WO2018143299A1 - Ink set for stereolithography, stereolithographic article, and method for producing stereolithographic article - Google Patents

Abstract

The present invention addresses the problem of providing: an ink set for stereolithography which is for obtaining a stereolithographic article exhibiting excellent dimensional accuracy; a stereolithographic article formed using the ink set for stereolithography; and a method for producing the stereolithographic article using the ink set for stereolithography. An ink set for stereolithography according to the present invention is provided with a model material composition and a support material composition. The model material composition includes: a radically polymerizable compound (A); a cationically polymerizable compound (B); a radical polymerization initiator (C); and a cationic polymerization initiator (D). The support material composition includes: 20-50 parts by weight of water-soluble monofunctional ethylenically unsaturated monomers (a); 20-49 parts by weight of polyalkylene glycol (b) including oxyethylene groups and/or oxypropylene groups; 35 or fewer parts by weight of a water-soluble organic solvent (c); and 1-20 parts by weight of a photopolymerization initiator (d).

Description

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

This patent application claims priority under the Paris Convention for Japanese Patent Application No. 2017-016123 (filing date: January 31, 2017), which is hereby incorporated by reference in its entirety. It shall be incorporated into the book.
The present invention relates to an optical modeling ink set used in an ink jet optical modeling method, an optical modeling product modeled using the optical modeling ink set, and a method of manufacturing an optical modeling product using the optical modeling ink set. About.

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

Among the modeling methods, in recent years, an optical modeling method by an ink jet method for forming a cured layer having a predetermined shape by discharging a photocurable composition from a nozzle and immediately irradiating it with ultraviolet rays or the like to cure. Hereinafter, ink jet stereolithography is reported (Patent Documents 1 to 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. For example, Patent Document 4 discloses a composition for a support material containing a large amount of non-polymerizable components such as polyoxypropylene glycol and water in order to improve the solubility of the support material in water.

Conventionally, a photopolymerizable composition contains a radical polymerizable compound that is cured by a radical polymerization reaction (Patent Documents 2 to 4).

JP 2004-255839 A JP 2010-155889 A JP 2010-155926 A JP 2012-111226 A

However, the photocurable composition containing a radical polymerizable compound has a problem that the cured shrinkage of a cured product obtained by curing the photocurable composition is large. On the other hand, cationically polymerizable compounds are more susceptible to water than radically polymerizable compounds. Therefore, the cationically polymerizable compound has a problem that the polymerization reaction is difficult to proceed in an environment where water is present, and as a result, insufficient curing tends to occur. Therefore, in the ink jet stereolithography method, when the composition for a model material containing a cationic polymerizable compound and the conventional composition for a support material containing a large amount of non-polymerizable components are used, the composition for a model material is Insufficient curing of the model material obtained by photocuring tends to occur. As a result, there has been a problem that an optically shaped article that is shaped using the model material composition and the support material composition has poor dimensional accuracy.

The present invention has been made in view of the above situation, and an optical modeling ink set for obtaining an optical modeling product with good dimensional accuracy, an optical modeling product modeled using the optical modeling ink set, and An object of the present invention is to provide a method for producing an optical modeling product using the optical modeling ink set.

The present inventors define a content of the non-polymerized component and the water-soluble monofunctional ethylenically unsaturated monomer of the support material composition within a predetermined range, thereby providing a model material containing a cationically polymerizable compound. It has been found that insufficient curing of the model material obtained by photocuring the composition is suppressed. That is, the present inventors can form an optically shaped article with good dimensional accuracy by using the support material composition, even when a model material composition containing a cationically polymerizable compound is used. I found it possible.

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

(1) A combination of a composition for a model material that is used in an ink jet optical modeling method and is used for modeling a model material, and a composition for a support material used for modeling a support material. An ink set for stereolithography,
The model material composition is:
A radically polymerizable compound (A) having at least one ethylenic double bond;
A cationically polymerizable compound (B) having one or more ethylenic double bonds;
A radical polymerization initiator (C);
A cationic polymerization initiator (D);
Wherein the cationically polymerizable compound (B) is a cyclic hetero compound or a vinyl ether compound,
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),
1 to 20 parts by weight of a photopolymerization initiator (d),
An ink set for stereolithography, containing

(2) In the composition for model material, the radical polymerizable compound (A) includes a radical polymerizable compound having a hydroxyl group, a radical polymerizable compound having one or more cyclic structures, and an alkyl (meth) acrylate. The optical modeling ink set according to (1) above, which contains at least one selected from radically polymerizable compounds of esters.

(3) In the model material composition, the cationically polymerizable compound (B) contains a hydroxyl group-containing compound and / or an oxirane compound, and the optical modeling ink set according to (1) or (2). .

(4) The optical modeling ink according to any one of (1) to (3), wherein in the model material composition, the radical polymerization initiator (C) contains an acylphosphine oxide compound. set.

