Active energy ray-curable resin composition

Abstract

To provide an active energy ray-curable resin composition which gives a cured product that exhibits good heat resistance and transparency and also has practically sufficient strength and impact resistance, and is excellent in high curability, low cure shrinkage and operability having viscosity in such a range as to be suitable for various systems of three-dimensional optical molding, and to provide a three-dimensional optically molded article which is obtained by optical molding using the active energy ray-curable resin composition and has high accuracy.SOLUTION: An active energy ray-curable resin composition contains a (meth)acrylic polymer (A) having an alicyclic structure and / or an aromatic ring structure, and an unsaturated compound (B).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active energy ray curable resin composition, an active energy ray curable ink for three-dimensional modeling containing the same, a cured product obtained using them, and a three-dimensional molded product.

Background Art

[0002] In a curing reaction using active energy rays such as ultraviolet rays (UV) and electron beams, generally, radical or ionic species are generated by irradiation with active energy rays, and a raw material having a polymerizable functional group such as an unsaturated group or an epoxy group is polymerized to solidify (cure) a liquid composition in a short time. Therefore, the active energy ray curing reaction is used in a wide range of fields such as paints, coating materials, adhesives, inkjet inks, sealing materials, dental hygiene materials, and optical materials. In particular, since it can be cured at an arbitrary location and shape, it is suitable for laminated modeling, and in recent years, three-dimensional modeling using active energy ray curing has also attracted attention.

[0003] In active energy ray curable three-dimensional modeling (three-dimensional optical modeling), a material injection method (inkjet method) in which a liquid active energy ray curable resin material (liquid resin) is ejected from a nozzle and cured (solidified) by ultraviolet irradiation, and a liquid tank photo polymerization method in which a photocurable resin (active energy ray curable resin) is placed in a liquid tank and cured by irradiating light (ultraviolet light) from the upper surface or the lower surface side toward the liquid surface are generally used. In the liquid tank photo polymerization method, there are a method of applying light to a cross section and a method of scanning a laser with a galvanometer mirror or the like (SLA), and a method of collectively exposing a cross-sectional shape using a projector (DLP). These three-dimensional optical modeling methods can achieve a fine lamination pitch, high precision, and a smooth finish, and are being used in a wide range of fields such as the production of test models that need to be manufactured in small lots or made to order, mold replacement, medical, jewelry, heavy industry, home appliances, sports, etc.

[0004] Among these, when three-dimensional optical modeling is used for evaluation models for fitting tests and functional tests, and final products in the fields of dentistry and medical applications, etc., high shaping accuracy is required, and in addition to sufficient strength and impact resistance that can be put into practical use, high heat resistance is also required. Further, when a flow path is formed inside the shaped article and the fluid passing through the flow path is monitored, high transparency is required for the shaped article. However, it is known that an active energy ray curable resin composition used for three-dimensional optical modeling shrinks due to the generation of shrinkage stress during photocuring, and in fields where high shaping accuracy is required, suppressing curing shrinkage has been an issue. In addition, it is difficult to obtain a cured product (shaped article) of the active energy ray curable resin composition having high transparency compared to general-purpose resins generally used in injection molding, and it has characteristics of being inferior in heat resistance, mechanical properties (strength and elongation), and impact resistance, etc., and it has been an issue to obtain a highly transparent three-dimensional optical shaped article having sufficient strength and impact resistance and high heat resistance.

[0005] As a method for improving the tensile strength and elongation at break of the mechanical properties of a three-dimensional optical shaped article, Patent Document 1 proposes adding to an active energy ray curable resin composition an unsaturated group-containing urethane oligomer having a structure derived from a polyol compound, a structure derived from an isocyanate compound, and a structure derived from a hydroxyl group-containing (meth)acrylamide, and an unsaturated group-containing urethane compound which is a polycondensate of a polyisocyanate monomer and a hydroxyl group-containing (meth)acrylic compound.

[0006] Further, as a method for suppressing the curing shrinkage of an active energy ray curable resin composition used for three-dimensional optical modeling, Patent Document 2 proposes a method in a manufacturing method of a three-dimensional optical shaped article including repeatedly performing a liquid film layer forming step of forming a liquid film layer by applying the active energy ray curable resin composition and a curing step of irradiating the liquid film layer with active energy rays to cure it, and laminating the cured layers, in which the intensity of the active energy rays irradiated on the last formed layer is made smaller than the intensity of the active energy rays irradiated on the first layer.

Prior Art Documents

Patent Document

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] Patent Document 1 does not mention the curing shrinkage of the active energy ray curable resin composition, nor does it mention the heat resistance and transparency of the cured product obtained by curing it.

[0009] The method for manufacturing a three-dimensional optical molded article proposed in Patent Document 2 solves the curing shrinkage of the active energy ray curable resin composition by adjusting the active energy ray intensity. However, when the intensity of the active energy ray with respect to the type and film thickness of the active energy ray curable resin composition used is smaller than appropriate, it does not cure sufficiently and molding defects such as surface roughness occur. When it is larger than appropriate, the curing shrinkage cannot be suppressed. Therefore, in order to obtain a three-dimensional optical molded article with high molding accuracy, complex adjustment of the active energy ray intensity is required, and costs for introducing a UV lamp capable of illuminance control and control software for performing this adjustment are necessary. In addition, Patent Document 2 does not mention anything about the approach of suppressing curing shrinkage by adjusting the composition of the active energy ray curable resin composition used.

[0010] Therefore, an object of the present invention is to provide an active energy ray curable resin composition having high curability, high compatibility, a low curing shrinkage rate, and excellent operability with a viscosity in a range suitable for various three-dimensional optical molding methods, which can obtain a cured product having good heat resistance and transparency and also having sufficient strength and impact resistance for practical use. Another object of the present invention is to provide a highly accurate three-dimensional optical molded article obtained by optical molding using the active energy ray curable resin composition.

Means for Solving the Problems

[0011] As a result of intensive research, the present inventors have found that an active energy ray-curable resin composition containing a (meth)acrylic polymer (A) having an alicyclic structure and / or an aromatic ring structure and an unsaturated compound (B) can solve the above problems, and thus have arrived at the present invention. By containing the (meth)acrylic polymer (A), the curing shrinkage of the active energy ray-curable resin composition is suppressed. Further, by an appropriate combination of the (meth)acrylic polymer (A) and the unsaturated compound (B), the active energy ray-curable resin composition has excellent compatibility of each component, has a viscosity in a range suitable for three-dimensional optical shaping, has excellent operability, and exhibits high curability, and thus can also be suitably used as an active energy ray-curable resin composition for three-dimensional optical shaping or an active energy ray-curable ink.

[0012] That is, the present invention relates to (1) An active energy ray-curable resin composition containing a (meth)acrylic polymer (A) having an alicyclic structure and / or an aromatic ring structure and an unsaturated compound (B), (2) The unsaturated compound (B) contains a monofunctional monomer (a) and / or a polyfunctional compound (b), the monofunctional monomer (a) is any one or more monomers selected from the group consisting of the following (a1) and (a2), and the polyfunctional compound (b) has a skeleton derived from a polyol and two or more polymerizable functional groups in the molecule, and at least one polymerizable functional group is a polyfunctional compound (b1) that is a methacrylamide group or an acrylamide group, and the active energy ray-curable resin composition according to the above (1), (a1): One or more monofunctional monomers selected from a methacrylate-based monofunctional monomer, an acrylate-based monofunctional monomer, a methacrylamide-based monofunctional monomer, and an acrylamide-based monofunctional monomer having an alicyclic structure and / or an aromatic ring structure; (a2): One or more monofunctional monomers selected from a methacrylamide-based monofunctional monomer and an acrylamide-based monofunctional monomer having no alicyclic structure and / or aromatic ring structure (3) The (meth)acrylic polymer (A) is a polymer containing structural units derived from one or more monofunctional monomers (a1) selected from methacrylate-based monofunctional monomers, acrylate-based monofunctional monomers, methacrylamide-based monofunctional monomers, and acrylamide-based monofunctional monomers, which have an alicyclic structure and / or an aromatic ring structure. The active energy ray curable resin composition according to (1) above is characterized in that, (4) The number average molecular weight (Mn) of the (meth)acrylic polymer (A) is 2,000 to 100,000. The active energy ray curable resin composition according to (1) or (3) above is characterized in that, (5) With respect to the total mass of the active energy ray curable resin composition, the content of the (meth)acrylic polymer (A) is 0.1 to 50.0% by mass, and the content of the unsaturated compound (B) is 50.0 to 99.9% by mass. The active energy ray curable resin composition according to any one of (1) to (4) above is characterized in that, (6) With respect to the total mass of the active energy ray curable resin composition, the content of the monofunctional monomer (a) as the unsaturated compound (B) is 20.0 to 70.0% by mass, and the content of the polyfunctional compound (b) is 1.0 to 75.0% by mass. The active energy ray curable resin composition according to any one of (1) to (5) above is characterized in that, (7) The unsaturated compound (B) contains a polyfunctional compound (b), and the polyfunctional compound (b) further contains a polyfunctional compound (b2) having two or more polymerizable functional groups in the molecule and not having a skeleton derived from a polyol. The active energy ray curable resin composition according to (2) or (6) above is characterized in that, (8) The unsaturated compound (B) contains a polyfunctional compound (b), and the polyfunctional compound (b) further contains a polyfunctional compound (b3) having two or more polymerizable functional groups in the molecule and having an isocyanurate ring. The active energy ray curable resin composition according to (2) or (6) above is characterized in that, (9) The polymerizable functional group is one or more functional groups selected from a methacrylate group, an acrylate group, a methacrylamide group, and an acrylamide group, and the active energy ray-curable resin composition according to any one of (2), (7), and (8) above, (10) The skeleton derived from the polyol is one or two or more skeletons selected from an ether skeleton, an ester skeleton, a carbonate skeleton, a silicone skeleton, an olefin skeleton, and an acrylic skeleton, and the active energy ray-curable resin composition according to (2) or (7) above, (11) The active energy ray-curable resin composition according to any one of (1) to (10) above, characterized in that it is used for three-dimensional optical modeling, (12) The active energy ray-curable resin composition according to any one of (1) to (11) above, characterized in that it is used for three-dimensional optical modeling by a liquid tank light polymerization method, (13) An active energy ray-curable ink comprising the active energy ray-curable resin composition according to any one of (1) to (11) above, characterized in that it is used for three-dimensional optical modeling by a material jetting method, (14) An active energy ray-curable ink comprising the active energy ray-curable resin composition according to any one of (1) to (11) above, characterized in that it is used for three-dimensional optical modeling by a material extrusion deposition method, (15) A three-dimensional optical modeling object comprising a cured product of the active energy ray-curable resin composition according to any one of (1) to (11) above, It is to provide the above.

Effect of the Invention

[0013] According to the present invention, it is possible to provide an active energy ray-curable resin composition having high curability, high compatibility, a low curing shrinkage rate, and excellent operability with a viscosity in a range suitable for various three-dimensional optical modeling methods. The active energy ray-curable resin composition can be used for various three-dimensional optical modeling methods, and by curing this, it is possible to provide a three-dimensional optical modeling object having sufficient strength and impact resistance for practical use, as well as excellent shaping accuracy with high heat resistance and high transparency.

