquids, such as a polymer dispersing agent, is mentioned.

  Specific examples of the polymer dispersant include, for example, polyoxyalkylene polyalkylene polyamine, vinyl polymer and copolymer, acrylic polymer and copolymer, polyester, polyamide, polyimide, polyurethane, amino polymer, silicon-containing polymer, and sulfur-containing polymer. , Fluorine-containing polymers, and epoxy resins having one or more types as main components.

  Commercially available polymer dispersants include, for example, Ajinomoto Fine Techno Co., Ltd. Ajisper series, Solspers series (Solsperse 36000 etc.) available from Noveon, BYK Co., Ltd. Dispersic series, Enomoto Kasei The company's Disparon series, etc. are listed.

  When the ink for forming the main body part contains a surfactant, the three-dimensional structure can have better abrasion resistance.

  The surfactant is not particularly limited. For example, polyester-modified silicone or polyether-modified silicone as a silicone-based surfactant can be used, and among them, polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane. Is preferably used.

  Specific examples of the surfactant include, for example, BYK-347, BYK-348, BYK-UV3500, 3510, 3530, 3570 (above, trade names manufactured by BYK).

Further, the main body forming ink may contain a solvent.
Thereby, the viscosity of the ink for forming the main body part can be suitably adjusted, and even when the ink for forming the main body part contains a high-viscosity component, the ejection stability of the ink for forming the main body part by the ink jet system is particularly good. It can be excellent.

  Examples of the solvent include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ethyl acetate, n-propyl acetate, iso-acetate Acetates such as propyl, n-butyl acetate and iso-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl n-butyl ketone, diisopropyl ketone, acetylacetone, etc. Ketones: Examples include alcohols such as ethanol, propanol, and butanol, and one or more selected from these can be used in combination.

  Further, the viscosity of the main body forming ink is preferably 10 mPa · s or more and 30 mPa · s or less, and more preferably 15 mPa · s or more and 25 mPa · s or less.

  Thereby, the discharge stability of the ink for forming the main body by the ink jet method can be made particularly excellent. In addition, in this specification, a viscosity means the value measured in 25 degreeC using an E-type viscosity meter (Tokyo Keiki Co., Ltd. VISCONIC ELD).

Moreover, you may use multiple types of ink for main-body-part formation for manufacture of a three-dimensional molded item.
For example, a main body forming ink containing a colorant (color ink) and a main body forming ink not containing a colorant (clear ink) may be used.

  Thereby, for example, on the appearance of the three-dimensional structure, using the ink for forming the main body part containing the colorant as the ink for forming the main body part to be applied to the region affecting the color tone, the color tone on the appearance of the three-dimensional structure The main body forming ink that does not contain a colorant can be used as the main body forming ink to be applied to the non-influenced region, which is advantageous from the viewpoint of reducing the production cost of the three-dimensional structure.

  Further, in the finally obtained three-dimensional structure, the outer surface of the region formed using the main body forming ink containing the colorant was formed using the main body forming ink not containing the colorant. A plurality of kinds of main body forming inks may be used in combination so as to provide the region (coat layer).

  A portion containing a colorant (particularly a pigment) is more brittle than a portion not containing a colorant, and is likely to cause scratches or chips, but is a region formed using a main body forming ink that does not contain a colorant ( Such a problem can be effectively prevented by providing the coating layer. In addition, even when the surface is worn due to long-term use of the three-dimensional structure, it is possible to effectively prevent and suppress a change in the color tone of the three-dimensional structure.

  Further, for example, a plurality of types of main body forming inks containing different colorants may be used.

  As a result, the color reproduction region that can be expressed can be widened by combining these main body forming inks.

  In the case of using a plurality of types of main body forming ink, at least a cyan main body forming ink, a magenta main body forming ink, and a yellow main body forming ink are used. Is preferred.

  Thereby, the color reproduction area which can be expressed can be made wider by the combination of these main body part forming inks.

