JP2018122499A - Ink set for photo-shaping, photo-shaped article, and method for producing photo-shaped article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set for photo-shaping for obtaining a shaped article having toughness and satisfactory dimensional accuracy, a photo-shaped article molded using the ink set for optical shaping, and a method for producing photo-shaped article using the ink set for optical shaping.SOLUTION: A composition for modeling material of a photo-shaping ink set comprises an ethylenic unsaturated monomer (A) having one or more ethylenic double bonds, a silane compound (B) having one or more ethylenic double bonds and a photopolymerization initiator (C). The composition for a support material comprises 20 to 50 pts.wt. of a water-soluble monofunctional ethylenic unsaturated monomer (a), 20 to 49 pts.wt. of a polyalkylene glycol (b) containing EO and/or PO, 35 pts.wt. or less of a water-soluble organic solvent (c) and 5 to 20 pts.wt. of a photopolymerization initiator (d).SELECTED DRAWING: None

Description

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

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

  Among the modeling methods, in recent years, an optical modeling method by an ink jet method for forming a cured layer having a predetermined shape by discharging a photocurable composition from a nozzle and immediately irradiating it with ultraviolet rays or the like to cure. Hereinafter, ink jet stereolithography is reported (Patent Documents 1 to 4). 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). And 4). 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.

  The three-dimensional structure produced using a photocurable composition is required toughness depending on the application. Patent Document 5 discloses a composition containing a silicon compound as a composition capable of obtaining a tough three-dimensional model. In Patent Document 5, a cured layer is formed one by one by irradiating the liquid surface of a composition containing a silicon compound with ultraviolet rays or the like to cure.

JP 2004-255839 A JP 2010-155889 A JP 2010-155926 A JP 2012-111226 A Japanese Patent Laying-Open No. 2015-10167

  In the inkjet stereolithography method, the stereolithography product obtained using the composition for a model material containing a silicon-based compound and the conventionally known composition for a support material has a problem that the dimensional system is lowered although it is tough. It was.

  The present invention has been made in view of the above-described present situation, and is formed using an optical modeling ink set for obtaining a optical modeling product having toughness and good dimensional accuracy, and the optical modeling ink set. It is an object of the present invention to provide an optical modeling product and a method for manufacturing the optical modeling product using the optical modeling ink set.

  The inventors diligently studied the cause of the reduction in the dimensional accuracy of the stereolithography product. As a result, the inventors of the optically shaped article with reduced dimensional accuracy immediately after discharging the model material composition and the support material composition from the inkjet head, the layer made of the model material composition and the layer Acquired knowledge that bleeding of the interface occurs when one of the composition for the model material and the composition for the support material moves to the other side at the interface with the layer made of the composition for the support material. It was. That is, the present inventors are one of the causes that the bleeding generated at the interface between the layer made of the model material composition and the layer made of the support material composition reduces the dimensional accuracy of the stereolithography product. I got the knowledge.

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

(1) A combination of a composition for a model material that is used in an ink jet optical modeling method and is used for modeling a model material, and a composition for a support material used for modeling a support material. An ink set for stereolithography,
The model material composition is:
An ethylenically unsaturated monomer (A) having one or more ethylenic double bonds;
A silane compound (B) having one or more ethylenic double bonds (excluding a compound corresponding to the ethylenically unsaturated monomer (A));
A photopolymerization initiator (C);
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),
5 to 20 parts by weight of a photopolymerization initiator (d),
An ink set for stereolithography, containing

  (2) In the model material composition, the content of the silane compound (B) is 1 to 500 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (A). The ink set for optical modeling as described in 1).

  (3) In the composition for model material, the ethylenically unsaturated monomer (A) includes a polyester acrylate (A1), a polyurethane acrylate (A2), a polyepoxy acrylate (A3), and a polyacrylic acrylate. The optical modeling ink set according to (1) or (2), wherein the ink set is one or more selected from (A4).

  (4) In the composition for a model material, the ethylenically unsaturated monomer (A) has a weight average molecular weight of 150 to 30,000, and any one of (1) to (3) The ink set for stereolithography as described.

  (5) The composition for a model material further includes a cyclic compound (D) including a ring structure having one or more ethylenic double bonds (provided that the ethylenically unsaturated monomer (A) and the silane The ink set for stereolithography according to any one of (1) to (4), further comprising a compound corresponding to the compound (B).

  (6) In the composition for model material, the cyclic compound (D) is a cyclic compound (D1) including a ring structure that does not contain a heteroatom, and the ink set for optical modeling according to the above (5) .

  (7) In the composition for a model material, the cyclic compound (D1) containing a ring structure not containing a heteroatom is a cyclic compound (D1-1) containing an alicyclic structure. The ink set for stereolithography as described.

  (8) The composition for a model material further includes a compound (E) having one or more ethylenic double bonds (provided that the ethylenically unsaturated monomer (A), the silane compound (B), and the The ink set for stereolithography according to any one of (1) to (7) above, which contains a compound corresponding to the cyclic compound (D).

  (9) In the model material composition, the content of the photopolymerization initiator (C) is 0.01 to 30 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 (8).

  (10) 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 ink set for stereolithography according to any one of (1) to (9), wherein

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

  (13) The support material composition further includes 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 1) to (12).

  (14) An optically modeled article formed by using the optical modeling ink set according to any one of (1) to (13) by an inkjet optical modeling method.

(15) A method for producing an optically shaped article by an inkjet optical modeling method using the optical modeling ink set according to any one of (1) to (13),
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 toughness and good dimensional accuracy, an optical modeling product modeled using the optical modeling ink set, and the light It is possible to provide a method for producing a stereolithographic product using a 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.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 this embodiment) will be described in detail. The present invention is not limited to the following contents. In the following description, “(meth) acrylate” is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to “(meth) acryloyl”, “(meth) acryl”, and “(meth) allyl”.

1. Model Material Composition <Ethylenically Unsaturated Monomer (A)>
The composition for model material contained in the optical modeling ink set according to the present embodiment contains an ethylenically unsaturated monomer (A) having one or more ethylenic double bonds. The ethylenically unsaturated monomer (A) is at least one selected from a polyester acrylate (A1), a polyurethane acrylate (A2), a polyepoxy acrylate (A3), and a polyacrylic acrylate (A4). Preferably there is.

