Active energy ray-curable resin composition and cured product thereof

Abstract

An object of the present application is to provide a curable resin composition which can maintain a low viscosity even when a high-viscosity component is contained, and which can exhibit properties corresponding to the use. The present application relates to a curable resin composition which is characterized by containing a cross-linkable compound (A) represented by the following general formula (1), an oligomer (B) having a viscosity of 1000 mPa-s or more at 25°C or a viscosity of 400 mPa-s or more at 60°C, and a polymerization initiator (C). (In the formula, Z represents an n-valent linking group. n is an integer of 2 or more.)

Description

TECHNICAL FIELD

[0001] The present application relates to a active energy ray-curable resin composition and a cured product thereof. More specifically, it relates to a active energy ray-curable resin composition capable of obtaining a cured product imparted with desired properties while maintaining low viscosity and a cured product thereof. BACKGROUND

[0002] A curable resin composition curable by heat or active energy rays can exhibit various properties depending on its composition, and is widely used in various applications such as paints, inks, adhesives, resists, various molding materials, and the like.

[0003] The above-mentioned curable resin composition contains a polymerizable compound having a polymerizable group curable by heat or active energy rays. As one of such polymerizable compounds, a crosslinkable compound having a plurality of (meth)acryloyl groups or alkylallyl ether groups or the like as a polymerizable group or a curable group is known. The above-mentioned crosslinkable compound has various polymerization mechanisms depending on the kind of functional groups it has, and is used in various fields by utilizing this property. For example, a crosslinkable compound having a (meth)acryloyl group as a polymerizable group is excellent in curing speed, internal curability, durability of chemical bonds formed, economy, and the like, and is widely used in various applications such as coating materials, adhesives, sealing materials, adhesives, paints, inks, resists, dental materials, lenses, molding materials, and the like.

[0004] As the above-mentioned crosslinkable compound, for example, a compound having an α-allyloxy methyl acryloyl group is described in Patent Literature 1. The crosslinkable compound described in Patent Literature 1 has both a radical polymerization mechanism inhibited by oxygen and an oxidation polymerization mechanism requiring oxygen, and can highly exhibit both curabilities, and is excellent in curing speed, internal curability, surface curability, and thin film curability.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent No. 5689628 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] In addition, various polymerizable compounds are combined to impart various properties to a cured product obtained by curing the curable resin composition. However, if a component having a high viscosity is used, the viscosity of the curable resin composition increases, and there is a problem in that handling properties and the like become difficult. Therefore, there is a problem in that the design range of the curable resin composition that can be used is limited. In recent years, higher performance in a wider range is required for curable resin compositions and cured products thereof that are used in various technical fields, and in response to this requirement, it is desirable to be able to freely design various curable resin compositions without being limited by the viscosity and the like.

[0010] The present application was made in view of the above-described circumstances, and aims to provide a curable resin composition that can maintain a low viscosity even when a high-viscosity component is included, and that can exhibit properties corresponding to the use.

[0011] Means for solving the problem

[0012] The present inventors have conducted various studies on curable resin compositions, and as a result, have found that by producing a curable resin composition that includes a cross-linkable compound having a specific structure, a high-viscosity component, and a polymerization initiator, it is possible to provide a cured product having heat decomposition resistance, hardness, adhesion, weather resistance, or the like according to the use while maintaining a low viscosity, and thus the present application has been completed.

[0013] That is, the present application relates to a curable resin composition for active energy rays, characterized by including a cross-linkable compound (A) represented by the following general formula (1), an oligomer (B) having a viscosity of 1000 mPa-s or more at 25°C or a viscosity of 400 mPa-s or more at 60°C, and a polymerization initiator (C).

[0014] [Chemical Formula 1]

[0015]

[0016] (In the formula, Z represents an n-valent linking group. n is an integer of 2 or more.)

[0017] In the above-described curable resin composition for active energy rays, the oligomer (B) preferably has a viscosity of 1000 mPa-s or more at 25°C and a viscosity of 400 mPa-s or more at 60°C.

[0018] The oligomer (B) is preferably at least one selected from the group consisting of a polyester (meth)acrylate, an epoxy (meth)acrylate, a urethane (meth)acrylate, and a polyacrylic (meth)acrylate.

[0019] The above-described curable resin composition for active energy rays preferably further includes a reactive diluent.

[0020] The ratio of the crosslinkable compound (A) to the oligomer (B) [(A) / (B)] in the above-mentioned active energy ray-curable resin composition is preferably 1 / 100 to 100 / 1 in terms of mass ratio.

[0021] The above-mentioned active energy ray-curable resin composition preferably further contains a compound represented by the following general formula (3).

[0022] [Chemical 2]

[0023]

[0024] The above-mentioned active energy ray-curable resin composition is preferably a resin composition for three-dimensional modeling.

[0025] The present application also relates to the use of the above-mentioned active energy ray-curable resin composition in the production of a material for three-dimensional modeling.

[0026] The present application also relates to a cured product of the above-mentioned active energy ray-curable resin composition.

[0027] Effects of the Invention

[0028] According to the present application, it is possible to provide an active energy ray-curable resin composition that can impart and balance viscosity, which tends to be in a trade-off relationship, and desired properties. The active energy ray-curable resin composition of the present application can provide a cured product having desired properties such as heat decomposition resistance, hardness, adhesion, toughness, or weather resistance, depending on the use. The active energy ray-curable resin composition of the present application and the cured product thereof can be appropriately used as industrial materials in a wide range of fields such as coating agents, inks, sealing materials, paints, adhesives, molding materials, and the like. DETAILED DESCRIPTION

[0029] The present application will be described in detail below.

[0030] Note that a mode in which two or more of the above-described preferred modes of the present application are combined is also a preferred mode of the present application.

[0031] In addition, in the present specification, "(meth)acrylate" means "acrylate and / or methacrylate", and "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid".

[0032] 1. Active energy ray-curable resin composition

[0033] The present invention relates to an active energy radiation-curable resin composition, characterized in that it comprises a crosslinking compound (A) represented by the following general formula (1), an oligomer (B) having a viscosity of 1000 mPa·s or more at 25°C or a viscosity of 400 mPa·s or more at 60°C, and a polymerization initiator (C).

[0034] [Chemistry 3]

[0035]

[0036] (In the formula, Z represents an n-valent linker. n is an integer greater than or equal to 2.)

[0037] The reason why the active energy ray curable resin composition of the present invention can maintain low viscosity while imparting the desired physical properties is that the crosslinking compound has an ether structure, and therefore is a component with relatively low viscosity. Even when mixed with high viscosity components, the overall viscosity of the curable resin composition can be kept low. In addition, the polymerizable groups of the crosslinking compound form ring structures and ethylene chains through curing, thus exhibiting properties such as hardness, resistance to thermal decomposition, toughness, adhesion, and weather resistance.

[0038] The components contained in the active energy ray curable resin composition of the present invention will now be described.

[0039] (A) Cross-linked compounds

[0040] The active energy ray curable resin composition of the present invention (hereinafter also referred to as "the curable resin composition of the present invention") comprises the following general formula (1):

[0041] [Chemistry 4]

[0042]

[0043] (In the formula, Z represents an n-valent linking group. n is an integer greater than or equal to 2.) This refers to the cross-linked compound.

[0044] In the above general formula (1), n ​​is not particularly limited as long as it is an integer of 2 or more. From the perspective of ease of synthesis and storage stability, it is preferably 2 to 100, more preferably 2 to 50. When the curable resin composition of the present invention is used for applications requiring low viscosity, such as reactive diluents, the above-mentioned n is further preferably 2 to 10, and most preferably 2 to 6. In addition, when the curable resin composition of the present invention is used for applications requiring film-forming properties, such as adhesive resins for coatings or inks, the above-mentioned n is further preferably 5 to 50, and most preferably 10 to 50.

[0045] In the above general formula (1), Z is not particularly limited as long as it is a linking group that can form two or more covalent bonds with the carbonyl group of α-allyloxymethacryloyl (hereinafter also referred to as "AMA group"), that is, a linking group with a covalent bond of 2 or more. It can be a linking group with a bond of 2 or more by only 1 atom, or it can be a linking group with a bond of 2 or more by 2 or more atoms. From the perspective of ease of synthesis and chemical stability, it is preferred to be a linking group with a bond of 2 or more by 2 or more atoms.

[0046] It should be noted that the AMA group mentioned above refers to the group shown in the following general formula (2).

[0047] [Chemistry 5]

[0048]

[0049] When Z is a 2-valent or higher linking group that is bonded by only one atom, there is no particular limitation on Z. Linking groups that include the following atoms can be cited: atoms of group 16 of the periodic table such as oxygen atom and sulfur atom; atoms of group 15 of the periodic table such as nitrogen atom and phosphorus atom; atoms of group 14 of the periodic table such as carbon atom, silicon atom and germanium atom. Specifically, the structure shown in the following structural formula group (3) can be cited as an example.

[0050] [Chemistry 6]

[0051]

[0052] In the formula, R and R' represent hydrogen atoms or organic groups, and R and R' can be the same or different. The organic group can be any monovalent organic group that can bond with the above atoms, preferably a hydrocarbon group with 1 to 30 carbon atoms, with or without substituents.

[0053] When Z is a linking group with a valence of two or more atoms bonded together, Z can be either a low-molecular-weight structure or a high-molecular-weight structure. The terms "low-molecular-weight structure" and "low-molecular-weight skeleton" (described later) generally refer to structures and skeletons that do not have repeating units composed of monomer units. Conversely, the terms "high-molecular-weight structure" and "high-molecular-weight skeleton" (described later) generally refer to structures and skeletons that have repeating units composed of monomer units.

[0054] The aforementioned Z at least includes a skeletal portion Q, and sometimes also includes a divalent linking group X that bonds an AMA group to Q, a divalent or higher linking group Y that bonds two or more skeletal portions Q, and a monovalent substituent W that is directly bonded to the skeletal portion Q. In the n-valent linking group Z, the n hydrogen atoms in the skeletal portion Q are sometimes replaced by an AMA group or X, and the remaining hydrogen atoms are replaced by Y and / or W.