(5) The optical modeling ink set according to any one of (1) to (4), wherein in the model material composition, the cationic polymerization initiator (D) contains a sulfonium salt compound. .

(6) In the composition for a model material, the content of the radical polymerizable compound (A) is 10 to 90 parts by weight with respect to 100 parts by weight as a whole of the composition for a model material. The ink set for stereolithography according to any one of (5) to (5).

(7) In the composition for a model material, the content of the cationic polymerizable compound (B) is 10 to 90 parts by weight with respect to 100 parts by weight of the entire composition for the model material. The optical modeling ink set according to any one of (6) to (6).

(8) In the model material composition, the content of the radical polymerization initiator (C) is 0.5 to 10 parts by weight with respect to 100 parts by weight of the entire model material composition (1) The optical modeling ink set according to any one of (1) to (7).

(9) In the model material composition, the content of the cationic polymerization initiator (D) is 0.5 to 10 parts by weight with respect to 100 parts by weight of the entire model material composition. The optical modeling ink set according to any one of 1) to (8).

(10) In the composition for model material, any one of the above (1) to (9), wherein the cationic polymerizable compound (B) contains at least one selected from an oxirane compound and an oxetane compound. The ink set for stereolithography described in 1.

(11) 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 (10), wherein

(12) In the composition for support material, the content of the polyalkylene glycol (b) is 25 to 45 parts by weight with respect to 100 parts by weight of the whole composition for support material. The ink set for stereolithography according to any one of (11).

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

(14) In the support material composition, the content of the photopolymerization initiator (d) is 5 to 20 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 (13).

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

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

(17) A method for producing an optically shaped article by an ink jet optical modeling method using the optical modeling ink set according to any one of (1) to (15),
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 with good dimensional accuracy, an optical modeling product modeled using the optical modeling ink set, and the optical modeling ink set are used. It is possible to provide a method for manufacturing an optically shaped article.

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 model material composition and each support material composition shown in Table 6. FIG. FIG. 3B is a cross-sectional view taken along the line AA in FIG.

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

1. Composition for model material <Radically polymerizable compound (A)>
The composition for model materials contained in the optical modeling ink set according to the present embodiment contains a radical polymerizable compound (A) having one or more ethylenic double bonds.

The radical polymerizable compound (A) is one or more functional groups selected from an alkoxy group, an ether group, a hydroxyl group and a keto group (excluding a carbonyl group directly bonded to an ethylenic double bond group). The radically polymerizable compound (A1) having a group is preferable. Among these, it is more preferable that the radical polymerizable compound (A1) has a hydroxyl group.

Among the radical polymerizable compounds (A1), examples of the compound having an alkoxy group include alkoxy group-containing (meth) acrylic acid such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate. Esters; (meth) acrylic acid-polyethylene glycols obtained by dehydration condensation of (meth) acrylic acid with methoxypolyethylene glycol; alkoxysilyl group-containing radical polymerization such as (meth) allylchlorosilane and (meth) allyltrimethoxysilane Compounds such as N-alkoxy group-containing (meth) acrylamides such as N-methoxymethyl (meth) acrylamide and N-methoxyethyl (meth) acrylamide. These may be used alone or in combination of two or more.

Among the radical polymerizable compounds (A1), examples of the compound having an ether group include alkylene oxide-containing (meth) acrylic acid derivatives such as alkylene oxide adducts of (meth) acrylic acid; (meth) acrylic acid Examples thereof include compounds obtained by dehydration condensation with alkyl-terminated polyethylene glycols such as lauroxy-polyethylene glycol, octoxypolyethylene glycol and stearoxy. These may be used alone or in combination of two or more.

Among the radical polymerizable compounds (A1), examples of the compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Acrylic acid compounds having a hydroxyl group such as: (meth) acrylic acid glycidyl lauric acid ester, (meth) acrylic acid glycidyl oleic acid ester, (meth) acrylic acid glycidyl stearic acid ester and the like (meth) acrylic acid ester A hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound such as 2- (acryloyloxy) ethyl 6-hydroxyhexanonate ( (Meth) acrylic acid ester; the hydroxy acid Hydroxyl-containing aliphatic compounds such as alkylene oxide-added (meth) acrylic acid esters in which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide are repeatedly added to compounds containing α, β-ethylenically unsaturated double bonds (Meth) acrylic acid esters; hydroxyl-containing aliphatic (meth) allyl such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal to which alkylene oxide such as (meth) allyl alcohol and isopropenyl alcohol is repeatedly added Alcohols or (meth) allyl ethers; propenediol, butenediol, heptenediol, octenediol, α, β-ethylenically unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as diglycol (meth) acrylate A hydroxyl group-containing (meth) acrylamide such as N-hydroxyethyl (meth) acrylamide and N-hydroxypropyl (meth) acrylamide; and 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 the radical polymerizable compounds (A1), examples of the compound having a keto group include one carbonyl group such as (meth) acrylic acid (methoxycarbonyl) methyl and (meth) acrylic acid (methoxycarbonyl) ethyl. Aliphatic (meth) acrylic esters; aliphatic (meth) having two carbonyl groups such as 2-oxobutanoylethyl (meth) acrylate and 2-oxobutanoylpropyl (meth) acrylate Acrylates; (meth) acrylamides having a carbonyl group such as N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide; acetic acid (meth) (Meth) allyl esters of saturated carboxylic acids such as allyl and propionic acid (meth) allyl; cis-succinic acid Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as allyl and 2-methylidene succinate; vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate and vinyl propionate; Aliphatic vinyl compounds having an acyl group such as vinyl acetoacetate and vinyl acetopropionate; aliphatic (meth) allyl having an acyl group such as (meth) allyl acetoacetate and (meth) allyl acetopropionate Examples thereof include compounds. These may be used alone or in combination of two or more.

