WO2018143303A1 - Ink set for stereolithography, stereolithographic article, and method for producing stereolithographic article - Google Patents

Abstract

The present invention addresses the problem of providing: an ink set for stereolithography which is for obtaining a stereolithographic article exhibiting excellent mechanical properties and excellent dimensional accuracy; a stereolithographic article formed using the ink set for stereolithography; and a method for producing the stereolithographic article using the ink set for stereolithography. An ink set for stereolithography according to the present invention is provided with a model material composition and a support material composition. The model material composition includes: monofunctional ethylenically unsaturated monomers (A) which have a Tg of 80˚C or higher, and which do not have urethane groups; polyfunctional ethylenically unsaturated monomers (B) which have a ring structure, have a Tg of 180˚C or higher, and do not have urethane groups; an oligomer (C); and a photopolymerization initiator (D). The support material composition includes: 20-50 parts by weight of water-soluble monofunctional ethylenically unsaturated monomers (a); 20-49 parts by weight of polyalkylene glycol (b) including AO groups and/or PO groups; 35 or fewer parts by weight of a water-soluble organic solvent (c); and a photopolymerization initiator (d).

Description

Optical modeling ink set, optical modeling product, and manufacturing method of optical modeling product

This patent application claims priority under the Paris Convention for Japanese Patent Application No. 2017-016125 (filing date: January 31, 2017), which is hereby incorporated by reference in its entirety. It shall be incorporated into the book.
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.

Conventionally, a modeling method using a photocurable composition that is cured by irradiating ultraviolet rays or the like is widely known as a method of 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 reduced in size 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 ink jet stereolithography method, when modeling a stereolithography product having a complicated shape such as a hollow shape, the model material and the support material are formed in combination to support the model material (Patent Documents 1 and 2). 4 and 5). The support material is created by irradiating the photocurable composition with ultraviolet rays or the like and curing the same as 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 5, the model material composition is obtained by photocuring 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 shaped article shaped using such a model material can be suitably used as, for example, a mold or a mechanism part.

JP 2004-255839 A 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. 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 has been a problem that the dimensional accuracy of the stereolithographic product modeled using the model material composition and the support material composition disclosed in Patent Document 5 is reduced.

The present invention has been made in view of the above-described present situation, and uses an optical modeling ink set for obtaining an optical modeling product having excellent mechanical characteristics and good dimensional accuracy, and the optical modeling ink set. It is an object of the present invention to provide a modeled stereolithographic product and a method for producing a stereolithographic product using the optical modeling ink set.

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.

The present invention has been made based on the above findings, and the gist thereof 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. An ink set for stereolithography,
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.
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, containing

(2) The optical modeling ink set according to (1), wherein the monofunctional ethylenically unsaturated monomer (A) has an alicyclic skeleton.

(3) The composition for a model material is for stereolithography according to (1) or (2), wherein the polyfunctional ethylenically unsaturated monomer (B) has an alicyclic skeleton or an aromatic ring. Ink set.

(4) The said model material composition is 1 or more types from which the said oligomer (C) is selected from the group which consists of a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, and a polyester (meth) acrylate oligomer. The ink set for stereolithography according to any one of (1) to (3), wherein

(5) In the model material composition, 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 model material composition as a whole. The ink set for stereolithography according to any one of (1) to (4).

(6) In the model material composition, 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 entire model material composition. The ink set for stereolithography according to any one of (1) to (5).

(7) In the composition for a model material, 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 a model material. The ink set for stereolithography according to any one of 1).

(8) In the composition for model material, the content of the photopolymerization initiator (D) is 0.5 to 15 parts by weight with respect to 100 parts by weight of the entire composition for model material (1) The optical modeling ink set according to any one of (1) to (7).

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

(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 stereolithography according to any one of (1) to (9), wherein

(11) In the composition for 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 support material. The ink set for stereolithography according to any one of (10).

(12) In the composition for a 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 as a whole of the composition for a support material. The ink set for stereolithography according to any one of (11).

(13) In the composition for 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 support material. The ink set for stereolithography according to any one of (12).

(14) The support material composition further comprises 0.05 to 3.0 parts by weight of a storage stabilizer (e) with respect to 100 parts by weight of the entire support material composition. The optical modeling ink set according to any one of 1) to (13).

(15) An optically modeled article modeled using the optical modeling ink set according to any one of (1) to (14) above by an inkjet stereolithography method.

