Curable resin composition and method of manufacturing article

Abstract

To provide a curable resin composition which enables formation of a cured product having impact resistance and high elastic modulus, and has low viscosity, thereby being suitable for three-dimensional shaping.SOLUTION: A curable resin composition contains component (A): an α-(unsaturated alkoxyalkyl)acrylic acid or acrylate, component (B): a bifunctional radical polymerizable oligomer, component (D): rubber particles, and component (E): a radical polymerizable initiator, may further contain component (C): a radical polymerizable compound other than the components (A) and (B), wherein the component (A) is represented by the following general formula (1), and the component (B) is composed of an oligomer site in which two or more monomer units are connected to each other by any one of a carbonate group, an ester group and an ether group, and two polymerizable functional groups. In the general formula (1), R1 is a hydrogen atom or an organic group; R2 is a methylene group; one of R3 and R4 is a methylene group, and the other is an oxygen atom; and R5 is a hydrogen atom, an alkyl group or an ester group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a curable resin composition, its cured product, and a method for producing articles. [Background technology]

[0002] A known optical stereolithography method (hereinafter referred to as stereolithography) is known in which a photocurable resin composition is selectively irradiated with light based on the three-dimensional shape of a three-dimensional model to form a cured resin layer, and this process is repeated to produce a molded object in which the cured resin layer is integrally laminated. Specifically, according to slice data generated from the shape data of the three-dimensional model to be fabricated, light from an ultraviolet laser or UV-LED is irradiated onto the surface of the liquid photocurable resin composition contained in a container, forming a cured resin layer with a predetermined thickness and a desired pattern. Next, one layer of the photocurable resin composition is supplied on top of this cured resin layer, and light is irradiated in the same way, thereby laminating a new cured resin layer that is continuous with the previously formed cured resin layer. In this way, by laminating cured resin layers according to the pattern based on the slice data, the desired object can be obtained. With this type of stereolithography method, even objects with complex shapes can be easily fabricated if the shape data of the three-dimensional model is available. Stereolithography is increasingly being applied to the creation of prototypes for shape verification (rapid prototyping), and the creation of working models and molds for functionality verification (rapid tooling). Furthermore, in recent years, the applications of stereolithography have begun to expand to the creation of actual products (rapid manufacturing). The resin compositions used in stereolithography require low viscosity from the standpoint of ease of handling during molding and molding accuracy. Furthermore, against the backdrop of the expanding range of applications mentioned above, there is a demand for the cured products to have impact resistance and high modulus of elasticity comparable to general-purpose engineering plastics. Patent Document 1 discloses a curable resin composition containing a urethane (meth)acrylate having a specific structure, a radical polymerizable compound, elastomer particles, and a radical polymerization initiator. Patent Document 2 also discloses a curable resin composition containing a cyclizable monomer having an acrylate moiety and an ethenyl or ethynyl moiety, wherein the α-carbon of the acrylate moiety and the α-carbon of the ethenyl or ethynyl moiety have a 1,5-, 1,6-, 1,7-, or 1,8- relationship. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2004-051665 [Patent Document 2] Special Publication No. 2020-505255 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, the curable resin composition disclosed in Patent Document 1 does not provide sufficient properties in terms of viscosity and impact resistance of the cured product. Furthermore, the curable resin composition disclosed in Patent Document 2 has low viscosity, and although its cured product has a high modulus of elasticity, it does not have sufficient impact resistance. Thus, a curable resin composition that simultaneously satisfies low viscosity, high modulus of elasticity of the cured product, and impact resistance has not yet been realized. The present invention aims to provide a curable resin composition that yields a cured product with impact resistance and a high modulus of elasticity, and which has low viscosity and excellent handling properties during molding. [Means for solving the problem]

[0005] The curable resin composition according to the present invention is Component (A): α-(unsaturated alkoxyalkyl)acrylic acid or its ester, Component (B): A bifunctional radical polymerizable oligomer, Component (D): rubber particles, and Component (E): radical polymerization initiator, and contains Furthermore, Component (C): a radical polymerizable compound other than the above components (A) and (B), may contain The component (A) is α-(unsaturated alkoxyalkyl) acrylic acid or an ester thereof represented by the following general formula (1),

[0006]

Chemical formula

Advantages of the Invention

[0007] According to the present invention, it is possible to form a cured product having impact resistance and a high elastic modulus, and it is possible to provide a curable resin composition having a low viscosity and suitable for three-dimensional shaping.

Brief Description of the Drawings

[0008] [Figure 1] It is a diagram showing a configuration example of a stereolithography apparatus.

Mode for Carrying Out the Invention

[0009] Hereinafter, embodiments of the present invention will be described. Note that the embodiments described below are merely one of the embodiments of the present invention, and the present invention is not limited to these embodiments.

[0010] <Component (A): α-(unsaturated alkoxyalkyl)acrylic acid or its ester> Component (A) is α-(unsaturated alkoxyalkyl)acrylic acid or its ester represented by the following general formula (1).

[0011]

Chemical formula

[0012] In the above general formula (1), R1 is a hydrogen atom or an organic group having 1 to 30 carbon atoms. The organic group represented by R1 is preferably a hydrocarbon group. The hydrocarbon group is composed of hydrocarbons, may have an ether structure, and the hydrogen atoms of the hydrocarbons may be substituted with substituents. Also, the organic group may be linear, branched, or may have a cyclic structure.

[0013] Examples of the hydrocarbon group include a linear saturated hydrocarbon having 1 or more carbon atoms, a linear unsaturated hydrocarbon having 3 or more carbon atoms, an alicyclic hydrocarbon group having 3 or more carbon atoms, an aromatic hydrocarbon group having 6 or more carbon atoms, and the like.

[0014] Among these, preferably, a linear saturated hydrocarbon group having 1 to 20 carbon atoms, a linear unsaturated hydrocarbon having 3 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a linear saturated hydrocarbon having 1 to 10 carbon atoms.

[0015] For example, the chain-like saturated hydrocarbon group can be any linear or branched hydrocarbon group and is not particularly limited, but suitable examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, n-amyl, s-amyl, t-amyl, neopentyl, n-hexyl, s-hexyl, n-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl, ceryl, and mericyl. Furthermore, at least some of the hydrogen atoms bonded to the carbon atoms constituting the chain-like saturated hydrocarbon group may be substituted with halogen atoms, cyano groups, trimethylsilyl groups, etc.

[0016] The linear unsaturated hydrocarbon group can be any linear or branched hydrocarbon group containing at least one carbon-carbon unsaturated bond that is not aromatic, and is not particularly limited. However, suitable examples include clotyl, 1,1-dimethyl-2-propenyl, 2-methyl-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 2-methyl-3-butenyl, oleyl, linole, linolene, and the like.

[0017] The alicyclic hydrocarbon group can be any hydrocarbon group containing a saturated cyclic structure with three or more members, or an unsaturated cyclic structure that does not have an aromatic attribute, and is not particularly limited. However, suitable examples include cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, tricyclodecanyl, isobornyl, adamantyl, dicyclopentanyl, and dicyclopentenyl.

[0018] The aromatic hydrocarbon group can be any hydrocarbon group containing a cyclic structure with six or more members and aromatic properties, and is not particularly limited. However, suitable examples include groups such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-t-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, and anthranyl.

[0019] The monovalent organic group consisting of a hydrocarbon skeleton containing an ether bond can be any structure in which an oxygen atom is inserted into at least one carbon-carbon bond constituting a chain-like saturated hydrocarbon group, a chain-like unsaturated hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and is not particularly limited, but for example, chain-like ether groups such as methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, and ethoxyethoxyethyl: cyclopentoxyethyl, cyclohexyloxyethyl, cyclopentoxyethoxyethyl, cyclohexyloxyethoxy Suitable examples include groups having both an alicyclic hydrocarbon group and a linear ether group, such as cycloethyl and dicyclopentenyloxyethyl; groups having both an aromatic hydrocarbon group and a linear ether group, such as phenoxyethyl and phenoxyethoxyethyl; and cyclic ether groups such as glycidyl, β-methylglycidyl, β-ethylglycidyl, 3,4-epoxycyclohexylmethyl, 2-oxetanemethyl, 3-methyl-3-oxetanemethyl, 3-ethyl-3-oxetanemethyl, tetrahydrofuranil, tetrahydrofurfuryl, tetrahydropyranil, dioxazolanil, and dioxanil.

