JP2015182427A - Apparatus for manufacturing three-dimensional molded article, method for manufacturing three-dimensional molded article, and three-dimensional molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for manufacturing a three-dimensional molded article and a method for manufacturing a three-dimensional molded article, by which a three-dimensional molded article can be efficiently manufactured with high dimensional accuracy, and to provide a three-dimensional molded article manufactured with high dimensional accuracy.SOLUTION: An apparatus 100 for manufacturing a three-dimensional molded article manufactures a three-dimensional molded article by stacking layers 1, and the apparatus includes: a molding unit 10 where a three-dimensional molded article is molded; an ejection unit 11 that ejects a curable ink to the molding unit 10 to form an ink layer 2; pre-curing means 12 for curing at least a part of a curable component in the ink layer 2; flattening means 13 for flattening the ink layer 2 formed of the curable ink ejected to the molding unit 10; and curing means for curing an uncured curable component included in the flattened ink layer 2.

Description

  The present invention relates to a three-dimensional structure manufacturing apparatus, a three-dimensional structure manufacturing method, and a three-dimensional structure.

  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, the three-dimensional data of the three-dimensional structure is formed by drawing and laminating a plane image obtained by the ink jet method, and the layer is formed by ejecting ink by the ink jet method. In this case, there is a problem that the dimensional accuracy of the finally obtained three-dimensional structure is lowered due to the variation in the thickness of each layer.

JP 2000-280354 A

  An object of the present invention is to provide a three-dimensional structure manufacturing apparatus and a method for manufacturing a three-dimensional structure that can efficiently manufacture a three-dimensional structure with high dimensional accuracy, and a three-dimensional object manufactured with high dimensional accuracy. It is to provide a model.

Such an object is achieved by the present invention described below.
The three-dimensional structure manufacturing apparatus of the present invention is a three-dimensional structure manufacturing apparatus for manufacturing a three-dimensional structure by laminating layers,
A modeling part where the three-dimensional modeled object is modeled;
A discharge part that discharges a curable ink containing a curable component and forms an ink layer on the modeling part;
Pre-curing means for curing at least a part of the curable component in the ink layer;
Flattening means for flattening the ink layer.

  Thereby, the three-dimensional structure manufacturing apparatus which can manufacture a three-dimensional structure efficiently with high dimensional accuracy can be provided.

In the three-dimensional structure manufacturing apparatus of the present invention, it is preferable that the apparatus has a main curing unit that cures the uncured curable component contained in the flattened ink layer.
Thereby, a three-dimensional structure with high dimensional accuracy can be manufactured more effectively.

In the three-dimensional structure manufacturing apparatus of the present invention, the flattening means is preferably a flat plate.
Thereby, the ink layer can be flattened more efficiently.

  In the three-dimensional structure manufacturing apparatus of the present invention, it is preferable to apply a slight vibration to the flattening means.

  Thereby, it can prevent effectively that curable ink adheres to a planarization means.

  In the three-dimensional structure manufacturing apparatus of the present invention, it is preferable that a liquid repellent treatment is performed on a region of the flattening unit that contacts the ink layer.

  Thereby, it can prevent effectively that curable ink adheres to a planarization means.

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,
An ink ejection step of ejecting a curable ink containing a curable component to form an ink layer;
A pre-curing step of curing at least a part of the curable component in the ink layer;
A planarization step of planarizing the ink layer.

  Thereby, the manufacturing method of the three-dimensional structure which can manufacture a three-dimensional structure efficiently with high dimensional accuracy can be provided.

  In the three-dimensional structure manufacturing method of the present invention, it is preferable that in the planarization step, a plurality of ink layers are simultaneously planarized.

  Thereby, an ink layer can be planarized more efficiently and the production efficiency of a three-dimensional structure can be improved.

In the three-dimensional structure manufacturing method of the present invention, in the ink discharge step, the curable ink is discharged from a droplet discharge head having a plurality of nozzles.
It is preferable to perform flattening based on variation data obtained by measuring variations in the discharge amount of the curable ink at each nozzle.