Modes for Carrying Out the Invention

[0014] Hereinafter, embodiments of the present invention will be described in detail. The 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 a composition containing a (meth)acrylic polymer (A) having an alicyclic structure and / or an aromatic ring structure and an unsaturated compound (B).

[0015] By containing the (meth)acrylic polymer (A) having an alicyclic structure and / or an aromatic ring structure, the active energy ray curable resin composition (E) suppresses the curing shrinkage when it is cured. Therefore, a cured product of the active energy ray curable resin composition (E) with excellent shaping accuracy can be obtained. Further, the cured product has high heat resistance.

[0016] The number average molecular weight (Mn) of the (meth)acrylic polymer (A) is preferably 2,000 to 100,000. If the number average molecular weight (Mn) of the (meth)acrylic polymer (A) is 2,000 or more, when curing the active energy ray curable resin composition (E), the effect of suppressing curing shrinkage can be exerted, shaping can be performed with high accuracy, and the obtained cured product is excellent in heat resistance and has sufficient impact resistance, which is preferable. If the number average molecular weight (Mn) of the (meth)acrylic polymer (A) is 100,000 or less, the viscosity of the active energy ray curable resin composition (E) can be maintained within a range suitable for three-dimensional optical shaping, which is preferable. From these viewpoints, the number average molecular weight (Mn) of the (meth)acrylic polymer (A) is more preferably 3,000 to 80,000, and even more preferably 4,000 to 60,000.

[0017] The content of the (meth)acrylic polymer (A) is preferably 0.1 to 50.0% by mass based on the total mass of the active energy ray curable resin composition (E). If the content of the (meth)acrylic polymer (A) is 0.1% by mass or more, it is preferable because the curing shrinkage rate of the active energy ray curable resin composition (E) can be suppressed and the cured product can be accurately shaped. If the content of the (meth)acrylic polymer (A) is 50.0% by mass or less, it is preferable because the viscosity of the active energy ray curable resin composition (E) can be maintained within a range suitable for three-dimensional optical shaping. From these viewpoints, the content of the (meth)acrylic polymer (A) is more preferably 0.5 to 25.0% by mass, still more preferably 1.0 to 20.0% by mass, and particularly preferably 5.0 to 20.0% by mass.

[0018] (Meth)acrylic polymer (A) having an alicyclic structure and / or an aromatic ring structure contains a structural unit derived from monofunctional monomer (a1). Monofunctional monomer (a1) is at least one monofunctional monomer selected from methacrylate-based monofunctional monomers, acrylate-based monofunctional monomers, methacrylamide-based monofunctional monomers, and acrylamide-based monofunctional monomers having an alicyclic structure and / or an aromatic ring structure. Therefore, (meth)acrylic polymer (A) containing a structural unit derived from monofunctional monomer (a1) has an alicyclic structure and / or an aromatic ring structure. When (meth)acrylic polymer (A) containing a structural unit derived from monofunctional monomer (a1) is contained in active energy ray curable resin composition (E), shrinkage during curing can be suppressed, and thus the cured product obtained by curing this has excellent shaping accuracy. From such a viewpoint, the content of the structural unit derived from monofunctional monomer (a1) in (meth)acrylic polymer (A) is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, based on the total mass of (meth)acrylic polymer (A). The upper limit of the content of the structural unit derived from monofunctional monomer (a1) in (meth)acrylic polymer (A) is not particularly limited, and may be 100% by mass based on the total mass of (meth)acrylic polymer (A), and preferably 90.0% by mass or less in order to maintain the balance between the curing shrinkage resistance of active energy ray curable resin composition (E) and the heat resistance of its cured product. Furthermore, the homopolymer of a monofunctional monomer having a (meth)acrylamide group usually has a high glass transition temperature (Tg). Therefore, from the viewpoint of improving the glass transition temperature (Tg), that is, the heat resistance of the cured product of active energy ray curable resin composition (E), it is preferable that monofunctional monomer (a1) is a methacrylamide-based monofunctional monomer and / or an acrylamide-based monofunctional monomer having an alicyclic structure and / or an aromatic ring structure.

[0019] Among the monofunctional monomers (a1), examples of methacrylate-based monofunctional monomers and acrylate-based monofunctional monomers include cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, adamantyl (meth)acrylate, phenoxyalkylene glycol (meth)acrylates having a functional group composed of a phenoxy group and an alkylene glycol group with 1 to 4 carbon atoms, alkylcyclohexyl (meth)acrylates having a linear, branched or cyclic alkyl group with 1 to 18 carbon atoms, dialkylcyclohexyl (meth)acrylates, trialkylcyclohexyl (meth)acrylates, alkylphenyl (meth)acrylates, alkylbenzyl (meth)acrylates, alkylphenoxyalkylene glycol (meth)acrylates, alkyldicyclopentanyl (meth)acrylates, alkyldicyclopentanyloxyethyl (meth)acrylates, alkyldicyclopentenyl (meth)acrylates, alkyldicyclopentenyl oxyethyl (meth)acrylates, alkyladamantyl (meth)acrylates, hydroxyalkylcyclohexyl (meth)acrylates having a linear, branched or cyclic hydroxyalkyl group with 1 to 18 carbon atoms, hydroxyalkylphenyl (meth)acrylates, hydroxyalkylbenzyl (meth)acrylates, hydroxyalkylphenoxyalkylene glycol (meth)acrylates, hydroxyalkyldicyclopentanyl (meth)acrylates, hydroxyalkyldicyclopentanyloxyethyl (meth)acrylates, hydroxyalkyldicyclopentenyl (meth)acrylates, hydroxyalkyldicyclopentenyl oxyethyl (meth)acrylates, hydroxyalkyladamantyl (meth)acrylates, linear with 1 to 6 carbon atoms,Examples of (meth)acryloyl group-containing polycyclic carboxamides include N-(meth)acryloyloxyalkyl norbornene carboxamide, N-(meth)acryloyloxyalkyl norbornane carboxamide, N-alkyl-N-(meth)acryloyloxyalkyl norbornene carboxamide, N-alkyl-N-(meth)acryloyloxyalkyl norbornane carboxamide, etc. The monofunctional monomer (a1) may be used alone or in combination of two or more. Here, (meth)acrylate means acrylate or methacrylate.,

[0020] Among the monofunctional monomers (a1), examples of methacrylamide-based monofunctional monomers and acrylamide-based monofunctional monomers include N-cyclohexyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-benzyl (meth)acrylamide, N-dicyclopentanyl (meth)acrylamide, N-dicyclopentanyloxyethyl (meth)acrylamide, N-dicyclopentenyl (meth)acrylamide, N-dicyclopentenyl oxyethyl (meth)acrylamide, N-bornyl (meth)acrylamide, N-isobornyl (meth)acrylamide, N-adamantyl (meth)acrylamide, N-alkyl-N-cyclohexyl (meth)acrylamide, N-alkyl-N-phenyl (meth)acrylamide, N-alkyl-N-benzyl (meth)acrylamide, N-alkyl-N-dicyclopentanyl (meth)acrylamide, N-alkyl-N-dicyclopentanyloxyethyl (meth)acrylamide, N-alkyl-N-dicyclopentenyl (meth)acrylamide, N-alkyl-N-dicyclopentenyl oxyethyl (meth)acrylamide, N-alkyl-N-bornyl (meth)acrylamide, N-alkyl-N-isobornyl (meth)acrylamide, N-alkyl-N-adamantyl (meth)acrylamide, etc., in which a linear or branched alkyl group having 1 to 8 carbon atoms is introduced. The monofunctional monomer (a1) may be used alone or in combination of two or more. Here, (meth)acrylamide means acrylamide or methacrylamide.,

[0021] (Meth)acrylic polymer (A) may be a polymer containing a structural unit derived from a monofunctional monomer (a2) selected from a methacrylamide-based monofunctional monomer and an acrylamide-based monofunctional monomer having no alicyclic structure and aromatic ring structure, in addition to a structural unit derived from a monofunctional monomer (a1). The monofunctional monomer (a2) is one or more monofunctional monomers selected from a methacrylamide-based monofunctional monomer and an acrylamide-based monofunctional monomer having no alicyclic structure and aromatic ring structure. As described above, since a homopolymer of a monofunctional monomer having a (meth)acrylamide group usually has a high glass transition temperature (Tg), the (meth)acrylamide polymer (A) containing a structural unit derived from the monofunctional monomer (a2) improves the glass transition temperature (Tg), that is, the heat resistance of the cured product of the active energy ray curable resin composition (E). From such a viewpoint, the content of the structural unit derived from the monofunctional monomer (a2) in the (meth)acrylic polymer (A) is preferably 0.5 to 50.0% by mass, more preferably 1.0 to 45.0% by mass, and particularly preferably 5.0 to 40.0% by mass with respect to the total mass of the (meth)acrylic polymer (A).

[0022] Examples of the monofunctional monomer (a2) include (meth)acrylamide, mono- or di-substituted (meth)acrylamide, (meth)acryloylmorpholine, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, and unsaturated dicarboxylic acid amides. Examples of the mono- or di-substituted (meth)acrylamide include N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide into which a linear or branched alkyl group having 1 to 18 carbon atoms is introduced, N-hydroxyalkyl(meth)acrylamide, N,N-di(hydroxyalkyl)(meth)acrylamide into which a hydroxyalkyl group having 1 to 6 carbon atoms is introduced, N-alkyl-N-hydroxyalkyl(meth)acrylamide into which a hydroxyalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms are introduced, N-alkoxyalkyl(meth)acrylamide, N,N-di(alkoxyalkyl)(meth)acrylamide into which an alkoxyalkyl group composed of an alkoxy group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms is introduced, N-alkyl-N-alkoxyalkyl(meth)acrylamide into which an alkoxyalkyl group composed of an alkoxy group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms are introduced, N-sulfoalkylacrylamide into which an alkylsulfonic acid group having 1 to 6 carbon atoms is introduced, N-alkylamino(meth)acrylamide into which an aminoalkyl group having 1 to 6 carbon atoms is introduced, N-alkylaminoalkyl(meth)acrylamide into which an N-alkylaminoalkyl group composed of an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms is introduced, N,N-dialkylaminoalkyl(meth)acrylamide into which an N,N-dialkylaminoalkyl group composed of an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms is introduced, etc. Examples of the unsaturated dicarboxylic acid amides include N-alkylmaleic acid monoamide, N-alkylfumaric acid monoamide, N-alkylitaconic acid monoamide, N,N-dialkylmaleic acid monoamide, N,N-dialkylfumaric acid monoamide, N,N-dialkylitaconic acid monoamide, etc. into which a linear alkyl group having 1 to 18 carbon atoms is introduced.The monofunctional monomer (a2) may be used alone or in combination of two or more kinds.