[0020] R2 is a methylene group which may have an alkyl group having 1 to 4 carbon atoms. R3 and R4 are either a methylene group which may have an alkyl group having 1 to 4 carbon atoms, or an oxygen atom. Here, it is preferable that R4 is a methylene group which may have an alkyl group having 1 to 4 carbon atoms, and R3 is an oxygen atom. More preferably, R2 and R4 are methylene groups, and R3 is an oxygen atom. In this case, polymerization forms an ether-containing ring structure with methylene groups on both sides, making it easier to obtain a cured product that has both elastic modulus and impact resistance.

[0021] R5 is one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an ester group. Of these, from the viewpoint of the impact resistance of the cured product, it is preferable that the part in question is not bulky and does not hinder the flexibility of the main chain, and for this reason, it is preferable that it is a hydrogen atom, a methyl group, a methyl ester group, or an ethyl ester group. More preferably, R5 is a hydrogen atom.

[0022] Examples of suitable compound names for component (A) include α-allyloxymethylacrylic acid, α-allyloxymethylacrylate methyl, α-allyloxymethylacrylate ethyl, α-allyloxymethylacrylate n-propyl, α-allyloxymethylacrylate i-propyl, α-allyloxymethylacrylate n-butyl, α-allyloxymethylacrylate n-amyl, α-allyloxymethylacrylate s-amyl, α-allyloxymethylacrylate t-amyl, α-allyloxymethylacrylate neopentyl, α-allyloxymethylacrylate n-hexyl methylacrylate, s-hexyl α-allyloxymethylacrylate, n-heptyl α-allyloxymethylacrylate, n-octyl α-allyloxymethylacrylate, s-octyl α-allyloxymethylacrylate, t-octyl α-allyloxymethylacrylate, 2-ethylhexyl α-allyloxymethylacrylate, capryl α-allyloxymethylacrylate, nonyl α-allyloxymethylacrylate, decyl α-allyloxymethylacrylate, undecyl α-allyloxymethylacrylate, α-allyloxymethylacrylate Lauryl oxymethylacrylate, Tridecyl α-allyloxymethylacrylate, Myristyl α-allyloxymethylacrylate, Pentadecyl α-allyloxymethylacrylate, Cetyl α-allyloxymethylacrylate, Heptadecyl α-allyloxymethylacrylate, Stearyl α-allyloxymethylacrylate, Nonadecyl α-allyloxymethylacrylate, Eicosyl α-allyloxymethylacrylate, Ceryl α-allyloxymethylacrylate, Melicyl α-allyloxymethylacrylate, α-allyloxymethyl Crotyl acrylate, 1,1-dimethyl-2-propenyl α-allyloxymethylacrylate, 2-methylbutenyl α-allyloxymethylacrylate, 3-methyl-2-butenyl α-allyloxymethylacrylate, 3-methyl-3-butenyl α-allyloxymethylacrylate, 2-methyl-3-butenyl α-allyloxymethylacrylate, oleyl α-allyloxymethylacrylate, linolenic α-allyloxymethylacrylate, linolene α-allyloxymethylacrylate, cyclopentyl α-allyloxymethylacrylateα-Allyloxymethyl acrylate cyclopentylmethyl, α-Allyloxymethyl acrylate cyclohexyl, α-Allyloxymethyl acrylate cyclohexylmethyl, α-Allyloxymethyl acrylate 4-methylcyclohexyl, α-Allyloxymethyl acrylate 4-t-butylcyclohexyl, α-Allyloxymethyl acrylate tricyclodecanyl, α-Allyloxymethyl acrylate isobornyl, α-Allyloxymethyl acrylate adamantyl, α-Allyloxymethyl acrylate dicyclopentanyl, α-Allyloxymethyl acrylate Dicyclopentenyl lylate, α-allyloxymethylacrylate phenyl, α-allyloxymethylacrylate methylphenyl, α-allyloxymethylacrylate dimethylphenyl, α-allyloxymethylacrylate trimethylphenyl, α-allyloxymethylacrylate 4-t-butylphenyl, α-allyloxymethylacrylate benzyl, α-allyloxymethylacrylate diphenylmethyl, α-allyloxymethylacrylate diphenylethyl, α-allyloxymethylacrylate triphenylmethyl, α-allyloxymethylacrylate Cinnamyl acid, naphthyl α-allyloxymethylacrylate, anthranyl α-allyloxymethylacrylate, methoxyethyl α-allyloxymethylacrylate, methoxyethoxyethyl α-allyloxymethylacrylate, methoxyethoxyethoxyethyl α-allyloxymethylacrylate, 3-methoxybutyl α-allyloxymethylacrylate, ethoxyethyl α-allyloxymethylacrylate, ethoxyethoxyethyl α-allyloxymethylacrylate, cyclopentoxyethyl α-allyloxymethylacrylate, α-allyloxy Cyclohexyloxyethyl methylacrylate, cyclopentoxyethoxyethyl α-allyloxymethylacrylate, cyclohexyloxyethoxyethyl α-allyloxymethylacrylate, dicyclopentenyloxyethyl α-allyloxymethylacrylate, phenoxyethyl α-allyloxymethylacrylate, phenoxyethoxyethyl α-allyloxymethylacrylate, glycidyl α-allyloxymethylacrylate, β-methylglycidyl α-allyloxymethylacrylate, β-ethylglycidyl α-allyloxymethylacrylateα-Allyloxymethylacrylate 3,4-epoxycyclohexylmethyl, α-Allyloxymethylacrylate 2-oxetanemethyl, α-Allyloxymethylacrylate 3-methyl-3-oxetanemethyl, α-Allyloxymethylacrylate 3-ethyl-3-oxetanemethyl, α-Allyloxymethylacrylate tetrahydrofuranyl, α-Allyloxymethylacrylate tetrahydrofurfuryl, α-Allyloxymethylacrylate tetrahydropyranyl, α-Allyloxymethylacrylate dioxazolanyl, α-Allyloxymethyl Dioxanyl acrylate, α-methallyloxymethylacrylic acid, α-methallyloxymethylacrylate methyl, α-methallyloxymethylacrylate ethyl, α-methallyloxymethylacrylate n-propyl, α-methallyloxymethylacrylate i-propyl, α-methallyloxymethylacrylate n-butyl, α-methallyloxymethylacrylate n-amyl, α-methallyloxymethylacrylate s-amyl, α-methallyloxymethylacrylate t-amyl, α-methallyloxymethylacrylate neopentyl, α-methallyloxymethyl n-hexyl acrylate, s-hexyl α-methallyloxymethylacrylate, n-heptyl α-methallyloxymethylacrylate, n-octyl α-methallyloxymethylacrylate, s-octyl α-methallyloxymethylacrylate, t-octyl α-methallyloxymethylacrylate, 2-ethylhexyl α-methallyloxymethylacrylate, capryl α-methallyloxymethylacrylate, nonyl α-methallyloxymethylacrylate, decyl α-methallyloxymethylacrylate, undecyl α-methallyloxymethylacrylate, α - Lauryl methallyloxymethylacrylate, tridecyl α-methallyloxymethylacrylate, myristyl α-methallyloxymethylacrylate, pentadecyl α-methallyloxymethylacrylate, cetyl α-methallyloxymethylacrylate, heptadecyl α-methallyloxymethylacrylate, stearyl α-methallyloxymethylacrylate, nonadecyl α-methallyloxymethylacrylate, eicosyl α-methallyloxymethylacrylate, ceryl α-methallyloxymethylacrylate, melicyl α-methallyloxymethylacrylateα-Methallyloxymethylacrylate clotyl, α-Methallyloxymethylacrylate 1,1-dimethyl-2-propenyl, α-Methallyloxymethylacrylate 2-methylbutenyl, α-Methallyloxymethylacrylate 3-methyl-2-butenyl, α-Methallyloxymethylacrylate 3-methyl-3-butenyl, α-Methallyloxymethylacrylate 2-methyl-3-butenyl, α-Methallyloxymethylacrylate oleyl, α-Methallyloxymethylacrylate linole, α-Methallyloxymethylacrylate linolene, α-Meth Cyclopentyl lyloxymethylacrylate, cyclopentylmethyl α-methallyloxymethylacrylate, cyclohexyl α-methallyloxymethylacrylate, cyclohexylmethyl α-methallyloxymethylacrylate, 4-methylcyclohexyl α-methallyloxymethylacrylate, 4-t-butylcyclohexyl α-methallyloxymethylacrylate, tricyclodecanyl α-methallyloxymethylacrylate, isobornyl α-methallyloxymethylacrylate, adamantyl α-methallyloxymethylacrylate, α-methally Dicyclopentanyl α-methallyloxymethylacrylate, dicyclopentenyl α-methallyloxymethylacrylate, phenyl α-methallyloxymethylacrylate, methylphenyl α-methallyloxymethylacrylate, dimethylphenyl α-methallyloxymethylacrylate, trimethylphenyl α-methallyloxymethylacrylate, 4-t-butylphenyl α-methallyloxymethylacrylate, benzyl α-methallyloxymethylacrylate, diphenylmethyl α-methallyloxymethylacrylate, diphenylethyl α-methallyloxymethylacrylate, triphenylmethyl α-methallyloxymethylacrylate, cinnamyl α-methallyloxymethylacrylate, naphthyl α-methallyloxymethylacrylate, anthranyl α-methallyloxymethylacrylate, methoxyethyl α-methallyloxymethylacrylate, methoxyethoxyethyl α-methallyloxymethylacrylate, methoxyethoxyethyl α-methallyloxymethylacrylate, 3-methoxybutyl α-methallyloxymethylacrylate, ethoxyethyl α-methallyloxymethylacrylateα-Methyloxymethylacrylate ethoxyethoxyethyl, α-Methyloxymethylacrylate cyclopentoxyethyl, α-Methyloxymethylacrylate cyclohexyloxyethyl, α-Methyloxymethylacrylate cyclopentoxyethoxyethyl, α-Methyloxymethylacrylate cyclohexyloxyethoxyethyl, α-Methyloxymethylacrylate dicyclopentenyloxyethyl, α-Methyloxymethylacrylate phenoxyethyl, α-Methyloxymethylacrylate phenoxyethyl Toxyethyl, α-methallyloxymethylacrylate glycidyl, α-methallyloxymethylacrylate β-methylglycidyl, α-methallyloxymethylacrylate β-ethylglycidyl, α-methallyloxymethylacrylate 3,4-epoxycyclohexylmethyl, α-methallyloxymethylacrylate 2-oxetanemethyl, α-methallyloxymethylacrylate 3-methyl-3-oxetanemethyl, α-methallyloxymethylacrylate 3-ethyl-3-oxetanemethyl, α-methallyloxymethylacrylate tetrahydride Lofuranil, α-methallyloxymethylacrylate tetrahydrofurfuryl, α-methallyloxymethylacrylate tetrahydropyranyl, α-methallyloxymethylacrylate dioxanyl, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate , di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(t-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(t-amyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(stearyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(lauryl)-2,2'-[oxybis(methylene)]bis-2-propenoate,Di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, Di(1-methoxyethyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, Di(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, Dibenzyl-2,2'-[oxybis(methylene)]bis-2-propenoate, Diphenyl-2,2'-[oxybis(methylene)]bis-2-propenoate, Dicyclohexyl-2,2'-[oxybis, Examples include (methylene)bis-2-propenoate, di(t-butylcyclohexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(tricyclodecanyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isobornyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, diadamantyl-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-propenoate.