  The polyester acrylate (A1) is not particularly limited as long as it is an acrylate having one or more ester bonds in the main chain skeleton. Examples of the polyester acrylate (A1) include molecules such as a terminal of a polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol or a hydroxyl group in a polyester chain, (meth) acrylic acid, maleic acid, and the like. A compound obtained by esterification with a compound having one or more carboxyl groups and an ethylenic double bond, or a carboxyl group in the terminal or polyester chain of polyester, and 2-hydroxyethyl (meth) acrylate, Examples thereof include compounds obtained by esterification with a compound having one or more hydroxyl groups and ethylenic double bonds in the molecule, such as (meth) acrylic acid 2-hydroxypropyl. In addition, examples of the polyester acrylate (A1) include a polyester acrylate obtained from an acid anhydride, glycidyl (meth) acrylate, and a compound having at least one hydroxyl group. These may be used alone or in combination of two or more.

  Examples of the polybasic acid include aliphatic, alicyclic, and aromatic polybasic acids, acid anhydrides, and the like.

  Examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid and the like, aliphatic dicarboxylic acids thereof, anhydrides and anhydride derivatives of the aliphatic dicarboxylic acids, and the like. Examples of the anhydride derivative of the aliphatic dicarboxylic acid include a derivative of succinic anhydride (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, etc.), a derivative of glutaric anhydride (glutaric anhydride, 3-allyl anhydride). Glutaric acid, etc.) and maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, etc.).

  Examples of the alicyclic polybasic acid include alicyclic dicarboxylic acids, anhydrides and anhydride derivatives of the alicyclic dicarboxylic acids, and the like. Examples of the alicyclic dicarboxylic acid include saturated dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclopropane-1α, 2β-dicarboxylic acid, cyclopropane-1β, 2α-dicarboxylic acid, and tetrahydrophthalic acid. Examples thereof include unsaturated alicyclic dicarboxylic acids having one or two ethylenic double bonds in the ring such as alicyclic dicarboxylic acid and 1-cyclobutene-1,2-dicarboxylic acid. Examples of the anhydride derivative of the alicyclic dicarboxylic acid include a derivative of hexahydrophthalic anhydride (such as 3-methyl-hexahydrophthalic anhydride) and a derivative of tetrahydrophthalic anhydride (1,2,3,6-tetrahydroanhydride). And hydrogenated phthalic anhydride derivatives such as phthalic acid and 3-methyl-1,2,3,6-tetrahydrophthalic anhydride.

  Examples of the aromatic polybasic acid include aromatic dicarboxylic acids and anhydrides of the aromatic dicarboxylic acids. Examples of the aromatic dicarboxylic acid include o-phthalic acid, isophthalic acid, terephthalic acid, and the like. Examples of the aromatic dicarboxylic acid anhydride include phthalic anhydride and 4-methylphthalic anhydride.

  Examples of the acid anhydrides include chlorendic anhydride and het anhydride.

  Examples of the polyhydric alcohol include low molecular weight polyols having a number average molecular weight (Mn) of about 50 to about 500, and high molecular weight polyols having a number average molecular weight (Mn) of about 500 to about 50,000. .

  Examples of the low molecular weight polyols include aliphatic or alicyclic diols such as ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, cyclopentadiene dimethanol, and dimer diol; Add alkylene oxide to 3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, bisphenol And aromatic diols such as added bisphenol. Examples of the raw material bisphenol of the addition type bisphenol include bisphenol A and bisphenol F. Examples of the raw material alkylene oxide of the addition type bisphenol include ethylene oxide and propylene oxide.

  Examples of the high molecular weight polyols include high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. The high molecular weight polycarbonate polyol is obtained by reacting the above-mentioned low molecular weight diol with a carbonate ester or phosgene.

  Examples of commercially available high molecular weight polyester polyols include Byron GK640 manufactured by Toyobo Co., Ltd. (number average molecular weight (hereinafter also referred to as “Mn”) = 18,000, glass transition temperature (hereinafter also referred to as “Tg”). Described) = 79 ° C., hydroxyl value = 5, acid value <4, linear type), Byron GK880 (Mn = 18,000, Tg = 84 ° C., hydroxyl value = 5, acid value <4, linear type), etc. Can be mentioned.

  Examples of commercially available high molecular weight polyamide polyols include TPAE617 (Mn = 15,000, Tg = 90 ° C., hydroxyl value = 16, acid value = 1, linear type) manufactured by Fuji Kasei Kogyo Co., Ltd.

  As a commercial product of the high molecular weight polycarbonate polyol, for example, Oxymer N112 (Mn = 1,000, Tg = 60 ° C., hydroxyl value = 112, acid value <0.5, linear type) manufactured by Perstorp; Asahi Kasei Chemicals Corporation PCDL-T5651 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type) and the like are available.

  Examples of commercially available high molecular weight polyurethane polyols include Byron UR1350 (Mn = 30,000, Tg = 3 ° C., hydroxyl value = 46, acid value <1, linear type) manufactured by Toyobo Co., Ltd., Byron UR1400 (Mn = 40,000, Tg = 83 ° C., hydroxyl value = 2, acid value <1, linear type) and the like.

  The high molecular weight polyester polyol is obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly (β-methyl-γ-valerolactone) diol, and polyvalerolactone diol, in addition to the polyester polyol described above. A polyester polyol etc. are mentioned.

  Examples of the polyurethane acrylate (A2) include compounds obtained by reacting a compound having one or more isocyanate groups with a compound having one or more hydroxyl groups and ethylenic double bonds in the molecule; 1 Reaction of a urethane prepolymer having a terminal isocyanate group obtained by reacting a compound having at least one isocyanate group with the polyhydric alcohol described above, and a compound having at least one hydroxyl group and ethylenic double bond in the molecule A compound obtained by reacting a urethane prepolymer of a terminal isocyanate group obtained by reacting a compound having one or more isocyanate groups with the polyhydric alcohol described above, and a compound having one or more amino groups. The resulting urethane prepolymer of the terminal isocyanate group and one or more hydroxyl groups in the molecule and Is reacted with a compound having an ethylenic double bond include the compounds obtained. These may be used alone or in combination of two or more. The polyester polyol in which the polyhydric alcohol is a high molecular weight polyol is included in the polyurethane acrylate. An acrylate containing a urea bond group obtained by reacting an isocyanate group with an amino group is also included in the polyurethane acrylate.

  Examples of the compound having one or more isocyanate groups include monofunctional or polyfunctional polyisocyanates. Examples of the polyisocyanate include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

  Examples of the monofunctional polyisocyanate include methyl isocyanate, ethyl isocyanate, propyl isocyanate and the like.

  Among the polyfunctional polyisocyanates, examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate and 4,4′-diphenyl diisocyanate.

  Among the polyfunctional polyisocyanates, examples of the aliphatic polyisocyanate include trimethylene diisocyanate and tetramethylene diisocyanate.

  Among the polyfunctional polyisocyanates, examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, and the like.

  Among the polyfunctional polyisocyanates, examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate.

  In addition, as the compound having one or more isocyanate groups, a 2-methylpentane-2,4-diol adduct of the polyisocyanate, a trimer having an isocyanurate ring, or the like can be used in combination.