  Further, by using a white (white) main body forming ink in combination with another colored main body forming ink, for example, the following effects can be obtained.

  That is, the finally obtained three-dimensional structure is a color other than the first region to which the white (white) main body forming ink is applied and the outer surface side of the first region. And a region (second region) to which the main body forming ink is applied. Thereby, the 1st area | region to which the white (white) main body part formation ink was provided can exhibit concealment property, and can raise the chroma of a three-dimensional structure more.

4). Sacrificial part forming ink The sacrificial part forming ink contains at least a curable resin (curing component).

(Curable resin)
Examples of the curable resin (curing component) constituting the sacrificial portion forming ink include those similar to the curable resin (curing component) exemplified as the constituent component of the main body forming ink.

  In particular, the curable resin (curing component) constituting the sacrificial part forming ink and the curable resin (curing component) constituting the main body part forming ink are cured by the same kind of energy rays. Is preferred.

  Thereby, it can prevent effectively that the structure of a three-dimensional structure manufacturing apparatus becomes complicated, and can make the productivity of a three-dimensional structure particularly excellent. In addition, the surface shape of the three-dimensional structure can be controlled more reliably.

  Moreover, it is preferable to use a cured product of the sacrificial portion forming ink having hydrophilicity. Thereby, it becomes possible to easily remove the sacrificial portion with an aqueous liquid such as water.

  Among the various curing components, the sacrificial part forming ink includes tetrahydrofurfuryl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, (meth) acryloylmorpholine, (meta It is preferable that it contains one or more selected from the group consisting of 2- (2-vinyloxyethoxy) ethyl acrylate.

  Thereby, the sacrificial part forming ink can be cured at a more appropriate curing rate, and the productivity of the three-dimensional structure can be made particularly excellent. Further, the hydrophilicity of the cured product can be made more suitable, and the sacrificial part can be easily removed.

  In addition, the mechanical strength and shape stability of the sacrificial part formed by curing the sacrificial part forming ink can be made particularly excellent. As a result, when the three-dimensional structure is manufactured, the sacrificial portion of the lower layer (first layer) can more suitably support the main body forming ink for forming the upper layer (second layer). Therefore, unintentional deformation (particularly sagging) of the three-dimensional structure can be prevented more suitably (the sacrificial portion of the first layer functions as a support material), and the finally obtained three-dimensional structure is obtained. The dimensional accuracy of the object can be further improved.

  In particular, when the sacrificial portion forming ink contains (meth) acryloylmorpholine, the following effects can be obtained.

  That is, (meth) acryloylmorpholine is soluble in various solvents such as water in a state where it is not completely cured even when the curing reaction proceeds (a polymer of (meth) acryloylmorpholine in a state where it is not completely cured). A high state is high. Therefore, when removing the sacrificial part, it is possible to selectively and reliably and efficiently remove the sacrificial part while more effectively preventing the body part from being defective. As a result, a three-dimensional structure having a desired form can be obtained with high productivity with higher reliability.

  In addition, if the sacrificial portion forming ink contains tetrahydrofurfuryl (meth) acrylate, the flexibility after curing is maintained, and the gelability is easily improved by treatment with a liquid that removes the sacrificial portion, thereby improving removability. The effect is obtained.

  Further, when the sacrificial part forming ink contains ethoxyethoxyethyl (meth) acrylate, tackiness is likely to remain even after curing, and an effect of improving the removability by the liquid for removing the sacrificial part is obtained.

  Further, when the sacrificial part forming ink contains polyethylene glycol di (meth) acrylate, when the liquid for removing the sacrificial part has water as a main component, the solubility in the liquid is increased and the removal is facilitated. An effect is obtained.

  The ink for forming the sacrificial part is selected from the group consisting of the specific curing components described above (tetrahydrofurfuryl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate), and (meth) acryloylmorpholine. 1 type or 2 types or more), the ratio of the specific curing component to the total curing component constituting the sacrificial part forming ink is preferably 80% by mass or more, and 90% by mass or more. More preferably, it is more preferably 100% by mass. Thereby, the effects as described above are more remarkably exhibited.