[0023] (Meth)acrylic polymer (A) may be a polymer containing structural units derived from monofunctional monomer (a1) and / or structural units derived from monofunctional monomer (a2), and also containing structural units derived from monomers having other polymerizable functional groups as required for controlling its molecular weight and improving its hydrophobicity. Monomers having other polymerizable functional groups are monofunctional monomers (a3) having one polymerizable functional group in the molecule, or polyfunctional monomers having two or more polymerizable functional groups in the molecule and having only one functional group selected from methacrylate group, acrylate group, methacrylamide group and acrylamide group. Monofunctional monomer (a3) is a monofunctional monomer excluding monofunctional monomers (a1) and (a2). Examples of monofunctional monomer (a3) include (meth)acrylate-based monofunctional monomers, vinyl-based monofunctional monomers, and allyl-based monofunctional monomers. These monofunctional monomers (a3) may be used alone or in combination of two or more kinds. When (meth)acrylic polymer (A) contains structural units derived from monofunctional monomer (a3), examples of its content include an embodiment of 0.5 to 60.0% by mass based on the total mass of (meth)acrylic polymer (A), and an embodiment of 5.0 to 50.0% by mass can also be mentioned.

[0024] Among the monofunctional monomers (a3), examples of the (meth)acrylate-based monofunctional monomers include (meth)acrylic acid, alkyl (meth)acrylates having a linear or branched alkyl group with 1 to 22 carbon atoms, hydroxyalkyl (meth)acrylates having a linear or branched hydroxyalkyl group with 1 to 18 carbon atoms, (meth)acrylic acid ethyl carboxylic acid composed of (meth)acrylic acid and hydroxyalkyl carboxylic acids, alkyl carboxylic acids of (meth)acrylic acid such as (meth)acrylic acid ethyl succinic acid, (meth)acrylic acid alkyl sulfonic acids having a linear or branched alkyl sulfonic acid group with 1 to 18 carbon atoms, (meth)acrylic acid alkyl phosphoric acids having a linear or branched alkyl phosphate group with 1 to 18 carbon atoms, alkoxyalkylene glycol (meth)acrylates having a functional group composed of an alkyl group with 1 to 18 carbon atoms and an alkylene glycol group with 1 to 4 carbon atoms, alkoxydialkylene glycol (meth)acrylates, alkoxytrialkylene glycol (meth)acrylates, alkoxypolyalkylene glycol (meth)acrylates, N-alkylamino (meth)acrylates having an aminoalkyl group with 1 to 6 carbon atoms, N-alkylaminoalkyl (meth)acrylates having an N-alkylaminoalkyl group composed of an aminoalkyl group with 1 to 6 carbon atoms and an alkyl group with 1 to 6 carbon atoms, N,N-dialkylaminoalkyl (meth)acrylates having an N,N-dialkylaminoalkyl group composed of an aminoalkyl group with 1 to 6 carbon atoms and an alkyl group with 1 to 6 carbon atoms, (meth)acrylates having an epoxy group such as glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether, (meth)acrylates having a heterocycle such as tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, and cyclic trimethylolpropane formal (meth)acrylate.

[0025] Among the monofunctional monomers (a3), examples of vinyl-based monofunctional monomers include vinyl carboxylates into which carboxylic acids having 1 to 22 carbon atoms such as vinyl acetate are introduced, alkyl vinyl ethers into which linear, branched, or cyclic alkyl groups having 1 to 22 carbon atoms are introduced, styrene, 2-alkylstyrenes, 3-alkylstyrenes, 4-alkylstyrenes into which linear, branched, or cyclic alkyl groups having 1 to 22 carbon atoms are introduced, vinyl chloride, N-vinyl oxazoline, 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, vinyl carboxylic acids, vinyl sulfonic acid, vinyl phosphoric acid, and the like.

[0026] Among the monomers having an allyl group in the monofunctional monomer (a3), examples include allyl oxazoline, allyl sulfonic acid, allyl phosphonic acid, allyl acetate, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, ethyl allyl ether, allyl trifluoroacetate, allyloxy tetrahydropyran, hydroxyethyl allyl ether, allyl sulfonate, allyl phosphonic acid, and the like.

[0027] The polymerization method of the (meth)acrylic polymer (A) is not particularly limited and can be obtained by a method known as a polymerization method for polymerizable functional groups. For example, in polymerization methods such as bulk polymerization, solution polymerization, precipitation polymerization, and emulsion polymerization, radical polymerization, anionic polymerization, cationic polymerization, etc. by active energy rays or heat can be employed. The polymerization temperature and time vary depending on the polymerization initiator and solvent used, but are usually calculated from the half-life of the initiator, and the treatment temperature is preferably usually 60°C to 120°C, the treatment time is preferably usually 2 hours to 20 hours, and particularly preferably 5 hours to 10 hours.

[0028] When polymerizing the (meth)acrylic polymer (A), a polymerization initiator may be used for the purpose of accelerating the polymerization reaction. As the polymerization initiator, known photoinitiators, thermal initiators, anionic polymerization initiators, and cationic polymerization initiators can be used. As photoinitiators, acetophenone-based, benzoin-based, benzophenone-based, α-amino ketone-based, xanthone-based, anthraquinone-based, acylphosphine oxide-based, polymer photoinitiator-based, etc. can be used. As thermal initiators, ordinary ones such as azo-based initiators, peroxide-based initiators, redox-based initiators, etc. can be used. As initiators for cationic polymerization, ordinary ones such as proton acids and Lewis acids can be used. For anionic polymerization, ordinary ones such as alkali metals and organometallic compounds can be used. When using a polymerization initiator, its content is not particularly limited, but from the viewpoint of accelerating the polymerization reaction, it is preferably 0.01 to 10.0% by mass based on the total mass of the monofunctional monomers used.

[0029] When synthesizing the (meth)acrylic polymer (A) by polymerization, a chain transfer agent can also be used for the purpose of controlling the molecular weight. As the chain transfer agent, mercaptoethanol, alkyl mercaptans having 4 to 18 carbon atoms, mercaptoacetic acid, mercaptopropionic acid, alkyl esters of mercaptoacetic acid having 4 to 18 carbon atoms, alkyl esters of mercaptopropionic acid, etc., mercaptans, α-methylstyrene, α-methylstyrene dimer, halides such as carbon tetrachloride, etc. can be mentioned, but it is not particularly limited. Mercaptans are preferred because molecular weight control is easy. The content of the chain transfer agent is not particularly limited, but from the viewpoint of appropriately adjusting the number average molecular weight of the (meth)acrylic polymer (A), it is preferably 0.1 to 10.0% by mass based on the total mass of the monofunctional monomers used.

[0030] When obtaining the (meth)acrylic polymer (A) by solution polymerization, the organic solvent used is not particularly limited, and examples 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; derivatives of polyhydric alcohols 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-dimethylpropionamide; pyrrolidones such as 2-pyrrolidone and N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but an embodiment in which it is 30 to 300% by mass based on the total mass of the monofunctional monomer used can be mentioned.

[0031] (Meth)acrylic polymer (A) can also be used as a polymer purified as needed after polymerization. The purification method of the polymer can be carried out by a known method such as reprecipitation. The composition of the polymer can be determined by known methods such as proton nuclear magnetic resonance spectroscopy ( 1 1H-NMR), infrared spectroscopy (IR), elemental analysis, and quantitative analysis of residual monofunctional monomers.

[0032] The active energy ray curable resin composition (E) contains an unsaturated compound (B). By containing the compound (B), the active energy ray curable resin composition (E) has high curability, can adjust its viscosity to a range suitable for three-dimensional optical shaping, and can obtain a cured product having sufficient strength and impact resistance. From such a viewpoint, the content of the unsaturated compound (B) is preferably 50.0 to 99.9% by mass, more preferably 75.0 to 95.0% by mass, and still more preferably 80.0 to 90.0% by mass based on the whole active energy ray curable resin composition (E).

[0033] The unsaturated compound (B) preferably contains a monofunctional monomer (a) and / or a polyfunctional compound (b). The monofunctional monomer (a) contained in the unsaturated compound (B) is any one or more monomers selected from the group consisting of the following (a1) and (a2). (a1): One or more monofunctional monomers selected from methacrylate-based monofunctional monomers, acrylate-based monofunctional monomers, methacrylamide-based monofunctional monomers, and acrylamide-based monofunctional monomers having an alicyclic structure and / or an aromatic ring structure (a2): One or more monofunctional monomers selected from methacrylamide-based monofunctional monomers and acrylamide-based monofunctional monomers having no alicyclic structure and / or aromatic ring structure

[0034] When the monofunctional monomer (a) is contained in the unsaturated compound (B), its content (that is, the total content of the monofunctional monomers (a1) and (a2)) is preferably 20.0 to 70.0% by mass, more preferably 25.0 to 60.0% by mass, based on the total mass of the active energy ray curable resin composition (E). If the content of the monofunctional monomer (a) is within this range, the viscosity of the active energy ray curable resin composition (E) can be adjusted to a range suitable for three-dimensional optical shaping by various methods, and thus a cured product with excellent shaping accuracy can be obtained.

[0035] Examples of the monofunctional monomer (a1) contained in the unsaturated compound (B) include one or more monofunctional monomers selected from methacrylate-based monofunctional monomers, acrylate-based monofunctional monomers, methacrylamide-based monofunctional monomers, and acrylamide-based monofunctional monomers having an alicyclic structure and / or an aromatic ring structure, which are listed as the monofunctional monomers (a1) constituting the structural units of the above (meth)acrylic polymer (A). Since the (meth)acrylic polymer (A) contains a structure derived from the monofunctional monomer (a1), it has good compatibility with the unsaturated compound (B) having the monofunctional monomer (a1). As a result, the effect of suppressing the curing shrinkage of the active energy ray-curable resin composition (E) by containing the (meth)acrylic polymer (A), the effect of improving the heat resistance and the shaping accuracy of the cured product thereof can be maximally exerted, and a cured product with high transparency can be obtained. From such a viewpoint, when the monofunctional monomer (a1) is contained in the unsaturated compound (B), its content is preferably 5.0 to 55.0% by mass, more preferably 10.0 to 30.0% by mass, based on the total mass of the active energy ray-curable resin composition (E). The monofunctional monomer (a1) may be used alone or in combination of two or more kinds.

[0036] The monofunctional monomer (a1) contained in the unsaturated compound (B) is preferably a methacrylamide-based monofunctional monomer and / or an acrylamide-based monofunctional monomer having an alicyclic structure and / or an aromatic ring structure from the viewpoint of improving the curability of the active energy ray-curable resin composition (E). Preferred examples include N-phenyl (meth)acrylamide, N-methyl-phenyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-methyl-N-cyclohexyl (meth)acrylamide, and the like. Further, the monofunctional monomer (a1) contained in the unsaturated compound (B) is preferably liquid at normal temperature from the viewpoint of easily adjusting the viscosity of the active energy ray-curable resin composition (E) to a range suitable for three-dimensional optical shaping. Preferred examples include cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, and the like. In this specification, normal temperature means 5°C to 35°C.