  Thereby, an ink layer can be planarized more efficiently and the production efficiency of a three-dimensional structure can be improved.

The three-dimensional structure of the present invention is manufactured using the three-dimensional structure manufacturing apparatus of the present invention.
Thereby, the three-dimensional structure manufactured with high dimensional accuracy can be provided.

The three-dimensional structure of the present invention is manufactured by the method for manufacturing a three-dimensional structure of the present invention.
Thereby, the three-dimensional structure manufactured with high dimensional accuracy can be provided.

It is sectional drawing which shows suitable embodiment of the three-dimensional structure manufacturing apparatus of this invention.

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

1. First, a preferred embodiment of the three-dimensional structure manufacturing apparatus of the present invention will be described.
FIG. 1 is a cross-sectional view showing a preferred embodiment of the three-dimensional structure manufacturing apparatus of the present invention.

  The three-dimensional structure manufacturing apparatus 100 is an apparatus that manufactures a three-dimensional structure by laminating layers (unit layers) 1 formed using curable ink.

  As shown in FIG. 1, the three-dimensional structure manufacturing apparatus 100 discharges curable ink containing a curable component to the modeling section 10 on which the three-dimensional structure is modeled, and the modeling section 10. A discharge portion 11 for forming the ink layer 2, an ultraviolet irradiation means (preliminary curing means) 12 for curing at least a part of the curable component in the ink layer 2, and a flat plate (flat) for flattening the precured ink layer 2 13).

  The modeling unit 10 is an ink layer after flattening in the ink layer stacking step in the modeling stage of the three-dimensional model manufacturing apparatus 100 or the modeling process of the three-dimensional model. A curable ink is discharged onto the modeling unit 10 to form the ink layer 2.

  The discharge unit 11 has a function of moving in the X-axis direction relative to the modeling unit 10 and discharging curable ink onto the modeling unit 10. The curable ink discharged on the modeling unit 10 forms an ink layer.

  The ejection unit 11 is mounted with a droplet ejection head that ejects droplets of curable ink by an inkjet method. Further, the discharge unit 11 includes a curable ink supply unit (not shown). In the present embodiment, a so-called piezo drive type droplet discharge head is employed. In the present embodiment, the discharge unit 11 employs a line head in which a plurality of nozzles are arranged in the Y-axis direction as a droplet discharge head. Here, the “line head” is provided so that the nozzle region formed in the Y-axis direction intersecting the X-axis direction can cover the entire modeling unit 10, and either the discharge unit 11 or the modeling unit 10. Is a droplet discharge head used in a three-dimensional structure manufacturing apparatus for forming a layer 1 by fixing the other and moving the other. In addition, the area | region of the nozzle of the Y-axis direction of a line head does not need to be able to cover the whole Y-axis direction of all the modeling parts 10 with which the three-dimensional structure manufacturing apparatus corresponds.

  The ultraviolet ray irradiation (preliminary curing means) 12 has a function of irradiating the ink layer 2 with ultraviolet rays to cure (preliminarily cure) the curable component in the ink layer 2. The ultraviolet irradiation means 12 of the present embodiment is configured to cure a part of the curable component in the ink layer 2. By curing a part of the curable component in the ink layer 2, the ink layer 2 is cured to such an extent that the fluidity is lost.

  Further, the ultraviolet irradiation means 12 is provided at both ends of the discharge unit in the X-axis direction, and is configured to move in the X-axis direction together with the discharge unit 11. When the ejection unit 11 moves to the left in the figure while ejecting the curable ink, the ink layer 2 is pre-cured by the ultraviolet irradiation means 12 on the right side in the figure. On the other hand, when the ejection unit 11 moves rightward in the figure while ejecting curable ink, the ink layer 2 is pre-cured by the ultraviolet irradiation means 12 on the left side in the figure.

The flat plate (flattening means) 13 has a function of flattening the ink layer 2.
Specifically, the surface of the ink layer 2 is flattened by pressing the surface of the ink layer 2 with the flat plate 13.

