JP7398299B2 - Photocurable composition set for 3D printers, photoprinted products using the same, and manufacturing methods thereof - Google Patents

Description

The present invention relates to a photocurable composition set for 3D printers, a stereolithographic article using the same, and a method for manufacturing the same.

In recent years, for 3D printers, an inkjet-based stereolithography method has been proposed in which a liquid photocurable composition discharged from an inkjet nozzle is cured and layered for stereolithography. The ink for 3D printers using this stereolithography method consists of a photocurable composition for the model material that forms the molded body by photocuring with UV or other light, and a photocurable composition for the support material when stacking the model materials three-dimensionally. It comes in a set with a sex composition. By layering model materials on top of support materials, it is possible to create overhang structures and hollow structures.

In the above stereolithography method, a photocurable composition for model material and a photocurable composition for support material are simultaneously discharged using a 3D printer, and then photocured layer by layer to form a cured product. The desired shaped object is obtained by removing the cured product of the photocurable composition for support material. In order to improve the modeling accuracy of the model material, the compatibility between the photocurable composition for model material and the photocurable composition for support material that are discharged at the same time is important. This is because, if the photocurable composition for model material and the photocurable composition for support material have poor compatibility when discharged, the components will precipitate or become cloudy at the interface where they come into contact. Therefore, efforts have been made to improve the compatibility at the interface.

Patent Document 1 describes a resin composition for model materials (photocurable composition for model materials) used in inkjet stereolithography and used for modeling model materials, and a resin composition for modeling support materials. An ink set for stereolithography formed by combining a resin composition for a support material (photocurable composition for a support material) used for a model material, wherein the surface tension Mt (mN/m) of the resin composition for a model material is is larger than the surface tension St (mN/m) of the support material resin composition, and the surface tension Mt and the surface tension St satisfy 0<Mt-St<5. has been done.

International Publication No. 2017/047692

The present inventors have discovered that, in a photocurable composition set for a 3D printer used in the above-mentioned stereolithography method, at the interface between the photocurable composition for model material and the photocurable composition for support material that are simultaneously discharged, It has been found that by having compatibility, it is possible to provide a photocurable composition set for 3D printers with excellent modeling properties.

Therefore, an object of the present invention is to create a photocurable composition for 3D printers with excellent modeling properties by having a photocurable composition for a model material and a photocurable composition for a support material have appropriate compatibility at the interface. The object of the present invention is to provide a product set, a stereolithographic product with excellent moldability using the same, and a method for manufacturing the same.

As a result of extensive research in order to solve the above problems, the present inventors have determined that the Hansen solubility parameter distance between the photocurable composition for support material and isobornyl acrylate in a photocurable composition set for 3D printers is The present invention has been completed by discovering that the above problem can be solved by satisfying a predetermined relationship.

That is, the photocurable composition set for a 3D printer of the present invention includes a photocurable composition for a model material containing a water-insoluble monomer (A) and a photopolymerization initiator (B), and a water-soluble monomer. a photocurable composition for a support material containing a polymer (C) and a photopolymerization initiator (D), and the Hansen solubility parameter distance HSPD between the photocurable composition for a support material and isobornyl acrylate is 12. .9 (MPa ^1/2 )<HSPD<17.3 (MPa ^1/2 ). When the HSPD is within this range, the compatibility and water solubility between the photocurable composition for model material and the photocurable composition for support material are excellent.

Further, the stereolithographic article of the present invention is obtained by photocuring the photocurable composition set for 3D printers.
Furthermore, the method for producing a stereolithographic article of the present invention includes a step (I) of photocuring the photocurable composition set for a 3D printer to obtain a cured product; The method includes a step (II) of removing a cured product obtained by photocuring the composition.

According to the photocurable composition set for 3D printers, the stereolithographic article using the same, and the manufacturing method thereof of the present invention, the photocurable composition for model material and the photocurable composition for support material can be properly mixed at the interface. By having such compatibility, it is possible to provide a photocurable composition set for a 3D printer with excellent moldability, and a photoprinted article using the same with excellent moldability.

FIG. 1 is a graph showing the relationship between Hansen solubility parameter distance HSPD and compatibility between a photocurable composition for a support material and isobornyl acrylate.

[Photocurable composition set for 3D printer]
The photocurable composition set for 3D printers (hereinafter sometimes simply referred to as composition set) according to the present invention is for model materials containing a water-insoluble monomer (A) and a photopolymerization initiator (B). It contains a photocurable composition, and a photocurable composition for a support material containing a water-soluble monomer (C) and a photopolymerization initiator (D). When the Hansen solubility parameter distance HSPD between the photocurable composition for support material and isobornyl acrylate is in the range of 12.9 (MPa ^1/2 )<HSPD<17.3 (MPa ^1/2 ) , the compatibility and water solubility between the photocurable composition for model material and the photocurable composition for support material are excellent.

(Photocurable composition for model material)
The photocurable composition for model materials (hereinafter sometimes simply referred to as the composition for model materials) included in the photocurable composition set for 3D printers according to the present invention contains a water-insoluble monomer (A). Contains a photopolymerization initiator (B).
The photocurable composition for model materials may contain monomers other than the water-insoluble monomer (A).