[0055] For example, a crosslinking compound having two AMA groups can be represented as shown in the following structural formula group (4).

[0056] It should be noted that, for the sake of simplicity, the AMA base is represented by A in the formula. In addition, the structural examples are only partial examples and are not limited to these.

[0057] [Chemistry 7]

[0058] (a) The case where Z consists only of Q

[0059] AQA AQ 1 -Q 2 -A

[0060] (b) The case where Z includes Q and X

[0061] AQXA AX 1 -QX 2 -A AX 1 -Q 1 -Q 2 -X 2 -A

[0062] (c) The case where Z includes Q and Y

[0063] AQ 1 -YQ 2 -A AQ 1 -YQ 2 -XA

[0064] AX 1 -Q 1 -γ-Q 2 -X 2 -A

[0065] (d) The case where Z includes Q and W

[0066]

[0067] In the formula, Q n X n Y n W n(n represents an integer greater than 1) represents the nth Q, X, Y, and W when there are n of each Q, X, Y, and W, which can be the same or different. Furthermore, in a crosslinked compound with two AMA groups, taking the case where Q is a cyclohexane skeleton, X is an oxygen atom, Y is a carbamate bond, and W is a fluorine atom as an example, the compounds shown in the following structural formula group (5) can be specifically cited. It should be noted that the compounds shown in structural formula group (5) are only some examples of this compound group, and not all examples are shown. As shown in structural formula group (5), there are also cases where two of the hydrogen atoms in the cyclohexane skeleton are replaced by AMA groups or X, and the remaining hydrogen atoms are replaced by Y and / or W.

[0068] [Chemistry 8]

[0069]

[0070] As described above, Z is composed of a skeletal portion Q, and sometimes also includes a divalent linking group X bonded to an AMA group, a divalent or higher linking group Y that bonds two or more skeletal portions Q, and a monovalent substituent W directly bonded to the skeletal portion Q. When Z is composed of two or more skeletal portions Q, Q can be directly bonded to each other without the linking group Y. Z can be composed of only Q, i.e., the AMA group can be directly bonded to Q, but considering ease of synthesis, availability of raw materials, and chemical stability, Z is preferably composed of at least Q and X, i.e., the AMA group is bonded to Q via X, and more preferably, the carbonyl group of the AMA group is bonded to X via a heteroatom. That is, Z is preferably an n-valent linking group bonded to the AMA group via a heteroatom. Y and W can be appropriately selected according to the synthetic method and the performance required in the intended use. Furthermore, Z can be composed of two or more types of Q, X, Y, and W.

[0071] Specific examples of Q, X, Y, and W are given below, but these are not the only examples. In the following examples of Q, the structures are shown in compound form. However, when these Qs become constituent elements of Z, the two or more hydrogen atoms in the structure of Q shown in compound form are replaced by atoms or groups of atoms bonded to Q (i.e., AMA groups or Q, X, Y, W). It should be noted that Q, X, Y, and W become constituent elements of Z, but Z is not limited to compounds capable of forming Q, X, Y, and W respectively. Examples of the structures of Z when structurally decomposed into Q, X, Y, and W, and the ways in which their structures are shown in compound form, are given below.

[0072] The aforementioned skeletal portion Q is acceptable as long as there are two or more atoms forming the skeletal structure and the AMA group and / or X can bond to the skeletal structure. If the structure of Q is shown in compound form, it represents a compound in which there are two or more atoms forming the skeletal structure and two or more hydrogen atoms (i.e., hydrogen atoms that can be substituted with AMA groups and / or X) are bonded to the atoms forming the skeletal structure. There is no particular limitation as long as the hydrogen atoms can be substituted with AMA groups and / or X to become the skeletal portion of Z. For example, the structure of the skeletal portion Q is shown in compound form as follows.

[0073] Examples include:

[0074] Saturated hydrocarbon structures such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and eicosane; hydrocarbon monoene structures such as ethylene, propylene, butene, pentene, hexene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecane, octadecene, nonadecanene, and eicosene; and hydrocarbon monoene structures such as propadiene, butadiene, pentadiene, hexadiene, nonadiene, decadiene, undecadiene, dodecadiene, and tridecadiene. Hydrocarbon diene structures such as alkene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, and icosae; hydrocarbon polyene structures such as heptadecene, heptadecene, octadecene, and octadecene; acetylene structures such as methylacetylene and hexadiyne; alicyclic structures such as cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, norbornane, norbornene, norbornadiene, cyclodecane, dicyclopentadiene, adamantane, cyclopentanone, cyclohexanone, cyclooctanone, and various compounds shown in the following chemical formula group (6);

[0075] [Chemistry 9]

[0076]

[0077] Benzene, naphthalene, anthracene, phenanthrene, tetraphenylene Aromatic hydrocarbon structures such as triphenylene, pyrene, perylene, biphenyl, and various compounds shown in the following chemical formula group (7);

[0078] [Chemistry 10]

[0079]

[0080] Ethylene oxide, acridine, oxadiazine, tetrahydrofuran, tetrahydropyran, dihydrofuran, dihydropyran, pyran, dioxane, pyrrolidine, piperidine, piperazine, morpholine, γ-lactone, δ-lactone, ε-caprolactone, γ-lactam, δ-lactam, ε-caprolactam, oxazoline, succinic anhydride, maleic anhydride, succinimide, maleimide, glutaric anhydride, glutarimide, and various compounds shown in the following chemical formula group (8) have heterocyclic structures;

[0081] [Chemistry 11]

[0082]

[0083] Pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, pyridine, pyridazine, pyrazine, benzofuran, indole, benzimidazole, benzoxazole, benzothiazole, quinoline, quinoxaline, acridine, pyrimidine, triazine, carbazole, phenothiazine, quinacridone, xanthones, cyanuric acid, phthalic anhydride, phthalimide, and various compounds shown in the following chemical formula group (9) have heteroaromatic structures;

[0084] [Chemistry 12]

[0085]

[0086] Low molecular weight skeleton.

[0087] Alternatively, examples could be given:

[0088] The polyethylene skeleton shown in formula (10) is obtained by (co)polymerization of noncyclic olefinic compounds such as ethylene, propylene, styrene, methyl acrylate, methyl methacrylate, and vinyl acetate.

[0089] [Chemistry 13]

[0090]

[0091] The following structural group (11) shows various main chain ring structure skeletons obtained by (co)polymerization of unsaturated cyclic compounds represented by cyclic alkenes such as norbornene, unsaturated anhydrides such as maleic anhydride, and maleimides such as phenylmaleimide.

[0092] [Chemistry 14]

[0093]

[0094] Polyethylene-backbone cyclic copolymer backbones obtained through copolymerization of the above-mentioned acyclic olefinic compounds and unsaturated cyclic compounds; polyether backbones with ether bonds in the main chain obtained through dehydration condensation (co)polymerization of glycols or ring-opening (co)polymerization of epoxides such as ethylene oxide, propylene oxide, and tetrahydrofuran; polyester backbones with ester bonds in the main chain obtained through dehydration condensation (co)polymerization of dicarboxylic acids and glycols or ring-opening (co)polymerization of cyclic lactones; polyamide backbones with amide bonds in the main chain obtained through dehydration condensation (co)polymerization of dicarboxylic acids and diamines or ring-opening (co)polymerization of cyclic lactams; polysiloxane backbones with siloxane bonds in the main chain obtained through dealcoholization condensation (co)polymerization of dialkyl diekoxysilanes or ring-opening (co)polymerization of cyclic siloxanes; polyurethane backbones with urethane structures in the main chain obtained through the reaction of diisocyanates and glycols; and other polymer backbones.

[0095] As the aforementioned backbone component Q, it can be appropriately selected based on the intended use of the crosslinking compound. For applications requiring low viscosity, such as reactive diluents, a low-molecular-weight backbone is preferred; for applications requiring film-forming properties, such as binder resins in coatings or resist materials, a high-molecular-weight backbone is preferred. Different backbones can be used depending on the application. Among the low-molecular-weight backbones, considering factors such as raw material availability and chemical stability, at least one structure selected from the group consisting of saturated hydrocarbon structures, alicyclic structures, and aromatic hydrocarbon structures is preferred. Among the high-molecular-weight backbones, considering factors such as ease of synthesis and chemical stability, at least one backbone selected from the group consisting of polyethylene backbones, polyethylene-main-chain ring copolymer backbones, and polyether backbones is preferred.

[0096] The above X is not particularly limited as long as it is a divalent linking group. Examples of bonding shown in the following structural group (12) are given (as an example, denoted as AXQ, where the atoms or groups of X are shown below).

[0097] [Chemistry 15]

[0098]

[0099] In the formula, R and R' may be the same or different, representing a hydrogen atom, an alkyl group with or without substituents having 1 to 30 carbon atoms, or an aryl group with or without substituents having 1 to 30 carbon atoms.

[0100] Among these, considering ease of synthesis and chemical stability, X is preferably an oxygen atom, a sulfur atom, a monosubstituted nitrogen atom, or a disubstituted carbon atom, with oxygen atom or a monosubstituted nitrogen atom being more preferred. That is, the bond in AX is more preferably an ester bond or an amide bond. It should be noted that when there are more than two X atoms in Z, X can be one type or more types.

[0101] There are no particular limitations on the above Y as long as it is a linking group with a valence of 2 or higher. Examples of bonding shown in the following structural formula group (13) are given.

[0102] [Chemistry 16]

[0103]

[0104] In the formula, R and R' may be the same or different, representing a hydrogen atom, an alkyl group with or without substituents having 1 to 30 carbon atoms, or an aryl group with or without substituents having 1 to 30 carbon atoms.