(16) A method for producing an optically shaped article by an ink jet optical modeling method using the optical modeling ink set according to any one of (1) to (14),
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.

According to the present invention, an optical modeling ink set for obtaining an optical modeling product having excellent mechanical properties and good dimensional accuracy, an optical modeling product modeled using the optical modeling ink set, and It is possible to provide a method for producing an optical modeling product using the optical modeling ink set.

Drawing 1 is a figure showing typically process (I) in a manufacturing method of an optical modeling article concerning this embodiment. FIG. 2 is a diagram schematically showing step (II) in the method for manufacturing an optically shaped product according to the present embodiment. FIG. 3A is a top view of a cured product obtained by using each resin composition for a model material and each resin composition for a support material shown in Table 6. FIG. 3B is a cross-sectional view taken along the line AA in FIG.

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 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 higher, the heat resistance of the model material obtained by photocuring the composition for model material 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.

The monofunctional ethylenically unsaturated monomer (A) preferably has, for example, 4 to 30 carbon atoms, and the homopolymer Tg of linear or branched alkyl (meth) acrylate is Among compounds [methyl (meth) acrylate] having a temperature of 80 ° C. or higher and (meth) acrylates having an alicyclic skeleton having 6 to 20 carbon atoms, those having a homopolymer Tg of 80 ° C. or higher [isobornyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate and the like], and (meth) acrylate having a heterocyclic skeleton include compounds having a homopolymer Tg of 80 ° C. or more. 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 20 to 80 weights with respect to 100 parts by weight of the whole 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 25 parts by weight or more, further preferably 45 parts by weight or more, and even more preferably 60 parts by weight or more. The amount is particularly 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 a polyfunctional ethylenic group having no urethane group Contains an unsaturated monomer (B).

When the Tg of the polyfunctional ethylenically unsaturated monomer (B) homopolymer 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, the polyfunctional ethylenically unsaturated monomer (B) is preferably dimethylol-tricyclodecane dimethacrylate or bisphenoxy fluorenedi (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 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, more preferably 30 parts by weight or less, and further preferably 25 parts by weight or less. preferable. 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, polyether (meth) acrylate oligomers, and the like. 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. In addition, the model material composition is a urethane (meth) acrylate oligomer from the viewpoint of improving the dimensional accuracy of the model material by having heat resistance capable of withstanding 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.

The content of the oligomer (C) is preferably 10 to 45 parts by weight with respect to 100 parts by weight of the entire model material composition. 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 45 parts by weight, the viscosity of the model material composition becomes high. Therefore, when the composition for model material is ejected from the ink jet head, jetting characteristics may be deteriorated and flight bending may occur. As a result, the dimensional accuracy of the model material may deteriorate. The content of the oligomer (C) with respect to 100 parts by weight of the whole model material composition is more preferably 35 parts by weight or less, still more preferably 25 parts by weight or less, and even more preferably 25 parts by weight or less. . 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)>
The model material composition included in the optical modeling ink set 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 having 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), and those having 8 to 18 carbon atoms. Acetophenone compounds [for example, 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.], an anthraquinone compound having 14 to 19 carbon atoms [for example, 2 -D Luanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc.], thioxanthone compounds having 13 to 17 carbon atoms [eg, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc. ] Ketal compounds having 16 to 17 carbon atoms [for example, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.], benzophenone compounds having 13 to 21 carbon atoms [for example, benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4 '-Bismethylaminobenzophenone, etc.], acylphosphine oxide compounds having 22 to 28 carbon atoms [eg 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis- (2,6-dimethyl) 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, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is preferable from the viewpoint of improving light resistance. Examples of the available acyl phosphine oxide compound include DAROCURE TPO manufactured by BASF.

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 entire model material composition. When the content of the photopolymerization initiator (D) is within the above range, the curability of the model material composition is improved, 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, further preferably 5 parts by weight or more, and more preferably 13 parts by weight or less. In addition, when the said (D) component is contained 2 or more types, the said content is 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 surfactant, a colorant, an antioxidant, a chain transfer agent, and a filler. 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 [dilauryl thiodipropionate, etc.], phosphorus compounds [triphenyl phosphite, etc. ], An amine compound [phenothiazine etc.] etc. are mentioned. The content of the polymerization inhibitor is preferably 0.05 parts by weight or more, preferably 5 parts by weight or less, and preferably 3 parts by weight or less with respect to 100 parts by weight of the entire model material composition. More preferably.