The water-insoluble monomer (A) contained in the photocurable composition for model materials is a photocurable monomer, preferably a water-insoluble ethylenically unsaturated monomer, and has a water solubility ( Examples include monofunctional ethylenically unsaturated monomers and polyfunctional ethylenically unsaturated monomers having a temperature of less than 20 g/L (20°C). Specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, t-butyl (meth)acrylate. Acrylate, 2-hydroxypropyl acrylate, linear or branched alkyl (meth)acrylates such as acrylic acid; cyclohexyl (meth)acrylate, 4-t-cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate; ) acrylate, dicyclopentanyl (meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, N-hydroxyphenyl (meth)acrylate, etc. ) Acrylate; Tetrahydrofurfuryl (meth)acrylate, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-cyclohexyl-1,3 - Heterocycle-containing (meth)acrylates such as dioxolane, adamantyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycidyl (meth)acrylate; tripropylene glycol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-n-butyl-2 - Straight chain or branched alkylene glycol (meth)acrylate such as ethyl-1,3-propanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, 2-(2-vinyloxyethoxy)ethyl(meth)acrylate ; (meth)acrylamides such as N-alkyl (meth)acrylamide into which an alkyl group having 1 to 12 carbon atoms has been introduced; vinyl compounds such as vinyl acetate, vinyl propionate, methyl vinyl ether, styrene, N-vinyl caprolactam, allyloxy Examples include methyl methyl acrylate. These may be used alone or in combination of two or more. Moreover, these water-insoluble monomers (A) are preferably monomers that do not contain metal components.

From the viewpoint of improving the curability of the photocurable composition for model materials, the content of the water-insoluble monomer (A) is 15% by mass based on 100% by mass of the entire photocurable composition for model materials. It is preferably at least 20% by mass, more preferably at least 20% by mass. Further, it is preferably 90% by mass or less, more preferably 80% by mass or less. In addition, when two or more types of the above-mentioned water-insoluble monomers (A) are contained, the content is the total content of each component.

In addition, the content of the water-insoluble monomer (A) relative to the total amount of monomers contained in the photocurable composition for model materials is determined from the viewpoint of improving the curability of the photocurable composition for model materials. It is preferably 50 to 100% by mass, more preferably 60 to 100% by mass. In addition, when two or more types of the above-mentioned water-insoluble monomers (A) are contained, the content is the total content of each component.

Examples of the photopolymerization initiator (B) contained in the photocurable composition for model materials include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2 -diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl Acetophenone compounds such as ketones, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amyl Anthraquinone compounds such as anthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, [3-(3,4-dimethyl-9-oxothioxanthen-2-yl)oxy-2-hydroxypropyl] - Thioxanthone compounds such as trimethylazanium chloride; Ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. Examples include phosphine oxide; and mixtures thereof.

The content of the photopolymerization initiator (B) is preferably 0.05 to 10.0% by mass, more preferably 0.1 to 9.0% by mass based on 100% by mass of the photocurable composition for model material. %, more preferably 2.0 to 8.0% by mass. In addition, when two or more types of photopolymerization initiators (B) are included, the content is the total content of each component.

The above-mentioned photocurable composition for model materials may contain other components as necessary within a range that does not impede the effects of the present invention. Specific examples include photoinitiation aids, polymerization inhibitors, surfactants, colorants, antioxidants, chain transfer agents, fillers, polymerizable oligomers, water-soluble monomers, and the like.

Photoinitiation aids include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethylamino-p-benzoic acid ethyl ester, N,N-dimethyl Examples include tertiary amine compounds such as amino-p-benzoic acid isoamylethyl ester, N,N-dihydroxyethylaniline, triethylamine and N,N-dimethylhexylamine.

Polymerization inhibitors include (alkyl)phenol, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, and nitrosinol. Benzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino-1, Examples include 3-dimethylbutylidene) aniline oxide, dibutyl cresol, cyclohexanone oximcresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, and cyclohexanone oxime.

Examples of surfactants include PEG-type nonionic surfactants such as ethylene oxide (hereinafter abbreviated as EO) 1 to 40 mol adduct of nonylphenol and 1 to 40 mol adduct of stearic acid; sorbitan palmitic acid monoester, sorbitan stearic acid. Polyhydric alcohol-type nonionic surfactants such as monoesters and sorbitan stearate triesters; fluorine-containing surfactants such as perfluoroalkyl EO 1 to 50 mole adducts, perfluoroalkyl carboxylates, perfluoroalkyl betaines; Examples include modified silicone oils such as ether-modified silicone oil and (meth)acrylate-modified silicone oil.

Colorants include toluidine red, permanent carmine FB, fast yellow G, disazo yellow AAA, disazo orange PMP, soluble azo pigment, condensed azo pigment, chelate azo pigment, phthalocyanine blue, indanthrone blue, quinacridone red, dioxazine violet, and base. Examples include natural pigments, acidic dyes, aniline black, daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, metal oxides as inorganic pigments, and carbon black.

As antioxidants, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, dilauryl 3,3'-thiodipropionate, Examples include triphenyl phosphite, octylated diphenylamine, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and the like.

Chain transfer agents include hydroquinone, diethylmethylamine, diphenylamine, diethyl disulfide, di-1-octyl disulfide, toluene, xylene, 1-butene, 1-nonene, dichloromethane, carbon tetrachloride, methanol, 1-butanol, ethylthiol. , 1-octylthiol, acetone, methyl ethyl ketone, 2-methyl-2-propyl aldehyde, 1-pentyl aldehyde, phenol, m-cresol, p-cresol, o-cresol and the like.

Fillers include alumina powder, silica powder, talc, mica, clay, aluminum hydroxide, calcium carbonate, calcium silicate, aluminum powder, copper powder, carbon fiber, glass fiber, cotton fiber, nylon fiber, acrylic fiber, and rayon. Examples include fibers, microballoons, carbon black, metal sulfides, and wood flour.

Examples of water-soluble monomers include (meth)acrylic acid; acryloylmorpholine; N-vinylpyrrolidone; Examples include ethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, glycerol (meth)acrylate, and methoxypolyethylene glycol acrylate.