  Examples of the compound having an amino group include aliphatic polyamines such as triethylamine, pyridine and aniline; alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4′-diamine; and aromatics such as phenylenediamine and xylylenediamine. Silylamines having monofunctional silylamino groups such as trimethylsilyldimethylamine and trimethylsilyldiethylamine; silylamines having bifunctional silylamino groups such as 1,1,3,3-tetramethyldisilazane and hexamethyldisilazane Tricyclic or higher functional silylamino groups such as 1,1,3,3,5,5-hexamethylcyclotrisilazane, 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane Silylamine possessing a Polypropylene glycol with an amino group bonded to a branched carbon (propylene skeleton diamine, products “Jefamine D230” and “Jeffamine D400” manufactured by Sun Techno Chemical Co., Ltd.), propylene skeleton triamines, products manufactured by Sun Techno Chemical Co., Ltd. T403 ", etc.), diamine of polyether skeleton in which methylene group is bonded to amine nitrogen such as ethylenediamine, propylenediamine, 1,5-diamino-2-methylpentane (" MPMD "manufactured by DuPont Japan), metaxylylenediamine Polyamines (such as “MXDA” manufactured by DuPont Japan Co., Ltd.) and polyamidoamines (“X2000” manufactured by Sanwa Chemical Co., Ltd.); dimer amines obtained by converting the carboxyl group of dimer acid into an amino group; Having dend Mer; polyoxyalkylene glycol diamines, and the like having both ends propoxy amine.

  Examples of the polyepoxy acrylate (A3) include a reaction between a compound having a glycidyl group and a compound having one or more carboxyl groups and an ethylenic double bond in a molecule such as (meth) acrylic acid and maleic acid. The compound etc. which are obtained by these are mentioned. Representative examples of the polyepoxy acrylate include polyepoxy acrylates such as bisphenol type, epoxidized oil type, novolac type, and alicyclic type.

  Examples of the bisphenol-type polyepoxy acrylate include bisphenol-type diglycidyl ether obtained by reacting bisphenols with epichlorohydrin, one or more carboxyl groups and ethylenic diesters in a molecule such as (meth) acrylic acid. Examples thereof include polyepoxy acrylates having a Mn of 400 to 2,000 obtained by reacting with a compound having a heavy bond.

  Examples of the epoxidized oil-type polyepoxy acrylate include epoxidized oil such as soybean oil, and one or more carboxyl groups and ethylenic double bonds in a molecule such as (meth) acrylic acid and maleic acid. And polyepoxy-based acrylates obtained by reaction with a compound having the above.

  As the novolak type polyepoxy acrylate, for example, a polyepoxy obtained by a reaction between a novolak type epoxy resin and a compound having one or more carboxyl groups and an ethylenic double bond in a molecule such as (meth) acrylic acid. And acrylates.

  The alicyclic polyepoxy acrylate is obtained, for example, by a reaction between an alicyclic epoxy resin and a compound having one or more carboxyl groups and an ethylenic double bond in the molecule such as (meth) acrylic acid. Examples include polyepoxy acrylates. The compound having one or more carboxyl groups and ethylenic double bonds in the molecule may be a compound having a plurality of ethylenic double bonds for the purpose of adjusting the crosslinking density by active energy ray polymerization.

  Examples of the polyacrylic acrylate (A4) include a modified polyether having an ethylenic double bond; a compound having an amine-modified ethylenic double bond; an alkyd resin, a spiroacetal resin, a polybutadiene resin, and a polythiol polyene resin. And oligomers or prepolymers of one or more compounds selected from compounds having an ethylenic double bond of polyfunctional compounds such as polyhydric alcohols.

  The weight average molecular weight of the ethylenically unsaturated monomer (A) (hereinafter also referred to as “Mw”) improves the cohesive density of the model material composition and compatibility with the cyclic compound (D) described later. In view of improving the durability of the model material, it is preferably 150 to 30,000. Moreover, it is more preferable that Mw of the said ethylenically unsaturated monomer (A) is 400-10,000. The ethylenically unsaturated monomer (A) may be an oligomer.

<Silane compound (B)>
The composition for a model material contained in the optical modeling ink set according to the present embodiment includes a silane compound (B) having one or more ethylenic double bonds (however, the ethylenically unsaturated monomer (A)). (Excluding applicable compounds). When the model material composition contains the silane compound (B), the model material obtained by photocuring the model material composition can have a texture like silicon rubber.

  Examples of the silane compound (B) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- ( (Meth) acryloyloxypropyltributoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- ( Alkoxysilyl group-containing (meth) acrylic acid esters such as (meth) acryloyloxypropylethyldipropoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane; (meth) allylchlorosilane , (Meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, tripropoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, vinyltrimethoxy Silane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltris (methoxypropoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane , Divinyldiisopropoxysilane, divinyldiacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyl Isopropoxysilane, methylvinyldiacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxysilane, methylallyldiacetoxysilane, etc. Examples include vinyl-based alkoxysilanes. These may be used alone or in combination of two or more.

  The content of the silane compound (B) is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (A). When the content of the silane compound (B) is 1 part by weight or more, the heat resistance and wet heat resistance of the model material can be improved by increasing the cohesive strength of the model material composition. When the content of the silane compound (B) is 500 parts by weight or less, the curing shrinkage of the model material can be reduced. Further, when the content of the silane compound (B) is within the above range, the surface tension can be controlled within an appropriate range. As a result, it is possible to suppress the occurrence of bleeding that occurs at the interface between the layer made of the model material composition and the layer made of the support material composition described later. The content of the silane compound (B) is more preferably 5 parts by weight or more and further preferably 10 parts by weight or more with respect to 100 parts by weight of the ethylenically unsaturated monomer (A). . Further, the content of the silane compound (B) is more preferably 400 parts by weight or less, and preferably 300 parts by weight or less with respect to 100 parts by weight of the ethylenically unsaturated monomer (A). Further preferred. In addition, when the said silane compound (B) is contained 2 or more types, the said content is the sum total of content of each silane compound (B).

<Photopolymerization initiator (C)>
The model material composition contained in the optical modeling ink set according to the present embodiment contains a photopolymerization initiator (C). The said photoinitiator (C) will not be specifically limited if it is a compound which accelerates | stimulates a radical reaction when irradiated with the light of the wavelength of an ultraviolet-ray, near-ultraviolet rays, or visible region. Examples of the photopolymerization initiator (C) include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4 ′. -Diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane Examples include -1-one, 4-oxanthone, camphorquinone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one. Commercially available products include, for example, Irgacure 184,907,651,1700,1800,819,369,261, DAROCUR-TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF), Darocur- 1173 (manufactured by Merck), Ezacure KIP150, TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.) and the like. As the photopolymerization initiator (C), a photopolymerization initiator having at least one (meth) acryloyl group in the molecule can also be used. These may be used alone or in combination of two or more.