The radical polymerizable compound (A1) may be an oligomer having a weight average molecular weight (Mw) of 300 to 30,000. The oligomer is preferably at least one selected from polyester oligomers, polyurethane oligomers, polyepoxy oligomers, and polyacrylic oligomers.

The polyester-based oligomer includes 1 at the end of the polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol on the main chain skeleton or a hydroxyl group in the polyester chain, and a molecule such as (meth) acrylic acid or maleic acid. A compound obtained by esterification with an α, β-ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups, a carboxyl group in the terminal or polyester chain of polyester, and 2-hydroxy (meth) acrylate Obtained from a compound obtained by esterification with a compound having a hydroxyl group such as ethyl or 2-hydroxypropyl (meth) acrylate, an acid anhydride, glycidyl (meth) acrylate and a compound having at least one hydroxyl group And polyester oligomers. These may be used alone or in combination of two or more.

Examples of the polyurethane oligomer include a compound obtained by reacting a compound having one or more isocyanate groups with the compound having a hydroxyl group; reacting a compound having one or more isocyanate groups and the polyhydric alcohol. A compound obtained by reacting a urethane prepolymer of a terminal isocyanate group obtained by reaction with the radical polymerizable compound (A1); a terminal obtained by reacting a compound having one or more isocyanate groups and a polyhydric alcohol Isocyanate group urethane prepolymer, and compound obtained by reacting a terminal isocyanate group urethane prepolymer obtained by reacting a compound having one or more amino groups with the hydroxyl group compound; isocyanate group Reacts with amino groups Were compounds containing a urea bond group obtained by the like. These may be used alone or in combination of two or more.

The polyepoxy oligomer includes an α, β-unsaturated compound having a glycidyl group and one or more hydroxyl groups or carboxyl groups in a molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, and maleic acid. A compound obtained by a reaction with a double bond group-containing compound, that is, a compound having substantially no glycidyl group and having an α, β-unsaturated double bond group-containing compound.

Examples of the polyepoxy oligomer include bisphenol type polyepoxy oligomer, epoxidized oil type polyepoxy oligomer, phenol novolac type polyepoxy oligomer, and alicyclic polyepoxy oligomer. These may be used alone or in combination of two or more.

Examples of the polyacrylic oligomer include a modified polyether having an α, β-unsaturated double bond group; an amine-modified α, β-unsaturated double bond group-containing compound; an alkyd resin, a spiroacetal resin, Examples include oligomers or prepolymers such as modified α, β-unsaturated double bond group-containing compounds obtained by adding α, β-unsaturated double bond groups to various compounds such as polybutadiene resins, polythiol polyene resins, polyhydric alcohols, and the like. It is done. These may be used alone or in combination of two or more.

The radical polymerizable compound (A) may be a radical polymerizable compound (A2) having one or more cyclic structures. Examples of the radical polymerizable compound (A2) include a radical polymerizable compound (A2-1) having a ring structure containing no hetero atom in the molecule, and a radical polymerizable compound having a ring structure containing a hetero atom in the molecule. Examples thereof include compound (A2-2), a radically polymerizable compound (A2-3) having one or more cyclic structures and a hydroxyl group.

Examples of the radical polymerizable compound (A2-1) include (meth) acrylic acid cyclic esters such as cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, and isobornyl (meth) acrylate. Kind;

(Meth) acrylamides containing a cyclic structure such as N- (4-carbamoylphenyl) (meth) acrylamide and β- (2-furyl) (meth) acrylamide;

Aromatic vinyl monomers such as styrene and α-methylstyrene;
Etc. These may be used alone or in combination of two or more.

