JP2019206111A - Photo-fabrication ink set, photo-fabricated article, and production method for photo-fabricated article - Google Patents

Abstract

To provide a photo-fabrication ink set for obtaining a photo-fabricated article having excellent mechanical properties and excellent dimensional accuracy by using a support material having excellent water removability as well as excellent self-standing properties.SOLUTION: A photo-fabrication ink set includes a model material composition and a support material composition. The model material composition includes a monofunctional ethylenic unsaturated monomer (A) that has Tg of 80°C or more and does not include urethane groups, a polyfunctional ethylenic unsaturated monomer (B) that includes a ring structure, has Tg of 180°C or more and does not include urethane groups, an oligomer (C), and a photopolymerization initiator (D). The support material composition includes 19-80 pts.mass of a water-soluble monofunctional ethylenically unsaturated monomer (a), and 15-75 pts.mass of a polyalkylene glycol that has a weight average molecular weight of 300 to 3000 and includes an oxybutylene group (b).SELECTED DRAWING: Figure 1

Description

  The present invention relates to an optical modeling ink set used in an ink jet optical modeling method, an optical modeling product modeled using the optical modeling ink set, and a method of manufacturing an optical modeling product using the optical modeling ink set. About.

  2. Description of the Related Art Conventionally, modeling methods using a photocurable composition that is cured by irradiating ultraviolet rays or the like are widely known as methods for creating a three-dimensional modeled object. Specifically, in such a modeling method, the cured layer having a predetermined shape is formed by irradiating the photocurable composition with ultraviolet rays or the like to cure. Thereafter, a photocurable composition is further supplied onto the cured layer and cured to form a new cured layer. A three-dimensional model is produced by repeating the above steps.

  Among the modeling methods, in recent years, an optical modeling method by an ink jet method for forming a cured layer having a predetermined shape by discharging a photocurable composition from a nozzle and immediately irradiating it with ultraviolet rays or the like to cure. Hereinafter, ink jet stereolithography is reported (Patent Documents 1 to 5). Inkjet stereolithography does not require the installation of a large resin bath and a dark room for storing the photocurable composition. Therefore, the modeling apparatus can be downsized as compared with the conventional method. Inkjet stereolithography is attracting attention as a modeling method realized by a 3D printer that can freely create a three-dimensional model based on CAD (Computer Aided Design) data.

  In the inkjet stereolithography method, when modeling a stereolithography product having a complicated shape such as a hollow shape, the model material and the support material are combined to form a model material (Patent Document 1). The support material is created by irradiating the photocurable composition with ultraviolet rays or the like, as in the case of the model material. After the model material is created, the support material can be removed by physically peeling the support material or dissolving the support material in an organic solvent or water.

  In recent years, there has been a demand for modeling an optical modeling product having excellent mechanical characteristics and good dimensional accuracy by using an optical modeling method using an ink jet method. In Patent Document 2, it is obtained by photocuring the model material composition by defining the glass transition temperature of the homopolymer of the ethylenically unsaturated monomer contained in the model material composition within a predetermined range. It is disclosed that the model material obtained is excellent in mechanical properties and dimensional accuracy. An optically modeled article modeled using such a model material can be suitably used as, for example, a mold, a mechanism part, or the like.

JP 2012-111226 A JP, 2006-20474, A

  Patent Document 2 discloses a composition for a support material containing a water-soluble monofunctional ethylenically unsaturated monomer, an AO adduct containing an oxypropylene group and / or water, and a photopolymerization initiator. Yes. However, even if such a support material composition is used, depending on the type and content of the components contained in the support material composition, the support material obtained by photocuring the support material composition The independence of was sometimes inferior. As a result, there was a problem that the dimensional accuracy of the stereolithographic product modeled using the composition for model material and the composition for support material disclosed in Patent Document 2 deteriorated.

  The present invention has been made in view of the above-described situation using a support material that is excellent in water removal property of the support material, and further excellent in self-supporting properties, and has excellent mechanical properties and good dimensional accuracy. It is an object to provide an optical modeling ink set for obtaining a product, an optical modeling product modeled using the optical modeling ink set, and a method of manufacturing an optical modeling product using the optical modeling ink set. And

  The present inventors obtain a support material excellent in self-supporting property by defining the content of the non-polymerized component and the water-soluble monofunctional ethylenically unsaturated monomer in the composition for the support material within a predetermined range. I found out that The present inventors form an optically shaped article with good dimensional accuracy by using the support material composition and the model material composition capable of obtaining a model material having excellent mechanical properties. I found that I can do it.

  This invention is made | formed based on the said knowledge, The summary is as follows.

  (1) A combination of a composition for a model material that is used in an ink jet optical modeling method and is used for modeling a model material, and a composition for a support material used for modeling a support material. A stereolithographic ink set, wherein the model material composition has a homopolymer glass transition temperature of 80 ° C. or higher and a monofunctional ethylenically unsaturated monomer (A) having no urethane group. A polyfunctional ethylenically unsaturated monomer (B) having a ring structure, a homopolymer having a glass transition temperature of 180 ° C. or higher and having no urethane group, an oligomer (C), and photopolymerization start The support material composition contains 19 to 80 parts by weight of a water-soluble monofunctional ethylenically unsaturated monomer (100 parts by weight based on 100 parts by weight of the entire support material composition). a) and 15-75 quality It contains a polyalkylene glycol (b) containing oxybutylene group parts, weight average molecular weight of the polyalkylene glycol (b) comprising the oxybutylene group is 300 to 3000, to provide an ink set for optical molding.

  (2) The monofunctional ethylenically unsaturated monomer (A) of the composition for model material has an alicyclic skeleton.

  (3) The polyfunctional ethylenically unsaturated monomer (B) of the model material composition has an alicyclic skeleton or an aromatic ring.

  (4) The said oligomer (C) of the said composition for model materials is 1 or more types selected from a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, and a polyester (meth) acrylate oligomer.

  (5) The content of the monofunctional ethylenically unsaturated monomer (A) in the model material composition is 60 to 80 parts by weight with respect to 100 parts by weight of the entire model material composition.

