JP7223389B2 - Active energy ray-curable resin composition for three-dimensional modeling support material - Google Patents

Description

The present invention provides an active energy ray-curable resin composition used for forming a support material for shape support in three-dimensional modeling, a photocurable ink containing the composition, a support material formed from the composition, It relates to a three-dimensional structure using the support material.

3D modeling technology Based on 3D shape data, thermoplastic resin, photocurable resin, powdered resin, powdered metal, etc. are fused and cured using melt extrusion, inkjet, laser light, electron beam, etc. It is a technique to obtain a desired three-dimensional model by stacking thin films by allowing them to form. Since it is possible to obtain molded objects directly from shape data and integrally mold complex shapes such as hollows and meshes, it is used in a wide range of fields such as small-lot or order-made test model creation, medical care, aircraft industry, and industrial robots. ing.

A modeling apparatus generally called a 3D printer is used to obtain a three-dimensional modeled object. Specifically, a method of layering photo-curable resins such as acrylic with a photo-curable inkjet 3D printer (photo-curable inkjet method), and a hot-melt lamination method using thermoplastic resins such as acrylonitrile, butadiene, and styrene resins. In addition, a powder molding method and an optical molding method are known.

Three-dimensional modeling can form a three-dimensional object with a complicated shape, but when manufacturing a hollow structure, a support for shape support is required in order to prevent the three-dimensional object from deforming due to its own weight. In particular, with the photo-curing inkjet method, in which the photo-curing resin is cured step by step, it is necessary to simultaneously create a three-dimensional model made of model material and a support made of support material to create a crude model. , a process for removing the support material from the crude model must be provided.

Various methods have been proposed for removing the support material from the crude model, including physical methods such as manual peeling using a spatula or brush, blowing off with a water jet, thermoplastic resin, and so on. A method of removing only the support material by heating and melting it using a heat-melting wax, a method of dissolving or disintegrating the support material using an alkaline aqueous solution, water or an organic solvent, and the like are used.

In particular, after 3D modeling, simply by immersing an integrated crude model consisting of model materials and support materials in water, the support materials dissolve in water, disperse, or absorb water and collapse from the crude model. The easy-to-remove method can efficiently remove the support material clogged in the details of the model without preparing a special cleaning liquid, and it is difficult to damage or deform the model, so it can be used for various supports. A resin composition for lumber has been proposed. For example, Patent Document 1 discloses a photocurable resin composition containing a water-soluble monofunctional ethylenically unsaturated monomer, polyoxypropylene glycol (PPG) and/or water as main components, and Patent Document 2 discloses a water-soluble monomer. A functional ethylenically unsaturated monomer, PPG, polyoxyethylene glycol (PEG) and a photocurable resin composition containing a water-soluble organic solvent as a main component, Patent Document 3 discloses a polyoxyethylene group, a polyoxypropylene group or A monofunctional ethylenically unsaturated monomer having a polyoxybutylene group, a photocurable resin composition containing a (meth)acrylic monomer as a main component, Patent Document 4 describes polyoxybutylene glycol (PTMG) and water proposed a photocurable resin composition based on a monofunctional ethylenically unsaturated monomer. However, these compositions contain PPG, PTMG, etc. as essential and major components, and such polyoxyalkyl glycols are soluble in water when the molecular weight is low, but as the molecular weight increases, the solubility in water increases. It is characterized by a sudden drop in the strength. Therefore, these support material compositions that use medium- or high-molecular-weight polyoxyalkyl glycols that can provide sufficient support force can be used when removing the support material by immersing the crude model in water after stereolithography. Although the entire support material can be peeled off from the model material, there is the problem that the polyoxyalkyl glycol diffuses in water as an oily residue and adheres to the surface of the model material and all parts that come into contact with water. Such an oily residue must be washed again with alcohol or the like or removed by a finishing operation such as wiping, which is very time-consuming and costly. There was also the problem of difficulty in wastewater treatment.

In order to solve the problem of contamination of a modeled object derived from a support material, Patent Document 5 proposed an active energy ray-curable resin composition containing an ionic monomer. According to this document, ionic monomers can be cured by irradiation with active energy rays and can provide supporting power. Since they are compatible, the resulting support material has a sufficient dissolution and dispersion rate in water, does not produce an oily residue, and the aqueous solution after washing is transparent and can be easily discarded. However, since ionic monomers have a high polarity, there is a risk of deformation of the support material due to moisture absorption during three-dimensional modeling work in a humid environment or when modeling large-sized items for a long time.

On the other hand, 3D printers using photo-curing ink jets are required to have larger scale, higher speed, higher precision, and higher performance. It is desired to develop a product that can deal with the above, does not cause surface contamination of the modeled object, does not require a finishing process, and can easily treat water after washing.

JP 2012-111226 A JP 2017-031249 A JP 2018-058974 A JP 2018-087291 A WO2016-121587

The present invention enables the support material to be efficiently removed simply by immersing an integral crude model consisting of a model material and a support material in a cleaning liquid such as water, does not require a finishing process, and produces a large three-dimensional model with high precision. An object of the present invention is to provide an active energy ray-curable resin composition for a support material from which a modeled object can be obtained, and a support material formed from the resin composition. Another object of the present invention is to provide a photocurable ink containing the active energy ray-curable resin composition, and a support material obtained by curing the photocurable ink. A further object of the present invention is to provide a three-dimensional structure that is manufactured using these support materials.

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have solved the above problems by using an active energy ray-curable resin composition containing a water-soluble polymer as a support material resin composition. , found that the target can be achieved, leading to the present invention.

