Active energy ray-curable resin composition, shaped article obtained by curing the same, and method for producing molded article using the shaped article

Abstract

To provide an active energy ray-curable resin composition which enables shaping of a highly precise shaped article at high shaping speed, and has high curability and low curing shrinkage, and an active energy ray-curable resin composition which has no dissolution capacity to a cured product obtained by curing the same.SOLUTION: An active energy ray-curable resin composition contains a non-polyfunctional polymerizable compound (A) and a non-crosslinkable polymer (B).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable resin composition, a shaped article obtained by curing the same, and a method for producing a molded article using the shaped article. [Background technology]

[0002] Curing reactions using active energy rays, such as ultraviolet (UV) rays and electron beams, generally generate radicals or ionic species through irradiation with active energy rays, which polymerize raw materials with polymerizable functional groups, such as unsaturated groups or epoxy groups, thereby solidifying (curing) liquid compositions in a short period of time. For this reason, active energy ray curing reactions are used in a wide range of fields, including paints and coatings, pressure-sensitive adhesives, inkjet inks, sealing materials, dental hygiene materials, and optical materials. In particular, three-dimensional modeling (3D photolithography) technology using active energy ray curing has attracted attention in recent years because it can be cured in any location and shape and enables highly accurate additive manufacturing.

[0003] Three-dimensional stereolithography (3D stereolithography) is a technique for curing an active energy ray-curable resin composition into a thin film using active energy rays based on three-dimensional shape data, and then stacking these thin films to create the desired three-dimensional object. Well-known 3D stereolithography methods using this technology include the material jetting method, in which a liquid active energy ray-curable resin composition is sprayed from a nozzle and cured by exposure to active energy rays, and the liquid tank photopolymerization method, in which the active energy ray-curable resin composition is placed in a liquid tank and cured by irradiating the liquid surface with active energy rays from above or below. Various methods have been proposed for liquid tank photopolymerization, including, for example, a method that uses a laser to scan the cross section using a galvanometer mirror (SLA), a method that uses a projector to expose the cross-sectional shape all at once (DLP), and a method that uses a liquid crystal display to expose the cross-sectional shape all at once (LCD). These 3D photopolymerization technologies can directly generate 3D objects from shape data, can integrally mold complex shapes such as hollow or mesh-like shapes, and can easily change the shape of the 3D object by changing the shape data. Therefore, they are used to create test models and prototypes in a variety of fields, including medicine, the aircraft industry, and industrial robots.

[0004] Active energy ray-curable resin compositions used in three-dimensional stereolithography are required to have low cure shrinkage because shrinkage during curing (curing shrinkage) can reduce the reproducibility and dimensional accuracy of the model, and distortions and the like caused by the curing shrinkage remain in the three-dimensional model (hereinafter also referred to as a cured product) after curing, causing deformation (warping) of the cured product over time. Furthermore, active energy ray-curable resin compositions are also required to have high cure speeds in order to accurately model three-dimensional models. For example, Patent Document 1 describes a composition for three-dimensional object creation containing a monofunctional monomer, a polyfunctional monomer, 2-5% by mass of an acylphosphine oxide-based photopolymerization initiator, and 1-4% by mass of an α-hydroxyphenone-based photopolymerization initiator. The composition suppresses warping of the resulting three-dimensional object by controlling the mass ratio of the monofunctional monomer to the polyfunctional monomer within a certain range and adjusting the difference in curing rate between the surface and the interior by incorporating the two specific photopolymerization initiators. At the same time, the composition reports that adjusting the content of each of the two specific photopolymerization initiators within a specific range increases the curing rate of the composition, thereby solving the problem of modeling accuracy of the three-dimensional object. However, while the composition for three-dimensional object creation has been shown to improve the modeling accuracy of three-dimensional objects created using a material jetting method, it is unclear whether similar improvements in modeling accuracy can be achieved using other methods.

[0005] Furthermore, in order to obtain a highly accurate shaped object having sharp sides, corners, and other sharp shapes by a three-dimensional stereolithography method, the active energy ray-curable resin composition used is further required to have no solubility in the cured product obtained by curing the composition. However, no active energy ray-curable resin composition for use in a three-dimensional stereolithography method has yet been reported that has high curability, low hardening shrinkage, and no solubility in the cured product, and that can be used to form a highly accurate shaped object at a high modeling speed. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent Publication No. 2019-137812 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide an active energy ray-curable resin composition that has high curability and low cure shrinkage and that can be used to form highly accurate objects at a high modeling speed, and that does not have the ability to dissolve the cured product obtained by curing the active energy ray-curable resin composition. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by an active energy ray-curable resin composition containing a non-polyfunctional polymerizable compound (A) and a non-crosslinkable polymer (B), and a shaped article obtained by curing the same.

[0009] That is, the present invention is (1) An active energy ray-curable resin composition containing a non-polyfunctional polymerizable compound (A) and a non-crosslinkable polymer (B), wherein the active energy ray-curable resin composition does not have the ability to dissolve a cured product thereof; (2) The active energy ray-curable resin composition according to (1) above, characterized in that the viscosity at 25°C is 30 to 100,000 mPa·s. (3) The active energy ray-curable resin composition according to (1) or (2), characterized in that the active energy ray-curable resin composition contains at least 10.0 to 99.9 mass% of a non-polyfunctional polymerizable compound (A) and 0.1 to 50.0 mass% of a non-crosslinkable polymer (B). (4) The active energy ray-curable resin composition according to any one of (1) to (3), wherein the non-polyfunctional polymerizable compound (A) comprises a monofunctional polymerizable compound (a1) and / or a polymerizable compound (a2) having an average number of unsaturated groups in the molecule of more than 1 and less than 2. (5) The active energy ray-curable resin composition according to (4), wherein the monofunctional polymerizable compound (a1) has one unsaturated group and one or more amide groups and / or oxyalkylene groups in the molecule. (6) The active energy ray-curable resin composition according to any one of (1) to (5), which is used for three-dimensional optical shaping. (7) The active energy ray-curable resin composition according to (6), wherein the three-dimensional optical shaping is performed by a liquid tank photopolymerization method. (8) A shaped object (X) obtained by curing the active energy ray-curable resin composition according to any one of (1) to (7). (9) The shaped article (X) according to (8) above, which is soluble, dispersible, or disintegrable in water, an organic solvent, or a mixture thereof; (10) A method for producing a molded product (Y) using a molding material, comprising the steps of: a first step of forming a hollow object (x1) using the active energy ray-curable resin composition according to any one of (1) to (7); a second step of filling the hollow portions of the obtained shaped object (x1) with a molding material and curing and / or solidifying the material to obtain a crude molded object; a third step of immersing the obtained crude molded product in water, an organic solvent or a mixture thereof, and removing the shaped product (x1) to obtain a molded product (Y); A method for producing a molded product (Y), comprising: (11) The method for producing the molded product (Y) according to (10), wherein in the second step, the molding material is cured and / or solidified by one or more of active energy rays, heat and / or moisture. (12) The molding material according to (10) or (11) is at least one selected from the group consisting of silicone resin, epoxy resin, polyester resin, urethane resin, acrylic resin, cyanoacrylate resin, biodegradable resin, natural resin, and metal; (13) The molding material according to (10) or (11) above is a molding material having a bio-based content of 25% or more. (14) The molding material according to (10) or (11) above is characterized in that it contains an organic filler and / or an inorganic filler. (15) The molded product (Y) according to (10) or (11) above is characterized in that it is decomposed by at least one of physical action, chemical action, and biological action. This provides: [Effects of the Invention]

[0010] The active energy ray-curable resin composition of the present invention has high curability, low cure shrinkage, and no ability to dissolve the cured product, and therefore can be used to form highly accurate objects at a high modeling speed.

[0011] Furthermore, by adjusting the composition of the active energy ray-curable resin composition of the present invention as needed, it is possible to form a shaped object that is soluble, dispersible, or degradable in water, an organic solvent, or a mixture thereof, and therefore, after using the shaped object for purposes such as a prototype under development or a test model for a product, the shape of the shaped object can be easily destroyed, which is expected to have the effect of preventing the leaking of ideas for appearance, etc. Furthermore, since the shaped object can be imparted with relatively high strength and heat resistance, the shaped object can be used to obtain another molded object, and in this case, it is possible to make the shaped object easily removable by immersing it in water, an organic solvent, or a mixture thereof, and a molded object with a fine structure can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described in detail. A first embodiment of the present invention is an active energy ray-curable resin composition (E). The active energy ray-curable resin composition (E) according to this embodiment (hereinafter also simply referred to as "active energy ray-curable resin composition (E)") is characterized by containing a non-polyfunctional polymerizable compound (A) and a non-crosslinkable polymer (B), and not having the ability to dissolve the cured product thereof.

[0013] As described above, three-dimensional stereolithography is a technique for curing an active energy ray-curable resin composition into a thin film using active energy rays based on three-dimensional shape data, and then laminating the thin-film cured product to obtain a desired object. During the three-dimensional stereolithography process, the active energy ray-curable resin composition is cured into a thin film using active energy rays. However, if the active energy ray-curable resin composition has the ability to dissolve the cured product, the uncured composition will dissolve during modeling, making it difficult to accurately obtain a model having a sharp shape, such as sharp sides or corners. In contrast, the active energy ray-curable resin composition (E) according to this embodiment has the characteristic of not having the ability to dissolve the cured product. Therefore, when three-dimensional stereolithography is performed using the active energy ray-curable resin composition (E), three-dimensional stereolithography can be performed without dissolving the uncured composition during modeling, making it possible to accurately obtain a model having a sharp shape, such as sharp sides or corners. In this specification, the term "solubility" means that 100 g of a solvent can dissolve 1 g or more of a solute at 25° C. under atmospheric pressure.

[0014] The viscosity of the active energy ray-curable resin composition (E) according to this embodiment is preferably 30 to 100,000 mPa·s at 25°C, and more preferably 100 to 10,000 mPa·s. A viscosity within this range provides good operability during modeling, making it suitable for use as a composition for various types of three-dimensional stereolithography, and enabling the production of highly accurate models. Furthermore, when the active energy ray-curable resin composition (E) is used for three-dimensional stereolithography using a liquid tank photopolymerization method, from the viewpoint of modeling operations such as smooth operation of the modeling table, the viscosity is more preferably 10,000 mPa·s or less at 25°C, even more preferably 2,000 mPa·s or less, and particularly preferably 500 mPa·s or less. Viscosity can be measured by the method described below.

[0015] The active energy ray-curable resin composition (E) contains a non-multifunctional polymerizable compound (A), making it curable and suitable for use in three-dimensional stereolithography. Furthermore, by incorporating both the non-crosslinkable polymer (B) and the non-multifunctional polymerizable compound (A), the active energy ray-curable resin composition (E) loses its ability to dissolve its cured product. The inventors speculate that this is because the polymer chains of the non-crosslinkable polymer (B) dissolved in the non-multifunctional polymerizable compound (A) become entangled and are fixed by polymerization of the non-multifunctional polymerizable compound (A) around the polymer chains, forming a network structure through the complexation of heterogeneous polymer chains. As mentioned above, the active energy ray-curable resin composition (E) lacks the ability to dissolve its cured product, and therefore, when used in three-dimensional stereolithography, highly accurate models can be obtained.

[0016] The Tg of the polymer obtained by polymerizing the non-polyfunctional polymerizable compound (A) is not particularly limited, but is preferably 40°C or higher. When such a non-polyfunctional polymerizable compound (A) is contained, the heat resistance of the cured product of the active energy ray-curable resin composition (E) is improved. From this viewpoint, the Tg of the polymer obtained by polymerizing the non-polyfunctional polymerizable compound (A) is more preferably 60°C or higher, and even more preferably 100°C or higher.

[0017] The content of the non-polyfunctional polymerizable compound (A) is preferably 10.0 to 99.9% by mass, based on the total mass of the active energy ray-curable resin composition (E). When the non-polyfunctional polymerizable compound (A) is contained within this range, it becomes easier to adjust the viscosity of the active energy ray-curable resin composition (E) to a range suitable for the above-mentioned three-dimensional stereolithography, and the strength of the cured product is improved, ensuring sufficient strength for practical use. From these viewpoints, the content of the non-polyfunctional polymerizable compound (A) is more preferably 20.0 to 90.0% by mass, and even more preferably 30.0 to 80.0% by mass.

[0018] The non-polyfunctional polymerizable compound (A) includes a monofunctional polymerizable compound (a1) and / or a polymerizable compound (a2) having an average number of unsaturated groups in the molecule greater than 1 and less than 2. The monofunctional polymerizable compound (a1) is a polymerizable compound having one unsaturated group in the molecule. The unsaturated group in (a1) is not particularly limited, but is preferably one unsaturated group selected from the group consisting of unsaturated groups such as (meth)acrylamide, (meth)acrylate, vinyl, vinyl ether, methyl vinyl ether, allyl, (meth)allyl ether, and maleimide. The inclusion of such (a1) acts synergistically with the non-crosslinkable polymer (B) to prevent dissolution of the cured product in the active energy ray-curable resin composition (E), thereby enabling the production of highly accurate shaped objects.

[0019] Examples of the monofunctional polymerizable compound (a1) having a (meth)acrylamide group as an unsaturated group include (meth)acrylamide, mono- or di-substituted (meth)acrylamide, (meth)acryloylmorpholine, (meth)acryloylpyrrolidine, (meth)acryloyl(2-alkylpyrrolidine) having a linear or branched alkyl group having 1 to 18 carbon atoms, (meth)acryloyl(3-alkylpyrrolidine) (meth)acryloylpiperidine, (meth)acryloyl(2-alkylpiperidine) having a linear or branched alkyl group having 1 to 18 carbon atoms, (meth)acryloyl Examples of mono- or di-substituted (meth)acrylamides include N-alkyl(meth)acrylamides, N-alkenyl(meth)acrylamides, N,N-dialkyl(meth)acrylamides, and N,N-dialkenyl(meth)acrylamides into which a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms has been introduced, and N-hydroxyalkyl(meth)acrylamides into which a hydroxyalkyl group having 1 to 6 carbon atoms has been introduced. N-alkoxyalkyl(meth)acrylamide, N,N-di(hydroxyalkyl)(meth)acrylamide, N-alkyl-N-hydroxyalkyl(meth)acrylamide having a hydroxyalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms introduced therein, N-alkoxyalkyl(meth)acrylamide having an alkoxyalkyl group consisting of an alkoxy group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms introduced therein, N,N-di(alkoxyalkyl)(meth)acrylamide, alkoxyalkyl group consisting of an alkoxy group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms, alkyl groups having 1 to 6 carbon atoms, N-Alkyl-N-alkoxyalkyl(meth)acrylamides having an alkyl group introduced therein, N-sulfoalkylacrylamides having an alkylsulfonic acid group having 1 to 6 carbon atoms introduced therein, N-Alkylamino(meth)acrylamides having an aminoalkyl group having 1 to 6 carbon atoms introduced therein, N-Alkylamino(meth)acrylamides having an N-Alkylaminoalkyl group consisting of an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms introduced therein, N,N-Dialkylaminoalkyl group consisting of an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms introduced therein,Examples of the monofunctional polymerizable compound (a1) having a (meth)acrylamide group include N-dialkylaminoalkyl(meth)acrylamides, succinic acid mono(hydroxyalkyl(meth)acrylamide) esters composed of hydroxyalkyl(meth)acrylamides having 1 to 18 carbon atoms and dibasic acids, phthalic acid mono(hydroxyalkyl(meth)acrylamide) esters, hexahydrophthalic acid mono(hydroxyalkyl(meth)acrylamide) esters, and other carboxylic acid group-introduced (meth)acrylamides, glycerin mono(meth)acrylamides and trimethylolpropane mono(meth)acrylamides having two hydroxyl groups introduced therein. The monofunctional polymerizable compound (a1) having a (meth)acrylamide group may be used alone or in combination of two or more.