[0105] Among these, considering ease of synthesis and chemical stability, ether bonds, thioether bonds, bonds formed by carbon atoms in the 2-4 valence phases, ketone bonds, ester bonds, amide bonds, carbamate bonds, or silicate bonds are preferred, especially ether bonds, bonds formed by carbon atoms in the 2-4 valence phases, ester bonds, amide bonds, or carbamate bonds. It should be noted that when Z contains two or more Y atoms, Y can be one type or two or more types.

[0106] As for the aforementioned W, there are no particular restrictions as long as it is a monovalent substituent that can bond with the Q portion of the skeleton.

[0107] If we exemplify the above-mentioned W, we can list: atoms of Group 17 of the periodic table such as fluorine, chlorine, bromine, and iodine; saturated hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, sec-octyl, tert-octyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, hexadecyl, heptadecanyl, stearyl, nonadecanyl, eicosyl, waxyl, and beeswaxyl; unsaturated hydrocarbon groups such as vinyl, allyl, methallyl, crotonyl, and propargyl; cyclopentyl, cyclohexyl, 4... -Alicyclic hydrocarbon groups such as methylcyclohexyl, 4-tert-butylcyclohexyl, tricyclodecyl, isoborneol, adamantyl, dicyclopentadienyl, etc.; aromatic hydrocarbon groups such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tert-butylphenyl, naphthyl, anthracene, etc.; alkoxy groups such as hydroxyl, methoxy, ethoxy, propoxy, butoxy, phenoxy, naphthoxy, etc.; amino groups such as amino, methylamino, dimethylamino, methylethylamino, methylphenylamino, etc.; (meth)acryloyl, mercapto, thioalkoxy, cyano, nitro, isocyanate, cyanothio, quaternary ammonium salts of amino, carboxyl or their salts, sulfonic acid or their salts, sulfinic acid or their salts, phosphate or their salts, etc. These W groups can be used separately according to their intended use.

[0108] As the aforementioned crosslinking compound, compounds represented by the following general formulas (z1) to (z3) are preferred.

[0109] AOR 1 -OA (z1)

[0110] (where R is in the formula) 1 Represents divalent hydrocarbon groups with 1 to 30 carbon atoms, -(R 2 -O) a -R 3 -or-(R) 2 -O) a -R 3 -(OR 4 ) b -. R 2 and R 4 The same or different indicates a divalent, straight-chain or branched saturated hydrocarbon group with 1 to 10 carbon atoms. R 3 This represents a divalent hydrocarbon group with 1 to 20 carbon atoms. 'a' is an integer from 1 to 20. 'b' is an integer from 1 to 20. 'A' represents the AMA group.

[0111] [A-(OR 5 ) c ] m -R 6 -[(R 7 -O) d -A] n (z2)

[0112] (where R is in the formula) 5 and R 7 The same or different indicates a divalent, straight-chain or branched saturated hydrocarbon group with 1 to 10 carbon atoms. R 6 express

[0113] [Chemistry 17]

[0114]

[0115] R 8 and R 9 "Same or different" indicates a straight-chain or branched saturated hydrocarbon group with 1 to 20 carbon atoms, with or without substituents. "c" represents an integer from 1 to 20. "d" represents an integer from 1 to 20. "m" and "n" can be the same or different, representing integers from 1 to 3. "A" represents an AMA group.

[0116] R 10 -[(R 11 -O) e -A]3 (z3)

[0117] (where R is in the formula) 10 Represents a trivalent heterocyclic or cyclic hydrocarbon group. R 11This represents a divalent, straight-chain or branched saturated hydrocarbon group with 1 to 10 carbon atoms. e is an integer from 1 to 20. A represents the AMA group.

[0118] In the above general formula (z1), R 1 Preferably, it is a divalent hydrocarbon group with 1 to 20 carbon atoms, and more preferably a divalent hydrocarbon group with 1 to 15 carbon atoms.

[0119] R 2 Preferably, it is a divalent straight-chain or branched saturated hydrocarbon group with 1 to 5 carbon atoms, and more preferably, it is a divalent straight-chain or branched saturated hydrocarbon group with 1 to 4 carbon atoms.

[0120] R 3 Preferably, it is a divalent hydrocarbon group with 1 to 15 carbon atoms, and more preferably a divalent hydrocarbon group with 1 to 10 carbon atoms.

[0121] R 4 Preferably, it is a divalent straight-chain or branched saturated hydrocarbon group with 1 to 5 carbon atoms, and more preferably, it is a divalent straight-chain or branched saturated hydrocarbon group with 1 to 4 carbon atoms.

[0122] In the above general formula (z1), the divalent hydrocarbon group can be any divalent straight-chain, branched, or cyclic saturated or unsaturated hydrocarbon group, such as alkylene, arylene, or divalent hydrocarbon groups having aromatic or alicyclic structures. Examples of alicyclic structures include cyclohexane skeletons, adamantane skeletons, and norbornene skeletons.

[0123] In the above general formula (z1), examples of the divalent straight-chain or branched saturated hydrocarbon groups include straight-chain alkylene groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, and heptylene, and branched alkylene groups such as -C(CH3)2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)(CH2CH3)-, and -CH2-CH(CH3)-.

[0124] In the above general formula (z1), a is preferably an integer from 1 to 10, and more preferably an integer from 1 to 5.

[0125] b is preferably an integer from 1 to 10, and more preferably an integer from 1 to 5.

[0126] In the above general formula (z2), R 5 and R 7 Whether the groups are the same or different, the preferred group is a divalent straight-chain or branched saturated hydrocarbon group with 1 to 5 carbon atoms, and more preferably a divalent straight-chain or branched saturated hydrocarbon group with 1 to 4 carbon atoms.

[0127] As the divalent straight-chain or branched saturated hydrocarbon group mentioned above, the same group as the divalent straight-chain or branched saturated hydrocarbon group in the above general formula (z1) can be cited.

[0128] R 8 and R 9 Whether the groups are the same or different, the preferred group is a monovalent straight-chain or branched saturated hydrocarbon group having or not having substituents, with 1 to 15 carbon atoms, and more preferably a monovalent straight-chain or branched saturated hydrocarbon group having 1 to 10 carbon atoms.

[0129] In the above general formula (z2), examples of the monovalent chain or branched saturated hydrocarbon groups include, for example, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpropyl, etc. Alkyl groups, such as 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, etc., are straight-chain or branched alkyl groups.

[0130] Examples of substituents mentioned above include hydroxyl, alkyl, and alkoxy groups.

[0131] In the above general formula (z2), c is preferably an integer from 1 to 10, and more preferably an integer from 1 to 5.

[0132] d is preferably an integer from 1 to 10, and more preferably an integer from 1 to 5.

[0133] m and n may be the same or different, representing integers from 1 to 3, but preferably m+n=3 to 6.

[0134] In the above general formula (z3), R 10 Represents a trivalent heterocyclic or cyclic hydrocarbon group. R 10 The number of carbon atoms is preferably 3 to 15, more preferably 3 to 10.

[0135] Examples of trivalent heterocyclic or cyclic hydrocarbon groups include, for instance, trivalent groups having alicyclic, aromatic, heterocyclic, or heteroaromatic structures, or groups having an isocyanuric acid skeleton. Among these, groups having an isocyanuric acid skeleton are preferred.

[0136] R 11Preferably, it is a divalent straight-chain or branched saturated hydrocarbon group with 1 to 10 carbon atoms, more preferably a divalent straight-chain or branched saturated hydrocarbon group with 1 to 5 carbon atoms.

[0137] As the divalent straight-chain or branched saturated hydrocarbon group mentioned above, the same group as the divalent straight-chain or branched saturated hydrocarbon group in the above general formula (z1) can be cited.

[0138] e is preferably an integer from 1 to 10, and more preferably an integer from 1 to 5.

[0139] As a specific example of the aforementioned crosslinking compound, the following examples are preferred.

[0140] [Chemistry 18]

[0141]

[0142] [Chemistry 19]

[0143]

[0144] As a method for manufacturing the aforementioned crosslinkable compound, any known method can be used without particular restriction as long as the aforementioned crosslinkable compound can be obtained. For example, the method for manufacturing the crosslinkable compound described in Japanese Patent No. 5689628 can be cited.

[0145] The curable resin composition of the present invention may contain only one of the above-mentioned crosslinking compounds, or it may contain two or more of the above-mentioned crosslinking compounds.

[0146] The content of the crosslinking compound in the curable resin composition of the present invention can be appropriately designed according to the purpose and use of the curable resin composition. It is preferably 0.05% to 99% by mass, more preferably 0.1% or more by mass, and even more preferably 0.5% or more by mass, relative to 100% by mass of the solid content of the curable resin composition. Furthermore, the content of the crosslinking compound is more preferably 95% or less by mass, and even more preferably 90% or less by mass, relative to 100% by mass of the solid content of the curable resin composition.

[0147] It should be noted that the solid component refers to the total amount of the components that form a cured product in the above-mentioned curable resin composition (excluding solvents, etc., that evaporate during the formation of the cured product).

[0148] When the curable resin composition of the present invention is used as a resin composition for three-dimensional modeling, the content of the crosslinking compound is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 10% to 35% by mass relative to 100% by mass of the solid content of the curable resin composition.

[0149] (B) Oligomers

[0150] The active energy ray-curable resin composition of the present invention further includes oligomers with a viscosity of 1000 mPa·s or higher at 25°C or 400 mPa·s or higher at 60°C. Even if the curable resin composition of the present invention also includes the aforementioned oligomers with relatively high viscosity, a low-viscosity resin composition can be prepared.

[0151] The viscosity of the aforementioned oligomer at 25°C is preferably 1100 mPa·s or higher, more preferably 1200 mPa·s or higher. There is no particular limitation on the upper limit of the viscosity of the aforementioned oligomer at 25°C, but from a processing perspective, it is preferably 6,000,000 mPa·s or lower.

[0152] Furthermore, the viscosity of the aforementioned oligomer at 60°C is preferably 420 mPa·s or higher, more preferably 450 mPa·s or higher. There is no particular limitation on the upper limit of the viscosity of the aforementioned oligomer at 60°C, but from a processing perspective, it is preferably 200,000 mPa·s or lower.