That is, the present invention provides (1) an active energy ray-curable resin composition for a three-dimensional modeling support material containing a water-soluble polymer (A), wherein the water-soluble polymer (A) polymerizes an unsaturated compound (a). an active energy ray-curable resin composition (E), which is a polymer consisting of
(2) The active energy ray-curable resin composition (E) according to (1) above, which contains 0.1 to 30.0% by mass of the water-soluble polymer (A);
(3) The unsaturated compound (a) is one selected from a monomer having a (meth)acrylate group, a monomer having a (meth)acrylamide group, a monomer having a vinyl group, a monomer having an allyl group, and a monomer having a maleimide group. The active energy ray-curable resin composition (E) according to (1) or (2), which is the above monomer,
(4) the unsaturated compound (a) is (meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl (meth) ) acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-methyl-N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N,N-bishydroxyethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-methoxy (iso)propyl (meth)acrylamide , N-methoxybutyl (meth)acrylamide, diacetone (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, acrylonitrile, vinyloxazoline, vinyl acetate, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethyl The monomer according to any one of (1) to (3) above, which is one or more monomers selected from vinyl ether, vinyl trifluoroacetate, vinyloxytetrahydropyran, hydroxyethyl vinyl ether, and hydroxyethyl maleimide. active energy ray-curable resin composition (E),
(5) The active energy ray-curable resin according to any one of (1) to (4), characterized by containing 15.0 to 99.9% by mass of the water-soluble monomer (B). Composition (E),
(6) The water-soluble monomer (B) is one or more monomers selected from water-soluble (meth)acrylates, (meth)acrylamides, and N-substituted (meth)acrylamides ( The active energy ray-curable resin composition (E) according to any one of 1) to (5),
(7) Water-soluble monomer (B) is (meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide , N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide , N-methyl-N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N,N-bishydroxyethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide ) The activity according to any one of (1) to (6) above, which is one or more monomers selected from acrylamide, N-methoxybutyl (meth)acrylamide, and diacetone (meth)acrylamide. energy ray-curable resin composition (E),
(8) The active energy ray-curable resin composition (E) according to any one of (1) to (7), further containing 5.0 to 50.0% by mass of the water-soluble organic solvent (C). ,
(9) The active energy ray according to any one of (1) to (8) above, wherein the water-soluble amide-based agent (C) is β-alkoxy-N,N-dialkylpropionamide. a curable resin composition (E),
(10) Water-soluble organic solvent (C) is β-methoxy-N,N-dimethylpropionamide, β-ethoxy-N,N-dimethylpropionamide, β-(iso)propoxy-N,N-dimethylpropionamide , β-(iso)butoxy-N,N-dimethylpropionamide. elastic resin composition (E),
(11) a photocurable ink (F) containing the active energy ray-curable resin composition according to any one of (1) to (10);
(12) In the three-dimensional modeling of the photocurable inkjet method, the water-soluble polymer (A) is 0.1 to 30.0% by mass, the water-soluble monomer (B) is 15.0 to 99.9% by mass, Photocuring according to (11), characterized in that the water-soluble organic solvent (C) contains 5.0 to 50.0% by mass and the photopolymerization initiator (D) contains 0 to 5.0% by mass. synthetic ink (F),
(13) In the three-dimensional modeling of the photocurable inkjet method, the water-soluble polymer (A) is 1.0 to 25.0% by mass, and the water-soluble monomer acryloylmorpholine (B1) is 35.0 to 94.0% by mass. The above ( 11) or the photocurable ink (F) described in (12),
(14) The active energy ray-curable resin composition (E) according to any one of (1) to (10) and/or the light according to any one of (11) to (13) A support material obtained by curing a curable ink (F) by irradiation with active energy rays;
(15) To provide a three-dimensional modeled object characterized by being modeled using the support material described in (14) above.

According to the present invention, the active energy ray-curable resin composition containing a water-soluble polymer is cured by active energy ray irradiation at the same time as or immediately after three-dimensional modeling, forming a support material, and being supported by the support material and it. A rough model united with the model material is obtained. By immersing the obtained crude model in a cleaning liquid such as water, the support material can be dissolved or dispersed in the cleaning liquid and easily peeled off and removed from the model material. Furthermore, by including a water-soluble polymer, the hardness of the obtained support material is high, and the support property for the model material is good. In addition, since the obtained support material has high moisture resistance, it is possible to form a three-dimensional model with high accuracy even during long-time modeling work. Furthermore, the support is easy to wash, the surface of the model is not contaminated after washing, and the finishing process can be omitted.

The present invention will be described in detail below.
The water-soluble polymer (A) used in the present invention is at least one water-soluble polymer selected from the group consisting of polymers obtained by polymerizing unsaturated compounds (a). In addition, water-soluble in the present invention means that the solubility in water (25° C.) is 1 (g/100 g of water) or more.

The content of the water-soluble polymer (A) in the present invention is preferably 0.1 to 30.0% by mass with respect to the entire active energy ray-curable resin composition (E). If it is 0.1% by mass or more, the support material obtained by curing the active energy ray-curable resin composition (E) is excellent in moisture resistance and hardness, and can be molded with high accuracy, which is preferable. When the content of the water-soluble polymer (A) is 30.0% by mass or less, the viscosity of the active energy ray-curable resin composition (E) is low, the ink jet suitability is excellent, and the support material obtained by curing is It is preferable because it has a sufficient dissolution rate and dispersion rate in washing water. Furthermore, it is more preferably 1.0 to 25.0% by mass, and particularly preferably 5.0 to 20.0% by mass.

The water-soluble polymer (A) in the present invention preferably has a number average molecular weight of 1,000 to 50,000. When the number average molecular weight is 1,000 or more, the support material obtained by curing the active energy ray-curable resin composition (E) is excellent in moisture resistance and hardness, and can be molded with high precision, which is preferable. When the number average molecular weight is 50,000 or less, the viscosity of the active energy ray-curable resin composition (E) is low, the ink jet suitability is excellent, and the support material obtained by curing is sufficiently soluble in washing water. It is preferable because it has speed and dispersion speed, and more preferably has a number average molecular weight of 2,000 to 20,000.

The unsaturated compound (a) is one or more selected from monomers having a (meth)acrylate group, monomers having a (meth)acrylamide group, monomers having a vinyl group, monomers having an allyl group, and monomers having a maleimide group. It is a monomer, and these unsaturated compounds (a) may be used singly or in combination of two or more.

Monomers having a (meth)acrylate group include (meth)acrylic acid, (meth)acrylic acid salts, N,N,N-trialkylammonium alkyl (meth)acrylate salts, water-soluble N,N-dialkylaminoalkyl ( meth) acrylate, water-soluble hydroxyalkyl (meth) acrylate, water-soluble polyalkylene glycol (meth) acrylate, water-soluble alkoxy polyalkylene glycol (meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate It is preferably one or more monomers selected from the above.

A monomer having a (meth)acrylamide group is (meth)acrylamide and/or water-soluble N-substituted (meth)acrylamide. N-substituted (meth)acrylamides include (meth)acryloylmorpholine, water-soluble N-alkyl(meth)acrylamides, water-soluble N-hydroxyalkyl(meth)acrylamides, and water-soluble N,N-dialkyl(meth)acrylamides. , water-soluble N,N-bishydroxyalkyl (meth)acrylamide, water-soluble N-alkyl-N-hydroxyalkyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, Water-soluble N-alkoxyalkyl (meth)acrylamide, diacetone (meth)acrylamide, water-soluble N,N-dialkylaminoalkyl (meth)acrylamide, water-soluble N,N,N-trialkylammonium alkyl (meth) It is preferably one or more monomers selected from acrylamide salts.

Monomers having a vinyl group include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, acrylonitrile, vinyloxazoline, vinyl acetate, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethyl vinyl ether, trifluorovinyl acetate, vinyloxy It is preferably one or more monomers selected from tetrahydropyran, hydroxyethyl vinyl ether, vinylsulfonic acid, vinylphosphonic acid, vinylsulfonate, and vinylphosphonate.

Monomers having an allyl group include N-allylpyrrolidone, N-allylcaprolactam, N-allylacetamide, acrylonitrile, allyloxazoline, allylsulfonic acid, allylphosphonic acid, allyl acetate, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, It is preferably one or more monomers selected from ethyl allyl ether, allyl trifluoroacetate, allyloxytetrahydropyran, hydroxyethyl allyl ether, allyl sulfonate, and allyl phosphonate.

Monomers having a maleimide group include monomers having a maleimide group, an α-substituted maleimide group in which a linear or branched alkyl group having 1 to 6 carbon atoms is introduced at the α-position and/or the β-position, and an α,β-substituted maleimide group. linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, hydroxyalkyl groups, alkyl (meth)acrylates, alkyl (meth)acrylamides, alkylcarboxylic acid groups, and alkoxysilane groups are introduced as N-substituents. preferably one or more monomers selected from α-alkyl-N-substituted maleimides, α,β-dialkyl-N-substituted maleimides, α-phenyl-N-substituted maleimides and N-substituted tetrahydrophthalimides.

When the unsaturated compound (a) contains a carboxylate, a phosphonate, a sulfonate, etc., the counter cations include inorganic cations such as Li ⁺ , Na ⁺ , K ⁺ , Ca ²⁺ , Mg ²⁺ , ammonium, imidazo At least one ion selected from organic cations such as lithium, choline, sulfonium, oxazolium, pyrazolium, pyridinium, pyrrolidinium, and phosphonium can be used. When the unsaturated compound (a) contains an ammonium salt or the like, counter anions include halogen ions such as Cl ⁻ , Br − , I ^{− , OH − ,} CH ₃ COO ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , PF _{6 .} ^- , BF ₄ ^- , HSO ₄ ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , CH ₃ C ₆ H ₆ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , One or more ions selected from inorganic acid anions such as ^SCN- and organic acid anions are included.

The unsaturated compound (a) is preferably a water-soluble monomer having an amide group. In the case of a monomer having an amide group, the water-soluble polymer (A) obtained by polymerization and the water-soluble polymer ( A) is preferable because the solubility in the water-soluble organic solvent (C) is good, and a uniform active energy ray-curable resin composition (E) is easy to prepare. -Methylacrylamide, N-ethylacrylamide, N-propylacrylamide and N-vinylpyrrolidone are more preferred, and acryloylmorpholine and N,N-dimethylacrylamide are particularly preferred.

The water-soluble polymer (A) is a polymer obtained by polymerizing the unsaturated compound (a), but the polymerization method in this case is not particularly limited, and it can be obtained by a known method for polymerizing unsaturated groups. can. For example, the unsaturated compound (a) can be subjected to bulk polymerization, solution polymerization, precipitation polymerization, or the like by radical polymerization, anionic polymerization, cationic polymerization, or the like using active energy rays or heat.

As the initiator used for polymerizing the unsaturated compound (a), known photoinitiators, thermal polymerization initiators, anionic polymerization initiators and cationic polymerization initiators can be used. Acetophenone-based, benzoin-based, benzophenone-based, α-aminoketone-based, xanthone-based, anthraquinone-based, acylphosphine oxide-based, polymer photoinitiators, and the like can be used as the photopolymerization initiator. Usual initiators such as azo initiators, peroxide initiators and redox initiators can be used as thermal polymerization initiators. Common initiators such as protonic acids and Lewis acids can be used as cationic polymerization initiators. Usual compounds such as alkali metals and organometallic compounds can be used for anionic polymerization.

The water-soluble polymer (A) can also be used as a purified polymer after polymerization of the unsaturated compound (a), if necessary. As a method for purifying the polymer, a known method such as reprecipitation can be used.

The water-soluble polymer (A) can also be obtained by solution polymerization of the unsaturated compound (a) in the water-soluble organic solvent (C). In that case, a predetermined amount of the water-soluble monomer (B) is added to the water-soluble organic solvent (C) solution of the water-soluble polymer (A) obtained, and if necessary, a photopolymerization initiator is added and mixed. and can be used directly as an active energy ray-curable resin composition (E).

The water-soluble monomer (B) used in the present invention is preferably at least one monomer selected from water-soluble (meth)acrylates, (meth)acrylamides and N-substituted (meth)acrylamides, The content of the water-soluble monomer (B) is preferably 15.0 to 99.9% by mass with respect to the entire active energy ray-curable resin composition (E). When the content of B is 15.0% by mass or more, the support material obtained by curing the active energy ray-curable resin composition (E) has excellent hardness and moisture resistance, and three-dimensional modeling can be performed with high accuracy. It is preferable because it can be done. When the content of B is 99.9% by mass or less, the support material obtained by curing has a sufficient dissolution rate and dispersion rate in washing water, which is preferable. Also, the B content is more preferably 35.0 to 94.9% by mass, particularly preferably 50.0 to 70.0% by mass. In addition, water-soluble in the present invention means that the solubility in water (25° C.) is 1 (g/100 g of water) or more.

Examples of water-soluble (meth)acrylates used in the present invention include (meth)acrylic ester-based monomers having 1 to 6 carbon atoms in the hydroxyalkyl group, and water-soluble polyalkylene glycol (meth)acrylates include carbon Examples include (meth)acrylic ester-based monomers that are monoesters of polyalkylene glycol and (meth)acrylic acid having an average number of added moles of alkylene oxide having a number of 2 to 4 in the range of 2 to 100, and water-soluble alkoxy Examples of polyalkylene glycol (meth)acrylates include (meth)acrylic ester-based monomers obtained by substituting the hydroxyl groups of the above water-soluble polyalkylene glycol (meth)acrylates with alkoxy groups having 1 to 4 carbon atoms.

The water-soluble N-substituted (meth)acrylamides used in the present invention include, for example, N-alkyl (meth)acrylamides into which an alkyl group having 1 to 3 carbon atoms is introduced, N,N-dialkyl (meth)acrylamides, N-hydroxyalkyl (meth)acrylamide, N,N-di(hydroxyalkyl)(meth)acrylamide, N-hydroxyalkyl-N-(4- hydroxyphenyl)(meth)acrylamide, N-alkyl-N-hydroxyalkyl(meth)acrylamide introduced with a hydroxyalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms, and having 1 to 6 carbon atoms N-alkoxyalkyl (meth)acrylamides, N,N-di(alkoxyalkyl)(meth)acrylamides, having 1 to 6 carbon atoms, into which an alkoxyalkyl group consisting of an alkoxy group of 6 and an alkylene group of 1 to 6 carbon atoms is introduced. An alkoxyalkyl group consisting of an alkoxy group and an alkylene group having 1 to 6 carbon atoms, N-alkyl-N-alkoxyalkyl (meth)acrylamide introduced with an alkyl group having 1 to 6 carbon atoms, N-hydroxyphenyl (meth) ) acrylamide, diacetone (meth)acrylamide, N-(meth)acryloylmorpholine and the like.

The water-soluble monomer (B) used in the present invention includes (meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl ( meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl ( meth)acrylamide, N-methyl-N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N,N-bishydroxyethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxy Ethyl (meth)acrylamide, N-methoxybutyl (meth)acrylamide, and diacetone (meth)acrylamide are preferred because of their high solubility in water and their high curability upon exposure to active energy rays. Particularly preferred are N-acryloylmorpholine (primary skin irritation index PII=0.5) and N-(2-hydroxyethyl)acrylamide (PII=0.0), which have low skin irritation, high safety and are easy to handle. .