[0023] Among these, compounds containing an ether structure in the main chain and polymerizing while forming a 5-membered or 6-membered ring are preferred, and α-allyloxymethylacrylate, α-allyloxymethylacrylate, α-methallyloxymethylacrylate, and dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate can be used more preferably. Among these, α-allyloxymethylacrylate, which forms a ring structure like the following structural formula (2) during polymerization, can be used most preferably from the viewpoint of impact resistance and elastic modulus of the cured product.

[0024] [ka]

[0025] The reason why particularly high impact resistance can be obtained in this structure is that the ether bond of the tetrahydrofuran ring and the methylene group adjacent to the tetrahydrofuran ring contribute to improving the flexibility of the main chain. On the other hand, because the ring structure is incorporated into the main chain, it also has a high modulus of elasticity in addition to its impact resistance. Note that commercially available α-allyloxymethylacrylate can be used, for example, it is available from Nippon Shokubai Co., Ltd. under the name AOMA.

[0026] The content of component (A) is not particularly limited, but from the viewpoint of the impact resistance of the cured product, it is preferable that the content is more than 70 parts by mass and 100 parts by mass or less, and more preferably 75 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the total of components (A) and (C). Furthermore, the total content of components (A) and (C) is preferably more than 70 parts by mass and less than 90 parts by mass, relative to 100 parts by mass of the total of components (A), (B), and (C). By setting the content within the above range, the impact resistance improvement effect of component (A) becomes clearly apparent.

[0027] <Component (B): Bifunctional radical polymerizable oligomer> Component (B) is a difunctional radical polymerizable oligomer consisting of an oligomer moiety in which two or more monomer units are linked by carbonate groups, ester groups, or ether groups, and two polymerizable functional groups. Examples of polymerizable functional groups include ethylenically unsaturated groups. Specifically, examples of ethylenically unsaturated groups include (meth)acryloyl groups and vinyl groups. In this specification, (meth)acryloyl group means acryloyl group or methacryloyl group.

[0028] Examples of component (B) include polycarbonate di(meth)acrylate, polyester di(meth)acrylate, and polyether di(meth)acrylate. Among these, it is preferable that the monomer unit consists of hydrocarbon groups, from the viewpoint of the impact resistance obtained when combined with component (A). Here, the monomer unit refers to the oligomer from which ether groups, ester groups, and carbonate groups have been removed. Examples of hydrocarbon groups include linear saturated hydrocarbons, linear unsaturated hydrocarbons, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and specific examples are the same as those described for component (A). Among these, polycarbonate di(meth)acrylate and polyether di(meth)acrylate, in which the monomer unit consists of hydrocarbon groups, are preferred, and polycarbonate di(meth)acrylate, in which the monomer unit consists of linear saturated hydrocarbons or alicyclic hydrocarbons, is particularly preferred.

[0029] Polycarbonate di(meth)acrylate, polyester di(meth)acrylate, and polyether(meth)diacrylate can be obtained by using polycarbonate diol, polyester diol, and polyether diol as raw materials and attaching (meth)acrylic groups to both ends.

[0030] Polycarbonate diols can be represented by the following general formula (3).

[0031] [ka]

[0032] (In the formula, n represents a number greater than or equal to 2. R is any base, and Rs may be identical or different.)

[0033] The polycarbonate diol represented by general formula (3) may be produced by any method, but can be obtained, for example, by a transesterification reaction between a diol compound and a carbonate ester.

[0034] The diol compounds used as raw materials for polycarbonate diols are not particularly limited, and include, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanodiol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, and other diols without side chains, 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-b Examples include diols with side chains such as ethyl-2-ethyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol; cyclic diols such as 1,4-cyclohexanedimethanol and 2-bis(4-hydroxycyclohexyl)-propane; hydroquinone, 1,4-benzenedimethanol, 3,6-bis(hydroxymethyl)julen, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, and diols with aromatic rings such as 4,4'-dihydroxybiphenyl and 4,4'-biphenyldimethanol. Furthermore, one or more of these diols can be used in combination.

[0035] Examples of carbonate esters used as raw materials for polycarbonate diols include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkylene carbonates such as ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. One or more carbonate esters from these can be used as raw materials. When dialkyl carbonates and / or diaryl carbonates are used, it is preferable because a polycarbonate diol satisfying a specific primary terminal OH ratio can be easily obtained by adjusting conditions such as the charging ratio of the diol and the carbonate. Furthermore, from the viewpoint of ease of availability and ease of setting the conditions for polymerization reactions, it is even more preferable to use ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, or dibutyl carbonate.

[0036] Commercially available polycarbonate diols can also be suitably selected. Suitable options for the present invention can be appropriately selected from products such as Duranol(R) (manufactured by Asahi Kasei Corporation), Beneviol(R) (manufactured by Mitsubishi Chemical Corporation), Eternacol(R) (manufactured by Ube Industries, Ltd.), Nipponan(R) 981, 980R, 982R, 976, 965, 963, 964, 968 (manufactured by Tosoh Corporation), and Kuraray Polyol(R) C-2090 (manufactured by Kuraray Co., Ltd.).

[0037] Polyester diols can be represented by the following general formula (4).

[0038] [ka]

[0039] (In the formula, n represents a number greater than or equal to 2. R is any base, and Rs may be identical or different.)

[0040] The polyester diol shown in general formula (4) may be produced by any method, but can be obtained, for example, by a dehydration condensation reaction between a diol compound and a dicarboxylic acid.

[0041] The diol compounds used as raw materials for polyester diols can be the same as those used as raw materials for polycarbonate diols.