The above additives may be used alone or in combination of two or more.
The content of the additive is preferably 0.05 to 30% by mass, more preferably 0.05 to 20% by mass based on 100% by mass of the composition.

The above photocurable composition for model materials can be prepared using the various components mentioned above, and the preparation means and conditions are not particularly limited, but for example, a general stirring blade, an ultrasonic homogenizer, a high-speed homogenizer, Examples include a method of stirring and mixing using a device that can mix or stir, such as a high-pressure homogenizer, a planetary stirrer, a three-roll mill, a ball mill, a kitty mill, a disk mill, a pin mill, and a dyno mill. After the solution is prepared, it may be filtered using various filters.

The photocurable composition for model material preferably has a viscosity of 20 mPa·s or less at the ejection temperature from the viewpoint of improving ejection properties from an inkjet head. The viscosity of the photocurable composition for model material is measured using an R100 viscometer in accordance with JIS Z 8803.

(Photocurable composition for support material)
The photocurable composition for support material (hereinafter sometimes simply referred to as the composition for support material) included in the photocurable composition set for 3D printers according to the present invention contains a water-soluble monomer (C) and photocurable composition. Contains a polymerization initiator (D). The photocurable composition for support material is water-soluble.

The water-soluble monomer (C) contained in the photocurable composition for support material is not particularly limited as long as it has a water solubility (20°C) of 20 g/L or more, and it has an ionic group and It may be an ionic monomer containing a counter ion or a nonionic monomer. Among these, ionic monomers containing an ionic group and a counter ion are preferred, and monomers having one or more ethylenically unsaturated groups in the molecule are preferred. More preferred is a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion.
The water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion has high water solubility because it contains an ionic group and a counter ion. The water solubility (at 20° C.) is preferably 100 g/L or more, more preferably 200 g/L or more, and even more preferably 500 g/L or more.

Ethylenically unsaturated groups include ethylene group, propenyl group, butenyl group, vinylphenyl group, (meth)acrylic group, allyl ether group, vinyl ether group, maleyl group, maleimide group, (meth)acrylamide group, acetylvinyl group, and Examples include vinylamide groups. In this specification, "(meth)acrylic" means "acrylic" and/or "methacrylic", and "(meth)acrylate" means "acrylate" and/or "methacrylate". means. Among these, (meth)acrylic group, vinyl ether group and (meth)acrylamide group are preferred, and (meth)acrylic group is more preferred.

Examples of the ionic group include carboxylic acid, phosphoric acid, and sulfonic acid. Among them, carboxylic acids are preferred.

Examples of the counter ions include monovalent counter ions such as sodium ions, potassium ions, and ammonium ions; polyvalent metal ions such as zinc ions, magnesium ions, calcium ions, aluminum ions, and neodymium ions. Among these, monovalent counter ions are preferred, sodium ions, potassium ions, or ammonium ions are more preferred, and potassium ions are even more preferred. In addition to monovalent counterions, it is also preferred to use polyvalent metal ions such as zinc ions, magnesium ions, calcium ions, aluminum ions, or neodymium ions.

When a water-soluble ethylenically unsaturated monomer containing a monovalent counter ion and a water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion are used together as counter ions, The support properties of the cured product obtained by photocuring the photocurable composition can be further improved. Moreover, in addition to these, it is a preferable form of the present invention to use together with an organic acid and/or a salt thereof, which will be described later. Preferred polyvalent metal ions are zinc ion, magnesium ion, and calcium ion.

The content of the water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion, which is preferably contained in the photocurable composition for a support material, is set as an upper limit based on 100% by mass of the composition. is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more. be. In this case, the support properties of the photocurable composition for support material can be further improved.

In addition, the content of the water-soluble ethylenically unsaturated monomer containing the ionic group and counter ion with respect to the total amount of monomers contained in the photocurable composition for support material is From the viewpoint of improving the water solubility of the composition, the amount is preferably 60 to 100% by mass, more preferably 70 to 100% by mass. In addition, when two or more kinds of water-soluble ethylenically unsaturated monomers containing the above-mentioned ionic group and counter ion are contained, the content is the total content of each component.

The total content of the water-soluble ethylenically unsaturated monomer containing a monovalent counterion as a counterion and the water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion as a counterion is The upper limit of 100% by mass of the photocurable composition for support material is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more.

The upper limit of the content of the water-soluble ethylenically unsaturated monomer containing a monovalent counterion is preferably 50% by mass or less, based on 100% by mass of the photocurable composition for support material. Preferably it is 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more.

The upper limit of the content of the water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion as a counter ion is preferably 40% by mass or less, more preferably 40% by mass or less in 100% by mass of the photocurable composition for support material. is 30% by mass or less, and the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
In the case described above, the support properties and solubility of the photocurable composition for support material can be further improved.

Examples of water-soluble ethylenically unsaturated monomers containing carboxylic acid as an ionic group and counter ions included in the photocurable composition for support materials include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. , 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth) Acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, N-(meth)acryloyl aspartic acid, ω-(meth) Monovalent salts such as alkali metal salts such as sodium salts and potassium salts and ammonium salts of acroylalkane-1,1 dicarboxylic acids; polyvalent salts such as zinc salts, magnesium salts, calcium salts, aluminum salts, or neodymium salts Examples include.
Among these, alkali metal salts such as sodium salts and potassium salts and monovalent salts such as ammonium salts are preferred, and sodium salts, potassium salts, and ammonium salts are more preferred. More preferred is potassium salt.