  The content of the curing component in the sacrificial part forming ink is preferably 83% by mass or more and 98.5% by mass or less, and more preferably 87% by mass or more and 95.4% by mass or less.

  As a result, the stability of the shape of the formed sacrificial part can be made particularly excellent. Can be more effectively prevented, and the upper unit layer can be suitably supported. As a result, the dimensional accuracy of the finally obtained three-dimensional structure can be made particularly excellent. In addition, the productivity of the three-dimensional structure can be made particularly excellent.

(Polymerization initiator)
The sacrificial part forming ink preferably contains a polymerization initiator.

  Thereby, the curing speed of the sacrificial part forming ink at the time of manufacturing the three-dimensional structure can be appropriately increased, and the productivity of the three-dimensional structure can be made particularly excellent.

  Moreover, the stability of the shape of the sacrificial part to be formed can be made particularly excellent, and the unit layer on the lower side becomes unintentional when the unit layer is overlapped at the time of manufacturing the three-dimensional structure. Deformation can be prevented more effectively, and the upper unit layer can be suitably supported. As a result, the dimensional accuracy of the finally obtained three-dimensional structure can be made particularly excellent.

  Examples of the polymerization initiator constituting the sacrificial part forming ink include the same polymerization initiators exemplified as the constituent components of the main body part forming ink.

  Among them, the sacrificial portion forming ink contains bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as a polymerization initiator. preferable.

  By including such a polymerization initiator, the sacrificial part forming ink can be cured at a more appropriate curing rate, and the productivity of the three-dimensional structure can be made particularly excellent.

  In addition, the mechanical strength and shape stability of the sacrificial part formed by curing the sacrificial part forming ink can be made particularly excellent. As a result, when the three-dimensional structure is manufactured, the sacrificial portion of the lower layer (first layer) can more suitably support the main body forming ink for forming the upper layer (second layer). Therefore, unintentional deformation (particularly sagging etc.) of the main body can be prevented more suitably (the sacrificial part of the first layer functions as a support material), and the finally obtained three-dimensional structure can be obtained. The dimensional accuracy can be further improved.

  The specific value of the content of the polymerization initiator in the sacrificial part forming ink is preferably 1.5% by mass to 17% by mass, and preferably 4.6% by mass to 13% by mass. Is more preferable.

  Thereby, the sacrificial part forming ink can be cured at a more appropriate curing rate, and the productivity of the three-dimensional structure can be made particularly excellent.

  In addition, the mechanical strength and shape stability of the sacrificial part formed by curing the sacrificial part forming ink can be made particularly excellent. As a result, when the three-dimensional structure is manufactured, the sacrificial portion of the lower layer (first layer) can more suitably support the main body forming ink for forming the upper layer (second layer). Therefore, unintentional deformation (particularly sagging etc.) of the main body can be prevented more suitably (the sacrificial part of the first layer functions as a support material), and the finally obtained three-dimensional structure can be obtained. The dimensional accuracy can be further improved.

  The preferred specific examples of the blending ratio of the curable resin and the polymerization initiator in the sacrificial part forming ink (ink composition excluding “other components” described below) are shown below. The sacrificial layer forming ink in the present invention It goes without saying that the composition of is not limited to those described below.