[0042] The dicarboxylic acids used as raw materials for polyester diols are not particularly limited and include, for example, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, fumaric acid, itaconic acid, and maleic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, and anthracenedicarboxylic acid; and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid. One or more dicarboxylic acids from these can be used as raw materials. Furthermore, the aforementioned dicarboxylic acid can also be used in the reaction in the form of an acid anhydride, in which case it reacts with water in the reaction system to produce the dicarboxylic acid.

[0043] Commercially available polyester diols can also be suitably selected. These include diols from Polylight(R) (manufactured by DIC Corporation), Maximol(R) RDK-133, RDK-142 (manufactured by Kawasaki Chemical Industries, Ltd.), Nipponran(R) 4002, 4040, 4009, 4010, 3027, 164, 4073, 136, 1004, 141, 4042, 5018, 5035 (manufactured by Tosoh Corporation), diols from Adeka New Ace(R) (manufactured by ADEKA Corporation), and Kuraray Polyol(R). From P-5010, P-2050, P-2010, P-2020, P-2030, P-1010, P-2011 (manufactured by Kuraray Co., Ltd.), Arronix(R) M-6000 series, M-7000 series, M-9000 series (manufactured by Toagosei Co., Ltd.), SATOMER CN2203, CN2254, CN2270, CN2271, CN2273, CN2274, etc., suitable for the present invention can be appropriately selected.

[0044] Polyetherdiols can be represented by the following general formula (5).

[0045] [ka]

[0046] (In the formula, n represents a number greater than or equal to 2. R is any base, and Rs may be identical or different.)

[0047] The polyetherdiol shown in general formula (5) may be produced by any method, but can be obtained, for example, by addition polymerization of a ring-opening polymerization of a cyclic ether. Alternatively, copolymerized polyetherdiols obtained by random copolymerizing one or more compounds selected from diol compounds, alkylene oxides, oxetanes, cyclic acetals, 3-methyltetrahydrofurans, and 2-methyltetrahydrofurans with a starting cyclic ether can be used as reaction initiators for ring-opening polymerization.

[0048] The diol compounds used as raw materials for polyether diols are the same as those used as raw materials for polycarbonate diols.

[0049] The cyclic ether used as a raw material for polyetherdiols is not particularly limited, and can be cyclic ethers such as tetrahydrofuran (THF), ethylene oxide, propylene oxide, oxetane, tetrahydropyran, and oxepan, or cyclic ether derivatives in which part of the hydrocarbon of the cyclic ether is substituted with an alkyl group. In addition, one or more of these cyclic ethers can be used as raw materials.

[0050] Commercially available polyetherdiols can also be suitably selected. Suitable options for the present invention can be appropriately chosen from products such as Exenol(R) (manufactured by Asahi Glass Co., Ltd.), Adeka Polyether(R) P, BPX, CM, PR (manufactured by ADEKA Corporation), Sannix(R) PL-2100, PP (manufactured by Sanyo Chemical Industries, Ltd.), and Toho Polyol (manufactured by Toho Chemical Industry Co., Ltd.).

[0051] The weight-average molecular weight (Mw) of component (B) is preferably 400 to 5,000, more preferably 400 to 4,000. A weight-average molecular weight of 400 or more is preferable because the impact resistance of the cured product tends to increase with decreasing crosslinking density. Furthermore, a weight-average molecular weight of 5,000 or less makes it easier to obtain high mechanical strength in addition to impact resistance. From the viewpoint of the viscosity of the curable resin composition, a weight-average molecular weight of 5,000 or less is also preferable. Note that the weight-average molecular weight (Mw) of component (B) is the weight-average molecular weight calculated on a standard polystyrene molecular weight basis, and was measured using high-performance liquid chromatography (Tosoh Corporation, high-performance GPC instrument "HLC-8220GPC") with a column: Shodex GPCLF-804 (exclusion limit molecular weight: 2 × 10⁻⁶). 6 Separation range: 300 to 2x10 6 The measurement is performed by using two of these in series.

[0052] The content of component (B) is not particularly limited, but it is desirable to have more than 10 parts by mass relative to 100 parts by mass of the total of components (A), (B), and (C). More preferably, it is more than 10 parts by mass and less than 30 parts by mass. If the amount of component (B) is more than 10 parts by mass, good impact resistance is likely to be obtained as a physical property of the cured product. Furthermore, if it is less than 30 parts by mass, high mechanical strength is likely to be obtained in addition to impact resistance.

[0053] The inventors diligently researched the conditions for an oligomer that can achieve both impact resistance and high modulus of elasticity when combined with a mixed system of component (A) and component (D), described later. As a result, as mentioned above, it was confirmed that when the monomer unit is a bifunctional radical polymerizable oligomer in which two or more monomer units are linked by either a carbonate group, an ester group, or an ether group, it exhibits unexpectedly excellent impact resistance and high modulus of elasticity. To explain the reason for this, we consider a polyfunctional urethane oligomer, which is outside the scope of the present invention. Generally, polyfunctional urethane oligomers have a structure consisting of hard segments and soft segments, and since the urethane bonds interact with each other via hydrogen bonds, they are suitably used as crosslinking agents to impart impact resistance and high modulus of elasticity to cured products. On the other hand, the unique impact resistance obtained in the mixed system of component (A) and component (D) is thought to be partly due to the flexibility of the main chain caused by its unique molecular structure, which effectively transmits external stress to component (D) via the polymer network, causing stress relaxation. In order to maximize this effect, it is desirable that there be no interactions between the crosslinking networks, such as hydrogen bonds between urethane bonds. To overcome the reduced flexibility of the polymer network caused by these urethane bonds, it is conceivable to use urethane oligomers with longer soft segments. However, in this case, a problem arises: the elastic modulus decreases as the crosslinking density decreases. On the other hand, when the monomer units are bifunctional radical polymerizable oligomers consisting of two or more monomer units linked by carbonate, ester, or ether groups, the interaction between the crosslinking networks is weak. Therefore, it is possible to improve the elastic modulus through crosslinking while maintaining the flexibility of the main chain due to component (A). Furthermore, when the monomer units are hydrocarbon groups without heteroatoms, the interaction between the crosslinking networks becomes even weaker, enabling the achievement of higher impact resistance. Notably, it has been found that in a mixed system of component (A) and the oligomer of the present invention, high impact resistance can be maintained even when the oligomer has a low molecular weight and a relatively high crosslinking density, specifically when the weight-average molecular weight is between 400 and 5,000. However, if the number of functional groups in the oligomer is three or more, impact resistance equivalent to that of the present invention will not be exhibited.One possible reason for this is that excessive crosslinking significantly reduces the flexibility of the polymer network, causing stress concentration in certain parts of the polymer network in response to external forces.

[0054] <Component (C): Radical polymerizable compounds other than components (A) and (B)> The curable resin composition of the present invention may contain a radical polymerizable compound other than components (A) and (B) as component (C). When component (C) is included, more than 75 parts by mass of monofunctional radical polymerizable compound per 100 parts by mass of the total of component (C) is present. The content of monofunctional radical polymerizable compound is preferably 80 parts by mass or more, and more preferably 90 parts by mass or more, per 100 parts by mass of the total of component (C). If the composition contains 25 parts by mass or more of polyfunctional radical polymerizable compound per 100 parts by mass of the total of component (C), the impact resistance will not be sufficiently exhibited. Examples of radical polymerizable functional groups include ethylenically unsaturated groups. Specifically, examples of ethylenically unsaturated groups include (meth)acryloyl groups and vinyl groups.

[0055] Examples of monofunctional radical polymerizable compounds having a (meth)acryloyl group include monofunctional acrylamide compounds and monofunctional (meth)acrylate compounds.

[0056] Examples of monofunctional acrylamide compounds include (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-methylol(meth)acrylamide, N,N-diacetone(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine, and N-[3-(dimethylamino)propyl]acrylamide.

[0057] Furthermore, examples of monofunctional (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, i-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, 3-hydroxy-1-atamantyl (meth)acrylate, 3,5-Dihydroxy-1-adamantyl(meth)acrylate, 2-methyl-2-adamantyl(meth)acrylate, 2-ethyl-2-adamantyl(meth)acrylate, 2-isopropyl-2-adamantyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, glycidyl(meth)acrylate, 3-methyl-3-oxetanyl-methyl(meth)acrylate, tetrahydrofurfuryl( Meth)acrylate, phenylglycidyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, phenyl cellosolve (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, biphenyl (meth)acrylate, 2-hydroxyethyl (meth)acryloyl phosphate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, benzyl (meth)acrylate, butoxytriethylene glycol (meth) )Acrylate, 2-ethylhexyl polyethylene glycol (meth)acrylate, nonylphenyl polypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, glycerol (meth)acrylate, trifluoromethyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, allyl (meth)acrylate Rate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H,octafluoropentyl (meth)acrylate, epichlorohydrin-modified butyl (meth)acrylate, epichlorohydrin-modified phenoxy (meth)acrylate, ethylene oxide (EO)-modified phthalate (meth)acrylate, EO-modified succinate (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,Examples include N-diethylaminoethyl (meth)acrylate, morpholino (meth)acrylate, EO-modified phosphate (meth)acrylate, (meth)acrylates having an imide group (product name: M-140, manufactured by Toagosei Co., Ltd.), and monofunctional (meth)acrylates having a siloxane structure.