Examples of the radical polymerizable compound (A2-2) include pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, 4- (pyrimidin-2-yl) piperazin-1-yl ( Heterocyclic (meth) acrylic acid esters containing a nitrogen atom such as (meth) acrylate;

Vinyl group-containing compounds having a nitrogen atom-containing heterocycle such as 1-vinylpyrrole and 1-vinyl-2-imidazoline;

Heterocyclic acrylamides such as 4-acryloylmorpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide;

Maleimide derivatives having both nitrogen and oxygen atoms such as maleimide and methylmaleimide;

Vinyl group-containing compounds having a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom, such as 2-vinyloxazole and 2-phenyl-4-vinyloxazole;

Heterocycle-containing (meth) acrylic acid esters having an oxygen atom such as (meth) acrylic acid glycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl;

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

Examples thereof include ethenyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom, such as 2-vinylthiazol and 4-methyl-5-vinylthiazole. These may be used alone or in combination of two or more.

Examples of the radical polymerizable compound (A2-3) include cyclic structures other than hydroxyl groups and heterocycles such as 1,2-cyclohexanedimethanol (meth) acrylic acid and 1,3-cyclohexanedimethanol (meth) acrylic acid. (Meth) acrylic acid esters having

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

2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro-2H -Hydroxyl-containing benzotriazole-based (meth) acrylic acid esters such as benzotriazole;

2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy- And hydroxyl group-containing triazine-based (meth) acrylic acid esters such as 4- {2- (meth) acryloyloxyethoxy}]-S-triazine. These may be used alone or in combination of two or more.

The radical polymerizable compound (A) may be a radical polymerizable compound (A3) other than the radical polymerizable compound (A1) and the radical polymerizable compound (A2). Examples of the radical polymerizable compound (A3) include (meth) acrylic acid-mono or di-alkylamino esters such as monomethylaminoethyl (meth) acrylate and monoethylaminoethyl (meth) acrylate;

(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate;

And (meth) acrylic acid esters containing (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl and the like and further containing unsaturated groups. These may be used alone or in combination of two or more.

The radical polymerizable compound (A) is selected from a radical polymerizable compound having a hydroxyl group, a radical polymerizable compound having one or more cyclic structures, and a radical polymerizable compound of (meth) acrylic acid alkyl esters. It is preferable to contain 1 or more types.

The content of the radical polymerizable compound (A) is preferably 10 to 90 parts by weight with respect to 100 parts by weight of the entire model material composition. The content of the radical polymerizable compound (A) is more preferably 50 parts by weight or more. 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.

<Cationically polymerizable compound (B)>
The model material composition contained in the optical modeling ink set according to the present embodiment contains a cationically polymerizable compound (B) having one or more ethylenic double bonds. From the viewpoint of reactivity, the cationically polymerizable compound (B) is preferably a cyclic hetero compound or a vinyl ether compound, and more preferably an oxirane compound that is a 3-membered ring ether.

Examples of the oxirane compound include aliphatic cyclic ether groups such as oxirane and methyloxirane; 3,4-oxiranecyclohexylmethyl 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl3,4 A group in which one or a plurality of hydrogen atoms are removed from a compound containing a three-membered cyclic ether group bonded to an alicyclic ring such as oxirane-6-methylcyclohexanecarboxylate, A compound bonded to a chemical structure.

The oxirane compound is preferably an oxirane compound having an aromatic ring. Examples of the substituent having an aromatic ring include phenyl and phenylene.

An oxirane compound having an aromatic ring is, for example, a compound in which a group in which one or more hydrogen atoms in a benzene derivative such as benzene or toluene are removed is bonded to another chemical structure.

Also, examples of the oxirane compound having an aromatic ring include cycloalkenes such as cyclopropene and cyclobutene;

[4n + 2] annulene having a carbon number other than benzene and having 3 or more carbon atoms constituting the ring;

Aromatic polycyclic compounds such as biphenyl and triphenylmethane;

Carbon-fused bicyclic systems such as pentalene and indene;

Carbon-fused tricyclic systems such as as-indacene and s-indacene;

Carbon-fused tetracyclic systems such as Trindene and Trindane;

Carbon-fused pentacyclic systems such as picene and perylene;

A group in which one or more hydrogen atoms in a cyclic compound such as corannulene, fluorene and the like having 6 or more rings are removed and bonded to another chemical structure.

The cyclic hetero compound other than the oxirane compound includes a 4-membered ether oxetanyl group-containing compound (oxetane compound), a 5-membered or higher cyclic ether compound, two or more oxygen or a compound having a hetero group other than oxygen. , Cyclic ester compounds, cyclic formal compounds, cyclic carbonate compounds, fluorine-containing cyclic compounds, and the like.

The cationically polymerizable compound (B) may be a compound having a hydroxyl group. Examples of the compound having a hydroxyl group include bisphenol type epoxy resin, glycerin monoglycidyl ether, glycerin diglycidyl ether, 3-ethyl-3-hydroxymethyloxetane, 4- (hydroxymethyl) -1,3-dioxolane-2- ON, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether and the like.

The cationic polymerizable compound (B) may contain one kind or a combination of two or more kinds. In particular, the cationically polymerizable compound (B) preferably contains at least one selected from an oxirane compound that is a 3-membered ring ether and an oxetane compound that is a 4-membered ring ether.