[0153] The oligomers described above are more preferably those whose viscosity at 25°C meets the above-mentioned range and whose viscosity at 60°C meets the above-mentioned range.

[0154] That is, the above-mentioned oligomers are further preferably 1000 mPa·s or more at 25°C and 400 mPa·s or more at 60°C, and particularly preferably 1100 mPa·s or more at 25°C and 420 mPa·s or more at 60°C.

[0155] In this invention, the viscosity is a value measured at a specified temperature using a viscometer such as a cone-plate viscometer (TV-20L, manufactured by Toki Sangyo Co., Ltd.).

[0156] As for the aforementioned oligomers, there is no particular limitation as long as they have the aforementioned viscosity. Examples of preferred oligomers include polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyacrylate (meth)acrylates, dendritic polymers (hyperbranched polymers), polybutadiene (meth)acrylates, silicone (meth)acrylates, and amino resin (meth)acrylates. Only one type may be used, or two or more may be used in combination. More preferably, the oligomers include at least one selected from the group consisting of polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, and polyacrylate (meth)acrylates.

[0157] Examples of the aforementioned polyester (meth)acrylates include (meth)acrylated derivatives of polyester polyols formed from polyols and polyacids. This compound can be obtained, for example, by esterification of the hydroxyl groups at the ends or in the polyester chain of a polyester obtained by polycondensing polyacids and polyols in the main chain backbone with (meth)acrylates such as (meth)acrylic acid that have one or more carboxyl groups within the molecule.

[0158] Examples of the aforementioned polyacids include: aliphatic polyacids such as oxalic acid, succinic acid, malonic acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, itaconic acid, succinic anhydride, and maleic anhydride; alicyclic polyacids such as dimer acid, cyclohexanedicarboxylic acid, and tetrahydrophthalic anhydride; and aromatic polyacids such as phthalic acid, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, trimellitic acid, and pyromellitic acid.

[0159] Examples of polyols mentioned above include glycols, hexanediol, diethylene glycol, tripropylene glycol, cyclohexanediol, and other polyols.

[0160] Specific examples of the aforementioned polyester (meth)acrylates include Aronix M-7100, Aronix M-8560 (manufactured by Toa Synthetic Co., Ltd.), and EBECRYL884 (manufactured by Daicel-Allnex Co., Ltd.).

[0161] Examples of the aforementioned epoxy (meth)acrylates include the products of addition reactions between compounds containing an ethylene oxide ring and carboxyl-containing (meth)acrylates.

[0162] Examples of compounds containing an ethylene oxide ring include aromatic epoxides such as bisphenol-type epoxides, aliphatic epoxides such as diglycidyl ethers of diols with 2 to 20 carbon atoms, and alicyclic epoxides.

[0163] Examples of carboxyl-containing (meth)acrylates include (meth)acrylic acid, β-carboxyethyl (meth)acrylate, mono-2-(2-acryloyloxy)hydroxyethanol succinic acid, mono-2-(2-methacryloyloxy)hydroxyethanol succinic acid, (meth)acrylic acid dimer, and (meth)acrylic acid caprolactam modified products.

[0164] Specific examples of the aforementioned epoxy (meth)acrylates include bisphenol type epoxy acrylates, phenolic varnish type epoxy acrylates, aliphatic type epoxy acrylates, and glycidyl ester type acrylates.

[0165] Examples of the above-mentioned urethane (meth)acrylates include the products of addition reactions of organic isocyanates with hydroxyl-containing (meth)acrylates and polyols.

[0166] Examples of the aforementioned organic isocyanates include: aliphatic isocyanates such as succinate, glutaraldehyde, and hexamethylene diisocyanate; alicyclic isocyanates such as cyclohexyl isocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate; and aromatic isocyanates such as toluene diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate.

[0167] Examples of hydroxyl-containing (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-hydroxypropyl (meth)acrylate.

[0168] Examples of the aforementioned polyols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, pentylene glycol, and butanediol.

[0169] Specific examples of the aforementioned urethane (meth)acrylates include, for example, EBECRYL230 (manufactured by Daicel-Allnex Co., Ltd.), CN929, CN964 (manufactured by Sartomer Co., Ltd.), and Ziguang (registered trademark) UV-1700B, Ziguang UV-3000B, Ziguang UV-7000B, and Ziguang UV-7650B (manufactured by Mitsubishi Chemical Corporation).

[0170] Examples of the aforementioned polyacrylate (meth)acrylates include polymers obtained by suspending acryloyl groups on a copolymer of acrylic monomers or vinyl monomers.

[0171] Specific examples of the aforementioned polyacrylates include substances formed by adding (meth)acrylic acid to a polymer obtained by polymerizing (meth)acrylate with an epoxy group-containing (meth)acrylate, and substances formed by adding an epoxy group-containing (meth)acrylate to a polymer obtained by polymerizing (meth)acrylate with (meth)acrylic acid.

[0172] Examples of the aforementioned (meth)acrylates include, for instance, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, n-pentyl (meth)acrylate, sec-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecanyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 2-phenoxyethyl (meth)acrylate.

[0173] Examples of epoxy-containing (meth)acrylates include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl) methyl methacrylate, and vinylcyclohexene oxide.

[0174] Examples of the aforementioned dendritic polymers (hyperbranched polymers) include SIRIUS-501 and SUBARU-501 (both manufactured by Osaka Organic Chemicals Co., Ltd.).

[0175] The weight-average molecular weight of the above-mentioned oligomers can be appropriately designed according to the purpose and use of the active energy radiation-curable resin composition according to the present invention, and is generally preferably 400 to 100,000. From the viewpoint of balancing processability and appropriate cured product characteristics, the above-mentioned weight-average molecular weight is more preferably 450 or more, further preferably 500 or more, more preferably 70,000 or less, and even more preferably 50,000 or less. The above-mentioned weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) according to the method described in the examples.

[0176] The curable resin composition of the present invention may contain only one of the above-mentioned oligomers, or it may contain two or more of the above-mentioned oligomers.

[0177] The content of the oligomers in the curable resin composition of the present invention can be appropriately designed according to the purpose and use of the curable resin composition. Generally, it is preferably 0.05% to 99% by mass relative to 100% by mass of the solid content of the curable resin composition, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, more preferably 95% by mass or less, and further preferably 90% by mass or less.

[0178] When the curable resin composition of the present invention is used as a resin composition for three-dimensional modeling, the content of the oligomers is preferably 20% to 80% by mass, more preferably 20% to 70% by mass, and even more preferably 30% to 70% by mass relative to 100% by mass of the solids content of the curable resin composition.

[0179] In the curable resin composition of the present invention, the content ratio of the crosslinking compound (A) to the oligomer (B) [(A) / (B)] is preferably 1 / 100 to 100 / 1 by mass. If the content ratio is within the above range, it is possible to better balance low viscosity with various properties such as hardness, thermal decomposition resistance, toughness, adhesion, and weather resistance of the cured product.

[0180] The above-mentioned content ratio, in terms of mass ratio, is more preferably 2 / 100 or more, further preferably 3 / 100 or more, more preferably 50 / 1 or less, and even more preferably 20 / 1 or less.

[0181] When the curable resin composition of the present invention is used as a resin composition for three-dimensional modeling, the above-mentioned content ratio [(A) / (B)] is preferably 5 / 80 to 50 / 30 by mass, and more preferably 10 / 70 to 35 / 30.

[0182] (C) Polymerization initiator

[0183] The active energy ray-curable resin composition of the present invention further comprises a polymerization initiator. The active energy ray-curable resin composition of the present invention can be cured by initiating free radical polymerization through heating and / or irradiation by active energy rays such as electromagnetic waves or electron beams. By including a free radical polymerization initiator, curing can be achieved more effectively.

[0184] Examples of free radical polymerization initiators include thermal free radical initiators that generate free radicals by heating and photofree radical initiators that generate free radicals by irradiation with active energy rays; one or more of these can be used.

[0185] In addition, one or more commonly used free radical polymerization accelerators, photosensitizers, etc., can be added as needed.

[0186] As examples of the aforementioned thermal free radical initiators, well-known organic peroxide initiators and azo initiators can be cited. Specific examples include the following substances.

[0187] Methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetoacetate peroxide, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclododecane, 1,1-bis(tert-butylperoxy)butane, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, terpenoid hydrogen peroxide, dicumyl hydroperoxide, 1,1,3,3-tetramethylbutylperoxy Hydrogen, cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide, α,α'-bis(tert-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxide dicarbonate, diisopropyl peroxide dicarbonate, bis(4-tert-butylcyclohexyl) peroxide dicarbonate, di- 2-Ethoxyethyl ester, di-2-ethoxyhexyl peroxide dicarbonate, di-3-methoxybutyl peroxide dicarbonate, di-sec-butyl peroxide dicarbonate, di(3-methyl-3-methoxybutyl) peroxide dicarbonate, α,α'-bis(neodecanylperoxide)diisopropylbenzene, cumyl peroxide neodecanoate, 1,1,3,3'-tetramethylbutyl peroxide neodecanoate, 1-cyclohexyl-1-methylethyl peroxide neodecanoate, tert-hexyl peroxide neodecanoate, tert-butyl peroxide neodecanoate, tert-hexyl peroxide pentyl ester, tert-butyl peroxide pentyl ester, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxide)hexanoate 1-Cyclohexyl-1-methylethylperoxide-2-ethylhexanoate, tert-hexyl peroxide (2-ethyl)hexanoate, tert-butyl peroxide (2-ethylhexanoate), tert-hexyl peroxide isopropyl monocarbonate, tert-butyl peroxide isobutyrate, tert-butyl peroxide maleate, tert-butyl peroxide-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxide isopropyl monocarbonate, tert-butyl peroxide-2-ethylhexyl monocarbonate, tert-butyl peroxide acetate, tert-butyl peroxide m-tolylbenzoate, tert-butyl peroxide benzoate, bis(tert-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(m-tolylperoxide)hexane, tert-hexyl peroxide benzoate, 2,5-dimethyl-2,Organic peroxide initiators include 5-bis(benzoyl peroxide)hexane, tert-butyl peroxide allyl monocarbonate, tert-butyltrimethylsilyl peroxide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,3-dimethyl-2,3-diphenylbutane.