[0037] Examples of the monofunctional monomer (a2) contained in the unsaturated compound (B) include one or more monofunctional monomers selected from methacrylamide-based monofunctional monomers and acrylamide-based monofunctional monomers that do not have an alicyclic structure and an aromatic ring structure, which are listed as the monofunctional monomers (a2) that can form the structural units of the above (meth)acrylic polymer (A). Since the monofunctional monomer (a2) has an amide group in its structure, the active energy ray-curable resin composition (E) containing the unsaturated compound (B) containing the monofunctional monomer (a2) has improved curability, and the glass transition temperature (Tg) of the cured product obtained by curing this is increased, thereby improving the heat resistance. Further, when the (meth)acrylic polymer (A) contains a structure derived from (a2), the compatibility between the (meth)acrylic polymer (A) and the unsaturated compound (B) is good, and the effect of suppressing the curing shrinkage of the active energy ray-curable resin composition (E) containing the (meth)acrylic polymer (A), and the effects of improving the heat resistance and shaping accuracy of the cured product can be maximally exerted, and a cured product with high transparency can be obtained. From such a viewpoint, when the monofunctional monomer (a2) is contained in the unsaturated compound (B), its content is preferably 5.0 to 50.0% by mass, more preferably 10.0 to 30.0% by mass, based on the total mass of the active energy ray-curable resin composition (E). The monofunctional monomer (a2) may be used alone or in combination of two or more. Further, the monofunctional monomer (a2) contained in the unsaturated compound (B) is preferably a liquid at normal temperature from the viewpoint of easily adjusting the viscosity of the active energy ray-curable resin composition (E) to a range suitable for three-dimensional optical shaping.

[0038] Examples of the polyfunctional compound (b) contained in the unsaturated compound (B) include the polyfunctional compounds of the following (b1), (b2), and (b3). (b1): A polyfunctional compound having a skeleton derived from a polyol and two or more polymerizable functional groups in the molecule, and at least one polymerizable functional group is a methacrylamide group or an acrylamide group (b2): A polyfunctional compound having two or more polymerizable functional groups in the molecule and not having a skeleton derived from a polyol (b3): A polyfunctional compound having two or more polymerizable functional groups in the molecule and having an isocyanurate ring Among these, it is preferable that the polyfunctional compound (b1) that improves the curability of the active energy ray curable resin composition (E) and suppresses the curing shrinkage rate is contained in the unsaturated compound (B).

[0039] When the polyfunctional compound (b) is contained in the unsaturated compound (B), its content (that is, the total content of the polyfunctional compounds (b1), (b2) and (b3)) is preferably 1.0 to 75.0% by mass, more preferably 10.0 to 60.0% by mass, based on the total mass of the active energy ray curable resin composition (E). If the content of the polyfunctional compound (b) is within this range, it is preferable because the curability of the active energy ray curable resin composition (E) is improved.

[0040] The polyfunctional compound (b1) is a polyfunctional compound having a skeleton derived from a polyol and two or more polymerizable functional groups in the molecule, and at least one polymerizable functional group is a methacrylamide group or an acrylamide group. As other polymerizable functional groups in the polyfunctional compound (b1), one or more functional groups selected from a methacrylate group, an acrylate group, a methacrylamide group, and an acrylamide group are preferable examples. As described above, when the polyfunctional compound (b1) is contained in the unsaturated compound (B), the curability of the active energy ray-curable resin composition (E) is improved by the methacrylamide group or acrylamide group which is a polymerizable functional group. Further, the curing shrinkage of the active energy ray-curable resin composition (E) can be suppressed, the molding accuracy is excellent, and a cured product having sufficient impact resistance can be obtained. From such a viewpoint, when the polyfunctional compound (b1) is contained in the unsaturated compound (B), its content is preferably 5.0 to 50.0% by mass, more preferably 10.0 to 40.0% by mass, based on the total mass of the active energy ray-curable resin composition (E). The number of polymerizable functional groups in the polyfunctional compound (b1) is preferably 2 or more from the viewpoint of improving the curability of the cured product of the active energy ray-curable resin composition, and is usually 10 or less, preferably 6 or less, from the viewpoint of suppressing the curing shrinkage of the active energy ray-curable resin composition (E). Further, as the skeleton derived from the polyol, one or more skeletons selected from an ether skeleton, an ester skeleton, a carbonate skeleton, a silicone skeleton, an olefin skeleton, and an acrylic skeleton are preferable examples. These polyfunctional compounds (b1) may be used alone or in combination of two or more kinds.

[0041] The production method of the polyfunctional compound (b1) is not particularly limited, and examples thereof include a method of reacting an isocyanate group-containing urethane prepolymer obtained by reacting a polyol compound and a diisocyanate compound with a hydroxyl group-containing (meth)acrylate and / or a hydroxyl group-containing (meth)acrylamide, and a method of mixing and reacting a polyol compound, a diisocyanate compound, a hydroxyl group-containing (meth)acrylate and / or a hydroxyl group-containing (meth)acrylamide. Known methods such as these can be mentioned.

[0042] Examples of the polyol compound used for producing the polyfunctional compound (b1) include 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. Among these, from the viewpoint of imparting sufficient impact resistance to the cured product obtained by curing the active energy ray curable resin composition (E), polyether diols, polyester diols, polycarbonate diols, hydrogenated polyalkadiene diols, and polyalkadiene diols having two hydroxyl groups in the molecule are mentioned as preferred examples. These can be used alone or in combination of two or more.

[0043] Examples of the polyether polyol include linear, branched, and 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, pentaerythritol tetra(polyoxy-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, poly(oxy-1,6-hexylene) glycol, and other alkylene glycols.

[0044] The polyester polyol consists of a polycarboxylic acid and a polyol, contains a polyester skeleton in the molecule and has a hydroxyl group at the terminal. 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, cyclohexanetetracarboxylic acid, etc. 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, pentaerythritol, etc.

[0045] The polycarbonate polyol consists of a carbonyl component and a polyol, and has a hydroxyl group at the terminal containing a carbonate skeleton in the molecule. Examples of the carbonyl component include phosgene, chloroformate ester, dialkyl carbonate, diaryl carbonate, and alkylene carbonate, etc. 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, pentaerythritol, etc.

[0046] Examples of the hydrogenated polyalkadiene polyol include 1,2-hydrogenated polybutadiene diol, 1,4-hydrogenated polybutadiene diol, hydrogenated polyisoprene polyol, etc. Examples of the polyalkadiene polyol include 1,2-polybutadiene diol, 1,4-polybutadiene diol, polyisoprene polyol, etc.

[0047] The diisocyanate compound used in the production of the polyfunctional compound (b1) is not particularly limited as long as it has two isocyanate groups in the molecule. For example, 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, 2,2,4-trimethylhexamethylene diisocyanate; aromatic diisocyanates such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, xylylene diisocyanate; alicyclic diisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, or adduct types, burette types, etc. of these can be mentioned. Among these, from the viewpoints of imparting sufficient impact resistance to the cured product obtained by curing the active energy ray curable resin composition (E) and suppressing yellowing (coloring over time), aliphatic diisocyanates and alicyclic diisocyanates are mentioned as preferred examples. These can be used alone or in combination of two or more.

[0048] Examples of the hydroxyl group-containing (meth)acrylate and / or hydroxyl group-containing (meth)acrylamide used in the production of the polyfunctional compound (b1) include hydroxyalkyl (meth)acrylate into which a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms is introduced, glycerin (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N-hydroxyalkyl (meth)acrylamide, polyalkylene glycol (meth)acrylate into which a polyalkylene glycol having a total number of atoms of 20 or less composed of alkylene glycols having 1 to 9 carbon atoms is introduced, N-polyalkylene glycol (meth)acrylamide, hydroxyphenyl (meth)acrylate, N-hydroxyphenyl (meth)acrylamide, N-alkyl(N-hydroxyalkyl)(meth)acrylamide, N-alkyl(N-polyalkylene glycol)(meth)acrylamide, N-alkyl(N-hydroxyphenyl)(meth)acrylamide, etc., in which a linear, branched, or cyclic alkyl group or alkylene group having 1 to 8 carbon atoms is introduced into the nitrogen atom of the (meth)acrylamide-based monomer.

[0049] As the hydroxyl group-containing (meth)acrylate and / or hydroxyl group-containing (meth)acrylamide, hydroxyl group-containing N-substituted acrylamides are preferred because they improve the cohesive force of the polyfunctional compound (b1), enhance the curability of the active energy ray-curable resin composition (E), and impart sufficient impact resistance to the cured product obtained by curing this. Examples of the hydroxyl group-containing N-substituted acrylamides include N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)methacrylamide, N-(2-hydroxypropyl)acrylamide, N-(2-hydroxypropyl)methacrylamide and the like. Among these, N-(2-hydroxyethyl)acrylamide is more preferred because it has a skin irritation of PII = 0.0 and high safety. These hydroxyl group-containing (meth)acrylates and / or hydroxyl group-containing (meth)acrylamides can be used alone or in combination of two or more.

[0050] The number average molecular weight (Mn) of the polyfunctional compound (b1) is preferably from 1,500 to 100,000, more preferably from 2,000 to 50,000. If the number average molecular weight (Mn) of the polyfunctional compound (b1) is within this range, the viscosity of the active energy ray-curable resin composition (E) can be adjusted to a suitable range, and sufficient impact resistance can be imparted to the cured product obtained by curing this.

[0051] The polyfunctional compound (b2) is a polyfunctional compound having two or more polymerizable functional groups in the molecule and not having a skeleton derived from a polyol. When the polyfunctional compound (b2) is contained in the unsaturated compound (B), the curability of the active energy ray-curable resin composition (E) is improved, and sufficient strength is imparted to the cured product obtained by curing the composition. From this viewpoint, when the polyfunctional compound (b2) is contained in the unsaturated compound (B), its content is preferably 5.0 to 30.0% by mass, more preferably 5.0 to 20.0% by mass, based on the total mass of the active energy ray-curable resin composition (E). Further, as the polymerizable functional group in the polyfunctional compound (b2), one or more functional groups selected from a methacrylate group, an acrylate group, a methacrylamide group, and an acrylamide group are preferable, and it is more preferable that at least one of the polymerizable functional groups is a methacrylamide group or an acrylamide group. The number of polymerizable functional groups in the polyfunctional compound (b2) is preferably two or more from the viewpoint of improving the curability of the active energy ray-curable resin composition (E) and imparting sufficient strength to the cured product, and is usually 10 or less, preferably 6 or less, from the viewpoint of ensuring the effect of suppressing the curing shrinkage by other components of the active energy ray-curable resin composition (E). Note that "not having a skeleton derived from a polyol" means not having any of an ether skeleton, an ester skeleton, a carbonate skeleton, a silicone skeleton, an olefin skeleton, and an acrylic skeleton. These polyfunctional compounds (b2) may be used alone or in combination of two or more. The production method of the polyfunctional compound (b2) is not particularly limited, but examples thereof include a method of reacting the above-described diisocyanate compound with the above-described hydroxyl group-containing (meth)acrylate and / or hydroxyl group-containing (meth)acrylamide.

[0052] As the hydroxyl group-containing (meth)acrylate and / or hydroxyl group-containing (meth)acrylamide used in the production of the polyfunctional compound (b2), those having one hydroxyl group and one (meth)acrylate group or (meth)acrylamide group in the molecule are preferable from the viewpoint of imparting sufficient strength to the cured product obtained by curing the active energy ray-curable resin composition (E).

[0053] The number average molecular weight (Mn) of the polyfunctional compound (b2) is preferably less than 1,500. If the number average molecular weight of the polyfunctional compound (b2) is less than 1,500, it is preferable for improving the curability of the active energy ray curable resin composition (E), and from this viewpoint, it is more preferably 1,000 or less. The lower limit of the number average molecular weight (Mn) of the polyfunctional compound (b2) is not particularly limited, but is usually 300 or more.