Examples of the surfactant include a compound having a number average molecular weight (hereinafter referred to as Mn) of 264 to 5,000, a PEG-type nonionic surfactant [nonylphenol EO 1 to 40 mol adduct, stearic acid EO 1 to 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 EO 1-50 mol adduct Perfluoroalkyl carboxylates, perfluoroalkyl betaines, etc.], modified silicone oils [polyether-modified silicone oils (for example, polyether-modified polydimethylsiloxane), (meth) acrylate-modified silicone oils, etc.], and the like. The content of the surfactant is preferably 0.05 parts by weight or more, preferably 3 parts by weight or less, and preferably 2 parts by weight or less, with respect to 100 parts by weight of the entire model material composition. More preferably.

The colorant includes pigments and / or dyes. The pigment includes an organic pigment and an inorganic pigment.

The content of the colorant is preferably 0.05 parts by weight or more, preferably 2 parts by weight or less, and preferably 1 part by weight or less with respect to 100 parts by weight of the entire model material composition. It is more preferable.

Examples of the antioxidant include a phenol compound [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.), bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol). ]], Polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene etc.]], sulfur compound (dilauryl 3) , 3′-thiodipropionate etc.), phosphorus compounds (triphenyl phosphite etc.), amine compounds (octylated diphenylamine etc.) and the like. The content of the antioxidant is preferably 0.1 parts by weight or more, preferably 3 parts by weight or less, and preferably 2 parts by weight or less with respect to 100 parts by weight of the entire model material composition. More preferably.

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 ethyl thiol and 1-octyl thiol); ketones (compounds having 3 to 24 carbon atoms such as acetone and methyl ethyl ketone); aldehydes (compounds having 2 to 18 carbon atoms such as 2-methyl- 2-propyl aldehyde, 1-pentyl aldehyde, etc .; phenol (a compound having 6 to 36 carbon atoms, such as phenol, m-, p- or o) Cresol and the like]; quinone (compound having 6 to 24 carbon atoms, such as hydroquinone); amine (compound having 3 to 24 carbon atoms, such as diethylmethylamine and diphenylamine); disulfide (compound having 2 to 24 carbon atoms, Examples thereof include diethyl disulfide and di-1-octyl disulfide. The content of the chain transfer agent is preferably 0.05 parts by weight or more, preferably 10 parts by weight or less, and preferably 5 parts by weight or less with respect to 100 parts by weight of the entire model material composition. More preferably.

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. The content of the filler is preferably 3 parts by weight or more, preferably 30 parts by weight or less, and preferably 20 parts by weight or less with respect to 100 parts by weight of the entire model material composition. More preferred.

The method for producing the model material composition included in the optical modeling ink set according to the present embodiment is not particularly limited. For example, the components (A) to (D) and, if necessary, the other additives can be produced by uniformly mixing them using a mixing and stirring device or the like.

The composition for a model material thus produced preferably has a viscosity at 25 ° C. of 70 mPa · s or less from the viewpoint of improving dischargeability from an 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.

The model material composition preferably has a Tg of 90 to 200 ° C. from the viewpoint of improving the heat resistance of the model material and reducing warpage. 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.

The Tg in the present invention can be measured using, for example, a differential heat measuring device (manufactured by Mac Science Co., Ltd., TG-DTA (2000S)).

2. Composition for Support Material <Water-soluble monofunctional ethylenically unsaturated monomer (a)>
The composition for support materials contained in the optical modeling ink set according to this 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 support material composition. Moreover, it is a component which dissolves the support material obtained by photocuring the composition for support material quickly in water.

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 being cured by energy rays. Examples of the component (a) include a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms [eg, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.), Mn 200-1,000 alkylene oxide adduct-containing (meth) acrylate [polyethylene glycol mono (meth) acrylate, monoalkoxy (1 to 4 carbon atoms) polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, mono Alkoxy (1 to 4 carbon atoms) polypropylene glycol mono (meth) acrylate, PEA-PPA block polymer mono (meth) acrylate, etc.], (meth) acrylamide derivatives having 3 to 15 carbon atoms ((meth) acrylic) Mido, 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-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide etc.], (meth) acryloylmorpholine and the like. These may be used alone or in combination of two or more.