When a monovalent salt of a carboxylic acid and a polyvalent metal salt are used together, the support properties of a cured product obtained by photocuring a photocurable composition for a support material can be further improved. Moreover, in addition to these, it is a preferable form of the present invention to use together with an organic acid and/or a salt thereof, which will be described later. Among the polyvalent metal carboxylic acid salts, preferred are zinc salts, magnesium salts, and calcium salts.

The upper limit of the total content of monovalent salts and polyvalent metal salts of carboxylic acid in 100% by mass of the photocurable composition for support material is preferably 60% by mass or less, more preferably 50% by mass or less, More preferably, it is 40% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more.

The upper limit of the content of the monovalent salt of carboxylic acid is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less in 100% by mass of the photocurable composition for support material. It is. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more.

The content of the polyvalent metal salt of carboxylic acid is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably 5% by mass as the lower limit, based on 100% by mass of the photocurable composition for support material. % or more, more preferably 10% by mass or more.
In the case described above, the support properties and solubility of the photocurable composition for support material can be further improved.

Examples of water-soluble ethylenically unsaturated monomers containing carboxylic acid as an ionic group and a counter ion include sodium salts, potassium salts, zinc salts, and calcium salts containing 3 to 15 carbon atoms in the carboxylic acid. are preferred, and sodium salts, potassium salts, zinc salts, and calcium salts having 3 to 12 carbon atoms are more preferred. The number of carbon atoms is more preferably 3 to 9 carbon atoms, and even more preferably 3 to 6 carbon atoms. Among these, potassium (meth)acrylate, sodium (meth)acrylate, zinc (meth)acrylate, and calcium (meth)acrylate are particularly preferred. By using a monomer with a small number of carbon atoms, the hydrophobic portion in the molecule can be made small, and the water solubility of the water-soluble ethylenically unsaturated monomer can be further increased.

The water-soluble ethylenically unsaturated monomer containing phosphoric acid as an ionic group and a counter ion, which is preferably contained in the photocurable composition for support materials, is, for example, mono(2-acryloyloxyethyl ) acid phosphate, mono(2-methacryloyloxyethyl) acid phosphate, diphenyl (2-acryloyloxyethyl) phosphate, diphenyl (2-methacryloyloxyethyl) phosphate, phenyl (2-acryloyloxyethyl) phosphate, acid phosphooxyethyl methacrylate , methacroyloxyethyl acid phosphate, phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol methacrylate, (meth)acryloyloxyethyl acid phosphate, (meth)acryloyloxypropyl acid phosphate, (meth)acryloyloxy -2-hydroxypropyl acid phosphate, (meth)acryloyloxy-3-hydroxypropyl acid phosphate, (meth)acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, as well as vinyl phosphoric acid, p-vinylbenzene phosphate, etc. Examples include sodium salts, potassium salts, and ammonium salts of compounds having a phosphono group in the molecule.

The water-soluble ethylenically unsaturated monomer containing sulfonic acid as an ionic group and a counter ion, which is preferably contained in the photocurable composition for support materials, includes, for example, allylsulfonic acid, isoprenesulfonic acid , 2-(meth)acrylamidoethylsulfonic acid, 3-(meth)acrylamidopropylsulfonic acid, 4-(meth)acrylamidobutylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, p-vinylbenzenesulfone Examples include sodium, potassium, and ammonium salts of acids and compounds such as vinylsulfonic acid. The above-exemplified water-soluble ethylenically unsaturated monomers containing an ionic group and a counter ion may be used alone or in combination of two or more.

The water-soluble ethylenically unsaturated monomer preferably contained in the photocurable composition for support material is preferably an acrylate, and alkali metal salts such as lithium, sodium, potassium, ammonium salts, amine salts, etc. More preferred are monovalent salts of acrylic acid, even more preferred are alkali metal salts or ammonium salts, particularly preferred are sodium salts, potassium salts or ammonium salts. Most preferred are potassium salts.

In addition to the above, water-soluble ethylenically unsaturated monomers preferably contained in the photocurable composition for support materials include acrylic acid salts such as zinc salts, magnesium salts, calcium salts, aluminum salts, or neodymium salts. It may also contain a polyvalent metal salt. Among the polyvalent metal salts of acrylic acid, preferred are zinc salts, magnesium salts, and calcium salts.

When a monovalent salt of acrylic acid and a polyvalent metal salt are used together, the support properties of a cured product obtained by photocuring a photocurable composition for a support material can be further improved. As a combination of a monovalent salt of acrylic acid and a polyvalent metal salt, a combination of potassium acrylate and zinc acrylate is preferred. By using zinc acrylate in combination, a cured product with higher strength can be obtained.

The upper limit of the total content of monovalent salts and polyvalent metal salts of acrylic acid in 100% by mass of the photocurable composition for support materials is preferably 60% by mass or less, more preferably 50% by mass or less, More preferably, it is 40% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more.
Among these, the total content of potassium acrylate and zinc acrylate is preferably 20 to 50% by mass, more preferably 31 to 40% by mass based on 100% by mass of the photocurable composition for support material. . By doing so, the viscosity of the composition can be lowered, and the cost can also be lowered by suppressing the amount of acrylate used.

The content of the monovalent salt of acrylic acid is preferably at most 50% by mass, more preferably at most 40% by mass, and even more preferably at most 30% by mass, based on 100% by mass of the photocurable composition for support material. % or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more.
The content of the polyvalent metal salt of acrylic acid is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably 5% by mass as the lower limit in 100% by mass of the photocurable composition for support material. % or more, more preferably 10% by mass or more.
In the case described above, the support properties and solubility of the photocurable composition for support material can be further improved.