  (6) The content of the polyfunctional ethylenically unsaturated monomer (B) in the model material composition is 5 to 30 parts by weight with respect to 100 parts by weight of the entire model material composition.

  (7) The content of the oligomer (C) in the model material composition is 10 to 15 parts by weight with respect to 100 parts by weight of the entire model material composition.

  (8) The glass transition temperature of the model material obtained by photocuring the model material composition is 90 to 200 ° C.

  (9) The said composition for support materials contains 1-20 mass parts photoinitiator (d).

  (10) The support material composition further contains a water-soluble organic solvent, and the content of the water-soluble organic solvent is 30 parts by mass or less with respect to 100 parts by mass of the total mass of the support material composition. It is.

  (11) The support material composition further contains a surface conditioner, and the content of the surface conditioner is 0.005 parts by mass or more with respect to 100 parts by mass of the total mass of the support material composition. 3.0 parts by mass or less.

(12) The present invention is a method for producing an optically shaped product by using the optical shaping ink set according to any one of (1) to (11) by an inkjet optical shaping method,
Step (I) of obtaining a model material by photocuring the composition for model material, and obtaining a support material by photocuring the composition for support material;
Removing the support material (II);
There is provided a method for manufacturing an optically shaped article.

  According to the present invention, the support material is excellent in water removability and is further made in view of the above situation using a support material that is excellent in self-supporting properties, and has excellent mechanical characteristics and good dimensional accuracy. To provide an optical modeling ink set for obtaining an optical modeling product, an optical modeling product modeled using the optical modeling ink set, and an optical modeling manufacturing method using the optical modeling ink set. Can do.

FIG. 1 is a schematic side view showing a state where an ink for a support material and an ink for a model material are ejected by an ink jet modeling method and are irradiated with energy rays. FIG. 2 is a schematic side view showing a state where the support material ink and the model material ink are discharged by the ink jet modeling method. FIG. 3 is a schematic side view showing a state in which energy rays are applied to the support material ink and the model material ink ejected by the ink jet modeling method. FIG. 4 is a schematic side view of a modeled article precursor composed of a support material and a model material formed by an ink jet modeling method. FIG. 5 is a schematic side view of a model formed by the ink jet modeling method.

  Hereinafter, an embodiment of the present invention (hereinafter also referred to as this embodiment) will be described in detail. The present invention is not limited to the following contents. In the following description, “(meth) acrylate” is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to “(meth) acryloyl” and “(meth) acryl”.

1. Composition for model material <Monofunctional ethylenically unsaturated monomer (A)>
The model material composition contained in the optical modeling ink set according to the present embodiment has a homopolymer glass transition temperature (hereinafter also referred to as Tg) of 80 ° C. or higher, and has no urethane group. The unsaturated unsaturated monomer (A) is contained.

  When the Tg of the homopolymer of the monofunctional ethylenically unsaturated monomer (A) is 80 ° C. or more, the heat resistance of the model material obtained by photocuring the model material composition is improved. The Tg of the homopolymer of the monofunctional ethylenically unsaturated monomer (A) is preferably 85 ° C. or higher, and more preferably 90 ° C. or higher. Further, the Tg of the homopolymer of the monofunctional ethylenically unsaturated monomer (A) is preferably 190 ° C. or lower, and more preferably 185 ° C. or lower.

  Examples of the monofunctional ethylenically unsaturated monomer (A) include a compound having a Tg of 80 ° C. or more of a homopolymer among linear or branched alkyl (meth) acrylates having 4 to 30 carbon atoms [methyl (Meth) acrylate, tert-butyl (meth) acrylate, etc.], (meth) acrylate having an alicyclic skeleton having 6 to 20 carbon atoms, a compound having a Tg of 80 ° C. or higher for its homopolymer [cyclohexyl (meth) Acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, etc.], (meth) acrylate having a heterocyclic skeleton, its homo Compound [4- (meth) acryloyloxymethyl-2 with Tg of polymer of 80 ° C. or higher Cyclohexyl-1,3-dioxolane], and the like. These may be used alone or in combination of two or more.

  The monofunctional ethylenically unsaturated monomer (A) is alicyclic from the viewpoint of withstanding the modeling temperature (50 to 90 ° C.) when the model material is cured and improving the dimensional accuracy of the model material. It preferably has a skeleton. Specifically, the monofunctional ethylenically unsaturated monomer (A) is at least one selected from isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate and adamantyl (meth) acrylate. Is preferred.

  The content of the monofunctional ethylenically unsaturated monomer (A) is 60 to 80 weights with respect to 100 parts by weight of the entire model material composition from the viewpoint of improving Tg and brittleness resistance of the model material. Part. The content of the monofunctional ethylenically unsaturated monomer (A) is more preferably 65 parts by weight or more, and more preferably 75 parts by weight or less. In addition, when the said (A) component is contained 2 or more types, the said content is the sum total of content of each (A) component.

<Polyfunctional ethylenically unsaturated monomer (B)>
The composition for a model material included in the optical modeling ink set according to the present embodiment has a ring structure, a homopolymer glass transition temperature of 180 ° C. or higher, and has no urethane group. Contains an unsaturated monomer (B).

  When the Tg of the homopolymer of the polyfunctional ethylenically unsaturated monomer (B) is 180 ° C. or higher, the heat resistance of the model material can be improved. The Tg of the polyfunctional ethylenically unsaturated monomer (B) homopolymer is preferably 200 ° C. or higher, more preferably 205 ° C. or higher, and further preferably 210 ° C. or higher. Moreover, Tg of the homopolymer of the polyfunctional ethylenically unsaturated monomer (B) is preferably 230 ° C. or less, and more preferably 220 ° C. or less.

  Examples of the polyfunctional ethylenically unsaturated monomer (B) include compounds having a homopolymer Tg of 180 ° C. or higher among di (meth) acrylates having an alicyclic skeleton having 10 to 30 carbon atoms [ Dimethylol-tricyclodecane dimethacrylate, etc.] Among di (meth) acrylates having an aromatic ring having 10 to 40 carbon atoms, compounds having a homopolymer Tg of 180 ° C. or higher [bisphenoxyfluorange (meth) acrylate, etc.] Etc. These may be used alone or in combination of two or more.