“Composition ratio example 1”
Tetrahydrofurfuryl acrylate: 36 parts by mass Ethoxyethoxyethyl acrylate: 55.75 parts by mass Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: 3 parts by mass 2,4,6-trimethylbenzoyl -Diphenyl-phosphine oxide: 5 parts by mass

“Composition ratio example 2”
Dipropylene glycol diacrylate: 37 parts by mass Polyethylene glycol (400) diacrylate: 55.85 parts by mass Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: 3 parts by mass 6-trimethylbenzoyl-diphenyl-phosphine oxide: 4 parts by mass

"Composition ratio example 3"
Tetrahydrofurfuryl acrylate: 36 parts by mass Acryloylmorpholine: 55.75 parts by mass Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: 3 parts by mass 2,4,6-trimethylbenzoyl- Diphenyl-phosphine oxide: 5 parts by mass

“Composition ratio example 4”
-2- (2-vinyloxyethoxy) ethyl acrylate: 36 parts by mass-Polyethylene glycol (400) diacrylate: 55.75 parts by mass-Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: 3 Part by mass · 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: 5 parts by mass In the case of the above blending, the effects as described above are more remarkably exhibited.

(Other ingredients)
Further, the sacrificial portion forming ink may contain components other than those described above. Examples of such components include various colorants such as pigments and dyes, dispersants, surfactants, sensitizers, polymerization accelerators, solvents, penetration accelerators, wetting agents (humectants), fixing agents, and prevention agents. Examples include glazes; antiseptics; antioxidants; ultraviolet absorbers; chelating agents; pH adjusters; thickeners; fillers;

  In particular, since the sacrificial part forming ink contains a colorant, the visibility of the sacrificial part is improved, and in the finally obtained three-dimensional structure, at least a part of the sacrificial part remains unintentionally. It can be surely prevented.

  Examples of the colorant constituting the sacrificial portion forming ink include the same colorants as exemplified as the constituent components of the main body portion forming ink, but were observed from the normal direction of the surface of the three-dimensional structure. At this time, it is preferable that the colorant be a color different from the color of the main body overlapping the sacrificial part formed by the sacrificial part forming ink (the color to be visually recognized on the appearance of the three-dimensional structure). Thereby, the effects as described above are more remarkably exhibited.

  When the sacrificial portion forming ink contains a pigment, the dispersibility of the pigment can be further improved by further containing a dispersant. Examples of the dispersant constituting the sacrificial portion forming ink include the same dispersants as exemplified as the constituent components of the main body portion forming ink.

  The viscosity of the sacrificial part forming ink is preferably 10 mPa · s or more and 30 mPa · s or less, and more preferably 15 mPa · s or more and 25 mPa · s or less.

  Thereby, the discharge stability of the sacrificial part forming ink by the ink jet method can be made particularly excellent.

Moreover, you may use multiple types of sacrificial part formation ink for manufacture of a three-dimensional molded item.
For example, two or more types of sacrificial part forming inks having different kinematic viscoelasticity at the time of curing of the main body part forming ink may be provided.

  Thereby, the three-dimensional structure finally obtained can be obtained as having a plurality of regions having different fine texture levels. As a result, a more complicated appearance can be expressed, and the aesthetic appearance (aesthetics), luxury, etc. of the three-dimensional structure can be made particularly excellent.

5. Three-dimensional structure The three-dimensional structure of the present invention can be manufactured using the manufacturing method as described above. Thereby, a high-quality three-dimensional structure can be provided.

  The use of the three-dimensional structure of the present invention is not particularly limited, and examples thereof include appreciation objects / exhibits such as dolls and figures; medical devices such as implants.

  Moreover, the three-dimensional structure of the present invention may be applied to any of prototypes, mass-produced products, and custom-made products.

  The three-dimensional structure of the present invention is a model (for example, vehicles such as automobiles, motorcycles, ships, airplanes, living things such as buildings, animals and plants, natural objects such as stones (non-living), models of various foods, etc. ).

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

  For example, in the method for producing a three-dimensional structure of the present invention, a pretreatment process, an intermediate treatment process, and a posttreatment process may be performed as necessary.

Examples of the pretreatment process include a stage cleaning process.
Examples of the post-processing step include a cleaning step, a shape adjusting step for performing deburring, and an additional curing treatment for increasing the degree of curing of the curable resin.