Examples of water-soluble ethylenically unsaturated monomers other than the above-mentioned water-soluble ethylenically unsaturated monomers containing an ionic group and a counter ion include (meth)acrylic acid; acryloylmorpholine; N-vinylpyrrolidone; ) acrylamide, acrylamide such as N,N-dimethylacrylamide, N-hydroxyethylacrylamide, N-isopropylacrylamide, methoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl ( Examples include meth)acrylate, glycerol (meth)acrylate, methoxypolyethylene glycol acrylate, and the like.

The upper limit of the total content of water-soluble monomers (C) contained in the photocurable composition for support materials is preferably 70% by mass or less, more preferably 60% by mass, based on 100% by mass of the composition. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, particularly preferably more than 20% by mass.

The photocurable composition for support material may contain an unsaturated monomer other than the water-soluble monomer (C) (for example, water solubility (20°C) is less than 20 g/L). . Examples of the other unsaturated monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and pentyl (meth)acrylate. , isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, iso Myristyl (meth)acrylate, isostearyl (meth)acrylate, n-stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, methyl 2-(hydroxymethyl)acrylate, and 2-ethylhexyl carbitol (meth)acrylate, etc. (Meth)acrylate; phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether, biphenyl-4-ol monoallyl ether, butyl allyl ether, cyclohexyl allyl ether, and cyclohexane Allyl ethers such as methanol monoallyl ether; butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, ethylhexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxyethoxy vinyl ether, cyclohexyl vinyl ether, adamantyl vinyl ether, etc. Vinyl ethers; maleimides such as phenylmaleimide, cyclohexylmaleimide, and n-hexylmaleimide; benzyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, bisphenol A diacrylate, EO adduct of bisphenol A bis(meth)acrylate, PO of bisphenol A Monomers with aromatic groups such as adduct bis(meth)acrylate, EO adduct of hydrogenated bisphenol A bis(meth)acrylate, and monomers with alicyclic group; polyoxyethylene di(meth)acrylate, polyoxypropylene Examples include polyoxyalkylene di(meth)acrylates such as di(meth)acrylate; hydroxyalkyl(meth)acrylates and the like.
These may be used alone or in combination of two or more.

The content of the other unsaturated monomers is preferably 50% by mass or less based on 100% by mass of the composition. More preferably, it is 40% by mass or less. Moreover, it is also preferable that the content of other unsaturated monomers is less than 2% by mass based on 100% by mass of the photocurable composition for support material. In this case, the odor of the photocurable composition for support material can be further suppressed.

In addition, from the viewpoint of improving the water solubility of the photocurable composition for support material, the content of the other unsaturated monomers is preferably 0% by mass or more and less than 50% by mass, and 0% by mass. More preferably, the content is less than 40% by mass. In addition, when two or more types of water-insoluble monomers are included, the content is the total content of each component.

The photocurable composition for support material may contain an organic acid and/or a salt thereof. The organic acid and/or its salt is a compound other than the above-mentioned water-soluble monomer (C) and the above-mentioned other unsaturated monomer.
Examples of the organic acid include organic sulfonic acids such as p-toluenesulfonic acid, organic phosphoric acids such as phenylphosphonic acid, organic carboxylic acids, and phosphoric esters. Among these, organic carboxylic acids are preferred. Examples of organic carboxylic acids include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, octylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. , behenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, benzoic acid, glycine, polyacrylic acid, polylactic acid Examples include. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, and salicylic acid. Among these, aliphatic carboxylic acids are more preferred, and lactic acid, propionic acid, and polyacrylic acid are even more preferred.
Examples of organic acid salts include metal carboxylates. Examples of the metal of the metal carboxylate include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as magnesium, calcium, strontium, and barium; zinc; and zirconium. Among them, alkali metals such as potassium are preferred. As the organic acid salt, potassium lactate and potassium propionate are preferred.
The storage stability of the photocurable composition for a support material is further improved when it contains an organic acid and/or a salt thereof.

The content of the organic acid and/or its salt is within a range where the water content is preferably 10% by mass or less based on 100% by mass of the photocurable composition for support material, and the upper limit is preferably 60% by mass or less. , more preferably 50% by mass or less, still more preferably 40% by mass or less, and the lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more. In this case, the support properties, solubility, and storage stability of the photocurable composition for support material can be further improved.

The photocurable composition for support material contains a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; 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-( Acetophenone compounds such as methylthio)phenyl-2-morpholinopropan-1-one; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; 2,4-diethylthioxanthone , 2-isopropylthioxanthone, 2-chlorothioxanthone, [3-(3,4-dimethyl-9-oxothioxanthen-2-yl)oxy-2-hydroxypropyl]-trimethylazanium chloride; thioxanthone compounds such as acetophenone dimethyl Ketal compounds such as ketal, benzyl dimethyl ketal; Benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis -(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and mixtures thereof.
These may be used alone or in combination of two or more.
The content of the photopolymerization initiator (D) is preferably 0.05 to 10.0% by mass, more preferably 0.1 to 7.0% by mass, and even more preferably 0. .2 to 5.0% by mass.

The photocurable composition for a support material may contain a solvent to the extent that the effects of the present invention are not impaired. The above solvents include water; monohydric alcohols such as methanol, ethanol, and propanol; alkylene oxide adducts containing oxypropylene groups such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, and polyoxypropylene glycol. glycols such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monopropyl ether, and glycol ether acetates such as propylene glycol monomethyl ether acetate. The above solvents may be used alone or in combination of two or more.
It is preferable to use the above-mentioned solvent so that the content of water is 10% by mass or less in 100% by mass of the photocurable composition for support material. As the solvent, preferred are glycols, glycol ethers, and glycol ether acetates having 3 to 9 carbon atoms.

