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

[0002] A known optical three-dimensional modeling method (hereinafter referred to as photolithography) is a method for producing a shaped object 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 the cured resin layers are then stacked together. Specifically, the surface of a liquid photocurable resin composition contained in a container is irradiated with light from an ultraviolet laser, UV-LED, or the like, according to slice data generated from the shape data of the three-dimensional model to be produced, forming a cured resin layer of a predetermined thickness and having a desired pattern. Next, a single layer of photocurable resin composition is supplied onto this cured resin layer, and similarly irradiated with light, forming a new cured resin layer continuous with the previously formed cured resin layer. In this way, by stacking cured resin layers in a pattern based on the slice data, a desired object can be obtained. This type of stereolithography method makes it possible to easily produce even complex-shaped objects, provided that the shape data of the three-dimensional model is available. Stereolithography is being increasingly applied to the creation of prototypes for shape confirmation (rapid prototyping), the creation of working models for functionality verification, and the creation of molds (rapid tooling).Furthermore, in recent years, the use of stereolithography has begun to expand to the creation of actual products (rapid manufacturing). Resin compositions used in stereolithography require low viscosity for ease of handling during modeling and modeling accuracy. Furthermore, with the expansion of the range of applications mentioned above, the cured product is required to have impact resistance and a high elastic modulus comparable to those of general-purpose engineering plastics. Patent Document 1 discloses a curable resin composition containing a urethane (meth)acrylate having a specific structure, a radically polymerizable compound, elastomer particles, and a radical polymerization initiator. Patent Document 2 discloses a curable resin composition containing a cyclopolymerizable 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-carbon relationship. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-051665 [Patent Document 2] Special Publication No. 2020-505255 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the curable resin composition disclosed in Patent Document 1 does not have sufficient properties in terms of viscosity and impact resistance of the cured product. Furthermore, the curable resin composition disclosed in Patent Document 2 has a low viscosity, and although the cured product thereof has a high elastic modulus, it has a problem of not having sufficient impact resistance. Thus, a curable resin composition that simultaneously satisfies low viscosity and high elastic modulus and impact resistance of the cured product has not been realized. An object of the present invention is to provide a curable resin composition that can give a cured product having impact resistance and a high elastic modulus, and that has low viscosity and is easy to handle during molding. [Means for solving the problem]

[0005] The curable resin composition according to the present invention comprises: 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): the component (A) and the component A radical polymerizable compound other than (B), may contain The component (A) is an α-(unsaturated alkoxyalkyl)acrylic acid or its ester represented by the following general formula (1):

[0006] [ka] [In the formula, R1 is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R2 is a methylene group which may have an alkyl group having 1 to 4 carbon atoms. One of R3 and R4 is a methylene group which may have an alkyl group having 1 to 4 carbon atoms, and the other is an oxygen atom. R5 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an ester group. The component (B) is an oligomer moiety in which two or more monomer units are linked by a carbonate group, an ester group, or an ether group, and two polymerizable functional groups. and does not contain urethane bonds It is a bifunctional radical polymerizable oligomer, The aforementioned component (A )and the total content of the component (C) is more than 70 parts by mass and less than 90 parts by mass relative to 100 parts by mass of the total of the component (A), the component (B), and the component (C); the content of the component (A) is more than 70 parts by mass and 100 parts by mass or less, relative to 100 parts by mass of the total of the components (A) and (C), the content of the component (D) is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the total of the components (A), (B), and (C), In the case where the component (C) is contained, the content of the monofunctional radical polymerizable compound contained in the component (C) is 80 Mass part That's all It is characterized by: Another 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, Component (E): a radical polymerization initiator; Contains The component (A) is an α-(unsaturated alkoxyalkyl)acrylic acid or its ester represented by the following general formula (1): [ka] [In the formula, R1 is a hydrogen atom or an organic group having 1 to 30 carbon atoms. R2 is a methylene group which may have an alkyl group having 1 to 4 carbon atoms. One of R3 and R4 is a methylene group which may have an alkyl group having 1 to 4 carbon atoms, and the other is an oxygen atom. R5 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an ester group. The component (B) is an oligomer moiety in which two or more monomer units are linked by a carbonate group, an ester group, or an ether group, and two polymerizable functional groups. and does not contain urethane bonds It is a bifunctional radical polymerizable oligomer. and either of the following: It is characterized by the following. Component (C): a radical polymerizable compound other than the component (A) and the component (B); Does not contain The content of the component (A) is more than 70 parts by mass and less than 90 parts by mass relative to 100 parts by mass of the total of the components (A) and (B), The content of the component (D) is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the total of the component (A) and the component (B), or Component (C): A radical polymerizable compound other than the components (A) and (B). Contains 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 relative to 100 parts by mass of the total of the component (A), the component (B), and the component (C); the content of the component (A) is more than 70 parts by mass and 100 parts by mass or less, relative to 100 parts by mass of the total of the components (A) and (C), the content of the component (D) is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the total of the components (A), (B), and (C), The content of the monofunctional radically polymerizable compound contained in the component (C) is 80 parts by mass or more per 100 parts by mass of the total of the components (C). [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a curable resin composition that can form a cured product having impact resistance and a high elastic modulus, and that has a low viscosity and is suitable for three-dimensional modeling. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram illustrating an example of the configuration of a photo-fabrication apparatus. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described. Note that the embodiment described below is 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 an α-(unsaturated alkoxyalkyl)acrylic acid or its ester represented by the following general formula (1).