  It is preferable that content of the said photoinitiator (C) is 0.01-30 weight part with respect to 100 weight part of the said whole composition for model materials from a reactive viewpoint. In addition, when 2 or more types of the said photoinitiators (C) are contained, the said content is the sum total of content of each photoinitiator (C).

  The composition for model material preferably does not substantially contain an organic solvent, and more preferably does not contain any organic solvent. However, the photopolymerization initiator (C) is often difficult to dissolve in the polymerizable component. Therefore, since the said composition for model materials melt | dissolves the said photoinitiator (C), it may contain a small amount of organic solvents. The content of the organic solvent is preferably 5 parts by weight or less with respect to 100 parts by weight of the entire model material composition.

  Moreover, in order to improve the performance of the said photoinitiator (C), the said composition for model materials may contain the active energy ray sensitizer. Examples of the active energy ray sensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds. Among these, the active energy ray sensitizer is preferably anthracene, benzophenone, thioxanthone, perylene, phenothiazine, rose bengal, or the like.

<Cyclic compound (D)>
The model material composition included in the optical modeling ink set according to the present embodiment further includes a cyclic compound (D) including a ring structure having one or more ethylenic double bonds (provided that the ethylenic unsaturation is included). (Excluding compounds corresponding to the monomer (A) and the silane compound (B)). The cyclic compound (D) is classified into a cyclic compound (D1) containing a ring structure not containing a hetero atom and a cyclic compound (D2) containing a ring structure containing a hetero atom. Moreover, the cyclic compound (D1) containing the ring structure which does not contain the said hetero atom includes the cyclic compound (D1-1) containing an alicyclic structure, the cyclic compound (D1-2) containing no alicyclic structure, and are categorized. The cyclic compound (D) is preferably a cyclic compound (D1) including a ring structure that does not contain a hetero atom from the viewpoint of high heat yellowing resistance and low odor. Moreover, the cyclic compound (D1) containing the ring structure which does not contain the hetero atom is a cyclic compound containing an alicyclic structure from the viewpoint of improving the hardness of the model material obtained by photocuring the model material composition. It is more preferable that it is a compound (D1-1). On the other hand, the cyclic compound (D1) containing a ring structure containing no hetero atom may be a cyclic compound (D1-2) containing no alicyclic structure from the viewpoint of suppressing curing shrinkage during the polymerization reaction. .

  Examples of the cyclic compound (D1-1) containing the alicyclic structure include cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, and 1-ethyl-1- (meth) acrylate. Cyclopentyl, 1-isopropyl-1-cyclopentyl (meth) acrylate, 1-methyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl (meth) acrylate 1-cyclohexyl, 1-ethyl-1-cyclooctyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate , (Meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid 2-ethyladamer Tyl-2-yl, 2-n-propyladamantyl-2-yl (meth) acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, 1- (adamantan-1-yl) (meth) acrylate -1-methylethyl, 1- (adamantan-1-yl) -1-ethylethyl (meth) acrylate, 1- (adamantan-1-yl) -1-methylpropyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid cyclic esters such as 1- (adamantan-1-yl) -1-ethylpropyl;

  Cyclic compounds containing an alkenyl group such as 5-vinylbicyclo [2.2.1] hept-2-ene and 2,5-bis (allyloxy) norbornane;

  Bifunctional (meth) acrylic acid cyclic esters such as di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate;

  Cyclic compounds containing an alkenyl group such as 5-vinylbicyclo [2.2.1] hept-2-ene and 2,5-bis (allyloxy) norbornane;

  Hydroxyl-containing cyclic (meth) acrylic esters such as (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol Kind;

  Examples include ethenyl group-containing cyclic compounds such as 3-allyladamantan-1-ol and cyclooctanedimethanol monovinyl ether. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving the hardness and durability of the model material, 1,4-cyclohexanedimethanol acrylate and dicyclopentanyl (meth) acrylate are preferable.

  Examples of the cyclic compound (D1-2) not containing the alicyclic structure include benzyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, and 2-phenoxyethyl (meth) acrylate. , (Meth) acrylic acid 2-oxo-1,2-phenylethyl, (meth) acrylic acid 2-oxo-1,2-diphenylethyl, (meth) acrylic acid 1-naphthyl, (meth) acrylic acid 2-naphthyl 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2 -(Meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyl Xylbutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) acrylic (Meth) acrylic acid cyclic esters such as acid-o-2-propenylphenyl;

  Bifunctional (meth) acrylic acid cyclic esters such as tetraethylene oxide adducts of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane;

  Cyclic compounds containing an alkenyl group such as 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid;

  Aromatic vinyl compounds having an acyl group such as vinyl benzoyl formate, vinyl benzoyl acetate, vinyl benzoyl propionate, vinyl benzoyl butyrate;

  Aromatic (meth) allyl compounds having an acyl group such as benzoyl formate (meth) allyl and benzoyl acetate (meth) allyl;

  Aromatic vinyl monomers such as styrene, α-methylstyrene, 2-methylstyrene;

  Aromatic vinyl ether monomers having a long chain alkyl group such as vinyl phenyl pentyl ether and vinyl phenyl hexyl ether;

  Vinyl benzoate or isopropenyl benzoate monomers having a long-chain alkyl group such as hexyl 4-vinylbenzoate and octyl 4-vinylbenzoate;

  Vinyl phenyl ether monomers having a long-chain polyalkylene oxide moiety such as tetra (ethylene oxide) vinyl phenyl ether and methyl tetra (ethylene oxide) vinyl phenyl ether;

  Isopropenyl phenyl monomers having a long-chain alkyl group such as isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether;

  Isopropenyl monomers having a polyalkylene oxide moiety such as poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether;

  Mono-long chain alkyl ester cyclic monomers of dicarboxylic acids such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

  Monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate;

  Polyalkylene oxides such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl polyvinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropylenylbenzoate poly (propylene oxide) Vinyl benzoate or isopropenyl benzoate monomers having a moiety;

  Alkenyl group-containing cyclic sulfonic acids such as styrenesulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid;

  Ammonium salts of styrene sulfonic acid such as ammonium styrene sulfonate and monomethyl ammonium styrene sulfonate;

  Alkenyl group-containing vinyloxybenzenesulfonic acid metal salts or ammonium salts such as sodium styrenesulfonate and potassium styrenesulfonate;

  2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonate sodium, 2-methyl-2-propenyloxybenzenesulfonate potassium and the like 2-methyl-2-propenyloxybenzenesulfonate Metal or ammonium salts of acids;