  In the present embodiment, the flat plate 13 has a function of heating the ink layer 2. By heating the ink layer 2, the uncured curable component of the ink layer 2 is cured. That is, the flat plate 13 also functions as a curing unit (main curing unit).

  The flat plate 13 is provided with vibration application means (not shown). When the ink layer 2 is pressed, vibration is applied by the vibration applying means so that the curable ink does not adhere to the surface of the flat plate 13.

  Further, the surface of the flat plate 13 is subjected to a liquid repellent treatment such as fluorine processing, and is configured such that the curable ink hardly adheres thereto.

  In this embodiment, as shown in FIG. 1, a plurality of ink layers 2 are flattened together by a flat plate 13. The ink layer 2 may be configured to be flattened one layer at a time.

  According to the three-dimensional structure manufacturing apparatus 100 having the above configuration, the ink layer 2 can be easily flattened, and the unit layer 1 having a uniform thickness can be formed. As a result, a three-dimensional structure can be manufactured with high dimensional accuracy.

  In the above description, the case where the ultraviolet irradiation unit 12 is used as the pre-curing unit for the curable ink has been described. However, the present invention is not limited to this, and a heating unit that cures by heating may be used.

  Moreover, although the case where a flat plate was used as the flattening means has been described, a roller may be used as the flattening means.

2. Next, the manufacturing method of the three-dimensional structure according to the present invention will be described.

  The method for manufacturing a three-dimensional structure according to the present embodiment is a method for manufacturing a three-dimensional structure by stacking layers 1 and forming an ink layer 2 by discharging curable ink. An ink ejection step, a precuring step for curing (precuring) at least a part of the curable component in the ink layer 2, a laminating step for laminating a plurality of precured ink layers 2, and flattening the ink layer 2 And a main curing step for curing the uncured curable component in the ink layer 2.

Hereinafter, the three-dimensional structure manufacturing apparatus 100 as described above will be described as an example.
First, curable ink is applied to the modeling unit 10 while the ejection unit 11 moves in the right direction in FIG. 1 to form the ink layer 2 (ink ejection process).

Further, at least a part of the curable component in the ink layer 2 is irradiated with ultraviolet rays by the ultraviolet curing means 12 that moves following the ejection unit 11 while ejecting the curable ink from the ejection unit 11. Is cured (pre-curing step).
Next, a plurality of pre-cured ink layers 2 are laminated.

  Next, the ink layer 2 laminated with a plurality of layers is pressed against the flat plate 13 and the ink layer 2 laminated with a plurality of layers, and the ink layer 2 is flattened (a flattening step). The ink layer 2 to be flattened is determined based on variation data obtained by measuring variations in the amount of curable ink discharged from each nozzle of the droplet discharge head. In other words, in consideration of the thickness variation of the ink layer 2 based on the variation data and the variation range that can be flattened by the flattening means, flattening is performed when it is most effective.

In addition, the ink layer 2 is heated by the flat plate 13 while the ink layer 2 is flattened by the flat plate 13 to cure the uncured curable component in the ink layer 2 (main curing step).
A heater for heating the surface of the flat plate 13 in contact with the ink layer 2 is disposed inside the flat plate 13. The flat plate 13 is maintained at a predetermined temperature (for example, 50 ° C. to 240 ° C., more preferably 80 ° C. to 130 ° C.), and the ink layer 2 is pressurized until a predetermined pressure is reached. Next, the ink layer 2 is flattened while maintaining a predetermined pressure. After flattening, the flat plate 13 in contact with the ink layer 2 is pulled away. When pulling apart, the flat plate 13 may be cooled and then pulled apart by turning off the power of the heater that heats the surface of the flat plate 13. Alternatively, the ink layer 2 may be pressurized at a predetermined pressure while heating the flat plate 13 from a predetermined temperature to a main curing temperature at which the uncured curable component in the ink layer 2 is cured.
The surface of the flat plate 13 is preferably mirror-like.

  Further, the surface roughness Ra of the surface of the flat plate 13 is preferably 0.8 μm or less, and more preferably 0.1 μm or less.

  By repeating these operations, a three-dimensional structure in which the layer 1 is laminated can be obtained.