[0058] Examples of monofunctional radical polymerizable compounds having ethylenically unsaturated groups other than (meth)acryloyl groups include styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; vinyl cyanide compounds such as (meth)acrylonitrile; and N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholin, and N-vinylacetamide.

[0059] These monofunctional radical polymerizable compounds may be used individually or in combination of two or more.

[0060] From the viewpoint of accelerating the curing speed, the monofunctional radical polymerizable compound used in the present invention preferably contains at least a monofunctional acrylamide compound, a monofunctional N-vinyl compound, or a monofunctional (meth)acrylate compound. In particular, it is preferable that it contains a monofunctional acrylamide compound. Examples of polyfunctional radical polymerizable compounds containing two or more radical polymerizable functional groups in the molecule and included as component (C) include polyfunctional (meth)acrylate compounds, vinyl ether group-containing (meth)acrylate compounds, polyfunctional (meth)acryloyl group-containing isocyanurate compounds, polyfunctional (meth)acrylamide compounds, polyfunctional maleimide compounds, polyfunctional vinyl ether compounds, and polyfunctional aromatic vinyl compounds. Examples of polyfunctional (meth)acrylate compounds include ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexamethylene di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(meth)acryloxyethyl isocyanurate, polyfunctional (meth)acrylates having a fluorine atom, and polyfunctional (meth)acrylates having a siloxane structure. Examples of vinyl ether group-containing (meth)acrylate compounds include 2-vinyloxyethyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, and 4-vinyloxycyclohexyl (meth)acrylate. Examples of polyfunctional (meth)acryloyl group-containing isocyanurate compounds include tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, and ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate. Examples of polyfunctional (meth)acrylamide compounds include N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, N,N'-(1,2-dihydroxyethylene)bisacrylamide, N,N'-methylenebismethacrylamide, and N,N',N''-triacryloyldiethylenetriamine. Examples of polyfunctional maleimide compounds include 4,4'-diphenylmethanebismaleimide, m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, and 1,6-bismaleimide-(2,2,4-trimethyl)hexane. Examples of polyfunctional vinyl ether compounds include ethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexanyl ether. Examples of polyfunctional aromatic vinyl compounds include divinylbenzene. These polyfunctional radical polymerizable compounds may be used individually or in combination of two or more.

[0061] The content of component (C) is not particularly limited, but it is preferably 0 parts by mass or more and less than 30 parts by mass, more preferably 0 parts by mass or more and 25 parts by mass or less, and may be 0 parts by mass, based on 100 parts by mass of the total of components (A) and (C). In other words, the curable resin composition of the present invention does not have to contain component (C). When the content of component (C) is within this range, the impact resistance improvement effect due to component (A) is clearly expressed in the cured product.

[0062] <Ingredients (D): Rubber particles> Component (D) is rubber particles. The curable resin composition of the present invention can have its impact resistance improved by adding rubber particles. The rubber particles used in the present invention are not particularly limited, but examples include butadiene rubber particles, ethylene / butadiene copolymer rubber particles, acrylonitrile / butadiene copolymer rubber particles, etc. Also, 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 ternary copolymer rubber particles, acrylic rubber particles, silicone / acrylic composite rubber particles, etc. These rubber particles may be used individually or in combination of two or more types. In particular, from the viewpoint of flexibility, it is preferable to use at least one particle selected from butadiene rubber particles, crosslinked butadiene rubber particles, styrene / butadiene copolymer rubber particles, acrylic rubber particles, and silicone / acrylic composite rubber particles.

[0063] Preferably, the rubber particles have a multilayer structure (core-shell structure) consisting of a core portion having rubber elasticity and at least one shell portion covering the core portion.

[0064] The glass transition temperature of the polymer constituting the core portion of the rubber particles is not particularly limited, but is preferably 0°C or lower, more preferably less than -10°C, and even more preferably -40°C or lower. Setting the glass transition temperature of the polymer to 0°C or lower tends to improve the impact resistance of the cured product. The glass transition temperature of the polymer constituting the core portion refers to the value calculated by the following Fox formula. The following Fox formula shows the case where the polymer constituting the core is a copolymer of monomer 1, monomer 2, ..., and monomer n. 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + W n / Tg n Tg: Glass transition temperature of the polymer constituting the core (unit: K) W i : Weight fraction of monomer i relative to the total amount of monomers constituting the polymer that makes up the core part Tg i Glass transition temperature of monomer i homopolymer (unit: K)

[0065] Glass transition temperature Tg of homopolymers i The values ​​listed in the literature can be used. For values ​​not listed in the literature, the glass transition temperature of a homopolymer obtained by polymerizing monomers using conventional methods, measured by differential scanning calorimetry, can be used.

[0066] The polymer constituting the core is not particularly limited, but it is preferably made of one of the following: butadiene rubber, crosslinked butadiene rubber, styrene / butadiene copolymer rubber, acrylic rubber, or silicone / acrylic composite rubber.

[0067] It is preferable that the polymer constituting the shell layer of the rubber particles is a different type of polymer from the polymer constituting the core.

[0068] The polymer constituting the shell layer can be a (meth)acrylic acid ester such as methyl (meth)acrylate, ethyl (meth)acrylate, or butyl (meth)acrylate, maleimide, styrene, α-(unsaturated alkoxyalkyl)acrylic acid or its ester (component (A)), etc., but the present invention is not limited to these.

[0069] The polymer constituting the shell layer may, as with the core portion, contain, in addition to the above monomers, reactive crosslinked monomers having two or more reactive functional groups in their molecule, such as divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, and butylene glycol diacrylate, as other monomer components.

[0070] The glass transition temperature of the polymer constituting the shell layer of the rubber particles is not particularly limited, but is preferably 0°C or higher, more preferably 15°C or higher, and even more preferably 30°C or higher. If the glass transition temperature of the shell layer falls below 0°C, the viscosity of the composition tends to increase significantly. If the glass transition temperature of the shell layer is 0°C or higher, the viscosity does not increase, and the composition tends to disperse well. The glass transition temperature of the shell layer is a calculated value obtained by the above Fox formula.

[0071] Rubber particles are obtained by covering the core portion with a shell layer. Examples of methods for covering the core portion with a shell layer include applying the shell layer to the core portion and grafting the shell layer onto the surface of the core portion, but the preferred method is grafting the shell layer onto the surface of the core portion.

[0072] The average particle size of the rubber particles is not particularly limited, but is preferably 20 nm to 2,000 nm, more preferably 20 nm to 900 nm, and even more preferably 30 nm to 800 nm. When the average particle size of the rubber particles is 20 nm or more, the effect of improving impact resistance by adding rubber particles is clearly evident. Furthermore, when the average particle size is 2,000 nm or less, it is easier to obtain a cured product with an excellent balance in terms of elastic modulus and heat resistance in addition to impact resistance.

[0073] The content of component (D) is not particularly limited, but it is preferably 5 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the total of components (A), (B), and (C). More preferably, it is 10 parts by mass or more and 40 parts by mass or less. By setting the content of component (D) within the above range, it is easier to obtain a cured product with an excellent balance of impact resistance and elastic modulus.

[0074] <Component (E): Radical polymerization initiator> Component (E) is a radical polymerization initiator. The radical polymerization initiator can be a photo-radical polymerization initiator or a thermal radical polymerization initiator.

[0075] Photoradical polymerization initiators are mainly classified into intramolecular cleavage type and hydrogen abstraction type. In intramolecular cleavage type photoradical polymerization initiators, absorption of light of a specific wavelength breaks bonds at specific sites, generating radicals at the broken sites. These radicals act as polymerization initiators, initiating the polymerization of ethylenically unsaturated compounds containing (meth)acryloyl groups. On the other hand, in the case of hydrogen abstraction type initiators, absorption of light of a specific wavelength leads to an excited state, and these excited species undergo hydrogen abstraction reactions from surrounding hydrogen donors, generating radicals. These radicals act as polymerization initiators, initiating the polymerization of radically polymerizable compounds.