The content of the cationic polymerizable compound (B) is preferably 10 to 90 parts by weight with respect to 100 parts by weight of the entire model material composition. The content of the cationic polymerizable compound (B) is more preferably 50 parts by weight or more. 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.

<Radical polymerization initiator (C)>
The model material composition contained in the optical modeling ink set according to the present embodiment contains a radical polymerization initiator (C).

Examples of the radical polymerization initiator (C) include acylphosphine oxide compounds, acetophenone compounds, α-aminoalkylphenone compounds, α-hydroxyketone compounds, benzophenone compounds, xanthofluorenone compounds, benzaldehyde. Compounds, anthraquinone compounds, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 4-thioxanthone, camphorquinone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like. These may be used alone or in combination of two or more. Examples of commercially available radical polymerization initiator (C) include Irgacure 184,907,651,1700,1800,819,369,261 (manufactured by IGM Resins), DAROCUR-TPO (manufactured by IGM Resins), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), Darocur-1173 (IGM Resins), Ezacure KIP150, TZT (Nihon Shibel Hegner), Kayacure BMS, Kayacure DMBI (Nippon Kayaku) Can be mentioned. The radical polymerization initiator (C) may be a compound having at least one (meth) acryloyl group in the molecule.

The content of the radical polymerization initiator (C) is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the entire model material composition. When the content of the radical polymerization initiator (C) is in the above range, the curability of the model material becomes good. The content of the radical polymerization initiator (C) is more preferably 0.8 parts by weight or more, and more preferably 5 parts by weight or less. In addition, when the said (C) component is contained 2 or more types, the said content is the sum total of content of each (C) component.

<Cationic polymerization initiator (D)>
The model material composition contained in the optical modeling ink set according to the present embodiment contains a cationic polymerization initiator (D). Examples of the cationic polymerization initiator (D) include sulfonium salt compounds such as UVACURE1590 (manufactured by Daicel-Cytec) and CPI-100P (manufactured by San Apro); IRGACURE250 (manufactured by Ciba Specialty Chemicals), WPI- 113 (manufactured by Wako Pure Chemical Industries, Ltd.) and iodonium salt compounds such as Rp-2074 (manufactured by Rhodia Japan). These may be used alone or in combination of two or more.

The content of the cationic polymerization initiator (D) is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the entire model material composition. When the content of the cationic polymerization initiator (D) is in the above range, the curability of the model material becomes good. The content of the cationic polymerization initiator (D) is more preferably 1 part by weight or more, and more preferably 7 parts by weight or less. In addition, when the said (D) component is contained 2 or more types, the said content is the sum total of content of each (D) component.

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

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

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

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

The water-soluble monofunctional ethylenically unsaturated monomer (a) is a water-soluble polymerizable monomer having one ethylenic double bond in a molecule having a property of being cured by energy rays. Examples of the 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 (1 to 4 carbon atoms) 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], (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, etc. It is done. These may be used alone or in combination of two or more.

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

The content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is 20 to 50 parts by weight with respect to 100 parts by weight of the entire support material composition. When the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is less than 20 parts by weight, the self-supporting property in the support material is not sufficient. Therefore, when the support material is disposed below the model material, the model material cannot be sufficiently supported. As a result, the dimensional accuracy of the model material is deteriorated. On the other hand, when the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) exceeds 50 parts by weight, the support material has poor solubility in water. If the immersion time in water until the support material is completely removed becomes long, the model material expands slightly. As a result, the dimensional accuracy may deteriorate in the microstructure portion of the model material. The content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is preferably 25 parts by weight or more, and preferably 45 parts by weight or less. In addition, when the said (a) component is contained 2 or more types, the said content is the sum total of content of each (a) component.

<Polyalkylene glycol (b) containing oxyethylene group and / or oxypropylene group>
The composition for support materials contained in the optical modeling ink set according to this embodiment contains a polyalkylene glycol (b) containing an oxyethylene group and / or an oxypropylene group. The polyalkylene glycol (b) can enhance the solubility of the support material in water.

The polyalkylene glycol (b) is obtained by adding at least ethylene oxide and / or propylene oxide to an active hydrogen compound. Examples of the polyalkylene glycol (b) include polyethylene glycol and polypropylene glycol. These may be used alone or in combination of two or more. Examples of the active hydrogen compound include monohydric to tetrahydric alcohols and amine compounds. Among these, dihydric alcohol or water is preferable.

The 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.