Among these, N, N′-dimethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine and the like are preferable from the viewpoint of improving the curability of the support material composition. . Furthermore, N-hydroxyethyl (meth) acrylamide and (meth) acryloylmorpholine are more preferable from the viewpoint of low skin irritation to the human body.

The content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is 20 to 50 parts by weight with respect to 100 parts by weight of the entire support material composition. When the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is less than 20 parts by weight, the self-supporting property in the support material is not sufficient. Therefore, when the support material is disposed below the model material, the model material cannot be sufficiently supported. As a result, the dimensional accuracy of the model material is deteriorated. 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. If the immersion time in water until the support material is completely removed becomes long, the model material expands slightly. 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 preferably 45 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.

<Polyalkylene glycol (b) containing oxyethylene group and / or oxypropylene group>
The composition for support materials contained in the optical modeling ink set according to this 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. Examples of the active hydrogen compound include monohydric to tetrahydric alcohols and amine compounds. 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 It is not compatible with the monofunctional ethylenically unsaturated monomer (a). As a result, the self-supporting property 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 further 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 support material composition. When the content of the polyalkylene glycol (b) is less than 20 parts by weight, the support material is poor in solubility in water. If the immersion time in water until the support material is completely removed becomes longer, the model material expands slightly. 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, the polyalkylene glycol (b) may ooze out when the support material composition is photocured. When the polyalkylene glycol (b) oozes out, the adhesion at the interface between the support material and the model material becomes poor. As a result, the model material is likely to be peeled off from the support material when cured and contracted, and the dimensional accuracy may deteriorate. Moreover, when content of the said polyalkylene glycol (b) exceeds 49 weight part, the viscosity of the composition for support materials will become high. Therefore, when the composition for a support material is ejected from the inkjet head, the jetting characteristics may be deteriorated and flight bending may occur. As a result, the dimensional accuracy of the support material is deteriorated. Therefore, the dimensional accuracy of the model material molded 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 preferably 45 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.

<Water-soluble organic solvent (c)>
The composition for support material contained in the optical modeling ink set 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.

Examples of the water-soluble organic solvent (c) include ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate, tripropylene glycol monoacetate, and 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, Lopylene 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, from the viewpoint of improving the solubility of the support material in water and adjusting the composition for the support material to low viscosity, it may be triethylene glycol monomethyl ether or dipropylene glycol monomethyl ether acetate. More preferred.

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 entire support material composition. When the content of the water-soluble organic solvent (c) exceeds 35 parts by weight, the water-soluble organic solvent (c) oozes when the support composition is photocured. Therefore, the dimensional accuracy of the model material molded 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 support material to a low viscosity. Is preferred, and more preferably 10 parts by weight or more. Moreover, it is preferable that content of the said water-soluble organic solvent (c) is 30 weight part or less. 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)>
The composition for support material contained in the optical modeling ink set according to the present 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 support material composition. When the content of the photopolymerization initiator (d) is in the above range, the self-supporting property of the support material composition becomes good. Therefore, the dimensional accuracy of the model material molded 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, further preferably 7 parts by weight or more, and more preferably 18 parts by weight or less. In addition, when the said (d) component is contained 2 or more types, the said content is the sum total of content of each (d) component.

<Surface conditioner (e)>
In order to adjust the surface tension of the composition to an appropriate range, the composition for a support material included in the optical modeling ink set according to the present embodiment preferably contains a surface conditioner (e). By adjusting the surface tension of the composition to an appropriate range, the model material composition and the support material composition can be prevented from being mixed at the interface. As a result, it is possible to obtain an optically shaped product with good dimensional accuracy using these compositions. In order to obtain this effect, the content of the surface conditioning agent (e) is preferably 0.005 to 3.0 parts by weight with respect to 100 parts by weight of the entire support material composition.

Examples of the surface conditioner (e) include silicone compounds. Examples of the silicone compound include a silicone compound having a polydimethylsiloxane structure. Specific examples include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyaralkyl-modified polydimethylsiloxane. These include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-370, BYK-375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570 (above, manufactured by BYK Chemie), TEGO-Rad2100 , TEGO-Rad2200N, TEGO-Rad2250, TEGO-Rad2300, TEGO-Rad2500, TEGO-Rad2600, TEGO-Rad2700 (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 the said (e) component is contained 2 or more types, the said content is the sum total of content of each (e) component.

