JP6517456B2 - Optical forming ink set, optical forming product, and method for producing optical forming product - Google Patents

Description

This patent application claims priority under the Paris Convention for Japanese Patent Application No. 2017-011125 (filing date: January 31, 2017), which is incorporated herein by reference in its entirety. Shall be incorporated into the book.
The present invention relates to an ink set for optical shaping used in an inkjet light shaping method, an optical shaping article shaped using the ink set for optical shaping, and a method for producing an optical shaping article using the ink set for optical shaping About.

  Heretofore, as a method of producing a three-dimensional object, a forming method using a photocurable composition which is cured by irradiation with ultraviolet light or the like is widely known. Specifically, in such a shaping method, a cured layer having a predetermined shape is formed by irradiating the photocurable composition with ultraviolet light and curing it. Thereafter, a photocurable composition is further supplied on the cured layer and cured to form a new cured layer. The three-dimensional object is produced by repeating the above-mentioned process.

  Among the above-mentioned molding methods, in recent years, an optical molding method by an ink jet method in which a cured layer having a predetermined shape is formed by discharging a photocurable composition from a nozzle and irradiating and curing ultraviolet rays immediately thereafter. Hereinafter, the inkjet light molding method is reported (patent documents 1-5). In the inkjet light shaping method, the installation of a large resin liquid tank and a dark room for storing the photocurable composition is not necessary. Therefore, compared with the conventional method, a modeling apparatus can be miniaturized. Ink-jet optical molding is attracting attention as a molding method realized by a 3D printer that can freely create a three-dimensional object based on CAD (Computer Aided Design) data.

  In the case of forming an optical shaped article having a complicated shape such as a hollow shape in the inkjet optical shaping method, in order to support the model material, the model material and the support material are formed in combination (patent documents 1 and 2) , 4 and 5). The support material is prepared by irradiating the photocurable composition with ultraviolet light and curing the same as the model material. After creating the model material, the support material can be removed by physically peeling it out or dissolving it in an organic solvent or water.

  In recent years, there is a demand for forming an optical shaped article excellent in mechanical characteristics and excellent in dimensional accuracy by using an optical forming method by an inkjet method. In Patent Document 5, it is obtained by photocuring the composition for a model material by defining the glass transition temperature of the homopolymer of the ethylenically unsaturated monomer contained in the composition for a model material in a predetermined range. It is disclosed that the model material obtained is excellent in mechanical characteristics and dimensional accuracy. The photofabricated article formed by using such a model material can be suitably used as, for example, a mold, a mechanical component, or the like.

Unexamined-Japanese-Patent No. 2004-255839 JP, 2010-155889, A JP, 2010-155926, A JP, 2012-111226, A JP, 2016-20474, A

  Patent Document 5 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. There is. However, even if such a composition for support material is used, depending on the type and content of the components contained in the composition for support material, a support material obtained by photocuring the composition for support material In some cases the autonomy of the As a result, there is a problem in that the dimensional accuracy is reduced in the model material composition disclosed in Patent Document 5 and the photofabricated article formed using the composition for support material.

  The present invention has been made in view of the above-mentioned present situation, and it is an ink set for photofabrication for obtaining a photofabricated article having excellent mechanical characteristics and good dimensional accuracy, and the ink set for photofabrication An object of the present invention is to provide a manufactured photofabricated product and a method of manufacturing a photofabricated product using the ink composition for photofabrication.

  The present inventors obtained a support material having excellent self-sustainability by defining the content of the non-polymerized component and the water-soluble monofunctional ethylenically unsaturated monomer in the composition for a support material in a predetermined range. Found out that The present inventors form an optical shaped article having good dimensional accuracy by using the composition for support material and the composition for model material capable of obtaining a model material excellent in mechanical characteristics. I found that I could do it.

  The present invention has been made based on the above findings, and the summary thereof is as follows.

(1) A combination of a composition for a model material used for inkjet light shaping and used to model a model material and a composition for support material used to model a support material It is an ink set for light shaping,
The composition for the model material is
A monofunctional ethylenically unsaturated monomer (A) having a glass transition temperature of a homopolymer of 80 ° C. or higher and 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 more, and having no urethane group,
An oligomer (C),
A photopolymerization initiator (D),
Contains
The composition for a support material is 100 parts by weight of the entire composition for a support material,
20 to 50 parts by weight of a water-soluble monofunctional ethylenically unsaturated monomer (a),
A polyalkylene glycol (b) containing 20 to 49 parts by weight of an oxyethylene group and / or an oxypropylene group;
35 parts by weight or less of a water-soluble organic solvent (c),
A photopolymerization initiator (d),
An ink set for stereolithography that contains

  (2) The ink composition for photofabrication according to (1), wherein the monofunctional ethylenically unsaturated monomer (A) has an alicyclic skeleton in the composition for model material.

  (3) The composition for model materials described above in (1) or (2), wherein the polyfunctional ethylenically unsaturated monomer (B) has an alicyclic skeleton or an aromatic ring Ink set.

  (4) The composition for model materials is at least one selected from the group consisting of urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, and polyester (meth) acrylate oligomers, as the oligomer (C). The ink set for photofabrication as described in any one of said (1)-(3) which is it.

  (5) In the composition for model materials, the content of the monofunctional ethylenically unsaturated monomer (A) is 20 to 80 parts by weight with respect to 100 parts by weight of the whole composition for model materials The ink set for photofabrication as described in any one of said (1)-(4).

  (6) In the composition for model materials, the content of the polyfunctional ethylenically unsaturated monomer (B) is 5 to 50 parts by weight with respect to 100 parts by weight of the whole composition for model materials. The ink set for photofabrication as described in any one of said (1)-(5).

  (7) In the composition for model materials, the content of the oligomer (C) is 10 to 45 parts by weight with respect to 100 parts by weight of the whole composition for model materials. The ink set for stereolithography described in any one of the above.

  (8) In the composition for model materials, the content of the photopolymerization initiator (D) is 0.5 to 15 parts by weight with respect to 100 parts by weight of the whole composition for model materials. The ink set for optical shaping | molding as described in any one of (7)-(7).

  (9) The composition for a model material is any of the above (1) to (8), wherein the glass transition temperature of the model material obtained by photocuring the composition for a model material is 90 to 200 ° C. The ink set for light shaping described in or one.

  (10) In the composition for a support material, the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is 25 to 45 parts by weight with respect to 100 parts by weight of the whole composition for a support material. The ink set for photofabrication as described in any one of said (1)-(9) which is it.

  (11) In the composition for a support material, the content of the polyalkylene glycol (b) is 25 to 45 parts by weight with respect to 100 parts by weight of the whole composition for a support material. The ink set for photofabrication as described in any one of (10).