[0188] 2-Phenylaszo-4-methoxy-2,4-dimethylpentanonitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carboxylonitrile), 2,2'-azobis(2-methylbutanonitrile), 2,2'-azobisisobutanonitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypentanonitrile), 2,2'-azobis(2-methylpropanediamine) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropanediamine) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2 [2,2'-Azobis[N-(4-hydrophenyl)-2-methylpropanediamine] dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propanediamine] dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propanediamine] dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropanediamine] dihydrochloride, 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-( ...methyl-N-(phenylmethyl)propanediamine] dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propanediamine] dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-imidazolin-2-yl)propanediamine] dihydrochloride, 2,2'-Azobis[2-methyl-N-(4-hydrophenyl)-2-methylpropanediamine] dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-imidazolin-2-yl)propanediamine] dihydrochloride, 2,2'-Azobis[2-methyl bis[2-(4,5,6,7-tetrahydro-1H-1,3-diaza-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis{2-methyl-N-[1,1-bis] Azo initiators include: (hydroxymethyl)-2-hydroxyethyl]propionamide, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis[2-(hydroxymethyl)propionitrile], etc.

[0189] As a free radical polymerization accelerator that can be used in conjunction with the aforementioned thermal free radical initiator, there are no particular limitations as long as it can promote the decomposition of the aforementioned thermal free radical initiator (initiate the generation of free radicals), and commonly used accelerators can be used. As the aforementioned free radical polymerization accelerator, commonly used free radical polymerization accelerators such as organic salts of metals, inorganic salts, oxides or metal complexes, amine compounds, quaternary ammonium salts, thiourea compounds, and ketone compounds can be used. Specific examples of the aforementioned free radical polymerization accelerators include, for example, the substance described in paragraph

[0089] of Japanese Patent No. 5689628.

[0190] As photoradical initiators, preferred examples include alkyl benzophenone compounds, benzophenone compounds, benzoin compounds, thioxanone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds, oxime ester compounds, dicene compounds, benzoate compounds, acridine compounds, anthraquinone compounds, ketal compounds, and phosphine oxide compounds. Specific examples include the following substances. 2,2-Diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropyl-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkyl phenyl ketone compounds; Benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone and other benzophenone-based compounds; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin-based compounds; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and other thioxanthone-based compounds; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)triazine and other halomethylated triazine compounds.

[0191] 2-Trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole and other halomethylated oxadiazole compounds; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4', Bimidazole compounds such as 5,5'-tetraphenyl-1,2'-biimidazole; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime); diacene compounds such as bis(n5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)-phenyl)titanium; benzoate compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine.

[0192] Anthraquinone compounds such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-pentylanthraquinone; ketal compounds such as acetophenone dimethyl ketal and benzoin dimethyl ether; and phosphine oxide compounds such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0193] Photosensitizers and free radical polymerization accelerators can be used together with the aforementioned photoradical initiators. There are no particular limitations on such photosensitizers and free radical polymerization accelerators; commonly used substances can be used. Specific examples of photosensitizers and free radical polymerization accelerators used with the aforementioned photoradical initiators include, for example, the substances described in paragraph

[0092] of Japanese Patent No. 5689628.

[0194] The curable resin composition of the present invention may contain only one of the above-mentioned polymerization initiators, or it may contain two or more of the above-mentioned polymerization initiators.

[0195] The content of the above-mentioned polymerization initiator is not particularly limited and can be appropriately designed according to the purpose and use. Generally, relative to 100% by mass of the solid content of the above-mentioned curable resin composition, it is preferably 0.01% to 10% by mass, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, more preferably 7% by mass or less, and even more preferably 5% by mass or less.

[0196] The total amount of the above-mentioned free radical polymerization accelerator and photosensitizer added is not particularly limited and can be appropriately designed according to the purpose and use. Generally, it is preferably 0 to 8% by mass, more preferably 0 to 7% by mass, and even more preferably 0 to 5% by mass, relative to 100% by mass of the solid content of the above-mentioned curable resin composition.

[0197] (D) Compound D

[0198] The active energy ray curable resin composition of the present invention preferably further comprises a compound represented by the following general formula (3) (hereinafter referred to as "compound D"). By including the above compound, processability and appropriate cured product properties can be better balanced.

[0199] [Chemistry 20]

[0200]

[0201] When the curable resin composition of the present invention contains the above-described compound D, the content of the above-described compound D is preferably 0.1% to 50% by mass, more preferably 0.1% to 40% by mass, and even more preferably 0.1% to 30% by mass relative to 100% by mass of the solids of the above-described curable resin composition.

[0202] (E) Other additives

[0203] The active energy ray-curable resin composition of the present invention may further include other additives depending on the purpose and use of the aforementioned curable resin composition. Examples of such other additives include, for instance, solvents, reactive diluents, curing accelerators such as desiccants, stabilizers, colorants, dispersants, fillers, adhesion improvers, release agents, plasticizers, ultraviolet absorbers, matting agents, defoamers, leveling agents, antistatic agents, slip agents, surface modifiers, coupling agents, and acid-generating agents. These additives are not particularly limited; appropriate selection from known substances may be made according to the purpose and use. Specifically, substances identical to those described in paragraphs

[0095] to

[0111] of Japanese Patent No. 5689628 may be appropriately used. The content of these additives may be appropriately set according to known techniques. Among the aforementioned additives, the active energy ray-curable resin composition preferably includes a reactive diluent.

[0204] (Reactive diluent)

[0205] The aforementioned reactive diluents are low-molecular-weight compounds having polymerizable groups that can polymerize through heating or irradiation by active energy rays. In particular, reactive diluents that are liquid and low-viscosity at room temperature also have viscosity-adjusting functions, and therefore can be used as a substitute for solvents, especially for solvent-free applications. As such reactive diluents, compounds having free radical polymerizable groups such as carbon-carbon unsaturated bonds are generally used; compounds having cationic polymerizable groups such as epoxy groups, oxobutyl groups, and vinyl ether groups are commonly used; and compounds having both free radical polymerizable groups and cationic polymerizable groups are also commonly used. When the curable resin composition of the present invention contains a reactive diluent, commonly used reactive diluents can be used, and one or more can be appropriately selected according to the purpose and application; there is no particular limitation. However, since the curable resin composition of the present invention contains crosslinking compounds with free radical polymerizable properties, reactive diluents having free radical polymerizable groups that can be cured through the same mechanism are preferred as they readily achieve a synergistic effect. Examples of reactive diluents for this type of free radical polymerization include monofunctional free radical polymerizable monomers having only one free radical polymerizable unsaturated group within the same molecule, and polyfunctional free radical polymerizable monomers having two or more free radical polymerizable unsaturated groups.

[0206] When the curable resin composition of the present invention is used as a resin composition for three-dimensional modeling, the reactive diluent used is preferably a compound having a free radical polymerizable group, a compound having a cationic polymerizable group, or a combination thereof. As a compound having a cationic polymerizable group, it is more preferably 3-ethyl-3-hydroxymethyloxetane, etc.

[0207] Examples of monofunctional free radical polymerizable monomers include (meth)acrylates, (meth)acrylamides, unsaturated polycarboxylic acids, unsaturated monocarboxylic acids, unsaturated acid anhydrides, aromatic vinyl groups, N-substituted maleimides, conjugated dienes, vinyl esters, vinyl ethers, N-vinyl compounds, and unsaturated isocyanates. Specifically, examples include the monofunctional free radical polymerizable monomers described in paragraphs

[0104] to

[0105] of Japanese Patent No. 5689628.

[0208] Examples of the aforementioned multifunctional free radical polymerizable monomers include, for example, multifunctional (meth)acrylates, multifunctional vinyl ethers, (meth)acrylates containing vinyl ether groups, multifunctional allyl ethers, allyl (meth)acrylates, isocyanurates containing multifunctional (meth)acryloyl groups, isocyanurates containing multifunctional allyl groups, isocyanurates containing multifunctional allyl groups, multifunctional urethane (meth)acrylates, and multifunctional aromatic vinyl groups. More specifically, examples include the monofunctional free radical polymerizable monomers described in paragraphs

[0106] to

[0108] of Japanese Patent No. 5689628.

[0209] When the curable resin composition of the present invention contains the above-mentioned reactive diluent, the content of the above-mentioned reactive diluent can be appropriately set according to the purpose and use, and is not particularly limited. It is preferably 0 to 1500% by mass, more preferably 0 to 1000% by mass, and even more preferably 0 to 800% by mass, relative to 100% by mass of the above-mentioned crosslinking compound.

[0210] (Stabilizer)

[0211] Furthermore, as the stabilizer mentioned above, there are no particular limitations on the type of compound that prevents polymerization by reacting with free radicals generated by photoradical polymerization initiators, etc., and compounds such as quinone-based, piperidine-based, phenolic-based, phosphorus-based, and nitroso-based compounds can be used. Among these, hydroquinone-based, semi-hindered phenolic, (thio)phosphite-based, phosphine-based, thioether-based, nitroso-based, and piperazine-based stabilizers are preferred, and semi-hindered phenolic, (thio)phosphite-based, and thioether-based stabilizers are more preferred. Specifically, the substances described in paragraphs

[0021] to

[0051] of Japanese Patent No. 6125933 may be appropriately used as the stabilizer. Only one stabilizer may be used, or two or more may be used in combination.

[0212] The content of the stabilizer is preferably 0.0001% to 5% by mass, more preferably 0.001% to 3% by mass, and even more preferably 0.01% to 2% by mass relative to 100% by mass of the solids in the curable resin composition.