The content of the solvent in 100% by mass of the composition has a lower limit of preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 30% by mass or more, and an upper limit of preferably 90% by mass. % or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.

The above-mentioned glycol having 3 to 9 carbon atoms, glycol ether, and glycol ether acetate are preferably contained in a total amount of 30 to 90% by mass, and preferably 40 to 90% by mass, based on 100% by mass of the above composition. is more preferable.
Among these, the content of propylene glycol is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, based on 100% by mass of the composition.

The above-mentioned photocurable composition for a support material may contain other additives as necessary within a range that does not impede the effects of the present invention. Specific examples include photoinitiation aids, polymerization inhibitors, surfactants, colorants, antioxidants, chain transfer agents, fillers, and the like. Specific examples of these are the same as those exemplified in the photocurable composition for model materials.

It is preferable that the photocurable composition for a support material has a uniform appearance and is transparent. Further, it is preferable that odor is suppressed. Specifically, it is preferable that the monomer has a slight irritating odor, and it is more preferable that the monomer has no irritating odor. In the photocurable composition for support material, the content of unsaturated monomers other than the water-soluble monomer (C) is preferably 2% by mass in 100% by mass of the photocurable composition for support material. When the content is less than % by mass, the odor can be suppressed more effectively.

It is preferable that the photocurable composition for a support material has excellent curability. As for curability, it is preferably cured by irradiation with light of 100 to 3000 mJ/cm ² , more preferably cured by irradiation of light of 100 to 2000 mJ/cm ² , and cured by irradiation of 100 to 1000 mJ/cm ² It is more preferable to cure the resin by irradiating it with light. Here, hardening means that it is no longer liquid and has no fluidity.

Since the photocurable composition for a support material is used as a support material after curing, the cured product has excellent water solubility, which is an essential requirement for the support material. Regarding water solubility, for example, when 0.5 g (surface area 4 cm ² ) of the cured product is placed on a wire mesh and immersed in 10 ml of water at room temperature (for example, around 25° C.), it is preferable that it dissolves within 1 hour. It is more preferable that most of it dissolves within 30 minutes, and even more preferably that it dissolves within 15 minutes and no insoluble matter is visually observed.

The content of water in the photocurable composition for support material is preferably 10% by mass or less, more preferably less than 10% by mass, and even more preferably 5% by mass based on 100% by mass of the photocurable composition for support material. The content is particularly preferably 3% by mass or less. The lower limit of the water content is preferably 0% by mass. By setting it as such a range, it can have excellent curability, sufficient hardness of the cured product after curing, improved supportability, and better solubility in a solvent. The water content in the photocurable composition for support material can be calculated from the water content of each compound charged. It can also be determined by Karl Fischer measurement. The support property (support force) is the ability of the cured product of the photocurable composition for support material to support the cured product of the model material, and is the hardness of the cured product of the support material (Shower E), which is measured by the method described below. ) can be expressed as

(Hansen solubility parameter distance HSPD)
In the photocurable composition set for 3D printers of the present invention, the Hansen solubility parameter distance HSPD between the photocurable composition for support material and isobornyl acrylate is 12.9 (MPa ^1/2 )<HSPD<17. 3 (MPa ^1/2 ), the compatibility and water solubility between the photocurable composition for model material and the photocurable composition for support material are excellent.
The Hansen solubility parameter distance HSPD (MPa ^1/2 ) is the distance between two points between the Hansen solubility parameter of the photocurable composition for support material and isobornyl acrylate. The Hansen solubility parameter expresses solubility as a multidimensional vector, and this vector is [δD: dispersion term (van der Waals force), δP: polar term (dipole moment force), δH: hydrogen It is expressed by three parameters: the bond term]. That is, the distance between two points between the vector coordinates [δDs, δPs, δHs] of the photocurable composition for support material and the vector coordinates [δDm, δPm, δHm] of the isobornyl acrylate is the Hansen solubility parameter. The distance HSPD (MPa ^1/2 ).
The Hansen solubility parameter distance HSPD is expressed by the following formula.

Furthermore, the Hansen solubility parameter of the mixture is determined by the volume ratio of the Hansen solubility parameters of each composition. for example,
Composition A ([δD _A , δP _A , δH _A ], density d _A (g/mL), weight proportion w _A (wt%))
Composition B ([δD _B , δP _B , δH _B ], density d _B (g/mL), weight ratio w _B (wt%))
The Hansen solubility parameters [δD ₁ , δP ₁ , δH ₁ ] of the mixture 1 consisting of the following are expressed by the following formula.

The Hansen solubility parameter distance HSPD (MPa ^1/2 ) can be determined using commercially available Hansen solubility parameter calculation software.

In the composition set according to the present invention, the Hansen solubility parameter distance HSPD between the photocurable composition for support material and the vector coordinates [δDm, δPm, δHm] of isobornyl acrylate is 12.9 (MPa ^1/2 ) < HSPD < 17.3 (MPa ^1/2 ), the compatibility and water solubility between the photocurable composition for model material and the photocurable composition for support material are excellent. This results in a composition set with excellent formability.

When the Hansen solubility parameter distance HSPD between the photocurable composition for support material and the vector coordinates [δDm, δPm, δHm] of isobornyl acrylate is smaller than 12.9 MPa ^1/2 , the photocurable composition for support material The water solubility of the composition and its cured product becomes low. In addition, if the Hansen solubility parameter distance HSPD between the photocurable composition for support material and the vector coordinates [δDm, δPm, δHm] of isobornyl acrylate is greater than 17.3 MPa ^1/2 , photocurable composition for model material The compatibility at the interface between the photocurable composition and the photocurable composition for support material decreases, and the interface condition deteriorates. The interface between the photocurable composition for model material and the photocurable composition for support material is preferably not cloudy.