  (12) In the composition for support material, the content of the water-soluble organic solvent (c) is 5 parts by weight or more with respect to 100 parts by weight of the whole composition for support material. The ink set for photofabrication as described in any one of (11).

  (13) In the composition for a support material, the content of the photopolymerization initiator (d) is 1 to 25 parts by weight with respect to 100 parts by weight of the whole composition for a support material. The ink set for photofabrication as described in any one of (12).

  (14) The composition for a support material further contains 0.05 to 3.0 parts by weight of a storage stabilizer (e) with respect to 100 parts by weight of the total composition for a support material. The ink set for optical shaping | molding as described in any one of 1)-(13).

  (15) A photoformed product formed by the inkjet light shaping method using the ink set for photo formation according to any one of the above (1) to (14).

(16) A method for producing a photoformed article by the ink set according to any one of the above (1) to (14), using an ink jet photoforming method,
Step (I) of obtaining a support material by photo-curing the composition for model material by photo-curing the composition for model material and photo-curing the composition for support material;
Removing the support material (II);
A method for producing a photofabricated article, comprising:

  According to the present invention, an ink set for photofabrication for obtaining a photofabricated article having excellent mechanical properties and good dimensional accuracy, a photoshaped product fabricated using the ink set for photofabrication, and The manufacturing method of the optical shaping article using the said ink set for optical shaping can be provided.

FIG. 1: is a figure which shows typically process (I) in the manufacturing method of the optical shaping article which concerns on this embodiment. FIG. 2: is a figure which shows typically process (II) in the manufacturing method of the optical molded article which concerns on this embodiment. FIG. 3A is a top view of a cured product obtained using the resin composition for each model material and the resin composition for each support material shown in Table 6. FIG.3 (b) is the sectional view on the AA line of Fig.3 (a).

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

1. Composition for Model Material <Monofunctional Ethylenically Unsaturated Monomer (A)>
The composition for a model material contained in the ink set for stereolithography according to the present embodiment is a monofunctional ethylene having a glass transition temperature (hereinafter also referred to as Tg) of a homopolymer of 80 ° C. or more and having no urethane group. Containing unsaturated unsaturated monomer (A).

  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 composition for a model material is improved. The Tg of the homopolymer of the monofunctional ethylenically unsaturated monomer (A) is preferably 85 ° C. or more, more preferably 90 ° C. or more. The Tg of the homopolymer of the monofunctional ethylenically unsaturated monomer (A) is preferably 190 ° C. or less, more preferably 185 ° C. or less.

  The monofunctional ethylenically unsaturated monomer (A) is, for example, preferably a linear or branched alkyl (meth) acrylate having a carbon number of 4 to 30, preferably having a Tg of a homopolymer thereof. Among compounds having a temperature of 80 ° C. or more [methyl (meth) acrylate] and (meth) acrylates having an alicyclic skeleton having 6 to 20 carbon atoms, compounds having a homopolymer Tg of 80 ° C. or more [isobornyl (meth) acrylate, Among the cyclopentanyl (meth) acrylate, adamantyl (meth) acrylate and the like], and (meth) acrylates having a heterocyclic skeleton, compounds having a homopolymer Tg of 80 ° C. or higher are mentioned. These may be used alone or in combination of two or more.

  The monofunctional ethylenically unsaturated monomer (A) is an alicyclic from the viewpoint of enduring the shaping temperature (50 to 90 ° C.) at the time of curing of the model material and improving the dimensional accuracy of the model material. It is preferable to have 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 20 to 80 parts by weight with respect to 100 parts by weight of the whole composition for a model material from the viewpoint of improving the Tg and the brittleness resistance of the model material It is preferably part. The content of the monofunctional ethylenically unsaturated monomer (A) is more preferably 25 parts by weight or more, still more preferably 45 parts by weight or more, and still more preferably 60 parts by weight or more The amount is preferably 65 parts by weight or more, and more preferably 75 parts by weight or less. In addition, when two or more types of said (A) component are contained, the said content is the sum total of content of each (A) component.

<Polyfunctional ethylenic unsaturated monomer (B)>
The composition for a model material contained in the ink set for stereolithography according to the present embodiment has a ring structure, a homopolymer having a glass transition temperature of 180 ° C. or more, and a polyfunctional ethylenic group having no urethane group. It contains unsaturated monomer (B).

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

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

  The polyfunctional ethylenic unsaturated monomer (B) is an alicyclic from the viewpoint of enduring the shaping temperature (50 to 90 ° C.) at the time of curing of the model material and improving the dimensional accuracy of the model material. It is preferable to have a skeleton or an aromatic ring. Specifically, the polyfunctional ethylenic unsaturated monomer (B) is preferably dimethylol-tricyclodecane dimethacrylate or bisphenoxyfluorene (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 50 with respect to 100 parts by weight of the whole composition for the model material. 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 further preferably 30 parts by weight or less, and further preferably 25 parts by weight or less preferable. In addition, when two or more types of the said (B) component are contained, the said content is the sum total of content of each (B) component.

<Oligomer (C)>
The composition for model materials contained in the ink set for photo-forming according to the present embodiment contains an 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).

  As said oligomer (C), a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a polyether (meth) acrylate oligomer etc. are mentioned, for example. These may be used alone or in combination of two or more. Among them, at least one selected from urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, and polyester (meth) acrylate oligomers from the viewpoint of improving the curability of the composition for model materials Is preferred. Further, 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.) at the time of light curing. Is more preferred.

  Further, among urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers, bifunctional or higher polyfunctional oligomers are preferable, and bifunctional It is more preferable that it is an oligomer of

  The content of the oligomer (C) is preferably 10 to 45 parts by weight with respect to 100 parts by weight of the whole composition for a model material. When the content of the oligomer (C) is less than 10 parts by weight, curing shrinkage of the model material is slightly increased. As a result, the dimensional accuracy of the model material may be degraded. On the other hand, when the content of the oligomer (C) exceeds 45 parts by weight, the viscosity of the composition for model material becomes high. Therefore, when the composition for a model material is discharged from the ink jet head, the jetting property may be deteriorated to cause a flight curve. As a result, the dimensional accuracy of the model material may be degraded. The content of the oligomer (C) is more preferably 35 parts by weight or less, still more preferably 25 parts by weight or less, still more preferably 25 parts by weight or less based on 100 parts by weight of the whole composition for model materials . In addition, when two or more types of the said (C) component are contained, the said content is the sum total of content of each (C) component.

<Photoinitiator (D)>
The composition for model materials contained in the ink set for photofabrication according to the present embodiment contains a photopolymerization initiator (D).