<Storage stabilizer (f)>
It is preferable that the composition for support material contained in the optical modeling ink set according to the present embodiment further contains a storage stabilizer (f). The storage stabilizer (f) can enhance the storage stability of the composition. Further, clogging of the head caused by polymerization of the polymerizable compound by thermal energy can be prevented. 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 support material composition.

Examples of the storage stabilizer (f) include hindered amine compounds (HALS), phenolic antioxidants, phosphorus antioxidants, and the like. Specifically, hydroquinone, methoquinone, benzoquinone, p-methoxyphenol, hydroquinone monomethyl ether, hydroquinone monobutyl ether, TEMPO, 4-hydroxy-TEMPO, TEMPOL, cuperon Al, IRGASTAB UV-10, IRGASTAB UV-22, FIRSTCURE ST- 1 (manufactured by ALBEMARLE), t-butylcatechol, pyrogallol, TINUVIN 111 FDL, TINUVIN 144, TINUVIN 292, TINUVIN XP40, TINUVIN XP60, TINUVIN 400, etc. manufactured by BASF. These may be used alone or in combination of two or more. In addition, when the said (f) component is contained 2 or more types, the said content is the sum total of content of each (f) component.

The support material composition included in the optical modeling ink set according to the present embodiment may contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of other additives include an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, a chain transfer agent, and a filler.

The method for producing the composition for support material included in the optical modeling ink set according to the present embodiment is not particularly limited. For example, the components (a) to (d) and, if necessary, the components (e) and (f) and other additives are uniformly mixed using a mixing and stirring device or the like. Can do.

The composition for a support material 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. The viscosity of the support material composition is measured according to JIS Z 8803 using an R100 viscometer.

3. Optical modeling product and its manufacturing method The optical modeling product concerning this embodiment is modeled using the ink set for optical modeling concerning this embodiment. Specifically, a process of obtaining a support material by photocuring the above-described composition for support material (I) by photocuring the above-mentioned composition for model material by ink-jet stereolithography (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 with the following method.

<Process (I)>
Drawing 1 is a figure showing typically process (I) in a manufacturing method of an optical modeling article concerning this embodiment. As shown in FIG. 1, the three-dimensional modeling apparatus 1 includes an inkjet head module 2 and a modeling table 3. The ink jet head module 2 includes a model material ink jet head 21 filled with a model material composition, a support material ink jet head 22 filled with a support material composition, 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, the model material composition is discharged from the model material inkjet head 21, and the support material inkjet is performed. By discharging the support material composition from the head 22, a composition layer composed of the model material composition and the support material composition is formed. And in order to make the upper surface of the said composition layer smooth, the roller 23 is used and the excess composition for model materials and the composition for support materials are removed. Then, these compositions are irradiated with light using a light source 24 to form a hardened layer made 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, a hardened layer made of the model material 4 and the support material 5 is further formed on the hardened layer by the same method as described above. By repeatedly performing these steps, a cured product 6 composed of the model material 4 and the support material 5 is produced.

Examples of the light for curing the composition include far infrared rays, infrared rays, visible rays, near ultraviolet rays, and ultraviolet rays. Among these, near ultraviolet rays or ultraviolet rays are preferable from the viewpoint of easy and efficient curing work.

Examples of the light source 24 include a mercury lamp, a metal halide lamp, an ultraviolet LED, and an ultraviolet laser. Among these, an ultraviolet LED is preferable from the viewpoint of miniaturization of equipment and power saving. In addition, when ultraviolet LED is used as the light source 24, it is preferable that the integrated light quantity of an ultraviolet-ray is about 500 mJ / cm < ² >.

<Process (II)>
FIG. 2 is a diagram schematically showing step (II) in the method for manufacturing an optically shaped product according to the present embodiment. As shown in FIG. 2, the cured product 6 made of the model material 4 and the support material 5 produced in step (I) is immersed in a solvent 8 placed in a 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, and well water. Among these, ion-exchanged water is preferable from the viewpoint of relatively few impurities and being available at low cost.

The stereolithographic product according to the present embodiment is obtained through the above steps. As described above, in the optical modeling ink set according to the present embodiment, the model material composition contained in the optical modeling ink set is photocured to provide a soft and excellent tensile strength model material. Obtainable. Moreover, in the optical modeling ink set according to the present embodiment, a support material excellent in self-supporting property can be obtained by photocuring the support material composition contained in the optical modeling ink set. The stereolithographic product manufactured using such a model material and support material has good dimensional accuracy.