The Hansen solubility parameter distance HSPD between the photocurable composition for support material and the vector coordinates [δDm, δPm, δHm] of isobornyl acrylate is 12.9 (MPa ^1/2 ) < HSPD < 17.3 (MPa ^1/2 ) can be adjusted by changing the composition of the photocurable composition for support material. An appropriate solvent may be added to the photocurable composition for support material.

In the photocurable composition set for 3D printers of the present invention, even when the photocurable composition for model material and the photocurable composition for support material are discharged simultaneously, the two photocurable compositions By having appropriate compatibility at the interface, the photocurable composition for support material and its cured product preferably have excellent moldability, and the above-mentioned photocurable composition for support material and its cured product preferably have excellent water solubility, thereby providing an optically shaped article with excellent moldability. can.

The above-mentioned photocurable composition for model material or the above-mentioned photocurable composition for support material (hereinafter, these may be collectively referred to as a composition) may be diluted with a medium. The medium is preferably a hydrophilic medium. Also in this case, the water content is preferably 10% by mass or less based on 100% by mass of each composition.

The above composition may contain other additives as necessary within a range that does not impair the effects of the present invention. Other additives include, for example, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, antifungal agents, rust preventives, pH adjusters, surface tension adjusters, antifoaming agents, viscosity modifiers, and dispersants. Known additives include agents, dispersion stabilizers, chelating agents, anti-drying agents (wetting agents), colorants, anti-fading agents, resistivity modifiers, film modifiers, antioxidants, and surfactants. . These various additives can be added directly to the composition, for example.

The above composition preferably has a viscosity of 5 to 300 mPa·s at 25°C. Further, the surface tension is preferably 25 to 70 mN/m.

The photocurable composition set for 3D printers of the present invention is preferably used for inkjet stereolithography, and is suitable as an ink for inkjet 3D printers.

[Cartridge for inkjet 3D printer]
The cartridge for an inkjet 3D printer is filled with each of the above compositions. The cartridge for an inkjet 3D printer only needs to be filled with the above composition, and any known form of the cartridge for an inkjet 3D printer can be used.

[Stereolithography]
The optically shaped article of the present invention is obtained by photocuring the above photocurable composition set for 3D printers. In the stereolithographic article of the present invention, since the photocurable composition set for 3D printers of the present invention is used, the photocurable composition for model material and the photocurable composition for support material are simultaneously applied. Even when discharged, the two photocurable compositions have appropriate compatibility at the interface, thereby making it possible to provide an optically shaped article with excellent formability.

[Manufacturing method for stereolithography]
The method for producing a stereolithographic article of the present invention includes a step (I) of photocuring the photocurable composition set for a 3D printer of the present invention to obtain a cured product, and a step (I) of obtaining a cured product by photocuring the photocurable composition set for a 3D printer of the present invention; The method includes a step (II) of removing a photocured cured product of the curable composition.

The photocurable composition for model material and the photocurable composition for support material included in the photocurable composition set for 3D printers of the present invention can be prepared using the various components described above, respectively. The preparation means and conditions are not particularly limited, but for example, a general stirring blade, an ultrasonic homogenizer, a high-speed homogenizer, a high-pressure homogenizer, a planetary stirring device, a three-roll mill, a ball mill, a kitty mill, a disk mill, a pin mill, a dyno mill, etc. Examples include a method of stirring and mixing using a mixing or stirring device. After the solution is prepared, it may be filtered using various filters.

In the step (I), preferably by inkjet stereolithography, the photocurable composition set for a 3D printer of the present invention is photocured to obtain a cured product. In step (I), a known method can be used except for using the photocurable composition for model material and the photocurable composition for support material. Specifically, the photocurable composition for model material and the photocurable composition for support material included in the photocurable composition set for 3D printers of the present invention are sprayed from each nozzle, and shaped by printing, etc. Thereafter, known methods such as irradiating ultraviolet rays of about 100 to 3000 mJ/cm ² to photocure to obtain a cured product can be used. The ultraviolet irradiation is preferably 100 to 2000 mJ/cm ² , even more preferably 100 to 1000 mJ/cm ² .

In the 3D printer stereolithography method, since the outer shape of the photocurable composition for model material is supported and modeled by the cured product of the photocurable composition for support material, the two come into contact to form an interface. The photocurable composition for model material and the photocurable composition for support material may be sprayed, printed, etc. from each nozzle at the same time.

Subsequently, in the step (II), the cured product in which the photocurable composition for support material is photocured is removed from the cured product. In the cured product obtained by photocuring the photocurable composition for model material and the photocurable composition for support material included in the photocurable composition set for 3D printers of the present invention, photocurable composition for support material Since the cured product obtained by photo-curing the composition has excellent water solubility, the cured product in this part can be easily removed with a polar solvent such as water. As the removal method, from the viewpoint of safety and cost, it is preferable to leave the cured product in water and remove the support material composition.

In the method for producing a stereolithographic object of the present invention, the photocurable composition for model material and the photocurable composition for support material are used. It has an appropriate compatibility at the interface with objects, and has excellent formability, and the cured product of the photocurable composition for support materials preferably has excellent water solubility, so it is a photocurable composition with excellent formability. Modeled products can be easily manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the Examples below, and modifications may be made as appropriate within the scope of the spirit of the preceding and following. Of course, other implementations are also possible, and all of them are included within the technical scope of the present invention.

<Photocurable composition for model material>
The components shown in Table 1 were mixed uniformly using a mixing and stirring device using the amounts (parts by mass) shown in Table 1, and No. Standard photocurable compositions for model materials Nos. 1 to 9 were prepared.