  The polyfunctional ethylenically unsaturated monomer (B) is alicyclic from the viewpoint of withstanding the modeling temperature (50 to 90 ° C.) when the model material is cured and improving the dimensional accuracy of the model material. It preferably has a skeleton or an aromatic ring. Specifically, it is preferable that the polyfunctional ethylenically unsaturated monomer (B) is dimethylol-tricyclodecane dimethacrylate or bisphenoxyfluorange (meth) acrylate.

  From the viewpoint of improving the mechanical strength and heat resistance of the model material, the content of the polyfunctional ethylenically unsaturated monomer (B) is 5 to 30 with respect to 100 parts by weight of the entire model material composition. It is preferable that it is a weight part. The content of the polyfunctional ethylenically unsaturated monomer (B) is more preferably 10 parts by weight or more, and more preferably 25 parts by weight or less. In addition, when the said (B) component is contained 2 or more types, the said content is the sum total of content of each (B) component.

<Oligomer (C)>
The model material composition included in the optical modeling ink set according to the present embodiment contains the oligomer (C). The oligomer (C) has a weight average molecular weight (hereinafter referred to as Mw) of 800 to 10,000. In addition, Mw means the weight average molecular weight of polystyrene conversion measured by GPC (Gel Permeation Chromatography).

  Examples of the oligomer (C) include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving the curability of the composition for model material, it is at least one selected from urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, and polyester (meth) acrylate oligomers. Is preferred. Furthermore, the composition for model material is a urethane (meth) acrylate oligomer from the viewpoint of improving the dimensional accuracy of the model material by having heat resistance that can withstand the temperature (50 to 90 ° C.) during photocuring. Is more preferable.

  Among urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers, polyfunctional oligomers having two or more functions are preferable. It is more preferable that the oligomer is.

  It is preferable that content of the said oligomer (C) is 10-15 weight part with respect to 100 weight part of the said whole composition for model materials. When the content of the oligomer (C) is less than 10 parts by weight, the shrinkage of the model material is slightly increased. As a result, the dimensional accuracy of the model material may deteriorate. On the other hand, when the content of the oligomer (C) exceeds 15 parts by weight, the viscosity of the model material composition becomes high. For this reason, when the model material composition is ejected from the inkjet head, jetting characteristics may be deteriorated and flight bending may occur. As a result, the dimensional accuracy of the model material may deteriorate. In addition, when the said (C) component is contained 2 or more types, the said content is the sum total of content of each (C) component.

<Photopolymerization initiator (D)>
It is preferable that the composition for model materials of this invention contains a photoinitiator. The photopolymerization initiator is not particularly limited as long as it is a compound that promotes a radical reaction when irradiated with light having a wavelength in the ultraviolet, near ultraviolet, or visible light region. The photopolymerization initiator is not particularly limited as long as the polymerization can be initiated with low energy. It is preferable to use a photopolymerization initiator containing at least one compound selected from the group consisting of and ketal compounds.

  Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide. 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 4-methylbenzoyldiphenylphosphine oxide, 4-ethylbenzoyldiphenylphosphine oxide, 4-isopropylbenzoyl Diphenylphosphine oxide, 1-methylcyclohexanoylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,4,6-trimethylbenzoylphenylphosphinic acid isopropyl ester, bis (2,6-dimethoxybenzoyl) -2,4 Examples include 4-trimethylpentylphosphine oxide. These may be used alone or in combination. Examples of the acylphosphine oxide compound available in the market include “DAROCURE TPO” manufactured by BASF.

Specific examples of the α-aminoalkylphenone compound include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) butanone-1, 2-methyl-1- [4- (methoxythio) -phenyl] -2-morpholinopropan-2-one and the like. These may be used alone or in combination. Examples of α-aminoalkylphenone compounds available on the market include “IRGACURE 369” and “IRGACURE 907” manufactured by BASF.
Specific examples of the α-hydroxyquinone compound include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-phenylpropan-1-one, 2-hydroxy-1- {4- [4 -(2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl -1-propan-1-one and the like. These may be used alone or in combination. Examples of the α-hydroxyquinone compounds available on the market include “IRGACURE 184”, “DAROCURE 1173”, “IRGACURE 2959”, “IRGACURE 127” and the like.

  Specific examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4. -Diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. These may be used alone or in combination. Examples of commercially available thioxanthone compounds include “MKAYACURE DETX-S” manufactured by Nippon Kayaku Co., Ltd. and “Chivacure ITX” manufactured by Double Bond Chemical.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether.

  Specific examples of the anthraquinone compound include 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone.

  Specific examples of the ketal compound include, for example, acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like, benzophenone compounds having 13 to 21 carbon atoms (for example, benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4 Examples include '-bismethylaminobenzophenone.

  Content of the said (D) component is 1-15 weight part with respect to 100 weight part of the whole resin composition. When the content of the component (D) is within the above range, the curability of the model material composition is improved, and the dimensional accuracy of the optically shaped article is improved. The content of the component (D) is preferably 2 parts by weight or more, and preferably 13 parts by weight or less. In addition, when the said (D) component is contained 2 or more types, the said content is defined as the sum total of content of each (D) component.

<Other additives>
The composition for a model material included in the optical modeling ink set according to the present embodiment can contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of other additives include a polymerization inhibitor, a surface conditioner, a colorant, an antioxidant, a chain transfer agent, and a filler. These may be used alone or in combination of two or more.

  The model material composition preferably contains a polymerization inhibitor. When the composition for model materials contains a polymerization inhibitor, it is possible to suppress excessive polymerization at a temperature (about 50 to 90 ° C.) at which the shaped article is molded. As a result, since the monomer can be stabilized, the model material composition is easily cured.

  Examples of the polymerization inhibitor include phenol compounds [hydroquinone, hydroquinone monomethyl ether and the like], sulfur compounds [dilauryl thiodipropionate and the like], phosphorus compounds [triphenyl phosphite and the like], amine compounds [phenothiazine and the like], and the like. Can be mentioned. These may be used alone or in combination of two or more.