  The photopolymerization initiator (D) is not particularly limited as long as it is a compound that promotes a radical reaction when irradiated with light of a wavelength in the ultraviolet, near ultraviolet, or visible light region. Examples of the photopolymerization initiator (D) include benzoin compounds having 14 to 18 carbon atoms (eg, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.), and having 8 to 18 carbon atoms Acetophenone compounds [e.g., acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one , Diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc.], anthraquinone compounds having 14 to 19 carbon atoms [eg, 2 -D Ruanthraquinone, 2-t-butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone, etc., thioxanthone compounds having 13 to 17 carbon atoms [eg, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc. A ketal compound having 16 to 17 carbon atoms [eg, acetophenone dimethyl ketal, benzyl dimethyl ketal etc.], a benzophenone compound having a carbon number of 13 to 21 [eg benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, '-Bismethylamino benzophenone etc.], acyl phosphine oxide compounds having 22 to 28 carbon atoms [eg, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis- (2,6-dimeth Kishibenzoiru) -2,4,4-trimethyl pentyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, etc.], a mixture of these compounds. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving light resistance, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is preferable. Moreover, as an acyl phosphine oxide compound which can be obtained, DAROCURE TPO made from BASF, etc. are mentioned, for example.

  The content of the photopolymerization initiator (D) is preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of the whole composition for a model material. When the content of the photopolymerization initiator (D) is in the above-mentioned range, the curability of the composition for model material becomes good, and the dimensional accuracy of the model material is improved. The content of the photopolymerization initiator (D) is more preferably 3 parts by weight or more, still more preferably 5 parts by weight or more, and still more preferably 13 parts by weight or less. In addition, when two or more types of the said (D) component are contained, the said content is the sum total of content of each (D) component.

<Other additives>
The composition for model materials contained in the ink set for stereolithography concerning this embodiment can be made to contain other additives if needed in the range which does not inhibit the effect of the present invention. Examples of other additives include polymerization inhibitors, surfactants, colorants, antioxidants, chain transfer agents, and fillers. These may be used alone or in combination of two or more.

  Examples of the polymerization inhibitor include phenol compounds [hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol) ), 1,1,3-Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane etc.], sulfur compounds [dilaurylthiodipropionate etc.], phosphorus compounds [triphenyl phosphite etc. And amine compounds [phenothiazine etc.] and the like. The content of the polymerization inhibitor is preferably 0.05 parts by weight or more, preferably 5 parts by weight or less, and 3 parts by weight or less, based on 100 parts by weight of the entire composition for model materials. It is more preferable that

  Examples of the surfactant include compounds having a number average molecular weight (hereinafter referred to as Mn) of 264 to 5,000, PEG type nonionic surfactant [EO 1 to 40 moles of nonylphenol adduct, 1 to 40 moles of stearic acid EO Adducts etc.], Polyhydric alcohol type nonionic surfactant [Sorbita palmitic acid monoester, sorbitan stearic acid monoester, sorbitan stearic acid triester etc.], fluorine-containing surfactant [Perfluoroalkyl EO 1 to 50 molar adducts Perfluoroalkylcarboxylic acid salts, perfluoroalkylbetaines, etc.], modified silicone oils [polyether modified silicone oils (eg, polyether modified polydimethylsiloxanes, etc.), (meth) acrylate modified silicone oils, etc.], etc. may be mentioned. The content of the surfactant is preferably 0.05 parts by weight or more, preferably 3 parts by weight or less, and 2 parts by weight or less with respect to 100 parts by weight of the whole composition for a model material. It is more preferable that

  Examples of the colorant include pigments and / or dyes. The pigments include organic pigments and inorganic pigments.

  The content of the coloring agent is preferably 0.05 parts by weight or more, preferably 2 parts by weight or less, and 1 part by weight or less based on 100 parts by weight of the entire composition for a model material. Is more preferred.

  Examples of the antioxidant include phenol compounds [monocyclic phenol (such as 2,6-di-t-butyl-p-cresol, etc.), bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol)] Etc.], polycyclic phenols [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene etc.] etc.], sulfur compounds (dilauryl 3) , 3'-thiodipropionate, etc.), phosphorus compounds (triphenyl phosphite, etc.), amine compounds (octylated diphenylamine, etc.), etc. The content of the antioxidant is preferably 0.1 parts by weight or more, preferably 3 parts by weight or less, and 2 parts by weight or less with respect to 100 parts by weight of the whole composition for a model material. It is more preferable that

  Examples of the chain transfer agent include hydrocarbons [compounds having 6 to 24 carbon atoms, such as aromatic hydrocarbons (toluene, xylene, etc.), unsaturated aliphatic hydrocarbons (1-butene, 1-nonene, etc.)]. Halogenated hydrocarbons (compounds having 1 to 24 carbon atoms such as dichloromethane, carbon tetrachloride etc.); alcohols (compounds having 1 to 24 carbon atoms such as methanol, 1-butanol etc); 24 compounds such as ethylthiol, 1-octylthiol etc .; ketones (compounds having 3 to 24 carbon atoms such as acetone, methyl ethyl ketone etc); aldehydes (compounds having 2 to 18 carbon atoms such as 2-methyl- 2-propyl aldehyde, 1-pentyl aldehyde etc .; phenol (compound having 6 to 36 carbon atoms, for example, phenol, m-, p- or o- Resole and the like); quinone (compound having 6 to 24 carbon atoms, such as hydroquinone and the like); amine (compound having 3 to 24 carbon atoms, such as diethylmethylamine and diphenylamine); disulfide (compound having 2 to 24 carbon atoms, For example, diethyl disulfide, di-1-octyl disulfide and the like can be mentioned. The content of the chain transfer agent is preferably 0.05 parts by weight or more, preferably 10 parts by weight or less, and 5 parts by weight or less based on 100 parts by weight of the entire composition for model materials. It is more preferable that

  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 (carbonate, etc.) Calcium, calcium silicate etc., fiber [inorganic fiber (carbon fiber, glass fiber, asbestos etc.), organic fiber (cotton, nylon, acrylic, rayon fiber etc.) etc], micro balloon (glass, shirasu, phenol resin etc) And carbons (carbon black, graphite, coal powder, etc.), metal sulfides (molybdenum disulfide, etc.), organic powder (wood powder, etc.), etc. The content of the filler is preferably 3 parts by weight or more, preferably 30 parts by weight or less, and 20 parts by weight or less based on 100 parts by weight of the entire composition for model materials. More preferable.

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

  The composition for model material manufactured in this manner preferably has a viscosity of 70 mPa · s or less at 25 ° C. from the viewpoint of improving the dischargeability from the ink jet 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.