The content of the polyalkylene glycol (b) is 20 to 49 parts by weight with respect to 100 parts by weight of the entire support material composition. When the content of the polyalkylene glycol (b) is less than 20 parts by weight, the support material is poor in solubility in water. If the immersion time in water until the support material is completely removed becomes longer, the model material expands slightly. As a result, the dimensional accuracy may deteriorate in the microstructure portion of the model material. On the other hand, when the content of the polyalkylene glycol (b) exceeds 49 parts by weight, the polyalkylene glycol (b) may ooze out when the support material composition is photocured. When leaching of the polyalkylene glycol (b) occurs, the polymerization reaction of the cationic polymerizable compound contained in the model material composition is difficult to proceed, and as a result, the model material is likely to be insufficiently cured. Become. Moreover, when content of the said polyalkylene glycol (b) exceeds 49 weight part, the viscosity of the composition for support materials will become high. Therefore, when the composition for a support material is ejected from the inkjet head, the jetting characteristics may be deteriorated and flight bending may occur. As a result, the dimensional accuracy of the support material is deteriorated. Therefore, the dimensional accuracy of the model material molded on the upper layer of the support material also deteriorates. The content of the polyalkylene glycol (b) is preferably 25 parts by weight or more, and preferably 45 parts by weight or less. In addition, when the said (b) component is contained 2 or more types, the said content is the sum total of content of each (b) component.

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

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

The content of the water-soluble organic solvent (c) is 35 parts by weight or less with respect to 100 parts by weight of the entire support material composition. When the content of the water-soluble organic solvent (c) exceeds 35 parts by weight, the water-soluble organic solvent (c) oozes when the support composition is photocured. When leaching of the water-soluble organic solvent (c) occurs, the polymerization reaction of the cationic polymerizable compound contained in the model material composition becomes difficult to proceed, resulting in insufficient curing of the model material. It becomes easy. 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). The photopolymerization initiator (d) is not particularly limited as long as it is a compound that promotes a radical reaction when irradiated with light having a wavelength in the ultraviolet, near ultraviolet, or visible light region.

Examples of the photopolymerization initiator (d) include benzoin compounds having 14 to 18 carbon atoms (eg, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether), and those having 8 to 18 carbon atoms. Acetophenone compounds [for example, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one Diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc.], an anthraquinone compound having 14 to 19 carbon atoms [for example, 2 - Thioanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc.], thioxanthone compounds having 13 to 17 carbon atoms [for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc. ] Ketal compounds having 16 to 17 carbon atoms [for example, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.], benzophenone compounds having 13 to 21 carbon atoms [for example, benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4 '-Bismethylaminobenzophenone, etc.], acylphosphine oxide compounds having 22 to 28 carbon atoms [ eg 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis- (2,6-dioxy) Tokishibenzoiru) -2,4,4-trimethyl pentyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, etc.], a mixture of these compounds. These may be used alone or in combination of two or more. Among these, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is preferable from the viewpoint of improving the light resistance of the model material obtained by photocuring the composition for model material. Examples of the available acyl phosphine oxide compound include DAROCURE TPO manufactured by BASF.

The content of the photopolymerization initiator (d) is preferably 1 to 20 parts by weight, and more 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 surface conditioning agent (e) is preferably 0.005 to 3.0 parts by weight with respect to 100 parts by weight of the entire support material composition.

Examples of the surface conditioner (e) include silicone compounds. Examples of the silicone compound include a silicone compound having a polydimethylsiloxane structure. Specific examples include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyaralkyl-modified polydimethylsiloxane. These include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-370, BYK-375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570 (above, manufactured by BYK Chemie), TEGO-Rad2100 , TEGO-Rad2200N, TEGO-Rad2250, TEGO-Rad2300, TEGO-Rad2500, TEGO-Rad2600, TEGO-Rad2700 (manufactured by Degussa), Granol 100, Granol 115, Granol 400, Grano Le 410, Granol 435, Granol 440, Granol 450, B-1484, Polyflow ATF-2, KL-600, UCR-L72, UCR-L93 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like may be used. These may be used alone or in combination of two or more. In addition, when the said (e) component is contained 2 or more types, the said content is the sum total of content of each (e) component.

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

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

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

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

The composition for a support material thus produced preferably has a viscosity at 25 ° C. of 70 mPa · s or less from the viewpoint of improving the dischargeability from the inkjet head. The viscosity of the support material composition is measured according to JIS Z 8803 using an R100 viscometer.

3. Optical modeling product and its manufacturing method The optical modeling product concerning this embodiment is modeled using the ink set for optical modeling concerning this embodiment. Specifically, a process of obtaining a support material by photocuring the above-described composition for support material (I) by photocuring the above-mentioned composition for model material by ink-jet stereolithography (I ) And the step (II) of removing the support material. Although the said process (I) and the said process (II) are not specifically limited, For example, it is performed with the following method.

<Process (I)>
Drawing 1 is a figure showing typically process (I) in a manufacturing method of an optical modeling article concerning this embodiment. As shown in FIG. 1, the three-dimensional modeling apparatus 1 includes an inkjet head module 2 and a modeling table 3. The ink jet head module 2 includes a model material ink jet head 21 filled with a model material composition, a support material ink jet head 22 filled with a support material composition, a roller 23, and a light source 24.