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

<Model material composition>
(Manufacture of compositions for model materials)
In the formulation shown in Table 1, the components (A) to (D) and other components were uniformly mixed using a mixing and stirring device, and the compositions for model materials of Examples M1 to M7 and Comparative Examples m1 to m3 The thing was manufactured.

IBXA: Isobornyl acrylate [Sartomer SR506D (ethylenic double bond / one molecule), manufactured by Arkema]
IBX: Isobornyl methacrylate [Light ester IB-X (ethylenic double bond / one molecule: one), manufactured by Kyoeisha Chemical Co., Ltd.]
MMA: methyl methacrylate [light ester M (ethylenic double bond / one molecule: one), manufactured by Kyoeisha Chemical Co., Ltd.]
PEA: 2-phenoxyethyl acrylate [Sartomer SR339A (ethylenic double bond / one molecule: 1), manufactured by Arkema Corporation]
SMA: stearyl methacrylate [light ester S (ethylenic double bond / one molecule: one), manufactured by Kyoeisha Chemical Co., Ltd.]
DCP-M: dimethylol-tricyclodecane dimethacrylate [light ester DCP-M (ethylenic double bond / 1 molecule: 2), manufactured by Kyoeisha Chemical Co., Ltd.]
A-BPEF: Bisphenoxy fluorene acrylate [A-BPEF (ethylenic double bond / one molecule: 2), manufactured by Kyoeisha Chemical Co., Ltd.]
4-EGA: PEG (Mn200) diacrylate [Light acrylate 4-EG-A (ethylenic double bond / one molecule: 2), manufactured by Kyoeisha Chemical Co., Ltd.]
EBECRYL811: Polyester acrylate oligomer [EBECRYL811 (ethylenic double bond / one molecule: 3), manufactured by Daicel Cytec Co., Ltd.]
Purple light UV3000B: urethane acrylate oligomer [purple light UV3000B (ethylenic double bond / 1 molecule: 2), manufactured by Nippon Synthetic Chemical Co., Ltd.]
EBECRYL600: Epoxy acrylate oligomer [EBECRYL600 (ethylenic double bond / one molecule: 2), manufactured by Daicel Cytec Co., Ltd.]
DAROCURE TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCURE TPO, manufactured by BASF]
TEGO-Rad2100: Silicon acrylate having a polydimethylsiloxane structure [TEGO-Rad2100, manufactured by Degussa]

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

In this example, as described later, the composition for a support material was cured using an ultraviolet LED as an irradiation means. About the composition for support materials of Example S17 (reference example), since the content of the photopolymerization initiator (d) exceeds 20 parts by weight, the photopolymerization initiator (d) is not sufficiently dissolved and dissolved. The rest has occurred. Thereby, even if it irradiated with ultraviolet LED to the composition for support materials of Example S17, it did not harden | cure satisfactorily. Therefore, all the following evaluations were not performed about the composition for support materials of Example S17.

HEAA: N-hydroxyethylacrylamide [HEAA (ethylenic double bond / one molecule: 1), manufactured by KJ Chemicals]
ACMO: acryloyl morpholine [ACMO (ethylenic double bond / one molecule: one), manufactured by KJ Chemicals]
DMAA: N, N′-dimethylacrylamide [DMAA (ethylenic double bond / one molecule: 1), manufactured by KJ Chemicals]
PPG-400: Polypropylene glycol [Uniol D400 (molecular weight 400), manufactured by NOF Corporation]
PPG-1000: Polypropylene glycol [Uniol D1000 (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 Co., Ltd.]
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]
TEGO-Rad2100: Silicon acrylate having a polydimethylsiloxane structure [TEGO-Rad2100, manufactured by Evonik Degussa Japan Co., Ltd.]
H-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl [HYDROXY-TEMPO, manufactured by Evonik Degussa Japan Ltd.]