  The content of the polymerization inhibitor is preferably 5 parts by weight or less with respect to 100 parts by weight of the entire model material composition from the viewpoint of improving the stability of the monomer and the polymerization rate. The amount is more preferably 0.1 parts by weight or less, and more preferably 0.1 parts by weight or more. In addition, when the said polymerization inhibitor is contained 2 or more types, the said content is the sum total of content of each polymerization inhibitor.

  Examples of the surface conditioner (E) include a PEG type nonionic surfactant [nonylphenol ethylene oxide (hereinafter abbreviated as EO) 1 to 40 mol adduct, stearin having a molecular weight of 264 or more and Mn 5,000 or less. Acid EO 1-40 mol adducts, etc.], polyhydric alcohol type nonionic surfactant (sorbitan palmitic acid monoester, sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactant (perfluoroalkyl EO1) ˜50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), modified silicone oils [polyether-modified silicone oil, (meth) acrylate-modified silicone oil, etc.] and the like. These may be used alone or in combination of two or more. Of the surface conditioners, silicone-based surface conditioners are preferable, and surface conditioners having a polydimethylsiloxane structure are particularly preferable.

  The content of the surface conditioning agent is 3 parts by weight or less with respect to 100 parts by weight of the entire model material composition from the viewpoint of improving the addition effect and the physical properties of the model material and the optically shaped article. It is preferably 2 parts by weight or less, more preferably 0.1 parts by weight or more. In addition, when 2 or more types of the said surface conditioning agents are contained, the said content is the sum total of content of each surface conditioning agent.

  Examples of the colorant include pigments and dyes. These may be used alone or in combination of two or more.

  The pigment includes an organic pigment and / or an inorganic pigment. Examples of the organic pigment include pigments exemplified below.

(Azo pigment)
Insoluble monoazo pigments (toluidine red, permanent carmine FB, fast yellow G, etc.), etc .;
(Polycyclic pigment)
Phthalocyanine blue, etc .;
(Dyed rake)
Basic dyes (Victoria Pure Blue BO Lake etc.) etc .;
(Other pigments)
Azine pigments (aniline black, etc.), daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, etc.

  Examples of the inorganic pigment include metal oxides (iron oxide, chromium oxide, titanium oxide, etc.), carbon black, and the like.

  The content of the colorant is 2 parts by weight or less with respect to 100 parts by weight of the entire model material composition, from the viewpoint of improving the coloring effect and the physical properties of the model material and the optically shaped article. Is preferably 1 part by weight or less, more preferably 0.1 part by weight or more. In addition, when the said coloring agent is contained 2 or more types, the said content is the sum total of content of each coloring agent.

  Examples of the antioxidant include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol etc.) and the like.

  The content of the antioxidant is 3 parts by weight or less with respect to 100 parts by weight of the entire model material composition from the viewpoint of improving the antioxidant effect and the physical properties of the model material and the optically shaped article. Preferably, it is 2 parts by weight or less, more preferably 0.1 part by weight or more. In addition, when 2 or more types of the said antioxidant is contained, the said content is the sum total of content of each antioxidant.

  Examples of the chain transfer agent include hydrocarbons [C6-24 compounds such as aromatic hydrocarbons (toluene, xylene, etc.), unsaturated aliphatic hydrocarbons (1-butene, 1-nonene, etc.), etc.]; Halogenated hydrocarbons (C1-24 compounds such as dichloromethane, carbon tetrachloride) and the like. These may be used alone or in combination of two or more.

  The content of the chain transfer agent is 10 parts by weight with respect to 100 parts by weight of the entire model material composition from the viewpoint of improving the polymerizability of the monomer and the compatibility between the monomer and the chain transfer agent. Is preferably 5 parts by weight or less, more preferably 0.05 parts by weight or more. In addition, when the said chain transfer agent is contained 2 or more types, the said content is the sum total of content of each chain transfer agent.

  Examples of the filler include metal powder (aluminum powder, copper powder, etc.), metal oxide (alumina, silica, talc, mica, clay, etc.), metal hydroxide (aluminum hydroxide, etc.), metal salt (carbonic acid). Calcium, calcium silicate, etc.), fiber [inorganic fiber (carbon fiber, glass fiber, asbestos, etc.), organic fiber (cotton, nylon, acrylic, rayon fiber, etc.)], microballoon (glass, shirasu, phenol resin, etc.) , Carbons (carbon black, graphite, coal powder, etc.), metal sulfides (molybdenum disulfide, etc.), organic powders (wood powder, etc.) and the like. These may be used alone or in combination of two or more.

  The content of the filler is 30% with respect to 100 parts by weight of the entire model material composition from the viewpoint of improving the filling effect, inkjet dischargeable viscosity, and physical properties of the model material and the stereolithographic product. Is preferably 20 parts by weight or less, more preferably 3 parts by weight or more. In addition, when the said filler is contained 2 or more types, the said content is the sum total of content of each filler.

  The content of the other additives is 30 parts by weight or less with respect to 100 parts by weight of the entire model material composition, from the viewpoint of adding effects and improving the physical properties of the model material and the optically shaped article. Preferably, it is 20 parts by weight or less, more preferably 0.05 part by weight or more. In addition, when the said other additive is contained 2 or more types, the said content is the sum total of content of each other additive.

  The manufacturing method of the composition for model materials contained in the optical modeling ink set which concerns on this embodiment is not specifically limited. For example, it can manufacture by mixing said (A)-(D) component and the said other additive as needed using a mixing stirrer, a disperser, etc. uniformly.

  The model material composition thus produced preferably has a viscosity at 25 ° C. of 70 mPa · s or less from the viewpoint of improving the dischargeability from the inkjet head. In addition, the measurement of the viscosity of the composition for model materials is performed using R100 type | mold viscosity meter based on JISZ8803.