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

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

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

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

<Process (II)>
FIG. 2 is a diagram schematically showing step (II) in the method for manufacturing an optically shaped product according to the present embodiment. As shown in FIG. 2, the cured product 6 made of the model material 4 and the support material 5 produced in step (I) is immersed in a solvent 8 placed in a container 7. Thereby, the support material 5 can be dissolved in the solvent 8 and removed.

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

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

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

<Model material composition>
(Manufacture of compositions for model materials)
In the formulation shown in Table 1, the components (A) to (D) were uniformly mixed using a mixing and stirring device to produce the compositions for model materials of Examples M1 and M2.

4HBA: 4-hydroxybutyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd.]
AIB: Isobutyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd.]
IBXA: Isobornyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd.]
GCDG: glycerin diglycidyl ether [manufactured by Kyoeisha Chemical Co., Ltd.]
2021P: 3,4-oxiranecyclohexylmethyl-3,4-oxiranecyclohexanecarboxylate [manufactured by Daicel]
DAROCURE TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCURE TPO, manufactured by BASF]
CPI-100P: Triarylsulfonium [manufactured by San Apro]

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

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

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

(Solubility in water)
2.0 g of each support material composition was collected in an aluminum cup having a diameter of 50 mm. Next, ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) was used as the irradiation means, and ultraviolet rays were irradiated and cured so that the total irradiation light amount was 500 mJ / cm ² to obtain a support material. Thereafter, the support material was released from the aluminum cup. Subsequently, the support material was immersed in 500 ml of ion-exchanged water placed in a beaker. The support material was visually observed every 10 minutes, and the time required from the start of immersion until complete dissolution or disappearance of the original shape (hereinafter referred to as water dissolution time) was measured, and the solubility was evaluated according to the following criteria. The evaluation results are shown in Tables 4 and 5.
○: Water dissolution time ≦ 1 hour Δ: 1 hour <Water dissolution time <1.5 hours ×: Water dissolution time ≧ 1.5 hours

(Evaluation of oil seepage)
1.0 g of each composition for support material was extract | collected to 100 mm x 100 mm aluminum foil. Next, ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) was used as the irradiation means, and ultraviolet rays were irradiated and cured so that the total irradiation light amount was 500 mJ / cm ² to obtain a support material. At this point, the support material is in a solid state. The support material was allowed to stand for 2 hours, and the presence or absence of oily oozing on the surface of the support material was visually observed and evaluated according to the following criteria. The evaluation results are shown in Tables 4 and 5.
○: No oily leaching was observed.
Δ: Slight oily oozing was observed.
X: Many oily leachings were observed.

(Evaluation of independence)
A glass plate (trade name “GLASS PLATE”, manufactured by ASONE, 200 mm × 200 mm × thickness 5 mm) used for evaluation is a quadrangle in plan view. Spacers with a thickness of 1 mm were arranged on the four sides of the upper surface of the glass plate to form a 10 cm × 10 cm square region. After casting the composition for each support material in the region, another glass plate was placed on top of each other. Then, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) was used as an irradiating means, and cured by irradiating with ultraviolet rays so that the total irradiation light amount was 500 mJ / cm ² , thereby obtaining a support material. Thereafter, the support material was released from the glass plate and cut into a shape of 10 mm length and 10 mm width by a cutter to obtain a test piece. Next, 10 test pieces were stacked to obtain a test piece group having a height of 10 mm. The test piece group was placed in an oven set at 30 ° C. with a weight of 100 g from the top, and left for 1 hour. Thereafter, the shape of the test piece was observed, and the independence was evaluated according to the following criteria. The evaluation results are shown in Tables 4 and 5.
○: No change in shape.
Δ: The shape changed slightly and the weight was inclined.
X: The shape changed greatly.

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

Further, 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. , S11 and S13 to S16, the support material obtained from the support material composition had higher solubility in water. Examples S1 to S10, S12, and S14 to S16 for support materials, wherein the polyalkylene glycol (b) content is 45 parts by weight or less and the water-soluble organic solvent (c) content 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 a support material of Examples S1 to S7, S9 to S12, S14, and S15, in which the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is 25 parts by weight or more, It had more sufficient independence.