(Measurement of viscosity)
The viscosity of each support material composition was measured using an R100 viscometer (manufactured by Toki Sangyo Co., Ltd.) under the conditions of 25 ° C. and cone rotation speed of 5 rpm, and evaluated according to the following criteria. The evaluation results are shown in Tables 4 and 5.
○: Viscosity ≦ 70 mPa · s
×: Viscosity> 70 mPa · s

(Solubility in water)
2.0 g of each support material composition was collected in an aluminum cup having a diameter of 50 mm. Next, ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) was used as the irradiation means, and 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 aluminum cup. Subsequently, the support material was immersed in 500 ml of ion-exchanged water placed in a beaker. The support material was visually observed every 10 minutes, and the time required from the start of immersion until complete dissolution or disappearance of the original shape (hereinafter referred to as water dissolution time) was measured, and the solubility was evaluated according to 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 ≧ 1.5 hours

(Evaluation of oil seepage)
1.0 g of each composition for support material was extract | collected to 100 mm x 100 mm aluminum foil. Next, ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) was used as the irradiation means, and ultraviolet rays were irradiated and cured so that the total irradiation light amount was 500 mJ / cm ² to obtain a support material. At this point, the support material is in a solid state. The support material was allowed to stand for 2 hours, and the presence or absence of oily oozing 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 leaching was observed.
Δ: Slight oily oozing was observed.
X: Many oily leachings were observed.

(Evaluation of independence)
A glass plate (trade name “GLASS PLATE”, manufactured by ASONE, 200 mm × 200 mm × thickness 5 mm) used for evaluation is a quadrangle in plan view. Spacers with a thickness of 1 mm were arranged on the four sides of the upper surface of the glass plate to form a 10 cm × 10 cm square region. After casting the composition for each support material in the region, another glass plate was placed on top of each other. Then, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) was used as an irradiating means, and cured by irradiating with ultraviolet rays so that the total irradiation light amount was 500 mJ / cm ² , thereby obtaining a support material. Thereafter, the support material was released from the glass plate and cut into a shape of 10 mm length and 10 mm width by a cutter to obtain a test piece. Next, 10 test pieces were stacked to obtain a test piece group having a height of 10 mm. The test piece 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 independence was evaluated according to the following criteria. The evaluation results are shown in Tables 4 and 5.
○: No change in shape.
Δ: The shape changed slightly and the weight was inclined.
X: The shape changed greatly.

As can be seen from the results in Tables 4 and 5, the compositions for the support materials of Examples S1 to S16 that satisfy all the requirements of the present invention had a viscosity suitable for ejection from an inkjet head. In addition, the support materials obtained by photocuring the support material compositions of Examples S1 to S16 were highly soluble in water and suppressed oil leaching. Furthermore, the support materials obtained by photocuring the support material compositions of Examples S1 to S15 had sufficient self-supporting properties. In addition, since the composition for a support material of Example S16 (reference example) contains less than 5 parts by weight of the photopolymerization initiator (d), the radical reaction is promoted even when irradiated with an ultraviolet LED. However, the support material obtained was not sufficiently self-supporting. When the mercury lamp or metal halide lamp is used as the irradiation means, the support material composition of Example S16 has sufficient support material even if the content of the photopolymerization initiator (d) is 3 parts by weight. Independent.

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% by weight. The support materials obtained from the compositions for the support materials of Examples S1 to S8, S10, S11, and S13 to S16, which are greater than or equal to parts, were more soluble in water. Examples S1 to S10 in which the content of the polyalkylene glycol (b) containing an oxyethylene group and / or 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 In the support materials obtained from the compositions for support materials of S14 to S16, oil seepage was further suppressed. 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 ethylenically unsaturated monomer (a) is 25 parts by weight or more, It had more sufficient independence.

On the other hand, since the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is less than 20 parts by weight, the support material composition of Comparative Example s1 was not sufficient for the support material to be self-supporting. . In the composition for support material of Comparative Example s2, the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) exceeds 50 parts by weight, and thus the solubility of the support material in water was low. Since the content of the polyalkylene glycol (b) containing an oxyethylene group and / or oxypropylene group exceeds 49 parts by weight, the composition for the support material of Comparative Example s3 has a high viscosity and is oily in the support material. A oozing occurred. In the support material composition of Comparative Example s4, since the content of the water-soluble organic solvent (c) exceeded 35 parts by weight, oily oozing occurred in the support material. Since the content of the polyalkylene glycol (b) containing an oxyethylene group and / or an oxypropylene group is less than 20 parts by weight, the support material composition of Comparative Example s5 has a solubility in water of the support material. It was low. Further, in the support material composition of Comparative Example s5, since the content of the water-soluble organic solvent (c) exceeded 35 parts by weight, oily oozing occurred in the support material. Since the content of the polyalkylene glycol (b) containing an oxyethylene group and / or oxypropylene group exceeds 49 parts by weight, the composition for the support material of Comparative Example s6 has a high viscosity and is oily in the support material. A oozing occurred.