[0020] The monofunctional polymerizable compound (a1) having a (meth)acrylamide group as an unsaturated group is preferably one or more selected from (meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-methyl-N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, N,N-bishydroxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, and diacetone(meth)acrylamide. The amide groups in these monomers readily form strong hydrogen bonds, resulting in strong entanglement of the polymer chains with the non-crosslinkable polymer (B) after polymerization. This synergistic effect with (B) prevents the cured product from dissolving in the active energy ray-curable resin composition (E), allowing for the production of highly accurate shaped objects.

[0021] Examples of the monofunctional polymerizable compound (a1) having a (meth)acrylate group as an unsaturated group include (meth)acrylic acid, alkyl (meth)acrylates having a linear or branched alkyl group having 1 to 22 carbon atoms, hydroxyalkyl (meth)acrylates having a linear or branched hydroxyalkyl group having 1 to 18 carbon atoms, succinic acid mono(hydroxyalkyl (meth)acrylate) esters composed of hydroxyalkyl (meth)acrylates having 1 to 18 carbon atoms and dibasic acids, and phthalic acid mono(hydroxyalkyl (meth)acrylate). (meth)acrylates having a carboxylic acid group introduced therein, such as hexahydrophthalic acid mono(hydroxyalkyl(meth)acrylate) ester, and hexahydrophthalic acid mono(hydroxyalkyl(meth)acrylate) ester; (meth)acrylic acid alkylsulfonic acids having a linear or branched chain alkylsulfonic acid group having 1 to 18 carbon atoms introduced therein; (meth)acrylic acid alkylphosphates having a linear or branched chain alkylphosphate group having 1 to 18 carbon atoms introduced therein; alkoxyalkylene glycol (meth)acrylates having a functional group consisting of an alkyl group having 1 to 18 carbon atoms and an alkylene glycol group having 1 to 4 carbon atoms introduced therein; Alkoxydialkylene glycol (meth)acrylates, alkoxytrialkylene glycol (meth)acrylates, alkoxypolyalkylene glycol (meth)acrylates, N-alkylamino(meth)acrylates having an aminoalkyl group of 1 to 6 carbon atoms introduced therein, N-alkylaminoalkyl(meth)acrylates having an N-alkylaminoalkyl group consisting of an aminoalkyl group of 1 to 6 carbon atoms and an alkyl group of 1 to 6 carbon atoms introduced therein, and N-alkylaminoalkyl(meth)acrylates having an N-alkylaminoalkyl group consisting of an aminoalkyl group of 1 to 6 carbon atoms and an alkyl group of 1 to 6 carbon atoms introduced therein. Examples of the monofunctional polymerizable compound (a1) having a (meth)acrylate group include N,N-dialkylaminoalkyl (meth)acrylates having an N,N-dialkylaminoalkyl group introduced therein, tetrahydrofurfuryl (meth)acrylate having a heterocycle introduced therein, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, etc. The monofunctional polymerizable compound (a1) having a (meth)acrylate group may be used alone or in combination of two or more.

[0022] Examples of the monofunctional polymerizable compound (a1) having a vinyl group, a vinyl ether group, or a methyl vinyl ether group as an unsaturated group include linear, branched, or cyclic saturated fatty acid vinyl esters having 1 to 22 carbon atoms, N-vinyl saturated fatty acid amides, N-vinylformamide, N-vinylpyrrolidone, N-vinylvalerolactam, N-vinylcaprolactam, and N-vinyloxazoline; linear, branched, or cyclic alkyl vinyl ethers having 1 to 22 carbon atoms, alkyl methyl vinyl ethers, hydroxyalkyl vinyl ethers, hydroxyalkyl methyl vinyl ethers, and polyalkylene glycols. Examples of the vinyl esters include carboxylic acid group-introduced vinyl esters such as ethanol vinyl ether, polyalkylene glycol methyl vinyl ether, alkyl polyalkylene glycol vinyl ether, alkyl polyalkylene glycol methyl vinyl ether, glycerin monovinyl ether, trimethylolpropane monovinyl ether, succinic acid monovinyl ester, phthalic acid monovinyl ester, and hexahydrophthalic acid monovinyl ester, as well as vinyl trifluoroacetate, vinyl sulfonic acid esters, vinyl sulfonates, vinyl phosphate esters, vinyl phosphate salts, and vinyl chloride. The monofunctional polymerizable compound (a1) having a vinyl group, a vinyl ether group, or a methyl vinyl ether group may be used alone or in combination of two or more, but is preferably used in combination with a monofunctional polymerizable compound (a1) having a (meth)acrylate group or a (meth)acrylamide group.

[0023] Examples of the monofunctional polymerizable compound (a1) having an allyl group or a (meth)allyl ether group as an unsaturated group include linear, branched, or cyclic saturated fatty acid allyl esters having 1 to 22 carbon atoms, N-allyl saturated fatty acid amides, N-allyl formamide, N-allyl pyrrolidone, N-allyl valerolactam, N-allyl caprolactam, allylamine, N,N-dialkyl-N-allylamine, linear, branched, or cyclic alkyl (meth)allyl ethers having 1 to 22 carbon atoms, hydroxyalkyl (meth)allyl ethers, polyalkylenes, etc. Examples include carboxylic acid group-introduced allyl esters such as glycol (meth)allyl ether, alkyl polyalkylene glycol (meth)allyl ether, glycerin mono(meth)allyl ether, trimethylolpropane mono(meth)allyl ether, succinic acid monoallyl ester, phthalic acid monoallyl ester, and hexahydrophthalic acid monoallyl ester, allyl trifluoroacetate, allyloxytetrahydropyran, allyl sulfonic acid ester, allyl sulfonate, allyl phosphonic acid ester, and allyl phosphonate. The monofunctional polymerizable compound (a1) having an allyl group or a (meth)allyl ether group may be used alone or in combination of two or more types, but is preferably used in combination with a monofunctional polymerizable compound (a1) having a (meth)acrylate group or a (meth)acrylamide group.

[0024] Examples of the monofunctional polymerizable compound (a1) having a maleimide group as an unsaturated group include N-alkylmaleimides having a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, N-hydroxyalkylmaleimides, N-(2-carboxyalkyl)maleimides, glycerin mono(N-hydroxyalkylmaleimide) esters, trimethylolpropane mono(N-hydroxyalkylmaleimide) esters, and phenylmaleimides.

[0025] The unsaturated group of the monofunctional polymerizable compound (a1) is preferably a (meth)acrylate group or a (meth)acrylamide group from the viewpoint of improving the curability of the active energy ray-curable resin composition (E), and more preferably a (meth)acrylamide group from the viewpoint of improving the strength and heat resistance of the cured product of the active energy ray-curable resin composition (E).

[0026] The monofunctional polymerizable compound (a1) preferably has one unsaturated group and one or more amide groups and / or oxyalkylene groups in the molecule. When the monofunctional polymerizable compound (a1) has one unsaturated group and one or more amide groups in the molecule, the strength and heat resistance of the cured product of the active energy ray-curable resin composition (E) are improved. Examples of such monofunctional polymerizable compounds (a1) include the monofunctional polymerizable compounds (a1) having a (meth)acrylamide group as the unsaturated group, N-vinylpyrrolidone, N-vinylvalerolactam, and N-vinylcaprolactam. On the other hand, when the monofunctional polymerizable compound (a1) has one unsaturated group and one or more oxyalkylene groups in the molecule, the cure shrinkage of the active energy ray-curable resin composition (E) is suppressed. Examples of such monofunctional polymerizable compounds (a1) include the above-mentioned hydroxyalkyl(meth)acrylates, polyalkylene glycol(meth)acrylates, and alkyl polyalkylene glycol(meth)acrylates. Polyalkylene glycol(meth)acrylates and alkyl polyalkylene glycol(meth)acrylates having a molecular weight of 200 or more are preferred because they shrink little during curing.

[0027] The polymerizable compound (a2) having an average number of unsaturated groups in the molecule greater than 1 and less than 2 is not particularly limited, as long as it is a compound in which the unsaturated groups are introduced via chemical bonds and is obtained by reaction so that the number of unsaturated groups introduced is less than 2. The chemical bond is preferably at least one selected from a urethane bond, an ester bond, an amide bond, and an ether bond. The unsaturated group is not particularly limited, but is preferably at least one selected from a (meth)acrylamide group, a (meth)acrylate group, a vinyl group, an allyl group, and a maleimide group. The inclusion of such a non-polyfunctional polymerizable compound (a2) prevents the cured product from dissolving in the active energy ray-curable resin composition (E) due to a synergistic effect with the non-crosslinkable polymer (B), thereby enabling the production of highly accurate shaped objects.

[0028] When the unsaturated group is introduced via a urethane bond, the polymerizable compound (a2) is not particularly limited as long as it is a polymerizable compound having one or more urethane bonds and less than two unsaturated groups in the molecule. As the unsaturated group, at least one unsaturated group is preferably a (meth)acrylamide group or a (meth)acrylate group. Examples of other unsaturated groups include one or more selected from the group consisting of a vinyl group, an allyl group, and a maleimide group.

[0029] The method for producing a polymerizable compound having one or more urethane bonds and less than two unsaturated groups in the molecule is not particularly limited, and examples thereof include known methods such as reacting a hydroxyl group-containing unsaturated compound with an isocyanate compound, reacting a polyol compound with a diisocyanate compound to obtain an isocyanate group-containing urethane prepolymer and then adding a hydroxyl group-containing unsaturated compound in an amount of less than two per molecule, mixing a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing unsaturated compound and then reacting the unsaturated compound in an amount of less than two per molecule, reacting an isocyanate group-containing unsaturated compound with an alcohol compound or a polyol compound and then reacting the unsaturated compound in an amount of less than two per molecule, and mixing a polyol compound, a polyisocyanate compound, and an isocyanate group-containing unsaturated compound and then reacting the unsaturated compound in an amount of less than two per molecule.

[0030] Examples of hydroxyl-containing unsaturated compounds used in the production of polymerizable compounds having one or more urethane bonds and less than two unsaturated groups in the molecule include hydroxyl-containing (meth)acrylamide compounds, hydroxyl-containing (meth)acrylate compounds, hydroxyl-containing vinyl compounds, hydroxyl-containing allyl compounds, and hydroxyl-containing maleimide compounds, and these may be used alone or in combination of two or more. Among these, it is preferable to use a hydroxyl-containing (meth)acrylamide compound from the viewpoint of improving the curability of the active energy ray-curable resin composition (E) and improving the strength of the cured product due to its high cohesive force.

[0031] The hydroxyl group-containing (meth)acrylamide compound is preferably a hydroxyl group-containing N-substituted (meth)acrylamide. Examples of the hydroxyl group-containing N-substituted (meth)acrylamide include N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-methyl-N-hydroxyethyl(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-hydroxybutyl(meth)acrylamide, N,N-dihydroxyethyl(meth)acrylamide, N-polyalkylene glycol(meth)acrylamide having a polyalkylene glycol of 1 to 4 carbon atoms, N-hydroxycyclohexyl(meth)acrylamide, and N-hydroxyphenyl(meth)acrylamide. N-hydroxyethyl(meth)acrylamide is more preferred because it has a PII of 0.0, which means it has low skin irritation and is highly safe. These hydroxyl group-containing (meth)acrylamide compounds may be used alone or in combination of two or more.

[0032] Examples of hydroxyl group-containing (meth)acrylate compounds include hydroxyalkyl (meth)acrylates having a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms introduced therein, glycerin (meth)acrylate, trimethylolpropane (meth)acrylate, pentaerythritol (meth)acrylate, dipentaerythritol (meth)acrylate, polyalkylene glycol (meth)acrylates having a polyalkylene glycol having 1 to 4 carbon atoms introduced therein, hydroxycyclohexyl (meth)acrylate, hydroxyphenyl (meth)acrylate, etc. These hydroxyl group-containing (meth)acrylates are preferably used in combination with hydroxyl group-containing (meth)acrylamides, and one type may be used alone, or two or more types may be used simultaneously.

[0033] Examples of hydroxyl group-containing vinyl compounds include linear, branched, or cyclic hydroxyalkyl vinyl ethers and hydroxyalkyl methyl vinyl ethers having 1 to 18 carbon atoms, examples of hydroxyl group-containing allyl compounds include linear, branched, or cyclic hydroxyalkyl (meth)allyl ethers having 1 to 18 carbon atoms, and examples of hydroxyl group-containing maleimide compounds include linear, branched, or cyclic N-hydroxyalkyl maleimides having 1 to 18 carbon atoms. These hydroxyl group-containing vinyl compounds, hydroxyl group-containing allyl compounds, and hydroxyl group-containing maleimide compounds are preferably used in combination with hydroxyl group-containing (meth)acrylamides, and one type may be used alone or two or more types may be used simultaneously.

[0034] Polyol compounds used in the production of polymerizable compounds having one or more urethane bonds and less than two unsaturated groups in the molecule include, for example, compounds having two or more hydroxyl groups in the molecule, such as polyether polyols having an ether skeleton, polyester polyols having an ester skeleton, polycarbonate polyols having a carbonate skeleton, hydroxyl group-containing silicones having a silicone skeleton, hydrogenated polyalkadiene polyols having an olefin skeleton, polyalkadiene polyols, and acrylic polyols having an acrylic skeleton. Polyether diols, polyester diols, polycarbonate diols, hydrogenated polyalkadiene diols, and polyalkadiene diols having two hydroxyl groups in the molecule are preferred because they are less likely to cause gelation due to crosslinking during urethane formation. These polyol compounds can be used alone or in combination of two or more.

[0035] Examples of polyether polyols include linear, branched, or cyclic polyalkylene glycols having 2 to 18 carbon atoms, such as polyethylene glycol, glycerin tri(polyoxyethylene) ether, trimethylolpropane tri(polyoxyethylene) ether, pentaerythritol tetra(polyoxyethylene) ether, poly(oxy-1,3-propylene) glycol, glycerin tri(polyoxy-1,3-propylene) ether, trimethylolpropane tri(polyoxy-1,3-propylene) ether, and pentaerythritol tetra(polyoxyethylene) ether. Examples of alkylene glycols include poly(oxy-1,3-propylene) ether, poly(oxy-1,2-propylene) glycol, glycerin tri(polyoxy-1,2-propylene) ether, trimethylolpropane tri(polyoxy-1,2-propylene) ether, pentaerythritol tetra(polyoxy-1,2-propylene) ether, poly(oxy-1,4-butylene) glycol, poly(oxy-1,5-pentylene) glycol, poly(oxy-3-methyl-1,5-pentylene) glycol, and poly(oxy-1,6-hexylene) glycol.

[0036] The polyester polyol is composed of a polycarboxylic acid and a polyol, contains a polyester skeleton in the molecule, and has a hydroxyl group at the end. Examples of the polycarboxylic acid component include phthalic acid, tetrahydrophthalic acid, terephthalic acid, isophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, maleic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,2,4-butanetricarboxylic acid, hemimellitic acid, trimellitic acid, trimesic acid, cyclohexanetricarboxylic acid, pyromellitic acid, and cyclohexanetetracarboxylic acid. Examples of polyol components include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol, isosorbide, neopentyl glycol, glycerin, trimethylolpropane, and pentaerythritol.

[0037] Polycarbonate polyols consist of a carbonyl component and a polyol, containing a carbonate skeleton in the molecule and hydroxyl groups at the terminals. Examples of the carbonyl component include phosgene, chloroformate ester, dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Examples of the polyol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol, isosorbide, neopentyl glycol, glycerin, trimethylolpropane, and pentaerythritol.