  Hydroxyl-containing cyclic (meth) acrylic acid esters such as (meth) acrylic acid 2-hydroxy-3-phenoxymethyl and (meth) acrylic acid 2-hydroxy-3-phenoxyethyl;

  Hydroxyl group-containing benzophenone-based (meth) acrylic esters such as 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone;

  Vinyl ethers having a hydroxyl group-containing alicyclic ring or aromatic ring, such as 1,2-cyclohexanedimethanol monovinyl ether and 1,3-cyclohexanedimethanol monovinyl ether;

  Hydroxyl-containing aromatic ethenyl compounds such as 2-hydroxystyrene, 3-hydroxystyrene and 4-hydroxystyrene;

  (Meth) allyl ethers having a hydroxyl group-containing alicyclic or aromatic ring such as 1,2-cyclohexanedimethanol mono (meth) allyl ether;

  and (meth) allyl group-containing compounds having a plurality of hydroxyl groups such as o-di (meth) allylbisphenol A, o-di (meth) allylbisphenol F, o-di (meth) allylbisphenol S, and the like. These may be used alone or in combination of two or more.

  Examples of the cyclic compound (D2) containing a ring structure containing a heteroatom include nitrogen atoms such as 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole. Polycyclic (meth) acrylic acid esters of the following: 6-membered nitrogen atoms such as 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine (Meth) acrylic acid esters having a ring; heterocyclic (meth) acrylic acid esters such as pentamethylpiperidinyl (meth) acrylate; containing an ethenyl group having a five-membered ring containing a nitrogen atom such as 1-vinylpyrrole Compounds; ethenyl group-containing compounds having a six-membered ring containing nitrogen atoms such as 2-vinylpiperazine; nitrogen-containing hete such as 1-vinylindole Polycyclic ethenyl group-containing compounds; compounds having a nitrogen atom-containing heterocyclic structure and two or more ethenyl groups, such as 1-methyl-4,5-divinyl-1H-imidazole; 1- (meth) allyl (Meth) allyl group-containing compounds having a nitrogen atom-containing heterocyclic structure such as -1H-imidazole; (meth) allyl having a nitrogen atom-containing heteropolycyclic structure such as 2- (meth) allyl-1H-indole Group-containing compounds; (meth) allyl group-containing compounds having a heterocyclic structure having both nitrogen and oxygen atoms such as imide (meth) acrylate; maleimide having both nitrogen and oxygen atoms such as maleimide Derivatives; ethenyl group-containing compounds having a heterocyclic structure containing a nitrogen atom and an oxygen atom such as 2-vinyloxazole.

  The content of the cyclic compound (D) is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (A). When the content of the cyclic compound (D) is less than 1 part by weight, the cohesive force of the model material composition decreases, and thus the model material obtained by photocuring the model material composition Heat resistance and heat-and-moisture resistance may be inferior. On the other hand, when the content of the cyclic compound (D) exceeds 500 parts by weight, the model material composition becomes brittle due to increased curing shrinkage during photocuring and deformation during molding. There is a case. In addition, when the said cyclic compound (D) is contained 2 or more types, the said content is the sum total of content of each cyclic compound (D).

<Compound (E) having one or more ethylenic double bonds>
The model material composition contained in the optical modeling ink set according to the present embodiment further includes a compound (E) having one or more ethylenic double bonds (however, the ethylenically unsaturated monomer (A)). And the silane compound (B) and the compound corresponding to the cyclic compound (D) are preferably included).

  From the viewpoint of improving the hardness of the model material obtained by photocuring the model material composition, the compound (E) having one or more ethylenic double bonds is a compound having a hydroxyl group (E-1) and Preferably, it is a compound (E-2) having a carboxyl group. The compound (E) having one or more ethylenic double bonds may be a compound having both a hydroxyl group and a carboxyl group. In addition, the compound (E-1) having a hydroxyl group may be used in combination with the cyclic compound (D1) containing a ring structure that does not contain a heteroatom.

  The compound (E-1) having a hydroxyl group is not particularly limited as long as it has a hydroxyl group in its structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxy (meth) acrylate Fatty acid ester (meth) acrylate such as propyl, or polylactone (meth) acrylate such as Plaxel FA2D (manufactured by Daicel Chemical Industries) having a hydroxyl group at the terminal by ring-opening addition of a lactone ring, or ethylene Hydroxyl group-containing aliphatic (meth) acrylic acid such as alkylene oxide addition system (meth) acrylic acid ester having a hydroxyl group at the terminal after repeated addition of alkylene oxide such as oxide and propylene oxide, (meth) acrylic acid 2-hydroxyethyl phosphate Esters;

  Hydroxyl-containing aliphatic vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, or alkylene oxide-added vinyl ether having a hydroxyl group at the terminal to which alkylene oxide such as ethylene oxide and propylene oxide is repeatedly added;

  Hydroxyl group-containing aliphatic (meth) allyl such as (meth) allyl alcohol, isopropenyl alcohol, or alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal after repeated addition of alkylene oxide such as ethylene oxide or propylene oxide Alcohols or (meth) allyl ethers;

  Compounds having a plurality of hydroxyl groups and one or more ethylenic double bonds such as propenediol, butenediol, heptenediol, octenediol, glycerol di (meth) acrylate;

  Examples thereof include monomers having a hydroxyl group and an ethenyl group such as vinyl alcohol. These may be used alone or in combination of two or more. Among these, carbon such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate from the viewpoint of reducing curing shrinkage of the model material obtained by photocuring the composition for model material Compounds having 2 to 18 numbers are preferred.

  The carboxyl group-containing compound (E-2) is not particularly limited as long as it has a carboxyl group in its structure. For example, (meth) acrylic acid, (meth) acrylic acid 2-carboxyethyl, Alternatively, polylactone type (meth) acrylic acid ester having a carboxyl group at the terminal by ring-opening addition of a lactone ring such as mono (meth) acrylic acid ω-carboxypolycaprolactone ester, or alkylene oxide such as ethylene oxide or propylene oxide. Examples include carboxyl group-containing aliphatic carboxylic acids such as esters of alkylene oxide addition-type succinic acid and (meth) acrylic acid having a carboxyl group at the terminal of repeated addition, and acid anhydrides thereof. These may be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, and 2-carboxypropyl acrylate are preferable from the viewpoint of reducing curing shrinkage of the model material obtained by photocuring the composition for model material.