  According to such a three-dimensional structure manufacturing method, the ink layer 2 can be easily flattened, and the unit layer 1 having a uniform thickness can be formed. As a result, a three-dimensional structure can be manufactured with high dimensional accuracy.

  In the above description, the planarization process is performed on the plurality of ink layers 2 at the same time, but the planarization may be performed layer by layer.

3. Curable ink The curable 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 curable ink, 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 itaconic acid esters 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 amide monomers 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. Examples thereof include 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.), trifunctional or higher 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 curing components described above, the curable ink includes, in particular, (meth) acrylic acid 2- (2-vinyloxyethoxy) ethyl, polyether aliphatic urethane (meth) acrylate oligomer, 2-hydroxy-3-phenoxypropyl. It is preferable that 1 type (s) or 2 or more types selected from the group which consists of (meth) acrylate and 4-hydroxybutyl (meth) acrylate are included. Thereby, the curable 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 strength, durability, and reliability of the three-dimensional structure can be made particularly excellent.

  In particular, when the curable ink contains 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, it is difficult to be inhibited by oxygen and can be cured at low energy, and is a copolymer containing other monomers. And the effect of increasing the strength of the modeled object can be obtained.

  Further, when the curable ink contains a polyether-based aliphatic urethane (meth) acrylate oligomer, an effect of achieving both high strength and high toughness of the molded article can be obtained.

  Moreover, when the curable ink contains 2-hydroxy-3-phenoxypropyl (meth) acrylate, an effect of having flexibility and improving elongation at break can be obtained.

  In addition, if the curable ink contains 4-hydroxybutyl (meth) acrylate, in addition to the self-cured product formed in the previous layer, by improving the adhesion to PMMA, PEMA particles, silica particles, metal particles, etc. The effect of increasing the strength of the shaped object can be obtained.

  The specific curing component (2- (2-vinyloxyethoxy) ethyl (meth) acrylate, polyether-based aliphatic urethane (meth) acrylate oligomer), 2-hydroxy-3-phenoxypropyl (meth) described above is the curable ink. Acrylate and one or more selected from the group consisting of 4-hydroxybutyl (meth) acrylate), the ratio of the specific curing component to the total curing component constituting the curable ink, It 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 curable component in the curable 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 curable ink preferably contains a polymerization initiator.

  Thereby, the cure speed of the curable ink at the time of manufacture of 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 curable ink includes bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. preferable.

  By including such a polymerization initiator, the curable 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 strength, durability, and reliability of the three-dimensional structure can be made particularly excellent.

  The specific value of the content of the polymerization initiator in the curable 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. preferable. Thereby, the curable 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 strength, durability, and reliability of the three-dimensional structure can be made particularly excellent.

  Preferred specific examples of the blending ratio of the curable resin and the polymerization initiator in the curable ink (ink composition excluding “other components” described below) are shown below. The composition of the curable ink in the present invention is as follows. It goes without saying that the present invention 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 curable 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 curable 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 a colorant, the light resistance of the curable 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 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 curable 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.

  As a result, the discharge stability of the curable ink and the dispersion stability of the pigment in the curable ink 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 curable ink contains a colorant, the content of the colorant in the curable 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 curable ink contains titanium oxide as a colorant, the content of titanium oxide in the curable ink is preferably 12% by mass to 18% by mass, and more preferably 14% by mass to 16% by mass. The following is more preferable. Thereby, a particularly excellent concealing property can be obtained.

  When the curable ink contains a pigment, the dispersibility of the pigment can be further improved if it further contains 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, Solsperse series (Solsperse 36000, etc.) available from Noveon, BYK Co., Ltd. Dispersic series, Enomoto Kasei The company's Disparon series, etc. are listed.

  If the curable ink 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).

Moreover, the curable ink may contain a solvent.
Thereby, the viscosity of the curable ink can be suitably adjusted, and even when the curable ink contains a high-viscosity component, the ejection stability of the curable ink by the ink jet method is particularly excellent. Can do.

  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.

