JP2021146524A - Photocurable composition set for 3d printer, photomolded article using the same and method for producing the same - Google Patents

Abstract

To provide a photocurable composition set for a 3D printer having excellent formability since a photocurable composition for a model material and a photocurable composition for a support material have moderate compatibility at the interface.SOLUTION: There is provided a photocurable composition set for a 3D printer which comprises a photocurable composition for a model material containing a water-insoluble monomer and a photopolymerization initiator and a photocurable composition for a support material containing a water-soluble monomer and a photopolymerization initiator, wherein the Hansen solubility parameter distance HSPD between the photocurable composition for a support material and an isobornyl acrylate is 12.9(MPa1/2)<HSPD<17.3(MPa1/2).SELECTED DRAWING: Figure 1

Description

The present invention relates to a photocurable composition set for a 3D printer, a stereolithographic product using the photocurable composition set, and a method for producing the same.

In recent years, in 3D printers, a stereolithography method by an inkjet method has been proposed in which a liquid photocurable composition discharged from an inkjet nozzle is cured, laminated, and photomolded. The ink for 3D printers using this stereolithography method is a photocurable composition for a model material that constitutes a molded body by photocuring such as UV, and a photocuring for a support material when the model materials are three-dimensionally stacked. It is a set with a sex composition. By laminating the model material on the support material, it is possible to form an overhang structure or a hollow structure.

In the above stereolithography method, a photocurable composition for a model material and a photocurable composition for a support material are simultaneously discharged by a 3D printer and then photocured for each layer to obtain a cured product. The desired model is obtained by removing the cured product of the photocurable composition for the support material. In order to improve the molding accuracy of the modeled object, the compatibility between the photocurable composition for the model material and the photocurable composition for the support material discharged at the same time is important. This is because if the photocurable composition for the model material and the photocurable composition for the support material are incompatible with each other when discharged, the contained components are precipitated or become cloudy at the contacting interface. Therefore, it has been studied to improve the compatibility at the interface.

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

International Publication No. 2017/047692

In the photocurable composition set for a 3D printer used in the above stereolithography method, the present inventors have appropriately discharged at the interface between the photocurable composition for a model material and the photocurable composition for a support material. It has been found that by having compatibility, it is possible to provide a photocurable composition set for a 3D printer having excellent formability.

Therefore, an object of the present invention is that the photocurable composition for a model material and the photocurable composition for a support material have appropriate compatibility at the interface, so that the photocurable composition for a 3D printer is excellent in formability. It is an object of the present invention to provide a product set, and to provide a stereolithographic product having excellent moldability using the product set and a method for producing the same.

As a result of intensive research to solve the above problems, the present inventors have conducted a Hansen solubility parameter distance between the photocurable composition for a support material and isobornyl acrylate in a photocurable composition set for a 3D printer. The present invention has been completed by finding that the above-mentioned problems 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 simple substance. A photocurable composition for a support material containing a monomer (C) and a photopolymerization initiator (D) is included, and the Hansen solubility parameter distance HSPD between the photocurable composition for the support material and isobornyl acrylate is 12. 9.9 (MPa ^1/2 ) <HSPD <17.3 (MPa ^1/2 ). When the HSPD is included in such a range, the photocurable composition for the model material and the photocurable composition for the support material are excellent in compatibility and water solubility.

Further, the stereolithographic product of the present invention is obtained by photocuring the above-mentioned photocurable composition set for a 3D printer.
Further, the method for producing a stereolithographic product of the present invention includes the step (I) of photocuring the photocurable composition set for a 3D printer to obtain a cured product, and the photocuring for a support material from the cured product. The sexual composition comprises a step (II) of removing the photocured cured product.

According to the photocurable composition set for a 3D printer of the present invention, a stereolithographic product using the set, and a method for producing the same, the photocurable composition for a model material and the photocurable composition for a support material are appropriately prepared at an interface. By having a good compatibility, it is possible to provide a photocurable composition set for a 3D printer having excellent formability, and a stereolithographic product using the photocurable composition set having excellent formability.

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

[Photocurable composition set for 3D printers]
The photocurable composition set for a 3D printer according to the present invention (hereinafter, may be simply referred to as a composition set) is for a model material 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 of the photocurable composition for a support material and isobornyl acrylate is included in the range of ^{12.9 (MPa 1/2} ) <HSPD <17.3 (MPa ^1/2). , The photocurable composition for the model material and the photocurable composition for the support material are excellent in compatibility and water solubility.