[0038] Examples of hydrogenated polyalkadiene polyols include 1,2-hydrogenated polybutadiene diol, 1,4-hydrogenated polybutadiene diol, and hydrogenated polyisoprene polyol, and examples of polyalkadiene polyols include 1,2-polybutadiene diol, 1,4-polybutadiene diol, and polyisoprene polyol.

[0039] The isocyanate compound used in producing a polymerizable compound having one or more urethane bonds and less than two unsaturated groups in the molecule is not particularly limited as long as it is a compound having an isocyanate group in the molecule, and examples thereof include monoisocyanate compounds, diisocyanate compounds, triisocyanate compounds, and polyisocyanate compounds, but monoisocyanates and diisocyanates are preferred because they are less likely to cause gelation due to crosslinking during urethanization. These can be used alone or in combination of two or more.

[0040] Examples of the monoisocyanate compound include linear, branched, or cyclic alkyl isocyanates having 1 to 20 carbon atoms, phenyl isocyanate, linear, branched, or cyclic alkylphenyl isocyanates having 1 to 20 carbon atoms, and phenyl alkylene isocyanates.

[0041] The diisocyanate compound is not particularly limited as long as it is a compound having two isocyanate groups in the molecule, and examples thereof include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4 Examples of suitable diisocyanates include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, and xylylene diisocyanate; and alicyclic diisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane. Examples of suitable diisocyanates include uretdione-type dimers of these diisocyanates, and adduct types with saturated alkylene diols having 2 to 8 carbon atoms, such as ethylene glycol and propylene glycol.

[0042] Examples of triisocyanate compounds include biuret types and isocyanurate types of the above-mentioned diisocyanates, as well as adduct types of diisocyanates with saturated alkylene triols having 3 to 8 carbon atoms, such as glycerin and trimethylolpropane. Examples of polyisocyanates include polyisocyanurates obtained by further isocyanuration of the above-mentioned diisocyanates.

[0043] When the unsaturated group is introduced via an ester bond, the polymerizable compound (a2) is not particularly limited as long as it is a polymerizable compound having one or more ester bonds and less than two unsaturated groups in the molecule. The unsaturated group may be one or more selected from the group consisting of a (meth)acrylamide group, a (meth)acrylate group, a vinyl group, an allyl group, and a maleimide group.

[0044] The method for producing a polymerizable compound into which an unsaturated group is introduced via an ester bond is not particularly limited, and examples thereof include a method of mixing a compound having a carboxylic acid group and an unsaturation (unsaturated group-containing carboxylic acid), a component consisting of a dibasic acid, its acid anhydride, or an esterification product of a dibasic acid and a lower alcohol such as methanol or ethanol, and a glycol component, and adjusting the amount of unsaturated groups introduced so that more than one and less than two are introduced per molecule, and performing esterification to obtain a polymerizable compound into which an unsaturated group is introduced via an ester bond; or a method of mixing an acid component consisting of a dibasic acid, its acid anhydride, or an esterification product of a dibasic acid and a lower alcohol such as methanol or ethanol, a compound having a hydroxyl group and an unsaturated group, and a glycol component, and adjusting the amount of unsaturated groups introduced so that more than one and less than two are introduced per molecule, and performing esterification to obtain a polymerizable compound into which an unsaturated group is introduced via an ester bond. Examples of esterification include known methods such as dehydration condensation of a carboxylic acid and a hydroxyl group, or transesterification of a carboxylic acid ester of a lower alcohol with a hydroxyl group.

[0045] Examples of dibasic acids, their anhydrides, or esters of dibasic acids with lower alcohols such as methanol or ethanol that can be used to produce polymerizable compounds in which an unsaturated group is introduced via an ester bond include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, nitrophthalic acid, halogenated phthalic acids, and their anhydrides, and their anhydrides or esters, as well as aliphatic or alicyclic saturated dibasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, and hexahydrophthalic acid, and their anhydrides, or esters of dibasic acids with lower alcohols such as methanol, ethanol, n-propanol, i-propanol, and vinyl alcohol. These may be used alone or in combination of two or more.

[0046] Examples of glycol components used in the production of polymerizable compounds into which unsaturated groups are introduced via ester bonds include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propylene glycol, di(1,2-propylene glycol), tri(1,2-propylene glycol), poly(1,2-propylene glycol), 1,3-propylene glycol, di(1,3-propylene glycol), tri(1,3-propylene glycol), poly(1,3-propylene glycol), 1,2-butanediol, di(1,2-butanediol), tri(1,2-butanediol), poly(1,2-butanediol), 1,3 1,3-butanediol, di(1,3-butanediol), tri(1,3-butanediol), poly(1,3-butanediol), 1,4-butanediol, di(1,4-butanediol), tri(1,4-butanediol), poly(1,4-butanediol), 2-methylpropane-1,3-diol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene oxide-modified bisphenol A, polyethylene oxide-modified bisphenol A, propylene oxide-modified bisphenol A, polypropylene oxide-modified bisphenol A, etc. These can be used alone or in combination of two or more.

[0047] Examples of unsaturated group-containing carboxylic acids used in the production of polymerizable compounds in which an unsaturated group is introduced via an ester bond include (meth)acrylic acid, hydroxyalkyl (meth)acrylates having 1 to 18 carbon atoms, N-hydroxyalkyl (meth)acrylamides, vinyl alcohol, allyl alcohol, or the like, and dibasic acids, such as succinic acid mono(hydroxyalkyl (meth)acrylate) esters, phthalic acid mono(hydroxyalkyl (meth)acrylate) esters, and hexahydrophthalic acid mono(hydroxyalkyl (meth)acrylate) esters, and carboxylic acid group-introduced (meth)acrylates, succinic acid mono(hydroxyalkyl (meth)acrylamide) esters, phthalic acid mono(hydroxyalkyl (meth)acrylate) esters, and the like. Examples of the carboxylic acid group-introduced (meth)acrylamides include mono(hydroxyalkyl(meth)acrylamide) ester and hexahydrophthalic acid mono(hydroxyalkyl(meth)acrylamide) ester; vinyl esters including monovinyl succinate, monovinyl phthalate, and monovinyl hexahydrophthalate; allyl esters including monoallyl succinate, monoallyl phthalate, and monoallyl hexahydrophthalate; maleimides including N-(2-carboxyalkyl)maleimides having 1 to 18 carbon atoms; and lower alcohol esters of (meth)acrylic acid such as methyl (meth)acrylate and ethyl (meth)acrylate.

[0048] Examples of compounds having a hydroxyl group and an unsaturated group that can be used to produce a polymerizable compound in which an unsaturated group is introduced via an ester bond include compounds having one hydroxyl group and one unsaturated group, such as hydroxyalkyl(meth)acrylates, N-hydroxyalkyl(meth)acrylamides, hydroxyalkyl vinyl ethers, hydroxyalkyl allyl ethers, and N-hydroxyalkylmaleimides, each of which has a hydroxyalkyl group having 1 to 18 carbon atoms introduced therein; and compounds having two hydroxyl groups and one unsaturated group, such as glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, glycerin mono(meth)acrylamide, trimethylolpropane mono(meth)acrylamide, N,N-di(hydroxyalkyl)(meth)acrylamide, glycerin monovinyl ether, trimethylolpropane monovinyl ether, glycerin monoallyl ether, trimethylolpropane monoallyl ether, glycerin mono(N-hydroxyalkylmaleimide) ester, and trimethylolpropane mono(N-hydroxyalkylmaleimide) ester.

[0049] When the unsaturated group is introduced via an ether bond, the polymerizable compound (a2) is not particularly limited as long as it is a polymerizable compound having one or more ether bonds and less than two unsaturated groups in the molecule.

[0050] When the unsaturated group is introduced via an amide bond, the polymerizable compound (a2) is not particularly limited as long as it is a polymerizable compound having one or more amide bonds and less than two unsaturated groups in the molecule.

[0051] The number-average molecular weight (Mn) of the polymerizable compound (a2) having an average number of unsaturated groups in the molecule greater than 1 and less than 2 is preferably 1,000 to 100,000, more preferably 2,000 to 50,000. When the number-average molecular weight (Mn) is within the above range, it becomes easy to adjust the average number of unsaturated groups in the molecule to greater than 1 and less than 2, and it becomes easy to adjust the viscosity of the active energy ray-curable resin composition (E) containing the polymerizable compound (a2) to a range suitable for three-dimensional stereolithography. Furthermore, curing shrinkage during curing of the resin composition (E) is suppressed, and the cured product obtained by curing has sufficient strength, allowing high-precision shaped objects to be obtained.

[0052] The non-polyfunctional polymerizable compound (A) may be composed of only a monofunctional polymerizable compound (a1), or only a polymerizable compound (a2) having an average number of unsaturated groups in the molecule of more than 1 and less than 2, or may be composed of (a1) and (a2).

[0053] When the non-polyfunctional polymerizable compound (A) is composed of a monofunctional polymerizable compound (a1) and a polymerizable compound (a2) having an average number of unsaturated groups in the molecule greater than 1 but less than 2, the mass ratio of (a1) to (a2) in (A) (i.e., (a1) / (a2)) is 1 / 1 to 1,000 / 1. When (a1) / (a2) is 1 / 1 or greater, it becomes easier to adjust the viscosity of the active energy ray-curable resin composition (E) to a range suitable for three-dimensional stereolithography. When (a1) / (a2) is 1,000 / 1 or less, the insolubility of the resulting cured product is improved and strength above practical levels can be achieved. From these viewpoints, it is preferable that (a1) / (a2) is 2 / 1 to 800 / 1.

[0054] The active energy ray-curable resin composition (E) contains a non-crosslinkable polymer (B). By containing the non-crosslinkable polymer (B), the active energy ray-curable resin composition (E) is prevented from shrinking during curing, making it possible to obtain a highly accurate shaped object.

[0055] The non-crosslinkable polymer (B) is a polymer that does not have a crosslinked structure within the molecule. The content of the non-crosslinkable polymer (B) is preferably 0.1 to 50.0 mass% relative to the total mass of the active energy ray-curable resin composition (E). When the content of the non-crosslinkable polymer (B) is within this range, the active energy ray-curable resin composition (E) does not have the ability to dissolve its cured product, making it possible to obtain a highly accurate shaped object, and also making it easier to adjust the viscosity of the active energy ray-curable resin composition (E) to a range suitable for three-dimensional stereolithography. From these viewpoints, the content of the non-crosslinkable polymer (B) is more preferably 0.5 to 40 mass%, more preferably 1.0 to 30.0 mass%, and even more preferably 3.0 to 25.0 mass%.

[0056] The monofunctional polymerizable compound (a1) can be used as a raw material for the non-crosslinkable polymer (B). Examples of the monofunctional polymerizable compound other than (a1) include styrene, 2-alkylstyrenes, 3-alkylstyrenes, and 4-alkylstyrenes each having a linear, branched, or cyclic alkyl group having 1 to 22 carbon atoms, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, maleic acid monoalkyl esters, maleic acid dialkyl esters, fumaric acid monoalkyl esters, fumaric acid dialkyl esters, itaconic acid monoalkyl esters, itaconic acid dialkyl esters, unsaturated fatty acid alkyl esters, unsaturated fatty acid amides, N-alkyl unsaturated fatty acid amides, and N,N-dialkyl unsaturated fatty acid amides.

[0057] The non-crosslinkable polymer (B) preferably contains structural units derived from a monomer having a (meth)acrylamide group. In this case, the non-crosslinkable polymer (B) exhibits relatively high cohesive strength due to hydrogen bonds formed between amide groups and intermolecular interactions within the polymer (B), and also has a relatively high glass transition temperature (Tg). When the active energy ray-curable resin composition (E) contains such a non-crosslinkable polymer (B), the strength and heat resistance of a shaped object obtained by curing (E) are improved. From this perspective, the content of the structural units derived from a monomer having a (meth)acrylamide group is preferably 10.0% by mass or more, more preferably 50.0% by mass or more, and may be 100% by mass, based on the total weight of the non-crosslinkable polymer (B). The monomer having a (meth)acrylamide group is preferably at least one selected from (meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-methyl-N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, N,N-bishydroxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, and diacetone(meth)acrylamide.

[0058] The non-crosslinkable polymer (B) may contain, in addition to a structural unit derived from a monomer having a (meth)acrylamide group, one or more structural units selected from a monomer having a (meth)acrylate group, a monomer having a vinyl group, and a monomer having an allyl group, and the content thereof is preferably 90.0 mass% or less, more preferably 50 mass% or less, based on the total non-crosslinkable polymer (B).

[0059] The number-average molecular weight (Mn) of the non-crosslinkable polymer (B) is preferably 2,000 to 500,000. When the Mn of the non-crosslinkable polymer (B) is 2,000 or higher, the polymer chains of (B) and the polymer chains formed by polymerization of the non-polyfunctional polymerizable compound (A) can be sufficiently entangled to form a network structure of heterogeneous polymer chains. This prevents the cured product of the active energy ray-curable resin composition (E) from dissolving in the resin composition (E), enabling the production of highly accurate objects when used in three-dimensional stereolithography. On the other hand, if the Mn of the non-crosslinkable polymer (B) exceeds 500,000, it becomes difficult to adjust the viscosity of the active energy ray-curable resin composition (E) to a range suitable for three-dimensional stereolithography. From these viewpoints, the Mn of the non-crosslinkable polymer (B) is more preferably 4,000 to 300,000, and even more preferably 5,000 to 100,000.

[0060] The glass transition temperature (Tg) of the non-crosslinkable polymer (B) is preferably 40°C or higher. When the Tg of the non-crosslinkable polymer (B) is 40°C or higher, heat resistance can be imparted to a shaped article obtained by curing the active energy ray-curable resin composition (E). From the viewpoint of improving the heat resistance of the shaped article, the Tg of the non-crosslinkable polymer (B) is more preferably 60°C or higher, and even more preferably 100°C or higher. The upper limit of the Tg of the non-crosslinkable polymer (B) is not particularly limited, but is usually 200°C or lower.

[0061] The non-crosslinkable polymer (B) is obtained by polymerizing a monofunctional polymerizable compound. The polymerization method is not particularly limited and can be obtained by any known method for polymerizing a polymerizable functional group. For example, in polymerization methods such as bulk polymerization, solution polymerization, precipitation polymerization, and emulsion polymerization, radical polymerization using active energy rays or heat, or oxidation-reduction reactions, anionic polymerization, or cationic polymerization can be used. The polymerization temperature and reaction time vary depending on the polymerization initiator and solvent used. When a thermal polymerization initiator is used, these are usually calculated based on the half-life of the thermal polymerization initiator. The treatment temperature is usually preferably 30°C to 120°C, and the treatment time is usually preferably 1 hour to 20 hours. When a photoinitiator using active energy rays is used, the polymerization conditions vary depending on the type, wavelength, and irradiance of the active energy rays. However, ultraviolet light is usually used using a high-pressure mercury lamp or a UV LED irradiation device with a wavelength of 365 nm to 405 nm, and the irradiance is preferably 0.1 mW / cm. 2 ~200,000mW / cm 2 The irradiation temperature is preferably 20 to 80°C, and the irradiation time for the active energy rays varies depending on the illuminance of the active energy rays to be irradiated, and it is preferable to proceed with polymerization by irradiation for a very short time of 1 second or less to several minutes to several tens of minutes.