[0011] [ka]

[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 and may have an ether structure, and the hydrogen atoms of the hydrocarbon may be substituted with a substituent. Furthermore, the organic group may be linear or branched, or may have a cyclic structure.

[0013] Examples of the hydrocarbon group include chain saturated hydrocarbons having one or more carbon atoms, chain unsaturated hydrocarbons having three or more carbon atoms, alicyclic hydrocarbon groups having three or more carbon atoms, and aromatic hydrocarbon groups having six or more carbon atoms.

[0014] Among these, preferred are chain saturated hydrocarbon groups having 1 to 20 carbon atoms, chain unsaturated hydrocarbon groups having 3 to 20 carbon atoms, alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms, and more preferred are chain saturated hydrocarbons having 1 to 10 carbon atoms.

[0015] For example, the chain saturated hydrocarbon group may be a linear or branched hydrocarbon group without any particular limitation, and 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, seryl, melissyl, etc. Furthermore, the chain saturated hydrocarbon group may be one in which at least a portion of the hydrogen atoms bonded to the carbon atoms constituting the chain saturated hydrocarbon group have been substituted with a halogen atom, a cyano group, a trimethylsilyl group, etc.

[0016] The chain unsaturated hydrocarbon group is not particularly limited as long as it is a linear or branched hydrocarbon group containing at least one non-aromatic carbon-carbon unsaturated bond, but suitable examples include crotyl, 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 is not particularly limited as long as it is a hydrocarbon group containing a saturated cyclic structure of three or more members or a non-aromatic unsaturated cyclic structure, but suitable examples include cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, tricyclodecanyl, isobornyl, adamantyl, dicyclopentanyl, and dicyclopentenyl groups.

[0018] The aromatic hydrocarbon group is not particularly limited as long as it contains a cyclic structure with aromatic properties and has six or more members. Suitable examples of the aromatic hydrocarbon group include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-t-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, anthranyl, and the like.

[0019] The monovalent organic group having a hydrocarbon skeleton containing an ether bond is not particularly limited as long as it has a structure in which an oxygen atom is inserted into at least one carbon-carbon bond constituting a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Examples of the monovalent organic group include chain ether groups such as methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, and ethoxyethoxyethyl; cyclopentoxyethyl, cyclohexyloxyethyl, cyclopentoxyethoxyethyl, and cyclohexyloxyethoxy; Suitable examples include groups having both an alicyclic hydrocarbon group and a chain ether group, such as diethyl and dicyclopentenyloxyethyl; groups having both an aromatic hydrocarbon group and a chain 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, tetrahydrofuranyl, tetrahydrofurfuryl, tetrahydropyranyl, dioxazolanyl, and dioxanyl.

[0020] R2 is a methylene group which may have an alkyl group having from 1 to 4 carbon atoms. One of R3 and R4 is a methylene group which may have an alkyl group having from 1 to 4 carbon atoms, and the other is an oxygen atom. Here, it is preferable that R4 is a methylene group which may have an alkyl group having from 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, an ether-containing ring structure with methylene groups on both sides is formed by polymerization, making it easier to obtain a cured product which has both elastic modulus and impact resistance.

[0021] R5 is either 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 moiety is not bulky and does not hinder the flexibility of the main chain, and for this reason, a hydrogen atom, a methyl group, a methyl ester group, or an ethyl ester group is preferred. More preferably, R5 is a hydrogen atom.

[0022] Examples of compounds suitable for component (A) include α-allyloxymethylacrylic acid, 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, and α-allyloxymethylacrylate. n-Hexyl α-Allyloxymethylacrylate, 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 α-allyloxymethylacrylate, Tridecyl α-allyloxymethylacrylate, Myristyl α-allyloxymethylacrylate, Pentadecyl α-allyloxymethylacrylate, Cetyl α-allyloxymethylacrylate, Heptadecyl α-allyloxymethylacrylate, Stearyl α-allyloxymethylacrylate, Nonadecyl α-allyloxymethylacrylate, Eicosyl α-allyloxymethylacrylate, Seryl α-allyloxymethylacrylate, Melissyl α-allyloxymethylacrylate, α-Allyloxymethylacrylate crotyl α-allyloxymethylacrylate, 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, linoleyl α-allyloxymethylacrylate, linolenic α-allyloxymethylacrylate, cyclopentyl α-allyloxymethylacrylateCyclopentylmethyl α-allyloxymethylacrylate, cyclohexyl α-allyloxymethylacrylate, cyclohexylmethyl α-allyloxymethylacrylate, 4-methylcyclohexyl α-allyloxymethylacrylate, 4-t-butylcyclohexyl α-allyloxymethylacrylate, tricyclodecanyl α-allyloxymethylacrylate, isobornyl α-allyloxymethylacrylate, adamantyl α-allyloxymethylacrylate, dicyclopentanyl α-allyloxymethylacrylate, α-allyloxymethylacrylate Dicyclopentenyl acrylate, 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, α-allyloxymethylacrylic Cinnamyl α-allyloxymethylacrylate, naphthyl α-allyloxymethylacrylate, anthranil 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-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, dioxazolyl α-allyloxymethylacrylate, α-allyloxymethyl acrylate Dioxanyl acrylate, α-methallyloxymethyl acrylic acid, methyl α-methallyloxymethyl acrylate, ethyl α-methallyloxymethyl acrylate, n-propyl α-methallyloxymethyl acrylate, i-propyl α-methallyloxymethyl acrylate, n-butyl α-methallyloxymethyl acrylate, n-amyl α-methallyloxymethyl acrylate, s-amyl α-methallyloxymethyl acrylate, t-amyl α-methallyloxymethyl acrylate, neopentyl α-methallyloxymethyl acrylate, α-methallyloxymethyl n-Hexyl acrylate, s-hexyl α-methallyloxymethyl acrylate, n-heptyl α-methallyloxymethyl acrylate, n-octyl α-methallyloxymethyl acrylate, s-octyl α-methallyloxymethyl acrylate, t-octyl α-methallyloxymethyl acrylate, 2-ethylhexyl α-methallyloxymethyl acrylate, capryl α-methallyloxymethyl acrylate, nonyl α-methallyloxymethyl acrylate, decyl α-methallyloxymethyl acrylate, undecyl α-methallyloxymethyl acrylate, α -Lauryl methallyloxymethyl acrylate, tridecyl α-methallyloxymethyl acrylate, myristyl α-methallyloxymethyl acrylate, pentadecyl α-methallyloxymethyl acrylate, cetyl α-methallyloxymethyl acrylate, heptadecyl α-methallyloxymethyl acrylate, stearyl α-methallyloxymethyl acrylate, nonadecyl α-methallyloxymethyl acrylate, eicosyl α-methallyloxymethyl acrylate, ceryl α-methallyloxymethyl acrylate, melissyl α-methallyloxymethyl acrylate,Crotyl α-methallyloxymethyl acrylate, 1,1-dimethyl-2-propenyl α-methallyloxymethyl acrylate, 2-methylbutenyl α-methallyloxymethyl acrylate, 3-methyl-2-butenyl α-methallyloxymethyl acrylate, 3-methyl-3-butenyl α-methallyloxymethyl acrylate, 2-methyl-3-butenyl α-methallyloxymethyl acrylate, oleyl α-methallyloxymethyl acrylate, linoleyl α-methallyloxymethyl acrylate, linolenic α-methallyloxymethyl acrylate, α-methallyloxymethyl acrylate α-Methallyloxymethylacrylate, cyclopentyl α-methallyloxymethylacrylate, 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-methallyl 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, anthranil α-methallyloxymethylacrylate, methoxyethyl α-methallyloxymethylacrylate, methoxyethoxyethyl α-methallyloxymethylacrylate, methoxyethoxyethoxyethyl α-methallyloxymethylacrylate, 3-methoxybutyl α-methallyloxymethylacrylate, ethoxyethyl α-methallyloxymethylacrylateEthoxyethoxyethyl α-methallyloxymethyl acrylate, cyclopentoxyethyl α-methallyloxymethyl acrylate, cyclohexyloxyethyl α-methallyloxymethyl acrylate, cyclopentoxyethoxyethyl α-methallyloxymethyl acrylate, cyclohexyloxyethoxyethyl α-methallyloxymethyl acrylate, dicyclopentenyloxyethyl α-methallyloxymethyl acrylate, phenoxyethyl α-methallyloxymethyl acrylate, phenoxyethyl α-methallyloxymethyl acrylate hydroxyethyl, glycidyl α-methallyloxymethyl acrylate, β-methylglycidyl α-methallyloxymethyl acrylate, β-ethylglycidyl α-methallyloxymethyl acrylate, 3,4-epoxycyclohexylmethyl α-methallyloxymethyl acrylate, 2-oxetanemethyl α-methallyloxymethyl acrylate, 3-methyl-3-oxetanemethyl α-methallyloxymethyl acrylate, 3-ethyl-3-oxetanemethyl α-methallyloxymethyl acrylate, tetrahydrofuran α-methallyloxymethyl acrylate Lofuranil, tetrahydrofurfuryl α-methallyloxymethylacrylate, tetrahydropyranyl α-methallyloxymethylacrylate, dioxanyl α-methallyloxymethylacrylate, 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, (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, di(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and the like.

[0023] Among these, compounds containing an ether structure in the main chain and polymerizing while forming a 5- or 6-membered ring are preferred, and more preferred are α-allyloxymethyl methyl acrylate, α-allyloxymethyl ethyl acrylate, α-methallyloxymethyl methyl acrylate, and dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate. Of these, α-allyloxymethyl methyl acrylate, which forms a ring structure as shown in structural formula (2) below during polymerization, is most preferred from the standpoint of impact resistance and elastic modulus of the cured product.

[0024] [ka]

[0025] The reason why such a structure provides particularly high impact resistance 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, the incorporation of a ring structure into the main chain provides not only impact resistance but also a high elastic modulus. Commercially available α-allyloxymethyl methyl acrylate can be used, for example, 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 preferably more than 70 parts by mass and not more than 100 parts by mass, more preferably 75 parts by mass or more and not more than 100 parts by mass, per 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, per 100 parts by mass of the total of components (A), (B), and (C). By setting the content within the above range, the impact resistance-improving effect of component (A) is clearly manifested.

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

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

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

[0030] The polycarbonate diol can be represented by the following general formula (3).

[0031] [ka]

[0032] (wherein n represents a number of 2 or more, R represents any group, and R may be the same or different from each other).

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

[0034] The diol compound used as a raw material for polycarbonate diol is not particularly limited, and examples thereof include diols having no side chain such as 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, and 1,12-dodecanediol, 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, and 2-butyl-1,6-pentanediol. and diols having a side chain such as 2-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, and diols having an aromatic ring such as hydroquinone, 1,4-benzenedimethanol, 3,6-bis(hydroxymethyl)durene, 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, 4,4'-dihydroxybiphenyl, and 4,4'-biphenyldimethanol. Furthermore, one or a combination of two or more of these diols can be used.

[0035] Carbonate esters that can be 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 of these carbonate esters can be used as raw materials. Using dialkyl carbonates and / or diaryl carbonates is preferred because it allows for easy production of polycarbonate diols that satisfy a specific primary terminal OH ratio by adjusting conditions such as the charging ratio of the diol and carbonate. Furthermore, from the viewpoint of availability and ease of setting polymerization reaction conditions, it is more preferable to use ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and dibutyl carbonate.

[0036] The polycarbonate diol may be suitably selected from commercially available products, such as Duranol® (manufactured by Asahi Kasei Corporation), Benebiol® (manufactured by Mitsubishi Chemical Corporation), Eternacol® (manufactured by Ube Industries, Ltd.), Nipporan® 981, 980R, 982R, 976, 965, 963, 964, and 968 (manufactured by Tosoh Corporation), and Kuraray Polyol® C-2090 (manufactured by Kuraray Co., Ltd.).

[0037] The polyester diol can be represented by the following general formula (4).

[0038] [ka]

[0039] (wherein n represents a number of 2 or more, R represents any group, and R may be the same or different from each other).

