Photocurable resin composition

Abstract

To provide a curable resin composition which can obtain a cured product excellent in impact resistance and flexural modulus and has low viscosity.SOLUTION: A photocurable resin composition contains components (A), (B) and (C), in which the component (A) is represented by formula (1), where R is H or a hydrocarbon group having 1 to 4 carbon atoms that may have a substituent, the component (B) is a compound having 3 to 15 ethyleneoxy groups or propyleneoxy groups and two or more radical-polymerizable groups in one molecule, and the component (C) is a radical polymerization initiator. The number X of the ethyleneoxy groups or propyleneoxy groups in the composition and the number Y of crosslinking groups in the composition are calculated by specific calculation formulae, respectively, X is 30 or more and 45 or less, and Y is 10 or more and 19 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photocurable resin composition, a cured product, and a method for producing an article. [Background technology]

[0002] In recent years, 3D Additive Manufacturing (AM) has been increasingly used as a means of manufacturing products, against the backdrop of the diversification of modeling materials and the evolution of equipment technology. Among these, there are modeling methods called liquid layer photopolymerization and stereolithography. This modeling method forms three-dimensional shapes by hardening liquid photocurable resin with a laser beam or lamp, and is characterized by its ability to model with high definition and precision. On the other hand, models made from photocurable resin are required to have high mechanical strength and environmental resistance, and progress is being made in improving the material properties such as flexural modulus, impact resistance, and heat resistance. Patent Document 1 describes that a curable composition having flexibility, high hardness, and heat resistance can be obtained by using a curable composition consisting of a radically polymerizable monomer and a polyfunctional radically polymerizable compound. Patent Document 2 describes that a molded object having mechanical properties similar to those of a thermoplastic resin can be obtained by using an ink containing a cyclic polymerizable monomer and an oligomer curable material for modeling with a 3D printer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2014-40585 A [Patent Document 2] Special Publication No. 2020-505255 Summary of the Invention [Problem to be solved by the invention]

[0004] However, depending on the application of the product, further improvement in mechanical properties is required, specifically, both impact resistance and flexural modulus are required. In addition, when used for high-definition and high-precision modeling, low liquid viscosity is also required from the viewpoint of preventing bubble entrapment and liquid leveling. Although the composition of Patent Document 1 can achieve low liquid viscosity, sufficient impact resistance cannot be obtained. In addition, the composition of Patent Document 2 produces a cured product with excellent mechanical properties such as flexural modulus, but the liquid viscosity is not sufficiently low and is not suitable for high-definition and high-precision modeling. The present invention aims to provide a curable resin composition that can produce a cured product with excellent impact resistance and flexural modulus and has a low viscosity. [Means for solving the problem]

[0005] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above object, and have thus completed the present invention, which relates to a photocurable resin composition containing a monofunctional acrylic monomer (component (A)) that forms a polymer containing a five-membered cyclic ether by radical polymerization, and a polyfunctional radically polymerizable compound (component (B)) that contains an ethyleneoxy group or a propyleneoxy group. Components (A) and (B) form a copolymer structure by radical polymerization. In the cured product after polymerization, the five-membered ring ether formed by polymerization of component (A) and the ethyleneoxy or propyleneoxy groups in component (B) have the function of absorbing shock, and the crosslinked structure formed by polyfunctional radically polymerizable compounds such as component (B) realizes a high elastic modulus of the polymer. In particular, it was found that the number of five-membered ring ethers and ethyleneoxy or propyleneoxy groups, and the distance between crosslinking points are necessary factors to achieve both the free volume required for shock absorption and a high elastic modulus. The photocurable resin composition according to the present embodiment is A photocurable resin composition comprising component (A), component (B) and component (C), The component (A) is a compound represented by the following general formula (1):

[0006] [ka] [In general formula (1), R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group may have a substituent.] The component (B) is a compound having 3 to 15 ethyleneoxy groups or propyleneoxy groups and 2 or more radical polymerizable groups in one molecule, The component (C) is a radical polymerization initiator, The number X of ethyleneoxy groups or propyleneoxy groups in the photocurable resin composition is calculated by the following formula (i): The number Y of crosslinking groups in the photocurable resin composition is calculated by the following formula (ii): X=x B n B / (x A +x B n B +x B m B ) × 100 (i) Y=x B m B / (x A +x B n B +x B m B ) × 100 (ii) [x A : Molar fraction of the component (A) x B : Molar fraction of the component (B) n B The number of ethyleneoxy groups or propyleneoxy groups in one molecule of the component (B) m B : the number of radically polymerizable groups in one molecule of the component (B) The X is in the range of 30 or more and 45 or less, and the Y is in the range of 10 or more and 19 or less. Effect of the Invention

[0007] According to the present invention, it is possible to provide a photocurable resin composition which can obtain a shaped object having excellent impact resistance and flexural modulus, has a low liquid viscosity before curing, and is suitable for shaping. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram showing an example of the configuration of a molding apparatus using a free surface method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The photocurable resin composition according to this embodiment (hereinafter, may be referred to as "composition") will be described in detail.

[0010] <Component (A): Monofunctional 2-(allyloxymethyl)acrylic acid or its ester> The component (A), monofunctional 2-(allyloxymethyl)acrylic acid or its ester, is represented by the following general formula (1).