(Photocurable composition for model material)
The photocurable composition for a model material (hereinafter, may be simply referred to as a composition for a model material) included in the photocurable composition set for a 3D printer according to the present invention is a water-insoluble monomer (A). Includes a photopolymerization initiator (B).
The photocurable composition for a model material may contain a monomer other than the water-insoluble monomer (A).

The water-insoluble monomer (A) contained in the photocurable composition for a model material is a photocurable monomer, preferably a water-insoluble ethylenically unsaturated monomer, and has a water solubility (water solubility (A)). Examples thereof 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). Linear or branched alkyl (meth) acrylates such as acrylates, 2-hydroxypropyl acrylates, acrylic acids; cyclohexyl (meth) acrylates, 4-t-cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, phenoxyethyl (meth). ) Acrylate-containing (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate, tricyclodecanedimethanol 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 -Dioxolan, adamantyl (meth) acrylate, cyclic trimethylolpropaneformal (meth) acrylate, heterocyclic-containing (meth) acrylate such as 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 Linear or branched alkylene glycol (meth) acrylates such as −ethyl-1,3-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. (Meta) acrylamide such as N-alkyl (meth) acrylamide introduced with an alkyl group having 1 to 12 carbon atoms; Vinyl compound such as vinyl acetate, vinyl propionate, methyl vinyl ether, styrene, N-vinylcaprolactam, allyloxy Methyl acrylate and the like can be mentioned. These may be used alone or in combination of two or more. Further, these water-insoluble monomers (A) are preferably monomers that do not contain a metal component.

The content of the water-insoluble monomer (A) is 15 with respect to 100% by mass of the entire photocurable composition for the model material from the viewpoint of improving the curability of the photocurable composition for the model material. It is preferably 1% by mass or more, and more preferably 20% by mass or more. Further, it is preferably 90% by mass or less, and more preferably 80% by mass or less. When two or more kinds of the water-insoluble monomer (A) are contained, the content is the total content of each component.

Further, the content of the water-insoluble monomer (A) with respect to the total amount of the monomers contained in the photocurable composition for a model material is determined from the viewpoint of improving the curability of the photocurable composition for a model material. It is preferably 50 to 100% by mass, more preferably 60 to 100% by mass. When two or more kinds of the water-insoluble monomer (A) are contained, the content is the total content of each component.

Examples of the photopolymerization initiator (B) contained in the photocurable composition for a model material 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-phenylpropane-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. Hosphin oxides; and mixtures thereof and the like.

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 a model material. %, More preferably 2.0 to 8.0% by mass. When two or more kinds of the photopolymerization initiator (B) are contained, the content is the total content of each component.

The photocurable composition for a model material may contain other components, if necessary, as long as the effects of the present invention are not impaired. Specific examples thereof include photoinitiator aids, polymerization inhibitors, surfactants, colorants, antioxidants, chain transfer agents, fillers, polymerizable oligomers, water-soluble monomers and the like.

Photoinitiator 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 thereof include tertiary amine compounds such as amino-p-benzoic acid isoamylethyl ester, N, N-dihydroxyethylaniline, triethylamine and N, N-dimethylhexylamine.

Examples of the polymerization inhibitor include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiline, p-benzoquinone, and nitroso. Benzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperon, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1, 3-Dimethylbutylidene) Aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guayacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxim, cyclohexanone oxime and the like can be mentioned.

Examples of the surfactant include PEG-type nonionic surfactants such as ethylene oxide (hereinafter abbreviated as EO) 1 to 40 mol additive of nonylphenol and EO 1 to 40 mol additive of stearate; sorbitan palmitate monoester, sorbitan stearate. Polyhydric alcohol-type nonionic surfactants such as monoesters and sorbitan stearic acid triesters; fluorine-containing surfactants such as perfluoroalkyl EO 1 to 50 molar additions, perfluoroalkyl carboxylates, perfluoroalkyl betaines; poly Examples thereof include modified silicone oils such as ether-modified silicone oils and (meth) acrylate-modified silicone oils.

Coloring agents 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, indantron blue, quinacridone red, dioxazine violet, base. Examples thereof include sex dyes, acidic dyes, aniline blacks, daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, metal oxides as inorganic pigments, carbon black and the like.

Antioxidants include 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, dilauryl 3,3'-thiodipropionate, Examples thereof include triphenylphosphite, octylated diphenylamine, 2,6-di-t-butyl-p-cresol, and 2,2'-methylenebis (4-methyl-6-t-butylphenol).

Chain transfer agents include hydroquinone, diethylmethylamine, diphenylamine, diethyldisulfide, di-1-octyldisulfide, toluene, xylene, 1-butene, 1-nonen, dichloromethane, carbon tetrachloride, methanol, 1-butanol, ethylthiol. , 1-octylthiol, acetone, methylethylketone, 2-methyl-2-propylaldehyde, 1-pentylaldehyde, phenol, m-cresol, p-cresol, o-cresol and the like.

As fillers, 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, rayon. Examples include fiber, microballoon, carbon black, metal sulfide, wood powder and the like.

Examples of the water-soluble monomer include (meth) acrylic acid; acryloylmorpholin; N-vinylpyrrolidone; (meth) acrylamide, N, N-dimethylacrylamide, N-hydroxyethylacrylamide, acrylamide such as N-isopropylacrylamide, and methoxytri. Examples thereof 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 photocurable composition for the model material can be prepared using the various components described above, and the preparation means and conditions thereof are not particularly limited. For example, a general stirring blade, an ultrasonic homogenizer, a high-speed homogenizer, etc. Examples thereof include a method of stirring and mixing using a device capable of mixing or stirring such as a high-pressure homogenizer, a planetary stirrer, a three-roll, a ball mill, a kitty mill, a disc mill, a pin mill, and a dyno mill. After preparing the solution, filtration may be performed using various filters.

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

(Photocurable composition for support material)
The photocurable composition for a support material (hereinafter, may be simply referred to as a composition for a support material) included in the photocurable composition set for a 3D printer according to the present invention includes a water-soluble monomer (C) and light. It contains a polymerization initiator (D). The photocurable composition for the support material is water-soluble.

The water-soluble monomer (C) contained in the photocurable composition for a support material is not particularly limited as long as it is a monomer having a water solubility (20 ° C.) of 20 g / L or more, and can be an ionic group. It may be an ionic monomer containing a counter ion or a non-ionic monomer. Among them, an ionic monomer containing an ionic group and a counterion is preferable, and a monomer having one or more ethylenically unsaturated groups in the molecule is preferable. More preferably, it is a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion.
The water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion is highly water-soluble by containing an ionic group and a counterion. The water solubility (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.

The 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 a vinylamide group. In the present specification, "(meth) acrylic" means both or either of "acrylic" and "methacryl", and "(meth) acrylate" means both or either of "acrylate" and "methacrylate". means. Among them, a (meth) acrylic group, a vinyl ether group and a (meth) acrylamide group are preferable, and a (meth) acrylic group is more preferable.

Examples of the ionic group include carboxylic acid, phosphoric acid, sulfonic acid and the like. Of these, carboxylic acid is preferable.

Examples of the counterion include monovalent counterions such as sodium ion, potassium ion and ammonium ion; and polyvalent metal ions such as zinc ion, magnesium ion, calcium ion, aluminum ion and neodium ion. Among them, a monovalent counterion is preferable, a sodium ion, a potassium ion, or an ammonium ion is more preferably used, and a potassium ion is more preferably used. In addition to the monovalent counterion, it is also preferable to use a polyvalent metal ion such as zinc ion, magnesium ion, calcium ion, aluminum ion, or neodium ion.

For a support material when a water-soluble ethylenically unsaturated monomer containing a monovalent counterion and a water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion are used in combination as counterions. The supportability of the cured product obtained by photocuring the photocurable composition can be further improved. Further, in addition to these, it is a preferable form of the present invention to be used in combination with an organic acid and / or a salt thereof, which will be described later. The polyvalent metal ion is preferably zinc ion, magnesium ion, or calcium ion.

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

The content of the water-soluble ethylenically unsaturated monomer containing the ionic group and the counterion with respect to the total amount of the monomers contained in the photocurable composition for the support material is the photocuring for the support material. From the viewpoint of improving the water solubility of the sex composition, it is preferably 60 to 100% by mass, more preferably 70 to 100% by mass. When two or more kinds of water-soluble ethylenically unsaturated monomers containing the above-mentioned ionic group and counterion 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 The upper limit of the photocurable composition for a 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, and further preferably 15% by mass or more.

The content of the water-soluble ethylenically unsaturated monomer containing a monovalent counterion as a counterion is preferably 50% by mass or less, preferably 50% by mass or less, based on 100% by mass of the photocurable composition for a support material. It is preferably 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, and further preferably 10% by mass or more.

The content of the water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion as a counterion is preferably 40% by mass or less, more preferably 40% by mass or less, based on 100% by mass of the photocurable composition for a 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.
When the above is done, the solubility of the photocurable composition for a support material as well as the supportability can be further improved.

Examples of the water-soluble ethylenically unsaturated monomer containing a carboxylic acid as an ionic group and a counterion contained in the photocurable composition for a support material include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. , 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) Acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-vinyl benzoic acid, 3-vinyl benzoic acid, 4-vinyl benzoic acid, N- (meth) acryloyl aspartic acid, ω- (meth) Acryloyl alkane-1,1 dicarboxylic acids, alkali metal salts such as sodium salt and potassium salt, and monovalent salts such as ammonium salt; polyvalent salts such as zinc salt, magnesium salt, calcium salt, aluminum salt, or neodium salt. And so on.
Among them, alkali metal salts such as sodium salt and potassium salt and monovalent salts such as ammonium salt are preferable, and sodium salt, potassium salt or ammonium salt is more preferable. More preferably, it is a potassium salt.

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

The total content of the monovalent salt and the polyvalent metal salt of the carboxylic acid is preferably 60% by mass or less, more preferably 50% by mass or less, based on 100% by mass of the photocurable composition for a support material. 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, and further preferably 15% by mass or more.

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

The content of the polyvalent metal salt of the carboxylic acid is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably 5% by mass as the upper limit in 100% by mass of the photocurable composition for a support material. % Or more, more preferably 10% by mass or more.
When the above is done, the solubility as well as the supportability of the photocurable composition for a support material can be further improved.

Examples of the water-soluble ethylenically unsaturated monomer containing a carboxylic acid as an ionic group and a counterion include a sodium salt, a potassium salt, a zinc salt, and a calcium salt having 3 to 15 carbon atoms contained in the carboxylic acid. Is preferable, and sodium salt, potassium salt, zinc salt, and calcium salt having 3 to 12 carbon atoms are more preferable. As the number of carbon atoms, 3 to 9 carbon atoms are more preferable, and 3 to 6 carbon atoms are further preferable. Of these, potassium (meth) acrylate, sodium (meth) acrylate, zinc (meth) acrylate, and calcium (meth) acrylate are particularly preferable. By using a monomer having a small number of carbon atoms, the hydrophobic portion in the molecule can be reduced, and the water solubility of the water-soluble ethylenically unsaturated monomer can be further enhanced.

Examples of the water-soluble ethylenically unsaturated monomer containing a phosphoric acid as an ionic group and a counterion, which are preferably contained in the photocurable composition for a support material, include 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 , Metacloyloxyethyl 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, and vinyl phosphate, p-vinylbenzene phosphate, etc. Examples thereof include sodium salt, potassium salt, and ammonium salt of compounds having a phosphono group in the molecule.

Examples of the water-soluble ethylenically unsaturated monomer containing sulfonic acid as an ionic group and counterion, which are preferably contained in the photocurable composition for a support material, include allyl sulfonic acid and isoprene sulfonic acid. , 2- (meth) acrylamide ethyl sulfonic acid, 3- (meth) acrylamide propyl sulfonic acid, 4- (meth) acrylamide butyl sulfonic acid, 2- (meth) acrylamide-2-methylpropan sulfonic acid, p-vinylbenzene sulfonic acid Examples include sodium salts, potassium salts, and ammonium salts of acids and compounds such as vinyl sulfonic acids. The water-soluble ethylenically unsaturated monomer containing the above-exemplified ionic group and counterion may be used alone or in combination of two or more.

As the water-soluble ethylenically unsaturated monomer preferably contained in the photocurable composition for a support material, an acrylic salt is preferable, and alkali metal salts such as lithium, sodium and potassium, ammonium salts, amine salts and the like are used. A monovalent salt of acrylic acid is more preferable, and an alkali metal salt or ammonium salt is more preferable, and a sodium salt, potassium salt or ammonium salt is particularly preferable. Most preferably, it is a potassium salt.

In addition to the above, the water-soluble ethylenically unsaturated monomer preferably contained in the photocurable composition for a support material includes acrylic acids such as zinc salt, magnesium salt, calcium salt, aluminum salt, and neodium salt. It may contain a polyvalent metal salt. The acrylic acid polyvalent metal salt is preferably a zinc salt, a magnesium salt, or a calcium salt.

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

The total content of the monovalent salt and the polyvalent metal salt of acrylic acid is preferably 60% by mass or less, more preferably 50% by mass or less, based on 100% by mass of the photocurable composition for a support material. 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, and further preferably 15% by mass or more.
Above all, 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 a support material. .. By doing so, the viscosity of the composition can be lowered, and the cost can be lowered by suppressing the amount of the acrylate used.

The content of the monovalent salt of acrylic acid is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass in 100% by mass of the photocurable composition for a support material. % Or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and further 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 upper limit in 100% by mass of the photocurable composition for a support material. % Or more, more preferably 10% by mass or more.
When the above is done, the solubility of the photocurable composition for a support material as well as the supportability can be further improved.

Examples of the water-soluble ethylenically unsaturated monomer other than the water-soluble ethylenically unsaturated monomer containing the ionic group and the counterion include (meth) acrylic acid; acryloylmorpholin; N-vinylpyrrolidone; (meth). ) Acrylamide, N, N-dimethylacrylamide, N-hydroxyethylacrylamide, acrylamide such as N-isopropylacrylamide, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2- (2-ethoxyethoxy) ethyl ( Examples thereof include meth) acrylate, glycerol (meth) acrylate, and methoxypolyethylene glycol acrylate.

The total content of the water-soluble monomer (C) contained in the photocurable composition for a support material is preferably 70% by mass or less, more preferably 60% by mass or less, with an upper limit of 100% by mass of the composition. The mass% or less, 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, and particularly preferably more than 20% by mass.

The photocurable composition for a support material may contain an unsaturated monomer other than the water-soluble monomer (C) (for example, a water solubility (20 ° C.) of less than 20 g / L). .. Examples of the other unsaturated monomer 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 (Meta) 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, 2-ethylhexyl carbitol (meth) acrylate, etc. (Meta) Acrylate; Phenylallyl Ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-all monoallyl ether, biphenyl-4-all 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, ethyl hexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxy ethoki. Vinyl ethers such as sivinyl ether, cyclohexyl vinyl ether, and adamantyl vinyl ether; maleimides such as phenylmaleimide, cyclohexylmaleimide, and n-hexylmaleimide; EO addition of benzyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, bisphenol A diacrylate, bisphenol A Monomer having an aromatic group such as bis (meth) acrylate, PO adduct bis (meth) acrylate of bisphenol A, EO adduct bis (meth) acrylate of hydrogenated bisphenol A, and monomer having an alicyclic group; poly Polyoxyalkylene di (meth) acrylates such as oxyethylene di (meth) acrylate and polyoxypropylene di (meth) acrylate; hydroxyalkyl (meth) acrylate and the like can be mentioned.
These may be used alone by 1 type, or may be used in combination of 2 or more type.

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

Further, from the viewpoint of improving the water solubility of the photocurable composition for a support material, the content of the other unsaturated monomer is preferably 0% by mass or more and less than 50% by mass, preferably 0% by mass. It is more preferably less than 40% by mass. When two or more kinds of water-insoluble monomers are contained, the content is the total content of each component.

The photocurable composition for a support material may contain an organic acid and / or a salt thereof. The organic acid and / or a salt thereof is a compound other than the water-soluble monomer (C) and the other unsaturated monomer.
Examples of the organic acid include an organic sulfonic acid such as p-toluene sulfonic acid, an organic phosphoric acid such as phenylphosphonic acid, an organic carboxylic acid, and a phosphoric acid ester. Of these, organic carboxylic acids are preferable. Examples of the organic carboxylic acid include an aliphatic carboxylic acid and an aromatic carboxylic acid. Examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanic acid, octanoic acid, octyl acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid and stearic acid. , Bechenic 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 And so on. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, salicylic acid and the like. Of these, aliphatic carboxylic acids are more preferable, and lactic acid, propionic acid, and polyacrylic acid are even more preferable.
Examples of the salt of the organic acid include a metal carboxylate. 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; zirconium and the like. Of these, alkali metals such as potassium are preferable. As the salt of the organic acid, potassium lactate and potassium propanoate are preferable.
When the photocurable composition for a support material contains an organic acid and / or a salt thereof, the storage stability is further improved.

The content of the organic acid and / or its salt is in the range where the content of water is preferably 10% by mass or less in 100% by mass of the photocurable composition for a support material, and the upper limit is preferably 60% by mass or less. , More preferably 50% by mass or less, further 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 storage stability can be further improved as well as the supportability and solubility of the photocurable composition for the support material.

The photocurable composition for a 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-hydroxycyclohexylphenylketone, 2-methyl-1- [4-( Methylthio) phenyl] -acetophenone compounds such as -2-morpholinopropan-1-one; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxanthone , 2-Isopropylthioxanthone, 2-Chlorothioxanthone, [3- (3,4-dimethyl-9-oxothioxanthen-2-yl) oxy-2-hydroxypropyl] -trimethylazanium chloride and other thioxanthone compounds; acetophenone dimethyl Ketal compounds such as ketal and benzyldimethyl ketal; benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis Phosphine oxides such as-(2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; and mixtures thereof.
These may be used alone by 1 type, or may be used in combination of 2 or more type.
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, still more preferably 0, based on 100% by mass of the composition. .2 to 5.0% by mass.

The photocurable composition for a support material may contain a solvent as long as the effect of the present invention is not impaired. Examples of the solvent 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. Glycol such as, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, glycol ether such as propylene glycol monopropyl ether, glycol ether acetate such as propylene glycol monomethyl ether acetate and the like. Only one type of the solvent may be used, or two or more types may be used in combination.
The solvent is preferably used so that the content of water is 10% by mass or less in 100% by mass of the photocurable composition for a support material. As the solvent, glycol having 3 to 9 carbon atoms, glycol ether, and glycol ether acetate are preferable.

The content of the solvent in 100% by mass of the composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, and preferably 90% by mass as the upper limit. % Or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.

The glycol, glycol ether, and glycol ether acetate having 3 to 9 carbon atoms are preferably contained in an amount of 30 to 90% by mass, preferably 40 to 90% by mass, based on 100% by mass of the composition. Is more preferable.
Above all, the content of propylene glycol in 100% by mass of the above composition is preferably 30 to 90% by mass, and more preferably 35 to 80% by mass.

The photocurable composition for a support material may contain other additives, if necessary, as long as the effects of the present invention are not impaired. Specific examples thereof include photoinitiator aids, polymerization inhibitors, surfactants, colorants, antioxidants, chain transfer agents, fillers and the like. Specific examples of these are the same as those illustrated in the above-mentioned photocurable composition for model materials.

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

The photocurable composition for a support material preferably has excellent curability. The curability is preferably cured by irradiating with light of 100 to 3000 mJ / cm ^{2 , more preferably by irradiating with light of 100 to 2000 mJ / cm 2} , and more preferably 100 to 1000 mJ / cm ^2. It is more preferable to cure by irradiating with the light of. Here, curing means that the liquid is no longer liquid and the fluidity is lost.

In the photocurable composition for a support material, since the cured product after curing is used as the support material, the water solubility of the cured product is excellent as an essential requirement for the support material. The water solubility is preferably dissolved within 1 hour 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 more preferable that it is almost dissolved within 30 minutes, and it is further preferable that it is dissolved within 15 minutes and the insoluble matter is not visually observed.

The content of water in the photocurable composition for a support material is preferably 10% by mass or less, more preferably less than 10% by mass, still more preferably 5% by mass, based on 100% by mass of the photocurable composition for a support material. Hereinafter, it is particularly preferably 3% by mass or less. The lower limit of the water content is preferably 0% by mass. Within such a range, the curability is more excellent, the hardness of the cured product after curing is sufficient, the supportability can be improved, and the solubility in a solvent can be improved. The water content in the photocurable composition for a support material can be calculated from the water content of each compound charged. It can also be obtained by the Karl Fischer measurement method. Supportability (supporting force) is the ability of the cured product of the photocurable composition for the support material to support the cured product of the model material, and the hardness of the cured product of the support material (Showa E) measured by the method described later. ) Can be expressed.

(Hansen solubility parameter distance HSPD)
In the photocurable composition set for a 3D printer of the present invention, 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. When it is contained in the range of 3 (MPa ^1/2 ), the photocurable composition for the model material and the photocurable composition for the support material are excellent in compatibility and water solubility.
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 a support material and isobornyl acrylate. The Hansen solubility parameter represents solubility as a multidimensional vector, which is [δD: dispersion term (Van der Waals force), δP: polar term (dipole moment force), δH: hydrogen. It is represented by the three parameters of [combination term]. That is, the distance between two points between the vector coordinates [δDs, δPs, δHs] of the photocurable composition for the support material and the vector coordinates [δDm, δPm, δHm] of the isobornyl acrylate is the Hansen solubility parameter. The distance is ASPD (MPa ^1/2 ).
The Hansen solubility parameter distance HSPD is expressed by the following formula.