[0076] Known intramolecular cleavage-type photoradical polymerization initiators include alkylphenone-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, and oxime ester-based photoradical polymerization initiators. These are of the type in which a bond adjacent to the carbonyl group undergoes α-cleavage to generate a radical species. Examples of alkylphenone-based photoradical polymerization initiators include benzylmethyl ketal-based photoradical polymerization initiators, α-hydroxyalkylphenone-based photoradical polymerization initiators, and aminoalkylphenone-based photoradical polymerization initiators. Specific compounds include, for example, benzylmethyl ketal-based photoradical polymerization initiators such as 2,2'-dimethoxy-1,2-diphenylethane-1-one (OMNIRAD® 651, manufactured by IGM RESINS BV), and α-hydroxyalkylphenone-based photoradical polymerization initiators such as 2-hydroxy-2-methyl-1-phenylpropan-1-one (OMNIRAD® 1173, manufactured by IGM RESINS BV), 1-hydroxycyclohexylphenyl ketone (OMNIRAD® 184, manufactured by IGM RESINS BV), and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (OMNIRAD® 2959, manufactured by IGM RESINS BV). Examples of aminoalkylphenone-based photoradical polymerization initiators include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (OMNIRAD® 127, manufactured by IGM RESINS BV), and others.Examples of acylphosphine oxide-based photoradical polymerization initiators include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucilin TPO, manufactured by BASF) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (OMNIRAD® TPO H, manufactured by IGM RESINS BV). Examples of oxime ester-based photoradical polymerization initiators include, but are not limited to, (2E)-2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (Irgacure OXE-01, manufactured by BASF). Examples of product names are listed in parentheses.

[0077] Examples of hydrogen abstraction-type radical polymerization initiators include, but are not limited to, anthraquinone derivatives such as 2-ethyl-9,10-anthraquinone and 2-t-butyl-9,10-anthraquinone, and thioxanthone derivatives such as isopropylthioxanthone and 2,4-diethylthioxanthone.

[0078] These photoradical polymerization initiators may be used individually or in combination of two or more types. They may also be used in combination with the thermal radical polymerization initiators described later.

[0079] The amount of photoradical polymerization initiator added is preferably 0.1 parts by mass to 15 parts by mass per 100 parts by mass of the total of components (A), (B), and (C). More preferably, it is 0.1 parts by mass to 10 parts by mass. If the amount of photoradical polymerization initiator is 0.1 parts by mass or more, polymerization will proceed sufficiently. If the amount of polymerization initiator is 15 parts by mass or less, the molecular weight will increase appropriately, and sufficient heat resistance and impact resistance can be obtained.

[0080] Furthermore, the thermal radical polymerization initiator is not particularly limited as long as it generates radicals upon heating, and conventionally known compounds can be used. For example, azo compounds, peroxides, and persulfates can be given as preferred examples. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane). Examples of peroxides include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di(4-t-butylcyclohexyl)peroxydicarbonate. Examples of persulfates include ammonium persulfate, sodium persulfate, and potassium persulfate.

[0081] The amount of thermal radical polymerization initiator added is preferably 0.1 parts by mass to 15 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, per 100 parts by mass of the total of components (A), (B), and (C). If the polymerization initiator is 15 parts by mass or less, the molecular weight will increase appropriately, and sufficient heat resistance and impact resistance can be obtained.

[0082] <Other non-radical polymerizable components (additives)> The curable resin composition of the present invention may contain various additives as other optional components, as long as they do not impair the objectives and effects of the present invention.

[0083] For example, as a property modifier to impart desired physical properties to a cured product, resins such as epoxy resin, polyurethane, polychloroprene, polyester, polysiloxane, petroleum resin, xylene resin, ketone resin, cellulose resin, or polycarbonate, modified polyphenylene ether, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, ultra-high molecular weight polyethylene, polyphenylsulfone, polysulfone, polyarylate, polyetherimide, polyetheretherketone, polyphenyl Engineering plastics such as polysulfide, polyethersulfone, polyamide-imide, liquid crystal polymers, polytrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; fluorine-based oligomers, silicone-based oligomers, and polysulfide-based oligomers; soft metals such as gold, silver, and lead; and layered crystalline materials such as graphite, molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, calcium fluoride, barium fluoride, lithium fluoride, silicon nitride, and molybdenum selenide may also be added.

[0084] Furthermore, as photosensitizers, polymerization inhibitors such as phenothiazine, 2,6-di-t-butyl-4-methylphenol, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, tertiary amine compounds, and xanthone compounds may be added.

[0085] Other additives include polymerization initiators, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, silane coupling agents, inorganic fillers, pigments, dyes, antioxidants, flame retardants, thickeners, and defoamers.

[0086] <Curable resin composition> The composition of the present invention is manufactured by placing appropriate amounts of component (A), component (B), component (C), component (D), and component (E), or, if component (C) is not included, component (A), component (B), component (D), and component (E), and optionally other optional components, into a stirring vessel and stirring at a temperature of 20°C to 120°C, preferably 40°C to 100°C. Then, if necessary, dispersion treatment using ultrasound, removal of volatile solvents, etc., can be performed to manufacture the composition.

[0087] The curable resin composition according to the present invention can be suitably used as a molding material for stereolithography. That is, by selectively irradiating the curable resin composition of the present invention with active energy rays such as ultraviolet / visible light, electron beams, X-rays, and radiation to supply the energy necessary for curing, it is possible to manufacture molded objects of a desired shape. When the curable resin composition of the present invention is used as a molding material for stereolithography, the viscosity at 25°C is preferably 10 mPa·s to 10,000 mPa·s, more preferably 10 mPa·s to 5,000 mPa·s, even more preferably 10 mPa·s to 1,000 mPa·s, and most preferably 10 mPa·s to 200 mPa·s.

[0088] <Cured product> The cured product of the present invention can be obtained by curing the aforementioned curable resin composition using known methods such as active energy ray irradiation or thermal irradiation. Examples of active energy rays include ultraviolet / visible light, electron beams, X-rays, and radiation. Among these, ultraviolet / visible light having a wavelength of 300 nm to 450 nm is preferably used due to its easy availability and compatibility with photoradical polymerization initiators. As a light source for ultraviolet / visible light, ultraviolet / visible light lasers (e.g., Ar lasers, He-Cd lasers, etc.), mercury lamps, xenon lamps, halogen lamps, fluorescent lamps, etc. can be used. Among these, laser light sources are preferably used because they can increase the energy level to shorten the molding time, and also have excellent light focusing properties, allowing for high molding accuracy. The curing method can be appropriately selected according to the type of radical polymerization initiator contained in the curable resin composition. Furthermore, the curing method may be used alone or in combination of multiple methods.

[0089] <Methods for shaping objects> The curable resin composition according to this embodiment can be suitably used in methods for manufacturing articles by optical stereolithography (stereolithography). A method for manufacturing articles using the curable resin composition according to this embodiment will be described below.

[0090] Conventional known methods can be used as the stereolithography method. That is, the method for manufacturing an article according to this embodiment includes a step of selectively irradiating the curable resin composition of this embodiment with active energy rays such as light to cure the curable resin composition to a predetermined thickness. Then, the step of curing the curable resin composition to a predetermined thickness is performed multiple times, and an article is manufactured by laminating the cured layers of the curable resin composition that have been cured to a predetermined thickness.

[0091] Fig. 1 shows a configuration example of a modeling apparatus using a stereolithography method. The stereolithography apparatus 100 has a tank 11 filled with a liquid photocurable resin composition 10. Inside the tank 11, a modeling stage 12 is provided so as to be vertically drivable by a drive shaft 13. The active energy ray 15 for curing the photocurable resin composition 10, which is emitted from a light source 14, is scanned on the surface of the tank 11 with its irradiation position changed by a galvano mirror 16 controlled by a control unit 18 according to the slice data of the three-dimensional model to be produced. In Fig. 1, the scanning range is indicated by a thick broken line.

[0092] The active energy ray 15 irradiated on the curable resin composition is not particularly limited as long as it is an active energy ray capable of curing the curable resin composition according to the present embodiment. Specific examples of the active energy ray 15 include electromagnetic waves such as ultraviolet rays, visible light rays, infrared rays, X-rays, gamma rays, laser light rays, and particle rays such as alpha rays, beta rays, and electron beams. Among these, ultraviolet rays are most preferable from the viewpoints of the absorption wavelength of the curing agent to be used and the cost of equipment introduction. The exposure amount is not particularly limited, but is preferably 0.001 J / cm 2 to 10 J / cm 2 or less. If it is 0.001 J / cm 2 or more, the curable resin composition is sufficiently cured, and if it is 10 J / cm 2 or less, the irradiation time is appropriate and preferable from the viewpoint of productivity.