[0054] The polyfunctional compound (b3) is a polyfunctional compound having two or more polymerizable functional groups in the molecule and having an isocyanurate ring. When the polyfunctional compound (b3) is contained in the unsaturated compound (B), the curability of the active energy ray-curable resin composition (E) is improved, the heat resistance of the cured product obtained by curing this is improved, and sufficient strength can be imparted to the cured product. From such a viewpoint, when the polyfunctional compound (b3) is contained in the unsaturated compound (B), its content is preferably 5.0 to 50.0% by mass, more preferably 5.0 to 40.0% by mass, based on the total mass of the active energy ray-curable resin composition (E). Further, as the polymerizable functional group in the polyfunctional compound (b3), one or more functional groups selected from a methacrylate group, an acrylate group, a methacrylamide group, and an acrylamide group are preferable, and it is more preferable that at least one of the polymerizable functional groups is a methacrylamide group or an acrylamide group. Examples of the polyfunctional compound (b3) include tris-(2-acryloxyethyl) isocyanurate, caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, and a compound having a structural unit derived from a polyisocyanate having an isocyanurate ring and the above hydroxyl group-containing (meth)acrylate and / or hydroxyl group-containing (meth)acrylamide. From the viewpoint of improving the curability of the active energy ray-curable resin composition (E) and the heat resistance of its cured product, the number of polymerizable functional groups in the polyfunctional compound (b3) is preferably 3 or more. On the other hand, the upper limit is usually 10 or less, preferably 6 or less, from the viewpoint of ensuring the effect of suppressing the curing shrinkage by other components in the active energy ray-curable resin composition (E). These polyfunctional compounds (b3) may be used alone or in combination of two or more. The production method of the polyfunctional compound (b3) is not particularly limited, but known methods such as a method of reacting a polyisocyanate having an isocyanurate ring with a hydroxyl group-containing (meth)acrylate and / or a hydroxyl group-containing (meth)acrylamide, and a method of reacting a polyisocyanate having an isocyanurate ring with the above polyol compound and a hydroxyl group-containing (meth)acrylate and / or a hydroxyl group-containing (meth)acrylamide can be mentioned.

[0055] Examples of the polyisocyanate having an isocyanurate ring used in the production of the polyfunctional compound (b3) include isocyanurate compounds of the above diisocyanate compounds, such as isocyanurate compounds of dicyclohexylmethane 4,4'-diisocyanate, isocyanurate compounds of hexamethylene diisocyanate, and isocyanurate compounds of isophorone diisocyanate.

[0056] From the viewpoints of improving the curability of the active energy ray-curable resin composition (E), improving the heat resistance of the cured product obtained by curing the composition, and imparting sufficient strength to the cured product, the hydroxyl group-containing (meth)acrylate and / or hydroxyl group-containing (meth)acrylamide used in the production of the polyfunctional compound (b3) preferably has one hydroxyl group and one (meth)acrylate group or one (meth)acrylamide group in the molecule.

[0057] The unsaturated compound (B) may contain other monomers. Examples of the other monomers include the monofunctional monomers listed as the monofunctional monomer (a3) capable of constituting the structural unit of the above (meth)acrylic polymer (A), and polyfunctional compounds (b4) excluding the polyfunctional compounds (b1), (b2), and (b3). The monofunctional monomer (a3) in the unsaturated compound (B) can adjust the viscosity of the active energy ray-curable resin composition (E) to a suitable range. Also, the polyfunctional compound (b4) in the unsaturated compound (B) can adjust the balance such as the crosslink density of the cured product obtained by curing the active energy ray-curable resin composition (E). From such viewpoints, the content of the other monomers in the unsaturated compound (B) is preferably 30.0% by mass or less, more preferably 25.0% by mass, based on the total mass of the active energy ray-curable resin composition (E). The lower limit of the content of the other monomers is not particularly limited, but is usually 0.1% by mass or more. The other monomers may be used alone or in combination of two or more.

[0058] The polyfunctional compound (b4) is not particularly limited as long as it is a monomer having two or more polymerizable functional groups in the molecule excluding the polyfunctional compounds (b1), (b2) and (b3). Examples of the polymerizable functional group include (meth)acrylate group, (meth)acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth)allyl ether group and maleimide group. Further, the polyfunctional compound (b4) may have two or more identical functional groups selected from these polymerizable functional groups in the molecule, or may have a combination of two or more different functional groups.

[0059] Examples of the polyfunctional compound (b4) include di(meth)acrylate compounds, di(meth)acrylamide compounds, divinyl ether compounds, dimethyl vinyl ether compounds, di(meth)allyl ether compounds, and compounds having the same polymerizable functional group, such as alkylene glycols, dialkylene glycols, trialkylene glycols, and polyalkylene glycols having 2 to 10 carbon atoms, and their di(meth)acrylate, di(meth)acrylamide, divinyl ether, dimethyl vinyl ether, and di(meth)allyl ether derivatives; methylene di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, polyester di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, methylene bis(meth)acrylamide, dicyclopentanyl di(meth)acrylamide, caprolactone-modified dicyclopentenyl di(meth)acrylamide, tricyclodecane dimethanol di(meth)acrylamide, polyester di(meth)acrylamide, ethylene oxide-modified bisphenol A di(meth)acrylamide, and propylene oxide-modified bisphenol A di(meth)acrylamide; difunctional compounds having different polymerizable functional groups, such as allyl (meth)acrylate, allyl (meth)acrylamide, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylamide, N-(2-acryloyloxyethyl)maleimide, and N-(2-hydroxyethylpropanamide)maleimide; trifunctional compounds, such as pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, trimethylolpropane (polyethylene glycol adduct) triacrylate, and succinic acid-modified pentaerythritol tri(meth)acrylate; tetrafunctional compounds, such as pentaerythritol tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol tetra(meth)acrylate.Examples of compounds with four or more functional groups include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin polyglycidyl ether poly(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, etc. These may be used alone or in combination of two or more.

[0060] The viscosity of the active energy ray-curable resin composition (E) according to this embodiment is preferably 1 to 100,000 mPa·s at 25°C. When the viscosity is within this range, it can be suitably used as a resin composition for three-dimensional stereolithography by various methods. The viscosity can be measured by the method described later.

[0061] The curing shrinkage rate of the active energy ray-curable resin composition (E) according to this embodiment is preferably less than 7%. When the curing shrinkage rate is within this range, a cured product with excellent shaping accuracy can be obtained. The curing shrinkage rate is measured and calculated by the method described later. Also, the shaping accuracy of the cured product is evaluated by the method described later.

[0062] The active energy ray-curable resin composition (E) according to this embodiment is a composition that cures by polymerization to become solid. In this case, the polymerization method is not particularly limited, and it can be obtained by a known method as the polymerization method of polymerizable functional groups. For example, radical polymerization, anionic polymerization, cationic polymerization, etc. by active energy rays or heat can be mentioned. Among these, polymerization by active energy rays is preferable because the polymerization can be easily controlled by adjusting the type and addition amount of the photoinitiator, and the illuminance and integrated light amount of the irradiated active energy rays.

[0063] The active energy rays used for curing the active energy ray-curable resin composition (E) refer to those having energy quanta among electromagnetic waves or charged particle beams, that is, active energy rays such as visible light, electron beams, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays, etc. For example, light sources such as high-pressure mercury lamps, halogen lamps, xenon lamps, metal halide lamps, LED lamps, electron beam acceleration devices, and radioactive elements can be mentioned. When an electron beam is used as the active energy ray source, usually, it is not necessary to contain a photoinitiator, but when other active energy ray sources are used, it is preferable to add a photoinitiator (C). As the active energy rays to be irradiated, ultraviolet rays are preferable in terms of the storage stability, curing rate, and low toxicity of the active energy ray-curable resin composition (E).

[0064] When curing the active energy ray-curable resin composition (E), after performing primary curing with active energy rays, further secondary curing may be performed by promoting curing with irradiation of active energy rays or heat. Also, the active energy rays used for secondary curing may have the same wavelength or a different wavelength from the active energy rays during primary curing. Furthermore, the same curing reaction as secondary curing may be carried out in multiple stages.

[0065] Examples of the photopolymerization initiator (C) include a photo radical initiator and a photoanionic polymerization initiator. As the photo radical polymerization initiator, ordinary ones such as acetophenone - based, benzoin - based, benzophenone - based, α - amino ketone - based, xanthone - based, anthraquinone - based, acylphosphine oxide - based, and polymer photo - polymerization initiator - based can be appropriately selected. For example, as acetophenones, diethoxyacetophenone, 2,2 - dimethoxy - 1,2 - diphenylethane - 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 - hydroxycyclohexyl phenyl ketone, 2 - methyl - 1 - (4 - methylthiophenyl) - 2 - morpholinopropan - 1 - one; as benzoins, benzoin, α - methylbenzoin, α - phenylbenzoin, α - allylbenzoin, α - benzoylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal; as benzophenones, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate; as α - amino ketones, 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; as xanthones, xanthone, thioxanthone; as anthraquinones, anthraquinone, 2 - methylanthraquinone, 2 - ethylanthraquinone; as acylphosphine oxides, bis(2,4,6 - trimethylbenzoyl) - phenylphosphine oxide, 2,4,6 - trimethylbenzoyl - diphenyl - phosphine oxide; as polymer photoinitiators, a polymer of 2 - hydroxy - 2 - methyl - 1 - (4 - (1 - methylvinyl)phenyl)propan - 1 - one, etc. can be mentioned.

[0066] Examples of the photoanionic polymerization initiator include initiators such as 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.

[0067] The content of the photopolymerization initiator (C) is preferably 0.1 to 10.0% by mass, more preferably 1.0 to 5.0% by mass, based on the total mass of the active energy ray curable resin composition (E). When the content of the photopolymerization initiator (C) is 0.1% by mass or more, the polymerization reaction of the active energy ray curable resin composition (E) by irradiation with active energy rays proceeds rapidly, the irradiation time can be shortened, and the residual monomer is reduced, which is preferable. When the content of the photopolymerization initiator (C) is 10.0% by mass or less, sufficient strength and impact resistance can be imparted to the cured product obtained using the active energy ray curable resin composition (E), and the storage stability of the active energy ray curable resin composition (E) is also good, which is preferable.

[0068] The irradiation amount (integrated light amount) of active energy rays required for curing the active energy ray curable resin composition (E) varies depending on the types and contents of the (meth)acrylic polymer (A) and the unsaturated compound (B) contained in the active energy ray curable resin composition (E), and when it has a photopolymerization initiator (C), it varies depending on the type and content thereof. Further, when forming a three-dimensional stereolithography object, the integrated light amount required for curing varies depending on the thickness of the object, so it is not particularly limited. However, from the viewpoint of efficient curing, it is usually 1 to 20,000 mJ / cm 2 is. When the active energy ray curable resin composition (E) is used as a resin composition for three-dimensional stereolithography, a method of sequentially laminating cured products of thin films (thickness: several μm to 1 mm) of the resin composition formed into a specific shape is generally used. Therefore, it is preferable that the integrated light amount required for curing the thin film of the active energy ray curable resin composition (E) is small because the irradiation time is short and the shaping speed is increased. From such a viewpoint, the integrated light amount required for curing the thin film of the active energy ray curable resin composition (E) is 1,000 mJ / cm 2The following is preferable, 500 mJ / cm 2 The following is more preferable, 200 mJ / cm 2 The following is even more preferable, 100 mJ / cm 2 If it is the following, since it can be suitably used as a resin composition for three-dimensional optical modeling of various methods, it is most preferable.