[0011] [ka]

[0012] In the general formula (1), R is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and the hydrocarbon group is a saturated or unsaturated hydrocarbon group, and may have a substituent. The hydrocarbon group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and may contain an ether bond. Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a vinyl group, an allyl group, a methallyl group, a crotyl group, a cyclopropyl group, a cyclobutyl group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a vinyloxyethyl group, an epoxy group, and an oxetanyl group. As the hydrocarbon group having 1 to 4 carbon atoms, a hydrocarbon group having 1 to 2 carbon atoms is particularly preferably used. Examples of the substituent that the hydrocarbon group may have include linear unsaturated hydrocarbon groups such as vinyl group, allyl group, methallyl group, crotyl group, etc.; cyclic ether structures such as epoxy group, glycidyl group, oxetanyl group, etc.; alkoxy groups such as methoxy group, ethoxy group, methoxyethoxy group, etc.; alkylthio groups such as methylthio group, ethylthio group, etc.; acyl groups such as acetyl group, propionyl group, etc.; acyloxy groups such as acetyloxy group, propionyloxy group, etc.; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, etc.; alkylthiocarbonyl groups such as methylthiocarbonyl group, ethylthiocarbonyl group, etc.; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; ureido group; amide group; cyano group; hydroxyl group; and trimethylsilyl group.

[0013] As the component (A), a commercially available product can be used, for example, AOMA (manufactured by Nippon Shokubai Co., Ltd.).

[0014] The impact resistance of the cured product is improved by including the five-membered ring ether formed by polymerization of component (A). Therefore, the content of component (A) is preferably 50% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 85% by mass or less, further preferably 60% by mass or more and 80% by mass or less, and even more preferably 65% ​​by mass or more and 75% by mass or less, based on the total amount of the composition.

[0015] <Component (B): Multifunctional radically polymerizable compound> The polyfunctional radically polymerizable compound of component (B) has 3 to 15 ethyleneoxy groups or propyleneoxy groups and 2 or more radically polymerizable groups in one molecule.

[0016] Component (B) may be any of a linear compound, a branched compound, and a cyclic compound, and the ethyleneoxy group or propyleneoxy group contained in component (B) may be contained in the main chain, the side chain, or the cyclic chain. The ethyleneoxy group or propyleneoxy group may form a repeating structure such as a polyoxyethylene or polyoxypropylene structure in the molecule. The ethyleneoxy group or propyleneoxy group may be present apart from each other. Specifically, for example, in a structure derived from a branched or cyclic compound such as pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, isocyanurate, etc., the ethyleneoxy group or propyleneoxy group may be present apart from each other. The propyleneoxy group may be linear or branched.

[0017] The radically polymerizable group contained in component (B) is preferably a group having a carbon-carbon double bond, and more preferably an acryloyl group.

[0018] Number of ethyleneoxy or propyleneoxy groups in one molecule n B n is between 3 and 15. B When n is small, the number of ethyleneoxy or propyleneoxy groups X in the composition is small, or in order to increase X, the number of radical polymerizable groups in the composition is increased, which results in an increase in the number of crosslinking groups Y in the composition, and therefore tends to reduce impact resistance. B If the number of n is less than 3, impact resistance sufficient for practical use cannot be obtained. BWhen the ratio of X to Y in the composition increases, the composition exhibits properties similar to those of a rubber component, and the elastic modulus tends to decrease. B If the number of n is more than 15, the elastic modulus drops sharply. B The range is preferably 3 or more and 14 or less, and more preferably 6 or more and 14 or less.

[0019] As the component (B), commercially available products can be used, for example, SR454, SR492, SR499, SR502, SR9035, SR494, SR344, CD561, SR602, SR610, SR205, SR209, SR252, SR480, SR603, SR644 (all manufactured by SARTOMER), A-200, A-400, A-600, APG200, APG400, APG700, A Examples of such copolymers include BE-300, A-BPE-4, ABPE-10, A-TMPT-3EO, A-TMPT-9EO, A-TMPT-3PO, A-TMPT-9PO, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-6P, A-GLY-9PA, A-DPH-12E, 3G, 4G, 9G, 14G, 3PG, 9PG, GLY-6E, and GLY-9E (all manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD PEG400DA, R551, R712, RP1040, and DPEA-12 (all manufactured by Nippon Kayaku Co., Ltd.), and Viscoat #310 and #700HVHP (all manufactured by Osaka Organic Chemical Industry Co., Ltd.).

[0020] <Number of ethyleneoxy or propyleneoxy groups X and number of crosslinking groups Y in the photocurable resin composition> Component (B) is preferably contained so that the number X of ethyleneoxy groups or propyleneoxy groups in the photocurable resin composition is in the range of 30 to 45, and the number Y of crosslinking groups in the photocurable resin composition is in the range of 10 to 19. The methods for calculating X and Y are described below.