  Examples of the compound having one or more ethylenic double bonds other than the compound (E-1) having a hydroxyl group and the compound (E-2) having a carboxyl group include, for example, methyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters such as ethyl acrylate;

  (Meth) acrylic acid esters containing (meth) acrylic acid (meth) acrylic acid and (meth) acrylic acid esters containing 1-butenyl (meth) acrylic acid;

  (Meth) acrylic acid perfluoroalkyl esters such as perfluoromethyl (meth) acrylate and perfluoroethyl (meth) acrylate;

  Amino group-containing (meth) acrylic acid esters such as (meth) acrylic acid N-methylaminoethyl and (meth) acrylic acid N-tributylaminoethyl;

  Heterocycle-containing (meth) acrylic acid esters having an oxygen atom such as glycidyl (meth) acrylate and (meth) acrylic acid (3-methyl-3-oxetanyl) methyl;

  Aliphatic (meth) acrylic acid esters having one carbonyl group such as (meth) acrylic acid (methoxycarbonyl) methyl and (meth) acrylic acid (methoxycarbonyl) ethyl;

  Aliphatic (meth) acrylic acid esters having two carbonyl groups such as (meth) acrylic acid 2-oxobutanoylethyl and (meth) acrylic acid 2-oxobutanoylpropyl;

  (Meth) acrylic acid alkyl esters containing a sulfonyl group such as sulfomethyl (meth) acrylate and 2-sulfoethyl (meth) acrylate;

  Metal salts and ammonium salts of (meth) acrylic acid esters containing sulfonyl groups such as (meth) acryloyloxydimethylethylammonium ethyl sulfate and (meth) acryloylaminopropyltrimethylammonium sulfate;

  Phosphonic acid group-containing (meth) acrylic acid esters such as (meth) acrylic acid phosphooxyethyl and (meth) acrylic acid phosphooxypropyl;

  Alkoxy group-containing (meth) acrylic acid esters such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate;

  Alkylene oxide-containing (meth) acrylic acid derivatives such as alkylene oxide adducts of (meth) acrylic acid;

  Aliphatic vinyl compounds having an acyl group such as vinyl acetoacetate and vinyl acetopropionate;

  Aliphatic vinyl ethers such as ethyl vinyl ether and 1-propyl vinyl ether;

  Fluorine-containing ethenyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;

  Alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;

  Metal salts or ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;

  Metal salts or ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, potassium 2-methyl-2-propenylsulfonate;

  Nitrile group-containing compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;

  Vinyl esters of carboxylic acids such as vinyl formate and vinyl acetate;

  (Meth) allyl esters of saturated carboxylic acids such as (meth) allyl acetate and (meth) allyl propionate;

  Aliphatic (meth) allyl compounds having an acyl group such as acetoacetic acid (meth) allyl and acetopropionic acid (meth) allyl;

  Glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

  Vinyl esters such as vinyl chloride, vinylidene chloride and allyl chloride;

  Dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

  compounds containing polyfunctional unsaturated bonds such as cis-diallyl succinate and diallyl 2-methylidene succinate;

  Alkenes such as ethylene, propylene, 1-butene, 2-butene, 2-methylpropene;

  Bifunctional (meth) acrylic acid esters such as di (meth) acrylic acid ethylene oxide and di (meth) acrylic acid triethylene oxide;

  Trifunctional (meth) acrylic acid esters such as tri (meth) acrylic acid 1,2,3-propanetriol, tri (meth) acrylic acid 2-methylpentane-2,4-diol;

  And polyfunctional (meth) acrylic acid esters such as tetra (meth) acrylic acid pentaerythritol and tetra (meth) acrylic acid ethoxylated pentaerythritol. These may be used alone or in combination of two or more.

  The compound (E) having one or more ethylenic double bonds preferably has a viscosity of 0.5 to 2000 mPa · s. When the viscosity of the compound (E) having one or more ethylenic double bonds is within the above range, the ethylenically unsaturated monomer (A), the silane compound (B), and the cyclic compound (D) ) To suppress the increase in viscosity of the model material composition, thereby improving the durability such as heat resistance and maintaining the polymerizability when irradiated with ultraviolet rays, and the hardness of the model material, Viscosity and moldability can be maintained.

<Silane compound (F)>
The model material composition included in the optical modeling ink set according to the present embodiment may further contain a silane compound (F) (excluding a compound corresponding to the silane compound (B)). . The silane compound (F) is not particularly limited as long as the adhesion to the substrate is improved, and a known silane compound can be used.

  Moreover, as said silane compound (F), a commercial product can also be used and the oligomer type silane which hydrolyzed and condensed two or more types of silane mixtures and oligomerized can also be used.

  The content of the silane compound (F) is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the entire model material composition from the viewpoint of reactivity. When the content of the silane compound (F) is less than 0.01 parts by weight, the heat resistance and heat-and-moisture resistance of the model material may be inferior. On the other hand, if the content of the silane compound (F) exceeds 10 parts by weight, the durability test for evaluating the heat resistance and moist heat resistance of the model material due to insufficient cohesive strength of the model material composition, In some cases, foaming of the polymer film tends to occur. In addition, when the model material composition is photocured, the hardness of the model material may decrease. The content of the silane compound (F) is more preferably 0.1 parts by weight or more and more preferably 5 parts by weight or less with respect to 100 parts by weight of the entire composition. In addition, when the said silane compound (F) is contained 2 or more types, the said content is the sum total of content of each silane compound (F).

  The composition for model material may further contain an antioxidant from the viewpoint of suppressing coloring of the model material after photocuring with time. Examples of the antioxidant include phenolic antioxidants such as ADK STAB AO-50 and ADK STAB AO-80 (Adeka), sulfur antioxidants such as IRGANOX-PS-800FD (BASF), and TINUBIN 622LD. And commercial products such as hindered amine light stabilizers such as TINUBIN 144 and TINUBIN 765 (all three are manufactured by BASF).

  The content of the antioxidant is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the entire model material composition. When the content of the antioxidant is less than 0.01 parts by weight, the antioxidant may be consumed at an early stage by irradiating ultraviolet rays or the like, so that the polymerization rate may decrease. On the other hand, when the content of the antioxidant exceeds 20 parts by weight, the polymerization rate increases, but the molecular weight of the cured product decreases. As a result, the cohesive strength of the model material composition is reduced, which may reduce the durability of the model material.

  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 organic or inorganic fillers. When the composition for a model material contains the filler, polymerization curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, There are effects such as coloring improvement. Examples of the filler include polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, and the like. The shape of the filler is not particularly limited, and may be particulate or fibrous. When a polymer is used as the filler, flexibility imparting agent, plasticizer, flame retardant, storage stabilizer, antioxidant, ultraviolet absorber, thixotropy imparting agent, dispersion stabilizer, fluidity imparting agent The polymer blend or polymer alloy may be obtained by mixing with a polymer such as an antifoaming agent, and the polymer blend or the polymer alloy may be dissolved, semi-dissolved, or microdispersed in the model material composition.