[0069] The active energy ray curable resin composition (E) of the present embodiment may contain other components (D) as necessary. Examples of the other components (D) include organic solvents, various additives, epoxy compounds, oxetane compounds, and the like.

[0070] Examples of the organic solvent include ketone solvents, ester solvents, amide solvents, ether solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and the like. The active energy ray curable resin composition (E) may be cured and used while containing the organic solvent, or may be cured after distilling off the organic solvent. The content of the organic solvent is not particularly limited as long as it does not adversely affect the properties exhibited by the active energy ray curable resin composition (E).

[0071] Examples of the various additives include ultraviolet sensitizers, thermal polymerization inhibitors, anti-aging agents, antioxidants, ultraviolet sensitizers, preservatives, phosphate esters and other flame retardants, surfactants, wetting and dispersing agents, antistatic agents, colorants, plasticizers, surface lubricants, leveling agents, softeners, thickeners, pigments, organic fillers, inorganic fillers, and the like. The addition amount of these various additives 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% by mass or less based on the total mass of the active energy ray curable resin composition.

[0072] Examples of the ultraviolet sensitizer include anthracene compounds such as 9,10-dialkoxyanthracene compounds and 9,10-bis(dihydroxyalkoxy)anthracene, thioxanthone compounds such as thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2-butylthioxanthone, 2-chlorothioxanthone, 2-propoxythioxanthone, and polymeric thioxanthone.

[0073] 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, β-naphthol, and the like.

[0074] Examples of the anti-aging agent include hindered phenol-based, benzotriazole-based, and hindered amine-based compounds such as butylated hydroxytoluene and butyl hydroxyanisole.

[0075] Examples of the surfactant include alkylene oxide adduct type nonionic surfactants such as polyethylene oxide adducts of nonylphenol, polyethylene oxide adducts of lauric acid, and polyethylene oxide adducts of stearic acid; polyhydric alcohol type nonionic surfactants such as sorbitan monopalmitate, sorbitan monostearate, and sorbitan tristearate; acetylene glycol compound type nonionic surfactants; acetylene polyalkylene glycol compound type nonionic surfactants; fluorine-containing surfactants such as perfluoroalkyl polyethylene oxide adducts, perfluoroalkyl carboxylates, and perfluoroalkyl betaines; modified silicone oils such as polyether-modified silicone oil and (meth)acrylate-modified silicone oil; and amphoteric polymer surfactants.

[0076] Examples of the antistatic agent include nonionic antistatic agents such as glycerin fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, bis(2-hydroxyethyl)alkylamines, and polyoxyethylene alkylamines; anionic antistatic agents such as alkyl sulfonates, alkyl benzene sulfonates, and alkyl phosphates; cationic antistatic agents such as tetraalkylammonium salts and trialkylbenzylammonium salts; amphoteric antistatic agents such as alkyl betaines and alkylimidazolium betaines; and polymerizable antistatic agents such as (meth)acryloylaminoethyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloylaminopropyltrimethylammonium bis(trifluoromethanesulfonyl)imide, and (meth)acryloyloxyethyltrimethylammonium bis(trifluoromethanesulfonyl)imide.

[0077] Examples of the epoxy compound include glycidyl compounds such as bisphenol A diglycidyl ether and hydrogenated bisphenol A diglycidyl ether, and alicyclic epoxy compounds such as cyclohexene oxide and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate. Examples of the oxetane compound include the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol and xylylene bisoxetane.

[0078] The cured product obtained by curing the active energy ray-curable resin composition (E) according to this embodiment has practical strength and impact resistance. The strength of the cured product is evaluated by the tensile strength measured by the method described below. When the tensile strength is 30 MPa or more, it is determined that the cured product has sufficient practical strength. The impact resistance of the cured product is evaluated by the Izod impact strength measured by the method described below. When the Izod impact strength is 20 J / m or more, it is determined that the cured product has sufficient practical impact resistance.

[0079] When the cured product obtained by curing the active energy ray-curable resin composition (E) according to this embodiment has a glass transition temperature (Tg) of 40°C or higher, it is judged to have heat resistance because it is difficult to deform at room temperature and can maintain a hard state. The Tg of the cured product can be measured by the method described later.

[0080] The cured product of the active energy ray-curable resin composition (E) according to this embodiment has high transparency and high heat resistance, and can be utilized in various applications as a resin having sufficient strength and impact resistance. Examples of the applications include, but are not necessarily limited to, structures constituting automobiles, electric appliances, furniture, etc., paints and coating materials, dental hygiene materials, optical materials, stereolithography materials, materials for reinforced plastics, resin compositions for model materials in three-dimensional stereolithography, etc.

[0081] The second embodiment of the present invention is an active energy ray-curable resin composition or an active energy ray-curable ink for a model material in three-dimensional stereolithography (hereinafter, also simply referred to as "active energy ray-curable resin composition" or "active energy ray-curable ink"). The active energy ray-curable resin composition (E) according to the first embodiment of the present invention described above can be used as an active energy ray-curable resin composition or an active energy ray-curable ink for a model material in a printer used for three-dimensional stereolithography, and a three-dimensional stereolithographic object can be formed as a model material by being cured by active energy rays. Examples of the printer for the three-dimensional stereolithography method include a material jetting method printer that laminates the surfaces on which the active energy ray-curable ink is drawn by an inkjet printer, an SLA method or DLP method liquid tank photopolymerization method printer that produces and laminates resin layers cured using a laser or a projector in a resin tank filled with the active energy ray-curable resin composition, and a 3D printer using a material extrusion deposition method using the active energy ray-curable ink, but are not necessarily limited to these.

[0082] The method of material extrusion deposition using an active energy ray-curable ink is a method in which an active energy ray-curable ink is filled into the material supply section of a printer, discharged in a sol state from a nozzle to a shaping area, and simultaneously irradiated with light to cure, and the cured products are laminated. There is no limitation on the output method, but for example, it can be output using a dispenser discharge device. For example, methods of extruding a liquid material by an air or solid plunger, gear, screw, etc., a method of squeezing a tube by a roller and extruding the liquid material in the tube, etc. can be mentioned. The active energy ray-curable ink is liquid at the time of discharge, and from the viewpoint of handling workability, it is preferably fluid in part or all of the temperature range of 20°C or higher and 150°C or lower. Regarding the method of irradiating the active energy rays, there is no particular limitation, as long as the active energy ray-curable ink is irradiated while being discharged and can be cured. For example, a method of partially curing the structure of a three-dimensional photomodel by surface irradiation with a light source such as a laser or a projector, a method of curing the entire active energy ray-curable ink output from a dispenser or the like by spot irradiation or surface irradiation, etc. can be used.

[0083] The viscosity of the active energy ray-curable resin composition or the active energy ray-curable ink according to this embodiment is preferably 1 to 100,000 mPa·s at 25°C from the viewpoint of operability when forming the structure of the cured product. When the active energy ray-curable resin composition (E) is used as the active energy ray-curable resin composition of a 3D printer by a liquid bath photopolymerization method such as the SLA method or the DLP method, from the viewpoint of shaping operations such as the smooth operation of the shaping table, its viscosity is preferably 20,000 mPa·s or less at 25°C, more preferably 10,000 mPa·s or less, still more preferably 5,000 mPa·s or less, and particularly preferably 2,000 mPa·s or less.

[0084] When the active energy ray-curable resin composition (E) is used as the active energy ray-curable ink of a photo-curing type inkjet 3D printer by a material jetting method, from the viewpoint of stable ejection from the inkjet nozzle, its viscosity is preferably 1 to 200 mPa·s at 25°C, and the ejection temperature is preferably in the range of 20°C to 100°C. When the ejection temperature is set high, the viscosity of the active energy ray-curable resin composition (E) decreases, and a resin with high viscosity can be ejected, but thermal denaturation and polymerization are likely to occur. Since ejection at a temperature of 80°C or lower is preferable from the viewpoint of the thermal stability of the active energy ray-curable resin composition (E), the viscosity of the active energy ray-curable resin composition (E) is more preferably 100 mPa·s or less.

[0085] When the active energy ray-curable resin composition (E) is used as the active energy ray-curable ink of a 3D printer by a material extrusion deposition method, from the viewpoint of stable ejection from a nozzle such as a dispenser, its viscosity is preferably 10,000 to 100,000 mPa·s at 25°C, and the ejection temperature is preferably in the range of 20°C to 100°C.

[0086] If the model material obtained by curing the active energy ray-curable resin composition or the active energy ray-curable ink has a tensile strength of 30 MPa or more and an Izod impact strength of 20 J / m or more, it is preferable because it has sufficient strength and impact resistance for practical use. The measurement of the tensile strength and the Izod impact strength can be carried out in the same manner as for the cured product of the active energy ray-curable resin composition (E).

[0087] The model material obtained by curing the active energy ray-curable resin composition or the active energy ray-curable ink preferably has a glass transition temperature (Tg) of 40°C or more as heat resistance. When the glass transition temperature (Tg) of the model material is 40°C or more, the model material is difficult to deform at normal room temperature and can maintain a hard state, which is preferable. This measurement can be carried out in the same manner as for the cured product of the active energy ray-curable resin composition (E).

[0088] In the production of a three-dimensional optical molding using the active energy ray curable resin composition (E) according to the first embodiment of the present invention, or the active energy ray curable resin composition or the active energy ray curable ink according to the second embodiment of the present invention, the shape of the three-dimensional optical molding is arbitrary, but when forming a hollow structure, it is common to use a support material as a support. The support material is formed and cured simultaneously with the three-dimensional optical molding and removed after the molding is completed, and is not particularly limited, and examples thereof include heat-meltable wax, resin, or active energy ray curable resin.

[0089] In the three-dimensional optical molding using the active energy ray curable resin composition (E) according to the first embodiment of the present invention, or the active energy ray curable resin composition or the active energy ray curable ink according to the second embodiment of the present invention, when performing three-dimensional optical molding by the liquid tank photo polymerization method, the same resin is often used for the model material and the support material. The active energy ray curable resin composition (E) of the present invention can be used not only as a model material for producing a three-dimensional optical molding but also as a support material for supporting the three-dimensional optical molding.

Examples

[0090] Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, "parts" and "%" are all based on mass unless otherwise specified.

