JP2024033862A - Photo-curable compositions for forming support materials for inkjet three-dimensional printers, ink for inkjet three-dimensional printers and cartridges for inkjet three-dimensional printers containing such compositions, and methods of manufacturing support materials and photo-fabricated objects using the photo-curable compositions - Google Patents

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

The present invention relates to a photocurable composition for forming a support material for an inkjet 3D printer, an ink for an inkjet 3D printer and a cartridge for an inkjet 3D printer containing the same, and a method for producing a support material using the photocurable composition. The present invention relates to a method for manufacturing a stereolithographic object.

In recent years, for inkjet 3D printers, an inkjet stereolithography method has been proposed in which a liquid photocurable composition discharged from an inkjet nozzle is cured and layered to form a stereolithography. The ink for an inkjet 3D printer using this stereolithography method includes a photocurable model material composition that forms a molded body (model material) by photocuring with UV light, etc. A photocurable composition that forms a support material by photocuring with UV or the like is used. By laminating a photocured model material on a photocured support material and then removing the support material, it becomes possible to form an overhang structure or a hollow structure.

Patent Document 1 discloses that an ionic group and a counter ion are used for the purpose of providing a photocurable support material composition for an inkjet 3D printer in which the cured product has excellent water solubility and sufficient hardness after curing. A photocurable support material composition for an inkjet 3D printer is described, which includes a water-soluble ethylenically unsaturated monomer containing the following: and a photopolymerization initiator.

Patent Document 2 provides a composition for a photocurable support material for an inkjet 3D printer that has excellent curability, has sufficient hardness of the cured product after curing, and has excellent solubility of the cured product in a solvent. An inkjet inkjet containing a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion, and having a water content of 10% by mass or less based on 100% by mass of the photocurable composition. Compositions for photocurable support materials for 3D printers are described.

As a photocurable composition for forming a support material for an inkjet 3D printer, there is a need for a photocurable composition that has excellent solubility of the cured product (support material) in a solvent by photocuring and that can yield a modeled object with excellent formability. It was getting worse.

International Publication No. 2018/043582 International Publication 2019/167948

Therefore, an object of the present invention is to create a photocurable composition for forming a support material for an inkjet 3D printer, which can provide a cured product (support material) by photocuring with excellent solubility in a solvent and a modeled article with excellent formability. An object of the present invention is to provide an inkjet 3D printer ink containing the same, an inkjet 3D printer cartridge containing the same, a method for manufacturing a support material using the photocurable composition, and a method for manufacturing a stereolithographic object.

As a result of extensive research to solve the above problems, the present inventors have discovered that alkoxypolyalkylene glycol methacrylate (A) and a water-soluble monomer (a compound other than the alkoxypolyalkylene glycol methacrylate (A)) B) A photocurable material for forming a support material for an inkjet 3D printer, which provides excellent solubility of the cured product (support material) in a solvent when photocured and provides a modeled object with excellent formability. The inventors have discovered that it is possible to provide a composition, and have completed the present invention.

That is, the photocurable composition for forming a support material for an inkjet 3D printer of the present invention comprises alkoxypolyalkylene glycol methacrylate (A) and a water-soluble monomer that is a compound other than the alkoxypolyalkylene glycol methacrylate (A). (B).
The photocurable composition for forming a support material for an inkjet 3D printer preferably further contains a photopolymerization initiator.

Moreover, the ink for an inkjet 3D printer of the present invention contains any of the above photocurable compositions for forming a support material for an inkjet 3D printer.

Further, the cartridge for an inkjet 3D printer of the present invention is filled with the above ink for an inkjet 3D printer.

Further, in the method for manufacturing a support material of the present invention, the support material is formed using any of the above photocurable compositions for forming a support material for an inkjet 3D printer or the above ink for an inkjet 3D printer.

Further, the method for producing a stereolithographic article of the present invention includes a method for producing a stereolithographic article using any of the above photocurable compositions for forming a support material for an inkjet 3D printer or the above ink for an inkjet 3D printer. The method includes a step of forming a support material using the photocurable composition or the ink; a step of forming a model material; and a step of removing the support material.

According to the present invention, a photocurable composition for forming a support material for an inkjet 3D printer, which has excellent solubility of a cured product (support material) in a solvent when cured by light, and provides a modeled object with excellent formability. The present invention can provide a product, an ink for an inkjet 3D printer, a cartridge for an inkjet 3D printer containing the same, a method for manufacturing a support material using the photocurable composition, and a method for manufacturing a stereolithographic object.

1. Photocurable composition for forming a support material for an inkjet 3D printer The photocurable composition for forming a support material for an inkjet 3D printer (hereinafter sometimes simply referred to as a photocurable composition) of the present invention is a photocurable composition for forming a support material for an inkjet 3D printer. It contains 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, a cured product (support material) obtained by curing the photocurable composition with light has excellent solubility in a solvent, and a shaped article with excellent formability can be obtained.

In this specification, having excellent formability means that in an inkjet 3D printer, after photocuring a photocurable composition for forming a support material and a photocurable composition for forming a model material, the cured support material is dissolved in a solvent. This means that when removed, the surface of the model material that was in contact with the support material will be clean (not rough). One of the indicators of the formability is the compatibility of the photocurable composition for forming the support material with the hydrophobic monomer, and the compatibility of the photocurable composition for forming the support material with the hydrophobic monomer is excellent. In this case, the formability is also excellent.

1-1 Alkoxypolyalkylene glycol methacrylate (A)
The photocurable composition of the present invention contains an alkoxypolyalkylene glycol methacrylate (A) and a water-soluble monomer (B). By including these, a cured product (support material) cured by light has excellent solubility in a solvent, and a shaped article with excellent formability can be obtained. Alkoxypolyalkylene glycol methacrylate (A) is a monomer that is polymerized by light or the like.

Examples of the alkoxy group in the alkoxy polyalkylene glycol methacrylate (A) included in the photocurable composition of the present invention include methoxy, ethoxy, propoxy, or butoxy groups, among which methoxy group is preferred.
Examples of the alkylene group in the alkoxypolyalkylene glycol methacrylate (A) include methylene, ethylene, propylene, or butylene groups, among which ethylene or propylene groups are preferred.

Examples of the alkoxy polyalkylene glycol methacrylate (A) include compounds represented by the following chemical formula (1) or (2).

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 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.

Specifically, the alkoxy polyalkylene glycol methacrylate (A) includes methoxydiethylene glycol EO2 methacrylate (a compound in which n=2 in the above chemical formula (1)), methoxytetraethylene glycol EO4 methacrylate (a compound in which n=2 in the above chemical formula (1)), = 4), methoxypolyethylene glycol EO9 methacrylate (compound where n = 9 in the above chemical formula (1)), methoxypolypropylene glycol PO9 methacrylate (compound where n = 9 in the above chemical formula (2)), methoxypolyethylene glycol EO13 methacrylate (a compound where n=13 in the above chemical formula (1)), polypropylene glycol PO13 methacrylate (a compound where n=13 in the above chemical formula (2)), methoxypolyethylene glycol EO23 methacrylate (a compound where n=13 in the above chemical formula (1)) 23), methoxypolyethylene glycol EO45 methacrylate (a compound where n = 45 in the above chemical formula (1)), or methoxypolyethylene glycol EO90 methacrylate (a compound where n = 90 in the above chemical formula (1)). .

The alkoxy polyalkylene glycol methacrylate (A) may be a mixture of compounds in which at least one of the alkoxy group, the alkylene chain, and n in the chemical formula (1) or (2) is different. When the alkoxy polyalkylene glycol methacrylate (A) is a mixture of compounds having different values of n in the chemical formula (1) or (2), n can be an average value thereof.

As the alkoxy polyalkylene glycol methacrylate (A), commercially available products can be used. Preferred commercial products include NK ester M-20G, M-40G, M-90G, M-130G, M-230G, or M-450G manufactured by Shin-Nakamura Chemical Industries, Ltd., or Blenmar PME-100 manufactured by NOF Corporation. , PME-200, PME-400, PME-1000, or PME-4000.

The molecular weight of the alkoxy polyalkylene glycol methacrylate (A) is not limited. The weight average molecular weight is preferably about 160 or more, and preferably 4,500 or less.

The weight average molecular weight can be measured using the following apparatus under the following conditions.
Equipment: Tosoh high-speed GPC equipment (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 Scientific Co., Ltd.
Eluent: 0.1N aqueous sodium acetate solution/acetonitrile = 3/1 (weight ratio)

The content of alkoxy polyalkylene glycol methacrylate (A) contained in the photocurable composition is preferably 60% by mass or less, more preferably 50% by mass or less, based on 100% by mass of the composition, More preferably, it is 40% by mass or less, and the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible. In addition, when two or more types of the above-mentioned alkoxy polyalkylene glycol methacrylates (A) are contained, the content is the total content of each component.

Further, the content of the alkoxy polyalkylene glycol methacrylate (A) based on 100% by mass of the total amount of monomers contained in the photocurable composition is preferably 10 to 70% by mass, and preferably 20 to 60% by mass. It is more preferable that In addition, when two or more types of the above-mentioned alkoxy polyalkylene glycol methacrylates (A) are contained, the content is the total content of each component. Note that the alkoxy polyalkylene glycol methacrylate (A) and the water-soluble monomer (B) are monomers, and are included in 100% by mass of the total amount of monomers.

1-2 Water-soluble monomer (B)
The water-soluble monomer (B) contained in the photocurable composition of the present invention is a compound other than the alkoxypolyalkylene glycol methacrylate (A) with a water solubility (20°C) of 20 g/L or more. The monomer is not particularly limited, and may be an ionic monomer containing an ionic group and a counter ion or a nonionic monomer. Among these, ionic monomers containing an ionic group and a counter ion are preferred, and monomers having one or more ethylenically unsaturated groups in the molecule are preferred. More preferred is a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion. Note that the monomer refers to a compound that is polymerized by light or the like.
The water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion has high water solubility because it contains an ionic group and a counter ion. The water solubility (at 20° C.) is preferably 100 g/L or more, more preferably 200 g/L or more, and even more preferably 500 g/L or more.

The content of the water-soluble monomer (B) contained in the photocurable composition is preferably 60% by mass or less, more preferably 50% by mass or less, based on 100% by mass of the composition; More preferably, it is 40% by mass or less, and the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible.

Further, the content of the water-soluble monomer (B) based on 100% by mass of the total amount of monomers contained in the photocurable composition is 30 to 100% by mass from the viewpoint of improving water solubility. is preferable, and more preferably 40 to 100% by mass. In addition, when two or more types of water-soluble monomers (B) are included, the content is the total content of each component.

The ethylenically unsaturated groups mentioned above 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, and acetylvinyl group. or a vinylamide group. In this specification, "(meth)acrylic" means "acrylic" and/or "methacrylic", and "(meth)acrylate" means "acrylate" and/or "methacrylate". means. Among these, a (meth)acrylic group, a vinyl ether group, or a (meth)acrylamide group is preferred, and a (meth)acrylic group is more preferred.

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

The above-mentioned counter ions include alkali metal ions such as sodium ions or potassium ions, monovalent counter ions such as ammonium ions; or polyvalent metal ions such as zinc ions, magnesium ions, calcium ions, aluminum ions, or neodymium ions. Examples include ions. Among these, a monovalent counter ion is preferred, an alkali metal ion such as a sodium ion or a potassium ion, or an ammonium ion is more preferably used, an alkali metal ion is more preferably used, and a potassium ion is particularly preferably used. In addition to monovalent counterions, it is also preferred to use polyvalent metal ions such as zinc ions, magnesium ions, calcium ions, aluminum ions, or neodymium ions.

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

The content of the water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion preferably contained in the photocurable composition is preferably an upper limit based on 100% by mass of the composition. The content is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible.

Further, the content of the water-soluble ethylenically unsaturated monomer containing the ionic group and the counter ion with respect to 100% by mass of the total amount of monomers contained in the photocurable composition is From the viewpoint of improving water solubility, the content is preferably 40 to 100% by mass, more preferably 50 to 100% by mass. In addition, when two or more kinds of water-soluble ethylenically unsaturated monomers containing the above-mentioned ionic group and counter ion are contained, the content is the total content of each component.

The total content of the water-soluble ethylenically unsaturated monomer containing a monovalent counterion as a counterion and the water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion as a counterion is In 100% by mass of the photocurable composition, the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible.

The upper limit of the content of the water-soluble ethylenically unsaturated monomer containing a monovalent counter ion is preferably 50% by mass or less, more preferably 40% by mass, based on 100% by mass of the photocurable composition. It is not more than 30% by mass, more preferably not more than 30% by mass. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible.

The upper limit of 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 30% by mass in 100% by mass of the photocurable composition. % or less, and the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible.

Examples of the water-soluble ethylenically unsaturated monomer containing carboxylic acid as an ionic group and a counter ion included in the 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)acryloyloxy Ethyl phthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, N-(meth)acryloyl aspartic acid, or ω-(meth)acryloyl Monovalent salts such as alkali metal salts such as sodium salts or potassium salts or ammonium salts of alkane-1,1 dicarboxylic acids; or polyvalent salts such as zinc salts, magnesium salts, calcium salts, aluminum salts, or neodymium salts. Examples include salt.
Among these, alkali metal salts such as sodium salts and potassium salts, and monovalent salts such as ammonium salts are preferred, and sodium salts, potassium salts, and ammonium salts are more preferred. More preferred is potassium salt.

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

The upper limit of the total content of monovalent salts and polyvalent metal salts of carboxylic acid in 100% by mass of the photocurable composition is preferably 60% by mass or less, more preferably 50% by mass or less, and still 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. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible.

The upper limit of the content of the monovalent salt of carboxylic acid in 100% by mass of the photocurable composition is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible.

The content of the polyvalent metal salt of carboxylic acid is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably 5% by mass or more as a lower limit, based on 100% by mass of the photocurable composition. More preferably, it is 10% by mass or more. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible.

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

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

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

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

In addition to the above, water-soluble ethylenically unsaturated monomers preferably contained in the photocurable composition include polyvalent metal acrylates such as zinc salts, magnesium salts, calcium salts, aluminum salts, or neodymium salts. May contain salt. Preferred polyvalent metal salts of acrylic acid are zinc salts, magnesium salts, and calcium salts.

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

The upper limit of the total content of monovalent salts and polyvalent metal salts of acrylic acid in 100% by mass of the photocurable composition is preferably 60% by mass or less, more preferably 50% by mass or less, and even 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.
Among these, the total content of potassium acrylate and zinc acrylate is preferably 1 to 50% by mass, more preferably 1 to 30% by mass based on 100% by mass of the photocurable composition. By doing so, the viscosity of the composition can be lowered, and the cost can also be lowered by suppressing the amount of acrylate used.

Further, the upper limit of the content of the monovalent salt of acrylic acid is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less based on 100% by mass of the photocurable composition. be. The lower limit is preferably 5% by mass or more, more preferably 10% 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 or more as a lower limit, based on 100% by mass of the photocurable composition. More preferably, it is 10% by mass or more.
To obtain a photocurable composition in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article having better formability can be obtained when the above method is performed. becomes possible.

Examples of water-soluble ethylenically unsaturated monomers other than the above-mentioned water-soluble ethylenically unsaturated monomers containing an ionic group and a counter ion include (meth)acrylic acid; acryloylmorpholine; N-vinylpyrrolidone; ) acrylamide, such as acrylamide, N,N-dimethylacrylamide, N-hydroxyethylacrylamide, or N-isopropylacrylamide; methoxytriethylene glycol (meth)acrylate; ethoxydiethylene glycol (meth)acrylate; 2-(2-ethoxyethoxy)ethyl Examples include (meth)acrylate; glycerol (meth)acrylate; and methoxypolyethylene glycol EO9 acrylate.

It is preferable that the water-soluble monomer (B) further contains a crosslinking component. The crosslinking component is preferably a polyvalent metal salt of (meth)acrylic acid.

The ratio of alkoxy polyalkylene glycol methacrylate (A) and water-soluble monomer (B) contained in the photocurable composition is expressed as a mass ratio of alkoxy polyalkylene glycol methacrylate (A):water-soluble monomer. Body (B)=1-99:99-1 is preferable, and 30-70:70-30 is more preferable. When the range is within this range, a photocurable composition is obtained in which a cured product (support material) by photocuring of the photocurable composition has better solubility in a solvent and a shaped article with better formability can be obtained. becomes possible.

1-3 Other Monomers The photocurable composition contains monomers other than the alkoxypolyalkylene glycol methacrylate (A) and the water-soluble monomer (B) (for example, water solubility (20°C ) may contain less than 20 g/L). Examples of the other monomers include other unsaturated monomers, specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. 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 Acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (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, Cyclopentanyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxy Propyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, Methyl 2-(hydroxymethyl) ) acrylate, and (meth)acrylates such as 2-ethylhexyl carbitol (meth)acrylate; phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether, biphenyl-4- Allyl ethers such as all monoallyl ether, butyl allyl ether, cyclohexyl allyl ether, and cyclohexane methanol monoallyl ether; butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, ethylhexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy Vinyl ethers such as vinyl ether, acetyl ethoxyethoxy vinyl ether, cyclohexyl vinyl ether, and adamantyl vinyl ether; maleimides such as phenylmaleimide, cyclohexylmaleimide, and n-hexylmaleimide; benzyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, bisphenol A diacrylate, bisphenol A monomer or alicyclic group having an aromatic group such as EO adduct bis(meth)acrylate of A, PO adduct bis(meth)acrylate of bisphenol A, or EO adduct bis(meth)acrylate of hydrogenated bisphenol A Polyoxyalkylene di(meth)acrylate such as polyoxyethylene di(meth)acrylate or polyoxypropylene di(meth)acrylate; or hydroxyalkyl(meth)acrylate.
These may be used alone or in combination of two or more.

The content of the other monomers is preferably 50% by mass or less based on 100% by mass of the composition. It is more preferably 30% by mass or less, still more preferably 10% or less, particularly preferably less than 2% by mass. In this case, the odor of the photocurable composition can be further suppressed.

1-4 Organic acid and/or its salt The photocurable composition may contain an organic acid and/or its salt. The organic acid and/or its salt is a compound other than the alkoxy polyalkylene glycol methacrylate (A), the water-soluble monomer (B), and the other unsaturated monomer.
Examples of the organic acid include organic sulfonic acids such as p-toluenesulfonic acid, organic phosphoric acids such as phenylphosphonic acid, organic carboxylic acids, and phosphoric esters. Among these, organic carboxylic acids are preferred. Examples of organic carboxylic acids include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, octylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. , behenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, benzoic acid, glycine, polyacrylic acid, or poly Examples include lactic acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, and salicylic acid. Among these, aliphatic carboxylic acids are more preferred, and lactic acid, propionic acid, or polyacrylic acid is even more preferred.
Examples of organic acid salts include metal carboxylates. Examples of the metal of the metal carboxylate include alkali metals such as lithium, sodium, or potassium; alkaline earth metals such as magnesium, calcium, strontium, or barium; zinc; or zirconium. Among them, alkali metals such as potassium are preferred. As the organic acid salt, potassium lactate or potassium propionate is preferred.
The storage stability of the photocurable composition is further improved when it contains an organic acid and/or a salt thereof.

The content of the organic acid and/or its salt is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and the lower limit of the content of the organic acid and/or its salt in 100% by mass of the photocurable composition. is preferably 1% by mass or more. In this case, the storage stability of the photocurable composition can be further improved.

1-5 Photopolymerization initiator The photocurable composition may contain a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, or 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, or 2-methyl-1-[4-(methylthio ) Acetophenone compounds such as phenyl]-2-morpholinopropan-1-one; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, or 2-amylanthraquinone; 2,4-diethylthioxanthone Acetophenone; Ketal compounds such as dimethyl ketal or benzyl dimethyl ketal; benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phosphine oxide such as bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, or bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; or mixtures thereof, etc. can be mentioned.
These may be used alone or in combination of two or more.
The content of the photopolymerization initiator is preferably 0.05 to 10.0% by mass, more preferably 0.1 to 7.0% by mass, even more preferably 0.2 to 10.0% by mass, based on 100% by mass of the above composition. It is 5.0% by mass.

1-6 Solvent The above-mentioned photocurable composition may contain a solvent to the extent that the effects of the present invention are not impaired. The above solvents include water; monohydric alcohols such as methanol, ethanol, or propanol; ethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene glycol, 1,2-hexanediol, diethylene glycol, triethylene glycol, polyethylene Glycols such as 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 propylene glycol monomethyl ether acetate, etc. Examples include glycol ether acetate. The above solvents may be used alone or in combination of two or more.

The solvent preferably contains glycol, glycol ether, or glycol ether acetate, and particularly preferably contains glycol. Among glycols, glycols containing an alkylene chain having 2 to 6 carbon atoms are preferred, and glycols containing an alkylene chain having 2 and/or 3 carbon atoms are more preferred; More preferred are glycols containing an alkylene chain.

Preferred examples of the glycol containing an alkylene chain having 2 carbon atoms include ethylene glycol; or polyethylene glycols such as diethylene glycol and triethylene glycol. Preferred examples of the glycol containing an alkylene chain having 3 carbon atoms include propylene glycol; or polypropylene glycol such as dipropylene glycol or tripropylene glycol.

Examples of the glycol containing an alkylene chain having 2 or 3 carbon atoms include polyalkylene glycol containing an ethylene chain and a propylene chain as the alkylene chain.

The above-mentioned glycol 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, and includes ethylene glycol and/or propylene glycol. It is more preferable to include propylene glycol, and even more preferably propylene glycol is included.

When a polyalkylene glycol is used as the glycol, it is preferable to include a polyalkylene glycol having 4 to 30 carbon atoms in the total alkylene chain. It is more preferable that the glycol contains a glycol having 25 or less carbon atoms in all alkylene chains. More preferably, the polyalkylene glycol contains the alkylene chain having 2 and/or 3 carbon atoms, and the total number of carbon atoms in the alkylene chain is within the above range.

The glycol includes the above-mentioned alkylene chain having 2 or 3 carbon atoms, and the total alkylene chain having 2 or 3 carbon atoms, and the above-mentioned glycol containing the above-mentioned alkylene chain having 2 and/or 3 carbon atoms, and It is preferable that the polyalkylene glycol has a total alkylene chain carbon number of 4 to 30.

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, and even more preferably 95% by mass based on 100% by mass of the solvent. % or more, particularly preferably 100% by mass. Further, 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, particularly preferably 100% by mass, based on 100% by mass of the solvent. It is.

The above solvent is preferably used so that the water content is 10% by mass or less based on 100% by mass of the photocurable composition. The content of water in the photocurable composition is more preferably less than 10% by mass, still more preferably 5% by mass or less, particularly preferably 3% by mass or less based on 100% by mass of the photocurable composition. The lower limit of the water content is preferably 0% by mass. By setting it within such a range, supportability can be improved.

The water content in the photocurable composition can be calculated from the water content of each compound charged. It can also be determined by Karl Fischer measurement. Support property (support power) is the ability of a cured product of a photocurable composition to support ^a model material after curing. It is preferable that

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

a glycol containing an alkylene chain having 2 or 3 carbon atoms, and the total alkylene chain having 2 or 3 carbon atoms; and a glycol containing the alkylene chain having 2 and/or 3 carbon atoms, and the total alkylene chain carbon The total amount of polyalkylene glycols having a number of 4 to 30 is preferably 30 to 90% by mass, more preferably 40 to 90% by mass, based on 100% by mass of the composition. Among these, the content of propylene glycol is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, based on 100% by mass of the composition.

1-7 Other Additives The above-mentioned photocurable composition may contain other additives as necessary within a range that does not impede the effects of the present invention. Specific examples include photoinitiation aids, polymerization inhibitors, surfactants, colorants, antioxidants, chain transfer agents, and fillers.

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

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

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

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

As antioxidants, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, dilauryl 3,3'-thiodipropionate, Examples thereof include triphenyl phosphite, 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, diethyl disulfide, di-1-octyl disulfide, toluene, xylene, 1-butene, 1-nonene, dichloromethane, carbon tetrachloride, methanol, 1-butanol, ethylthiol. , 1-octylthiol, acetone, methyl ethyl ketone, 2-methyl-2-propyl aldehyde, 1-pentyl aldehyde, phenol, m-cresol, p-cresol, or o-cresol.

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

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

The above-mentioned photocurable composition can be prepared using the various components mentioned above, and the preparation means and conditions are not particularly limited. Examples include a method of stirring and mixing using a device capable of mixing or stirring, such as a planetary stirring device, three-roll mill, ball mill, kitty mill, disk mill, pin mill, or dyno mill. After preparing the solution, it may be filtered using various filters.

The photocurable composition preferably has a viscosity of 20 mPa·s or less at the ejection temperature from the viewpoint of improving ejection properties from the inkjet head. The photocurable composition preferably has a viscosity of 5 to 300 mPa·s at 25°C. Further, the surface tension is preferably 25 to 70 mN/m. The viscosity of the photocurable composition is measured using an R100 viscometer in accordance with JIS Z 8803.

It is preferable that the photocurable composition has a uniform appearance and is transparent. Further, it is preferable that odor is suppressed. Specifically, it is preferable that the monomer contained in the photocurable composition has little irritating odor, and it is more preferable that the monomer has no irritating odor. In the photocurable composition, the content of monomers other than the alkoxy polyalkylene glycol methacrylate (A) and the water-soluble monomer (B) is preferably set based on 100% by mass of the photocurable composition. , less than 2% by mass, the odor can be suppressed more effectively.

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

Since the cured product of the above-mentioned photocurable composition is used as a support material, an essential requirement for the support material is that the cured product has excellent solubility in a solvent. Examples of the solvent include water, methanol, ethanol, and monohydric alcohols such as propanol. Among them, water is preferred.
The solubility of the cured product in a solvent can be determined by, for example, placing 3.0 g of the cured product on a wire mesh, immersing it in 2.7 g of water at room temperature (for example, around 25°C), and leaving it for 1 hour. It is preferable that no cured product remains afterwards.

The photocurable composition may be diluted with a medium. The medium is preferably a hydrophilic medium. Also in this case, the water content is preferably 10% by mass or less based on 100% by mass of the photocurable composition.

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

The photocurable composition of the present invention can be prepared using the various components described above, and the preparation means and conditions are not particularly limited. Examples include a method of stirring and mixing using a mixing or stirring device such as a homogenizer, a planetary stirring device, a three-roll mill, a ball mill, a kitty mill, a disk mill, a pin mill, or a dyno mill. After the solution is prepared, it may be filtered using various filters.

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

2. Ink for Inkjet 3D Printers The ink for inkjet 3D printers of the present invention contains at least one of the photocurable compositions described above. The photocurable composition contained in the ink for an inkjet 3D printer may be diluted with a medium.

The photocurable composition can be used as it is (or directly) as an ink for an inkjet 3D printer, or the ink for an inkjet 3D printer according to the present invention can be produced by mixing a medium and the photocurable composition. You can also do that. The medium is preferably a hydrophilic medium. Also in this case, it is preferable that the content of water is 10% by mass or less in 100% by mass of the ink for an inkjet 3D printer.

The above-mentioned ink for inkjet 3D printers may contain other additives as necessary within a range that does not impair the effects of the present invention. Other additives include, for example, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, antifungal agents, rust preventives, pH adjusters, surface tension adjusters, antifoaming agents, viscosity modifiers, and dispersants. Known additives such as additives, dispersion stabilizers, chelating agents, anti-drying agents (wetting agents), colorants, anti-fading agents, resistivity modifiers, film modifiers, antioxidants, and surfactants can be mentioned. . These various additives can be added directly to the ink liquid, for example.

The lower limit of the content of the photocurable composition in 100% by mass of the inkjet 3D printer ink is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and the upper limit. The content is preferably 100% by mass or less.

The above ink for inkjet 3D printers preferably has a viscosity of 5 to 300 mPa·s at 25°C. Further, the surface tension is preferably 25 to 70 mN/m.

3. Inkjet 3D Printer Cartridge The inkjet 3D printer cartridge of the present invention is filled with the above inkjet 3D printer ink. The cartridge for an inkjet 3D printer of the present invention only needs to be filled with the above ink for an inkjet 3D printer, and any known form of the cartridge for an inkjet 3D printer can be used.

4. Method for manufacturing a support material In the method for manufacturing a support material of the present invention, a support material is formed using any of the above photocurable compositions for forming a support material for an inkjet 3D printer or the above ink for an inkjet 3D printer. . The method for manufacturing the support material of the present invention may use the above-mentioned ink for inkjet 3D printers, and is not particularly limited, but after modeling by jetting from a nozzle, printing, etc., the ink is approximately 100 mJ/cm ² to 3000 mJ/cm ² A known method such as curing by irradiation with ultraviolet rays can be used. The ultraviolet irradiation is preferably 100 to 2000 mJ/cm ² , even more preferably 100 to 1000 mJ/cm ² .

5. Method for manufacturing a stereostructured object The method for producing a stereostructured object of the present invention is a method for producing a stereostructured object using any of the above photocurable compositions for forming a support material for an inkjet 3D printer or the above ink for an inkjet 3D printer. A method of manufacturing,
a step of forming a support material using the photocurable composition for forming a support material for an inkjet 3D printer or the ink for an inkjet 3D printer;
Forming process of model material;
and a step of removing the support material.

In the method for manufacturing a stereolithographic object, any known method can be used, except for using the photocurable composition for forming a support material for an inkjet 3D printer or the ink for an inkjet 3D printer in the step of forming the support material.

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

Subsequently, a cured product (support material) in which a photocurable composition for forming a support material is photocured is removed from the cured product. The cured product obtained by photocuring the photocurable composition for forming a support material of the present invention has excellent solubility in solvents, so it is easy to cure the support material with a polar solvent such as water. can be removed. As a removal method, from the viewpoint of safety and cost, it is preferable to leave the support material in water and remove it.

In the method for producing a stereolithographic object of the present invention, the photocurable composition for forming the support material or the support material obtained by curing the ink for an inkjet 3D printer has excellent solubility in a solvent and is resistant to hydrophobic monomers. Due to the excellent compatibility of the photocurable composition for forming the support material, the surface condition of the model material that was in contact with the support material is good (the surface adjacent to the support material may not become rough). Therefore, it is possible to easily produce a stereolithographic object with excellent formability.

Examples of the photocurable composition for the 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 a monofunctional ethylenically unsaturated monomer having a water solubility (20°C) of less than 20 g/L. Examples include monomers and polyfunctional ethylenically unsaturated monomers. Specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, t-butyl (meth)acrylate. Acrylate, 2-hydroxypropyl acrylate, or linear or branched alkyl (meth)acrylates such as acrylic acid; cyclohexyl (meth)acrylate, 4-t-cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl ( Alicycle-containing compounds such as meth)acrylate, dicyclopentanyl (meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, or N-hydroxyphenyl(meth)acrylate (Meth)acrylate; Tetrahydrofurfuryl (meth)acrylate, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-cyclohexyl-1 , 3-dioxolane, adamantyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, or heterocycle-containing (meth)acrylates 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- Straight chain or branched alkylene glycols such as butyl-2-ethyl-1,3-propanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, or 2-(2-vinyloxyethoxy)ethyl(meth)acrylate (Meth)acrylate; (meth)acrylamide such as N-alkyl (meth)acrylamide into which an alkyl group having 1 to 12 carbon atoms has been introduced; vinyl acetate, vinyl propionate, methyl vinyl ether, styrene, or N-vinyl caprolactam, etc. Vinyl compounds; or methyl allyloxymethyl acrylate. These may be used alone or in combination of two or more. Furthermore, these hydrophobic monomers are preferably monomers that do not contain metal components.