  It is preferable that Tg of the said model material is 90-200 degreeC from the viewpoint of improving the heat resistance of the said model material, and reducing the curvature for the said composition for model materials. The Tg of the model material is more preferably 95 ° C. or more, and still more preferably 100 ° C. or more. The Tg of the model material is more preferably 190 ° C. or less, and still more preferably 180 ° C. or less.

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

2. Composition for Support Material <Water-soluble monofunctional ethylenically unsaturated monomer (a)>
The composition for a support material contained in the ink set for photo-forming according to the present embodiment contains a water-soluble monofunctional ethylenically unsaturated monomer (a). The water-soluble monofunctional ethylenically unsaturated monomer (a) is a component that is polymerized by light irradiation to cure the composition for a support material. Moreover, it is a component which dissolves the support material obtained by photocuring the composition for support materials in water quickly.

  The water-soluble monofunctional ethylenically unsaturated monomer (a) is a water-soluble polymerizable monomer having one ethylenic double bond in a molecule having a property of curing by energy rays. As said (a) component, C5-C15 hydroxyl-containing (meth) acrylate [For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate etc.], Alkylene oxide adduct-containing (meth) acrylates having a Mn of 200 to 1,000 (polyethylene glycol mono (meth) acrylates, monoalkoxy (C1-C4) polyethylene glycol mono (meth) acrylates, polypropylene glycol mono (meth) acrylates, mono Alkoxy (C1-C4) polypropylene glycol mono (meth) acrylate, mono (meth) acrylate of PEA-PPA block polymer, etc.], C3-C15 (meth) acrylamide derivative [(meth) acryl , N-methyl (meth) acrylamide, 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- hydroxy propyl (meth) acrylamide, N- hydroxy butyl (meth) acrylamide etc.], (meth) acryloyl morpholine etc. are mentioned. These may be used alone or in combination of two or more.

  Among these, N, N'-dimethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, (meth) acryloyl morpholine and the like are preferable from the viewpoint of improving the curability of the composition for support material . Furthermore, it is more preferable that they are N-hydroxyethyl (meth) acrylamide and (meth) acryloyl morpholine from a viewpoint of the skin hypoallergenicity to a human body.

  The content of the water-soluble monofunctional ethylenic unsaturated monomer (a) is 20 to 50 parts by weight with respect to 100 parts by weight of the whole composition for a support material. If the content of the water-soluble monofunctional ethylenic unsaturated monomer (a) is less than 20 parts by weight, the supportability of the support material is not sufficient. Therefore, when the support material is disposed in the lower layer of the model material, the model material can not be sufficiently supported. As a result, the dimensional accuracy of the model material is degraded. On the other hand, when the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) exceeds 50 parts by weight, the support material has poor solubility in water. When the immersion time in water until the support material is completely removed, the model material slightly expands. As a result, the dimensional accuracy may deteriorate in the microstructure portion of the model material. The content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is preferably 25 parts by weight or more, and more preferably 45 parts by weight or less. In addition, when two or more types of said (a) component are contained, the said content is the sum total of content of each (a) component.

<Polyalkylene Glycol Containing Oxyethylene Group and / or Oxypropylene Group (b)>
The composition for a support material contained in the ink set for photo-forming according to the present embodiment contains a polyalkylene glycol (b) containing an oxyethylene group and / or an oxypropylene group. The polyalkylene glycol (b) can enhance the solubility of the support material in water.

  The polyalkylene glycol (b) is obtained by adding at least ethylene oxide and / or propylene oxide to an active hydrogen compound. Examples of the polyalkylene glycol (b) include polyethylene glycol and polypropylene glycol. These may be used alone or in combination of two or more. As an active hydrogen compound, a mono- to 4-hydric alcohol, an amine compound, etc. are mentioned. Among these, dihydric alcohol or water is preferable.

  The Mn of the polyalkylene glycol (b) is preferably 100 to 5,000. When the Mn of the polyalkylene glycol (b) is within the above range, it is compatible with the water-soluble monofunctional ethylenically unsaturated monomer (a) before photocuring, and the water solubility after photocuring Incompatible with the monofunctional ethylenically unsaturated monomer (a). As a result, the supportability of the support material can be enhanced, and the solubility of the support material in water can be enhanced. The Mn of the polyalkylene glycol (b) is more preferably 200 to 3,000, and still more preferably 400 to 2,000.

  The content of the polyalkylene glycol (b) is 20 to 49 parts by weight with respect to 100 parts by weight of the entire composition for a support material. When the content of the polyalkylene glycol (b) is less than 20 parts by weight, the support material has poor solubility in water. As the immersion time in water until the support material is completely removed, the model material slightly expands. As a result, the dimensional accuracy may deteriorate in the microstructure portion of the model material. On the other hand, when the content of the polyalkylene glycol (b) exceeds 49 parts by weight, exudation of the polyalkylene glycol (b) may occur when the composition for a support material is photocured. When the leakage of the polyalkylene glycol (b) occurs, the adhesion at the interface between the support material and the model material deteriorates. As a result, when the model material cures and shrinks, it may be easily peeled off from the support material, and the dimensional accuracy may be deteriorated. When the content of the polyalkylene glycol (b) exceeds 49 parts by weight, the viscosity of the composition for support material is increased. Therefore, when the composition for a support material is discharged from the ink jet head, the jetting property may be deteriorated to cause a flight curve. As a result, the dimensional accuracy of the support material is degraded. Therefore, the dimensional accuracy of the model material formed on the upper layer of the support material also deteriorates. The content of the polyalkylene glycol (b) is preferably 25 parts by weight or more, and more preferably 45 parts by weight or less. In addition, when 2 or more types of the said (b) component are contained, the said content is the sum total of content of each (b) component.

<Water-soluble organic solvent (c)>
The composition for a support material contained in the ink set for photo-forming according to the present embodiment contains a water-soluble organic solvent (c). The water-soluble organic solvent (c) is a component that improves the solubility of the support material in water. Moreover, it is a component which adjusts the composition for support materials to low viscosity.

  As the water-soluble organic solvent (c), for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate, tripropylene glycol monoacetate, tetraethylene glycol monoacetate , Tetrapropylene glycol monoacetate, 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 mono Butyl ether, Pyrene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, ethylene glycol diacetate, propylene glycol diacetate, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether Ethylene glycol dibutyl ether, propylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl 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 the like. These may be used alone or in combination of two or more. Among these, triethylene glycol monomethyl ether or dipropylene glycol monomethyl ether acetate from the viewpoint of improving the solubility of the support material in water and adjusting the composition for the support material to a low viscosity More preferable.