The water-soluble organic solvent (C) used in the present invention has a solubility in water (25° C.) of 1 (g/100 g of water) or more, and a water-soluble polymer (A) and a water-soluble monomer (B) is a non-reactive organic solvent. Examples of the water-soluble organic solvent (C) include nitrogen-containing compounds, sulfur-containing compounds, and oxygen-containing compounds. Nitrogen-containing compounds include amines such as water-soluble linear or cyclic alkylamines, dialkylamines, trialkylamines, allylamines, alkylenediamines and alkanolamines, acetamide, formamide, N-methylformamide, N,N-dimethylformamide. , hexamethylphosphortriamide, N,N-dialkylacetamide, N,N-dialkylpropionamide, N-alkylpyrrolidone, N-alkylcaprolactam, amides such as β-alkoxy-N,N-dialkylpropionamide, acetonitrile, Nitriles such as propionitrile, pyrrolidones such as 2-pyrrolidone and N-methyl-2-pyrrolidone, morpholine, N-ethylmorpholine, N-formylmorpholine, aniline, imidazole, caprolactam, tetramethylurea, picoline, hydrazine, pipecoline, piperazine, piperidine, pyridine, pyrrolidine and the like. Sulfur-containing compounds include dimethylsulfoxide, sulfolane, and the like. Oxygen-containing compounds include water-soluble linear or cyclic alcohols, ethylene glycol, propylene glycol, trimethylene glycol, chloropropanediol, butanediol, pentanediol, hexylene glycol, cyclohexanediol, octylene glycol, diethylene glycol, dipropylene Polyhydric alcohols such as glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, glycerin, trimethylolethane, trimethylolpropane, polyethylene glycol, polypropylene glycol, ethylene glycol diglycidyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate tart, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethoxymethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol diacetate, diethylene glycol dibenzoate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monoethyl acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene Derivatives of polyhydric alcohols such as glycol monomethyl ether, dipropylene glycol monoethyl ether, glycerin glycidyl ether, glycerin monoacetate, glycerin diacetate, glycerin triacetate, diethyl ether, dipropyl ether, dioxane, tetrahydropyran , ethers such as tetrahydrofuran, acetals, acetone, diacetone alcohol, ketones such as methyl ethyl ketone, aldehydes such as acetaldehyde, and esters such as butyrolactone. Among these water-soluble organic solvents, the boiling point is preferably 100° C. or higher from the viewpoint of ejection suitability when used as an inkjet ink and prevention of deterioration of support properties due to evaporation during three-dimensional modeling. 150° C. or higher is more preferable, and 200° C. or higher is particularly preferable. These water-soluble organic solvents (C) can be used singly or in combination of two or more.

As the water-soluble organic solvent (C) used in the present invention, a water-soluble organic solvent having an amide group is preferable because it can dissolve both the water-soluble polymer (A) and the water-soluble monomer (B). Specifically, amide solvents such as dialkylformamides, dialkylacetamides, dialkylpropionamides, N-alkylpyrrolidone, N-alkylcaprolactam into which alkyl groups having 1 to 4 carbon atoms are introduced, alkoxy groups having 1 to 4 carbon atoms, and alkoxy groups having 1 to 4 carbon atoms. Examples include β-alkoxy-N,N-dialkylpropionamides into which 1 to 4 alkyl groups have been introduced, and β-alkoxy-N,N-dialkylpropionamides are more preferred.

β-alkoxy-N,N-dialkylpropionamides include β-methoxy-N,N-dimethylpropionamide, β-ethoxy-N,N-dimethylpropionamide, β-(iso)propoxy-N,N-dimethyl Propionamide and β-(iso)butoxy-N,N-dimethylpropionamide are more preferable, and β-methoxy-N,N-dimethylpropionamide is particularly preferable because industrial products are readily available. These water-soluble organic solvents (C) can be used singly or in combination of two or more.

The content of the water-soluble organic solvent (C) used in the present invention is preferably 5.0 to 50.0% by mass with respect to the entire active energy ray-curable resin composition (E). When it is 5.0% by mass or more, the viscosity of the active energy ray-curable resin composition (E) is lowered, the ejection suitability as an inkjet ink is excellent, and the support material obtained by curing is sufficient against washing water. It is preferable because it has a good dissolution rate and dispersion rate. If it is 50.0% by mass or less, the support material obtained by curing is excellent in moisture resistance and hardness, and three-dimensional modeling can be performed with high accuracy, which is preferable. Also, it is more preferably 5.0 to 40.0% by mass, and particularly preferably 10.0 to 30.0% by mass.

The active energy ray-curable resin composition (E) of the present invention is a composition that cures and becomes solid by polymerization. It can be obtained by a known method. Examples thereof include radical polymerization, anionic polymerization, and cationic polymerization using active energy rays or heat. Polymerization using active energy rays is preferable because the polymerization can be easily controlled by adding a photoinitiator or adjusting the irradiation dose.

The active energy ray used for curing the active energy ray-curable resin composition (E) is an electromagnetic wave or charged particle beam that has an energy quantum, i.e., visible light, electron beam, ultraviolet ray, infrared ray, X-ray, It refers to active energy rays such as α-rays, β-rays, and γ-rays. Examples thereof include radiation sources such as high-pressure mercury lamps, halogen lamps, xenon lamps, metal halide lamps, LED lamps, electron beam accelerators, and radioactive elements. When an electron beam is used as an active energy ray source, it is usually not necessary to contain a photoinitiator, but when other active energy ray sources are used, a photoinitiator (D) may be added. preferable. As the active energy ray to be irradiated, ultraviolet rays are preferable because of the storage stability and curing speed of the active energy ray-curable resin composition (E) and low toxicity.

As the photopolymerization initiator (D) used in the present invention, acetophenone-based, benzoin-based, benzophenone-based, α-aminoketone-based, xanthone-based, anthraquinone-based, acylphosphine oxide-based, polymer photoinitiators, and the like are commonly used. can be selected as appropriate. For example, acetophenones include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4- isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl- 1-(4-methylthiophenyl)-2-morpholinopropane-1, benzoins such as benzoin, α-methylbenzoin, α-phenylbenzoin, α-allylbenzoin, α-benzoylbenzoin, benzoin methyl ether, benzoin ethyl ether , benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenones such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, α-aminoketones such as 2-methyl-1-(4-methylthiophenyl)-2- (4-morpholinyl)-1-propanone, 2-benzyl-2-(dimethylamino)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2-(dimethylamino)-2-(4- methylphenyl)methyl-1-(4-(4-morpholinyl)phenyl)-1-butanone, xanthone and thioxanthone as xanthone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone and acylphos as anthraquinone Fin oxides include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and polymeric photoinitiators include 2-hydroxy- Examples include polymers of 2-methyl-1-(4-(1-methylvinyl)phenyl)propan-1-one. These photoinitiators can be used singly or in combination of two or more.

The content of the photopolymerization initiator (D) used in the present invention is preferably 5.0% by mass or less with respect to the entire active energy ray-curable resin composition (E), and is 0.05 to 5.0%. % by mass is more preferred, and 0.5 to 3% by mass is particularly preferred. When it is 0.05% by mass or more, the curable resin composition (E) is sufficiently subjected to a polymerization reaction by irradiation with active energy rays, and the residual monomer in the support material obtained by curing is small, and the cured product is The hardness and moisture resistance are sufficiently maintained, the support property is good, and bleeding out of the non-polymerizable water-soluble organic solvent (C) can be suppressed. Moreover, when it is 5% by mass or less, the pot life of the active energy ray-curable resin composition is long, and the occurrence of troubles such as gelation during storage can be suppressed.

The active energy ray irradiation amount (integrated light amount) necessary for curing the active energy ray-curable resin composition (E) of the present invention is not particularly limited. It varies depending on the type and amount of the water-soluble polymer (A), water-soluble monomer (B), and water-soluble organic solvent (C) used in the active energy ray-curable resin composition (E), and the cumulative amount of light is 50 mJ. /cm ² or more and 1000 mJ/cm ² or less. When the integrated amount of light is 50 mJ/cm ² or more, curing proceeds sufficiently, the cured product has good hardness and moisture resistance, and a highly accurate three-dimensional model can be obtained. Further, when the integrated light amount is 1000 mJ/cm ² or less, the irradiation time of the active energy ray is short, which leads to an improvement in the productivity of three-dimensional modeling, which is preferable.

The active energy ray-curable resin composition (E) of the present invention contains the water-soluble polymer (A), the water-soluble monomer (B), the water-soluble organic solvent (C), and the photopolymerization initiator (D). Non-polymerizable compounds (G) can also be used. The non-polymerizable compound (G) is compatible with the water-soluble polymer (A), the water-soluble monomer (B), the water-soluble organic solvent (C) and the photopolymerization initiator (D), but does not react with them. It is not particularly limited as long as it is non-polymerizable and non-polymerizable. For example, alkylene glycols (excluding the water-soluble organic solvent (C)), polyalkylene glycols (excluding the water-soluble organic solvent (C)) having an average added mole number of alkylene oxide in the range of 2 to 100, alkylene groups and/or Alkylene glycol monoalkyl ethers (excluding water-soluble organic solvents (C)), alkylene glycol dialkyl ethers (excluding water-soluble organic solvents (C)), alkylene glycol monoalkyl ether acetates (water-soluble organic solvents ( C)), the average added mole number of alkylene oxide is in the range of 2 to 100 (excluding the water-soluble organic solvent (C)), polyalkylene glycol monoalkyl ethers (excluding the water-soluble organic solvent (C)), Polyalkylene glycol dialkyl ethers (excluding water-soluble organic solvent (C)), polyalkylene glycol monoalkyl ether acetates (excluding water-soluble organic solvent (C)), alkyl acetate, alkyl propionate, alkyl butanoate, etc. Carboxylic acid esters (excluding water-soluble organic solvent (C)), ketones (excluding water-soluble organic solvent (C)), water, ionic liquids, etc., and these non-polymerizable compounds are limited to one type. It can be used alone or in combination of two or more.

The content of the non-polymerizable compound (G) used in the present invention is preferably 50.0% by mass or less with respect to the entire active energy ray-curable resin composition (E). When it is 50.0% by mass or less, it is preferable because it does not adversely affect the moisture resistance and hardness of the support material obtained by curing the active energy ray-curable resin composition (E), and is 30.0% by mass or less. is more preferable.

Various additives can be used for the active-energy-ray-curable resin composition (E) of this invention as needed. Additives include thermal polymerization inhibitors, antioxidants, antioxidants, UV sensitizers, preservatives, phosphate esters and other flame retardants, surfactants, wetting and dispersing agents, antistatic agents, and coloring agents. , plasticizers, surface lubricants, leveling agents, softeners, pigments, organic fillers, inorganic fillers, and the like. The amount of these various resins and additives to be added is not particularly limited as long as it does not adversely affect the properties exhibited by the active energy ray-curable resin composition according to the present invention. It is preferably 5% by mass or less.

Examples of thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy- 2,2,6,6-tetramethylpiperidine-1-oxyl, phenothiazine, pyrogallol, β-naphthol and the like.

Anti-aging agents include, for example, hindered phenol-based compounds such as butylated hydroxytoluene and butylhydroxyanisole, benzotriazole-based compounds, and hindered amine-based compounds.

Examples of surfactants include alkylene oxide addition type nonionic surfactants such as nonylphenol polyethylene oxide adducts, lauric acid polyethylene oxide adducts, and stearic acid polyethylene oxide adducts, sorbitan palmitate monoester, and sorbitan stearate monoester. , Polyhydric alcohol type nonionic surfactants such as sorbitan stearic acid triester, acetylene glycol compound type nonionic surfactants, acetylene type polyalkylene glycol compound type nonionic surfactants, perfluoroalkyl polyethylene oxide adducts, Fluorine-containing surfactants such as perfluoroalkylcarboxylates and perfluoroalkylbetaines, modified silicone oils such as polyether-modified silicone oils and (meth)acrylate-modified silicone oils, and amphoteric polymeric surfactants.

Examples of antistatic agents include nonionic charge agents such as glycerin fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, bis(2-hydroxyethyl)alkylamines, polyoxyethylene alkylamines, etc. Antistatic agents, anionic antistatic agents such as alkylsulfonates, alkylbenzenesulfonates, and alkylphosphates, nonionic antistatic agents such as tetraalkylammonium salts and trialkylbenzylammonium salts, alkylbetaines, alkylimidazoliumbetaines, etc. amphoteric antistatic agents, (meth)acryloylaminoethyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloylaminopropyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxyethyltrimethylammonium bis(trifluoro and polymerizable antistatic agents such as romethanesulfonyl)imide.

As a preferred method of using the active energy ray-curable resin composition (E) of the present invention, the active energy ray-curable resin composition is formed into a predetermined shape pattern at the same time as or immediately after formation, and the active energy ray is irradiated. It is more preferably used as a photocurable ink (F) used in a photocurable inkjet 3D printer that is ejected by inkjet and cured by irradiation with active energy rays.

The viscosity of the active energy ray-curable resin composition (E) of the present invention is preferably from 1 mPa·s to 2,000 mPa·s at 25° C. from the viewpoint of operability when forming the structure of the support material. stomach. In particular, when the photocurable ink (F) is ejected from an inkjet nozzle, the viscosity is preferably 1 mPa·s to 200 mPa·s at 25°C from the viewpoint of stable ejection, and the ejection temperature is in the range of 20 to 100°C. is preferably When the ejection temperature is set to a high temperature, the viscosity of the photocurable ink (F) is lowered, and a high-viscosity resin can be ejected, but denaturation and polymerization due to heat are likely to occur. From the viewpoint of thermal stability of the photocurable ink (F), it is preferable to discharge the ink at a temperature lower than 80° C., so the viscosity of the photocurable ink (F) is more preferably 100 mPa·s or less.

As a method for using the active energy ray-curable resin composition (E) of the present invention, a photocurable ink (F) is used as a photocurable ink jet 3D printer, and fine droplets are ejected from an ink jet nozzle into a predetermined shape. A method of forming a cured thin film by irradiating an active energy ray after discharging so as to draw a pattern is preferable. Specifically, first, based on the three-dimensional CAD data of the three-dimensional object to be modeled with model materials, as data for three-dimensional modeling, a hardened thin film of the model material corresponding to the three-dimensional object to be modeled is laminated. Sliced cross-sectional shape data and sliced data in the direction in which a hardened thin film of support material for supporting the model material during modeling is laminated are created. For example, if there is a so-called overhanging portion of the model material in the upper position, the support material installation data supports the overhanging part from below by arranging the support material around the model material in the lower position. Create so that support materials are provided. A thin film layer of the resin was formed by ejecting the photocurable ink for the model material or the photocurable ink (F) for the support material from the inkjet nozzle in a desired pattern according to the cross-sectional shape data of the model material and the support material. After that, the thin film layer of the resin is cured by irradiating an active energy ray from a light source. Next, a photocurable ink for model material and/or a photocurable ink (F) for support material is supplied from an inkjet nozzle onto the cured resin thin film layer according to the following cross-sectional shape. By repeating the above steps, hardened thin films of model materials and supporting materials corresponding to each cross-sectional shape are layered to form a support that supports the desired 3D object made of the model material and the 3D object made of the supporting material. do. A support is usually formed between the planar stage and the three-dimensional object. The photocurable ink (F) for the support material and the photocurable ink for the model material may be ejected from the same inkjet nozzle, or may be ejected from separate inkjet nozzles.

The support material of the present invention can be obtained by curing an active energy ray-curable resin composition by irradiating an active energy ray, and by using it as a shape support support material in three-dimensional modeling, a three-dimensional model is supported. It is possible to obtain a crude model supported by the material. The three-dimensionally shaped article can be easily obtained by immersing the obtained crudely shaped article in a cleaning liquid and removing the support material by dissolving or dispersing it in the cleaning liquid.

As the cleaning liquid for the support material of the present invention, ordinary water is used, and as the water, tap water, pure water, ion-exchanged water, or the like is used. Further, if the supporting material obtained by curing the active energy ray-curable resin composition of the present invention is dissolved or dispersed and the three-dimensionally shaped object is not dissolved or swollen, an alkaline aqueous solution, an electrolyte solution, or an organic solvent can be used. is also possible. Alkaline aqueous solutions include aqueous solutions of hydroxides of alkali metals and alkaline earth metals, such as sodium hydroxide aqueous solutions, potassium hydroxide aqueous solutions, and calcium hydroxide aqueous solutions. Electrolyte solutions include potassium carbonate, sodium carbonate, and sodium bicarbonate. , ammonia, and aqueous solutions of electrolytes such as tetramethylammonium hydroxide. Examples of organic solvents include alcohols, ketones, alkylene glycols, polyalkylene glycols, glycol ethers, glycol esters and the like. These water, alkaline aqueous solution, electrolytic solution, and organic solvent can be used singly or in combination of two or more. Water is particularly preferable as the cleaning liquid because it does not dissolve the three-dimensional object, the supporting material is easily dissolved or dispersed in the cleaning liquid, and the safety is ensured.

The washing time of the support material is preferably 24 hours or less, more preferably 10 hours or less. From the viewpoint of production efficiency, if the cleaning time is 24 hours or less, the cleaning cycle can be repeated every day, which is preferable because it is efficient. It is more preferable because the washing can be completed on the next day and the production can be performed more efficiently. Also, the shorter the washing time is, the more preferable it is, because the production efficiency is improved.

The support material can be washed at any temperature between 0°C and 100°C. Since the dissolution and dispersion of the solvent proceeds more rapidly at higher temperatures, washing at 10°C or higher and 40°C or lower is more preferable.

The shape of the support material is arbitrary as long as it is provided so as to support the shape of the three-dimensional object, but the support material of the present invention can be obtained as a support that can be removed by dissolution or dispersion by immersing it in washing water. It is also possible to provide multiple supports in contact with any outer surface of the rough model. By providing a large number of supports in this way, not only does it prevent deformation due to its own weight, but it also has the effect of shielding light from the finished part of the modeling, preventing deterioration of the crude model due to excessive active energy ray irradiation. You can also

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, all "parts" and "%" below are based on mass unless otherwise specified.

The following (A-1) to (A-6) were used as the water-soluble polymer (A). The number average molecular weight of the water-soluble polymer (A-1) was determined by high performance liquid chromatography (LC-10A manufactured by Shimadzu Corporation, using a Shodex GPC KF-806L column (exclusion limit molecular weight: 2×10 ⁷ , separation Range: 100 to 2×10 ⁷ , Number of theoretical plates: 10,000 plates/line, Filler material: Styrene-divinylbenzene copolymer, Filler particle diameter: 10 μm), Tetrahydrofuran was used as the eluent). and calculated by standard polystyrene molecular weight conversion.

A: Water-soluble polymer A-1: N,N-dimethylacrylamide (a-1) (Kohsylmer (registered trademark) DMAA (registered trademark), manufactured by KJ Chemicals) homopolymer with a number average molecular weight of 2,100 .
A-2: A homopolymer of (a-1) having a number average molecular weight of 45,000.
A-3: A homopolymer of (a-1) having a number average molecular weight of 16,000.
A-4: A copolymer (5:1 molar ratio) of (a-1) and maleimide acrylate (a-2) (Aronix M-145 manufactured by Toagosei Co., Ltd.), having a number average molecular weight of 8,000.
A-5: Homopolymer of (a-1) with a number average molecular weight of 6,800.
A-6: A homopolymer of N-acryloylmorpholine (a-3) (Kohsylmer (registered trademark) ACMO (registered trademark), manufactured by KJ Chemicals) with a number average molecular weight of 14,000.
A-7: A homopolymer of N-vinylpyrrolidone (a-4) with a number average molecular weight of 15,000.

Active energy ray-curable resin compositions (E-1) to (E-14) for examples and active energy ray-curable resin compositions (I-1) to (I-5) for comparative examples
Example 1
10.0 parts by mass of the water-soluble polymer (A-1), 89.5 parts by mass of N-acryloylmorpholine (B-1), and 0.5 parts by mass of Omnirad 184 (D-1) were charged in a container and heated to 25°C. By stirring for 1 hour, a homogeneous and transparent active energy ray-curable resin composition (E-1) of Example 1 was obtained.

Examples 2-14
By performing the same operation as in Example 1 with the composition shown in Table 1, active energy ray-curable resin compositions (E-2) to (E-14) corresponding to Examples 2 to 14 were obtained.

Comparative Examples 1-5
By performing the same operation as in Example 1 with the composition shown in Table 1, active energy ray-curable resin compositions (I-1) to (I-5) corresponding to Comparative Examples 1 to 5 were obtained. Here, Comparative Example 2 is Example 2-1 described in Patent Document 1 (JP 2012-111226), and Comparative Example 3 is an example described in Patent Document 2 (JP 2017-031249). S4, Comparative Example 4 is Example 2 described in Patent Document 4 (JP 2018-087291), Comparative Example 5 is Example 5 described in Patent Document 3 (JP 2018-058974). I used it as a reference.

Explanation of Abbreviations in Table 1 A: Water-soluble polymers A-1 to A-7 are as described above.
B: Water-soluble monomer B-1: N-acryloylmorpholine (Kohsylmer (registered trademark) ACMO (registered trademark), manufactured by KJ Chemicals)
B-2: N-(2-hydroxyethyl)acrylamide (Kohsylmer (registered trademark) HEAA (registered trademark), manufactured by KJ Chemicals)
B-3: Methoxy polyethylene glycol monoacrylate (PEG average molecular weight 400) (NK ester AM90G, manufactured by Shin-Nakamura Chemical Co., Ltd.)
C: Water-soluble organic solvent C-1: β-methoxy-N,N-dimethylpropionamide (KJCMPA (registered trademark)-100, manufactured by KJ Chemicals)
C-2: Tripropylene glycol monomethyl ether C-3: Polypropylene glycol with a number average molecular weight of 400 (Uniol D-400, manufactured by NOF Corporation)
C-4: β-n-butoxy-N,N-dimethylpropionamide (KJCBPA (registered trademark)-100, manufactured by KJ Chemicals)
C-5: Triethylene glycol monomethyl ether C-6: Polyethylene glycol having a number average molecular weight of 200 D: Photopolymerization initiator D-1: Omnirad 184 (1-hydroxycyclohexylphenyl ketone, manufactured by IGM Resins B.V.)
D-2: Omnirad TPO (diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, manufactured by IGM Resins B.V.)
D-3: Omnirad 819 (Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, manufactured by IGM Resins B.V.)
D-4: Omnirad 2959 (2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, manufactured by IGM Resins B.V.)
G: non-polymerizable compound G-1: deionized water G-2: polypropylene glycol with a number average molecular weight of 1000 (Uniol D-1000, manufactured by NOF Corporation)
G-3: Polybutylene polyethylene glycol with a number average molecular weight of 1000 (Polycerin DC-1100, manufactured by NOF Corporation)
H: Various additives and other components H-1: Surfynol 440 (manufactured by Air Products Japan)
H-2: Acryloylaminopropyltrimethylammonium bis(trifluoromethanesulfonyl)imide H-3: BYK307 (polyether-modified polydimethylsiloxane, manufactured by BYK Chemie Japan Co., Ltd.)
H-4: (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy) radical H-5: Emanone 1112 (polyethylene oxide laurate, manufactured by Kao Corporation)
H-6: TEGORad2100 (silicon acrylate having a polydimethylsiloxane structure, manufactured by Evonik Degussa)
H-7: Uniox PKA-5009 (methoxy polyethylene glycol monoallyl ether, manufactured by NOF Corporation)

Active energy ray-curable resin compositions for forming support materials obtained in Examples 1 to 14 and Comparative Examples 1 to 5 (E-1) to (E-14), (I-1) to (I-5) ) was performed by the following method, and the results are shown in Table 2.

Viscosity measurement Using a cone-plate viscometer (device name: RE550 type viscometer manufactured by Toki Sangyo Co., Ltd.), at 25 ° C. in accordance with JIS K5600-2-3, obtained in each example and comparative example The viscosity of the active energy ray-curable resin composition was measured.

Supportability A cylindrical spacer with a thickness of 10 mm and an inner diameter of 20 mm was placed on a polymethyl methacrylate plate (PMMA plate) with a thickness of 1 mm placed horizontally, and the activation energy obtained in each example and comparative example was placed inside the spacer. After filling each 0.3 g of the ray-curing resin composition, it is irradiated with ultraviolet rays (equipment: manufactured by igraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: manufactured by igraphics M04-L41, ultraviolet illuminance 300 mW / cm ² , the cumulative amount of light was 1,000 mJ/cm ² ) to obtain a cured support material. Further, 0.3 g of the active energy ray-curable resin composition was added onto the cured supporting material, and similarly cured by UV irradiation to laminate a thin film of the supporting material. Thereafter, the same hardening was repeated to obtain a support material having thin films laminated up to a thickness of 10 mm. After that, the Shore A hardness of the obtained support material was measured at room temperature (25° C.) to evaluate the support performance of the support material as a support.
◎: Good supportability (Shore A hardness ≥ 80)
○: Sufficient supportability is observed (80> Shore A hardness ≥ 60)
△: Slightly supportive but insufficient (60> Shore A hardness ≥ 40)
×: No support (40> Shore A hardness)

Humidity resistance A 75 μm thick heavy release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) is attached to a horizontally installed glass plate, and a spacer with a thickness of 1 mm and an inside of 50 mm × 20 mm is placed. After filling the active energy ray-curable resin composition obtained in each example and comparative example, a 50 μm thick easy peeling PET film (manufactured by Toyobo Co., Ltd., polyester film E7002) is layered thereon, and ultraviolet light is applied. is irradiated (equipment: Eyegraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: Eyegraphics M04-L41, ultraviolet illuminance 300 mW/cm ² , integrated light intensity 1,000 mJ/cm ² ), and active energy rays. The curable resin composition was cured. After that, the cured product prepared by removing the peeled PET films on both sides was used as a test piece, left to stand for 24 hours in a constant temperature and humidity bath set at 25 ° C. and 50% RH, and the surface of the test piece before and after standing was visually observed. was evaluated by
◎: Deformation due to moisture absorption of the cured product after standing is not observed ○: Bleed-out due to moisture absorption of the cured product is slightly observed after standing, but almost no deformation is observed △: The cured product is due to moisture absorption after standing Bleed-out is slightly observed, and deformation is slightly observed ×: The cured product dissolves due to moisture absorption after standing, and deformation is observed

Cleanability A 1mm thick polymethyl methacrylate (PMMA) plate (PMMA plate) placed horizontally with a spacer of 50mm x 40mm inside and a 1mm thick curable resin before light curing forms a model material inside the spacer. After filling 1 g each of "LH100white" manufactured by Mimaki Engineering Co., Ltd. as a composition and the active energy ray curable resin composition obtained in each example and comparative example so that they are in contact with each other, ultraviolet irradiation (apparatus: Inverter-type conveyor device ECS-4011GX manufactured by Eyegraphics, metal halide lamp: M04-L41 manufactured by Eyegraphics, ultraviolet illuminance of 300 mW/cm ² , integrated light intensity of 1,000 mJ/cm ² ) to obtain a model material and a support material. . Thereafter, at room temperature (25°C), the obtained model material and support material on the PMMA plate are immersed in ion-exchanged water as a washing liquid, the support material is dissolved or dispersed in water, and the model material and the support material are removed from the PMMA plate. After the was removed, the condition of the model material and the PMMA plate was checked, and the washability was evaluated by the following evaluation method.
◎: All the support material is removed (no roughness or oily stickiness on the contact part with the model material and the PMMA plate surface)
○: Most of the support material has been removed (the part in contact with the model material and the surface of the PMMA plate are slightly rough and oily, but can be washed with water)
△: Most of the support material is removed, but there is residue, oily stickiness, etc. (Cannot be washed with water flow)
△ ×: Part of the support material remains (part of the support material remains in the contact area with the model material and on the PMMA surface, and cannot be washed with a water flow)
×: Support material not removed

Washing time The washability of the support material was evaluated by the following evaluation method by confirming the time required for the support material to be dissolved or dispersed in water and removed.
◎: Supporting material dissolved or dispersed in water for less than 1 hour and removed ○: Supporting material dissolved or dispersed in water for 1 hour or more and less than 5 hours and removed △: Supporting material dissolved or dispersed in water for 5 hours or more 10 Dissolved or dispersed in water and removed within less than 1 hour △ ×: Support material dissolved or dispersed in water and removed within 10 hours or more and less than 24 hours ×: 24 hours or more required to remove support material

Condition of Washing Solution With regard to the washability of the support material, the condition of the washing solution after the support material was dissolved or dispersed in water was confirmed and evaluated by the following evaluation method.
◎: The cleaning liquid is uniform and transparent, and there is no residue ○: The cleaning liquid is uniform and slightly cloudy, and there is no residue Condition where oily residue is observed