<Photocurable composition for support material>
The water-soluble monomers and solvents shown in Tables 2 to 4 were uniformly mixed using a mixing and stirring device using the amounts (parts by mass) shown in Tables 2 to 4. A photocurable composition for support material was prepared.

<Hansen solubility parameter>
The Hansen solubility parameters of the photocurable composition for support material and the vector coordinates [δDm, δPm, δHm] of isobornyl acrylate are determined by performing a dissolution experiment in a solvent with a known Hansen solubility parameter, and using the actual measurement results with commercially available software. It was input into HSPiP5.1.03 and determined using the Sphere function.
The Hansen solubility parameter of isobornyl acrylate was as follows.
Hansen solubility parameter δD: 17.0MPa ^1/2
δP: 3.1MPa ^1/2
δH: 3.7MPa ^1/2

<Hansen solubility parameter distance HSPD (MPa ^1/2 )>
The Hansen solubility parameter distance HSPD (MPa ^1/2 ) between the photocurable composition for support material and the vector coordinates [δDm, δPm, δHm] of isobornyl acrylate was calculated using commercially available software HSPiP5.1.03. sought each.
Tables 2 to 4 show the Hansen solubility parameter distance HSPD (MPa ^1/2 ) between each photocurable composition for support material and isobornyl acrylate.

<Compatibility test>
The obtained photocurable compositions for support materials and photocurable compositions for model materials No. 1 to 9 were weighed into a screw tube so that the mass ratio was 1:1, and the appearance of each mixture after stirring at 100 rpm for 30 seconds was visually confirmed. The evaluation criteria are as follows. The results are shown in Tables 2 to 4.
○: Photocurable composition for support material and photocurable composition for each model material No. The two liquids 1 to 9 are all mixed together without becoming cloudy.
×: Photocurable composition for support material and photocurable composition for each model material No. Among the two liquids 1 to 9, the mixture of any two liquids becomes cloudy.

<Water solubility test>
3.0 g of cured pieces of each of the obtained photocurable compositions for support materials were placed in a 10 mL screw tube, and 2.7 g of water was added to evaluate water solubility. The evaluation criteria are as follows. The results are shown in Tables 2-4.
○: No cured product remains and is dissolved.
×: Cured material remains.

FIG. 1 shows the relationship between the Hansen solubility parameter distance HSPD (MPa ^1/2 ) and compatibility. On the horizontal axis of FIG. 1 to 7 are Comparative Examples 1 to 7, No. 8 to 29 are Examples 1 to 22, No. Nos. 30 and 31 correspond to Comparative Examples 8 and 9.
As shown in Tables 2 to 4 and FIG. 1, the Hansen solubility parameter distance HSPD of the photocurable composition for support material and isobornyl acrylate is 12.9 (MPa ^1/2 ) < HSPD < 17.3 (MPa ^{1 /2} ), the two liquids, the photocurable composition for model material and the photocurable composition for support material, were mixed with almost no cloudiness and had appropriate compatibility at the interface. . The photocurable composition for support material also had excellent water solubility. Thereby, it is possible to provide a photocurable composition set for 3D printers with excellent modeling properties.

The compound names in Tables 1 to 4 are as follows.
IBOA: Isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)
ACMO: Acryloylmorpholine (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
DCP-A: Dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
CN968: Aliphatic urethane acrylate (manufactured by Sartomer)
MEHQ: 4-methoxyphenol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
AAK: Potassium acrylate (manufactured by Nippon Shokubai Co., Ltd.)
_AA2Zn : Zinc acrylate (manufactured by Nippon Shokubai Co., Ltd.)
PEGA: Methoxypolyethylene glycol #400 acrylate (manufactured by Shin Nakamura Chemical Co., Ltd.)
NVP: N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd.)
HEAA: 2-hydroxyethylacrylamide (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
NIPAM: N-isopropylacrylamide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
PG: Propylene glycol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
PGME: Propylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
DPGME: Dipropylene glycol monomethyl ether (manufactured by Kanto Kagaku Co., Ltd.)
DPGMPE: Dipropylene glycol monopropyl ether (manufactured by Kanto Kagaku Co., Ltd.)
PGMPE: Propylene glycol monopropyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)
GLMA: Glycerol methacrylate (manufactured by NOF Corporation)
LA: Lactic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
DPG: Dipropylene glycol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
DG: Diethylene glycol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
PEG200: Polyethylene glycol 200 (manufactured by Wako Pure Chemical Industries, Ltd.)

Claims (3)

A photocurable composition for a model material containing a water-insoluble monomer (A) and a photoinitiator (B), and
A photocurable composition for a support material containing a water-soluble monomer (C) and a photopolymerization initiator (D),
Containing a water-insoluble ethylenically unsaturated monomer as the water-insoluble monomer (A) from 50 to 100% by mass based on the total amount of monomers contained in the photocurable composition for model materials,
As the water-soluble monomer (C), a water-soluble ethylenically unsaturated monomer containing a monovalent counter ion and a water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion, The total content is 5% by mass or more and 60% by mass or less in 100% by mass of the photocurable composition for support material,
The 3D Hansen solubility parameter distance HSPD between the photocurable composition for support material and isobornyl acrylate is within the range of 12.9 (MPa ^1/2 )<HSPD<17.3 (MPa ^1/2 ) Photocurable composition set for printers. An optically shaped article obtained by photocuring the photocurable composition set for a 3D printer according to claim 1. A step (I) of photocuring the photocurable composition set for a 3D printer according to claim 1 to obtain a cured product, and a cured product obtained by photocuring the photocurable composition for a support material from the cured product. Step (II) of removing
A method for manufacturing a stereolithographic product, including: