A photocurable composition for forming support material for inkjet 3D printers, inkjet 3D printer ink and inkjet 3D printer cartridge containing the same, and a method for manufacturing support material and a method for manufacturing stereolithography using the photocurable composition.

Abstract

To provide a photo-curable composition for forming a support material for inkjet three-dimensional printers, which has excellent solubility in a solvent of a cured material (support material) by photo-curing and also produces molded objects with excellent moldability.SOLUTION: The photo-curable composition for forming support materials for inkjet three-dimensional printers contains alkoxy polyalkylene glycol methacrylate (A) and a water-soluble monomer (B) which is a compound other than alkoxy polyalkylene glycol methacrylate (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photocurable composition for forming support material for inkjet 3D printers, an inkjet 3D printer ink containing the same, an inkjet 3D printer cartridge, and a method for manufacturing support material and a method for manufacturing stereolithography using the photocurable composition. [Background technology]

[0002] In recent years, a photopolymerization method using an inkjet system has been proposed for inkjet 3D printers, in which a liquid photocurable composition extruded from an inkjet nozzle is cured and layered to create a stereopolymer. The inks used for inkjet 3D printers employing this stereopolymerization method include a photocurable model material composition that forms a molded body (model material) through photocuring with UV light, and a photocurable composition that forms support material through photocuring with UV light when stacking the model material three-dimensionally. After layering the photocured model material on top of the photocured support material, the support material can be removed to create overhang structures and hollow structures.

[0003] Patent Document 1 describes a photocurable support material composition for inkjet 3D printers, comprising a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion, and a photopolymerization initiator, with the aim of providing a photocurable support material composition for inkjet 3D printers in which the cured product has excellent water solubility and sufficient hardness.

[0004] Patent Document 2 describes a photocurable support material composition for inkjet 3D printers that has excellent curability, sufficient hardness of the cured product after curing, and excellent solubility of the cured product in a solvent. The composition contains a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion, and the water content is 10% by mass or less per 100% by mass of the photocurable composition.

[0005] Furthermore, there was a need for a photocurable composition for forming support materials for inkjet 3D printers that exhibits excellent solubility of the cured material (support material) in solvents, as well as producing molded objects with excellent formability. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2018 / 043582 [Patent Document 2] International Publication No. 2019 / 167948 [Overview of the project] [Problems that the invention aims to solve]

[0007] Accordingly, the object of the present invention is to provide a photocurable composition for forming support material for inkjet 3D printers that yields a molded product with excellent solubility in a solvent and excellent moldability, an ink for inkjet 3D printers and a cartridge for inkjet 3D printers containing the same, and a method for manufacturing support material and a method for manufacturing a stereolithographic product using the photocurable composition. [Means for solving the problem]

[0008] As a result of diligent research to solve the above problems, the present inventors have found that by including alkoxy polyalkylene glycol methacrylate (A) and a water-soluble monomer (B) other than alkoxy polyalkylene glycol methacrylate (A), it is possible to provide a photocurable composition for forming support material for inkjet 3D printers that exhibits excellent solubility in the solvent of the cured product (support material) when photocured, and also produces a molded product with excellent moldability, thus completing the present invention.

[0009] In other words, the photocurable composition for forming support material for inkjet 3D printers according to the present invention comprises an alkoxypolyalkylene glycol methacrylate (A) and a water-soluble monomer (B) which is a compound other than the alkoxypolyalkylene glycol methacrylate (A). The above-mentioned photocurable composition for forming support material for inkjet 3D printers preferably further contains a photopolymerization initiator.

[0010] Furthermore, the ink for inkjet 3D printers of the present invention includes any of the above-mentioned photocurable compositions for forming support materials for inkjet 3D printers.

[0011] Furthermore, the inkjet 3D printer cartridge of the present invention is filled with the above-mentioned inkjet 3D printer ink.

[0012] Furthermore, in the method for manufacturing support materials of the present invention, support materials are formed using any of the above-mentioned photocurable compositions for forming support materials for inkjet 3D printers or the above-mentioned inkjet 3D printer inks.

[0013] Furthermore, the present invention relates to a method for manufacturing a stereolithographic product using any of the above-described photocurable compositions for forming support materials for inkjet 3D printers or inks for inkjet 3D printers, comprising: a step of forming a support material using the photocurable composition or ink; a step of forming a model material; and a step of removing the support material. [Effects of the Invention]

[0014] According to the present invention, a photocurable composition for forming support material for inkjet 3D printers is provided, which yields a cured product (support material) with excellent solubility in a solvent when cured by light and a molded product with excellent formability. The present invention also provides an inkjet 3D printer ink and an inkjet 3D printer cartridge containing the same, as well as a method for manufacturing support material and a method for manufacturing stereolithography using the photocurable composition. [Modes for carrying out the invention]

[0015] 1. Photocurable composition for forming support material for inkjet 3D printers The photocurable composition for forming support material for inkjet 3D printers of the present invention (hereinafter sometimes simply referred to as the photocurable composition) comprises an alkoxypolyalkylene glycol methacrylate (A) and a water-soluble monomer (B) which is a compound other than the alkoxypolyalkylene glycol methacrylate (A). According to the photocurable composition of the present invention, the cured product (support material) obtained by curing the photocurable composition with light exhibits excellent solubility in solvents and yields a molded product with excellent formability.

[0016] In this specification, "excellent formability" means that, in an inkjet 3D printer, after photocuring the photocurable composition for support material formation and the photocurable composition for model material formation, when the cured support material is dissolved and removed with a solvent, the surface of the model material that was in contact with the support material is clean (not rough). One indicator of such formability is the compatibility of the photocurable composition for support material formation with hydrophobic monomers, and when the compatibility of the photocurable composition for support material formation with hydrophobic monomers is excellent, the formability is also excellent.

[0017] 1-1 Alkoxypolyalkylene glycol methacrylate (A) The photocurable composition of the present invention comprises alkoxy polyalkylene glycol methacrylate (A) and a water-soluble monomer (B). The inclusion of these elements results in excellent solubility of the cured material (support material) in the solvent, as well as the ability to produce molded objects with superior formability. Alkoxy polyalkylene glycol methacrylate (A) is a monomer that polymerizes upon exposure to light or other light sources.

[0018] Examples of the alkoxy group in the alkoxypolyalkylene glycol methacrylate (A) contained in the photocurable composition of the present invention include a methoxy, ethoxy, propoxy, or butoxy group, etc., among which a methoxy group is preferred. Examples of the alkylene group in the alkoxypolyalkylene glycol methacrylate (A) include a methylene, ethylene, propylene, or butylene group, etc., among which an ethylene or propylene group is preferred.

[0019] Examples of the alkoxypolyalkylene glycol methacrylate (A) include compounds represented by the following chemical formula (1) or (2).

[0020]

Chemical formula

[0021]

Chemical formula

[0022] In the above chemical formulas (1) and (2), n is an integer of 2 or more. In the above chemical formulas (1) and (2), n is preferably from 2 to 90, more preferably 4 or more. The upper limit is more preferably 50 or less, even more preferably 25 or less, and particularly preferably 23 or less.

[0023] Examples of the above-mentioned alkoxy polyalkylene glycol methacrylate (A) include methoxydiethylene glycol EO2 methacrylate (a compound where n=2 in chemical formula (1) above), methoxytetraethylene glycol EO4 methacrylate (a compound where n=4 in chemical formula (1) above), methoxy polyethylene glycol EO9 methacrylate (a compound where n=9 in chemical formula (1) above), methoxy polypropylene glycol PO9 methacrylate (a compound where n=9 in chemical formula (2) above), methoxy polyethylene glycol EO13 methacrylate (a compound where n=13 in chemical formula (1) above), polypropylene glycol PO13 methacrylate (a compound where n=13 in chemical formula (2) above), methoxy polyethylene glycol EO23 methacrylate (a compound where n=23 in chemical formula (1) above), methoxy polyethylene glycol EO45 methacrylate (a compound where n=45 in chemical formula (1) above), or methoxy polyethylene glycol EO90 methacrylate (a compound where n=90 in chemical formula (1) above).

[0024] The above alkoxy polyalkylene glycol methacrylate (A) may be a mixture in which at least one of the alkoxy group, alkylene chain, and n in the above chemical formula (1) or (2) is different. If the above alkoxy polyalkylene glycol methacrylate (A) is a mixture in which the value of n in the above chemical formula (1) or (2) is different, then n may be the average value thereof.

[0025] As the above-mentioned alkoxy polyalkylene glycol methacrylate (A), a commercially available product can be used. Preferred commercially available products include NK ester M-20G, M-40G, M-90G, M-130G, M-230G, or M-450G manufactured by Shin Nakamura Chemical Industry Co., Ltd., or Bremmer PME-100, PME-200, PME-400, PME-1000, or PME-4000 manufactured by NOF Corporation.

[0026] The molecular weight of the above alkoxy polyalkylene glycol methacrylate (A) is not limited. A weight-average molecular weight of approximately 160 or more is preferred, and 4500 or less is preferred.

[0027] The weight-average molecular weight can be measured using the following apparatus under the following conditions. Equipment: Tosoh High-Speed ​​GPC System (HLC-8320GPC) Detector: RI Column: SHODEX Asahipak manufactured by Showa Denko GF-310-HQ, GF-710-HQ, GF-1G 7B Column temperature: 40℃ Flow rate: 0.5ml / min Calibration curve: POLYACRYLIC ACID STANDARD, manufactured by Sowa Kagaku Co., Ltd. Eluent: 0.1N sodium acetate aqueous solution / acetonitrile = 3 / 1 (by weight)

[0028] The content of alkoxy polyalkylene glycol methacrylate (A) in the above photocurable composition is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, out of 100% by mass of the composition. When the content is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in the solvent and produces molded products with superior moldability. If two or more types of alkoxy polyalkylene glycol methacrylate (A) are included, the content is the sum of the content of each component.

[0029] Furthermore, the content of the alkoxy polyalkylene glycol methacrylate (A) relative to 100% by mass of the total amount of monomers contained in the above photocurable composition is preferably 10 to 70% by mass, and more preferably 20 to 60% by mass. If two or more types of alkoxy polyalkylene glycol methacrylate (A) are included, the content is the sum of the content of each component. The alkoxy polyalkylene glycol methacrylate (A) and water-soluble monomer (B) are monomers and are included in 100% by mass of the total amount of monomers.

[0030] 1-2 Water-soluble monomer (B) The water-soluble monomer (B) contained in the photocurable composition of the present invention is not particularly limited as long as it is a compound other than the alkoxypolyalkylene glycol methacrylate (A) described above and has a water solubility (20°C) of 20 g / L or more, and may be an ionic monomer containing an ionic group and a counterion, or a nonionic monomer. Among these, an ionic monomer containing an ionic group and a counterion is preferred, and a monomer having one or more ethylenically unsaturated groups in its molecule is preferred. More preferably, it is a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion. Note that a monomer refers to a compound that polymerizes by light or the like. The water-soluble ethylenically unsaturated monomer containing the above-mentioned ionic group and counterion exhibits high water solubility due to the presence of the ionic group and counterion. 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.

[0031] The content of the water-soluble monomer (B) in the above-mentioned photocurable composition is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and preferably 5% by mass or more, and more preferably 10% by mass or more, per 100% by mass of the composition. When the content is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in the solvent and can produce molded products with superior moldability.

[0032] Furthermore, the content of the above-mentioned water-soluble monomer (B) relative to 100% by mass of the total amount of monomers contained in the above-mentioned photocurable composition is preferably 30 to 100% by mass, and more preferably 40 to 100% by mass, from the viewpoint of improving water solubility. If two or more types of the above-mentioned water-soluble monomer (B) are included, the content is the sum of the content of each component.

[0033] Examples of the above-mentioned ethylenically unsaturated groups include ethylene, propenyl, butenyl, vinylphenyl, (meth)acrylic, allyl ether, vinyl ether, maleyl, maleimide, (meth)acrylamide, acetylvinyl, or vinylamide. In this specification, "(meth)acrylic" means either or both "acrylic" and "methacrylic," and "(meth)acrylate" means either or both "acrylate" and "methacrylate." Among these, (meth)acrylic, vinyl ether, or (meth)acrylamide is preferred, and (meth)acrylic is more preferred.

[0034] Examples of the ionic group mentioned above include carboxylic acids, phosphoric acid, or sulfonic acid. Among these, carboxylic acids are preferred.

[0035] Examples of the above-mentioned counterions include alkali metal ions such as sodium ions or potassium ions, monovalent counterions such as ammonium ions, or polyvalent metal ions such as zinc ions, magnesium ions, calcium ions, aluminum ions, or neodymium ions. Among these, monovalent counterions are preferred, alkali metal ions such as sodium ions or potassium ions, or ammonium ions are more preferably used, and alkali metal ions are even more preferably used, with potassium ions being particularly preferred. In addition to monovalent counterions, it is also preferable to use polyvalent metal ions such as zinc ions, magnesium ions, calcium ions, aluminum ions, or neodymium ions.

[0036] 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 support properties of the cured product obtained by photocuring the photocurable composition can be further improved. Furthermore, in addition to these, it is a preferred embodiment of the present invention to be used in combination with organic acids and / or salts thereof as described later. The polyvalent metal ions are preferably zinc ions, magnesium ions, or calcium ions.

[0037] The content of the water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion, which is preferably included in the above photocurable composition, is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and preferably 5% by mass or more, and more preferably 10% by mass or more, per 100% by mass of the above composition. When the content is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in the solvent and can produce molded products with superior moldability.

[0038] Furthermore, the content of the water-soluble ethylenically unsaturated monomer containing the ionic group and counterion, relative to 100% by mass of the total amount of monomers in the above photocurable composition, is preferably 40 to 100% by mass, and more preferably 50 to 100% by mass, from the viewpoint of improving the water solubility of the above photocurable composition. If two or more water-soluble ethylenically unsaturated monomers containing the ionic group and counterion are included, the content is the sum of the content of each component.

[0039] The total content of a water-soluble ethylenically unsaturated monomer containing a monovalent counterion and a water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion as a counterion is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, per 100% by mass of the photocurable composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. When the content is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in the solvent and produces a molded product with superior moldability.

[0040] The content of a water-soluble ethylenically unsaturated monomer containing a monovalent counterion as a counterion is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, per 100% by mass of the photocurable composition. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. When the content is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in the solvent and produces molded products with superior moldability.

[0041] The content of water-soluble ethylenically unsaturated monomers containing polyvalent metal ions as counterions is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably 5% by mass or more, and more preferably 10% by mass or more, per 100% by mass of the photocurable composition. When the content is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in solvents and produces molded products with superior moldability.

[0042] Examples of water-soluble ethylenically unsaturated monomers containing a carboxylic acid and a counterion as an ionic group, included in the above-mentioned photocurable composition, include acrylic acid, methacrylic acid, maleic acid, fumaric acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, N-(meth)acryloylaspartic acid, or monovalent salts such as alkali metal salts (sodium or potassium salts) or ammonium salts of ω-(meth)acroylalkane-1,1dicarboxylic acids; or polyvalent salts such as zinc salts, magnesium salts, calcium salts, aluminum salts, or neodymium salts. Among these, alkali metal salts such as sodium salts and potassium salts, or monovalent salts such as ammonium salts are preferred, and sodium salts, potassium salts, or ammonium salts are more preferred. Potassium salts are even more preferred.

[0043] When a monovalent salt of a carboxylic acid and a polyvalent metal salt are used in combination, the support properties of the cured product obtained by photocuring the photocurable composition can be further improved. Furthermore, in addition to these, a preferred embodiment of the present invention is to use them in combination with organic acids and / or their salts as described later. The polyvalent metal salt of the carboxylic acid is preferably a zinc salt, a magnesium salt, or a calcium salt.

[0044] The total content of monovalent carboxylic acid salts and polyvalent metal salts is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, per 100% by mass of the photocurable composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. When the content is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in the solvent and produces molded products with superior moldability.

[0045] The content of the monovalent salt of the 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, per 100% by mass of the photocurable composition. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. When the content is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in the solvent and produces molded products with superior moldability.

[0046] The content of polyvalent metal salts of carboxylic acids is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably 5% by mass or more, and more preferably 10% by mass or more, per 100% by mass of the photocurable composition. When the content is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in the solvent and produces molded products with superior moldability.

[0047] As a water-soluble ethylenically unsaturated monomer containing a carboxylic acid and a counterion as an ionic group, a sodium, potassium, zinc, or calcium salt of the carboxylic acid with 3 to 15 carbon atoms is preferred, and a sodium, potassium, zinc, or calcium salt with 3 to 12 carbon atoms is more preferred. More preferably, a carbon number of 3 to 9 is preferred, and a carbon number of 3 to 6 is even more preferred. Among these, potassium (meth)acrylate, sodium (meth)acrylate, zinc (meth)acrylate, or 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 reduced, and the water solubility of the water-soluble ethylenically unsaturated monomer can be further increased.

[0048] Examples of water-soluble ethylenically unsaturated monomers containing phosphoric acid and counterions as ionic groups, preferably included in the above photocurable composition, 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, methachloroyloxyethyl acid phosphate, and phosphooxypolyoxyethylene glycol monomethac Examples include sodium salts, potassium salts, or ammonium salts of compounds having a phosphono group in the molecule, such as relate, acid phosphopolyoxypropylene 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, vinyl phosphate, or p-vinylbenzene phosphate.

[0049] Examples of water-soluble ethylenically unsaturated monomers containing sulfonic acid as an ionic group and a counterion, preferably included in the above-mentioned photocurable composition, include sodium salts, potassium salts, or ammonium salts of compounds such as allyl sulfonic acid, 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-methylpropane sulfonic acid, p-vinylbenzene sulfonic acid, or vinyl sulfonic acid. The above-exemplary water-soluble ethylenically unsaturated monomers containing an ionic group and a counterion may be used individually or in combination of two or more.

[0050] The water-soluble ethylenically unsaturated monomer preferably included in the above photocurable composition is preferably an acrylate salt, more preferably a monovalent salt of acrylic acid such as an alkali metal salt such as lithium, sodium, or potassium, an ammonium salt, or an amine salt, even more preferably an alkali metal salt or an ammonium salt, and particularly preferably a sodium salt, potassium salt, or ammonium salt. Most preferably a potassium salt.

[0051] In addition to the above, the photocurable composition may also contain polyvalent metal salts of acrylic acid, such as zinc salts, magnesium salts, calcium salts, aluminum salts, or neodymium salts. The polyvalent metal salts of acrylic acid are preferably zinc salts, magnesium salts, or calcium salts.

[0052] When a monovalent salt of acrylic acid is used in combination with a polyvalent metal salt, the support properties of the cured product obtained by photocuring the photocurable composition can be further improved. A preferred combination of monovalent acrylic acid and polyvalent metal salt is potassium acrylate and zinc acrylate. By using zinc acrylate in combination, a cured product with higher strength can be obtained.

[0053] The total content of monovalent acrylic acid salts and polyvalent metal salts is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, per 100% by mass of the photocurable composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. In particular, the total content of potassium acrylate and zinc acrylate is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass, of 100% by mass of the photocurable composition. By doing so, the viscosity of the composition can be lowered, and costs can also be reduced by suppressing the amount of acrylate used.

[0054] Furthermore, the content of monovalent acrylic acid is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, per 100% by mass of the photocurable composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The content of polyvalent metal salts in acrylic acid is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably 5% by mass or more, and more preferably 10% by mass or more, per 100% by mass of the photocurable composition. In the manner described above, it becomes possible to obtain a photocurable composition that exhibits superior solubility in the solvent of the cured product (support material) produced by photocuring of the photocurable composition, as well as superior moldability.

[0055] Other water-soluble ethylenically unsaturated monomers besides the water-soluble ethylenically unsaturated monomers containing the above-mentioned ionic group and counterion include (meth)acrylic acid; acryloylmorpholine; N-vinylpyrrolidone; acrylamides such as (meth)acrylamide, N,N-dimethylacrylamide, N-hydroxyethylacrylamide, or N-isopropylacrylamide; methoxytriethylene glycol (meth)acrylate; ethoxydiethylene glycol (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; glycerol (meth)acrylate; or methoxypolyethylene glycol EO9 acrylate.

[0056] The above water-soluble monomer (B) preferably further contains a crosslinking component. The crosslinking component is preferably a polyvalent metal salt of (meth)acrylic acid.

[0057] The ratio of alkoxypolyalkylene glycol methacrylate (A) to water-soluble monomer (B) contained in the above photocurable composition is preferably alkoxypolyalkylene glycol methacrylate (A):water-soluble monomer (B) = 1 to 99:99 to 1 by mass ratio, and more preferably 30 to 70:70 to 30. When the ratio is within this range, it is possible to obtain a photocurable composition in which the cured product (support material) obtained by photocuring of the photocurable composition has superior solubility in the solvent and produces a molded product with superior moldability.

[0058] 1-3 Other monomers The above photocurable composition may contain other monomers (for example, those with a water solubility (20°C) of less than 20 g / L) other than the above alkoxy polyalkylene glycol methacrylate (A) and the above water-soluble monomer (B). Examples of the above other monomers include other unsaturated monomers, specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, and Uryl (meth)acrylate, Tridecyl (meth)acrylate, Isomiristyl (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) (Meth)acrylates such as acrylate, 2-cyanoethyl (meth)acrylate, methyl-2-(hydroxymethyl)acrylate, and 2-ethylhexylcarbitol (meth)acrylate; allyl ethers such as 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 cyclohexanemethanol monoallyl ether;Examples include vinyl ethers such as 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, and adamantyl vinyl ether; maleimides such as phenyl maleimide, cyclohexyl maleimide, and n-hexyl maleimide; monomers having aromatic groups or alicyclic groups such as benzyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, bisphenol A diacrylate, bis(meth)acrylate (EO adduct of bisphenol A), bis(meth)acrylate (PO adduct of bisphenol A), or bis(meth)acrylate (EO adduct of hydrogenated bisphenol A); polyoxyalkylenedi(meth)acrylates such as polyoxyethylene di(meth)acrylate or polyoxypropylene(meth)acrylate; or hydroxyalkyl(meth)acrylates. These can be used individually or in combination of two or more types.

[0059] The content of the other monomers mentioned above is preferably 50% by mass or less of 100% by mass of the above composition. More preferably 30% by mass or less, even more preferably 10% by mass or less, and particularly preferably less than 2% by mass. In this case, the odor of the photocurable composition can be further suppressed.

[0060] 1-4 Organic acids and / or their salts The above photocurable composition may contain an organic acid and / or a salt thereof. The organic acid and / or salt thereof is a compound other than the above alkoxy polyalkylene glycol methacrylate (A), the above water-soluble monomer (B), and the above other unsaturated monomer. Examples of organic acids include organic sulfonic acids such as p-toluenesulfonic acid, organic phosphoric acids such as phenylphosphonic acid, organic carboxylic acids, or phosphate esters. Organic carboxylic acids are preferred among these. Examples of organic carboxylic acids include aliphatic carboxylic acids or 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, octicic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, 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, or polylactic acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, or salicylic acid. Among these, aliphatic carboxylic acids are more preferred, and lactic acid, propionic acid, or polyacrylic acid are even more preferred. Examples of salts of organic acids include metal carboxylates. Examples of metals in metal carboxylates include alkali metals such as lithium, sodium, or potassium; alkaline earth metals such as magnesium, calcium, strontium, or barium; zinc; or zirconium. Among these, alkali metals such as potassium are preferred. As for salts of organic acids, potassium lactate or potassium propionate are preferred. The above photocurable composition exhibits improved storage stability when it contains an organic acid and / or a salt thereof.

[0061] The content of organic acids and / or their salts is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and preferably 1% by mass or more, per 100% by mass of the photocurable composition. In this case, the storage stability of the photocurable composition can be further improved.

[0062] 1-5 Photopolymerization initiators The above photocurable composition may contain a photopolymerization initiator. Examples of photopolymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, or benzoin isobutyl ether; acetophenone compounds such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, or 2-amylanthraquinone; and 2,4-diethylthiooxant Examples include thioxanthone compounds such as 2-isopropylthioxanthone, 2-chlorothioxanthone, or [3-(3,4-dimethyl-9-oxothioxanthene-2-yl)oxy-2-hydroxypropyl]-trimethylazanium chloride; ketal compounds such as acetophenone dimethyl ketal or benzyl dimethyl ketal; benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, or bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; or mixtures thereof. These can be used individually or in combination of two or more types. The photopolymerization initiator content 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, based on 100% by mass of the above composition.

[0063] 1-6 Solvents The above photocurable composition may contain a solvent insofar as it does not impair the effects of the present invention. Examples of the solvent include water; monohydric alcohols such as methanol, ethanol, or propanol; glycols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene glycol, 1,2-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, or polyoxypropylene glycol; glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, or propylene glycol monopropyl ether; or glycol ether acetates such as propylene glycol monomethyl ether acetate. Only one of the above solvents may be used, or two or more may be used in combination.

[0064] The solvent may preferably include glycol, glycol ether, or glycol ether acetate, and more preferably glycol. Among glycols, glycols containing alkylene chains with 2 to 6 carbon atoms as the alkylene chain constituting the glycol molecule are preferred, glycols containing alkylene chains with 2 and / or 3 carbon atoms are more preferred, and glycols containing alkylene chains with 3 carbon atoms are even more preferred.

[0065] Examples of glycols containing an alkylene chain with two carbon atoms include, for example, polyethylene glycol such as ethylene glycol, diethylene glycol, or triethylene glycol. Examples of glycols containing an alkylene chain with three carbon atoms include, for example, polypropylene glycol such as propylene glycol, dipropylene glycol, or tripropylene glycol.

[0066] Examples of glycols containing alkylene chains with 2 and 3 carbon atoms include polyalkylene glycols containing ethylene chains and propylene chains as alkylene chains.

[0067] The glycol described above preferably includes a glycol in which the total number of carbon atoms in all alkylene chains contained in one molecule (also referred to as the total number of carbon atoms in the alkylene chain) is 2 and / or 3, more preferably includes ethylene glycol and / or propylene glycol, and even more preferably includes propylene glycol.

[0068] When polyalkylene glycol is used as the glycol, it is preferable that the polyalkylene glycol has a total alkylene chain with 4 to 30 carbon atoms. It is more preferable that the glycol has a total alkylene chain with 25 carbon atoms or less. It is even more preferable that the polyalkylene glycol contains alkylene chains with 2 and / or 3 carbon atoms, and that the total alkylene chain with carbon atoms is within the above range.

[0069] The glycol preferably includes a glycol containing an alkylene chain having 2 or 3 carbon atoms, and having a total alkylene chain with 2 or 3 carbon atoms, and a polyalkylene glycol containing an alkylene chain having 2 and / or 3 carbon atoms, and having a total alkylene chain with 4 to 30 carbon atoms.

[0070] The total content of the glycol, glycol ether, and glycol ether acetate is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, based on 100% by mass of the solvent. Furthermore, the content of the glycol is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, based on 100% by mass of the solvent.

[0071] The above solvent is preferably used such that the water content is 10% by mass or less per 100% by mass of the photocurable composition. The water content in the above photocurable composition is more preferably less than 10% by mass, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less per 100% by mass of the photocurable composition. The lower limit of the water content is preferably 0% by mass. By keeping it within this range, the support properties can be improved.

[0072] The water content in a photocurable composition can be calculated from the water content of each compound used. It can also be determined using the Karl Fischer assay. Support (support strength) refers to the ability of the cured product of a photocurable composition to support the cured model material; for example, 100 mW / cm². 2 It is preferable to cure the material by irradiating it with ultraviolet light for 10 seconds.

[0073] In 100% by mass of the above composition, the content of the above solvent is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0074] The glycol containing the above-mentioned alkylene chain having 2 or 3 carbon atoms, and the total number of carbon atoms in the alkylene chain being 2 or 3, and the polyalkylene glycol containing the above-mentioned alkylene chain having 2 and / or 3 carbon atoms, and the total number of carbon atoms in the alkylene chain being 4 to 30, preferably together make up 30 to 90% by mass of the above composition, and more preferably 40 to 90% by mass. In particular, the content of propylene glycol in the above composition is preferably 30 to 90% by mass, and more preferably 35 to 80% by mass.

[0075] 1-7 Other Additives The above-mentioned photocurable composition may contain other additives as needed, provided that they do not impair the effects of the present invention. Specifically, examples include photoinitiators, polymerization inhibitors, surfactants, colorants, antioxidants, chain transfer agents, or fillers.

[0076] Examples of photoinitiation aids include tertiary amine compounds such as N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethylamino-p-benzoate ethyl ester, N,N-dimethylamino-p-benzoate isoamyl ethyl ester, N,N-dihydroxyethylaniline, triethylamine, or N,N-dimethylhexylamine.

[0077] Polymerization inhibitors include (alkyl)phenol, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino-1,3-dimethylbutylidene)aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, or cyclohexanone oxime.

[0078] Examples of surfactants include PEG-type nonionic surfactants such as ethylene oxide (EO) adducts of nonylphenol (hereinafter abbreviated as EO) 1 to 40 molars, or stearate EO adducts 1 to 40 molars; polyhydric alcohol-type nonionic surfactants such as sorbitan palmitate monoester, sorbitan stearate monoester, or sorbitan stearate triester; fluorine-containing surfactants such as perfluoroalkyl EO adducts 1 to 50 molars, perfluoroalkyl carboxylates, or perfluoroalkyl betaine; or modified silicone oils such as polyether-modified silicone oil or (meth)acrylate-modified silicone oil.

[0079] Examples of colorants include toluidine red, permanent carmine FB, fast yellow G, disazo yellow AAA, disazo orange PMP, soluble azo pigments, condensed azo pigments, chelate azo pigments, phthalocyanine blue, indanthron blue, quinacridone red, dioxazine violet, basic dyes, acid dyes, aniline black, daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, or inorganic pigments such as metal oxides or carbon black.

[0080] Examples of antioxidants include 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, dilauryl 3,3'-thiodipropionate, triphenyl phosphite, octylated diphenylamine, 2,6-di-t-butyl-p-cresol, or 2,2'-methylenebis(4-methyl-6-t-butylphenol).

[0081] Examples of 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-propylaldehyde, 1-pentylaldehyde, phenol, m-cresol, p-cresol, or o-cresol.

[0082] Examples of 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, rayon fiber, microballoons, carbon black, metal sulfides, or wood powder.

[0083] The above additives may be used individually or in combination of two or more. The content of the above additive is preferably 0.05 to 30% by mass, and more preferably 0.05 to 20% by mass, of 100% by mass of the above composition.

[0084] The above-mentioned photocurable composition can be prepared using the various components described above, and the means and conditions for preparation are not particularly limited. For example, a method of stirring and mixing can be used with a general stirring blade or a mixing or stirring device such as an ultrasonic homogenizer, high-speed homogenizer, high-pressure homogenizer, planetary stirring device, three-roll mill, ball mill, kitty mill, disc mill, pin mill, or dyno mill. After solution preparation, the mixture may be filtered using various filters.

[0085] From the viewpoint of improving ejection performance from the inkjet head, the above-mentioned photocurable composition preferably has a viscosity of 20 mPa·s or less at the ejection temperature. For the above-mentioned photocurable composition, the viscosity at 25°C is preferably 5 to 300 mPa·s. Furthermore, the surface tension is preferably 25 to 70 mN / m. The viscosity of the photocurable composition is measured in accordance with JIS Z 8803 using an R100 type viscometer.

[0086] In the above photocurable composition, it is preferable that the appearance is uniform and, more preferably, transparent. It is also preferable that the odor is suppressed. Specifically, it is preferable that the irritating odor from the monomers contained in the above photocurable composition is slight, and it is more preferable that there is no irritating odor from the monomers. In the above photocurable composition, the above odor can be more effectively suppressed by preferably setting the content of monomers other than the alkoxy polyalkylene glycol methacrylate (A) and water-soluble monomer (B) to less than 2% by mass of 100% by mass of the photocurable composition.

[0087] The above-mentioned photocurable composition preferably exhibits excellent curability. The curability should be between 100 and 3000 mJ / cm². 2 It is preferable that the curing occurs by irradiation with light, at a concentration of 100-2000 mJ / cm². 2 It is more preferable that the curing occurs by irradiation with light, at a concentration of 100-1000 mJ / cm². 2 It is even more preferable that the material hardens by irradiation with light. Here, hardening means that the material ceases to be liquid and loses its fluidity.

[0088] Since the cured product of the above photocurable composition is used as a support material, a key requirement for the support material is that the cured product has excellent solubility in the solvent. Examples of solvents include water, methanol, ethanol, or monohydric alcohols such as propanol. Water is preferred among these. The solubility of the cured product in a solvent after curing is preferably such that, for example, 3.0 g of the cured product is placed on a wire mesh, immersed in 2.7 g of water at room temperature (e.g., around 25°C), and left to stand for 1 hour, after which no cured product remains.

[0089] The above photocurable composition may be diluted with a medium. A hydrophilic medium is preferred as the medium. In this case as well, it is preferable that the water content is 10% by mass or less per 100% by mass of the above photocurable composition.

[0090] The above photocurable composition may optionally contain other additives, to the extent that they do not impair the effects of the present invention. Examples of other additives include known additives such as emulsifying stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, fungicides, rust inhibitors, pH adjusters, surface tension adjusters, defoamers, viscosity adjusters, dispersants, dispersion stabilizers, chelating agents, drying inhibitors (wetting agents), colorants, fade inhibitors, resistivity adjusters, film adjusters, antioxidants, or surfactants. These various additives can, for example, be added directly to the above photocurable composition.

[0091] The photocurable composition of the present invention can be prepared using the various components described above, and the means and conditions for preparation are not particularly limited. For example, a method of stirring and mixing can be used with a general stirring blade or a mixing or stirring device such as an ultrasonic homogenizer, high-speed homogenizer, high-pressure homogenizer, planetary stirring device, three-roll mill, ball mill, kitty mill, disc mill, pin mill, or dyno mill. After solution preparation, filtration may be performed using various filters.

[0092] The photocurable composition of the present invention is preferably for use in inkjet photopolymerization and is suitable as an ink for inkjet 3D printers.

[0093] 2. Ink for inkjet 3D printers The ink for inkjet 3D printers of the present invention comprises at least one of the above-described photocurable compositions. The photocurable composition contained in the inkjet 3D printer ink may be diluted with a medium.

[0094] The above photocurable composition can be used as is (or directly) as ink for an inkjet 3D printer, or the inkjet 3D printer ink according to the present invention can be manufactured by mixing the medium with the above photocurable composition. A hydrophilic medium is preferred as the above medium. In this case as well, it is preferable that the water content is 10% by mass or less per 100% by mass of the inkjet 3D printer ink.

[0095] The inkjet 3D printer ink described above may contain other additives as needed, within limits that do not impair the effects of the present invention. Examples of other additives include known additives such as emulsifying stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, fungicides, rust inhibitors, pH adjusters, surface tension adjusters, defoamers, viscosity adjusters, dispersants, dispersion stabilizers, chelating agents, drying inhibitors (wetting agents), colorants, fade inhibitors, resistivity adjusters, film adjusters, antioxidants, or surfactants. These various additives can be added directly to the ink solution, for example.

[0096] In 100% by mass of the above inkjet 3D printer ink, the content of the above photocurable composition is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and preferably 100% by mass or less as the lower limit.

[0097] For the inkjet 3D printer inks mentioned above, the viscosity at 25°C is preferably 5 to 300 mPa·s. Furthermore, the surface tension is preferably 25 to 70 mN / m.

[0098] 3. Cartridges for inkjet 3D printers The inkjet 3D printer cartridge of the present invention is filled with the above-mentioned inkjet 3D printer ink. The inkjet 3D printer cartridge of the present invention only needs to be filled with the above-mentioned inkjet 3D printer ink, and any known form of inkjet 3D printer cartridge can be used.

[0099] 4. Method for manufacturing support material In the method for manufacturing support materials of the present invention, support materials are formed using any of the above-mentioned photocurable compositions for forming support materials for inkjet 3D printers or the above-mentioned inkjet 3D printer inks. The method for manufacturing support materials of the present invention is not particularly limited as long as the above-mentioned inkjet 3D printer ink is used, but after molding by spraying from a nozzle, printing, etc., 100 mJ / cm² is applied. 2 ~3000 mJ / cm 2 Known methods such as curing by irradiating with ultraviolet light of a certain degree can be used. More preferably, the ultraviolet irradiation is 100 to 2000 mJ / cm². 2 Light, more preferably 100-1000 mJ / cm² 2 It is the light of [something].

[0100] 5. Method for manufacturing stereolithography objects The present invention relates to a method for manufacturing a stereolithographic object using any of the above-described photocurable compositions for forming support materials for inkjet 3D printers or the above-described inkjet 3D printer inks, A process for forming support material using the above-mentioned photocurable composition for forming support material for inkjet 3D printers or the ink for the inkjet 3D printer; The process of forming the model material; This includes the process of removing the support material mentioned above.

[0101] In the above method for manufacturing stereolithography, known methods can be used, except that the support material formation step uses the above-mentioned photocurable composition for forming support material for inkjet 3D printers or the above-mentioned inkjet 3D printer ink.

[0102] In 3D printing using stereolithography, the cured form of the photocurable composition for support material supports the outer shape of the photocurable composition for model material, thus creating an interface between the two. The photocurable composition for model material and the photocurable composition for support material formation may be sprayed or printed from their respective nozzles simultaneously.

[0103] Next, the cured product (support material) formed by the photocurable composition for support material formation is removed from the cured product. In the cured product obtained by photocuring the photocurable composition for support material formation of the present invention, the cured product has excellent solubility in solvents, so the support material can be easily removed with a polar solvent such as water. As a removal method, from the standpoint of safety and cost, it is preferable to remove the support material by letting it stand in water.

[0104] In the method for manufacturing stereolithography of the present invention, the support material obtained by curing the photocurable composition for support material formation or the inkjet 3D printer ink has excellent solubility in solvents, and the photocurable composition for support material formation has excellent compatibility with hydrophobic monomers. As a result, the surface condition of the model material that was in contact with the support material is good (roughening of the surface adjacent to the support material is suppressed), making it possible to easily manufacture stereolithography objects with excellent formability.

[0105] Examples of photocurable compositions for the above-mentioned model material include those containing a hydrophobic monomer and a photopolymerization initiator. The hydrophobic monomer is a photocurable monomer, preferably a water-insoluble ethylenically unsaturated monomer, and examples include monofunctional ethylenically unsaturated monomers and polyfunctional ethylenically unsaturated monomers having a water solubility (20°C) of less than 20 g / L.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, 2-hydroxypropyl acrylate, or linear or branched alkyl (meth)acrylates such as acrylic acid; cyclohexyl (meth)acrylate, 4-t-cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, phenoxy Alicyclic ring-containing (meth)acrylates such as ethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, or N-hydroxyphenyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, Heterocyclic (meth)acrylates such as adamantyl (meth)acrylate, cyclic trimethylolpropaneformal (meth)acrylate, or 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-ethyl-1,3-propanediol di Examples include linear or branched alkylene glycol (meth)acrylates such as (meth)acrylate, pentaerythritol tri(meth)acrylate, or 2-(2-vinyloxyethoxy)ethyl (meth)acrylate; (meth)acrylamides such as N-alkyl(meth)acrylamide with an alkyl group having 1 to 12 carbon atoms; vinyl compounds such as vinyl acetate, vinyl propionate, methyl vinyl ether, styrene, or N-vinylcaprolactam; or methyl allyloxymethylacrylate. These may be used individually or in combination of two or more. Furthermore, it is preferable that these hydrophobic monomers are monomers that do not contain metal components.

[0106] From the viewpoint of improving the curability of the photocurable composition for model materials, the content of the above hydrophobic monomer is preferably 15% by mass or more, more preferably 20% by mass or more, based on 100% by mass of the entire photocurable composition for model materials. Furthermore, it is preferably 90% by mass or less, and more preferably 80% by mass or less. If two or more of the above hydrophobic monomers are included, the content is the sum of the content of each component.

[0107] Furthermore, the content of the above hydrophobic monomer relative to 100% by mass of the total amount of monomers contained in the photocurable composition for model materials is preferably 50 to 100% by mass, and more preferably 60 to 100% by mass, from the viewpoint of improving the curability of the photocurable composition for model materials. If two or more of the above hydrophobic monomers are included, the content is the sum of the content of each component. [Examples]

[0108] The present invention will be described in more detail below with reference to examples.

[0109] <Photocurable composition for support material formation> [Example 1] In a 20 mL brown screw tube, 10 parts by mass of potassium acrylate (manufactured by Nippon Shokubai Co., Ltd.) and 5 parts by mass of zinc acrylate (manufactured by Nippon Shokubai Co., Ltd.) as water-soluble monomers (B), 20 parts by mass of M-90G (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) as alkoxy polyalkylene glycol methacrylate (A), 35 parts by mass of propylene glycol (manufactured by ADEKA Corporation), 30 parts by mass of polypropylene glycol 400 (manufactured by NOF Corporation), and 1.0 part by mass of Omnirad 184 (manufactured by IGM RESINS) were added and stirred to obtain a photocurable composition (1).

[0110] [Examples 2, 3, Comparative Examples 1, 2] In Example 1, except that the alkoxypolyalkylene glycol methacrylate (A), the water-soluble monomer (B), and the compounds and amounts (parts by mass) shown in Table 1 were used as the solvent, the photocurable compositions (2) and (3) according to Examples 2 and 3 and the photocurable compositions (c1) and (c2) according to Comparative Examples 1 and 2 were obtained in the same manner as in Example 1.

[0111] <Compatibility test> Each of the obtained photocurable compositions was weighed into a screw tube so that the hydrophobic monomer isobornyl acrylate and the photocurable composition: isobornyl acrylate = 3:1 (mass ratio), 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 Table 1. ○: The two liquids of the photocurable composition and isobornyl acrylate are mixed without turbidity. ×: The mixed liquid of the photocurable composition and isobornyl acrylate is turbid.

[0112] <Solubility test> 3.0 g of a cured product piece obtained by irradiating each of the obtained photocurable compositions with ultraviolet rays of 100 mW / cm 2 for 10 seconds for photocuring was placed in a 10 mL screw tube, 2.7 g of water at 25 °C was added, and the solubility after standing for 1 hour was visually evaluated. The evaluation criteria are as follows. The results are shown in Table 1. ○: The cured product does not remain and dissolves. ×: The cured product remains.

[0113]

Table 1

[0114] The components of the support material composition described in Table 1 used the following commercially available products. M-90G: Methoxypolyethylene glycol methacrylate, n average value: about 9, NK Ester M-90G manufactured by Shin-Nakamura Chemical Co., Ltd. M-130G: Methoxypolyethylene glycol methacrylate, n average value: approximately 13, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. NK Ester M-130G M-230G: Methoxypolyethylene glycol methacrylate, n average value: approximately 23, manufactured by Shin Nakamura Chemical Industry Co., Ltd. NK Ester M-230G Potassium acrylate: Manufactured by Nippon Shokubai Co., Ltd. Zinc acrylate: Manufactured by Nippon Shokubai Co., Ltd. Hydroxyethyl methacrylate: Manufactured by Nippon Shokubai Co., Ltd. Propylene glycol: Manufactured by ADEKA Corporation Polypropylene glycol (diol type, Mn=400): Manufactured by NOF Corporation Omnirad184: Manufactured by IGM Resins.

[0115] As shown in Table 1, the photocurable compositions of the examples obtained exhibited excellent solubility of the cured product (support material) in solvents such as water, as well as excellent compatibility of the photocurable composition with hydrophobic monomers, resulting in photomolded products with excellent moldability.

Claims

1. A photocurable composition for forming support material for an inkjet 3D printer, comprising an alkoxypolyalkylene glycol methacrylate (A) and a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion, which is a compound other than the alkoxypolyalkylene glycol methacrylate (A), wherein the content of the alkoxypolyalkylene glycol methacrylate (A) is 20 to 60% by mass with respect to 100% by mass of the total amount of monomers contained in the photocurable composition. A photocurable composition for forming support materials for inkjet 3D printers.

2. Furthermore, it contains a photopolymerization initiator. A photocurable composition for forming support material for an inkjet 3D printer, as described in claim 1.

3. An inkjet 3D printer ink comprising a photocurable composition for forming support material for inkjet 3D printers according to claim 1 or 2.

4. An inkjet 3D printer cartridge filled with the inkjet 3D printer ink described in claim 3.

5. A support material is formed using the photocurable composition for forming support materials for inkjet 3D printers described in claim 1 or 2. A method for manufacturing support materials.

6. A support material is formed using the inkjet 3D printer ink described in claim 3. A method for manufacturing support materials.

7. A method for manufacturing a stereolithographic object using a photocurable composition for forming support material for an inkjet 3D printer as described in claim 1 or 2, A process for forming a support material using the photocurable composition, The process of forming the model material, The process of removing the support material and A method for manufacturing stereolithography, including [the specified method].

8. A method for manufacturing a stereolithographic object using inkjet 3D printer ink as described in claim 3, A process for forming a support material using the ink, The process of forming the model material, The process of removing the support material and A method for manufacturing stereolithography, including [the specified method].

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