  The viscosity of the curable 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 curable ink by the inkjet 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 curable ink for manufacture of a three-dimensional structure.
For example, a curable ink containing a colorant (color ink) and a curable ink containing no colorant (clear ink) may be used.

  Thereby, for example, on the appearance of the three-dimensional structure, a curable ink containing a colorant is used as a curable ink to be applied to a region that affects the color tone, and the color tone is not affected on the appearance of the three-dimensional structure. A curable ink containing no colorant can be used as the curable ink applied to the 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, an area formed using a curable ink not containing a colorant (coat layer) on an outer surface of an area formed using a curable ink containing a colorant ) May be used in combination. Thereby, even if the surface is worn by long-term use of the three-dimensional structure, a change in the color tone of the three-dimensional structure can be effectively prevented and suppressed.

Further, for example, a plurality of types of curable inks containing colorants having different compositions may be used.
Thereby, the color reproduction range which can be expressed can be made wide by the combination of these curable inks.

  When a plurality of types of curable inks are used, it is preferable to use at least a cyan curable ink, a magenta curable ink, and a yellow (yellow) curable ink.

  Thereby, the color reproduction area which can be expressed can be made wider by the combination of these curable inks.

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

  That is, the finally obtained three-dimensional structure is obtained by curing a colored region other than the first region to which the white (white) curable ink is applied and the outer surface side of the first region. And a region (second region) to which the property ink is applied. Thereby, the 1st area | region to which the white (white) curable ink was provided can exhibit concealment property, and can further raise the saturation of a three-dimensional structure.

  In addition, the effect of obtaining the fine texture as described above and the effect of increasing the saturation work synergistically, and the aesthetic appearance (aesthetics) of the three-dimensional structure can be made particularly excellent. .

4). Three-dimensional structure The three-dimensional structure of the present invention can be manufactured using the manufacturing method as described above. Thereby, the three-dimensional structure manufactured with high dimensional accuracy 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 ... Layer 2 ... Ink layer 10 ... Modeling part 11 ... Discharge part 12 ... Ultraviolet irradiation means (precuring means)
13 ... Flat plate (flattening means)
100. Three-dimensional structure manufacturing apparatus

Claims (10)

A three-dimensional structure manufacturing apparatus that manufactures a three-dimensional structure by laminating layers,
A modeling part where the three-dimensional modeled object is modeled;
A discharge part that discharges a curable ink containing a curable component and forms an ink layer on the modeling part;
Pre-curing means for curing at least a part of the curable component in the ink layer;
A three-dimensional structure manufacturing apparatus comprising: a flattening means for flattening the ink layer.   The three-dimensional structure manufacturing apparatus according to claim 1, further comprising a main curing unit that cures the uncured curable component contained in the planarized ink layer.   The three-dimensional structure manufacturing apparatus according to claim 1, wherein the flattening means is a flat plate.   The three-dimensional structure manufacturing apparatus according to any one of claims 1 to 3, wherein a fine vibration is applied to the flattening means.   The three-dimensional structure manufacturing apparatus according to any one of claims 1 to 4, wherein a liquid repellent treatment is performed on a region of the flattening unit that contacts the ink layer. It is a manufacturing method of a three-dimensional structure that manufactures a three-dimensional structure by laminating layers,
An ink ejection step of ejecting a curable ink containing a curable component to form an ink layer;
A pre-curing step of curing at least a part of the curable component in the ink layer;
And a flattening step of flattening the ink layer.   The method for manufacturing a three-dimensional structure according to claim 6, wherein in the planarization step, a plurality of the ink layers are simultaneously planarized. In the ink discharge step, the curable ink is discharged from a droplet discharge head having a plurality of nozzles.
The method for producing a three-dimensional structure according to claim 6 or 7, wherein flattening is performed based on variation data obtained by measuring variation in the discharge amount of the curable ink at each nozzle.   A three-dimensional structure manufactured using the three-dimensional structure manufacturing apparatus according to any one of claims 1 to 5.   A three-dimensional structure manufactured by the method for manufacturing a three-dimensional structure according to any one of claims 6 to 8.

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