  From the viewpoint of improving the heat resistance of the model material and reducing warpage, the model material composition preferably has a Tg of 90 to 200 ° C. The Tg of the model material is more preferably 95 ° C. or higher, and further preferably 100 ° C. or higher. The Tg of the model material is more preferably 190 ° C. or lower, and further preferably 180 ° C. or lower.

  In addition, Tg in this invention can be measured, for example using a differential-heat measuring apparatus (The Mac Science company make, TG-DTA (2000S)).

2. Support Material Composition A support material composition is a photocurable composition for a support material that provides a support material by photocuring. After the model material is created, it can be removed from the model material by physically peeling the support material from the model material or by dissolving the support material in an organic solvent or water. The composition for a model material of the present invention can be used in combination with various conventionally known compositions as a composition for a support material, but does not damage the model material when the support material is removed, and the environment. It is preferable that the support material composition constituting the stereolithography composition set of the present invention is water-soluble because the support material can be removed easily and cleanly in detail.

In the present invention, the water-soluble support material composition comprises at least one water-soluble monofunctional ethylenically unsaturated monomer (a), at least one polyalkylene glycol (b), and a photopolymerization initiator (c). It is preferable to contain.
<Water-soluble monofunctional ethylenically unsaturated monomer (a)>
The water-soluble monofunctional ethylenically unsaturated monomer contained in the composition for a support material of the present invention is preferably a radical polymerizable compound. For example, a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms (for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.), number average molecular weight (Mn) 200 to 1,000 hydroxyl group-containing (meth) acrylate [for example, polyethylene glycol mono (meth) acrylate, monoalkoxy (1 to 4 carbon atoms) polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, monoalkoxy (carbon number 1-4) Polypropylene glycol mono (meth) acrylate, mono (meth) acrylate of PEG-PPG block polymer, etc.], (meth) acrylamide derivatives [eg (meth) acrylamide, N-methyl (meth) acryl Amide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N- Hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide and the like], (meth) acryloylmorpholine and the like. These may be used alone or in combination of two or more.

The content of the water-soluble monofunctional ethylenically unsaturated monomer (a) contained in the support material composition is preferably 19 to 80 parts by mass with respect to 100 parts by mass of the support material composition. More preferably, it is 22 parts by mass or more, more preferably 25 parts by mass or more, more preferably 76 parts by mass or less, and further preferably 73 parts by mass or less. When the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is within the above range, the removability of the support material with water can be improved without reducing the support power of the support material.
<Polyalkylene glycol (b)>
The polyalkylene glycol (b) that can be included in the composition for a support material may be either a linear type or a multi-chain type. Moreover, as long as it melt | dissolves in water, the alkyl group may be included in the terminal, for example, Preferably it may contain the C6 or less alkyl chain. Specific examples of such polyalkylene glycol (b) include polyalkylene glycol having an oxybutylene group. These may be used alone or in combination of two or more.

The polyalkylene glycol (b) containing an oxybutylene group that can be contained in the composition for a support material is not particularly limited as long as the polyalkylene glycol (b) contains an oxybutylene group. For example, an oxybutylene group (oxy A polybutylene glycol having only a tetramethylene group), or a polybutylene polyoxyalkylene glycol having both an oxybutylene group and another oxyalkylene group (for example, polybutylene polyethylene glycol). . For example, the polybutylene glycol is represented by the following chemical formula (1), and the polybutylene polyethylene glycol is represented by the following chemical formula (2).

  In the above chemical formula (2), m is preferably an integer of 5 to 300, and n is preferably an integer of 2 to 150. More preferably, m is 6 to 200, and n is 3 to 100. Further, the oxybutylene group in the chemical formula (1) and the chemical formula (2) may be a straight chain or may be branched.

  When the composition for a support material contains the polyalkylene glycol (b) containing an oxybutylene group, the removability by water can be further improved without reducing the support force of the support material. These may be used alone or in combination of two or more.

  Component (b) has a weight average molecular weight of 300 or more, preferably less than 3000, more preferably 800 or more, and more preferably less than 2000. If the weight average molecular weight of component (b) is less than 300, bleeding of the support material occurs when the support material composition is cured. Bleeding is a phenomenon in which a liquid component oozes from the inside of a cured support material to the support material surface. Moreover, since the weight average molecular weight of polyalkylene glycol is smaller than 3000, it is excellent in the discharge stability of the composition for support materials.

  (B) Two or more types of components may be used. When two or more types of polyalkylene glycol are used, the content of polyalkylene glycol having a weight average molecular weight of less than 300 or greater than 3000 is preferably small.

The content of the polyalkylene glycol (b) in the support material composition is preferably 15 to 75 parts by mass, more preferably 17 parts by mass or more, with respect to 100 parts by mass of the support material composition. More preferably, it is 20 mass parts or more, More preferably, it is 72 mass parts or less, More preferably, it is 70 mass parts or less. When the content of the polyalkylene glycol (b) is within the above range, the removability of the support material with water or a water-soluble solvent can be improved without reducing the support power of the support material.
<Water-soluble organic solvent (c)>
The composition for a support material may contain a water-soluble organic solvent (c). The water-soluble organic solvent (c) is a component that improves the solubility of the support material obtained by photocuring the support material composition in water. Moreover, it has the function to adjust the composition for support materials to low viscosity.

  As the water-soluble organic solvent (c), it is preferable to use a glycol solvent. Specifically, for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate. Glycol ester solvents such as acetate, tripropylene glycol monoacetate, tetraethylene glycol monoacetate, tetrapropylene glycol monoacetate, ethylene glycol diacetate, propylene glycol diacetate; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, triethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol Monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, Glycol ether solvents such as ethylene glycol dipropyl ether, propylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, propylene glycol Methyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monobutyl ether acetate And glycol monoether acetate solvents such as These may be used alone or in combination of two or more.

  Among them, the low-viscosity support material composition is easy to prepare, and the support material obtained by curing is excellent in water solubility. Therefore, as the water-soluble organic solvent (c), triethylene glycol monomethyl ether, diethylene glycol diethyl Ether and dipropylene glycol monomethyl ether acetate are preferred.