In addition, the Hansen solubility parameter of the mixture is determined to be mixed by the volume ratio of the Hansen solubility parameter of each composition. for example,
Composition _{A ([δD A, δP A} , δH A], a density _d A (g / mL), the weight ratio _w A (wt%))
Composition _{B ([δD B, δP B} , δH B], the density _d B (g / mL), the weight ratio _w B (wt%))
Mixture Hansen solubility parameter of _{1 [δD 1, δP 1,} δH 1] made of is represented by the following formula.

The Hansen solubility parameter distance HSPD (MPa ^1/2 ) can be obtained 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 a 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 photocurable composition for the model material and the photocurable composition for the support material are excellent in compatibility and water solubility. As a result, a composition set having excellent formability is obtained.

When the Hansen solubility parameter distance HSPD between the photocurable composition for the support material and the vector coordinates [δDm, δPm, δHm] of the isobornyl acrylate is ^{smaller than 12.9 MPa 1/2} , the photocurability for the support material The water solubility of the composition and its cured product is reduced. Further, when the Hansen solubility parameter distance HSPD between the photocurable composition for the support material and the vector coordinates [δDm, δPm, δHm] of the isobornyl acrylate is ^{larger than 17.3 MPa 1/2} , the photocuring for the model material is performed. The compatibility between the sex composition and the photocurable composition for a support material becomes low, and the interface state deteriorates. It is preferable that the interface between the photocurable composition for the model material and the photocurable composition for the support material does not become cloudy.

The Hansen solubility parameter distance HSPD between the photocurable composition for a 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 the support material. An appropriate solvent may be added to the photocurable composition for the support material.

In the photocurable composition set for a 3D printer of the present invention, the two photocurable compositions even when the photocurable composition for a model material and the photocurable composition for a support material are simultaneously discharged. By having an appropriate compatibility at the interface between the two, the photocurable composition for a support material and the cured product thereof are preferably excellent in water solubility and excellent in moldability. can.

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

If necessary, the above composition may contain other additives as long as the effects of the present invention are not impaired. Other additives include, for example, emulsion stabilizers, penetration promoters, UV absorbers, preservatives, fungicides, rust preventives, pH adjusters, surface tension regulators, defoamers, viscosity regulators, dispersions. Known additives such as agents, dispersion stabilizers, chelating agents, anti-drying agents (wetting agents), colorants, anti-fading agents, specific resistance regulators, film regulators, antioxidants, and surfactants can be mentioned. .. These various additives can be added directly to the composition, for example.

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

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

[Cartridge for inkjet 3D printer]
Inkjet 3D printer cartridges are filled with the above compositions. The cartridge for an inkjet 3D printer may be filled with the above composition, and a known form of the cartridge for an inkjet 3D printer can be used.

[Stereolithography]
The stereolithographic product of the present invention is obtained by photocuring the above-mentioned photocurable composition set for a 3D printer. Since the stereolithographic product of the present invention uses the above-mentioned photocurable composition set for a 3D printer of the present invention, the above-mentioned photocurable composition for a model material and the above-mentioned photocurable composition for a support material are simultaneously used. Even when discharged, it is possible to provide a stereolithographic product having excellent formability by having an appropriate compatibility at the interface between the two photocurable compositions.

[Manufacturing method of stereolithography]
The method for producing a stereolithographic product of the present invention includes the step (I) of photocuring the above-mentioned photocurable composition set for a 3D printer of the present invention to obtain a cured product, and light for a support material from the cured product. The curable composition comprises a step (II) of removing the photocured cured product.

The photocurable composition for a model material and the photocurable composition for a support material included in the photocurable composition set for a 3D printer of the present invention can be prepared by using the above-mentioned various components, 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, a ball mill, a kitty mill, a disc mill, a pin mill, a dyno mill, etc. Examples thereof include a method of stirring and mixing using a device capable of mixing or stirring. After preparing the solution, filtration may be performed using various filters.

In the above step (I), preferably by an inkjet stereolithography method, the above-mentioned photocurable composition set for a 3D printer of the present invention is photocured to obtain a cured product. In the step (I), a known method can be used other than using the photocurable composition for a model material and the photocurable composition for a support material. Specifically, the photocurable composition for a model material and the photocurable composition for a support material included in the photocurable composition set for a 3D printer of the present invention are molded by injection, printing, etc. from each nozzle. After that, a known method such as irradiating ultraviolet rays of about 100 to 3000 mJ / cm ² and photo-curing to obtain a cured product can be used. The ultraviolet irradiation is more preferably 100 to 2000 mJ / cm ² light, and even more preferably 100 to 1000 mJ / cm ² light.