[0091] The raw materials used in the (meth)acrylic polymer (A) having an alicyclic structure and / or an aromatic ring structure in the examples, the active energy ray curable resin composition (E), and the active energy ray curable resin composition (F) in the comparative examples are shown. <Mono-functional monomer (a1)> a1-1: Isobornyl methacrylate (Light Ester IB-X, manufactured by Kyoeisha Chemical Co., Ltd.) (liquid at room temperature) a1-2: N-acryloyloxyethyl norbornene carboxamide (registered trademark "Kohshylmer", manufactured by AENA KJ Chemicals Co., Ltd.) (solid at room temperature) a1-3: Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Acrylate IB-XA) (liquid at room temperature) a1-4: Phenoxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Acrylate PO-A) (liquid at room temperature) a1-5: Dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-513AS) (liquid at room temperature) a1-6: t-Butylcyclohexyl acrylate (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd., TBCHA) (liquid at room temperature) a1-7: N-Phenylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) (solid at room temperature) <Mono-functional monomer (a2)> a2-1: N-Acryloylmorpholine (registered trademark "Kohshylmer", "ACMO", manufactured by KJ Chemicals Co., Ltd.) (liquid at room temperature) a2-2: N-Vinylpyrrolidone (manufactured by BASF Corporation, Chemical Intermediates, NVP) (liquid at room temperature) a2-3: N-(2-Hydroxyethyl)acrylamide (registered trademark "Kohshylmer", "HEAA", manufactured by KJ Chemicals Co., Ltd.) (liquid at room temperature) a2-4: N-Vinylcaprolactam (manufactured by BASF Corporation, Chemical Intermediates, NVC) (solid at room temperature) a2-5: N,N-Dimethylacrylamide (registered trademark "Kohshylmer", "DMAA", manufactured by KJ Chemicals Co., Ltd.) (liquid at room temperature) a2-6: N,N-Diethylacrylamide (registered trademark "Kohshylmer", "DEAA", manufactured by KJ Chemicals Co., Ltd.) (liquid at room temperature)

[0092] <Poly-functional compounds (b1) to (b3)> b3-1: Tris(2-acryloyloxyethyl) isocyanurate (A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) b3-3: Caprolactone-modified tris-(2-acryloxyethyl) isocyanurate (A-9300-1CL, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0093] Table 1 shows the molecular weights of the polyfunctional compounds (b1-1) to (b1-5), (b2-1) to (b2-3), and (b3-2) used in the examples, the types and numbers of polymerizable functional groups they contain, the structures of the raw material polyols, and the structures of the raw material isocyanates.

[0094]

Table 1

[0095] The number average molecular weight (Mn) of the polyfunctional compound (b) was measured by high performance liquid chromatography (using LC10A manufactured by Shimadzu Corporation, the column was Shodex GPC KF-806L (exclusion limit molecular weight: 2×10 7 , separation range: 100~2×10 7 , theoretical plate number: 10,000 plates per column), and tetrahydrofuran was used as the eluent.), and calculated by converting to standard polystyrene molecular weight.

[0096] <Other monomers (monofunctional monomer (a3))> a3-1: Methyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Inc.) a3-2: Acrylic acid (manufactured by Mitsubishi Chemical Corporation) a3-3: Butyl acrylate (manufactured by Mitsubishi Chemical Corporation) a3-4: Tetrahydrofurfuryl acrylate (Biscoat #150, Osaka Organic Chemical Industry Co., Ltd.) a3-5: Methacrylic acid (manufactured by Mitsubishi Chemical Corporation) a3-6: Cyclic trimethylolpropane formal acrylate (Biscoat #200, Osaka Organic Chemical Industry Co., Ltd.) a3-7: Ethyl acrylate (manufactured by Mitsubishi Chemical Corporation) <Other monomers (polyfunctional compound (b4))> b4-1: Ethoxylated Bisphenol A Diacrylate (NK Ester A-BEP10, manufactured by Shin-Nakamura Chemical Co., Ltd., average molecular weight: 705) b4-2: Dimethylol-tricyclodecane Diacrylate (Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 304) b4-3: Allyl Methacrylate (manufactured by Mitsubishi Chemical Corporation)

[0097] <Photoinitiator (C)> C-1: Omnirad TPO (Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide, manufactured by IGM Resins B.V.) C-2: Omnirad 184 (1-Hydroxycyclohexylphenyl Ketone, manufactured by IGM Resins B.V.) C-3: Omnirad 819 (Phenylbis(2,4,6-trimethylbenzoyl)phosphine Oxide, manufactured by IGM Resins B.V.)

[0098] <Other Components (D)> D-1: Isopropyl Thioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.) D-2: Poly(1-vinylpyrrolidone-co-vinyl acetate) (1-vinylpyrrolidone / vinyl acetate = 1.3 / 1.0 (mol ratio)), Mw: 50,000, manufactured by Sigma-Aldrich

[0099] Table 2 shows the composition and physical properties of the (meth)acrylic polymers (A-1) to (A-15) having an alicyclic structure and / or an aromatic ring structure used in the examples and comparative examples.

[0100] (Number-average molecular weight of the (meth)acrylic polymers (A-1) to (A-15)) (The number-average molecular weight of the (meth)acrylic polymers (A-1) to (A-15)) was measured by high performance liquid chromatography using LC10A manufactured by Shimadzu Corporation, and the column was Shodex GPC KF-806L (exclusion limit molecular weight: 2×10 7 , separation range: 100~2×10 7, Theoretical stages: 10,000 stages / book), Tetrahydrofuran was used as the eluent.), Measured by), and calculated by converting to standard polystyrene molecular weight.

[0101]

Table 2

[0102] <Example 1> (50.0 parts by mass of (meth)acrylic polymer (A-1), 24.0 parts by mass of isobornyl methacrylate (a1-1), 5.0 parts by mass of phenoxyethyl acrylate (a1-4), 20.0 parts by mass of N-acryloylmorpholine (a2-1), and 1.0 part by mass of Omnirad TPO (C-1) were charged into a container and stirred at 50°C for 1 hour to obtain a uniform and transparent active energy ray curable resin composition (E-1) of Example 1.

[0103] <Examples 2 to 15> By performing the same operations as in Example 1 with the compositions shown in Table 3, uniform and transparent active energy ray curable resin compositions (E-2) to (E-15) corresponding to Examples 2 to 15 were obtained.

[0104] <Comparative Examples 1 to 2> By performing the same operations as in Example 1 with the compositions shown in Table 3, active energy ray curable resin compositions (F-1) and (F-2) corresponding to Comparative Examples 1 and 2 were obtained.

[0105] (Viscosity of active energy ray curable resin composition) Using a Brookfield viscometer (device name: Digital Viscometer LV DV2T manufactured by Eiko Seiki Co., Ltd.), in accordance with JIS K5600-2-3, the viscosities of the active energy ray curable resin compositions (E) and (F) obtained in each example and comparative example were measured at 25°C.

[0106] (Compatibility of each component of active energy ray curable resin composition) The active energy ray-curable resin compositions (E) and (F) obtained in each of the examples and comparative examples were visually observed, and the compatibility of each component in the composition was evaluated according to the following criteria. ◎: Transparent ○: Slightly cloudy ×: Cloudy

[0107] (Strength of the cured product of the active energy ray-curable resin composition) A 75-μm-thick heavy release PET film (manufactured by Toyobo Co., Ltd., polyester film E7001) was adhered onto a horizontally placed glass plate, and a spacer with a thickness of 1 mm and punched into a No. 2 dumbbell shape conforming to JIS K6251 was installed. After filling the inside of the spacer with the active energy ray-curable resin composition (E) or (F) obtained in each of the examples and comparative examples, a 50-μm-thick light release PET film (manufactured by Toyobo Co., Ltd., polyester film E7002) was further overlaid thereon, and ultraviolet rays were irradiated from both sides (apparatus: EC-4011GX inverter type conveyor apparatus manufactured by Eye Graphics Co., Ltd., metal halide lamp: M04-L41 manufactured by Eye Graphics Co., Ltd., ultraviolet illuminance 200 mW / cm 2 , integrated light quantity 1000 mJ / cm 2 ) to cure the resin composition. Thereafter, the release PET films on both sides were removed to obtain test pieces of the cured product for the examples and the cured product for the comparative examples. According to JIS K7161, using a desktop precision universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation), the tensile strength was measured under the conditions of a temperature environment of 25 °C, a tensile speed of 10 mm / min, and a chuck distance of 50 mm, and the strength was evaluated according to the criteria shown below. ◎: Tensile strength of 40 MPa or more ○: Tensile strength of 30 MPa or more and less than 40 MPa △: Tensile strength of 20 MPa or more and less than 30 MPa ×: Tensile strength of less than 20 MPa

[0108] (Transparency of the cured product of the active energy ray-curable resin composition) A cured product was produced in the same manner as the test piece for the tensile test, and the transparency was visually evaluated as follows. ◎: Transparent ○: Slightly turbid △: Turbid ×: Separation

[0109] (Glass transition temperature (Tg) of the cured product of the active energy ray curable resin composition) A cured product was prepared in the same manner as the test piece for the tensile test, and the glass transition temperature (Tg) of the cured product was measured using a differential scanning calorimeter (DSC-60plus manufactured by Shimadzu Corporation).

[0110] (Heat resistance of the cured product of the active energy ray curable resin composition) Based on the measured glass transition temperature (Tg) of the cured product, the following evaluation of heat resistance was performed. ◎: Cured product Tg 80°C or higher ○: Cured product Tg 40°C or higher and less than 80°C ×: Cured product Tg less than 40°C

[0111] (Curing shrinkage resistance of the active energy ray curable resin composition) The curing shrinkage rate was determined from the density change before and after curing of the active energy ray curable resins (E) and (F) as shown in the following calculation formula (1) according to JIS K5600 2-4. Regarding the density before and after curing of the active energy ray curable resins (E) and (F), measurements were made in accordance with JIS K7112 using an electronic specific gravity meter (MDS-300 manufactured by Alpha Mirage Co., Ltd.). The cured product was prepared in the same manner as the test piece for the tensile test. The following evaluation was performed based on the obtained curing shrinkage rate. (Curing shrinkage rate) = (Ds - Dl) / Dl × 100 ··· Calculation formula (1) (In the formula, Ds is the density after curing of (E) and (F), and Dl is the density before curing of (E) and (F).) ◎: 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

[0112] (Curability of the active energy ray curable resin composition) Hardness: A 100-μm-thick PET film (Cosmoshine A4100, polyester film, manufactured by Toyobo Co., Ltd.) was closely adhered to a horizontally placed glass plate with the easy-adhesion surface facing up. Using a bar coater No. 30, the active energy ray-curable resin compositions (E) or (F) obtained in each example and comparative example were each applied. Then, a 50-μm-thick lightly peelable PET film (E7002, polyester film, manufactured by Toyobo Co., Ltd.) was overlaid on top, and ultraviolet rays were irradiated at a predetermined integrated light quantity (device: tabletop batch-type UV-LED curing device MUVBA-0.3×0.3×0.5, manufactured by ITEC SYSTEMS Co., Ltd., wavelength 405 nm, illuminance (UV-V) 50 mW / cm 2 ) to cure the resin composition. After that, the peelable PET film was removed to obtain test pieces of the cured products for evaluating the curability of the examples and comparative examples. The tack on the surface of the obtained cured product was evaluated, and the following evaluation was performed at the integrated light quantity at which the tack disappeared. ◎: Integrated light quantity less than 200 mJ / cm 2 and the tack disappears ○: Integrated light quantity 200 mJ / cm 2 or more and less than 500 mJ / cm 2 and the tack disappears ×: Integrated light quantity 500 mJ / cm 2 or more and the tack disappears