[0062] When synthesizing the non-crosslinkable polymer (B) by polymerization, a polymerization initiator may be used to promote the polymerization reaction. Examples of polymerization initiators that can be used include known photopolymerization initiators, thermal polymerization initiators, anionic polymerization initiators, and cationic polymerization initiators. Examples of photopolymerization initiators that can be used include acetophenone-based, benzoin-based, benzophenone-based, α-aminoketone-based, xanthone-based, anthraquinone-based, acylphosphine oxide-based, and polymeric photopolymerization initiators. Examples of thermal polymerization initiators that can be used include conventional azo-based initiators, peroxide-based initiators, and redox-based initiators. Conventional initiators for cationic polymerization, such as protonic acids and Lewis acids, can be used. Conventional initiators for anionic polymerization, such as alkali metals and organometallic compounds, can be used. When a polymerization initiator is used, its content is not particularly limited, but from the viewpoint of promoting the polymerization reaction, it is preferably 0.01 to 10.0% by mass relative to the total mass of the monofunctional polymerizable compound used.

[0063] When synthesizing the non-crosslinkable polymer (B) by polymerization, a chain transfer agent can be used to control the molecular weight. Examples of chain transfer agents include, but are not limited to, mercaptans such as mercaptoethanol, alkyl mercaptans having 4 to 18 carbon atoms, mercaptoacetic acid, mercaptopropionic acid, alkyl mercaptoacetate esters having 4 to 18 carbon atoms, and alkyl mercaptopropionic acid esters; α-methylstyrene, α-methylstyrene dimer; halides such as carbon tetrachloride; and quinone compounds. Mercaptans are preferred because they facilitate molecular weight control. The content of the chain transfer agent is not particularly limited, but is preferably 0.1 to 10.0 mass% based on the total mass of the monofunctional polymerizable compounds used, from the viewpoint of appropriately adjusting the number-average molecular weight of the non-crosslinkable polymer (B).

[0064] The organic solvent used to obtain the non-crosslinkable polymer (B) by solution polymerization is not particularly limited, and examples thereof include aromatic organic solvents such as toluene, xylene, and methoxybenzene; esters such as ethyl acetate and butyl acetate; polyhydric alcohols such as ethanol, isopropanol, ethylene glycol, propylene glycol, trimethylene glycol, and propylene glycol; polyhydric alcohol derivatives such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethers such as diethyl ether, dioxane, and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; amide solvents such as dimethylformamide and 3-methoxy-N,N-dimethylpropionic acid amide; and pyrrolidones such as 2-pyrrolidone and N-methyl-2-pyrrolidone. These solvents may be used alone or in combination. The amount of solvent used is not particularly limited, but may be 30 to 300% by mass based on the total mass of the monofunctional polymerizable compound used.

[0065] The non-crosslinkable polymer (B) can also be used as a polymer that has been purified as necessary after polymerization. The polymer can be purified by known methods such as washing and reprecipitation. The polymer composition can be quantified by proton nuclear magnetic resonance spectroscopy ( 1 This can be carried out by known methods such as 1 H-NMR, infrared spectroscopy (IR), elemental analysis, and quantitative analysis of the remaining monofunctional polymerizable compound.

[0066] The active energy ray-curable resin composition (E) may contain a photopolymerization initiator (C). By including the photopolymerization initiator (C), the active energy ray-curable resin composition (E) can exist as a stable composition before irradiation with active energy rays, and the polymerization reaction proceeds upon irradiation with active energy rays, resulting in high curability and enabling the formation of shaped objects at a high modeling speed. The content of the photopolymerization initiator (C) used in the present invention is preferably 0.1 to 10.0 mass% based on the total active energy ray-curable resin composition (E). A content of 0.1 mass% or more is preferred because the polymerization reaction of the active energy ray-curable resin composition (E) upon irradiation with active energy rays proceeds quickly, shortening the irradiation time and reducing the amount of residual non-polyfunctional polymerizable compounds. A content of 10.0 mass% or less is preferred because the pot life of the active energy ray-curable resin composition is long and problems such as gelation during storage do not occur. From these perspectives, the content of the photopolymerization initiator (C) is more preferably 0.5 to 5.0 mass%. Furthermore, the photopolymerization initiator (C) may be either a type that generates radicals by intramolecular cleavage after absorbing light (intramolecular cleavage type) or a type that generates radicals by exchanging hydrogen or electrons between two molecules (hydrogen abstraction type and electron donor type). When the content of the photopolymerization initiator (C) exceeds 5.0 mass%, it is more preferable to use a hydrogen abstraction type photopolymerization initiator (C) in consideration of the influence of residues derived from the photopolymerization initiator (C).

[0067] The active energy rays used to cure the active energy ray-curable resin composition (E) refer to electromagnetic waves or charged particle rays having an energy quantum, i.e., active energy rays such as visible light, electron beams, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, and γ-rays. Examples of such radiation sources include high-pressure mercury lamps, halogen lamps, xenon lamps, metal halide lamps, LED lamps, semiconductor lasers, electron beam accelerators, and radioactive elements. As the active energy rays to be irradiated, ultraviolet rays are preferred in view of the storage stability, curing speed, and low harmfulness of the active energy ray-curable resin composition (E), and radiation sources such as LED lamps and semiconductor lasers are preferred in view of ease of handling.

[0068] Examples of the photopolymerization initiator (C) include photoradical initiators, photocationic polymerization initiators, and photoanionic polymerization initiators. The photoradical polymerization initiator may be appropriately selected from common initiators such as cleavage-type (Type I photoradical polymerization initiators) acetophenone-based, benzoin-based, α-aminoketone-based, and acylphosphine oxide-based initiators, hydrogen abstraction-type (Type II photoradical polymerization initiators) benzophenone-based, xanthone-based, α-oxobenzeneacetic acid-based, and anthraquinone-based initiators, and polymeric photoinitiators. 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-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1, and benzoins include benzoin, α-methylbenzoin, α-phenylbenzoin, α-allylbenzoin, α-benzoylbenzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. benzoin isobutyl ether, benzil dimethyl ketal, 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, acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, benzophenones such as benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4,Examples of xanthones include 4'-bis(diethylamino)benzophenone, benzoylbenzoic acid, and methyl benzoylbenzoate; xanthone, thioxanthone, diethylthioxanthone, and isopropylthioxanthone; α-oxobenzeneacetic acids include methyl α-oxobenzeneacetate, diethylene glycol di(α-oxobenzeneacetic acid) ester, and diethylene glycol mono(α-oxobenzeneacetic acid); anthraquinones include anthraquinone, 2-methylanthraquinone, and 2-ethylanthraquinone; polymeric photoinitiators include polymers of 2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propan-1-one; and photocationic polymerization initiators include antimony-based initiators such as diphenyliodonium hexafluoroarsenate and non-antimony-based initiators such as triphenylsulfonium tetrafluoroborate and bis(4-t-butylphenyl)iodonium hexafluorophosphate. Examples of photoanionic polymerization initiators include acetophenone o-benzoyloxime and 2-(9-oxoxanthen-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene. These photopolymerization initiators can be used alone or in combination of two or more.

[0069] The active energy ray-curable resin composition (E) may further contain a viscosity modifier (D). By containing the viscosity modifier (D), the viscosity of the active energy ray-curable resin composition (E) can be easily adjusted to a high or low value depending on the purpose. The content of the viscosity modifier (D) is preferably 60.0 mass% or less, more preferably 50.0 mass%, and even more preferably 40.0 mass%, based on the total mass of the active energy ray-curable resin composition (E). On the other hand, the lower limit of the content of (D) is not particularly limited, but is usually 0.1 mass% or more.

[0070] The viscosity modifier (D) is not particularly limited as long as it does not have an unsaturated group in the molecule and is compatible with a mixture of a non-polyfunctional polymerizable compound (A) and a non-crosslinkable polymer (B) at a predetermined mass ratio, which are essential components of the active energy ray-curable resin composition (E). From the viewpoint of preventing the viscosity modifier (D) from bleeding out over time from the cured product of the active energy ray-curable resin composition (E), the viscosity modifier (D) preferably has a molecular weight of 100 or more. From the viewpoint of preventing the viscosity modifier (D) from volatilizing over time from the active energy ray-curable resin composition (E) and its cured product, the viscosity modifier (D) preferably has a boiling point at normal pressure of 150°C or more, more preferably 200°C or more.

[0071] Furthermore, from the viewpoint of suppressing bleeding out from the cured product of the active energy ray-curable resin composition (E), the viscosity modifier (D) preferably contains a functional group capable of forming an interaction through a hydrogen bond with the non-polyfunctional polymerizable compound (A) and the non-crosslinkable polymer (B). The functional group is preferably a hydroxyl group, an ether group, an ester group, or an amide group capable of forming a hydrogen bond. Examples of the viscosity modifier (D) having such a functional group include alcohol compounds, polyether compounds, ester compounds, ether compounds, and amide compounds. One type may be used alone, or two or more types may be used in combination.

[0072] Specific examples of the alcohol compounds used in the viscosity modifier (D) include linear, branched, or cyclic alkyl monools having 6 to 20 carbon atoms, linear, branched, or cyclic alkylene diols having 5 to 20 carbon atoms, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0073] Specific examples of polyether compounds used in the viscosity modifier (D) include dialkylene glycols, trialkylene glycols, polyalkylene glycols having 2 to 4 carbon atoms, dialkylene glycol monoalkyl ethers having an alkyl group having 1 to 20 carbon atoms introduced therein, dialkylene glycol dialkyl ethers, dialkylene glycol monoalkyl ether acetates, trialkylene glycol monoalkyl ethers, trialkylene glycol dialkyl ethers, trialkylene glycol monoalkyl ether acetates, polyalkylene glycol monoalkyl ethers, polyalkylene glycol dialkyl ethers, and polyalkylene glycol monoalkyl ether acetates.

[0074] Specific examples of the ester compounds used in the viscosity modifier (D) include polyalkylene glycol mono-fatty acid esters and polyalkylene glycol di-fatty acid esters each composed of a linear, branched, or cyclic fatty acid having 2 to 20 carbon atoms and a polyalkylene glycol having 2 to 4 carbon atoms, glycerin mono-fatty acid esters and glycerin di-fatty acid esters and glycerin tri-fatty acid esters each composed of a fatty acid and glycerin, polyalkylene glycol glycerin mono-fatty acid esters, sorbitan mono-fatty acid esters and sorbitan tri-fatty acid esters each composed of a fatty acid and sorbitol, sorbitan di-fatty acid esters and sorbitan tri-fatty acid esters, and alkylene glycol sorbitan mono-fatty acid esters.

[0075] Specific examples of the amide compounds used in the viscosity modifier (D) include N-alkylamides and N,N-dialkylamides having a molecular weight of 100 or more, into which a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms has been introduced; fatty acid amides consisting of a linear, branched, or cyclic fatty acid having 2 to 20 carbon atoms and a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; N-alkyl fatty acid amides and N,N-dialkyl fatty acid amides; N-alkylpyrrolidones, N-alkylpiperidones, and N-alkyl-ε-caprolactams into which a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms has been introduced; and β-alkoxy-N-alkylpropionamides and β-alkoxy-N,N-dialkylpropionamides into which a linear, branched, or cyclic alkyl group or alkoxy group having 1 to 20 carbon atoms has been introduced.

[0076] The active energy ray-curable resin composition (E) of the present embodiment may contain other components (G) as needed. Examples of the other components (G) include various additives and polyfunctional polymerizable compounds having two or more unsaturated groups in the molecule.

[0077] Examples of the various additives include ultraviolet sensitizers, thermal polymerization inhibitors, antiaging agents, antioxidants, ultraviolet sensitizers, preservatives, phosphate ester and other flame retardants, surfactants, wetting and dispersing agents, antistatic agents, colorants, plasticizers, surface lubricants, leveling agents, softeners, thickeners, pigments, organic fillers, inorganic fillers, etc. The amount of these various additives added is not particularly limited as long as it does not adversely affect the properties exhibited by the active energy ray-curable resin composition (E), and is preferably 10.0 mass% or less based on the total mass of the active energy ray-curable resin composition.

[0078] Examples of the ultraviolet sensitizer include anthracene compounds such as 9,10-dialkoxyanthracene compounds and 9,10-bis(dihydroxyalkoxy)anthracene, and thioxanthone compounds such as thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2-butylthioxanthone, 2-chlorothioxanthone, 2-propoxythioxanthone, and polymeric thioxanthone.

[0079] Examples of the thermal polymerization inhibitor 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, and β-naphthol.

[0080] Examples of antioxidants include hindered phenol-based compounds such as butylated hydroxytoluene and butylated hydroxyanisole, benzotriazole-based compounds, and hindered amine-based compounds.

[0081] Examples of surfactants include fluorine-containing surfactants such as perfluoroalkyl polyethylene oxide adducts, perfluoroalkyl carboxylates, and perfluoroalkyl betaines; modified silicone oils such as polyether-modified silicone oils and (meth)acrylate-modified silicone oils; and amphoteric polymer surfactants.

[0082] Examples of antistatic agents include nonionic antistatic agents such as glycerin fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, bis(2-hydroxyethyl)alkylamines, and polyoxyethylene alkylamines; anionic antistatic agents such as alkyl sulfonates, alkylbenzene sulfonates, and alkyl phosphates; nonionic antistatic agents such as tetraalkylammonium salts and trialkylbenzylammonium salts; amphoteric antistatic agents such as alkyl betaines and alkyl imidazolium betaines; and polymerizable antistatic agents such as (meth)acryloylaminoethyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloylaminopropyltrimethylammonium bis(trifluoromethanesulfonyl)imide, and (meth)acryloyloxyethyltrimethylammonium bis(trifluoromethanesulfonyl)imide. Furthermore, polymerizable antistatic agents are more preferred because they are less likely to bleed out over time from the cured product of the active energy ray-curable resin composition (E) and can provide a semi-permanent antistatic effect.

[0083] The polyfunctional polymerizable compound having two or more unsaturated groups in the molecule is not particularly limited as long as it is a compound having two or more unsaturated groups in the molecule, such as a (meth)acrylamide group, a (meth)acrylate group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth)allyl ether group, or a maleimide group. Examples of the polyfunctional polymerizable compound include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, polyester di(meth)acrylate, polycarbonate di(meth)acrylate, and dimethylol tricyclodeca. di(meth)acrylates such as di(meth)acrylate of polyurethane di(meth)acrylate, methylene bis(meth)acrylamide, alkylene glycol di(meth)acrylamide, polyalkylene glycol di(meth)acrylamide, polyester di(meth)acrylamide, polycarbonate di(meth)acrylamide, dimethylol tricyclodecane di(meth)acrylamide, polyurethane di(meth)acrylamide and other di(meth)acrylamides, allyl (meth)acrylate, vinyl (meth)acrylate, Maleimidoalkyl(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethyl Roll propane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, N,Examples include N-bis(2-acrylamidoethyl)acrylamide, N-[tris(3-acrylamidopropoxymethyl)methyl]acrylamide, and N,N'-1,2-ethanediylbis{N-[2-(acryloylamino)ethyl]acrylamide}.

[0084] The curing shrinkage of the active energy ray-curable resin composition (E) according to this embodiment is preferably less than 8%, since it allows for the production of highly accurate objects when various types of three-dimensional stereolithography are used, particularly when using a liquid vat photopolymerization method. A curing shrinkage of 7% or less is more preferable, and a curing shrinkage of 6% or less is even more preferable. The curing shrinkage is measured and calculated by the method described below. The modeling precision of the object is evaluated by the method described below.