  The content of the water-soluble organic solvent (c) is 35 parts by weight or less with respect to 100 parts by weight of the whole composition for a support material. When the content of the water-soluble organic solvent (c) exceeds 35 parts by weight, when the composition for a support material is photocured, an exudation of the water-soluble organic solvent (c) occurs. Therefore, the dimensional accuracy of the model material formed on the upper layer of the support material is deteriorated. The content of the water-soluble organic solvent (c) is 5 parts by weight or more from the viewpoint of improving the solubility of the support material in water and adjusting the composition for the support material to a low viscosity. Is preferable, and 10 parts by weight or more is more preferable. Moreover, it is preferable that content of the said water-soluble organic solvent (c) is 30 weight part or less. In addition, when two or more types of the said (c) component are contained, the said content is the sum total of content of each (c) component.

<Photoinitiator (d)>
The composition for a support material contained in the ink set for photofabrication according to this embodiment contains a photopolymerization initiator (d). As said photoinitiator (d), the component similar to the photoinitiator (D) contained in the said composition for model materials can be used.

  The content of the photopolymerization initiator (d) is preferably 1 to 25 parts by weight, and more preferably 2 to 20 parts by weight with respect to 100 parts by weight of the entire composition for a support material. When the content of the photopolymerization initiator (d) is in the above range, the self-supporting property of the composition for support material is improved. Therefore, the dimensional accuracy of the model material formed on the upper layer of the support material is improved. The content of the photopolymerization initiator (d) is more preferably 5 parts by weight or more, still more preferably 7 parts by weight or more, and still more preferably 18 parts by weight or less. In addition, when two or more types of the said (d) component are contained, the said content is the sum total of content of each (d) component.

<Surface modifier (e)>
In order to adjust the surface tension of the composition to an appropriate range, it is preferable that the composition for a support material contained in the ink set for photo-forming according to this embodiment contain a surface conditioner (e). By adjusting the surface tension of the composition to an appropriate range, mixing of the composition for model material and the composition for support material at the interface can be suppressed. As a result, by using these compositions, a photofabricated article with good dimensional accuracy can be obtained. In order to obtain this effect, the content of the surface conditioner (e) is preferably 0.005 to 3.0 parts by weight with respect to 100 parts by weight of the entire composition for a support material.

  As said surface conditioner (e), a silicone type compound etc. are mentioned, for example. Examples of silicone compounds include silicone compounds having a polydimethylsiloxane structure. Specifically, polyether modified polydimethylsiloxane, polyester modified polydimethylsiloxane, polyaralkyl modified polydimethylsiloxane etc. are mentioned. As these, it is trade name with BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-330. BYK-331, BYK-333, BYK-337, BYK-344, BYK-370, BYK-375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570 (above, made by Bick Chemie), TEGO-Rad2100 TEGO-Rad 2200N, TEGO-Rad 2250, TEGO-Rad 2300, TEGO-Rad 2500, TEGO-Rad 2600, TEGO-Rad 2700 (all manufactured by Degussa), Granol 100, Granol 115, Granol 400, Grano Le 410, Granol 435, Granol 440, Granol 450, B-1484, Polyflow ATF-2, KL-600, UCR-L72, UCR-L93 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like may be used. These may be used alone or in combination of two or more. In addition, when two or more types of the said (e) component are contained, the said content is the sum total of content of each (e) component.

<Storage stabilizer (f)>
It is preferable that the composition for a support material contained in the ink set for photo-forming according to the present embodiment further contain a storage stabilizer (f). The storage stabilizer (f) can enhance the storage stability of the composition. In addition, it is possible to prevent head clogging caused by the polymerization of the polymerizable compound by thermal energy. In order to obtain these effects, the content of the storage stabilizer (f) is preferably 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the entire composition for a support material.

  Examples of the storage stabilizer (f) include hindered amine compounds (HALS), phenolic antioxidants, and phosphorus antioxidants. Specifically, hydroquinone, methoquinone, benzoquinone, p-methoxyphenol, hydroquinone monomethyl ether, hydroquinone monobutyl ether, TEMPO, 4-hydroxy-TEMPO, TEMPOL, cuperone Al, IRGASTAB UV-10, IRGASTAB UV-22, FIRSTCURE ST- 1 (manufactured by ALBEMARLE), t-butyl catechol, pyrogallol, TINUVIN 111 FDL manufactured by BASF, TINUVIN 144, TINUVIN 292, TINUVIN XP40, TINUVIN XP60, TINUVIN 400, and the like. These may be used alone or in combination of two or more. In addition, when two or more types of the said (f) component are contained, the said content is the sum total of content of each (f) component.

  In the composition for a support material contained in the ink set for photo-forming according to the present embodiment, other additives can be added as needed, as long as the effects of the present invention are not impaired. Examples of other additives include antioxidants, colorants, ultraviolet light absorbers, light stabilizers, polymerization inhibitors, chain transfer agents, and fillers.

  The manufacturing method of the composition for support materials contained in the ink set for photofabrication which concerns on this embodiment is not specifically limited. For example, the components (a) to (d) and, if necessary, the components (e) and (f), and other additives may be produced by uniformly mixing them using a mixing and stirring apparatus or the like. Can.

  The composition for a support material manufactured in this manner preferably has a viscosity of 70 mPa · s or less at 25 ° C. from the viewpoint of improving the dischargeability from the ink jet head. In addition, the measurement of the viscosity of the composition for support materials is performed using R100 type | mold viscosity meter based on JISZ8803.

3. Optical Shaped Article and Method of Manufacturing the Same The optical formed article according to the present embodiment is formed using the ink set for optical formation according to the present embodiment. Specifically, a step of obtaining a support material by photo-curing the above-described composition for support material while obtaining the model material by photo-curing the above-mentioned composition for model material by the inkjet light shaping method (I And the step (II) of removing the support material. Although the said process (I) and the said process (II) are not specifically limited, For example, it is performed by the following method.

<Step (I)>
FIG. 1: is a figure which shows typically process (I) in the manufacturing method of the optical shaping article which concerns on this embodiment. As shown in FIG. 1, the three-dimensional shaping apparatus 1 includes an inkjet head module 2 and a shaping table 3. The inkjet head module 2 includes an inkjet head 21 for model material filled with the composition for model material, an inkjet head 22 for support material filled with the composition for support material, a roller 23, and a light source 24.