[0021] X is calculated by the following formula (i), and Y is calculated by the following formula (ii). X=x B n B / (x A +xB n B +x B m B ) × 100 (i) Y=x B m B / (x A +x B n B +x B m B ) × 100 (ii) [x A : Molar fraction of component (A) x B : Molar fraction of component (B) n B : Number of ethyleneoxy or propyleneoxy groups in one molecule of component (B) m B : Number of radically polymerizable groups in one molecule of component (B)

[0022] When the composition contains, as component (D), a polyfunctional radically polymerizable compound different from component (B), X is calculated by the following formula (iii), and Y is calculated by the following formula (iv). X=x B n B / (x A +x B n B +x B m B +x D m D ) × 100 (iii) Y=x B m B +x D m D / (x A +x B n B +x B m B +x D m D ) × 100 (iv) [x A : Molar fraction of component (A) x B : Molar fraction of component (B) x D : Molar fraction of component (D) n B: Number of ethyleneoxy or propyleneoxy groups in one molecule of component (B) m B : Number of radically polymerizable groups in one molecule of component (B) m D : Number of radically polymerizable groups in one molecule of component (D)

[0023] When the composition contains, as component (E), a monofunctional radically polymerizable compound different from component (A), X is calculated by the following formula (v), and Y is calculated by the following formula (vi). X=x B n B / (x A +x E +x B n B +x B m B ) × 100 (v) Y=x B m B / (x A +x E +x B n B +x B m B ) × 100 (vi) [x A : Molar fraction of component (A) x B : Molar fraction of component (B) x E : Molar fraction of component (E) n B : Number of ethyleneoxy or propyleneoxy groups in one molecule of component (B) m B : Number of radically polymerizable groups in one molecule of component (B)

[0024] The mole fraction of each component is calculated from the amount (mass) and molecular weight of each compounded component of the composition. The mole fraction is the ratio of the amount of substance of each component to the sum of the amounts of substance of all the components, and is a dimensionless quantity with no unit.

[0025] When multiple types of compounds are contained as component (B), x B n B , x B m Bis the sum of the products of the mole fractions calculated for each compound and the number of ethyleneoxy or propyleneoxy groups in one molecule, or the number of radically polymerizable groups. x when multiple types of compounds are contained as component (D) D m D The same applies to.

[0026] The range of X that can obtain a shaped object having impact resistance and elastic modulus sufficient for practical use is from 30 to 45. The ethyleneoxy group or propyleneoxy group contained in component (B) has the effect of absorbing impact, but if X is below 30, the impact resistance decreases, and if X exceeds 45, the properties similar to those of a rubber component are expressed, resulting in a decrease in the elastic modulus.

[0027] The range of Y that can be used to obtain molded objects with impact resistance and elastic modulus sufficient for practical use is between 10 and 19. When Y is 10 or more, a high flexural modulus can be achieved, but when it exceeds 19, the number of breaking points increases when an impact is applied, resulting in a decrease in impact resistance.

[0028] By satisfying both the ranges of X and Y, it is possible to obtain a cured product with little deformation under load while securing the free volume necessary for shock absorption after radical polymerization. In particular, when the range of X is 30 to 45 and the range of Y is 10 to 19, it is possible to obtain a cured product with particularly excellent flexural modulus and impact resistance.

[0029] <Component (C): Radical polymerization initiator> The radical polymerization initiator can be appropriately selected depending on the curing conditions (irradiation wavelength, irradiation amount) of the curable resin.

[0030] Examples of polymerization initiators that generate radical species upon irradiation with light include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4'-diphenylbenzophenone, and 4,4'-diphenoxybenzophenone.

[0031] Furthermore, examples of the polymerization initiator that generates radical species by heat include azo compounds such as azobisisobutylnitrile (AIBN), and peroxides such as benzoyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyneohexanoate, tert-hexyl peroxyneohexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, cumyl peroxyneohexanoate, and cumyl peroxyneodecanoate, but are not limited to these.

[0032] The radical polymerization initiator can be used alone or in combination of two or more. The amount of the radical polymerization initiator added is preferably in the range of 0.01 to 10.00 parts by mass relative to 100 parts by mass of the radical polymerizable compound. The addition ratio of the radical polymerization initiator may be appropriately selected depending on the amount of light irradiation and further the additional heating temperature. It may also be adjusted depending on the target average molecular weight of the resulting polymer.

[0033] <Component (D): Multifunctional radical polymerizable compound different from component (B)> A polyfunctional radically polymerizable compound different from component (B) can be added as component (D) to the photocurable resin composition of the present invention, to the extent that a significant decrease in the performance of the cured product does not occur.

[0034] Examples of the component (D) include the following polyfunctional (meth)acrylates. For example, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tri ... Examples of the component (D) include, but are not limited to, erythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dioxane glycol diacrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, dioxane glycol diacrylate, dicyclopentanyl di(meth)acrylate, etc. Also, the component (D) may be used alone or in combination with a plurality of components as long as the mechanical properties of the cured product are not deteriorated.

[0035] <Component (E): Monofunctional radically polymerizable compound different from component (A)> To the photocurable resin composition of the present invention, a monofunctional radically polymerizable compound different from component (A) can be added as component (E) to the extent that a significant decrease in the performance of the cured product does not occur.

[0036] Examples of the component (E) include the following monofunctional (meth)acrylates. For example, 4-tert-butylcyclohexanol (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3-hydroxy-1-(meth)acryloyloxyadamantane, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, dicyclopentaenyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, Acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, α-(meth)acryloxy γ-butyrolactone, 2-hydroxy-o-phenylphenolpropyl (meth)acrylate, acryloylmorpholine, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, cyclohexyl (meth)acrylate, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isooctyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenylglycidyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, isooctyl (meth)acrylate (meth)acrylate, tridecyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxyditripropylene glycol (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentadieneoxyethyl (meth)acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxy methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, and the like, but are not limited to these.Furthermore, the component (E) may be added alone or in combination with a plurality of types thereof, as long as the mechanical properties of the cured product are not deteriorated.