In the 3D printer stereolithography method, the cured product of the photocurable composition for the support material supports the outer shape of the photocurable composition for the model material, so that the two are in contact with each other to form an interface. The photocurable composition for the model material and the photocurable composition for the support material may be jetted, printed, or the like from each nozzle at the same time.

Subsequently, in the step (II), the cured product obtained by photocuring the photocurable composition for the support material is removed from the cured product. The cured product obtained by photocuring the photocurable composition for a model material and the photocurable composition for a support material included in the photocurable composition set for a 3D printer of the present invention is a photocurable product for a support material. Since the cured product of the portion obtained by photo-curing the sex composition is excellent in water solubility, the cured product of this portion can be easily removed with a polar solvent such as water. As a removing method, from the viewpoint of safety and cost, a method of allowing the cured product to stand in water to remove the composition for the support material is preferable.

In the method for producing a stereolithographic article of the present invention, the photocurable composition for a model material and the photocurable composition for a support material are used, and the photocurable composition for a model material and the photocurable composition for a support material are used. Since the cured product of the photocurable composition for a support material is preferably excellent in water solubility because it has an appropriate compatibility with an object, it is excellent in formability. The modeled product 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 following examples as well as the present invention, and appropriate modifications are made to the extent that it can be adapted to the gist of the above and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.

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

<Photocurable composition for support material>
The water-soluble monomers and solvents shown in Tables 2 to 4 were uniformly mixed using an amount (parts by mass) shown in Tables 2 to 4 using a mixing and stirring device, and each of Examples and Comparative Examples was used. A photocurable composition for a support material was prepared.

<Hansen solubility parameter>
For the Hansen solubility parameter of the photocurable composition for support material and the vector coordinates [δDm, δPm, δHm] of isobornyl acrylate, a dissolution experiment was conducted in a solvent having a known Hansen solubility parameter, and the actual measurement result was obtained by commercially available software. It was input to HSPiP 5.1.03 and determined by the Vector function.
The Hansen solubility parameter of isobornyl acrylate was as follows.
Hansen solubility parameter δD: 17.0 MPa ^1/2
δP: 3.1 MPa ^1/2
δH: 3.7 MPa ^1/2

<Hansen solubility parameter distance HSPD (MPa ^1/2 )>
^{The Hansen solubility parameter distance HSPD (MPa 1/2} ) between the photocurable composition for a support material and the vector coordinates [δDm, δPm, δHm] of isobornyl acrylate was measured using commercially available software HSPiP 5.1.03. I asked for each.
Tables 2 to 4 show ^{the Hansen solubility parameter distance HSPD (MPa 1/2} ) between the photocurable composition for each support material and the isobornyl acrylate.

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

<Water solubility test>
3.0 g of a cured product piece obtained by curing the obtained photocurable composition for each support material was placed in a 10 mL screw tube, 2.7 g of water was added, and the water solubility was evaluated. The evaluation criteria are as follows. The results are shown in Tables 2-4.
◯: The cured product does not remain and dissolves.
X: A cured product remains.

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

The compound names in Tables 1 to 4 are as follows.
IBOA: Isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)
ACMO: Acryloyl morpholine (manufactured by Tokyo Chemical Industry Co., Ltd.)
DCP-A: Dimethylol-tricyclodecanediacrylate (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.)
AA ₂ Zn: Zinc acrylate (manufactured by Nippon Shokubai Co., Ltd.)
PEGA: Methoxypolyethylene glycol # 400 acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
NVP: N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd.)
HEAA: 2-Hydroxyethyl acrylamide (manufactured by Tokyo Chemical Industry 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 Chemical Co., Inc.)
DPGMPE: Dipropylene glycol monopropyl ether (manufactured by Kanto Chemical Co., Inc.)
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 photopolymerization initiator (B), and
A photocurable composition for a support material containing a water-soluble monomer (C) and a photopolymerization initiator (D).
The Hansen solubility parameter distance HSPD between the photocurable composition for the support material and the isobornyl acrylate is within the range of ^{12.9 (MPa 1/2} ) <HSPD <17.3 (MPa ^{1/2), 3D.} Photocurable composition set for printers. A stereolithographic product obtained by photocuring the photocurable composition set for a 3D printer according to claim 1. The step (I) of photocuring the photocurable composition set for a 3D printer according to claim 1 to obtain a cured product, and the cured product obtained by photocuring the photocurable composition for a support material from the cured product. Step (II)
A method for manufacturing a stereolithography product, including.

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