[0093] The method of irradiating a curable resin composition with active energy rays is not limited to the configuration shown in Figure 1. When irradiating with light energy as the active energy ray, for example, the following methods can be employed. The first method is to use light focused into a point shape, such as laser light, as shown in Figure 1, and scan the curable resin composition two-dimensionally with this light. In this case, the two-dimensional scanning may be a point-drawing method or a line-drawing method. The second method is a surface exposure method in which light is irradiated onto the shape of the cross-sectional data using a projector or the like. In this case, the active energy ray may be irradiated in a planar manner through a planar drawing mask formed by arranging multiple micro-light shutters such as liquid crystal shutters or digital micro-mirror shutters.

[0094] The thickness d of the photocurable resin composition 10 cured by the active energy rays 15 is a value determined based on the settings when generating the slice data, and affects the accuracy of the resulting molded object 17 (reproducibility of the shape data of the molded article). The thickness d is achieved by the control unit 18 controlling the amount of drive of the drive shaft 13.

[0095] First, the control unit 18 controls the drive shaft 13 based on the settings, and a photocurable resin composition is supplied onto the molding stage 12 in a thickness d. Based on slice data, active energy rays are selectively irradiated onto the liquid curable resin composition on the molding stage 12 to form a cured layer having a desired pattern. Next, by moving the molding stage 12 in the direction of the white arrow, an uncured curable resin composition is supplied to the surface of the cured layer in a thickness d. Then, active energy rays 15 are irradiated based on slice data, and a cured product is formed that is integrated with the previously formed cured layer. By repeating this layered curing process, the desired three-dimensional object 17 can be obtained.

[0096] The object produced by the stereolithography method described above is subjected to post-processing as needed to obtain an article. Post-processing may include, for example, cleaning the surface of the produced object with a cleaning agent such as an organic solvent. Alternatively, the produced object may be subjected to further light irradiation or heat treatment to harden any unreacted residual components that may remain on the surface or inside the object as a post-cure. Furthermore, machining such as surface polishing to smooth out surface irregularities or creating screw holes may also be performed. Multiple of these processes may be combined. [Examples]

[0097] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0098] <Material> The materials used in the examples and comparative examples are listed below. [Ingredients (A)] A-1: α-Allyloxymethylacrylate (manufactured by Nippon Shokubai Co., Ltd., AOMA)

[0099] [Component (B)] B-1: Polycarbonate diacrylate; "UH-100DA" (Weight-average molecular weight: approximately 3,000, manufactured by Ube Industries, Ltd.) B-2: Polycarbonate dimethacrylate; "UM-90(1 / 3)DM" (Weight-average molecular weight: approximately 2,800, manufactured by Ube Industries, Ltd.) B-3: Polyether diacrylate; "BPEM-4" (Weight-average molecular weight: approximately 600, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) B-4: Polyether diacrylate; "ABE-300" (Weight-average molecular weight: approximately 500, manufactured by Shin-Nakamura Kogyo Co., Ltd.) B-5: Polyester diacrylate; "M-6100" (Weight-average molecular weight: approx. 760, manufactured by Toagosei Co., Ltd.) B-6: Polyester diacrylate; "M-6250" (Weight-average molecular weight: approx. 660, manufactured by Toagosei Co., Ltd.) B-7: Polyester diacrylate; "M-6500" (Weight-average molecular weight: approx. 740, manufactured by Toagosei Co., Ltd.) B-8: Polyester diacrylate; "CN2254-NS" (Weight-average molecular weight: approximately 3800, manufactured by SARTOMER)

[0100] [Component (B'): A bifunctional radical polymerizable oligomer other than component (B)] B'-1: Difunctional urethane acrylate; "CN9001NS" (manufactured by SARTOMER, weight-average molecular weight: approximately 5,400) B'-2: Bifunctional urethane acrylate; "KUA-PC2T" (manufactured by KSM Co., Ltd., weight-average molecular weight: approximately 10,000)

[0101] [Component (C)] (1) Monofunctional radical polymerizable compounds C1-1: Acryloylmorpholin; "ACMO" (manufactured by KJ Chemicals) C1-2:4-tert-butylcyclohexyl acrylate; "TBCHA" (manufactured by KJ Chemicals)

[0102] (2) Polyfunctional radical polymerizable compounds C2-1:1,6-Hexanediol diacrylate C2-2: Tricyclodecanedimethanol diacrylate C2-3: Trimethylolpropane triacrylate

[0103] [Component (D)] D-1: Core-shell type rubber particles; "KaneAce(R) M-511" (manufactured by Kaneka Corporation, average particle size 200 nm, core: cross-linked butadiene rubber, shell: acrylic copolymer)

[0104] [Component (E)] E-1: Photoradical generator; "Omnirad819" (manufactured by IGM RESINS BV)

[0105] <Manufacturing of curable resin compositions> Components (A) to (C) were blended according to the mixing ratios shown in Tables 1 and 2 and mixed uniformly. Secondary particulate powder of component (D) was added to this mixture according to the mixing ratios shown in Tables 1 and 2. Then, a stirring bar was placed in the mixture and it was stirred with a magnetic stirrer at 750 rpm for 1 hour to obtain a gel-like mixture. Subsequently, the mixture was dispersed using a Tommy Seikou Co., Ltd. ultrasonic homogenizer "UD-200" at an output of 60 W for 10 minutes twice with a 2-minute interval between treatments to obtain a homogeneous mixture. Then, component (E) was added according to the mixing ratios shown in Tables 1 and 2 and mixed uniformly to obtain the curable resin compositions shown in Tables 1 and 2.

[0106] <Preparation of test specimens> A cured product was prepared from the prepared curable resin composition using the following method. First, a mold measuring 80 mm in length, 10 mm in width, and 4 mm in thickness was placed between two sheets of quartz glass, and the curable resin composition was poured into it. The poured curable resin composition was then treated with an ultraviolet irradiation device (HOYA CANDEO OPTRONICS, product name "LIGHT SOURCE EXECURE3000") at 5 mW / cm². 2 The material was irradiated with ultraviolet light. Post-curing was performed on the resulting cured material as needed, including additional ultraviolet irradiation and heating, to the extent that the shape of the test piece was not impaired, to obtain a test piece measuring 80 mm in length, 10 mm in width, and 4 mm in thickness.

[0107] <Rating> [Weight average molecular weight] A gel permeation chromatography (GPC) system (Tosoh Corporation, HLC-8220GPC) is used with a Shodex GPC LF-804 column (Showa Denko Corporation, exclusion limit molecular weight: 2 × 10⁶). 6 Separation range: 300~2×10 6 Two ) were placed in series, and measurements were taken at 40°C using THF as the developing solvent and with an RI (Refractive Index) detector. The obtained weight-average molecular weight is the value on a standard polystyrene basis.

[0108] [Charpy impact strength] In accordance with JIS K 7111, a 2mm deep, 45° notch was made in the center of the test specimen using a notching machine (manufactured by Toyo Seiki Seisakusho, product name "Notching Tool A-4"). An impact testing machine (manufactured by Toyo Seiki Seisakusho, product name "IMPACT TESTER IT") was used to fracture the test specimen with an energy of 2J from the back of the notch. The energy required for fracture was calculated from the angle at which the hammer, which had been swung up to 150°, rose after the test specimen fractured, and this was defined as the Charpy impact strength, which was used as an indicator of impact resistance. The impact resistance was evaluated as follows. A (Very Good): 15 kJ / m 2 That's all. B (good): 10kJ / m 2 More than 15kJ / m 2 less than. C (defective): 10kJ / m 2 less than.

[0109] [Flexural modulus] In accordance with JIS K 7171, a three-point bending test was performed on the test specimen using a tensile and compression testing machine (A&D Co., Ltd., product name "Tensilon Universal Material Testing Machine RTF-1250C") under the conditions of a test speed of 2 mm / min, a support distance of 64 mm, an indenter radius of 5 mm, and a support base radius of 5 mm). The bending modulus was calculated from the measured stress gradient from 0.05% to 0.25% strain. The evaluation of the bending modulus was as follows. A (Excellent): 2.4 GPa or higher. B (Good): 2 GPa or higher but less than 2.4 GPa. C (Poor): Less than 2 GPa.