From the viewpoint of improving the curability of the photocurable composition for model materials, the content of the hydrophobic monomer is 15% by mass or more based on 100% by mass of the entire photocurable composition for model materials. The content is preferably 20% by mass or more, and more preferably 20% by mass or more. Further, it is preferably 90% by mass or less, more preferably 80% by mass or less. In addition, when two or more kinds of the above-mentioned hydrophobic monomers are contained, the content is the total content of each component.

In addition, from the viewpoint of improving the curability of the photocurable composition for model materials, the content of the hydrophobic monomer based on 100% by mass of the total amount of monomers contained in the photocurable composition for model materials is 50% by weight. It is preferably from 100% by mass, more preferably from 60 to 100% by mass. In addition, when two or more kinds of the above-mentioned hydrophobic monomers are contained, the content is the total content of each component.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

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

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

<Compatibility test>
Weigh each of the obtained photocurable compositions into a screw tube so that the hydrophobic monomer isobornyl acrylate and the photocurable composition: isobornyl acrylate = 3:1 (mass ratio), After stirring at 100 rpm for 30 seconds, the appearance of each mixture was visually confirmed. The evaluation criteria are as follows. The results are shown in Table 1.
Good: The two liquids of the photocurable composition and isobornyl acrylate are mixed without becoming cloudy.
×: The two-liquid mixture of the photocurable composition and isobornyl acrylate becomes cloudy.

<Solubility test>
To each of the obtained photocurable compositions, 3.0 g of a cured material piece was photocured by irradiating 100 mW/cm ² of ultraviolet rays for 10 seconds and put into a 10 mL screw tube, and 2.7 g of water at 25° C. was added. After standing for 1 hour, the solubility was visually evaluated. The evaluation criteria are as follows. The results are shown in Table 1.
○: No cured product remains and is dissolved.
×: Cured material remains.

The components of the support material composition listed in Table 1 were commercially available as shown below.
M-90G: Methoxypolyethylene glycol methacrylate, n average value: approximately 9, NK ester manufactured by Shin-Nakamura Chemical Industry Co., Ltd. M-90G
M-130G: Methoxypolyethylene glycol methacrylate, n average value: approximately 13, NK ester manufactured by Shin-Nakamura Chemical Industry Co., Ltd. M-130G
M-230G: Methoxypolyethylene glycol methacrylate, n average value: approximately 23, NK ester manufactured by Shin-Nakamura Chemical Industry Co., Ltd. M-230G
Potassium acrylate: Nippon Shokubai Co., Ltd. Zinc acrylate: Nippon Shokubai Co., Ltd. Hydroxyethyl methacrylate: Nippon Shokubai Co., Ltd. Propylene glycol: ADEKA Co., Ltd. Polypropylene glycol (diol type, Mn= 400): Manufactured by NOF Corporation Omnirad184: Manufactured by IGM RESINS

As shown in Table 1, the photocurable composition of the example has excellent solubility of the cured product (support material) in solvents such as water, and has a high compatibility with hydrophobic monomers. A photocurable composition with excellent solubility and from which a shaped article with excellent formability was obtained was obtained.

Claims (8)

comprising an alkoxy polyalkylene glycol methacrylate (A) and a water-soluble monomer (B) which is a compound other than the alkoxy polyalkylene glycol methacrylate (A),
A photocurable composition for forming a support material for an inkjet 3D printer. The photocurable composition for forming a support material for an inkjet 3D printer according to claim 1, further comprising a photopolymerization initiator. An ink for an inkjet 3D printer, comprising the photocurable composition for forming a support material for an inkjet 3D printer according to claim 1 or 2. An inkjet 3D printer cartridge filled with the inkjet 3D printer ink according to claim 3. Forming a support material using the photocurable composition for forming a support material for an inkjet 3D printer according to claim 1 or 2.
Method of manufacturing support material. Forming a support material using the inkjet 3D printer ink according to claim 3,
Method of manufacturing support material. A method for producing a stereolithographic object using the photocurable composition for forming a support material for an inkjet 3D printer according to claim 1 or 2,
a step of forming a support material using the photocurable composition;
Forming process of model material,
and a step of removing the support material. A method for producing a stereolithographic object using the inkjet 3D printer ink according to claim 3,
a step of forming a support material using the ink;
Forming process of model material,
and a step of removing the support material.