[0037] <Component (F): Other polymerizable compounds> Other polymerizable materials may be added as component (F) to adjust viscosity or impart functionality. There are no particular limitations on the other polymerizable compounds, and examples of such compounds include cationic polymerizable compounds such as monofunctional or bifunctional or higher functional epoxy or oxetane compounds.

[0038] Examples of monofunctional or difunctional or higher functional epoxy and oxetane compounds include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD ​​diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, cyclohexane dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl- 3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, ε-caprolactone modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, bis(3,4-epoxycyclohexyl)methane, 2,2-bis(3,4-epoxycyclohexyl)propane, 1,1-bis(3,Examples of the hydroxymethyl ether include, but are not limited to, 4-epoxycyclohexylethane, alpha-pinene oxide, camphoraldehyde, limonene monoxide, limonene dioxide, 4-vinylcyclohexene monoxide, 4-vinylcyclohexene dioxide, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3-n-butyloxetane, and 3-hydroxymethyl-3-propyloxetane.

[0039] In addition, when a cationic polymerizable compound is added, a polymerization initiator that generates cationic species upon irradiation with light, a photoacid generator, or a photobase generator may be added to the composition to promote the polymerization reaction of the cationic polymerizable compound. A suitable polymerization initiator that generates cationic species upon irradiation with light is, but is not limited to, iodonium (4-methylphenyl) [4-(2-methylpropyl) phenyl]-hexafluorophosphate. Examples of photoacid generators include, but are not limited to, triarylsulfonium hexafluoroantimonate, triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis-[4-(diphenylsulfonio)phenyl]sulfide bisdihexafluoroantimonate, bis-[4-(di-4'-hydroxyethoxyphenylsulfonio)phenyl]sulfide bisdihexafluoroantimonate, bis-[4-(diphenylsulfonio)phenyl]sulfide bisdihexafluorophosphate, and diphenyliodonium tetrafluoroborate.

[0040] <Other additives> To the composition of the present invention, a polymerization inhibitor, a photosensitizer, a light stabilizer, a heat stabilizer, an antioxidant, a chain transfer agent, a curing aid, etc. can be added within a range that does not significantly deteriorate the performance of the cured product.

[0041] Examples of the polymerization inhibitor include hydroquinone-based polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinone monopropyl ether, hydroquinone monobutyl ether, hydroquinone monopentyl ether, hydroquinone monohexyl ether, hydroquinone monooctyl ether, and hydroquinone monoheptyl ether, and phenol-based polymerization inhibitors having a substituent such as 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. However, hydroquinone-based polymerization inhibitors such as hydroquinone and benzoquinone-based polymerization inhibitors such as benzoquinone may turn yellow when exposed to UV light, and are therefore suitable for obtaining thin-film cured products such as coatings. Examples of the polymerization inhibitor include, but are not limited to, those mentioned above as polymerization inhibitors during reaction and storage. The amount of addition is preferably in the range of 0.01% by mass or more and 1.00% by mass or less relative to the composition. In addition, only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used in combination. In consideration of the reduction in coloration, it is preferable to use a hydroquinone-based polymerization inhibitor in combination.

[0042] Examples of the photosensitizer include benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2,2-diethoxyacetophenone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, acylphosphine oxide, etc. The amount of the photosensitizer added is preferably in the range of 0.01% by mass to 10.00% by mass based on the composition.

[0043] There are no particular limitations on the light resistance stabilizer as long as it does not significantly affect the properties of the cured product. Examples of such stabilizers include 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, and 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol. Benzotriazole compounds such as 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)]-4-(1,1,3,3-tetramethylbutyl)phenol, and 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol; cyanoacrylate compounds such as ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate; triazine compounds; and benzophenone compounds such as octabenzone and 2,2'-4,4'-tetrahydrobenzophenone. The light resistance stabilizer may also function as a photosensitizer, in which case the photosensitizer need not be added. The amount of the additive is preferably in the range of 0.01% by mass to 10.00% by mass relative to the composition.

[0044] There are no particular limitations on the heat stabilizer as long as it does not significantly affect the properties of the cured product, and examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid having a side chain and a carbon number of 7 to 9, 4,6-bis(octylthiomethyl)-o-cresol, Examples of such compounds include hindered phenol compounds such as 4,6-bis(dodecylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)]propionate, and hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, phosphorus compounds such as tris(2,4-di-tert-butylphenyl)phosphite, and sulfur compounds such as dioctadecyl-3,3'-thiodipropionate. The amount of such compounds added is preferably in the range of 0.01% by mass to 10.00% by mass based on the composition.

[0045] There are no particular limitations on the antioxidant as long as it does not significantly affect the properties of the cured product, and examples of the antioxidant include hindered amine compounds such as bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate. The amount of the antioxidant added is preferably in the range of 0.01% by mass to 10.00% by mass based on the composition.