  First, the inkjet head module 2 is scanned in the X direction and the Y direction with respect to the modeling table 3 in FIG. 1, and the composition for the model material is discharged from the inkjet head 21 for the model material, and the inkjet for the support material By discharging the composition for support material from the head 22, a composition layer composed of the composition for model material and the composition for support material is formed. Then, in order to smooth the upper surface of the composition layer, the excess composition for model material and the composition for support material are removed using a roller 23. Then, the composition is irradiated with light using the light source 24 to form a hardened layer composed of the model material 4 and the support material 5 on the modeling table 3.

  Next, the modeling table 3 is lowered in the Z direction in FIG. 1 by the thickness of the hardened layer. Thereafter, in the same manner as described above, a hardened layer composed of the model material 4 and the support material 5 is further formed on the hardened layer. By repeating these steps, a cured product 6 composed of the model material 4 and the support material 5 is produced.

  As light which hardens a composition, far infrared rays, infrared rays, visible light, near ultraviolet rays, ultraviolet rays, etc. are mentioned, for example. Among these, near-ultraviolet light or ultraviolet light is preferable from the viewpoint of the easiness and efficiency of the curing operation.

Examples of the light source 24 include a mercury lamp, a metal halide lamp, an ultraviolet LED, and an ultraviolet laser. Among these, from the viewpoint of downsizing of equipment and power saving, ultraviolet LEDs are preferable. When the ultraviolet light LED is used as the light source 24, it is preferable that the integrated light quantity of the ultraviolet light is about 500 mJ / cm ² .

<Step (II)>
FIG. 2: is a figure which shows typically process (II) in the manufacturing method of the optical molded article which concerns on this embodiment. As shown in FIG. 2, the cured product 6 composed of the model material 4 and the support material 5 produced in the step (I) is immersed in the solvent 8 contained in the container 7. Thereby, the support material 5 can be dissolved in the solvent 8 and removed.

  Examples of the solvent 8 for dissolving the support material include ion exchange water, distilled water, tap water, well water and the like. Among these, ion-exchanged water is preferable from the viewpoint of relatively low impurities and availability at low cost.

  The photofabricated product according to the present embodiment can be obtained by the above steps. As described above, the photoforming ink set according to the present embodiment is soft and has excellent tensile strength by photocuring the composition for model material contained in the photoforming ink set. You can get it. Moreover, in the ink set for photofabrication which concerns on this embodiment, the support material excellent in self-supporting property can be obtained by photocuring the composition for support materials contained in this ink set for photofabrication. The photofabricated article manufactured using such a model material and a support material has a good dimensional accuracy.

  Hereinafter, the example which disclosed this embodiment more concretely is shown. The present invention is not limited to these examples.

<Composition for Model Material>
(Production of composition for model material)
In the composition shown in Table 1, the components (A) to (D) and the other components are uniformly mixed using a mixing and stirring apparatus, and the compositions for model materials of Examples M1 to M7 and Comparative Examples m1 to m3. Made things.

IBXA: Isobornyl acrylate [Sartomer SR506D (ethylenic double bond / 1 molecule: 1 piece), manufactured by Arkema]
IBX: Isobornyl methacrylate [Light ester IB-X (ethylenic double bond / 1 molecule: 1 unit), manufactured by Kyoeisha Chemical Co., Ltd.]
MMA: methyl methacrylate [light ester M (ethylenic double bond / 1 molecule: 1 piece), manufactured by Kyoeisha Chemical Co., Ltd.]
PEA: 2-Phenoxyethyl acrylate [Sartomer SR339A (ethylenic double bond / 1 molecule: 1 piece), manufactured by Arkema]
SMA: stearyl methacrylate [light ester S (ethylenic double bond / 1 molecule: 1 unit), manufactured by Kyoeisha Chemical Co., Ltd.]
DCP-M: dimethylol-tricyclodecane dimethacrylate [light ester DCP-M (ethylenic double bond / 1 molecule: 2 pieces), manufactured by Kyoeisha Chemical Co., Ltd.]
A-BPEF: Bisphenoxyfluorene acrylate [A-BPEF (ethylenic double bond / 1 molecule: 2), manufactured by Kyoeisha Chemical Co., Ltd.]
4-EGA: PEG (Mn 200) diacrylate [light acrylate 4-EG-A (ethylenic double bond / 1 molecule: 2 pieces), manufactured by Kyoeisha Chemical Co., Ltd.]
EBECRYL 811: polyester acrylate oligomer [EBECRYL 811 (ethylenic double bond / 1 molecule: 3 pieces), manufactured by Daicel-Cytec]
Purple light UV3000B: Urethane acrylate oligomer [purple light UV3000B (ethylenic double bond / 1 molecule: 2 pieces), manufactured by Japan Synthetic Chemical Industry Co., Ltd.]
EBECRYL 600: epoxy acrylate oligomer [EBECRYL 600 (ethylenic double bond / 1 molecule: 2 pieces), manufactured by Daicel-Cytec]
DAROCURE TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCURE TPO, manufactured by BASF Corporation]
TEGO-Rad 2100: Silicon acrylate having a polydimethylsiloxane structure [TEGO-Rad 2100, manufactured by Degussa]

<Composition for support material>
(Production of composition for support material)
The components (a) to (f) were uniformly mixed using the mixing and stirring apparatus according to the formulations shown in Tables 2 and 3, and the compositions for support materials of Examples S1 to S17 and Comparative Examples s1 to s6 were manufactured. . And the following evaluation was performed using these compositions for support materials.

  In the present example, as described later, the support material composition was cured using an ultraviolet LED as an irradiation unit. In the composition for a support material of Example S17 (Reference Example), the content of the photopolymerization initiator (d) exceeds 20 parts by weight, and therefore the photopolymerization initiator (d) is not sufficiently dissolved, and the composition is dissolved. The rest has happened. Thereby, even if it irradiated ultraviolet LED to the composition for support materials of Example S17, it did not fully cure | harden. Therefore, the following evaluation was not performed about the composition for support materials of Example S17.

HEAA: N-hydroxyethyl acrylamide [HEAA (ethylenic double bond / 1 molecule: 1 piece), manufactured by KJ Chemicals]
ACMO: Acryloyl morpholine [ACMO (ethylenic double bond / 1 molecule: 1 unit), manufactured by KJ Chemicals]
DMAA: N, N'-dimethyl acrylamide [DMAA (ethylenic double bond / 1 molecule: 1 unit), manufactured by KJ Chemicals]
PPG-400: polypropylene glycol [Uniol D400 (molecular weight 400), manufactured by NOF Corporation]
PPG-1000: polypropylene glycol [Uniol D 1000 (molecular weight 1000), manufactured by NOF Corporation]
PEG-400: polyethylene glycol [PEG # 400 (molecular weight 400), manufactured by NOF Corporation]
PEG-1000: polyethylene glycol [PEG # 1000 (molecular weight 1000), manufactured by NOF Corporation]
MTG: triethylene glycol monomethyl ether [MTG, manufactured by Nippon Emulsifier]
DPMA: Dipropylene glycol monomethyl ether acetate [Dawanol DPMA, manufactured by Dow Chemical Company]
DAROCURE TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCURE TPO, manufactured by BASF Corporation]
TEGO-Rad 2100: Silicon acrylate having a polydimethylsiloxane structure [TEGO-Rad 2100, manufactured by Evonik Degussa Japan Ltd.]
H-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl [HYDROXY-TEMPO, manufactured by Evonik Degussa Japan Co., Ltd.]