[0110] [viscosity] The obtained curable resin composition was measured using a viscoelasticity measuring device (MCR302, manufactured by Anton Paar) as follows. Approximately 0.5 mL of the sample was filled into the measuring device fitted with a cone-plate type measuring jig (25 mm diameter, 2°) and adjusted to 20°C. Shear rate: 5 s -1 The value obtained under these conditions was defined as viscosity. The viscosity was evaluated as follows. A (Very Good): Less than 200 mPa·s. B (Good): 200 mPa·s or more and less than 1000 mPa·s. C (defective): 1000mPa·s or more.

[0111] [Table 1]

[0112] [Table 2]

[0113] In Tables 1 and 2, each part by mass is calculated relative to a total of 100 parts by mass of radical polymerizable compounds. The results of the Charpy impact test were used to evaluate the impact resistance of the cured resin compositions prepared using the mixing ratios listed in Tables 1 and 2. The results of the flexural modulus measurement were used to evaluate the elastic modulus, and the results of the viscosity measurement were used to evaluate the moldability. The effectiveness of the present invention will be explained using Tables 1 and 2, with reference to examples and comparative examples.

[0114] [Efficacy of ingredient (A)] By comparing Example 1 with Comparative Example 9, it can be confirmed that the presence of component (A) significantly contributes to the impact resistance and reduced viscosity of the cured product.

[0115] [Efficacy of ingredient (B)] By comparing Examples 1 to 8 with Comparative Examples 1, 2, and 11, it can be confirmed that the presence of component (B) greatly contributes to the impact resistance of the cured product, and that component (B) exhibits an even higher elastic modulus because it is a bifunctional radical polymerizable oligomer consisting of an oligomer portion in which two or more monomer units are linked by either an ether group, an ester group, or a carbonate group, and two polymerizable functional groups. This confirms that urethane oligomers outside the present invention cannot exhibit equivalent performance in terms of elastic modulus.

[0116] [Efficacy of ingredient (C)] By comparing Examples 9 to 11 with Comparative Examples 3 to 8, it was found that the impact resistance of the cured product was good when component (C) contained more than 75 parts by mass of monofunctional polymerizable compound per 100 parts by mass of the total component (C). On the other hand, it was confirmed that when component (C) contained 25 parts by mass or more of polyfunctional polymerizable compound per 100 parts by mass of the total component (C), it was not possible to achieve equivalent performance in terms of impact resistance.

[0117] [Efficacy of ingredient (D)] By comparing Example 1 with Comparative Example 10, it can be confirmed that the presence of component (D) significantly contributes to the impact resistance of the cured product.

[0118] From the above results, it has become clear that when the composition of the present invention is used, the composition has low viscosity and can be suitably used for optical three-dimensional molding, and furthermore, the cured product can achieve both impact resistance and high modulus of elasticity. [Explanation of Symbols]

[0119] 10: Photocurable resin composition, 11: Tank, 12: Build stage, 13: Drive shaft, 14: Light source, 15: Active energy ray, 16: Galvano mirror, 17: Manufactured object, 18: Control unit, 100: Stereolithography apparatus

Claims

1. Component (A): α-(unsaturated alkoxyalkyl)acrylic acid or its ester, Component (B): a bifunctional radical polymerizable oligomer, Component (D): rubber particles, Component (E): a radical polymerization initiator; Contains moreover, Component (C): a radical polymerizable compound other than the components (A) and (B); may contain The component (A) is an α-(unsaturated alkoxyalkyl)acrylic acid or an ester thereof represented by the following general formula (1): 【Chemistry 1】 [In the formula, R 1 is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R 2 is a methylene group which may have an alkyl group having 1 to 4 carbon atoms. R 3 , R 4 one of which is a methylene group which may have an alkyl group having 1 to 4 carbon atoms, and the other is an oxygen atom. R 5 is either a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an ester group. The component (B) is a bifunctional radically polymerizable oligomer having an oligomer moiety in which two or more monomer units are linked by any one of a carbonate group, an ester group, and an ether group, and two polymerizable functional groups; The total content of the component (A) and the component (C) is more than 70 parts by mass and less than 90 parts by mass with respect to 100 parts by mass of the total of the components (A), (B), and (C), The content of the component (D) is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total of the components (A), (B), and (C), When the component (C) is contained, the content of the monofunctional radical polymerizable compound contained in the component (C) is more than 75 parts by mass per 100 parts by mass of the total of the components (C).

2. The curable resin composition described in Claim 1, characterized in that the component (A) is a compound that contains an ether structure in its main chain and polymerizes while forming a five-membered or six-membered ring.

3. 3. The curable resin composition according to claim 1, wherein the component (A) is methyl α-allyloxymethylacrylate or ethyl α-allyloxymethylacrylate.

4. The curable resin composition according to any one of claims 1 to 3, characterized in that the content of the component (A) is more than 70 parts by mass and not more than 100 parts by mass, relative to 100 parts by mass of the total of the components (A) and (C).

5. The curable resin composition according to any one of claims 1 to 4, characterized in that the content of the (A) component is 75 parts by mass or more and 100 parts by mass or less, relative to a total of 100 parts by mass of the (A) component and the (C) component.

6. The curable resin composition according to any one of claims 1 to 5, characterized in that the content of the component (B) is more than 10 parts by mass per 100 parts by mass of the total of the components (A), (B), and (C).

7. 7. The curable resin composition according to claim 1, wherein the weight average molecular weight of the component (B) is 400 or more and 5,000 or less.

8. 8. The curable resin composition according to claim 1, wherein the monomer unit of the component (B) is a hydrocarbon group.

9. 9. The curable resin composition according to claim 1, wherein the component (B) is a polyether di(meth)acrylate or a polycarbonate di(meth)acrylate.

10. The curable resin composition according to any one of claims 1 to 9, characterized in that the component (C) contains at least any one of a monofunctional acrylamide-based compound, a monofunctional N-vinyl-based compound, and a monofunctional (meth)acrylate-based compound.

11. The curable resin composition according to any one of claims 1 to 10, wherein the content of the component (C) is 0 parts by mass relative to a total of 100 parts by mass of the component (A) and the component (C).

12. The curable resin composition according to any one of claims 1 to 11, wherein all of the components (C) are monofunctional radically polymerizable compounds.

13. 13. The curable resin composition according to claim 1, wherein the average particle size of the component (D) is 20 nm or more and 2,000 nm or less.

14. The curable resin composition according to any one of claims 1 to 13, characterized in that the component (D) is a rubber particle having a core-shell structure, and the core of the core-shell structure is made of any one of butadiene rubber, crosslinked butadiene rubber, styrene / butadiene copolymer rubber, acrylic rubber, and silicone / acrylic composite rubber.

15. Component (A): α-(unsaturated alkoxyalkyl)acrylic acid or its ester, Component (B): a bifunctional radical polymerizable oligomer, Component (D): rubber particles, Component (E): a radical polymerization initiator; Contains The component (A) is an α-(unsaturated alkoxyalkyl)acrylic acid or an ester thereof represented by the following general formula (1): 【Chemistry 2】 In the formula, R 1 represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. R 2 is a methylene group which may have an alkyl group having 1 to 4 carbon atoms. Either R 3 or R 4 is a methylene group which may have an alkyl group having 1 to 4 carbon atoms, and the other is an oxygen atom. R 5 is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an ester group. The component (B) is a curable resin composition characterized in that the monomer unit is a bifunctional radically polymerizable oligomer consisting of an oligomer moiety in which two or more monomer units are linked by any one of a carbonate group, an ester group, and an ether group, and two polymerizable functional groups.

16. Component (C): a radical polymerizable compound other than components (A) and (B), The curable resin composition according to claim 15, characterized in that it does not contain.

17. Furthermore, Component (C): A radical polymerizable compound other than the components (A) and (B). Contains The curable resin composition according to claim 15, characterized in that the content of the monofunctional radically polymerizable compound contained in the component (C) is more than 75 parts by mass per 100 parts by mass of the total of the components (C).

18. A cured product obtained by curing the curable resin composition according to claim 1 .

19. A method for manufacturing an article using a stereolithography method, comprising the steps of: disposing a photocurable resin composition in a layer; a step of irradiating the layered photocurable resin composition with light energy based on slice data of a model to cure the composition and form a model; Including, A method for producing an article, comprising the photocurable resin composition according to claim 1 .

20. The method for manufacturing an article according to claim 19, further comprising a step of processing the shaped object.

21. The method for manufacturing an article according to claim 20, characterized in that in the step of processing the shaped object, at least one process selected from cleaning, post-cure, and mechanical processing is performed.

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