Table 2

As is clear from the results in the table, the active energy ray-curable resin compositions of Examples 1 to 14 have viscosities of 1,000 mPa·s or less at 25°C and excellent operability. 3, 4, and 6 to 14 had viscosities of 100 mPa·s or less, which were excellent in operability and had viscosities that gave good ejection properties as inkjet inks. The support materials obtained by curing the active energy ray-curable resin compositions of Examples were excellent in hardness and moisture resistance, and were suitable resins exhibiting good support properties even in long-time modeling. Furthermore, all of the examples show good solubility and dispersibility in ion-exchanged water, can completely remove the support material in a short time at a low temperature, and contain a water-soluble organic solvent, so that the support material in the cleaning solution The solubility and dispersibility of the material were improved, and the reattachment of the support material after washing to the PMMA plate surface was suppressed. On the other hand, among the comparative examples containing no water-soluble polymer, Comparative Examples 1 to 4 exhibited good washing times, but none of the other physical properties were satisfactory. In Comparative Example 1, since the water-soluble polymer (A) was not included, the support material obtained by curing had low moisture resistance, and long-term modeling was impossible. Comparative Example 2 referring to Example 2-1 described in Patent Document 1 (JP 2012-111226), Example S4 described in Patent Document 2 (JP 2017-031249) was referred to In Comparative Example 3, the hardness of the support material obtained by curing was as low as less than Shore A60, and the moisture resistance was also low. The washing water used to remove the material was cloudy, and there was a yellow oily residue, which was seen as a yellow oily deposit on the PMMA plate surface and the interface of the model material. On the other hand, in Comparative Example 4 referring to Example 2 described in Patent Document 4 (JP 2018-087291), the hardness of the cured product was high and the supportability was good, but Comparative Examples 2 and 3 Similarly, the washing water used to remove the support material became cloudy, and part of the dispersed support material appeared as yellow oily deposits on the PMMA plate surface and the interface of the model material. Surface contamination derived from support materials such as oil droplets was found on the modeled object, and a finishing process such as wiping with an organic solvent such as alcohol was required. In addition, in Comparative Example 5, which refers to Example 5 described in Patent Document 3 (JP-A-2018-058974), washing with deionized water at 25° C. cannot sufficiently wash the supporting material in 24 hours. there were.

As explained above, the active energy ray-curable resin composition of the present invention can be suitably used for forming a support material for three-dimensional modeling. In addition, the active energy ray-curable resin composition of the present invention has low viscosity and excellent operability, and can be used as a photocurable ink for three-dimensional modeling with a photocurable inkjet 3D printer. Furthermore, when a three-dimensional article supported by the support material of the present invention is immersed in a cleaning liquid, the support material can be efficiently removed, and a large three-dimensional article can be produced with high precision without the need for a finishing process. You can get the sculpture. In addition, by including a water-soluble polymer, the support material has excellent support properties, excellent modeling accuracy can be obtained, and it has the effect of improving moisture resistance, making it possible to model for a long time. manufacturing is possible. The support material of the present invention exhibits excellent removability and has the advantage of being able to accurately form a large three-dimensional model. There is an advantage that high-performance modeling is possible.

Claims (15)

Water-soluble polymer (A) 0.1 to 30.0% by mass, water-soluble monomer (B) 15.0 to 94.9% by mass, and water-soluble organic solvent (C) 5.0 to 50.0% by mass %, wherein the water-soluble polymer (A) is a polymer obtained by polymerizing the unsaturated compound (a), and the water-soluble organic solvent (C ) has a boiling point of 100° C. or higher, the active energy ray-curable resin composition (E). Water-soluble polymer (A) 0.1-30.0% by mass, water-soluble monomer (B) 15.0-60.0% by mass, water-soluble organic solvent (C) 5.0-50.0% by mass , the active energy ray-curable resin composition (E) according to claim 1 , containing 1.0 to 50.0% by mass of the non-polymerizable compound (G). The unsaturated compound (a) is one or more monomers selected from monomers having a (meth)acrylate group, monomers having a (meth)acrylamide group, monomers having a vinyl group, monomers having an allyl group, and monomers having a maleimide group. The active energy ray-curable resin composition (E) according to claim 1 or 2, characterized in that: The unsaturated compound (a) is (meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-methyl-N-hydroxyethyl (meth)acrylamide, N-hydroxy Propyl (meth)acrylamide, N,N-bishydroxyethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-methoxy (iso)propyl (meth)acrylamide, N- Methoxybutyl (meth)acrylamide, diacetone (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, acrylonitrile, vinyloxazoline, vinyl acetate, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethyl vinyl ether, tri 4. The active energy ray-curable resin according to any one of claims 1 to 3, which is one or more monomers selected from vinyl fluoroacetate, vinyloxytetrahydropyran, hydroxyethyl vinyl ether, and hydroxyethyl maleimide. Composition (E). Claims 1 to 4, wherein the water-soluble monomer (B) is one or more monomers selected from water-soluble (meth)acrylates, (meth)acrylamides and N-substituted (meth)acrylamides. The active energy ray-curable resin composition (E) according to any one of . Water-soluble monomer (B) is (meth) acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N- Methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N- methyl-N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N,N-bishydroxyethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, 6. The active energy ray-curable resin composition according to any one of claims 1 to 5, which is one or more monomers selected from N-methoxybutyl (meth)acrylamide and diacetone (meth)acrylamide. Thing (E). The active energy ray-curable resin composition (E) according to any one of claims 1 to 6, wherein the water-soluble organic solvent (C) is β-alkoxy-N,N-dialkylpropionamide. . Water-soluble organic solvent (C) is β-methoxy-N,N-dimethylpropionamide, β-ethoxy-N,N-dimethylpropionamide, β-(iso)propoxy-N,N-dimethylpropionamide, β- 8. The active energy ray-curable resin composition (E ). A photocurable ink (F) containing the active energy ray-curable resin composition according to any one of claims 1 to 8. In the three-dimensional modeling of the photocurable inkjet method, the water-soluble polymer (A) is 0.1 to 30.0% by mass, the water-soluble monomer (B) is 15.0 to 94.9% by mass, and the water-soluble organic 10. The photocurable ink (F ). In the three-dimensional modeling of the photocurable inkjet method, the water-soluble polymer (A) is 1.0 to 25.0% by mass, and the water-soluble monomer acryloylmorpholine (B1) is 35.0 to 80.0% by mass. 0% by mass, a water-soluble organic solvent (C) of 5.0 to 30.0% by mass, and a photopolymerization initiator (D) of 0.05 to 5.0% by mass. The photocurable ink (F) according to claim 9 or claim 10. After obtaining the water-soluble polymer (A) by solution polymerization of the unsaturated compound (a) in the water-soluble organic solvent (C), The method for producing an active energy ray-curable resin composition (E) according to any one of claims 1 to 8, wherein the reactive monomer (B) is added and mixed. After obtaining the water-soluble polymer (A) by solution polymerization of the unsaturated compound (a) in the water-soluble organic solvent (C), a water-soluble monomer is added to the solution of the obtained polymer (A) in the organic solvent (C). The method for producing a photocurable ink (F) according to any one of claims 9 to 11, wherein the body (B) and the photopolymerization initiator (D) are added and mixed. The active energy ray-curable resin composition (E) according to any one of claims 1 to 8 or the photo-curable ink (F) according to any one of claims 9 to 11 is applied with an active energy ray. A support material obtained by curing by irradiation. A three-dimensional modeled object characterized by being modeled using the support material according to claim 14 .