[0046] Examples of chain transfer agents and curing assistants include β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, 1-butanethiol, cyclohexanethiol, cyclohexyl 3-mercaptopropionate, 1-decanethiol, 2,4-diphenyl-4-methyl-1-pentene, 1-dodecanethiol, 3-mercaptopropionate, dodecyl mercaptoacetate, 2-ethylhexyl mercaptoacetate, 2-ethylhexyl 3-mercaptopropionate, ethyl mercaptoacetate, 1-hexadecanethiol, hexyl 3-mercaptopropionate, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, mercaptoacetic acid, sodium 2-mercaptoethanesulfonate, 3-mercaptopropionic acid, methyl mercaptoate, mercaptosuccinic acid, methyl 3-mercaptopropionate, octyl 3-mercaptopropionate Tadecyl, octyl 3-mercaptopropionate, 1-octanethiol, 1-octadecanethiol, tridecyl 3-mercaptopropionate, thiophenol, polyfunctional thiols such as bis(2-mercaptoethyl)sulfide, 3,6-dioxa-1,8-octanedithiol, trimethylolpropane tris(3-mercaptopropionate), 1,4-butanediol bis(thioglycolate), pentaerythritol tetra(3-mercaptopropionate), 1,4-benzene Thiol, 3,7-dithia-1,9-nonanol, DL-1,4-dimercapto-2,3-butanediol, 1,5-dimercaptonaphthalene, dithioerythritol, ethylene bisthioglycolate, pentaerythritol tetrakismercaptoacetate, tris-[(3-mercaptopropionyloxyethyl)-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 3,Examples of commercially available products include 3'-thiodipropionic acid, dithiodipropionic acid, laurylthiopropionic acid (dodecylthiopropionic acid), and TS-G, C3TS-G, TA-G, and LDAIC (manufactured by Shikoku Chemical Industry Co., Ltd.), Karenz MTPE1, BD1, NR1, and TPMB (manufactured by Showa Denko K.K.).

[0047] Furthermore, pigments, fillers, etc. may be added to adjust viscosity or impart functionality. There is no particular limitation on the filler, and it is sufficient as long as it does not deteriorate the mechanical properties of the cured product. Types of fillers include metal salts, metal oxides, polymer fine particles, rubber particles, inorganic fibers, organic fibers, carbon, etc. Metal oxides include, but are not limited to, silicon oxide, titanium oxide, aluminum oxide, etc. Polymer fine particles include, but are not limited to, acrylic fine particles, polystyrene fine particles, nylon particles, etc. Rubber particles include, but are not limited to, butadiene rubber particles, styrene-butadiene rubber copolymer particles, acrylonitrile-butadiene copolymer rubber particles, or saturated rubber particles obtained by hydrogenating or partially hydrogenating these diene rubbers, crosslinked butadiene rubber particles, isoprene rubber particles, chloroprene rubber particles, natural rubber particles, silicone rubber particles, ethylene / propylene / diene monomer terpolymer rubber particles, acrylic rubber particles, acrylic / silicone composite rubber particles, etc. Organic fibers include, but are not limited to, nylon fibers, cellulose nanofibers, etc.

[0048] <Viscosity> If the viscosity (liquid viscosity of the uncured composition measured in an atmosphere at 23°C) is less than 1,000 cps (mPa·s), modeling by liquid layer photopolymerization or photolithography is possible. However, if the viscosity is 200 cps or more, bubbles may be mixed into the cured product, or time may be required for leveling the resin liquid surface. Therefore, the composition of the present invention achieves a viscosity (liquid viscosity of the uncured composition measured in an atmosphere at 23°C) of less than 200 cps. A more preferred viscosity is 100 cps or less, and even more preferably 10 cps or less. The low liquid viscosity can suppress the mixing of bubbles, and further improves handling properties such as shortening the time required for leveling the resin liquid surface and simplifying the cleaning process performed after modeling. It can also be suitably used in spraying such as inkjet methods.

[0049] <Method of preparing the composition> The method for preparing the composition of the present invention is not particularly limited, and the simplest method is to weigh all the materials and then heat and stir them. However, if there is a concern that polymerization may occur due to heating, a polymerization inhibitor may be added as appropriate. If it is difficult to mix uniformly by heating alone, the composition may be prepared by dissolving all the materials in a solvent such as acetone and then distilling off the solvent. Furthermore, stirring using a dispersing machine such as an ultrasonic homogenizer, a ball mill, or a disk mill may be used.

[0050] <How to create an item> In the curing step of the composition, the shape of the cured product and the curing method are not particularly limited. Examples of the curing method include a method of applying the composition onto a substrate and then irradiating it with light, a method of injecting the composition into a mold and then irradiating it with light, and a photolithography method (stereolithography) in which thin films of cured products are stacked.

[0051] The method of applying the composition onto the substrate is not particularly limited. For example, the composition may be applied onto the substrate to a desired thickness using a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a slit coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater to form a coating film.

[0052] The method of performing stereolithography using the composition of the present invention can use any of the conventional stereolithography methods and devices. A preferred method is a method of stacking a cured layer obtained by photocuring a composition to a predetermined thickness. A representative example of a preferred stereolithography method is a method having a step of repeatedly disposing and curing a curable resin composition to a predetermined thickness based on slice data generated based on three-dimensional shape data of a manufacturing object (three-dimensional model).