  The manufacturing method of the composition for model materials contained in the optical modeling ink set which concerns on this embodiment is not specifically limited. For example, the components (A) to (C) and, if necessary, the components (D) to (F) and other additives are uniformly mixed using a mixing and stirring device. Can do.

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

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 the molecule having the property of being cured by energy rays. Examples of the water-soluble monofunctional ethylenically unsaturated monomer (a) include a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms [for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, etc.], Mn 200-1,000 alkylene oxide adduct-containing (meth) acrylate [polyethylene glycol mono (meth) acrylate, monoalkoxy (carbon number 1 to 4) polyethylene glycol mono (meth) acrylate , Polypropylene glycol mono (meth) acrylate, monoalkoxy (1 to 4 carbon atoms) polypropylene glycol mono (meth) acrylate, mono (meth) acrylate of PEA-PPA block polymer, etc.], (meth) acrylic having 3 to 15 carbon atoms Mido derivatives [(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-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, etc.], (meth) acryloylmorpholine and the like. It is done. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of improving the curability of the support material composition, N, N′-dimethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine, and the like are preferable. . 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 active hydrogen compounds include 1 to 4 alcohols and amine compounds. Among these, dihydric alcohol or water is preferable.

  The number average molecular weight 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.

  Content of the said polyalkylene glycol (b) shall be 20-49 weight part with respect to 100 weight part of the said whole composition for support materials. 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, 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, 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 the photopolymerization initiator (d), the same components as in the model material composition can be used.

  The content of the photopolymerization initiator (d) is preferably 5 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 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 component (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. As these, 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 (above, 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 component (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, and TINUVIN 400 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 contained 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 manufacturing method of the composition for support materials contained 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 support material composition thus produced preferably has a viscosity at 25 ° C. of 70 mPa · s or less from the viewpoint of improving the dischargeability from the inkjet head. In addition, the measurement of the viscosity of the said composition for support materials is performed using R100 type | mold viscosity meter based on JISZ8803.

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, the step (I) of obtaining a model material by photocuring the composition for model material by ink jet stereolithography, and obtaining the support material by photocuring the composition for support material; 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, the model material composition included in the optical modeling ink set according to the present embodiment includes a silane compound, and thus has toughness. In addition, the composition for model material and the composition for support material included in the optical modeling ink set according to the present embodiment include an interface between the layer made of the model material composition and the layer made of the support material composition. Bleeding is less likely to occur. From the above, the optical modeling product manufactured using the optical modeling ink set according to the present embodiment has toughness and good dimensional accuracy.

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

<Model material composition>
(Manufacture of compositions for model materials)
In the formulation shown in Table 1, the components (A) to (E) and other additives are uniformly mixed using a mixing and stirring device, and the compositions for model materials of Examples M1 to M9 and Comparative Examples m1 and m2 are mixed. Manufactured. And the following evaluation was performed using these compositions for model materials.

EBECRYL811: Polyester acrylate oligomer [EBECRYL811 (ethylenic double bond / one molecule: 3), manufactured by Daicel Cytec Co., Ltd.]
Purple light UV3000B: polyurethane acrylate oligomer [purple light UV3000B (ethylenic double bond / 1 molecule: 2), manufactured by Nippon Synthetic Chemical Co., Ltd.]
EBECRYL600: Polyepoxyacrylate oligomer [EBECRYL600 (ethylenic double bond / one molecule: 2), manufactured by Daicel Cytec Co., Ltd.]
KBE502: 3-methacryloxypropylmethyldiethoxysilane [KBE502 (ethylenic double bond / one molecule: one), manufactured by Shin-Etsu Chemical Co., Ltd.]
KBE503: 3-methacryloxypropyltriethoxysilane [KBE503 (ethylenic double bond / one molecule), manufactured by Shin-Etsu Chemical Co., Ltd.]
KBM5103: 3-acryloxypropyltrimethoxysilane [KBM5103 (ethylenic double bond / one molecule: one), manufactured by Shin-Etsu Chemical Co., Ltd.]
DAROCURE TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCURE TPO, manufactured by Ciba]
CHOHA: acrylic acid 1,4-cyclohexanedimethanol [Sartomer CD406 (ethylenic double bond / 1 molecule: 2), manufactured by Sartomer]
IBOA: Isobornyl acrylate [Sartomer SR506D (ethylenic double bond / one molecule), manufactured by Sartomer]
DCPA: Dicyclopentanyl acrylate [Fancryl FA-513AS (ethylenic double bond / one molecule: 1), manufactured by Hitachi Chemical Co., Ltd.]
PEA: 2-phenoxyethyl acrylate [Sartomer SR339A (ethylenic double bond / 1 molecule: 1), manufactured by Sartomer]
4HBA: 4-hydroxybutyl acrylate [4HBA (ethylenic double bond / one molecule), manufactured by Osaka Organic Chemical Industry Co., Ltd.]
HEA: 2-hydroxyethyl acrylate [HEA (ethylenic double bond / 1 molecule), manufactured by Osaka Organic Chemical Industry Co., Ltd.]
IRGAUTAB UV-10: Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate [IRGASTAB UV10, manufactured by Ciba]

(Evaluation of curability)
First, each model material composition was printed on a film made of polyethylene terephthalate (A4300, manufactured by Toyobo Co., Ltd., 100 mm × 150 mm × thickness 188 μm) with a bar coater (# 4), and printed with a thickness of 3 μm. A film was formed. The printed film was cured by irradiating with ultraviolet rays so that the total irradiation light amount was 500 mJ / cm ² using an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) as the irradiation means. The printed film thus cured was touched with a finger, and the presence or absence of ink adhering to the finger was visually examined to evaluate curability according to the following criteria. This evaluation was performed by rubbing the image with a finger from the image portion toward the non-print portion. The evaluation results are shown in Table 1.
○: The surface was smooth and there was no adhesion to the finger.
(Triangle | delta): The surface was a little moist and the feeling of adhesion to the finger was a prickly feeling.
X: The surface was sticky and a part of uncured ink adhered to the finger.

(Evaluation of continuous discharge performance)
The continuous discharge property of each composition for model materials was evaluated according to the following criteria by conducting a discharge property test in which ink was continuously discharged for 30 minutes using an ink jet recording apparatus equipped with a piezo ink jet nozzle. The evaluation results are shown in Table 1. The ink supply system includes an ink tank, a supply pipe, a front chamber ink tank immediately before the head, and a piezo head. The droplet size was about 7 pl, and it was driven at a driving frequency of 10 KHz.
○: No discharge failure occurs.
X: Nozzle chipping occurs or satellites are generated.

  As can be seen from the results in Table 1, the compositions for model materials of Examples M1 to M9 that satisfy all the requirements of the present invention are excellent in continuous discharge properties and are obtained by photocuring the composition for model materials. The model material showed excellent curability.