[0085] The amount of active energy ray irradiation (cumulative light dose) required for curing the active energy ray-curable resin composition (E) varies depending on the types and contents of the non-polyfunctional polymerizable compound (A), non-crosslinkable polymer (B), and photopolymerization initiator (C) contained in the active energy ray-curable resin composition (E), as well as the addition of a polymerization inhibitor or photosensitizer. Furthermore, when forming a three-dimensional optically shaped object, the cumulative light dose required for curing differs depending on the thickness of the object. Therefore, although there are no particular limitations, from the viewpoint of efficient curing, it is usually 1 to 50,000 mJ / cm. 2 When the active energy ray-curable resin composition (E) is used as a resin composition for three-dimensional stereolithography, a method is generally used in which thin films (thickness: several μm to 1 mm) of the resin composition shaped into a specific shape are successively laminated as cured products. Therefore, it is preferable that the cumulative light dose required to cure the thin film of the active energy ray-curable resin composition (E) is small, since this shortens the irradiation time until curing and increases the modeling speed. From this perspective, the cumulative light dose required to cure the thin film of the active energy ray-curable resin composition (E) is 1,000 mJ / cm 2 Less than 500 mJ / cm is preferable. 2 Less than 200 mJ / cm is more preferable. 2 More preferably, 100 mJ / cm or less 2If the active energy ray curable resin composition (E) is used, it can be suitably used as a resin composition for three-dimensional stereolithography in various methods, and is therefore most preferred. On the other hand, when three-dimensional stereolithography is performed using the active energy ray curable resin composition (E), modeling is performed with the minimum integrated light amount that can maintain the shape of the model, and after the model is obtained, post-curing may be performed by further irradiating the model with active energy rays to completely cure the model and thereby develop sufficient physical properties. When post-curing is performed, it is necessary to penetrate the active energy rays deep into the model, so that it is preferable to use an active energy ray curable resin composition (E) with an integrated light amount of 1,000 mJ / cm or less. 2 It is preferable to perform the above irradiation.

[0086] The cured product obtained by curing the active energy ray-curable resin composition (E) of the present invention can be made soluble, dispersible, or degradable in water, organic solvents, or mixtures thereof by adjusting the composition of (E). Examples of water to be used include tap water, pure water, ion-exchanged water, alkaline aqueous solutions, and electrolyte aqueous solutions. In the present invention, alkaline aqueous solutions include aqueous solutions of alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide. Examples of electrolyte aqueous solutions include aqueous solutions of electrolytes such as potassium carbonate, sodium carbonate, sodium bicarbonate, ammonia, and tetramethylammonium hydroxide. However, from the standpoint of safety, tap water, pure water, and ion-exchanged water are preferred. Examples of organic solvents include alcohols, ketones, alkylene glycols, polyalkylene glycols, glycol ethers, and glycol esters. Furthermore, since the active energy ray-curable resin composition (E) does not have the ability to dissolve its cured product, it is preferable to select a solvent with a polarity different from that of (E) to dissolve the cured product of (E). For example, when the polarity of the active energy ray-curable resin composition (E) is low, methanol, ethanol, acetonitrile, and the like, which have high polarity, are preferred as organic solvents for dissolving the cured product. When the polarity of the active energy ray-curable resin composition (E) is high, toluene, methyl ethyl ketone, ethyl acetate, and the like, which have low polarity, are preferred as organic solvents for dissolving the cured product. These water and organic solvents can be used alone or in combination of two or more. Furthermore, from the viewpoint of ease of dissolving, dispersing, or disintegrating the cured product and particularly high safety, water or a mixture of water with methanol or ethanol is more preferred, and water is the most preferred.

[0087] The active energy ray-curable resin composition (E) of the present invention can be cured with active energy rays to obtain a shaped object (X) according to a second embodiment of the present invention. Because the viscosity of the active energy ray-curable resin composition (E) at 25°C can be easily adjusted to 30 to 100,000 mPa·s, various three-dimensional stereolithography methods and 3D printers can be used to produce the shaped object (X) using the resin composition (E). Examples of such printers include a material jet printer that uses the active energy ray-curable resin composition (E) as an inkjet ink and laminates a surface drawn by an inkjet printer; a liquid tank photopolymerization printer such as an SLA printer, a DLP printer, a CLIP printer, or an LCD printer that prepares and laminates cured resin layers in a resin tank filled with the active energy ray-curable resin composition using a laser, projector, or liquid crystal display; and an active energy ray-curable material extrusion deposition printer. Although not necessarily limited to these, when a liquid tank photopolymerization printer is used, the viscosity range of the usable active energy ray-curable resin composition (E) is wide, and a shaped object (X) having various physical properties depending on the purpose can be obtained with high precision, and thus is preferred.

[0088] When forming a 3D object (X) using the active energy ray-curable resin composition (E) of the present invention, the 3D stereolithography object may have any shape. However, a support material may be used as needed to maintain the shape of the object when forming a hollow structure. The support material is formed simultaneously with the 3D stereolithography object and removed after the formation is complete. The material used is not particularly limited. For example, the support material may be a meltable wax or resin, or an active energy ray-curable resin. However, when performing 3D stereolithography using a liquid tank photopolymerization method, the same resin is often used for the object and the support material. Therefore, the active energy ray-curable resin composition (E) of the present invention can be used not only as the resin (also referred to as a model material) for forming the 3D object (X) but also as a resin for the support material that supports the 3D object (X).

[0089] When the shaped article (X) according to the second embodiment of the present invention, which is produced using the active energy ray-curable resin composition (E) of the present invention, is a hollow shaped article (x1), the hollow portion of the hollow shaped article (x1) can be filled with a molding material (H) and molded to obtain a molded article (Y) according to the third embodiment of the present invention. In this case, the hollow shaped article (x1) is used as a mold for molding the molded article (Y) using the molding material (H), and a crude molded article (Y) having the same shape as the hollow portion of the hollow shaped article (x1) and the molded article (Y) can be obtained. The crude molded article is then immersed in water, an organic solvent, or a mixture thereof, whereby the shaped article (x1) is separated from or removed from the molded article (Y) by dissolution, dispersion, or disintegration, thereby obtaining the molded article (Y).

[0090] When the hollow structured object (x1) is used as a mold for the molded product (Y), the specific procedure includes a first step of molding the hollow structured object (x1) using the active energy ray-curable resin composition (E) of the present invention; a second step of using the hollow structured object (x1) thus obtained as a mold to fill the hollow portion of the object (x1) with a molding material (H) and cure and / or solidify it to obtain a crude molded product; and a third step of immersing the crude molded product thus obtained in water, an organic solvent, or a mixture thereof, and removing the object (x1) to obtain the molded product (Y).

[0091] The immersion liquid used to immerse the crude shaped object may be the same as or different from water, an organic solvent, or a mixture thereof that is soluble, dispersible, or disintegrable in the cured product obtained by curing the active energy ray-curable resin composition (E). Furthermore, from the viewpoint of not dissolving or swelling the molded object (Y), it is preferable to use a liquid with a polarity different from that of the molded object (Y). When the molded object (Y) is molded from a molding material (H) with low polarity, it is more preferable to use water, methanol, ethanol, or a mixture thereof as the immersion liquid. Furthermore, from the viewpoint of the ease with which the molded object (x1) is dissolved, dispersed, or disintegrated, water is the most preferable immersion liquid because of its particularly high safety.

[0092] In the method for producing the molded product (Y) of the present invention, a first step involves immersing a crude molded product in water, an organic solvent, or a mixture thereof, and then removing the molded product (x1) used as a mold to obtain the molded product (Y). The hollow molded product (x1) can be easily produced by three-dimensional stereolithography using the activation energy ray-curable resin composition (E) of the present invention, as described above. The hollows in the molded product (x1) may be through or non-through, cylindrical, circular, elliptical, or honeycomb-shaped holes with a diameter of 1 mm or less, or may have a complex structure or a fine structure with curved surfaces. The molded product (Y) having such a complex or fine structure can be obtained by using the molded product (x1) having such a complex or fine structure. In particular, when molding a low-strength, soft molded object (Y) such as an artificial organ, the molded object (x1) can be easily and completely removed from the crude molded object, without damaging the complex and fine internal structure, making it possible to mold a molded object (Y) that could not be achieved with conventional molding methods. When molding a molded object (x1) having a hollow structure, for example, if a liquid vat photopolymerization method or the like is used as three-dimensional stereolithography, it is possible to mold not only linear but also curved columnar structures with a diameter of 0.3 mm or more with high molding accuracy, which is preferable because it makes it possible to produce a molded object (Y) having a hollow structure of 0.3 mm or more.

[0093] The molding material (H) can be cured and / or solidified (hereinafter, the formation of the molded product (Y) is also referred to as molding) by one or more of the following methods: active energy rays, heat, and moisture. When curing by active energy rays, a liquid photocurable resin can be filled into the hollow portion of the molded product (x1) having a hollow structure and cured by a photoreaction such as photoradical polymerization, photocationic polymerization, or photoanionic polymerization, resulting in molding. When molding by heat, examples include a method in which a liquid thermosetting resin is filled into the hollow portion and then heated to harden and mold the hollow portion; or a method in which a thermoplastic material is preheated to melt and liquefy it, then filled into the hollow portion, cooled to solidify (solidify), and then molded. When molding by moisture, examples include a method in which water and the molding material are mixed and quickly filled into the hollow portion and then hardened over time or heat; or a method in which a hygroscopic molding material is filled into the hollow portion and hardened while absorbing moisture from the air.

[0094] When an active energy ray-curable resin is used as the molding material (H), there are no particular limitations as long as it is curable by active energy rays. Commercially available active energy ray-curable resin compositions for model materials that can be used in three-dimensional stereolithography are preferred because they have good operability during molding, low cure shrinkage during curing, and enable precise molding.

[0095] When a thermosetting resin is used as the molding material (H), there are no particular limitations, and examples include thermosetting phenolic resins, melamine resins, urea resins, silicone resins, epoxy resins, polyester resins, urethane resins, and acrylic resins. Furthermore, resins that can be cured at a temperature equal to or lower than the heat distortion temperature of the hollow structure-containing object (x1) are preferred. Specifically, resins that can be cured at 130°C or lower are preferred, resins that can be cured at 100°C or lower are more preferred, resins that can be cured at 60°C or lower are even more preferred, and resins that can be cured at 40°C or lower are particularly preferred. From these perspectives, two-component curing thermosetting resins are particularly preferred, as they can be cured at relatively low temperatures. Specifically, silicone resins, epoxy resins, polyester resins, urethane resins, and acrylic resins are preferred as two-component curing thermosetting resins.

[0096] When a thermoplastic material is used as the molding material (H), there are no particular restrictions, but a material that can melt at a temperature below the heat distortion temperature of the hollow structured object (x1) is preferred. Specifically, a material with a melting point of 130°C or less is preferred. Specific examples include thermoplastic materials such as crystalline polyester, natural wax, synthetic wax, and rosin, thermoplastic foods such as chocolate and cheese, and low-melting-point metals such as gallium with a melting point of approximately 30°C, tin-indium-bismuth alloy with a melting point of approximately 50°C, and bismuth-tin-lead-cadmium alloy with a melting point of 100°C or less.

[0097] When a moisture-curable material is used as the molding material (H), there are no particular limitations, and examples include gypsum, cement, mortar, etc., and moisture-curable resins such as cyanoacrylate resins. Furthermore, when the hollow structured object (x1) is soluble, dispersible, or disintegrable in water, it is preferable to use, as the moisture-curable material, fast-drying mortar, concrete, gypsum, etc. that can be cured in a short time, or hygroscopic cyanoacrylate resins, from the viewpoint of suppressing deformation of the object (x1) used as a molding mold.

[0098] In the manufacturing method of the molded product (Y) according to this embodiment, thermosetting silicone resin, epoxy resin, polyester resin, urethane resin, acrylic resin, and moisture-curing cyanoacrylate resin, which cannot be used as modeling materials for 3D printers, can also be used as the molding material (H), and a molded product (Y) with unique physical properties that cannot be modeled using a 3D printer can be obtained.

[0099] From the perspective of creating a recycling-oriented society, it is preferable to use a biomass-derived material for the molding material (H). There are no particular limitations on the biomass-based material, but examples include natural waxes such as fatty acid waxes made from carnauba wax, beeswax, castor oil, or beef tallow fatty acids, fatty acid ester wax, and other natural waxes; polyesters produced by microorganisms such as polyhydroxyalkanoic acid; polyester resins made from bio-based raw materials such as lactic acid, succinic acid, isosorbide, and ethylene glycol; and urethane resins made from bio-based polyether polyols, polyester polyols, polycarbonate polyols, and diisocyanate compounds. Furthermore, it is more preferable for bio-based materials to have a bio-based content of 25% or more. The bio-based content is calculated according to ISO 16620-2 based on the biomass-derived carbon content of the total carbon in the material.

[0100] From the viewpoint of forming a recycling-oriented society, it is preferable to use a biodegradable material as the molding material (H). There are no particular limitations on the material as long as it is biodegradable, but examples include biodegradable ester waxes such as carnauba wax and fatty acid ester wax, polyhydroxyalkanoic acid, polylactic acid, and succinic acid-based polyester resins.

[0101] The molding material (H) is preferably a material capable of forming a crosslinked structure depending on the purpose. For example, when producing a molded product (Y) having strength, durability, rubber elasticity, etc., it is preferable to use a material capable of forming a crosslinked structure. On the other hand, when producing a molded product (Y) such as a candle that requires remeltability or a biodegradable molded product (Y), it is preferable to use a material that does not form a crosslinked structure or a material that forms a low crosslinked structure. Examples of molding materials (H) capable of forming a crosslinked structure include commercially available active energy ray-curable resin compositions for model materials in three-dimensional stereolithography, thermosetting silicone resins, epoxy resins, polyester resins, urethane resins, acrylic resins, and moisture-curing cyanoacrylate resins. Examples of molding materials (H) that do not form a crosslinked structure include crystalline polyesters and waxes. The molding material (H) that forms a crosslinked structure can be prepared by appropriately combining at least one molding material capable of forming a crosslinked structure with at least one molding material that does not form a crosslinked structure.

[0102] The molding material (H) preferably contains an organic filler and / or an inorganic filler depending on the purpose, for example, to reduce the weight of the molded product (Y) or to improve its strength, heat resistance, etc. The shape of the organic filler and / or inorganic filler may be any of spherical, plate-like, flake-like, needle-like, fibrous, mesh-like, irregular, etc. A dispersant may be added to the molding material (H) to uniformly disperse the filler.

[0103] The organic filler is not particularly limited, and specific examples include plant-derived substances that are insoluble or poorly soluble in organic solvents, such as cellulose, lignin, and cellulose nanofibers; organic beads such as polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyethylene fluoride resin beads, and polyethylene resin beads; organic fibers such as cellulose fibers, aramid fibers, and polyamide fibers; organic pigments; graphite, carbon black, carbon nanotubes, and carbon fibers.

[0104] The inorganic filler is not particularly limited, and specific examples include silica, alumina, silica alumina, zirconia, talc, clay, mica, glass, glass beads, glass fiber, glass balloons, shirasu balloons, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, iron oxide, calcium oxide, magnesium oxide, and inorganic pigments.

[0105] The organic filler and / or inorganic filler may be used alone or in combination of two or more. The content of the filler in the molding material (H) is not particularly limited as long as it does not impede molding, but is preferably 0.1 to 80% by mass relative to the total mass of the molding material (H).

[0106] The molded product (Y) according to this embodiment is formed using a hollow shaped object (x1) as a mold. The shaped object (x1) can have a complex or fine structure, allowing for extremely high flexibility in structural design. Furthermore, a wide variety of materials, such as hard resins, thermoplastic waxes, rubber-like resins, biodegradable resins, and food products, can be used as the molding material (H) used to form the molded product (Y). By appropriately combining the shaped object (x1) used as the mold with the molding material (H), molded products (Y) with various shapes, structures, and properties can be produced, potentially enabling a wide range of applications. Industrial applications include, for example, the production of prototypes and trial products, the production of customized medical and nursing care products, the production of structures and parts for various uses such as learning materials, jewelry, hobbies, and building materials, the production of various machine parts or food products, and the production of resin molds for injection molding and press molding.

[0107] When molded product (Y) is used as a prototype, it is possible to check the molding accuracy from the shape of the prototype, select a practical resin from actual measurement data of the strength and heat resistance of the prototype, and optimize the shape and structure of structures, parts, machine parts, and resin molds.