[0053] There are two main types of stereolithography: the free surface method and the controlled surface method.

[0054] Fig. 1 shows an example of the configuration of a modeling apparatus 100 using the free surface method. The modeling apparatus 100 has a tank 11 that contains a liquid curable resin composition 10. Inside the tank 11, a modeling stage 12 is provided so as to be drivable in the vertical direction by a drive shaft 13. An active energy ray 15 for curing the curable resin composition 10, which is emitted from a light source 14, is changed in its irradiation position by a galvanometer mirror 16 controlled by a control unit 18 according to slice data, and the surface of the tank 11 is scanned. In Fig. 1, the scanning range is indicated by a thick dashed line.

[0055] The thickness d of the photocurable resin composition 10 cured by the active energy beam 15 is a value determined based on the settings at the time of generating the slice data, and affects the accuracy of the obtained article (reproducibility of the three-dimensional shape data of the article to be molded). The thickness d is achieved by the control unit 18 controlling the drive amount of the drive shaft 13.

[0056] First, the control unit 18 controls the drive shaft 13 based on the settings, and the curable resin composition is supplied to the stage 12 at a thickness d. The liquid curable resin composition on the stage 12 is selectively irradiated with active energy rays 15 based on slice data so as to obtain a cured layer having a desired pattern, and a cured layer is formed. Next, the stage 12 is moved in the direction of the white arrow, and an uncured curable resin composition is supplied to the surface of the cured layer at a thickness d. Then, based on the slice data, active energy rays 15 are irradiated to form a cured product integrated with the previously formed cured layer. By repeating this layer-by-layer curing process, the desired three-dimensional model 17 can be obtained.

[0057] When forming a cured layer having a predetermined pattern by irradiating a surface made of a curable resin composition with active energy rays, the resin can be cured by a pointillist method or a line drawing method using light energy rays focused in a dotted or line shape. Alternatively, the resin can be cured by irradiating the active energy rays in a planar manner through a planar drawing mask formed by arranging a plurality of microscopic light shutters such as liquid crystal shutters or digital micromirror shutters.

[0058] Like the free liquid level method, modeling by the regulated liquid level method is also preferable. A modeling apparatus using the regulated liquid level method is configured such that the stage 12 of the modeling apparatus 100 in FIG. 1 is provided so as to raise the model 17 above the liquid level, and the light irradiation means is provided below the tank 11. A typical modeling example by the regulated liquid level method is as follows. First, the support surface of the support stage, which is provided so as to be freely raised and lowered, and the bottom surface of the tank containing the curable resin composition are set at a predetermined distance, and the curable resin composition is supplied between the support surface of the support stage and the bottom surface of the tank. Next, light is selectively irradiated from the bottom surface side of the tank containing the curable resin composition by a laser light source or a projector according to slice data to the curable resin composition between the stage support surface and the bottom surface of the tank. The curable resin composition between the stage support surface and the bottom surface of the tank is cured by the irradiation of light, and a solid cured layer is formed. After that, the support stage is raised, and the cured layer is peeled off from the bottom surface of the tank.

[0059] Next, the height of the support stage is adjusted so that the distance between the cured layer formed on the support stage and the bottom surface of the tank is a predetermined distance. Then, as before, a curable resin composition is supplied between the bottom surface of the tank and the cured layer, and a new cured layer is formed between the cured layer and the bottom surface of the tank by irradiating light according to the slice data. By repeating this process multiple times, a model 17 in which multiple cured layers are integrally laminated can be obtained.

[0060] The shaped object 17 thus obtained is removed from the tank 11, and any unreacted curable resin composition remaining on its surface is removed. After that, the desired article can be obtained by carrying out post-processing as necessary.

[0061] Post-processing includes cleaning, post-curing, cutting, polishing, assembly, and the like.

[0062] As a cleaning agent used for cleaning, an alcohol-based organic solvent such as isopropyl alcohol, ethyl alcohol, etc. may be used. In addition, a ketone-based organic solvent such as acetone, ethyl acetate, methyl ethyl ketone, etc., or an aliphatic organic solvent such as terpenes may be used.

[0063] After washing, post-curing may be performed by light irradiation, heat irradiation, or both, as necessary. Post-curing can cure unreacted curable resin composition that may remain on the surface and inside of the three-dimensional object, suppress stickiness of the surface of the three-dimensional object, and improve the initial strength of the three-dimensional object.

[0064] Examples of active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequency waves. Among them, ultraviolet rays having a wavelength of 300 nm to 430 nm are preferably used from an economical point of view, and as a light source in this case, ultraviolet lasers (e.g., semiconductor pumped solid-state lasers, Ar lasers, He-Cd lasers, etc.), high pressure mercury lamps, ultra-high pressure mercury lamps, mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light emitting diodes), fluorescent lamps, etc. can be used. Among them, ultraviolet lasers are preferably used because they have excellent light collecting properties, can increase the energy level to shorten the modeling time, and can obtain high modeling accuracy.