<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 will be described later, the support material composition was cured using an ultraviolet LED as the irradiation means. About the composition for support materials of Example S17, since content of a photoinitiator (d) exceeds 20 weight part, a photoinitiator (d) did not fully melt | dissolve but the undissolved residue produced. . 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. The support material composition of Example S17 was cured even when the content of the photopolymerization initiator (d) was 25 parts by weight when a mercury lamp or a metal halide lamp was used as the irradiation means.

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 Co., 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 the inkjet head. Moreover, the support material obtained by photocuring the composition for support materials of Examples S1-S16 had high solubility in water, and oily leaching was suppressed. Furthermore, the support material obtained by photocuring the composition for support material of Examples S1-S15 had sufficient self-supporting property. In addition, since the content of the photopolymerization initiator (d) is less than 5 parts by weight, the composition for the support material of Example S16 is obtained without promoting the radical reaction even when irradiated with the ultraviolet LED. Support material was not 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, Examples S1 to S8, S10 in which 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) is 25 parts by weight or more. The support material obtained from the composition for a support material of S11, S13 to S16 had higher solubility in water. Composition for support material of Examples S1-S10, S12, S14-S16 whose content of polyalkylene glycol (b) is 45 parts by weight or less and whose content of water-soluble organic solvent (c) is 30 parts by weight or less In the support material obtained from the product, the oil seepage was further suppressed. The support material obtained from the composition for the 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 composition for the support material of Comparative Example s3 had a polyalkylene glycol (b) content exceeding 49 parts by weight, the viscosity was high and oily oozing occurred in the support material. 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. The composition for support material of Comparative Example s5 had a low solubility of the support material in water because the polyalkylene glycol (b) content was less than 20 parts by weight. 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 composition for the support material of Comparative Example s6 had a polyalkylene glycol (b) content exceeding 49 parts by weight, the viscosity was high and oily oozing occurred in the support material.

<Optical modeling products>
(Evaluation of dimensional accuracy of stereolithography products)
Test No. shown in Table 6 Hardened | cured material was created using each composition for model materials of 1-13, and each composition for support materials. The shape and target dimensions of the cured product are shown in FIGS. 3 (a) and 3 (b). The step 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 stereolithographic products 1 to 13 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. The average value of the dimensional change rate in each of the stereolithographic products 1 to 13 was determined, 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

(Evaluation of bleeding of each composition)
First, on a film made of polyethylene terephthalate (A4300, manufactured by Toyobo Co., Ltd., 100 mm × 150 mm × thickness 188 μm), test Nos. 0.02 mL of each 1-13 composition for model materials and each composition for support materials were dripped using the micropipette. At this time, in the composition for the model material and the composition for the support material, the distance between the central portions of the respective droplets was 10 mm, and the respective droplets were independent. Thereafter, the respective droplets gradually spread and spread, and after about 10 seconds, the respective droplets were combined. At this time, the interface state of each droplet was visually observed from above, and bleeding was evaluated according to the following criteria. The results are shown in Table 6.
A: The interface between the layer made of the model material composition and the layer made of the support material composition was linear when viewed from above, and no bleeding occurred.
X: Bleeding occurred at the interface between the layer made of the model material composition and the layer made of the support material composition.

  As can be seen from the results in Table 6, the test No. manufactured using the optical modeling ink set that satisfies all of the requirements of the present invention. The optically shaped products 1 to 9 had no bleeding at the interface between the layer made of the model material composition and the layer made of the support material composition, and had good dimensional accuracy.

  The optical modeling ink set of the present invention can be suitably used when a three-dimensional modeled object requiring toughness is manufactured using an inkjet optical modeling method.

4 Model material 5 Support material

Claims (15)

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:
An ethylenically unsaturated monomer (A) having one or more ethylenic double bonds;
A silane compound (B) having one or more ethylenic double bonds (excluding a compound corresponding to the ethylenically unsaturated monomer (A));
A photopolymerization initiator (C);
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),
5 to 20 parts by weight of a photopolymerization initiator (d),
An ink set for stereolithography, containing   The said composition for model materials WHEREIN: Content of the said silane compound (B) is 1-500 weight part with respect to 100 weight part of said ethylenically unsaturated monomers (A). Ink set for optical modeling.   In the model material composition, the ethylenically unsaturated monomer (A) includes a polyester acrylate (A1), a polyurethane acrylate (A2), a polyepoxy acrylate (A3), and a polyacrylic acrylate (A4). The ink set for optical modeling according to claim 1, wherein the ink set is one or more selected from the group consisting of:   The optical modeling ink according to any one of claims 1 to 3, wherein in the composition for a model material, the ethylenically unsaturated monomer (A) has a weight average molecular weight of 150 to 30,000. set.   The model material composition further includes a cyclic compound (D) containing a ring structure having one or more ethylenic double bonds (provided that the ethylenically unsaturated monomer (A) and the silane compound (B) The ink set for stereolithography according to any one of claims 1 to 4, further comprising:   The optical modeling ink set according to claim 5, wherein in the model material composition, the cyclic compound (D) is a cyclic compound (D1) including a ring structure not containing a heteroatom.   The said modeling material composition WHEREIN: The cyclic compound (D1) containing the ring structure which does not contain the said hetero atom is the optical compound of Claim 6 which is a cyclic compound (D1-1) containing an alicyclic structure. Ink set.   The model material composition further comprises a compound (E) having one or more ethylenic double bonds (provided that the ethylenically unsaturated monomer (A), the silane compound (B), and the cyclic compound). The ink set for stereolithography according to any one of claims 1 to 7, comprising a compound corresponding to (D).   In the model material composition, the content of the photopolymerization initiator (C) is 0.01 to 30 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.   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 ink set for optical modeling according to any one of claims 1 to 9.   In the said composition for support materials, content of the said polyalkylene glycol (b) is 25-45 weight part with respect to 100 weight part of this whole composition for support materials, Any one of Claims 1-10. The ink set for stereolithography as described in one.   In the said composition for support materials, content of the said water-soluble organic solvent (c) is 5 weight part or more with respect to 100 weight part of this composition for support materials as a whole. The ink set for stereolithography as 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 entire composition for a support material. The ink set for stereolithography according to any one of the above.   An optically modeled article modeled using the optical modeling ink set according to any one of claims 1 to 13 by an ink jet optical modeling method. It is a method of manufacturing an optical modeling article using an ink modeling optical modeling according to any one of claims 1 to 13 by an inkjet optical modeling method,
Step (I) of obtaining a model material by photocuring the composition for model material, and obtaining a support material by photocuring the composition for support material;
Removing the support material (II);
A method for manufacturing an optically shaped article.

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