(Measurement of viscosity)
The viscosity of each composition for support materials was measured using a R100 viscometer (manufactured by Toki Sangyo Co., Ltd.) under conditions of 25 ° C. and a cone rotation number of 5 rpm, and was evaluated based on the following criteria. The evaluation results are shown in Tables 4 and 5.
○: viscosity ≦ 70 mPa · s
X: viscosity> 70 mPa · s

(Solubility in water)
In an aluminum cup of 50 mm in diameter, 2.0 g of the composition for each support material was collected. Next, an ultraviolet ray LED (NCCU 001E, manufactured by Nichia Chemical Industries, Ltd.) was used as an irradiation unit, and ultraviolet rays were irradiated to be cured so that the total irradiation light amount is 500 mJ / cm ² to obtain a support material. Thereafter, the support material was released from the aluminum cup. Subsequently, the support material was immersed in 500 ml of ion exchange water placed in a beaker. The support material was visually observed every 10 minutes, and the time required for complete dissolution or disappearance of the original shape from the start of immersion (hereinafter, referred to as water dissolution time) was measured, and the solubility was evaluated based on the following criteria. The evaluation results are shown in Tables 4 and 5.
○: Water dissolution time ≦ 1 hour Δ: 1 hour <water dissolution time <1.5 hours ×: Water dissolution time 時間 1.5 hours

(Evaluation of oily spill)
1.0 g of each composition for support materials was extract | collected to aluminum foil of 100 mm x 100 mm. Next, an ultraviolet ray LED (NCCU 001E, manufactured by Nichia Chemical Industries, Ltd.) was used as an irradiation unit, and ultraviolet rays were irradiated to be cured so that the total irradiation light amount is 500 mJ / cm ² to obtain a support material. At this point, the support material is in a solid state. The support material was left to stand for 2 hours, and the presence or absence of oily seepage on the surface of the support material was visually observed and evaluated according to the following criteria. The evaluation results are shown in Tables 4 and 5.
○: no oily spill was observed.
Δ: A slight oily spill was observed.
X: Many oily spills were observed.

(Evaluation of independence)
The glass plate (trade name "GLASS PLATE", manufactured by AS ONE Corporation, 200 mm x 200 mm x thickness 5 mm) used for the evaluation is a square in plan view. Spacers of 1 mm in thickness were disposed on four sides of the upper surface of the glass plate to form a square area of 10 cm × 10 cm. After casting each composition for support material in the area | region, another said glass plate was accumulated and mounted. Then, using an ultraviolet LED (NCCU 001E, manufactured by Nichia Chemical Industries, Ltd.) as an irradiation means, ultraviolet rays were irradiated and cured so that the total irradiation light amount was 500 mJ / cm ² , to obtain a support material. Thereafter, the support material was released from the glass plate, and cut into a shape of 10 mm long and 10 mm wide with a cutter to obtain a test piece. Next, 10 pieces of the test pieces were stacked to obtain a test piece group having a height of 10 mm. The test specimen group was placed in an oven set at 30 ° C. with a weight of 100 g from the top, and left for 1 hour. Thereafter, the shape of the test piece was observed, and the self-supporting property was evaluated according to the following criteria. The evaluation results are shown in Tables 4 and 5.
○: There was no change in the shape.
Δ: The shape slightly changed, and the weight was inclined.
X: The shape has changed significantly.

  As can be seen from the results in Tables 4 and 5, the compositions for support materials of Examples S1 to S16 satisfying all the requirements of the present invention had viscosities suitable for ejection from the ink jet head. In addition, the support material obtained by photocuring the composition for support material of Examples S1 to S16 had high solubility in water and suppressed oil-like oozing. Furthermore, the support material obtained by photocuring the composition for support materials of Examples S1-S15 had sufficient self-supporting property. In the composition for a support material of Example S16 (Reference Example), since the content of the photopolymerization initiator (d) is less than 5 parts by weight, the radical reaction is promoted even when the ultraviolet LED is irradiated. In addition, the supportability of the obtained support material was not sufficient. When a mercury lamp or a metal halide lamp is used as the irradiation means, the composition for a support material of Example S16 has a sufficient support material to be obtained even if the content of the photopolymerization initiator (d) is 3 parts by weight Self-sustaining.

  Furthermore, the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is 45 parts by weight or less, and the content of the polyalkylene glycol (b) containing an oxyethylene group and / or an oxypropylene group is 25 parts by weight The support material obtained from the composition for support materials of Examples S1-S8, S10, S11, and S13-S16 which are more than a part had higher solubility in water. Examples S1 to S10 in which the content of the polyalkylene glycol (b) containing an oxyethylene group and / or the oxypropylene group is 45 parts by weight or less, and the content of the water-soluble organic solvent (c) is 30 parts by weight or less And the support material obtained from the composition for support materials of S14-S16 had more suppression of oil-like oozing. The support material obtained from the composition for a support material of Examples S1 to S7, S9 to S12, S14, and S15 in which the content of the water-soluble monofunctional ethylenic unsaturated monomer (a) is 25 parts by weight or more is: It had more sufficient autonomy.

  On the other hand, in the composition for support material of Comparative Example s1, since the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is less than 20 parts by weight, the supportability of the support material is not sufficient. . Since the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) exceeded 50 parts by weight, the composition for a support material of Comparative Example s2 had a low solubility of the support material in water. The composition for a support material of Comparative Example s3 has a high viscosity because the content of the polyalkylene glycol (b) containing an oxyethylene group and / or an oxypropylene group exceeds 49 parts by weight, and the support material is oily. An exudation occurred. The composition for a support material of Comparative Example s4 had an oily spill over the support material because the content of the water-soluble organic solvent (c) exceeded 35 parts by weight. Since the composition for a support material of Comparative Example s5 contains less than 20 parts by weight of a polyalkylene glycol (b) containing an oxyethylene group and / or an oxypropylene group, the solubility of the support material in water is increased. It was low. Moreover, since the content of the water-soluble organic solvent (c) exceeds 35 parts by weight in the composition for a support material of Comparative Example s5, an oily spill occurred in the support material. The composition for a support material of Comparative Example s6 has a high viscosity because the content of the polyalkylene glycol (b) containing an oxyethylene group and / or an oxypropylene group exceeds 49 parts by weight, and the support material is oily. An exudation occurred.