[0065] <Application> The composition of the present invention can be suitably used in three-dimensional additive manufacturing, particularly in photolithography. In addition, the cured product of the present invention and the molded product obtained by a 3D printer can be widely used in the field of optical three-dimensional molding. The application fields are not limited in any way, but representative fields include prototype models of industrial products, design models, working models, base models for producing molds, direct molds for prototype molds, service parts, housings, parts of industrial products, etc. In particular, the composition of the present invention can be used to manufacture housings and parts of industrial products because it has both elastic modulus and impact resistance. EXAMPLES

[0066] Examples 1 to 12 and Comparative Examples 1 to 7 <Ingredients> Each component used in the examples and comparative examples is shown in Table 1 together with its molecular weight, the number of ethyleneoxy or propyleneoxy groups in one molecule, and the number of radically polymerizable groups in one molecule.

[0067] [Table 1]

[0068] <Production of Composition> The components were blended in the blending ratios (mass ratios) shown in Table 2 and mixed uniformly to prepare compositions.

[0069] <Production of Cured Test Pieces> A cured product was produced using the prepared composition by the following method. First, a mold 80 mm long, 10 mm wide, and 4 mm thick was placed between two pieces of quartz glass, and the composition was poured into the mold. The poured composition was irradiated with an ultraviolet ray irradiator (EX250 manufactured by HOYA CANDEO OPTRONICS Corporation) and an illuminance meter (UIT-250 manufactured by Ushio Inc.) at 10 mW / cm. 2 The UV rays were irradiated for 120 seconds, six times in total, with the irradiated surface being turned over, and then the mold was removed to obtain a cured product (total irradiated energy was 7200 mJ / cm 2 The cured product was then placed in a 50°C oven for 1 hour and then placed in a 100°C oven for 1 hour for heat treatment to obtain a cured product for test specimens.

[0070] <Evaluation of bending modulus> The flexural modulus of the obtained test pieces was measured using a universal material testing machine (INSTRON, 5581) in accordance with JIS K 7171. The flexural modulus was calculated from the stress gradient in the specified strain range (0.05% to 0.25%) under the condition of 2 mm / min. The flexural modulus was also evaluated according to the following criteria. The results are shown in Table 2. A (very good): Flexural modulus is 2.0 GPa or more. B (Good): Flexural modulus is 1.5 GPa or more and less than 2.0 GPa. C (poor): Flexural modulus is less than 1.5 GPa.

[0071] <Impact resistance evaluation> The obtained test specimen was cut with a 2 mm deep 45° notch in the center using a notch forming machine (manufactured by Toyo Seiki Seisakusho, product name "Notching Tool A-4") in accordance with JIS K 7111. Then, using an impact tester (manufactured by Toyo Seiki Seisakusho, product name "IMPACT TESTER IT"), the test specimen was broken with an energy of 2 J from the back of the notch. The energy required for breaking was calculated from the angle at which the hammer, which had been swung up to 150°, swung up after the test specimen was broken, and this Charpy impact strength was used as an index of impact resistance. In addition, impact resistance was evaluated according to the following criteria. The results are shown in Table 2. A (very good): Charpy impact strength is 6 kJ / m 2 The end. B (Good): Charpy impact strength is 5 kJ / m 2 More than 6kJ / m 2 less than. C (poor): Charpy impact strength is 5 kJ / m 2 less than.

[0072] <Measurement of liquid viscosity> The liquid viscosity of the uncured composition was measured in an atmosphere of 23° C. using an ultrasonic vibration viscometer (manufactured by Sekonic Corporation, product name "VM-10A-L"). The liquid viscosity was evaluated according to the following criteria. The results are shown in Table 2. A (very good): Liquid viscosity is less than 200 cps. B (Good): Liquid viscosity is 200 cps or more and less than 1,000 cps.

[0073] <Stereolithography> A 3D printer (ML-48, manufactured by Mutoh Engineering Co., Ltd.) was used to create a model of 80 mm in length, 10 mm in width, and 4 mm in thickness by stereolithography under conditions of a layer pitch of 0.1 mm and an exposure time of 60 seconds per layer. The resulting model was subjected to a secondary curing process at a temperature of 60° C. for 60 minutes using a secondary curing tool (Formcure, manufactured by Formlabs). The obtained cured product was evaluated for impact resistance and flexural modulus in the same manner as the test specimen cured product. The evaluation results of the cured product obtained by stereolithography and the test specimen cured product are shown in Table 3.

[0074] [Table 2]

[0075] [Table 3]

[0076] As shown in Table 2, in comparison between Examples 1 to 6, which use a compound (component (B)) having 3 to 15 ethyleneoxy or propyleneoxy groups and 2 or more radically polymerizable groups in one molecule as the polyfunctional radically polymerizable compound, and Comparative Example 9, which uses a polyfunctional radically polymerizable material D-1 having no ethyleneoxy or propyleneoxy groups in the molecule, the cured products of Examples 1 to 6 have high impact resistance. On the other hand, compared to Comparative Example 14, which uses D-3 having more than 15 ethyleneoxy or propyleneoxy groups in one molecule, the cured products of Examples 1 to 6 have high flexural modulus.

[0077] In addition, when comparing Examples 1 to 6 in which X is within the range of 30 to 45 and Y is within the range of 10 to 19 with Comparative Examples 1 to 15 in which X and Y are not within these ranges, it is clear that Examples 1 to 6 can achieve both high flexural modulus and impact resistance. In addition, the liquid viscosity was 10 cps or less in all cases.

[0078] Furthermore, as can be seen from Table 3, the test pieces obtained by stereolithography have performance equivalent to that of molded products.