[0213] Even when containing high-viscosity oligomers, the viscosity of the curable resin composition of the present invention remains low due to the relatively low viscosity of the aforementioned crosslinking compounds. Therefore, the compositional range of the aforementioned curable resin composition can be very broad, and it can possess various properties required for different applications.

[0214] The viscosity of the curable resin composition of the present invention is not particularly limited, and can be appropriately set according to the purpose and use. It is preferably 10 mPa·s to 10000 mPa·s, more preferably 10 mPa·s to 5000 mPa·s, further preferably 10 mPa·s to 2000 mPa·s, and particularly preferably 10 mPa·s to 1500 mPa·s.

[0215] The viscosity values ​​mentioned above were measured at 25°C using a viscometer such as a cone-plate viscometer (TV-20L, manufactured by Toki Sangyo Co., Ltd.).

[0216] (Preparation method of active energy ray-curable resin composition)

[0217] The method for preparing the active energy ray curable resin composition of the present invention is not particularly limited, and can be prepared by mixing the above-mentioned (A) crosslinking compound, (B) oligomer and (C) polymerization initiator with other additives as needed using known devices such as paint mixers, bead mills, kneaders and mixers.

[0218] (Curing method for curable resin compositions)

[0219] The method for curing the active energy ray-curable resin composition of the present invention is not particularly limited, and can be appropriately selected from known methods such as heating, irradiation with active energy rays, and exposure in an oxygen-containing atmosphere, depending on the purpose and use of the curable resin composition. Only one of these methods may be performed, or two or more may be used in combination. Among these, irradiation with active energy rays is preferred.

[0220] The temperature conditions for the aforementioned heat curing can be appropriately set according to the composition of the curable resin composition. For example, without the use of a curing accelerator, from the perspective of promoting curing and reducing thermal decomposition, 30°C to 400°C is preferred, 70°C to 350°C is more preferred, and 100°C to 350°C is even more preferred. With the use of a curing accelerator, curing can be achieved at a lower temperature than when it is not used, preferably 0°C to 400°C, more preferably 10°C to 350°C, and even more preferably 20°C to 350°C.

[0221] Curing by heating can be carried out in one stage or in two or more stages. It can be performed before or after curing by exposure to active energy rays and / or exposure to an oxygen-containing atmosphere. For example, after temporary cross-linking to some extent by heating at low temperatures or short-term exposure to active energy rays, followed by development or other treatments, and then curing at a high temperature preferably above 150°C, more preferably above 180°C, and even more preferably above 200°C, this process is also called post-baking or post-curing, and is preferred as it allows for further cross-linking reaction.

[0222] As for the active energy rays used in the aforementioned curing method involving irradiation with active energy rays, commonly used active energy rays can be used, including electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible light, and infrared rays, as well as particle beams such as electron beams, neutron beams, and proton beams. Among these, considering the energy intensity and the energy ray generating device, gamma rays, X-rays, extreme ultraviolet rays, ultraviolet rays, visible light, and electron beams are preferred, extreme ultraviolet rays, ultraviolet rays, visible light, and electron beams are more preferred, and ultraviolet rays are most preferred. When a curing accelerator is not used, active energy rays with high energy such as gamma rays, X-rays, and electron beams are preferred. When a curing accelerator is used, active energy rays with relatively low energy but easy to generate and more economical, such as ultraviolet rays and visible light, are preferred.

[0223] The curing method described above, which involves exposure to an oxygen-containing atmosphere, refers to a method of curing the aforementioned curable resin composition by exposing it to an oxygen-containing atmosphere. The oxygen concentration in the atmosphere is preferably 5% by volume or more, more preferably 10% by volume or more, and most preferably 18% by volume or more. That is, the most preferred concentration is equal to or higher than the oxygen concentration in air. Furthermore, it can be used in conjunction with the aforementioned curing method utilizing heat and / or curing method utilizing active energy rays. In particular, the curing method involving heating in air and / or irradiation with active energy rays is a preferred curing method as it can be easily combined.

[0224] 2. Cured product

[0225] As described above, the active energy ray-curable resin composition of the present invention maintains a relatively low viscosity even when mixed with high-viscosity components. Therefore, compared with the past, curable resin compositions can be designed more extensively, and the cured products obtained by curing the above-described curable resin composition can be endowed with desired properties. Such cured products of the above-described active energy ray-curable resin composition are also part of the present invention.

[0226] When the cured product is a cured film, its thickness can be appropriately set according to the purpose and application, for example, 0.1μm to 5000μm, preferably 0.5μm to 1000μm, and more preferably 1μm to 300μm.

[0227] The properties of the cured material can be modified by adjusting the composition of the active energy ray curable resin composition, for example, to achieve excellent physical properties such as heat resistance to decomposition, hardness, adhesion to the substrate, toughness, and weather resistance.

[0228] 3. Uses

[0229] The active energy ray-curable resin composition of the present invention exhibits extremely excellent curability due to the inclusion of the aforementioned crosslinking compound. Furthermore, even when mixed with high-viscosity oligomers, a curable resin composition with relatively low viscosity can be prepared, providing cured products with properties required for the application, such as resistance to thermal decomposition, adhesion to the substrate, hardness, toughness, or weather resistance.

[0230] The active energy radiation-curable resin composition and its cured products of the present invention can be suitably used, for example, as adhesives, biomaterials, dental materials, optical components, information recording materials, optical fiber materials, color filter resists, solder resists, electroplating resists, black resists, semiconductor photoresists, TFT forming resists, EUV, KrF, ArF, gamma-ray, and i-ray resists, three-dimensional modeling materials (preferably 3D printing resins), UV-curable inkjet inks, photolithographic spacers / black pillars, automotive UV-curable coatings / coating materials, optical fiber coating materials, hard coating materials for films, UV-curable coatings / coating materials for electrical products, buffer coatings, redistribution forming materials, back-grinding tapes, cutting tapes, UV-curable coatings, insulators, and sealing materials. It has a wide range of applications, including inkjet inks, printing inks, coatings, molding materials, UV-curable coatings, decorative panels, WPC, coating materials, photosensitive printing plates, OCA / OCR for touch panels, coating films, dry films, dry film resist layers, lining materials, civil engineering materials, putty, repair materials, flooring materials, paving materials, gel paints, outer coatings, molding materials for hand application, spraying, drawing, winding, SMC / BMC, etc., polymer solid electrolytes, resins for lens molding, and resins for microlens molding.

[0231] Among these applications, from the perspective of further improving performance and easily balancing the characteristics in a trade-off relationship, it is preferred for use in adhesives, bonding agents, three-dimensional modeling materials, UV-curable inkjet inks, sealing materials, or UV-curable coatings.

[0232] Furthermore, when using the active energy ray curable resin composition of the present invention as a material for three-dimensional modeling, there are no particular limitations on the type of 3D printer that can be used. Any method in which the above-mentioned curable resin composition can be used as a photocurable material, such as Vat Photopolymerization (LASER, DLP, etc.) or Ink-Jet, can be employed.

[0233] As described above, the active energy ray curable resin composition and its cured product of the present invention can form the desired composition while maintaining low viscosity, and can appropriately impart the properties required in various technical fields and applications.

[0234] Example

[0235] The following examples illustrate the invention in more detail, but the invention is not limited to these examples. It should be noted that, unless otherwise stated, "parts" refers to "parts by mass" and "%" refers to "% by mass".

[0236] In this embodiment, the determination of various physical properties is carried out by the following methods.

[0237] Viscosity

[0238] The viscosity of the curable resin composition was measured using a cone-plate viscometer (TV-20L, manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25°C.

[0239] <Thermal decomposition temperature>

[0240] The thermal decomposition temperature of the cured resin composition was determined using a thermogravimetric differential thermal analysis apparatus (TG-DTA2010SA, manufactured by Bruker) under the following conditions.

[0241] Measurement temperature range: room temperature to 500℃

[0242] Heating rate: 10℃ / min

[0243] Atmosphere and flow rate: Nitrogen - 50 ml / min

[0244] Glass transition temperature (Tg)

[0245] According to JIS K7121, the glass transition temperature (Tg) of the cured resin composition was determined by the midpoint method using a differential scanning calorimeter and the conditions described below.

[0246] Device: DSC3500 (manufactured by Netch Japan)

[0247] Heating rate: 10℃ / min

[0248] Atmosphere and flow rate: Nitrogen - 50 ml / min

[0249] Tensile strength, fracture strain, tensile modulus

[0250] (1) Preparation of test pieces

[0251] Using a curable resin composition, a light model was created using a Nobel 1.0 laser (manufactured by XYZ PRINTING) with a 100 μm thick cured resin layer and standard resin (transparent) under laser irradiation conditions according to JIS K 7161-2 1BA (t 2 mm). Next, the resin composition adhering to the outer surface of the resulting light model was removed using 2-propanol. Then, the cleaned light model was subjected to a second curing using a MultiCure 180 (manufactured by XYZ PRINTING) under standard resin irradiation conditions (wavelength (nm) 365+385+405, power level (%) 100, curing time (min) 7, rotation on / off) to obtain a test piece.

[0252] (2) Measurement

[0253] According to JIS K 7161-2, using Shimadzu Autograph (AGS-X series, manufactured by Shimadzu Corporation), the tensile strength, fracture strain and tensile modulus of the test piece obtained in (1) above were determined under the following test conditions.

[0254] Test piece: JIS K 7161-2 1BA type (t2mm)

[0255] Test temperature: 23℃

[0256] Test speed: 1 mm / min

[0257] Chuck spacing: 58mm

[0258] Number of measurements: n = 7

[0259] (Manufacturing Example 1) Manufacturing of Crosslinking Compound (TPG-AOMA)

[0260] Place a stir bar in a detachable flask and weigh out 2.27 g (8 mmol) of tetraisopropoxytitanium (TTIP), 38.5 g (200 mmol) of tripropylene glycol (TPG), 124.9 g (800 mmol) of α-allyloxymethyl methacrylate (AOMA), 120 mg (1000 ppm relative to AOMA) of polymerization inhibitor (6-tert-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.), 60 mg (500 ppm relative to AOMA) of polymerization inhibitor (Polystop 7300P, manufactured by Hakuto Co., Ltd.), and 60.0 g of toluene as an azeotropic agent. While bubbling the mixed gas (N2 / O2 = 92 / 8 (v / v)), reduce the pressure in the system to 300 Torr and simultaneously raise the temperature to 100°C. Remove the appropriate fraction, add the same mass of toluene back into the system and allow it to react, then continue heating until the triethylene glycol conversion is >99%.