The content of the water-soluble organic solvent (c) in the support material composition is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, with respect to 100 parts by mass of the support material composition. More preferably, it is 25 parts by mass or less. When the content of the water-soluble organic solvent (c) is within the above range, the removability of the support material with water or the water-soluble solvent can be improved without reducing the support power of the support material.
<Photopolymerization initiator (d)>
As the photopolymerization initiator (d), the compounds described above as photopolymerization initiators that can be contained in the model material composition can be similarly used. The content of the photopolymerization initiator in the support material composition is preferably 1 to 20 parts by mass and more preferably 2 to 18 parts by mass with respect to 100 parts by mass of the support material composition.
When the content of the photopolymerization initiator is within the above range, unreacted polymerization components can be sufficiently reduced, and the curability of the support material can be sufficiently enhanced.

  By including each of the above components in a content within the above range, a composition for a support material having both excellent water solubility and support ability can be obtained. In particular, since the support power is excellent, there is no concern that the moisture in the air is taken in during modeling and the support power is reduced, and an optical modeling product with good dimensional accuracy can be obtained.

  If necessary, the composition for a support material may contain other additives. Examples of other additives include surface conditioners, antioxidants, colorants, pigment dispersants, storage stabilizers, ultraviolet absorbers, light stabilizers, polymerization inhibitors, chain transfer agents, and fillers. .

  The surface tension of the support material composition can be controlled within an appropriate range by blending the surface conditioning agent (d) into the support material composition, and the model material composition and the support material composition Mixing at the interface can be suppressed. Thereby, a stereolithography product with favorable dimensional accuracy can be obtained. As the surface conditioner that can be contained in the support material composition, the same as those exemplified as the surface conditioner that can be used in the model material composition of the present invention can be used. It is preferable that it is 0.005 mass part or more and 3.0 mass part or less with respect to 100 mass parts of things. Of the surface conditioners, silicone-based surface conditioners are preferable, and surface conditioners having a polydimethylsiloxane structure are particularly preferable.

  Moreover, storage stability can be improved by mix | blending a storage stabilizer with the composition for support materials. As the storage stabilizer that can be contained in the support material composition, those exemplified as the storage stabilizer that can be used in the model material composition of the present invention can be used. It is preferable that it is 0.05-3 mass parts with respect to 100 mass parts of things.

  In the present invention, the viscosity of the support material composition is preferably 30 to 200 mPa · s at 25 ° C., more preferably 35 mPa · s or more, and still more preferably, from the viewpoint of improving dischargeability from the inkjet nozzle. Is 40 mPa · s or more, more preferably 170 mPa · s or less, and still more preferably 150 mPa · s or less. In addition, the measurement of the said viscosity can be performed using R100 type | mold viscosity meter based on JISZ8803.

  In the present invention, the surface tension of the support material composition is preferably 24 to 30 mN / m, more preferably 24.5 to 29.5 mN / m, and further preferably 25 to 29 mN / m. When the surface tension is within the above range, it is possible to normally form droplets ejected from the nozzle, to ensure an appropriate droplet amount and landing accuracy, and to suppress the occurrence of satellites, It becomes easy to ensure high modeling accuracy. In addition, the surface tension of the composition for support material can be measured in accordance with the method similar to the measuring method of the surface tension in the composition for model materials.

  The manufacturing method of the composition for support materials of this invention is not specifically limited, For example, it can manufacture by mixing the component which comprises the composition for support materials uniformly using a mixing stirring apparatus etc.

3. Optical modeling product and manufacturing method thereof The manufacturing method of the optical modeling object of the present embodiment is a manufacturing method of an optical modeling object using the composition set for material jet optical modeling (ink set for optical modeling) described in the above embodiment. After discharging the composition for the model material or the composition for the support material using a material jet (inkjet) printer, the model material composition is photocured to obtain the model material, and for the water-soluble support material It comprises a step of photocuring the composition to obtain a water-soluble support material, and a step of removing the water-soluble support material by immersing it in water.

  Since the manufacturing method of the optical modeling thing of this embodiment is using the said composition set for material jet optical modeling, it can form the optical modeling thing excellent in modeling precision.

  Hereinafter, the manufacturing method of the optical modeling thing of this embodiment is explained based on a drawing. FIG. 1 is a schematic side view showing a state in which a support material composition and a model material composition are ejected by a material jet modeling method and irradiated with energy rays. In FIG. 1, the three-dimensional modeling apparatus 10 includes an inkjet head module 11 and a modeling table 12. The ink jet head module 11 includes an optical modeling ink unit 11a, a roller 11b, and a light source 11c. Further, the optical modeling ink unit 11a includes a model material inkjet head 11aM filled with the model material ink 13 and a support material inkjet head 11aS filled with the support material ink.

  The model material composition 13 is ejected from the model material inkjet head 11aM, the support material composition 14 is ejected from the support material inkjet head 11aS, and the energy beam 15 is irradiated and ejected from the light source 11c. The model material composition 13 and the support material composition 14 are cured to form the model material 13PM and the support material 14PS. FIG. 1 shows a state in which the first layer model material 13PM and the support material 14PS are formed.

  Next, the manufacturing method of the optical modeling thing of this embodiment is demonstrated still in detail based on drawing. In the method of manufacturing an optically shaped object according to the present embodiment, first, as shown in FIG. 2, the inkjet head module 11 is scanned in the X direction (right direction in FIG. 2) with respect to the modeling table 12, and the inkjet for model material is used. The model material composition 13 is discharged from the head 11aM, and the support material composition 14 is discharged from the support material inkjet head 11aS. Thereby, on the modeling table 12, the layer which consists of the model material precursor 13M, and the layer which consists of the support material precursor 14S are arrange | positioned adjacently so that each interface may contact.

Next, as shown in FIG. 3, the inkjet head module 11 is scanned in the reverse X direction (left direction in FIG. 3) with respect to the modeling table 12, and the model material precursor 13 </ b> M and the support material precursor 14 </ b> S with the roller 11 b. After smoothing the surface of the layer made of the material, the energy beam 15 is irradiated from the light source 11c to cure the layer made of the model material precursor 13M and the support material precursor 14S, and the first model material 13PM and the support material 14PS. A layer consisting of is formed.