  Further, the present invention repeats a powder lamination method (that is, a series of operations of forming a layer using powder and applying a curable ink to a predetermined portion of the layer to form a cured portion. It may be applied to a method of obtaining a three-dimensional structure as a laminate having a plurality of layers provided with a cured portion.

DESCRIPTION OF SYMBOLS 1 ... Normal dot 2A, 2B, 2C ... 1st gradation dot 3 ... 1st adjacent dot 4A, 4B, 4C ... 2nd gradation dot 5 ... 2nd adjacent dot 10 ... Bit map data 11 ... Smoothing process data 12 ... Main unit main data 13, 13A, 13B ... Main unit main sub data 14 ... Layer (unit layer)
DESCRIPTION OF SYMBOLS 15 ... Main part main data layer 41 ... Tone reversal data 42 ... Sacrificial part main data 43, 43A, 43B ... Sacrificial part subdata 44 ... Sacrificial part 45 ... Sacrificial part main data layer 141, 441 ... Recessed part A, B ... 3D data

Claims (4)

It is a manufacturing method of a three-dimensional structure that manufactures a three-dimensional structure by laminating layers,
A step of creating the three-dimensional data B of the layer from the three-dimensional data A of the three-dimensional structure;
Converting the three-dimensional data B into bitmap data of a predetermined resolution, further performing a smoothing process, and creating smoothing process data of the layer;
A first gradation dots gradation representation of the smoothing processing data, and contact with the inside of the first gradation dot the layer, and a first adjacent dots present in the interior of the layer, the smoothing processing data Generating data thinned out as main part main data;
Main data is composed of data in which the first gradation dot is arranged at a position where the first adjacent dot is present and data in which the first adjacent dot is arranged as it is at a position where the first adjacent dot is present Generating as sub-sub data;
Reversing the gradation of the first gradation dot and the area on the surface side of the three-dimensional structure in the smoothing processing data, and creating gradation reversal data;
In the gradation inversion data, a second gradation dot obtained by reversing the gradation of the first gradation dot, and a second adjacent dot that is in contact with the second gradation dot on the side opposite to the first adjacent dot , Storing the data thinned out from the gradation inversion data as sacrifice part main data;
Sacrificial data composed of data in which the second gradation dot is arranged at the position where the second adjacent dot is present and data in which the second adjacent dot is arranged as it is at the position where the second adjacent dot is present A step of saving as sub-data;
Forming a main body main data layer using main body forming ink based on the main body main data ;
Forming a sacrificial portion main data layer using a sacrificial portion forming ink based on the sacrificial portion main data ;
A step of discharging the main body forming ink based on the main body sub data;
Based on the sacrificial portion sub data, have a, a step of discharging the sacrificial portion forming ink,
When ejecting the main body forming ink, when the density of the first gradation dot of the main body sub data is 100% when the density of one dot of the main body main data is 100%, The discharge amount of the main body portion forming ink discharged to the first gradation dot portion is controlled to be reduced to X%, and when the sacrifice portion forming ink is discharged, the density of one dot of the sacrifice portion main data When the density of the second gradation dot of the sacrificial portion sub-data when Y is 100% is Y%, the discharge amount of the sacrificial portion forming ink discharged to the second gradation dot portion is Y. The manufacturing method of the three-dimensional structure characterized by controlling to reduce to% . After the main body main data layer and the sacrificial part main data layer are formed, the main body main data layer and the sacrificial part main data layer are cured, and then the main body main data layer and the sacrificial part main data layer The manufacturing method of the three-dimensional structure according to claim 1 , wherein the main body portion forming ink and the sacrificial portion forming ink are ejected to the thinned portion.   The method for manufacturing a three-dimensional structure according to claim 1 or 2, wherein the main body portion forming ink and the sacrificial portion forming ink include a photocurable resin.   The method for producing a three-dimensional structure according to any one of claims 1 to 3, wherein the main body portion forming ink and the sacrificial portion forming ink have a viscosity of 10 mPa · s to 30 mPa · s.

Images