[0261] After the reaction, the system was bubbled with a mixed gas (N2 / O2 = 92 / 8 (v / v)) while the pressure was reduced. Toluene and residual AOMA were removed by distillation. The target fraction was then separated using a medium-pressure separating liquid chromatography apparatus (YFLC AI-580, manufactured by Yamazen Corporation). In the separated fraction, a polymerization inhibitor (6-tert-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.) at 300 ppm relative to the target sample and a polymerization inhibitor (triphenyl phosphite, manufactured by ADEKA Corporation) at 500 ppm relative to the target sample were added. The solvent was removed by distillation, and the target sample TPG-AOMA was separated.

[0262] (Manufacturing Example 2) Manufacturing of Crosslinking Compound (DPG-AOMA)

[0263] In Manufacturing Example 1, dipropylene glycol (DPG) was used instead of tripropylene glycol, and otherwise the crosslinking compound (DPG-AOMA) was obtained by the same method as in Manufacturing Example 1.

[0264] (Manufacturing Example 3) Manufacturing of Crosslinked Compound (TPG-AOMA)

[0265] In a detachable flask equipped with a stirring blade, weigh out 432.5 g (2.2 mol) of tripropylene glycol (TPG), 2319.3 g (14.8 mol) of methyl α-allyloxymethacrylate (AOMA), 2.3 g (1000 ppm relative to AOMA) of polymerization inhibitor (6-tert-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1.2 g (500 ppm relative to AOMA) of polymerization inhibitor (Polystop 7300P, manufactured by Hakuto Co., Ltd.), 202.9 g (90 mmol) of azeotropic agent heptane, and 25.6 g (90 mmol) of tetraisopropoxytitanium (TTIP). While bubbling the gas mixture (N2 / O2 = 92 / 8 (v / v)), reduce the pressure in the system to 300 Torr and simultaneously raise the temperature to 100 °C. Remove the appropriate fraction, add the same mass of heptane back into the system and allow it to react, then continue heating until the triethylene glycol conversion is >98%.

[0266] After the reaction, 590 g of 5% oxalic acid aqueous solution was added to wash the reaction solution. The reaction solution was then washed twice with 590 g of pure water. After washing, while bubbling a mixed gas (N2 / O2 = 92 / 8 (v / v)), light boiling substances were removed by vacuum distillation until the liquid at the bottom reached 115°C (5 Torr), yielding TPG-AOMA containing 2% AOMA.

[0267] (Examples 1-6, Comparative Examples 1-3)

[0268] The curable resin compositions of Examples 1-6 were prepared by mixing the crosslinking compound, oligomer, and polymerization initiator according to the formulations shown in Table 1. The viscosity of the obtained curable resin compositions was evaluated. The results are shown in Table 1.

[0269]

[0270] The crosslinking compounds, oligomers, and polymerization initiators listed in Table 1 use the substances described below. Furthermore, the mixing amounts of each component listed in Table 1 are converted from solid component amounts.

[0271] TPG-AOMA: Crosslinking compound used in manufacturing Example 1

[0272] DPG-AOMA: Crosslinking compound used in manufacturing Example 2

[0273] Polyester acrylate: EBECRYL884, viscosity (25℃) 25000 mPa·s, manufactured by Daicel-Allnex.

[0274] urethane acrylate: CN964, viscosity (60℃) 1770 mPa·s, manufactured by Sartomer.

[0275] Epoxy acrylate: 70 PA, viscosity (25°C) 1174 mPa·s, manufactured by Kyoei Chemical Co., Ltd.

[0276] Polymerization initiator: Omnirad 184, manufactured by IGM Resins.

[0277] Table 1 confirms that the curable resin composition containing a crosslinking compound with an AMA group, an oligomer, and a polymerization initiator has a very low viscosity compared to the case of the oligomer alone containing the high-viscosity component.

[0278] (Comparative Examples 4-9)

[0279] In addition, the curable resin compositions of Comparative Examples 4 to 9 were prepared by mixing oligomers, polymerization initiators and reactive diluents according to the formulations shown in Table 2.

[0280] Each of the curable resin compositions of Examples 1-6 and Comparative Examples 4-9 obtained above was placed in an aluminum dish and irradiated with ultraviolet light under the following conditions to obtain evaluation samples of the cured products. The thermal decomposition temperature and glass transition temperature (Tg) of the evaluation samples were measured. The results are shown in Table 2.

[0281] UV irradiation device: HCT400B-28HB (manufactured by SEN Special Light Source Co., Ltd.)

[0282] Cumulative light intensity: 15 J / cm 2

[0283]

[0284] The oligomers, polymerization initiators, and reactive diluents listed in Table 2 use the following substances. Additionally, the mixing amounts of each component listed in Table 2 are converted from solid component amounts.

[0285] Polyester acrylate: EBECRYL884, viscosity (25℃) 25000 mPa·s, manufactured by Daicel-Allnex.

[0286] urethane acrylate: CN964, viscosity (60℃) 1770 mPa·s, manufactured by Sartomer.

[0287] Epoxy acrylate: 70 PA, viscosity (25°C) 1174 mPa·s, manufactured by Kyoei Chemical Co., Ltd.

[0288] Polymerization initiator: Omnirad 184, manufactured by IGM Resins.

[0289] TPG-A: Tripropylene glycol diacrylate, APG-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0290] PEA: Phenoxyethyl acrylate

[0291] Table 2 confirms that curable resin compositions containing crosslinking compounds with AMA groups, oligomers, and polymerization initiators provide cured products with superior thermal decomposition resistance and heat resistance compared to curable resin compositions containing reactive diluents with two or more acryloyl groups, oligomers, and polymerization initiators, and curable resin compositions that do not contain crosslinking compounds.

[0292] (Example 7, Comparative Example 10)

[0293] Furthermore, the curable resin compositions of Examples 7 and Comparative Example 10 were prepared by mixing the crosslinking compound, oligomer, polymerization initiator, and reactive diluent according to the formulations shown in Table 3. The viscosity, tensile strength, strain at break, and tensile modulus of the obtained curable resin compositions were measured using the methods described above. The results are shown in Table 3.

[0294] [Table 3]

[0295]

[0296] The crosslinking compounds, oligomers, polymerization initiators, and reactive diluents listed in Table 3 use the substances described below. Furthermore, the mixing amounts of each component listed in Table 3 are converted from solid component amounts.

[0297] TPG-AOMA: Crosslinking compound used in manufacturing Example 3

[0298] TPG-A: Tripropylene glycol diacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0299] Carbamate acrylate: UV-7650B (registered trademark), viscosity (60℃) 5500 mPa·s, manufactured by Mitsubishi Chemical Corporation.

[0300] TPO: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide

[0301] IBOA: Isoborneol Acrylate

[0302] Table 3 confirms that the cured resin composition containing a crosslinking compound with AMA groups, oligomers, and polymerization initiators exhibits higher tensile strength, strain at break, and tensile modulus, and demonstrates superior strength and toughness compared to the cured resin composition containing crosslinking compounds without AMA groups, oligomers, and polymerization initiators. Furthermore, it is confirmed that although the viscosity of the aforementioned cured resin composition containing crosslinking compounds with AMA groups, oligomers, and polymerization initiators is slightly higher, it is below 600 mPa·s, thus indicating relatively low viscosity and good processability.

Claims

1. A resin composition that can be cured by active energy rays, characterized in that, It includes a crosslinking compound (A), an oligomer (B) with a viscosity of 1000 mPa·s or more and 6,000,000 mPa·s or less at 25°C, or a viscosity of 400 mPa·s or more and 200,000 mPa·s or less at 60°C, and a polymerization initiator (C). The crosslinking compound (A) comprises at least one of the following compounds: The oligomer (B) is at least one selected from the group consisting of polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyacrylate (meth)acrylate, dendritic polymers (i.e., hyperbranched polymers), polybutadiene (meth)acrylate, silicone (meth)acrylate, and amino resin (meth)acrylate. The dendritic polymer, or hyperbranched polymer, is SIRIUS-501 or SUBARU-501 manufactured by Osaka Organic Chemical Industry Co., Ltd.

2. The active energy ray-curable resin composition as described in claim 1, wherein, The content of the crosslinking compound (A) is 0.05% to 99% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

3. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the crosslinking compound (A) is 0.1% by mass or more relative to 100% by mass of the solid component of the active energy ray curable resin composition.

4. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the crosslinking compound (A) is 0.5% by mass or more relative to 100% by mass of the solid component of the active energy ray curable resin composition.

5. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the crosslinking compound (A) is less than 95% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

6. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the crosslinking compound (A) is less than 90% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

7. The active energy ray-curable resin composition as described in claim 1, wherein, The oligomer (B) has a viscosity of 1100 mPa·s or higher at 25°C.

8. The active energy radiation-curable resin composition as described in claim 1, wherein, The oligomer (B) has a viscosity of 1200 mPa·s or higher at 25°C.

9. The active energy radiation-curable resin composition as described in claim 1, wherein, The oligomer (B) has a viscosity of 420 mPa·s or higher at 60°C.

10. The active energy radiation-curable resin composition as described in claim 1, wherein, The oligomer (B) has a viscosity of 450 mPa·s or higher at 60°C.

11. The active energy radiation-curable resin composition according to claim 1, characterized in that, The oligomer (B) has a viscosity of 1000 mPa·s or more at 25°C and a viscosity of 400 mPa·s or more at 60°C.

12. The active energy ray-curable resin composition according to claim 1, characterized in that, The oligomer (B) has a viscosity of 1100 mPa·s or higher at 25°C and a viscosity of 420 mPa·s or higher at 60°C.