  Subsequently, the modeling table 12 is lowered by one layer in the Z direction, the same process as described above is performed, and a second layer of the model material and the support material is formed. Thereafter, by repeating the above steps, as shown in FIG. 4, an optically shaped product precursor 16 composed of the model material 13PM and the support material 14PS is formed.

  Finally, the optical modeling product precursor 16 shown in FIG. 4 is immersed in water to dissolve and remove the support material 14PS, and the optical modeling product 17 as shown in FIG. 5 is formed.

In the method for producing an optically shaped object of the present embodiment, for example, a high pressure mercury lamp, a metal halide lamp, a UV-LED, or the like can be used as the light source. From the viewpoint that the three-dimensional modeling apparatus 10 can be miniaturized and the power consumption is small, UV-LED is preferable. The amount of light is preferably 200 to 500 mJ / cm ² from the viewpoint of the hardness and dimensional accuracy of the shaped product. When a UV-LED is used as the light source, it is preferable to use a light having a center wavelength of 385 to 415 nm because light easily reaches a deep layer and the hardness and dimensional accuracy of the optically shaped product can be improved. As the energy rays 15 irradiated from the light source 11c, ultraviolet rays, near ultraviolet rays, visible rays, infrared rays, far infrared rays, electron beams, α rays, γ rays, X-rays, and the like can be used. And from a viewpoint of efficiency, ultraviolet rays or near ultraviolet rays are preferable.

  In the manufacturing method of the present invention, for example, based on the three-dimensional CAD data of the object to be manufactured, the data of the composition for the model material that forms the three-dimensional structure by stacking by the material jet method, and the three-dimensional modeling in the process of preparation The data of the composition for the support material that supports the object is prepared, and further, the slice data for discharging each composition by the material jet type 3D printer is prepared, and each of the material for the model material and the support material is based on the prepared slice data. After the composition is discharged, the photocuring treatment is repeated for each layer to produce an optically shaped article composed of a cured product of the model material composition (model material) and a cured product of the support material composition (support material). it can.

  The thickness of each layer constituting the three-dimensional model is preferably thin from the viewpoint of modeling accuracy, but is preferably 5 to 30 μm from the balance with the modeling speed.

  The obtained optically shaped object is a combination of a model material and a support material. The support material is removed from the stereolithography product to obtain a stereolithography product as a model material. The support material can be removed by, for example, immersing an optical modeling object obtained in a removal solvent that dissolves the support material, softening the support material, and then removing the support material from the model material surface with a brush or the like. preferable. Water or a water-soluble solvent such as a glycol solvent or an alcohol solvent may be used as the solvent for removing the support material. These may be used alone or in combination.

  The optically shaped article has suppressed water absorption and swelling when contacted with water, and is less likely to cause breakage and deformation of the fine structure portion. Further, the stereolithographic product is excellent in water and oil repellency and hardly contaminated.

Hereinafter, examples that more specifically disclose the present embodiment will be described. In addition, this invention is not limited only to these Examples.

<Model material composition>
(Manufacture of compositions for model materials)
As shown in Tables 1 and 2, the components were uniformly mixed using a mixing and stirring device to produce compositions for model materials of Examples M1 to M7 and Comparative Examples m1 to m3.

<Composition for support material>
<Resin composition for support material>
Table 3 summarizes the components used in the support material composition in the following Examples and Comparative Examples.

(Examples S1 to S13)
First, Examples S1 to S13 and Comparative Example s1 Support material compositions were prepared as follows. That is, each support material composition was prepared by measuring each component shown in Table 3 in a plastic bottle in the blending amount (unit: parts by mass) shown in Table 4 and mixing them.

  Next, with respect to the support material compositions of Examples S1 to S13 and Comparative Example s1, the low temperature stability of the support material composition and the high temperature and high humidity of the cured support material obtained by curing the support material composition by the methods described below. Condition stability (supporting power) and water removability were evaluated.

<Low temperature stability of support material composition>
The stability of the support material composition at low temperature was evaluated. Each support material composition was put into a glass bottle, and the glass bottle with the support material composition was stored in a thermostatic bath set at a temperature of 10 ° C. for 24 hours. Thereafter, the state of the support material composition after storage was visually confirmed, and the low temperature stability of the support material composition was evaluated according to the following criteria.

When the support material composition is maintained in a liquid state: low temperature stability A (excellent)
When the support material composition is partially solidified (solidified): low temperature stability B (good)
When the support material composition is solidified (solidified): low temperature stability C (poor)
<Supporting power of cured support material>
A frame is formed on a glass plate with a frame-shaped silicon rubber having a length of 30 mm, a width of 30 mm, and a thickness of 5 mm, each support material composition is poured into the frame, and an ultraviolet ray with an integrated light amount of 500 mJ / cm ² is obtained by a metal halide lamp. Was irradiated to produce a cured support material. Subsequently, the cured product was placed in a glass petri dish, and the petri dish containing the cured product was left in a thermostatic bath at a temperature of 40 ° C. and a relative humidity of 90% for 2 hours. Thereafter, the state of the cured product after standing was visually confirmed, and the support force of the cured support material was evaluated according to the following criteria.

When there is no generation of liquid substances on the surface of the cured product and no softening of the cured product is confirmed: Support strength A (excellent)
When a slight amount of liquid material is generated on the surface of the cured product and softening of the cured product is confirmed slightly: Support strength B (good)
When a liquid substance is generated on the surface of the cured product and softening of the cured product is confirmed: Support force C (defect)
<Water removability of the cured support material>
A cured support material was produced in the same manner as in the evaluation of the support force of the cured support material. Next, the cured product is placed in a beaker filled with 50 mL of ion exchange water, treated with an ultrasonic cleaner while maintaining the water temperature at 25 ° C., and the time until the cured product is dissolved is measured. The water removal property of the support material cured product was evaluated based on the standard.