[0108] When the molded product (Y) is used as a learning material, examples of the molded product (Y) include three-dimensional models as mathematics teaching materials, molecular models as chemistry teaching materials, topographical models and three-dimensional maps as social studies teaching materials, scaled-down building models as architecture teaching materials, organ models as medical teaching materials, and simulated blood vessels and simulated organs used for practicing medical procedures.

[0109] When the molded article (Y) is used as a medical or nursing care product, examples of the product include medical products such as artificial skin, artificial bone, artificial blood vessel, artificial limb, cast, etc.; medical equipment products such as artificial dialysis and artificial heart-lung machines; dental products such as dentures, false teeth, and orthodontic mouthpieces; nursing care products such as wheelchairs, bedsore prevention mats, and bathing care products; post-operative body shape support materials, tools used to restore physical abilities, and rehabilitation products such as supports.

[0110] When the molded article (Y) is used as a structure or part, examples of decorative items include custom-made rings, necklaces, earrings, brooches, etc.; examples of art include replica production, three-dimensional renderings of paintings, and molded art objects; examples of hobbies include key chains, stuffed animals, figures, plastic models, and game controllers; examples of sports equipment include athletic shoe overlays, insoles, and soles, ski boots, skates, bats, rackets for various ball games, helmets for various sports, mouthpieces, elbow pads, leg guards, gloves, and protectors; examples of furniture include chairs, desks, dressers, bookshelves, and beds, which are used for furniture tailored to individual needs or original designs; examples of building materials include exterior and interior walls, structural materials, roofs, and window frames for homes; examples of miscellaneous goods include writing implements, mouse pads, stamps, earplugs, toothbrushes, cosmetics, face shields, and food samples, which are used for miscellaneous goods tailored to individual needs or original designs.

[0111] When the molded article (Y) is used as a machine part, examples thereof include machine parts for transportation machinery, electrical appliances, industrial machinery, space development equipment, etc. Examples of transportation machinery include automobiles, motorcycles, bicycles, railroad vehicles, ships, and aircraft, including parts such as engines, batteries, motors, fuel tanks, wheels, brakes, suspensions, chassis, frames, and cargo beds; exterior parts such as windows, bumpers, front panels, side panels, rear panels, door parts, and aero parts; and interior parts such as handlebars, panels, seats, harnesses, seat belts, and grips. Examples of electrical appliances include various office automation equipment such as televisions, personal computers, and printers, and various home appliances such as refrigerators, washing machines, air conditioners, and vacuum cleaners. Examples of electrical appliance parts include exterior parts, various parts, and replacement parts for electrical appliances, as well as customized applications such as headphones, VR goggles, and earphones, and decorative applications for mobile phones and smartphones. Examples of industrial machinery include industrial machinery used for various purposes such as painting, assembly, and parts manufacturing on production lines, etc., industrial machinery such as safety valves for high-pressure cylinders, automatic fire hydrants, sprinklers, and other safety devices, and industrial machinery used in logistics, etc., such as warehouse automation, automatic delivery systems, and automatic packaging systems, as well as structural materials and various parts of these industrial machinery, and particularly jig parts that need to be tailored to the target. Examples of space development equipment include engines, exteriors, and interiors of accessories for rockets, shuttles, launch pads, etc., as well as exteriors, interiors, and various parts of artificial satellites.

[0112] When the shaped product (Y) is used as a food product, examples of the shaped product include shaped products of crafts such as chocolate and candy, shaped products of artificial meat, protein, food paste, wheat flour-based dough such as bread, pasta, and pizza, and shaped dairy products such as cheese.

[0113] When the molded product (Y) is used as a resin mold, examples of the molded product include a resin mold for injection molding, a resin mold for press molding, etc. In particular, when a thermosetting resin having high heat resistance and durability is used, examples of the molded product (Y) include a resin mold for injection molding of engineering plastics or super engineering plastics. [Example]

[0114] 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 the following, "parts" and "%" are all by mass unless otherwise specified.

[0115] The raw materials used in the active energy ray-curable resin composition (E) of the example and the composition (F) for the comparative example are as follows. <Non-polyfunctional polymerizable compound (A)> <Monofunctional polymerizable compound (a1)> <Monofunctional polymerizable compound (a1-1) containing an amide group> a1-1-1: N-acryloylmorpholine (registered trademark "Kohshylmer" or "ACMO" manufactured by KJ Chemicals Co., Ltd., homopolymer Tg = 145°C) a1-1-2: N,N-diethylacrylamide (registered trademark "Kohshylmer" or "DEAA" manufactured by KJ Chemicals Co., Ltd., homopolymer Tg = 81°C) a1-1-3: N,N,N-trimethylammonium propylacrylamide p-toluenesulfonate (registered trademarks "Kohshylmer", "Quatermer", "DMAPAA-TSMQ", manufactured by KJ Chemicals Co., Ltd., homopolymer Tg = 175°C) a1-1-4: N,N-dimethylacrylamide (registered trademark "Kohshylmer", "DMAA", manufactured by KJ Chemicals Co., Ltd., homopolymer = Tg = 119°C) a1-1-5: N-acryloyloxyethyl norbornenecarboxamide (registered trademark "Kohshylmer" manufactured by KJ Chemicals Co., Ltd., homopolymer Tg = 170°C) a1-1-6: N-(2-hydroxyethyl)methacrylamide (registered trademark "Kohshylmer" manufactured by KJ Chemicals Co., Ltd., homopolymer Tg = 190°C) a1-1-7: N-(2-hydroxyethyl)acrylamide (registered trademark "Kohshylmer", "HEAA", manufactured by KJ Chemicals Co., Ltd., homopolymer Tg = 98°C) a1-1-8: N-oleyl acrylamide (registered trademark "Kohshylmer" manufactured by KJ Chemicals Co., Ltd., homopolymer Tg = 29°C) a1-1-9: Dimethylaminopropylacrylamide (registered trademark "Kohshylmer", "DMAPAA", manufactured by KJ Chemicals Co., Ltd., homopolymer Tg = 134°C) a1-1-10: Diacetone acrylamide (registered trademark "Kohshylmer" manufactured by KJ Chemicals Co., Ltd., homopolymer Tg = 77°C) a1-1-11: N-vinylpyrrolidone (NVP, manufactured by BASF Corporation, Chemical Intermediates, homopolymer Tg = 80°C)

[0116] <Oxyalkylene Group-Containing Monofunctional Polymerizable Compound (a1-2)> a1-2-1: Hydroxyl-terminated polypropylene glycol monomethacrylate (PPG average molecular weight 800) (PP-800, manufactured by NOF Corporation, homopolymer Tg = -62°C) a1-2-2: Methoxypolyethylene glycol monoacrylate (PEG average molecular weight 550) (MPE550A, manufactured by Osaka Organic Chemical Co., Ltd., homopolymer Tg = -50°C) a1-2-3: Hydroxyl-terminated polyethylene glycol monoacrylate (PEG average molecular weight 400) (AE-400, NOF Corporation, homopolymer Tg = -66°C) a1-2-4: Phenoxy-polyethylene glycol acrylate (Light Acrylate P-200A, manufactured by Kyoeisha Chemical Co., Ltd., homopolymer Tg = -25°C) a1-2-5: Methoxy-triethylene glycol acrylate (Light Acrylate MTG-A, manufactured by Kyoeisha Chemical Co., Ltd., homopolymer Tg = -50°C) a1-2-6: Methoxypolyethylene glycol monomethacrylate (PEG average molecular weight 1,000) (PME-1000, NOF Corporation, homopolymer Tg = -52°C) a1-2-7: Methoxy-dipropylene glycol acrylate (Light Acrylate DPM-A, manufactured by Kyoeisha Chemical Co., Ltd., homopolymer Tg = -50°C)

[0117] <Other monofunctional polymerizable compounds (a1-3)> a1-3-1: Cyclohexylmaleimide (homopolymer Tg>250℃) a1-3-2: Hydroxyethyl methacrylate (homopolymer Tg = 55°C) a1-3-3: t-butylcyclohexyl acrylate (TBCHA TM , registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd., homopolymer Tg=77℃) a1-3-4: Isobornyl acrylate (IBXA, manufactured by Osaka Organic Chemical Industry Ltd., homopolymer Tg = 97°C)

[0118] <Polymerizable Compound (a2) Having an Average Number of Unsaturated Groups in the Molecule of More than 1 and Less than 2> a2-1: Polyethylene glycol (20)-incorporated bisphenol A (acrylic 1.01 equivalent modified product, Mn = 1200, Tg = -31°C) a2-2: Polyether-based urethane acrylamide (registered trademark "Quick Cure", 1.5 functional groups, Mn = 35000, Tg = -42°C) a2-3: Polycarbonate-based urethane acrylamide (registered trademark "Quick Cure", 1.1 functional group, manufactured by KJ Chemicals Co., Ltd., Mn = 15,000, Tg = -2°C) a2-4: Polyester-based urethane acrylamide (registered trademark "Quick Cure", 1.2 functional groups, Mn=9000, Tg=8°C) a2-5: Unsaturated polyester (3-allyloxy-1,2-propanediol / butanediol / succinic acid = 1.9 / 4.1 / 5 (molar ratio) (1.9 functional group, Mn = 1500, Tg = 103°C) a2-6: Polyether-based urethane acrylate (1.1 functional group, Mn=5000, Tg=-45°C) a2-7: Polyether-based urethane maleimide (1.1 functional group, Mn=5000, Tg=-38°C)

[0119] Non-crosslinkable polymer (B) B-1: Homopolymer of N,N-diethylacrylamide (Tg=81℃, Mn=450,000) B-2: Homopolymer of N,N-dimethylacrylamide (Tg=119℃, Mn=10,000) B-3: Homopolymer of N-isopropylacrylamide (Tg=134℃, Mn=48,000) B-4: Homopolymer of N-(2-hydroxyethyl)acrylamide (Tg=98℃, Mn=4,000) B-5: Homopolymer of N,N-dimethylacrylamide (Tg=60℃, Mn=2,100) B-6: Copolymer of N,N-diethylacrylamide and methoxy-triethylene glycol acrylate (9 / 1) (mass ratio) (Tg = 60°C, Mn = 5,000) B-7: Copolymer of t-butylcyclohexyl acrylate and N,N-diethylacrylamide (1 / 1) (mass ratio) (Tg = 79°C, Mn = 7,000) B-8: Homopolymer of N,N-diethylacrylamide (Tg=81℃, Mn=7,000) B-9: Copolymer of N,N-diethylacrylamide, hydroxyethyl methacrylate, and hydroxyethyl acrylate (10 / 45 / 45) (mass ratio) (Tg = 21°C, Mn = 12,000) B-10: Homopolymer of N-acryloylmorpholine (Tg=145℃, Mn=8,000) B-11: Copolymer of N-(2-hydroxyethyl) methacrylamide and methoxytriethylene glycol acrylate (3 / 2) (mass ratio) (Tg = 43°C, Mn = 14,000) B-12: Copolymer of diacetone acrylamide and N,N-dimethyl acrylamide (1 / 1) (mass ratio) (Tg = 97°C, Mn = 12,000)

[0120] <Photoinitiator (C)> C-1: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (Omnirad TPO, manufactured by IGM Resins BV) C-2: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resins BV) C-3: Diethylene glycol di(α-oxobenzeneacetic acid) ester and diethylene glycol mono(α-oxobenzeneacetic acid) ester mixture (Omnirad 754, manufactured by IGM Resins BV) C-4: 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins BV) C-5: Benzophenone (Omnirad BP, manufactured by IGM Resins BV)

[0121] <Viscosity modifier (D)> D-1: Hydroxypropyl methylcellulose (PMC-40H(S), manufactured by Tomoe Engineering Co., Ltd.) D-2: 3-Methoxy-N,N-dimethylpropionamide (registered trademark "KJCMPA", boiling point 215°C, manufactured by KJ Chemicals) D-3: Polytetramethylene glycol (average molecular weight 650, PTMG650, manufactured by Mitsubishi Chemical Corporation) D-4: 3-Butoxy-N,N-dimethylpropionamide (registered trademark "KJCBPA", boiling point 252°C, manufactured by KJ Chemicals Co., Ltd.) D-5: Polyoxyethylene monostearyl ether (PEG average molecular weight 650) (Nonion S-215, NOF Corporation) D-6: Tripropylene glycol monomethyl ether (boiling point 215°C) D-7: 1,8-octanediol (boiling point 279°C) D-8: Polypropylene glycol with a number average molecular weight of 400 (Uniol D400, manufactured by NOF Corporation)

[0122] <Other Additives (G)> G-1: Dimethylol-tricyclodecane diacrylate (Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., homopolymer Tg > 250°C) G-2: TEGORad2100 (a silicone polyfunctional acrylate with a polydimethylsiloxane structure, manufactured by Evonik Degussa) G-3: Phenothiazine G-4: (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy) radical G-5: Ethylene glycol-modified trimethylolpropane triacrylate (Aronix M360, manufactured by Toagosei Co., Ltd., homopolymer Tg = 53°C) G-6: Polyurethane diacrylate (UV6630B, 2.0 functional group, weight average molecular weight = 3000, Tg 38°C, manufactured by Mitsubishi Chemical Corporation)

[0123] Example 1 Active energy ray-curable resin composition (E-1) 50.0 parts by mass of N-acroylmorpholine (a1-1-1), 29.9 parts by mass of hydroxyl-terminated polypropylene glycol monomethacrylate (PP-800, manufactured by NOF Corporation) (a1-2-1), 20.0 parts by mass of cyclohexylmaleimide (a1-3-1), and 0.1 parts by mass of N,N-diethylacrylamide homopolymer (Tg = 81 ° C, Mn = 450,000) (B-1) were placed in a container and stirred at 25 ° C for 1 hour to obtain the active energy ray-curable resin composition (E-1) of Example 1 as a homogeneous, transparent liquid. The viscosity of the active energy ray-curable resin composition and its cure shrinkage resistance were measured using the methods described below, and the results are shown in Table 1.

[0124] Examples 2 to 24 Active energy ray-curable resin compositions (E-2) to (E-24) Active energy ray-curable resin compositions (E-2) to (E-24) were obtained as homogeneous, transparent liquids using the compositions shown in Table 1 and the same procedures as in Example 1. The viscosity of each active energy ray-curable resin composition was measured and its resistance to cure shrinkage was evaluated by the methods described below. The results are shown in Table 1.

[0125] Comparative Examples 1 to 4 Comparative Compositions (F-1) to (F-4) Comparative compositions (F-1) to (F-4) were obtained using the compositions shown in Table 1 and by carrying out the same operations as in Example 1. The viscosity of the obtained comparative compositions (F-1) to (F-4) was measured and their resistance to cure shrinkage was evaluated by the methods described below. The results are shown in Table 1.

[0126] (1) Viscosity measurement The viscosities of the active energy ray-curable resin compositions (E-1) to (E-24) obtained in the examples and the comparative compositions (F-1) to (F-4) were measured at 25°C using a Brookfield viscometer (digital viscometer LV DV2T, manufactured by Eiko Seiki Co., Ltd.) in accordance with JIS K5600-2-3.