13. The active energy radiation-curable resin composition as described in claim 1, wherein, The oligomer (B) is at least one selected from the group consisting of polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate and polyacrylate (meth)acrylate.

14. The active energy radiation-curable resin composition as described in claim 1, wherein, The weight-average molecular weight of the oligomer (B) is 400 to 100,000.

15. The active energy ray-curable resin composition as described in claim 1, wherein, The weight-average molecular weight of the oligomer (B) is 450 or higher.

16. The active energy ray-curable resin composition as described in claim 1, wherein, The weight-average molecular weight of the oligomer (B) is 500 or more.

17. The active energy ray-curable resin composition according to claim 1, wherein, The weight-average molecular weight of the oligomer (B) is below 70,000.

18. The active energy ray-curable resin composition as claimed in claim 1, wherein, The weight-average molecular weight of the oligomer (B) is below 50,000.

19. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the oligomer (B) is 0.05% to 99% by mass relative to 100% by mass of the solids component of the active energy ray-curable resin composition.

20. The active energy radiation-curable resin composition of claim 1, wherein, The content of the oligomer (B) is 0.1% by mass or more relative to 100% by mass of the solids component of the active energy ray-curable resin composition.

21. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the oligomer (B) is 0.5% by mass or more relative to 100% by mass of the solids component of the active energy ray-curable resin composition.

22. The active energy radiation-curable resin composition of claim 1, wherein, The content of the oligomer (B) is 95% by mass or less relative to 100% by mass of the solids content of the active energy ray-curable resin composition.

23. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the oligomer (B) is less than 90% by mass relative to 100% by mass of the solids content of the active energy ray-curable resin composition.

24. The active energy ray-curable resin composition as described in claim 1, wherein, The polymerization initiator (C) is a free radical polymerization initiator.

25. The active energy radiation-curable resin composition as described in claim 1, wherein, The polymerization initiator (C) is a thermal free radical initiator or a photofree radical initiator. The photoradical initiator is an alkyl benzophenone compound, a benzophenone compound, a benzoin compound, a thioxanone compound, a halomethylated triazine compound, a halomethylated oxadiazole compound, a biimidazole compound, an oxime ester compound, a dicene compound, a benzoate compound, an acridine compound, an anthraquinone compound, a ketal compound, or a phosphine oxide compound.

26. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the polymerization initiator (C) is 0.01% to 10% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

27. The active energy ray-curable resin composition as claimed in claim 1, wherein, The content of the polymerization initiator (C) is 0.05% by mass or more relative to 100% by mass of the solids component of the active energy ray curable resin composition.

28. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the polymerization initiator (C) is 0.1% by mass or more relative to 100% by mass of the solids component of the active energy ray curable resin composition.

29. The active energy radiation-curable resin composition as described in claim 1, wherein, The content of the polymerization initiator (C) is less than 7% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

30. The active energy radiation-curable resin composition of claim 1, wherein, The content of the polymerization initiator (C) is less than 5% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

31. The active energy radiation-curable resin composition as described in claim 1, wherein, It also contains a free radical polymerization accelerator or a photosensitizer, the total amount of which is 0 to 8% by mass relative to 100% by mass of the solids content of the active energy ray curable resin composition.

32. The active energy radiation-curable resin composition as described in claim 1, wherein, It also contains a free radical polymerization accelerator or a photosensitizer, the total amount of which is 0 to 7% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

33. The active energy radiation-curable resin composition as described in claim 1, wherein, It also contains a free radical polymerization accelerator or a photosensitizer, the total amount of which is 0 to 5% by mass relative to 100% by mass of the solids content of the active energy ray curable resin composition.

34. The active energy radiation-curable resin composition according to claim 1, characterized in that, It also contains reactive diluents.

35. The active energy radiation-curable resin composition of claim 34, wherein, The reactive diluent is a reactive diluent with free radical polymerizable groups.

36. The active energy radiation-curable resin composition of claim 34, wherein, The content of the reactive diluent is 0 to 1500% by mass relative to 100% by mass of the crosslinking compound (A).

37. The active energy radiation-curable resin composition of claim 34, wherein, The content of the reactive diluent is 0 to 1000% by mass relative to 100% by mass of the crosslinking compound (A).

38. The active energy radiation-curable resin composition of claim 34, wherein, The content of the reactive diluent is 0 to 800% by mass relative to 100% by mass of the crosslinking compound (A).

39. The active energy radiation-curable resin composition according to claim 1, characterized in that, The ratio of the crosslinking compound (A) to the oligomer (B) by mass is 1 / 100 to 100 / 1.

40. The active energy radiation-curable resin composition according to claim 1, characterized in that, The ratio of the crosslinking compound (A) to the oligomer (B) by mass is 2 / 100 or more.

41. The active energy radiation-curable resin composition according to claim 1, characterized in that, The ratio of the crosslinking compound (A) to the oligomer (B) by mass is 3 / 100 or more.

42. The active energy ray-curable resin composition according to claim 1, characterized in that, The ratio of the crosslinking compound (A) to the oligomer (B) by mass is 50 / 1 or less.

43. The active energy radiation-curable resin composition according to claim 1, characterized in that, The ratio of the crosslinking compound (A) to the oligomer (B) by mass is 20 / 1 or less.

44. The active energy radiation-curable resin composition according to claim 1, characterized in that, It also includes compounds represented by the following general formula (3), [Chemistry 2] 45. The active energy radiation-curable resin composition of claim 44, wherein, The content of the compound represented by the general formula (3) is 0.1% to 50% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

46. ​​The active energy ray-curable resin composition of claim 44, wherein, The content of the compound represented by the general formula (3) is 0.1% to 40% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

47. The active energy ray-curable resin composition of claim 44, wherein, The content of the compound represented by the general formula (3) is 0.1% to 30% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

48. The active energy radiation-curable resin composition as described in claim 1, wherein, It also contains stabilizers.

49. The active energy radiation-curable resin composition of claim 48, wherein, The stabilizer is a hydroquinone-based, semi-hindered phenol-based, thiophosphite-based, phosphite-based, phosphine-based, thioether-based, nitroso-based, or piperazine-based stabilizer.

50. The active energy radiation-curable resin composition of claim 48, wherein, The stabilizer is a semi-hindered phenolic, thiophosphite, phosphite, or thioether stabilizer.

51. The active energy radiation-curable resin composition of claim 48, wherein, The content of the stabilizer is 0.0001% to 5% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

52. The active energy radiation-curable resin composition of claim 48, wherein, The content of the stabilizer is 0.001% to 3% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

53. The active energy radiation-curable resin composition of claim 48, wherein, The content of the stabilizer is 0.01% to 2% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

54. The active energy radiation-curable resin composition as described in claim 1, wherein, The viscosity of the active energy ray-curable resin composition is 10 mPa·s to 10000 mPa·s.

55. The active energy radiation-curable resin composition as described in claim 1, wherein, The viscosity of the active energy ray-curable resin composition is 10 mPa·s to 5000 mPa·s.

56. The active energy radiation-curable resin composition as described in claim 1, wherein, The viscosity of the active energy ray-curable resin composition is 10 mPa·s to 2000 mPa·s.

57. The active energy ray-curable resin composition as described in claim 1, wherein, The viscosity of the active energy ray-curable resin composition is 10 mPa·s to 1500 mPa·s.

58. The active energy radiation-curable resin composition as described in claim 1, wherein, The active energy radiation-curable resin composition is used as an adhesive, bonding agent, material for three-dimensional modeling, UV-curable inkjet ink, sealant, or UV-curable coating agent.

59. The active energy radiation-curable resin composition as described in claim 1, wherein, The active energy ray curable resin composition is a resin composition for three-dimensional modeling.

60. The active energy radiation-curable resin composition of claim 59, wherein, The content of the crosslinking compound (A) is 5% to 50% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

61. The active energy radiation-curable resin composition of claim 59, wherein, The content of the crosslinking compound (A) is 10% to 40% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

62. The active energy radiation-curable resin composition of claim 59, wherein, The content of the crosslinking compound (A) is 10% to 35% by mass relative to 100% by mass of the solids component of the active energy ray curable resin composition.

63. The active energy radiation-curable resin composition as described in claim 59, wherein, The content of the oligomer (B) is 20% to 80% by mass relative to 100% by mass of the solids component of the active energy ray-curable resin composition.

64. The active energy radiation-curable resin composition of claim 59, wherein, The content of the oligomer (B) is 20% to 70% by mass relative to 100% by mass of the solids component of the active energy ray-curable resin composition.

65. The active energy radiation-curable resin composition of claim 59, wherein, The content of the oligomer (B) is 30% to 70% by mass relative to 100% by mass of the solids component of the active energy ray-curable resin composition.

66. The active energy radiation-curable resin composition of claim 59, wherein, The ratio of the crosslinking compound (A) to the oligomer (B) by mass is 5 / 80 to 50 / 30.

67. The active energy radiation-curable resin composition of claim 59, wherein, The ratio of the crosslinking compound (A) to the oligomer (B) by mass is 10 / 70 to 35 / 30.

68. The active energy radiation-curable resin composition as described in claim 59, wherein, It also includes a reactive diluent, which is a compound having a free radical polymerizable group, a compound having a cationic polymerizable group, or a combination thereof.

69. The active energy radiation-curable resin composition of claim 68, wherein, The compound having a cationic polymerizable group is 3-ethyl-3-hydroxymethyloxetane.

70. The cured product of the active energy ray curable resin composition according to claim 1.

71. The cured product as claimed in claim 70, wherein, The cured product is a cured film. The thickness of the cured film ranges from 0.1 μm to 5000 μm.

72. The cured product as claimed in claim 70, wherein, The cured product is a cured film. The thickness of the cured film ranges from 0.5 μm to 1000 μm.

73. The cured product as claimed in claim 70, wherein, The cured product is a cured film. The thickness of the cured film ranges from 1 μm to 300 μm.

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