On the other hand, since the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is less than 20 parts by weight, the support material composition of Comparative Example s1 was not sufficient for the support material to be self-supporting. . In the composition for support material of Comparative Example s2, the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) exceeds 50 parts by weight, and thus the solubility of the support material in water was low. Since the 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)
A cured product was prepared using an optical modeling ink set obtained by combining each of the model material compositions shown in Table 1 and each of the support material compositions shown in Tables 2 and 3. The shape and target dimensions of the cured product are shown in FIGS. 3 (a) and 3 (b). The process of discharging each model material composition and each support material composition from the inkjet head was performed so that the resolution was 600 × 600 dpi and the thickness of one layer of the composition layer was about 13 to 14 μm. . In addition, the process of photocuring each composition for model materials and each composition for support materials uses an LED light source with a wavelength of 385 nm installed on the back side of the inkjet head with respect to the scanning direction, and an illuminance of 250 mW / cm. ^{2. The} measurement was performed under the condition of an integrated light amount of 300 mJ / cm ² per composition layer. Next, the support material was removed by immersing the cured product in ion-exchanged water to obtain a stereolithographic product. Thereafter, the obtained stereolithography product was allowed to stand in a desiccator for 24 hours and sufficiently dried. Through the above-described steps, the test No. Five to three stereolithographic products were manufactured. About the stereolithography goods after drying, the dimension of the x direction in FIG. 3A and the y direction was measured using calipers, and the rate of change from the target dimension was calculated. The dimensional accuracy is determined according to test no. An average value of the dimensional change rate in each of the optically shaped products 1 to 3 was obtained, and evaluation was performed according to the following criteria using the average value. The evaluation results are shown in Table 6.
○: Average dimensional change rate is less than ± 1.0% ×: Average dimensional change rate is ± 1.0% or more

As can be seen from the results in Table 6, test No. manufactured using the optical modeling ink set that satisfies all the requirements of the present invention. The optically shaped products 1 and 2 had good dimensional accuracy.

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

DESCRIPTION OF SYMBOLS 1 3D modeling apparatus 2 Inkjet head module 21 Inkjet head for model material 22 Inkjet head for support material 23 Roller 24 Light source 3 Modeling table 4 Model material 5 Support material 6 Hardened material 7 Container 8 Solvent

Claims (17)

1. For optical modeling, which is a combination of a composition for a model material that is used in an inkjet optical modeling method and is used for modeling a model material, and a composition for a support material that is used to model a support material An ink set,
   The model material composition is:
   A radically polymerizable compound (A) having at least one ethylenic double bond;
   A cationically polymerizable compound (B) having one or more ethylenic double bonds;
   A radical polymerization initiator (C);
   A cationic polymerization initiator (D);
   Wherein the cationically polymerizable compound (B) is a cyclic hetero compound or a vinyl ether compound,
   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),
   1 to 20 parts by weight of a photopolymerization initiator (d),
   An ink set for stereolithography, containing
2. In the model material composition, the radical polymerizable compound (A) is a radical polymerizable compound having a hydroxyl group, a radical polymerizable compound having one or more cyclic structures, and (meth) acrylic acid alkyl esters. The ink set for stereolithography according to claim 1, comprising one or more selected from radically polymerizable compounds.
3. The ink set for stereolithography according to claim 1 or 2, wherein in the model material composition, the cationic polymerizable compound (B) contains a compound having a hydroxyl group and / or an oxirane compound.
4. The optical modeling ink set according to any one of claims 1 to 3, wherein, in the model material composition, the radical polymerization initiator (C) contains an acylphosphine oxide compound.
5. The optical modeling ink according to any one of claims 1 to 4, wherein in the model material composition, the cationic polymerization initiator (D) contains at least one selected from sulfonium salt compounds. set.
6. The content of the radical polymerizable compound (A) in the model material composition is 10 to 90 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.
7. 7. The model material composition, wherein the content of the cationically polymerizable compound (B) is 10 to 90 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 the above.
8. In the model material composition, the content of the radical polymerization initiator (C) is 0.5 to 10 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.
9. In the model material composition, the content of the cationic polymerization initiator (D) is 0.5 to 10 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.
10. The stereolithographic compound according to any one of claims 1 to 9, wherein in the model material composition, the cationically polymerizable compound (B) contains at least one selected from an oxirane compound and an oxetane compound. Ink set.
11. In the support material composition, the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is 25 to 45 parts by weight with respect to 100 parts by weight of the entire support material composition. The optical modeling ink set according to any one of claims 1 to 10.
12. The content of the polyalkylene glycol (b) in the support material composition is 25 to 45 parts by weight with respect to 100 parts by weight of the entire support material composition. The ink set for stereolithography according to one.
13. In the support material composition, 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 entire support material composition. The ink set for stereolithography according to one.
14. The content of the photopolymerization initiator (d) in the support material composition is 5 to 20 parts by weight with respect to 100 parts by weight of the entire support material composition. The ink set for stereolithography according to one.
15. The support material composition further comprises 0.05 to 3.0 parts by weight of a storage stabilizer (e) with respect to 100 parts by weight of the entire support material composition. The ink set for stereolithography according to any one of the above.
16. An optical modeling product formed by using the optical modeling ink set according to any one of claims 1 to 15 by an ink jet optical modeling method.
17. A method for producing a stereolithographic product using the stereolithography ink set according to any one of claims 1 to 15, by an inkjet stereolithography method,
    Step (I) of obtaining a model material by photocuring the composition for model material, and obtaining a support material by photocuring the composition for support material;
    Removing the support material (II);
    A method for manufacturing an optically shaped article.

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