When it takes 30 minutes for the cured product to completely dissolve: Water removability A (excellent)
When it takes 1 hour for the cured product to completely dissolve: Water removability B (good)
When it takes 2 hours for the cured product to completely dissolve: water removability C (poor)
The results are shown in Table 5.

  It can be seen that the support material compositions of Examples S1 to S13 obtained satisfactory results for all evaluation items.

<Optical modeling products>
<Composition set for material jet stereolithography (ink set)>
Examples 1-4 and Comparative Examples 1-3 were prepared by combining the composition for model materials and the composition for support materials as shown in Table 6.

A spacer having a thickness of 1 mm was arranged on the four upper surfaces of a glass plate (trade name “GLASS PLATE”, manufactured by ASONE, 200 mm × 200 mm × thickness 5 mm), and was partitioned into 10 cm × 10 cm squares. After casting the composition for the support material in the square, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) is used as the irradiation means, and ultraviolet rays are irradiated so that the total irradiation light amount becomes 500 mJ / cm ^2. And cured to obtain a support material.

Next, spacers having a thickness of 1 mm were arranged on the four sides of the upper surface of the support material and partitioned into squares of 10 cm × 10 cm. After casting the composition for the model material in the square, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) is used as the irradiation means, and ultraviolet rays are irradiated so that the total irradiation light amount becomes 500 mJ / cm ^2. And cured to obtain a model material.
(Evaluation of adhesion)
In this state, it was left in a thermostatic bath at 30 ° C. for 12 hours, the state of adhesion between the model material and the support material was visually confirmed, and evaluated according to the following criteria. The results are shown in Table 6.
○: The model material and the support material were in close contact.
X: Peeling occurred at the interface between the model material and the support material, and the model material was peeled off so as to be warped by the curing shrinkage of the model material.

  As can be seen from the results in Table 6, Examples 1 to 4 in which both the composition for the model material and the composition for the support material satisfy the requirements of the present invention do not cause peeling at the interface between the model material and the support material, Model material and support material were more closely attached. Thus, if the model material and the support material are in close contact with each other, an optically shaped product with good dimensional accuracy can be obtained.

  On the other hand, in Comparative Examples 1 to 3, in which one or both of the model material composition and the support material composition did not satisfy the requirements of the present invention, peeling occurred at the interface between the model material and the support material. As described above, when the adhesion between the model material and the support material is poor, the dimensional accuracy of the stereolithography product deteriorates.

  The optical modeling ink set of the present invention can be suitably used when an optical modeling product with good dimensional accuracy is manufactured using an inkjet optical modeling method.

DESCRIPTION OF SYMBOLS 10 3D modeling apparatus 11 Inkjet head module 11a Optical modeling ink unit 11aM Model material inkjet head 11aS Support material inkjet head 11b Roller 11c Light source 12 Modeling table 13 Model material ink 13M Model material precursor 13PM Model material 14 Support material Ink 14S support material precursor 14PS support material 15 energy beam 16 modeled object precursor 17 modeled object

Claims (12)

For optical modeling, which is a combination of a composition for a model material that is used in an inkjet optical modeling method and is used for modeling a model material, and a composition for a support material that is used to model a support material An ink set,
The model material composition is:
A monofunctional ethylenically unsaturated monomer (A) having a glass transition temperature of the homopolymer of 80 ° C. or higher and having no urethane group;
A polyfunctional ethylenically unsaturated monomer (B) having a ring structure, having a glass transition temperature of a homopolymer of 180 ° C. or higher, and having no urethane group;
An oligomer (C);
A photopolymerization initiator (D);
Containing
The support material composition is based on 100 parts by weight of the entire support material composition.
19 to 80 parts by mass of a water-soluble monofunctional ethylenically unsaturated monomer (a) and 15 to 75 parts by mass of a polyalkylene glycol (b) containing an oxybutylene group, and containing the oxybutylene group An ink set for stereolithography, wherein the alkylene glycol (b) has a weight molecular weight of 300 or more and less than 3000.   2. The optical modeling ink set according to claim 1, wherein the monofunctional ethylenically unsaturated monomer (A) has an alicyclic skeleton.   3. The optical modeling ink set according to claim 1, wherein the polyfunctional ethylenically unsaturated monomer (B) has an alicyclic skeleton or an aromatic ring.   The composition for model materials according to any one of claims 1 to 3, wherein the oligomer (C) is composed of a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, and a polyester (meth) acrylate oligomer. An ink set for stereolithography that is one or more selected.   5. The model material composition according to claim 1, wherein the content of the monofunctional ethylenically unsaturated monomer (A) is 100 parts by weight of the entire model material composition. Ink set for optical modeling that is 60 to 80 parts by weight.   6. The model material composition according to claim 1, wherein the content of the polyfunctional ethylenically unsaturated monomer (B) is based on 100 parts by weight of the model material composition as a whole. Ink set for stereolithography that is 5 to 30 parts by weight.   The composition for model materials according to any one of claims 1 to 6, wherein the content of the oligomer (C) is 10 to 15 parts by weight with respect to 100 parts by weight of the entire composition for model materials. An optical modeling ink set.   The optical modeling according to claim 1, wherein the model material composition has a glass transition temperature of 90 to 200 ° C. of the model material obtained by photocuring the model material composition. Ink set.   2. The optical modeling ink set according to claim 1, wherein the support material composition contains 1 to 20 parts by mass of a photopolymerization initiator (d). In Claim 1 or 9, the composition for a support material further contains a water-soluble organic solvent,
The ink set for optical modeling, wherein the content of the water-soluble organic solvent is 30 parts by mass or less with respect to 100 parts by mass of the total mass of the composition for support material. The support composition according to claim 1 or 10, further comprising a surface conditioner,
The ink set for optical modeling, wherein the content of the surface conditioning agent is 0.005 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the total mass of the support material composition. It is a method of manufacturing an optical modeling article using an ink modeling for optical modeling according to any one of claims 1 to 11 by an inkjet optical modeling method,
Step (I) of obtaining a model material by photocuring the composition for model material, and obtaining a support material by photocuring the composition for support material;
Removing the support material (II);
A method for manufacturing an optically shaped article.

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