[0113] (Sculpting accuracy of the cured product of the active energy ray-curable resin composition) A 75-μm-thick heavily peelable PET film (E7001, polyester film, manufactured by Toyobo Co., Ltd.) was closely adhered to a horizontally placed glass plate. A spacer with a thickness of 10 mm and an internal size of 10×10 mm was installed. After filling the inside of the spacer with 1 mm thickness of the active energy ray-curable resin compositions (E) or (F) obtained in each example and comparative example, the surface was smoothed by keeping it at 60°C for 30 seconds, and then ultraviolet rays were irradiated (device: inverter-type conveyor device ECS-4011GX, manufactured by Aigraphics Co., Ltd., metal halide lamp: M04-L41, manufactured by Aigraphics Co., Ltd., ultraviolet illuminance 200 mW / cm 2 , (E-1) to (E-15) and (F-1) and (F-2) have an integrated light quantity of 1,000 mJ / cm 2, (F-3) had an integrated light quantity of 5,000 mJ / cm 2 ) and cured the resin composition. Thereafter, the active energy ray-curable resin compositions (E) or (F) were each filled to a thickness of 1 mm and cured a total of 10 times to obtain cured products of 10×10×10 mm. The height of the obtained cured products was measured. Also, the side surfaces of the obtained cured products were visually observed. Combining these results, the molding accuracy was evaluated according to the following criteria. ◎: The height is less than 10 mm ± 0.1 mm and there are no irregularities on the side surface. ○: The height is 10 mm ± 0.1 mm or more and less than ± 0.2 mm, or there are very slight irregularities on the side surface. △: The height is 10 mm ± 0.2 mm or more and less than ± 0.3 mm, or there are slight irregularities on the side surface. ×: The height is 10 mm ± 0.3 mm or more, or there are obvious irregularities on the side surface.

[0114] (Impact resistance) A 75-μm-thick heavy release PET film (manufactured by Toyobo Co., Ltd., polyester film E7001) was adhered to a horizontally installed glass plate, a spacer with a thickness of 4 mm and an internal space of 10×80 mm was installed, and the active energy ray-curable resin compositions (E) or (F) obtained in each of the examples and comparative examples with a thickness of 4 mm were filled inside the spacer. Thereafter, a 50-μm-thick light release PET film (manufactured by Toyobo Co., Ltd., polyester film E7002) was further placed on top, and ultraviolet rays were irradiated from both sides (device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics Co., Ltd., metal halide lamp: M04-L41 manufactured by Eye Graphics Co., Ltd., ultraviolet illuminance 200 mW / cm 2 , (E-1) to (E-15) and (F-1) had an integrated light quantity of 1,000 mJ / cm 2 , (F-2) had an integrated light quantity of 5,000 mJ / cm 2 ) and cured the resin composition. Thereafter, the release PET films on both sides were removed, and ultraviolet rays were further irradiated at a predetermined integrated light quantity (device: Desktop batch type UV-LED curing device MUVBA-0.3×0.3×0.5 manufactured by Aitech System Co., Ltd., wavelength 405 nm, illuminance (UV-V) 50 mW / cm 2, (E-1) to (E-15) and (F-1) have an integrated light quantity of 5,000 mJ / cm 2 , (F-2) has an integrated light quantity of 15,000 mJ / cm 2 ), the post-curing of the resin composition was carried out to completely cure it. Then, using the test pieces obtained by curing the active energy ray curable resin composition (E) or (F), the Izod impact strength (with notch) was measured according to JIS K-7110, and the following evaluation was conducted for the impact resistance. In addition, an Izod Charpy impact tester "Model No. 195-R" manufactured by Yasuda Seiki Seisakusho Co., Ltd. was used. ◎: 40 J / m or more ○: 30 J / m or more and less than 40 J / m △: 20 J / m or more and less than 30 J / m ×: less than 20 J / m

[0115]

Table 3

[0116]

Table 4

[0117] As is clear from the results in Table 4, the active energy ray curable resin compositions (E-1) to (E-15) of the present invention shown in Examples 1 to 15 have a viscosity in a range suitable for three-dimensional optical shaping by using a (meth)acrylic polymer (A) having an alicyclic structure and / or an aromatic ring structure and an unsaturated compound (B) in combination, are excellent in workability, can suppress shrinkage during curing, and the cured products obtained by curing show good heat resistance. In particular, (E-8) and (E-9) can ensure an appropriate viscosity as ink for inkjet because their viscosities are 100 mPa·s or less, and (E-6) shows a viscosity in a range suitable for the material extrusion deposition method using an active energy ray curable ink of 10,000 mPa·s or more. It was also shown that the balance of tensile strength, elongation at break, and Young's modulus is good, excellent toughness is exhibited, and a cured product with excellent shaping accuracy can be obtained while maintaining heat resistance and suppressing the curing shrinkage rate.

[0118] On the other hand, the active energy ray-curable resin composition (F-1) shown in Comparative Example 1 is a composition containing a copolymer of N-vinylpyrrolidone (NVP) and vinyl acetate (VAc) and an unsaturated compound (B) instead of the (meth)acrylic polymer (A). Since the copolymer does not have an alicyclic structure or an aromatic ring structure unlike the (meth)acrylic polymer (A), it cannot suppress the curing shrinkage of the composition, and a cured product with good shaping accuracy could not be obtained. Further, the copolymer separated during curing, and a transparent and uniform cured product could not be obtained. As a result, the cured product was inferior in strength and impact resistance. Furthermore, the active energy ray-curable resin composition (F-2) shown in Comparative Example 2 is a composition containing a (meth)acrylic polymer (A) having a curable allyl group in the side chain and not containing an unsaturated compound (B). Since the composition (F-2) does not contain an unsaturated compound (B), the compatibility between the (meth)acrylic polymer (A-15) and the photoinitiator (C-1) is poor, and the curability is inferior. In addition, the effect of suppressing curing shrinkage is also inferior, and a cured product with good shaping accuracy could not be obtained. Also, each property (heat resistance, transparency, strength, and impact resistance) of the cured product was inferior.

Industrial Applicability

[0119] As described above, the active energy ray-curable resin composition of the present invention can suppress curing shrinkage before and after curing by irradiation with active energy rays, and the cured product obtained by curing this composition exhibits excellent transparency, heat resistance, sufficient strength, and impact resistance. Therefore, it can be suitably used as a coating material, a sealing material, a material for elastomers, an adhesive, a material for sealing, a dental hygiene material, an optical material, a stereolithography material, a material for reinforced plastics, a resin composition for three-dimensional stereolithography, and the like. In addition, since the active energy ray-curable resin composition of the present invention has a viscosity in a range suitable for three-dimensional stereolithography and excellent workability, it can be suitably used as a resin composition for three-dimensional stereolithography. Furthermore, since the active energy ray-curable resin composition of the present invention keeps its curing shrinkage rate at a low level and improves the shaping accuracy of the cured product, when used as an active energy ray-curable resin composition for a model material and an active energy ray-curable ink of a 3D printer using a vat photopolymerization method, a material jetting method, and a material extrusion deposition method using a photocurable resin composition, it can provide a three-dimensional stereolithographic product having excellent heat resistance, transparency, sufficient strength, and impact resistance for practical use.

Claims

1. An active energy ray-curable resin composition containing an (meth)acrylic polymer (A) having an aliphatic ring structure and / or an aromatic ring structure and an unsaturated compound (B), wherein the unsaturated compound (B) contains a polyfunctional compound (b), and the polyfunctional compound (b) has a skeleton derived from a polyol and two or more polymerizable functional groups in the molecule, and at least one polymerizable functional group is a polyfunctional compound (b1) that is a methacrylamide group or an acrylamide group. An active energy ray-curable resin composition.

2. The unsaturated compound (B) contains a monofunctional monomer (a), and the monofunctional monomer (a) is any one or more monomers selected from the group consisting of the following (a1) and (a2). The active energy ray-curable resin composition according to claim 1. (a1): One or more monofunctional monomers selected from methacrylate-based monofunctional monomers, acrylate-based monofunctional monomers, methacrylamide-based monofunctional monomers, and acrylamide-based monofunctional monomers having an aliphatic ring structure and / or an aromatic ring structure; (a2): One or more monofunctional monomers selected from methacrylamide-based monofunctional monomers and acrylamide-based monofunctional monomers having no aliphatic ring structure and / or aromatic ring structure

3. The (meth)acrylic polymer (A) is a polymer containing a structural unit derived from one or more monofunctional monomers (a1) selected from one or more monofunctional monomers selected from methacrylate-based monofunctional monomers, acrylate-based monofunctional monomers, methacrylamide-based monofunctional monomers, and acrylamide-based monofunctional monomers having an alicyclic structure and / or an aromatic ring structure. The active energy ray-curable resin composition according to claim 1 or 2.

4. The number average molecular weight (Mn) of the (meth)acrylic polymer (A) is 2,000 to 100,000. The active energy ray-curable resin composition according to claim 1 or 3.

5. Based on the total mass of the active energy ray-curable resin composition, the content of the (meth)acrylic polymer (A) is 0.1 to 50.0% by mass, and the content of the unsaturated compound (B) is 50.0 to 99.9% by mass. The active energy ray-curable resin composition according to any one of claims 1 to 4.

6. With respect to the total mass of the active energy ray-curable resin composition, the content of the monofunctional monomer (a) as the unsaturated compound (B) is 20.0 to 70.0% by mass, and the content of the polyfunctional compound (b) is 1.0 to 75.0% by mass. The active energy ray-curable resin composition according to any one of claims 1 to 5.

7. The polyfunctional compound (b) includes a polyfunctional compound (b2) having two or more polymerizable functional groups in the molecule and not having a skeleton derived from polyol and an isocyanurate ring. The active energy ray-curable resin composition according to any one of claims 1 to 6.

8. The polyfunctional compound (b) includes a polyfunctional compound (b3) having two or more polymerizable functional groups in the molecule, not having a skeleton derived from polyol, and having an isocyanurate ring. The active energy ray-curable resin composition according to any one of claims 1 to 7.

9. The polymerizable functional group is one or more functional groups selected from a methacrylate group, an acrylate group, a methacrylamide group, and an acrylamide group. The active energy ray-curable resin composition according to any one of claims 1 to 8.

10. The skeleton derived from polyol is one or two or more skeletons selected from an ether skeleton, an ester skeleton, a carbonate skeleton, a silicone skeleton, an olefin skeleton, and an acrylic skeleton. The active energy ray-curable resin composition according to any one of claims 1 to 9.

11. Characterized by being used for three-dimensional optical shaping. The active energy ray-curable resin composition according to any one of claims 1 to 10.

12. Characterized by being used for three-dimensional optical shaping by the liquid tank light polymerization method. The active energy ray-curable resin composition according to any one of claims 1 to 11.

13. Characterized by being used for three-dimensional optical shaping by the material jetting method. An active energy ray-curable ink comprising the active energy ray-curable resin composition according to any one of claims 1 to 11.

14. Characterized by being used for three-dimensional optical shaping by the material extrusion deposition method. An active energy ray-curable ink comprising the active energy ray-curable resin composition according to any one of claims 1 to 11.

15. A three-dimensional optical shaped article comprising a cured product of the active energy ray-curable resin composition according to any one of claims 1 to 11.

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