[0127] (2) Evaluation of cure shrinkage resistance A 75 μm thick heavy-release PET film (Polyester Film E7001, manufactured by Toyobo Co., Ltd.) was placed on a horizontally placed glass plate, and a spacer with an internal volume of 10 mm × 10 mm × 10 mm was placed thereon. The active energy ray-curable resin compositions (E-1) to (E-24) obtained in the examples and the comparative compositions (F-1) to (F-4) were filled inside the spacer to a thickness of 1 mm. The active energy ray-curable resin compositions were kept at 60°C for 30 seconds until the liquid surface became smooth. After that, ultraviolet light was irradiated (desktop batch-type UV-LED curing device MUVBA-0.3 × 0.3 × 0.5, manufactured by ITEC System Co., Ltd., wavelength 365 nm, illuminance 50 mW / cm). 2 , cumulative light intensity 1,000mJ / cm 2) and curing the resin composition to obtain one layer of cured product. Subsequently, nine more layers were cured on top of the first cured layer using the same procedure to obtain a cured product measuring 10 × 10 × 10 mm. The cure shrinkage was calculated from the change in density before and after curing of the active energy ray-curable resin composition (E) and the comparative composition (F) as shown in the following calculation formula (1) in accordance with JIS K5600 2-4. The densities before and after curing of the active energy ray-curable resin composition (E) and the comparative composition (F) were measured using an electronic hydrometer (MDS-300 manufactured by Alpha Mirage Co., Ltd.) in an environment of 25°C in accordance with JIS K7112. The cure shrinkage resistance was evaluated from the obtained cure shrinkage using the following criteria. Curing shrinkage rate (%) = (Ds - Dl) / Dl x 100 Calculation formula (1) (In the formula, Ds is the density of (E) and (F) after curing, and Dl is the density of (E) and (F) before curing.) ◎◎: Curing shrinkage rate less than 6% ◎: Curing shrinkage rate 6% or more and less than 7% ○: Curing shrinkage rate 7% or more and less than 8% ×: Curing shrinkage rate 8% or more

[0128] [Table 1]

[0129] Example 25 Manufacture of sculpture (x1-1) Using an ARM-10 (Roland DG Corporation) as a hanging-type DLP type liquid tank photopolymerization device, the liquid tank was filled with the active energy ray-curable resin composition (E-1) obtained in Example 1, and ultraviolet light was irradiated (wavelength 405 nm, illuminance 0.2 mW / cm) so that the thickness of one layer became 0.15 mm. 2 , cumulative light intensity 5mJ / cm 2) to form the object shown in Figure 1. Immediately after printing, the object was immersed in isopropanol for 1 minute (twice) to remove the uncured resin composition. After that, UV light was irradiated as a post-cure (ITEC System Co., Ltd., tabletop batch-type UV-LED curing device MUVBA-0.3 x 0.3 x 0.5, wavelength 365 nm, illuminance 50 mW / cm). 2 , cumulative light intensity 10,000mJ / cm 2 ) to obtain a molded object (x1-1) with a hollow structure as shown in Figure 1. (The molded object was a 25 x 20 x 15 mm rectangular parallelepiped with a 15 x 10 x 10 mm cubic cavity in the center, with two crossed cylinders with a diameter of 0.5 mm in the center of the hollow part.)

[0130] Examples 26 to 28, 31, 32, 34, 36 to 48 Production of objects (x1-2) to (x1-4), (x1-7), (x1-8), (x1-10), (x1-12) to (x1-24) The same procedure as in Example 24 was carried out using active energy ray-curable resin compositions (E-2) to (E-4), (E-7), (E-8), (E-10), and (E-12) to (E-24), to obtain shaped objects (x1-2) to (x1-4), (x1-7), (x1-8), (x1-10), and (x1-12) to (x1-24).

[0131] Example 29 Manufacture of sculptures (x1-5) Using an ARM-10 (Roland DG Corporation) as a hanging-type DLP type liquid tank photopolymerization device, the liquid tank was filled with the active energy ray-curable resin composition (E-5) obtained in Example 5, and ultraviolet light was irradiated (wavelength 405 nm, illuminance 0.2 mW / cm) so that the thickness of one layer became 0.05 mm. 2 , cumulative light intensity 35mJ / cm 2 ) to form the object shown in Figure 1. Immediately after formation, the object was immersed in isopropanol for 1 minute (twice) to remove the uncured resin composition, thereby obtaining object (x1-5).

[0132] Examples 30, 33, and 35 Production of sculptures (x1-6), (x1-9), and (x1-11) The same procedure as in Example 28 was carried out using the active energy ray-curable resin compositions (E-6), (E-9), and (E-11), to obtain shaped objects (x1-6), (x1-9), and (x1-11).

[0133] Comparative Examples 5 to 8 Manufacture of comparative examples (s1-1) to (s1-4) Comparative compositions (F-1) to (F-4) were used in the same manner as in Example 25 to obtain comparative shaped objects (s1-1) to (s1-4).

[0134] Examples 49 to 72 and Comparative Examples 9 to 12 Manufacturing and physical property evaluation of objects (x2-1) to (x2-24) and objects (s2-1) to (s2-4) A 75 μm thick heavy-release PET film (Toyobo Co., Ltd., polyester film E7001) was placed on a horizontally placed glass plate, and a spacer with an internal volume of 20 mm × 20 mm × 20 mm was placed. The active energy ray-curable resin compositions (E-1) to (E-24) obtained in the examples and the comparative compositions (F-1) to (F-4) were filled inside the spacer to a thickness of 1 mm. The mixture was kept at 60°C for 30 seconds until the liquid surface became smooth, after which ultraviolet light was irradiated (ITEC System Co., Ltd., tabletop batch-type UV-LED curing device MUVBA-0.3 × 0.3 × 0.5, wavelength 365 nm, illuminance 50 mW / cm). 2 , cumulative light intensity 1,000mJ / cm 2 ) and cured the resin composition to obtain one layer of cured product. Subsequently, 19 more layers were cured on top of the first cured layer using the same procedure, obtaining 20 × 20 × 20 mm solid cubic objects (x2-1) to (x2-24) and objects (s2-1) to (s2-4). The resulting objects were evaluated for molding accuracy, non-solubility, and heat resistance using the methods described below, and the results are shown in Table 2.

[0135] (3) Evaluation of molding accuracy The molding accuracy of the cubic object (x2) and the cubic object (s2) obtained in the above-mentioned Examples and Comparative Examples was evaluated as follows. ⊚: The length of each side of the cube is 19.8 mm to 20.0 mm, and the shape of each corner is sharp. Good: The length of each side of the cube is 19.5 mm to less than 19.8 mm, and the shape of each corner is slightly rounded. △: The length of each side of the cube is less than 19.5 mm, or each corner is significantly chipped. ×: Not formed as a cube.

[0136] (4) Insolubility evaluation A 75 μm thick heavy release PET film (Toyobo Co., Ltd., polyester film E7001) was placed in close contact with a horizontally placed glass plate, a spacer with an internal volume of 10 mm × 10 mm × 1 mm was placed, and the active energy ray curable resin compositions (E-1) to (E-24) obtained in the examples and the comparative compositions (F-1) to (F-4) were filled to a thickness of 1 mm inside the spacer. The active energy ray curable resin compositions (E-1) to (E-24) obtained in the examples and the comparative compositions (F-1) to (F-4) were each filled to a thickness of 1 mm inside the spacer, and the mixture was kept at 60°C for 30 seconds to smooth the liquid surface. After that, a 50 μm thick light release PET film (Toyobo Co., Ltd., polyester film E7002) was placed on top of the liquid surface, and ultraviolet light was irradiated (ITEC System Co., Ltd., desktop batch-type UV-LED curing device MUVBA-0.3 × 0.3 × 0.5, wavelength 365 nm, illuminance 5 mW / cm). 2 , cumulative light intensity 100mJ / cm 2 ) and cured the resin composition. The thickness of the resulting cured product was measured and recorded as the cured product thickness before testing. The cured product was placed in a 50 mL beaker, and 10 g of the active energy ray-curable resin composition (E) or the comparative composition (F), which are the raw materials for the cured product, was added to each beaker, and the beaker was left to stand at 25°C for 1 hour. Thereafter, each cured product was removed from the beaker and washed with isopropanol. The thickness of the cured product was then measured and recorded as the cured product thickness after testing. The insolubility of the cured product was evaluated based on the change in thickness of the cured product (the difference between the thickness of the cured product before testing and the thickness of the cured product after testing) and the condition of the cured product after testing. ⊚: There is no change in thickness of the cured product, and no dissolution or swelling of the cured product is observed. ◯: The change in thickness of the cured product was less than 0.1 mm, and slight dissolution of the cured product was observed. △: The thickness of the cured product changed by 0.1 mm or more, and partial dissolution was observed. ×: The cured product was completely dissolved.

[0137] (5) Heat resistance evaluation The heights (in the stacking direction) of the cubic objects (x2) and (s2) obtained in the Examples and Comparative Examples were measured and recorded as the thickness before testing. A fluororesin sheet (25 mm × 25 mm × 1 mm) was placed on top of the object, and a 100 g weight was placed on top of the sheet. The object was then placed in an incubator set to 30°C, 50°C, 70°C, 90°C, 110°C, or 130°C and allowed to stand for one hour. The cured object was then removed and allowed to stand for one hour at 25°C, and the height was measured and recorded as the thickness after testing. The heat resistance of the cured object was evaluated based on the change in thickness before and after testing at each temperature. That is, the highest test temperature at which the thickness change was less than 0.1 mm was recorded as the heat resistance temperature. Note that if the thickness change of the cured object in the 30°C test was 0.1 mm or more, the heat resistance temperature was recorded as less than 30°C (<30°C). The heat resistance evaluation results (heat resistance temperature) are shown in Table 2.

[0138] [Table 2]

[0139] Examples 73 to 97 and Comparative Examples 13 to 16 Production of molded products (Y-1) to (Y-25) and molded products (Z-1) to (Z-4) The molded objects (x1-1) to (x1-24) produced in Examples 25 to 48 and the molded objects (s1-1) to (s1-4) produced in Comparative Examples 5 to 8 were used as molds. Liquid molding materials (H-1) to (H-15) were filled into the hollow spaces under the molding conditions listed in Table 3, and cured and / or solidified to obtain crude molded objects. The crude molded objects were then immersed in immersion liquids (I-1) to (I-6) listed in Table 3 at 25°C for 24 hours. The molds were removed by dissolving, dispersing, or disintegrating them, yielding molded objects (Y-1) to (Y-25) and (Z-1) to (Z-4) with the shapes shown in Figure 2. Details of the molding material (H), the method for mixing the molding materials before filling, and the immersion liquid (I) used to produce these molded objects are described below. Evaluations of mold removability, molding accuracy, and molded object strength were performed using the methods described below, and the results are shown in Table 3.

[0140] <Molding material (H)> The molding materials (H-1), (H-4) to (H-10) are as follows. The two-component curable molding materials (H-1), (H-4), (H-5), and (H-7) to (H-9) were mixed in the specified proportions just before filling. The thermoplastic molding materials (H-6) and (H-10) were heated to the filling temperature shown in Table 3 just before filling and melted before use. H-1: Two-component curing unsaturated polyester resin (TP-153 (DIC Materials) / Mepox 55 (Kawaguchi Pharmaceuticals) = 100 / 1, mass ratio) H-4: Two-component curing (condensation) silicone (KE-12 / CAT-RS = 100 / 0.5, mass ratio, manufactured by Shin-Etsu Silicones Co., Ltd.) H-5: Two-component curing (addition) silicone (KE-1316 / CAT-1316 = 100 / 10, mass ratio, manufactured by Shin-Etsu Silicones Co., Ltd.) H-6: Beeswax (granular, melting point 63°C, manufactured by Yamakei Sangyo Co., Ltd.) H-7: Two-component curing polyurethane rubber (ADAPT 60L (base / curing agent = 100 / 33, mass ratio), manufactured by Nissin Resin Co., Ltd.) H-8: Two-component curing epoxy resin (EP-4530 / EH-6024 = 100 / 40, mass ratio, manufactured by ADEKA Corporation) H-9: Two-component curing (casting) urethane resin (ADAPT RU42AN / RU42B = 100 / 100, mass ratio), manufactured by Nissin Resin Co., Ltd. H-10: Bismuth-tin-lead-cadmium alloy with a melting point of 70°C (U Alloy 70G (Osaka Asahi Metal Factory Co., Ltd.))

[0141] H-2: Active energy ray curable molding material Manufacturing of molding material (H-2) 20.0 parts by mass of N-acroylmorpholine, 20.0 parts by mass of phenoxyethyl acrylate, 20.0 parts by mass of ethoxylated bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), 10.0 parts by mass of a reaction product of isophorone diisocyanate and N-(2-hydroxyethyl)acrylamide, 25.0 parts by mass of polyester-based urethane diacrylamide (registered trademark "Quick Cure"), and 5.0 parts by mass of Omnirad TPO were charged into a container and stirred at 25°C for 1 hour to obtain an active energy ray-curable molding material (H-2) as a homogeneous, transparent liquid.

[0142] H-3: Active energy ray curable molding material containing inorganic filler Manufacturing of molding material (H-3) Five parts by mass of silica fine particles (Seahoster KE-P100, manufactured by Nippon Shokubai Co., Ltd.) were added to 100 parts by mass of molding material (H-2), and the mixture was stirred at 25°C with a homomixer at a rotation speed of 3000 rpm for 5 minutes to obtain an inorganic filler-containing active energy ray-curable molding material (H-3) as a uniform dispersion.

[0143] After production, the active energy ray-curable molding materials (H-2) and (H-3) are preferably stored in a light-shielding container until immediately before filling, and more preferably used immediately after production. After filling the mold with molding material (H-2) or (H-3), ultraviolet light (ITEC System Co., Ltd., tabletop batch-type UV-LED curing device MUVBA-0.3 x 0.3 x 0.5, wavelength 405 nm, illuminance 10 mW / cm², cumulative light dose 10,000 mJ / cm²) was applied from above the mold. 2 ), the molding material (H-2) or (H-3) is cured, and a crude molding can be formed.

[0144] H-11: Thermoplastic molding material made of biodegradable polyester resin Manufacturing of molding material (H-11) A reaction vessel equipped with a fractionator, Liebig condenser, stirrer, and nitrogen inlet tube was charged with 15.0 parts by mass of ethylene glycol, 90.1 parts by mass of 1,4-butanediol, 118 parts by mass of biosuccinic acid (BioXtra succinate, Sigma-Aldrich), and 0.6 parts by mass of tetrabutyl titanate (Sigma-Aldrich). The temperature was gradually increased from 190 to 240°C under atmospheric pressure in a nitrogen atmosphere, while the resulting water was distilled off. The reaction was continued until the distilled water reached the theoretical amount. The pressure in the reaction vessel was then reduced to 10 hPa, and the reaction was continued at 230°C for 4 hours. After the reaction was completed, the reaction vessel was returned to atmospheric pressure, and the viscous liquid was removed from the reaction vessel to obtain a biodegradable polyester resin molding material (H-11). The number average molecular weight (Mn) of (H-11) was 26,000, the melting point was 98.5°C, and the bio-based content was 47%. The thermoplastic molding material (H-11) was heated to the filling temperature shown in Table 3 just before filling and melted before use.

[0145] H-12: Thermosetting molding material containing inorganic filler Manufacturing of molding material (H-12) Five parts by weight of silica microparticles (Seahoster KE-P100, manufactured by Nippon Shokubai Co., Ltd.) were added to 100 parts by weight of a two-component curing polyurethane rubber (ADAPT 60L) base material, and the mixture was stirred at 3,000 rpm in a homomixer at 25°C for 5 minutes to obtain a uniform dispersion. Next, 33 parts by weight of ADAPT 60L curing agent was added to the resulting dispersion, and the mixture was stirred at 25°C for 5 minutes to obtain a silica-containing thermosetting molding material (H-12). (H-12) was filled into a molded object immediately after production, and molding was performed under the molding conditions shown in Table 3.

[0146] H-13: Thermosetting molding material containing organic filler Manufacturing of molding material (H-13) In the production of H-12, 0.5 parts by mass of multi-walled carbon nanotubes (diameter 40-60 nm, length 1-2 μm, manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of the silica fine particles to obtain a thermosetting molding material (H-13) containing carbon nanotubes. Immediately after production, (H-13) was filled into a molded object, and molding was carried out under the molding conditions shown in Table 3.