<Optical modeling products>
(Evaluation of dimensional accuracy of stereolithography products)
A cured product was prepared using an optical modeling ink set obtained by combining each of the model material compositions shown in Table 1 and each of the support material compositions shown in Tables 2 and 3. The shape and target dimensions of the cured product are shown in FIGS. 3 (a) and 3 (b). The process of discharging each model material composition and each support material composition from the inkjet 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. . In addition, the process of photocuring each composition for model materials and each composition for support materials uses an LED light source with a wavelength of 385 nm installed on the back side of the inkjet head with respect to the scanning direction, and an illuminance of 250 mW / cm. ^{2. The} measurement was performed under the condition of an integrated light amount of 300 mJ / cm ² per composition layer. Next, the support material was removed by immersing the cured product in ion-exchanged water to obtain a stereolithographic product. Thereafter, the obtained stereolithography product was allowed to stand in a desiccator for 24 hours and sufficiently dried. Through the above-described steps, the test No. Five to three stereolithographic products were manufactured. About the stereolithography goods after drying, the dimension of the x direction in FIG. 3A and the y direction was measured using calipers, and the rate of change from the target dimension was calculated. The dimensional accuracy is determined according to test no. An average value of the dimensional change rate in each of the stereolithographic products 1 to 10 was obtained, and evaluation was performed according to the following criteria using the average value. The evaluation results are shown in Table 6.
○: Average dimensional change rate is less than ± 1.0% ×: Average dimensional change rate is ± 1.0% or more

As can be seen from the results in Table 6, test No. manufactured using the optical modeling ink set that satisfies all the requirements of the present invention. The stereolithographic products 1 to 7 had good dimensional accuracy.

The ink set for optical modeling according to 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 1 3D 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 Hardened material 7 Container 8 Solvent

Claims (16)

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.
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, containing The composition for model material is the ink set for stereolithography according to claim 1, wherein the monofunctional ethylenically unsaturated monomer (A) has an alicyclic skeleton. The composition for model material is an ink set for optical modeling according to claim 1 or 2, wherein the polyfunctional ethylenically unsaturated monomer (B) has an alicyclic skeleton or an aromatic ring. In the model material composition, 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 optical modeling ink set according to any one of claims 1 to 3. In the model material composition, 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 entire model material composition. The optical modeling ink set according to any one of 1 to 4. The content of the polyfunctional ethylenically unsaturated monomer (B) in the model material composition is 5 to 50 parts by weight with respect to 100 parts by weight of the entire model material composition. The optical modeling ink set according to any one of 1 to 5. The content of the oligomer (C) in the model material composition is 10 to 45 parts by weight based on 100 parts by weight of the entire model material composition. The ink set for stereolithography described in 1. In the model material composition, the content of the photopolymerization initiator (D) is 0.5 to 15 parts by weight with respect to 100 parts by weight of the entire model material composition. The ink set for stereolithography according to any one of the above. The model material composition according to any one of claims 1 to 8, wherein the model material obtained by photocuring the model material composition has a glass transition temperature of 90 to 200 ° C. Ink set for stereolithography. In the support material composition, 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 entire support material composition. The optical modeling ink set according to any one of claims 1 to 9. The content of the polyalkylene glycol (b) in the support material composition is 25 to 45 parts by weight with respect to 100 parts by weight of the entire support material composition. The ink set for stereolithography as described in one. The content of the water-soluble organic solvent (c) in the support material composition is 5 parts by weight or more with respect to 100 parts by weight of the entire support material composition. The ink set for stereolithography as described in one. The content of the photopolymerization initiator (d) in the support material composition is 1 to 25 parts by weight with respect to 100 parts by weight of the entire support material composition. The ink set for stereolithography as described in one. The support material composition further comprises 0.05 to 3.0 parts by weight of a storage stabilizer (e) with respect to 100 parts by weight of the entire support material composition. The ink set for stereolithography according to any one of the above. 15. An optically shaped article formed by using the optical modeling ink set according to any one of claims 1 to 14 by an ink jet optical modeling method. A method for producing a stereolithographic product by using the stereolithography ink set according to any one of claims 1 to 14, by an inkjet stereolithography 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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