<Photofabricated product>
(Evaluation of dimensional accuracy of photofabricated products)
A cured product was prepared using the photoforming ink set formed by combining each model material composition shown in Table 1 and each support material composition shown in Tables 2 and 3. The shape of the cured product and the target dimensions are shown in FIGS. 3 (a) and (b). The step of discharging each composition for model material and each composition for support material from the ink jet head was performed so that the resolution was 600 × 600 dpi and the thickness of one layer of the composition layer was about 13 to 14 μm. . Further, the step of photocuring each of the composition for model materials and the composition for each support material is performed using an LED light source with a wavelength of 385 nm installed on the back side of the ink jet head in the scanning direction. ²⁾ Conducted under the condition of 300 mJ / cm ² of integrated light quantity per one layer of the composition layer. Next, the support was removed by immersing the cured product in ion exchange water to obtain a photofabricated product. Thereafter, the resulting light-shaped article was allowed to stand in a desiccator for 24 hours to be sufficiently dried. According to the above-described process, test No. 1 is performed. Five to ten light-shaped articles were produced each. With respect to the dried optical shaped article, the dimensions in the x direction and y direction in FIG. 3A were measured using a caliper, and the rate of change from the target dimension was calculated. For the dimensional accuracy, test No. The average value of the dimensional change rate in each of the 1 to 10 light-shaped articles was determined, and the evaluation was performed according to the following criteria using the average value. The evaluation results are shown in Table 6.
○: Average dimensional change is less than ± 1.0% ×: Average dimensional change is ± 1.0% or more

  As can be seen from the results in Table 6, test No. 4 produced using the stereolithography ink set satisfying all the requirements of the present invention. The photofabricated products of 1 to 7 had good dimensional accuracy.

  The ink set for photofabrication of the present invention can be suitably used when manufacturing a photofabricated article with good dimensional accuracy using an inkjet photofabrication method.

Reference Signs List 1 three-dimensional modeling apparatus 2 inkjet head module 21 inkjet head for model material 22 inkjet head for support material 23 roller 24 light source 3 modeling table 4 model material 5 support material 6 cured product 7 container 8 solvent

Claims (15)

For optical shaping formed by combining a composition for model material used for inkjet photofabrication and used for shaping a model material and a composition for support material used for shaping a support material An ink set,
The composition for the model material is
A monofunctional ethylenically unsaturated monomer (A) having a glass transition temperature of a homopolymer of 80 ° C. or higher and 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 more, and having no urethane group,
An oligomer (C),
A photopolymerization initiator (D),
Contains
The composition for a support material is 100 parts by weight of the entire composition for a support material,
20 to 50 parts by weight of a water-soluble monofunctional ethylenically unsaturated monomer (a),
A polyalkylene glycol (b) containing 20 to 49 parts by weight of an oxyethylene group and / or an oxypropylene group;
35 parts by weight or less of a water-soluble organic solvent (c),
A photopolymerization initiator (d),
Wherein the water-soluble monofunctional ethylenically unsaturated monomer (a) is a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms, and an alkylene oxide adduct-containing (meth) of Mn 200 to 1,000. ) Acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, 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- hydroxy propyl (meth) acrylamide, N- hydroxy butyl (meth) acrylamide, and (meth) acryloyl morpholine from Consisting of one or more selected
An ink set for light shaping.   The ink set for photofabrication according to claim 1, wherein the monofunctional ethylenically unsaturated monomer (A) has an alicyclic skeleton in the composition for model material.   The ink set for photofabrication according to claim 1 or 2, wherein in the composition for model material, the polyfunctional ethylenic unsaturated monomer (B) has an alicyclic skeleton or an aromatic ring.   In the composition for model materials, the oligomer (C) is at least one selected from the group consisting of a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, and a polyester (meth) acrylate oligomer. The ink set for photofabrication as described in any one of Claims 1-3.   In the composition for model materials, the content of the monofunctional ethylenic unsaturated monomer (A) is 20 to 80 parts by weight with respect to 100 parts by weight of the whole composition for model materials. The ink set for optical modeling as described in any one of 1-4.   In the composition for model materials, the content of the polyfunctional ethylenically unsaturated monomer (B) is 5 to 50 parts by weight with respect to 100 parts by weight of the whole composition for model materials. The ink set for photofabrication as described in any one of 1-5.   The composition for a model material according to any one of claims 1 to 6, wherein a content of the oligomer (C) is 10 to 45 parts by weight with respect to 100 parts by weight of the whole composition for a model material. The ink set for light shaping described in.   In the composition for model materials, the content of the photopolymerization initiator (D) is 0.5 to 15 parts by weight with respect to 100 parts by weight of the whole composition for model materials. The ink set for photofabrication as described in any one.   The composition for model materials according to any one of claims 1 to 8, wherein the glass transition temperature of the model material obtained by photocuring the composition for model materials is 90 to 200 ° C. An ink set for light shaping.   In the composition for support material, the content of the water-soluble monofunctional ethylenic unsaturated monomer (a) is 25 to 45 parts by weight with respect to 100 parts by weight of the whole composition for support material. The ink set for photofabrication as described in any one of Claims 1-9.   The composition for a support material according to any one of claims 1 to 10, wherein the content of the polyalkylene glycol (b) is 25 to 45 parts by weight with respect to 100 parts by weight of the whole composition for a support material. The stereolithography ink set described in one.   The composition for a support material according to any one of claims 1 to 11, wherein a content of the water-soluble organic solvent (c) is 5 parts by weight or more with respect to 100 parts by weight of the whole composition for a support material. The stereolithography ink set described in one.   The composition for a support material, wherein the content of the photopolymerization initiator (d) is 1 to 25 parts by weight with respect to 100 parts by weight of the whole composition for a support material. The stereolithography ink set described in one.   The composition for a support material further contains 0.05 to 3.0 parts by weight of a storage stabilizer (e) with respect to 100 parts by weight of the total composition for a support material. The ink set for stereolithography described in any one of the above. A method for producing a photofabricated article using the ink set for photofabrication according to any one of claims 1 to 14 by an inkjet photofabrication method,
Step (I) of obtaining a support material by photo-curing the composition for model material by photo-curing the composition for model material and photo-curing the composition for support material;
Removing the support material (II);
A method for producing a photofabricated article, comprising:

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