[0147] H-14: Thermoplastic molding material made of biodegradable polyester resin containing organic and inorganic fillers Manufacturing of molding material (H-14) 100 parts by weight of thermoplastic biodegradable polyester resin molding material (H-11) was heated to 120°C and melted. Then, 2.5 parts by weight of Eposter MA1002 (average particle size 5 μm, manufactured by Nippon Shokubai Co., Ltd.) as an acrylic styrene-based organic filler and 2.5 parts by weight of titanium (IV) oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an inorganic filler were added, and the mixture was stirred at 300 rpm in a homomixer at 120°C for 1 hour to obtain a uniform dispersion of biodegradable polyester resin molding material (H-14) containing an acrylic styrene-based organic filler and a titanium oxide-based inorganic filler. (H-14) was filled into a molded object immediately after production and molded under the molding conditions shown in Table 3.

[0148] H-15: Two-component thermosetting molding material containing organic filler Manufacturing of molding material (H-15) To 100 parts by weight of an N-methylpyrrolidone dispersion (0.75 wt% dispersion) of cellulose nanofibers prepared as described in Example 1 of JP 2017-218595, 100 parts by weight of unsaturated polyester resin (TP-153, manufactured by DIC Materials Corporation) was added. The mixture was stirred at 3,000 rpm in a homomixer at 25°C for 5 minutes to obtain a uniform dispersion. After removing the N-methylpyrrolidone from the dispersion using an evaporator, 1.0 part by weight of Mepox 55 (manufactured by Kawaguchi Pharmaceutical Co., Ltd.) was added and the mixture was stirred at 3,000 rpm in a homomixer at 25°C for 5 minutes to obtain a thermosetting molding material (H-15) containing cellulose nanofibers. (H-15) was filled into a molded object immediately after production and molded under the molding conditions shown in Table 3.

[0149] <Immersion liquid (I)> I-1: Tap water I-2: Ion-exchanged water I-3: Methanol I-4: 50 wt% methanol aqueous solution I-5: 3-Methoxy-N,N-dimethylpropionamide (registered trademark "KJCMPA", manufactured by KJ Chemicals) I-6: Ethanol

[0150] (6) Removability evaluation The crude molded products obtained in Examples 73 to 97 and Comparative Examples 13 to 16 were immersed in immersion liquid (I) at 25°C for 10 hours or 24 hours. After that, molded product (Y) separated from the mold was removed, and its outer periphery and hollow portion were washed with immersion liquid. The state of the obtained molded product (Y) was visually observed, and the removability of the mold was evaluated. The mold removal method (dissolution, dispersion, or disintegration) is shown in Table 3. ⊚: The mold was completely removed from both the outer periphery and the inside of the molded product (Y), and the time required for removing the mold was less than 10 hours. ◯: The mold was completely removed from both the outer periphery and the inside of the molded product (Y), and the time required to remove the mold was 10 hours or more and 24 hours or less. ×: The mold was not completely removed even after immersion for 24 hours.

[0151] (7) Evaluation of molding accuracy The diameter of the cylindrical hollow portion was measured and the molding accuracy was evaluated using the molded products (Y) and (Z) obtained in Examples 73 to 97 and Comparative Examples 13 to 16, along with visual observation. The designed diameter of the cylinder was 0.5 mm, and the molded products were designed so that two cylinders penetrated the center of the molded product (Y) or (Z) and had sharp corners on the outer periphery. ◎: The diameter of the cylinder is less than 0.5±0.1 mm, two cylinders penetrate each other at the center, and the corners on the outer periphery are sharp. ○: The diameter of the cylinder is 0.5±0.1 mm or more and 0.5±0.2 mm or less, the two cylinders penetrate each other at the center, and the corners on the outer periphery are almost sharp. △: The diameter of the cylinder was 0.5±0.2 mm or more, or the two cylinders did not penetrate through the center, or the corners of the outer periphery were rounded. ×: No cylinder is formed.

[0152] (8) Strength evaluation of molded products <Preparation of Test Specimens (y1) for Evaluating the Strength of Molded Products Using a PET Spacer) A 75-μm thick peelable PET film (E7001 polyester film, manufactured by Toyobo Co., Ltd.) was adhered to a horizontally placed glass plate, and a 3 mm × 10 mm × 130 mm spacer was installed. In Examples 73 to 97 and Comparative Examples 13 to 16, spacers were used instead of the mold (x1), and strip-shaped test specimens (y1-1) to (y1-25) for evaluating the strength of molded products with a thickness of 3 mm, a width of 10 mm, and a length of 130 mm were obtained.

[0153] <Preparation of Test Specimens (y2) for Evaluating the Strength of Molded Products Using a Stereolithography Spacer) Using the active energy ray curable resin compositions (E-1) to (E-24) and the compositions (F-1) to (F-4), spacers having a 3 mm × 10 mm × 130 mm space shown in FIG. 3 were manufactured by a liquid tank photopolymerization apparatus in the same manner as in Examples 25 to 48. Thereafter, in Examples 73 to 97 and Comparative Examples 13 to 16, these stereolithography spacers were used instead of the molded object (x1), and strip-shaped test specimens (y2-1) to (y2-25) for evaluating the strength of molded products with a thickness of 3 mm, a width of 10 mm, and a length of 130 mm were obtained.

[0154] Using a tabletop precision universal testing machine (Autograph AGS-X, manufactured by Shimadzu Corporation), tensile tests of the strip-shaped test specimens (y1-1) to (y1-25) and (y2-1) to (y2-25) were performed under a temperature environment of 25°C and at a speed of 100 mm / min, and the tensile fracture strength was measured. The ratio of the strength of the molded product formed with the stereolithography spacer to the strength of the molded product formed with the PET spacer was determined as the strength retention rate by the following calculation formula (2), and the strength of the molded product obtained using the hollow structure (spacer) of the molded object (x2) having a hollow structure formed by the three-dimensional stereolithography method was evaluated. Strength retention rate (%) = Strength (y2) / Strength (y1) × 100 Calculation formula (2) (In the formula, Strength (y2) is the tensile fracture strength of the test specimens (y2-1) to (y2-25), and Strength (y1) is the tensile fracture strength of the test specimens (y1-1) to (y1-25).) ○: The strength retention rate is 90% or more ×: The strength retention rate is less than 90%

[0155] [Table 3]

[0156] Example 98 Decomposition test of molded products due to physical action Using molding material (H-14) immediately after production using the above method, a 40 μm-thick coating was formed on a glass substrate and left to stand in a 60°C incubator for 240 minutes to obtain a test piece (y3-1) (glass substrate and the coating thereon) for a physical degradation test. The resulting test piece was subjected to a 1,000-hour weathering test using a sunshine carbon arc lamp weathering tester in accordance with JIS K 7350-4. After the weathering test, the coating on the test piece was peeled from the glass substrate and molecular weight measurement was performed. The molecular weight (Mn) of the polyester resin in the coating after the weathering test was 18,000. Since the molecular weight (Mn) of the polyester resin, a component of molding material (H-14), was 26,000, a decrease in molecular weight was confirmed during the weathering test, i.e., decomposition of the molded product (y3-1) due to physical effects was confirmed.

[0157] Example 99 Decomposition test of molded products due to chemical action Molding material (H-11) prepared using the above method was heated to 75°C and melted. A 40 μm thick coating was then formed on a glass substrate. This was then allowed to stand at 25°C for 60 minutes to obtain a test piece (y3-2) (glass substrate and coating thereon) for chemical decomposition testing. The coating from the resulting test piece was peeled from the glass substrate, and 1 g of the coating was weighed out and placed in a 20 ml light-proof screw bottle with 10 ml of 0.1 N aqueous sodium hydroxide. The bottle was then closed and stirred at 37°C and 150 rpm for 60 days. The remaining components were then filtered off, and the molecular weight was measured. The molecular weight (Mn) of the polyester resin after testing was 1,800. Since the molecular weight (Mn) of the polyester resin in molding material (H-11) was 26,000, a significant decrease in molecular weight was confirmed during the test, i.e., chemical decomposition of the molded product (y3-2) was confirmed.

[0158] Example 100 Biological degradation test of molded products The molding material (H-11) prepared by the above method was heated to 75°C and melted. A 40 μm thick coating was then formed on a glass substrate. This was then allowed to stand at 25°C for 60 minutes to obtain a test piece (y3-3) (glass substrate and the coating thereon) for biological degradation testing. The coating film on the resulting test piece was peeled off the glass substrate, and 1 g of the coating was weighed and placed in a 20 ml light-proof screw bottle. 10 ml of 0.1 mM phosphate buffer (pH 7.4) and 2 mg of Aspergillus niger were added to the screw bottle, which was then closed and stirred at 37°C and 150 rpm for 60 days. The liquid in the screw bottle was then concentrated and the molecular weight was measured. The molecular weight (Mn) of the polyester resin after the test was 500. Since the molecular weight (Mn) of the polyester resin of molding material (H-11) is 26,000, a significant decrease in molecular weight was confirmed by the test, i.e., decomposition of the molded product, test piece (y3-3), due to biological action was confirmed.

[0159] As is clear from the results in Tables 1 and 2, the active energy ray-curable resin compositions (E-1) to (E-24) of the present invention have viscosities within a range suitable for three-dimensional stereolithography, exhibit high resistance to cure shrinkage, and are suitable for use in various methods of three-dimensional stereolithography. Because the active energy ray-curable resin compositions of the present invention do not dissolve their cured products, they can be used to form highly accurate, heat-resistant objects using a liquid tank photopolymerization method. Furthermore, the resulting objects can be dissolved, dispersed, or disintegrated by immersion in water, an organic solvent, or a mixture thereof. Such hollow-structured objects (x1) can be suitably used as molds for molding various thermosetting resins, photocurable resins, and thermoplastic materials such as beeswax, crystalline polyesters, and low-melting-point metals. Furthermore, such molds can be easily removed by immersion in water, an organic solvent, or a mixture thereof, and can be used to easily produce molded objects (Y) with fine or complex structures. On the other hand, the comparative composition (F-1) used a polyfunctional polymerizable compound instead of the non-polyfunctional polymerizable compound (A), and the comparative compositions (F-2) and (F-3) did not contain a non-crosslinkable polymer (B), so all of the comparative compositions had high cure shrinkage and low molding accuracy. Furthermore, the comparative composition (F-4) was difficult to mold accurately because the composition had the ability to dissolve its cured product. Therefore, even when molded objects using the compositions of any of the comparative examples were used as molds for other molded objects, the mold removability and molding accuracy of the molded objects were unsatisfactory.

[0160] [Brief explanation of the drawings]

[0161] [Figure 1] Hollow structure (x1) [Figure 2] Molded object (Y) [Figure 3] Test piece for evaluating molded product strength (y2) [Industrial Applicability]

[0162] As described above, the active energy ray-curable resin composition of the present invention has a viscosity within a range suitable for three-dimensional stereolithography, exhibits low cure shrinkage before and after curing by active energy ray irradiation, and can produce highly accurate shaped objects, particularly by liquid tank photopolymerization. Furthermore, by adjusting the components of the active energy ray-curable resin composition of the present invention according to the purpose, the resulting cured product can be made soluble, dispersible, or disintegrable in water, organic solvents, etc., and can be suitably used as a removable molding die by immersion in water, organic solvents, etc. Furthermore, when a molded object made using the active energy ray-curable resin composition of the present invention is used as a molding die, not only photocurable resins and thermoplastic materials but also thermosetting resins, which have been difficult to use in conventional 3D printers, can be molded using the molding die. Furthermore, because the molding die is dissolved, dispersed, or disintegrated in water, organic solvents, etc. and can be easily removed, it is possible to produce molded objects with complex, fine structures and shapes that cannot be molded using general-purpose molds, etc. This allows for the easy production of complex-shaped molded objects using not only materials compatible with 3D printers, such as photocurable resins, wax, and thermoplastic materials like polylactic acid and ABS resin, but also thermosetting resins like flexible silicone resins, urethane resins, hard epoxy resins, and unsaturated polyester resins. These molded objects can be effectively used in a variety of fields, including prototypes, custom-made medical and nursing care products, fine arts, and jewelry, as well as in fields requiring small-lot or custom-made production of learning materials, structural materials like furniture and building materials, mechanical parts for transportation machinery, industrial machinery, home appliances, and space development, small-lot production of replacement parts, and even food products like chocolate and candy. The molding method using the molded object of the present invention as a mold also enables the three-dimensional molding of engineering plastics and super-engineering plastics, which could not be produced by conventional three-dimensional molding.

Claims

1. An active energy ray-curable resin composition containing a non-polyfunctional polymerizable compound (A) and a non-crosslinkable polymer (B), The non-polyfunctional polymerizable compound (A) includes a polymerizable compound (a2) having a number average molecular weight of 1,000 to 100,000 and an average number of unsaturated groups in the molecule of more than 1 and less than 2, The non-crosslinkable polymer (B) is a polymer that contains a structural unit derived from a monomer having a (meth)acrylamide group and does not have a crosslinked structure in the molecule, The active energy ray-curable resin composition is characterized in that it does not have the ability to dissolve the cured product thereof.

2. 2. The active energy ray-curable resin composition according to claim 1, wherein the viscosity at 25° C. is 30 to 100,000 mPa·s.

3. The active energy ray-curable resin composition according to claim 1 or 2, characterized in that the active energy ray-curable resin composition contains at least 10.0 to 99.9 mass% of a non-polyfunctional polymerizable compound (A) and 0.1 to 50.0 mass% of a non-crosslinkable polymer (B).

4. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the non-polyfunctional polymerizable compound (A) contains a monofunctional polymerizable compound (a1).

5. The active energy ray-curable resin composition according to claim 4, wherein the monofunctional polymerizable compound (a1) has one unsaturated group and one or more amide groups and / or oxyalkylene groups in the molecule.

6. The active energy ray-curable resin composition according to any one of claims 1 to 5, which is used for three-dimensional optical shaping.

7. 7. The active energy ray-curable resin composition according to claim 6, wherein the three-dimensional photo-fabrication is performed by a liquid tank photopolymerization method.

8. A shaped object (X) obtained by curing the active energy ray-curable resin composition according to any one of claims 1 to 7.

9. 9. The shaped object (X) according to claim 8, which is soluble, dispersible or disintegrable in water, an organic solvent or a mixture thereof.

10. A method for producing a molded product (Y) from a molding material, comprising: A first step of forming a hollow object (x1) using the active energy ray-curable resin composition according to any one of claims 1 to 7; a second step of filling a molding material into the hollow portion of the obtained shaped object (x1) and hardening and / or solidifying the molding material to obtain a crude molded object; a third step of immersing the obtained crude molded product in water, an organic solvent or a mixture thereof, and removing the shaped product (x1) to obtain a molded product (Y); A method for producing a molded product (Y), comprising:

11. The method for producing a molded product (Y) according to claim 10, characterized in that in the second step, the molding material is cured and / or solidified by one or more of active energy rays, heat, and moisture.

12. The method for producing a molded product (Y) according to claim 10 or 11, characterized in that one or more molding materials selected from the group consisting of silicone resins, epoxy resins, polyester resins, urethane resins, acrylic resins, cyanoacrylate resins, biodegradable resins, natural resins, and metals are used.

13. The method for producing a molded product (Y) according to claim 10 or 11, characterized in that a molding material having a bio-based content of 25% or more is used.

14. 12. The method for producing a molded product (Y) according to claim 10 or 11, characterized in that a molding material containing an organic filler and / or an inorganic filler is used.

15. 12. The method for producing a molded product (Y) according to claim 10 or 11, characterized in that the molded product (Y) is decomposed by one or more of physical action, chemical action and biological action.

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