[0079] From the above results, it is clear that the composition of the present invention can give a cured product that has both high impact resistance and flexural modulus, and since the liquid viscosity in the uncured state is low, it is also clear that the composition can be suitably used for optical three-dimensional modeling. [Explanation of symbols]

[0080] 10: curable resin composition, 12: stage, 15: active energy ray, 17: modeled object, 100: modeling device

Claims

1. A photocurable resin composition comprising component (A), component (B) and component (C), The component (A) is a compound represented by the following general formula (1): 【Chemistry 1】 [In the general formula (1), R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group may have a substituent.] The component (B) is a compound having 3 to 15 ethyleneoxy groups or propyleneoxy groups and 2 or more radical polymerizable groups in one molecule, The component (C) is a radical polymerization initiator, The number X of ethyleneoxy groups or propyleneoxy groups in the photocurable resin composition is calculated by the following formula (i): The number Y of crosslinking groups in the photocurable resin composition is calculated by the following formula (ii): X=x B n B / (x A +x B n B +x B m B )×100 ・・・(i) Y=x B m B / (x A +x B n B +x B m B )×100 ・・・(ii) [x A : Molar fraction of the component (A) x B : Molar fraction of the component (B) n B : the number of ethyleneoxy groups or propyleneoxy groups in one molecule of the component (B) m B : the number of radically polymerizable groups in one molecule of the component (B) A photocurable resin composition, wherein X is in the range of 30 or more and 45 or less, and Y is in the range of 10 or more and 19 or less.

2. 2. The photocurable resin composition according to claim 1, wherein the content of the component (A) is 60% by mass or more and 80% by mass or less.

3. 2. The photocurable resin composition according to claim 1, wherein the content of the component (A) is 65% by mass or more and 75% by mass or less.

4. 4. The photocurable resin composition according to claim 1, having a viscosity of less than 200 cps.

5. 5. The photocurable resin composition according to claim 1, wherein the component (B) has 6 to 14 ethyleneoxy groups or propyleneoxy groups in one molecule.

6. 6. The photocurable resin composition according to claim 1, wherein the component (B) contains a group having a carbon-carbon double bond as the radical polymerizable group.

7. 7. The photocurable resin composition according to claim 6, wherein the group having a carbon-carbon double bond is an acryloyl group.

8. A photocurable resin composition comprising component (A), component (B), component (C) and component (D), The component (A) is a compound represented by the following general formula (1): 【Chemistry 2】 [In the general formula (1), R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group may have a substituent.] The component (B) is a compound having 3 to 15 ethyleneoxy groups or propyleneoxy groups and 2 or more radical polymerizable groups in one molecule, The component (C) is a radical polymerization initiator, The component (D) is a polyfunctional radical polymerizable compound different from the component (B), The number X of ethyleneoxy groups or propyleneoxy groups in the photocurable resin composition is calculated by the following formula (iii): The number Y of crosslinking groups in the photocurable resin composition is calculated by the following formula (iv): X=x B n B / (x A +x B n B +x B m B +x D m D )×100 ・・・(iii) Y=x B m B +x D m D / (x A +x B n B +x B m B +x D m D )×100 ・・・(iv) [x A : Molar fraction of the component (A) x B : Molar fraction of the component (B) x D : Molar fraction of the component (D) n B : the number of ethyleneoxy groups or propyleneoxy groups in one molecule of the component (B) m B : the number of radically polymerizable groups in one molecule of the component (B) m D : the number of radically polymerizable groups in one molecule of the component (D) A photocurable resin composition, wherein X is in the range of 30 or more and 45 or less, and Y is in the range of 10 or more and 19 or less.

9. The photocurable resin composition according to claim 8 , wherein the content of the component (A) is 60% by mass or more and 80% by mass or less.

10. The photocurable resin composition according to claim 8 , wherein the content of the component (A) is 65% by mass or more and 75% by mass or less.

11. 11. The photocurable resin composition according to claim 8, having a viscosity of less than 200 cps.

12. 12. The photocurable resin composition according to claim 8, wherein the component (B) has 6 to 14 ethyleneoxy groups or propyleneoxy groups in one molecule.

13. 13. The photocurable resin composition according to claim 8, wherein the component (B) contains a group having a carbon-carbon double bond as the radical polymerizable group.

14. 14. The photocurable resin composition according to claim 13, wherein the group having a carbon-carbon double bond is an acryloyl group.

15. A cured product obtained by curing the photocurable resin composition according to claim 1 .

16. The cured product described in Claim 15, characterized in that the flexural modulus of the cured product is 1.5 GPa or more.

17. The cured product according to claim 15 or 16, characterized in that the Charpy impact strength of the cured product is 6 kJ / m 2 or more.

18. A method for producing an article, comprising repeating a step of photocuring the photocurable resin composition according to claim 1 to a predetermined thickness to form a cured layer multiple times.

19. disposing a curable resin composition at a predetermined thickness; a step of irradiating the curable resin composition with light energy based on slice data of a three-dimensional model to cure the composition; 20. The method of claim 18, comprising:

20. The method for manufacturing an article according to claim 19, further comprising a step of washing or post-curing a shaped object obtained by repeating a step of disposing the curable resin composition to a predetermined thickness and a step of irradiating the curable resin composition with light energy to cure the composition multiple times.

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