[0040] The polyester diol represented by the 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] As the diol compound serving as a raw material for the polyester diol, the same diol compound as the raw material for the polycarbonate diol can be used.

[0042] The dicarboxylic acid used as a raw material for the polyester diol is not particularly limited, and examples thereof include 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 the raw material. The above-mentioned dicarboxylic acids can also be subjected to the reaction in the form of acid anhydrides, in which case they react with water in the reaction system to produce dicarboxylic acids.

[0043] As the polyester diol, commercially available products may be suitably selected, such as diols of Polylite® (manufactured by DIC Corporation), Maximol® RDK-133, RDK-142 (manufactured by Kawasaki Chemical Industries, Ltd.), Nipporan® 4002, 4040, 4009, 4010, 3027, 164, 4073, 136, 1004, 141, 4042, 5018, 5035 (manufactured by Tosoh Corporation), diols of Adeka New Ace® (manufactured by ADEKA Corporation), and Kuraray Polyol®. Those suitable for the present invention can be appropriately selected from P-5010, P-2050, P-2010, P-2020, P-2030, P-1010, P-2011 (manufactured by Kuraray Co., Ltd.), Aronix(R) M-6000 series, M-7000 series, M-9000 series (manufactured by Toagosei Co., Ltd.), CN2203, CN2254, CN2270, CN2271, CN2273, CN2274 manufactured by SATOMER, and the like.

[0044] The polyether diol can be represented by the following general formula (5).

[0045] [ka]

[0046] (wherein n represents a number of 2 or more, R represents any group, and R may be the same or different from each other).

[0047] The polyether diol represented by general formula (5) may be produced by any method, for example, by addition polymerization of ring-opening polymerization of a cyclic ether. Alternatively, a copolymerized polyether diol obtained by random copolymerization of one or more compounds selected from a diol compound, alkylene oxide, oxetane, cyclic acetal, 3-methyltetrahydrofuran, and 2-methyltetrahydrofuran with a cyclic ether as a raw material can be used as a reaction initiator for ring-opening polymerization.

[0048] As the diol compound serving as a raw material for the polyether diol, the same diol compound as the raw material for the polycarbonate diol can be used.

[0049] The cyclic ether used as a raw material for polyether diol is not particularly limited, and examples thereof include cyclic ethers such as tetrahydrofuran (THF), ethylene oxide, propylene oxide, oxetane, tetrahydropyran, and oxepane, as well as cyclic ether derivatives in which the hydrocarbons of the cyclic ether are partially substituted with alkyl groups. One or more of these cyclic ethers can be used as raw materials.

[0050] The polyether diol may be a commercially available product, such as EXCENOL® (manufactured by Asahi Glass Co., Ltd.), ADEKA POLYETHER® P, BPX, CM, PR (manufactured by ADEKA Corporation), SANNICS® PL-2100, PP (manufactured by Sanyo Chemical Industries, Ltd.), or TOHO POLYOL (manufactured by Toho Chemical Industry Co., Ltd.).

[0051] The weight average molecular weight (Mw) of component (B) is preferably 400 or more and 5,000 or less, more preferably 400 or more and 4,000 or less. A weight average molecular weight of 400 or more is preferred because the impact resistance of the cured product tends to increase as the crosslink density decreases. Furthermore, a weight average molecular weight of 5,000 or less is likely to provide high mechanical strength in addition to impact resistance. Furthermore, from the viewpoint of the viscosity of the curable resin composition, a weight average molecular weight of 5,000 or less is also preferred. The weight average molecular weight (Mw) of component (B) is the weight average molecular weight converted into standard polystyrene molecular weight, and is measured using a high performance liquid chromatograph (Tosoh Corporation, high-speed GPC apparatus "HLC-8220GPC") with a column: Shodex GPCLF-804 (exclusion limit molecular weight: 2 × 10 6 , Separation range: 300 to 2 × 10 6 ) in series.

[0052] The content of component (B) is not particularly limited, but is desirably more than 10 parts by mass per 100 parts by mass of the total of components (A), (B), and (C). It is more preferably more than 10 parts by mass and less than 30 parts by mass. When 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, when it is less than 30 parts by mass, high mechanical strength is likely to be obtained in addition to impact resistance.

[0053] The present inventors conducted extensive research into the conditions for an oligomer that can achieve both impact resistance and a high modulus of elasticity when combined with a mixture of component (A) and component (D), as described below. As a result, they confirmed that, as described above, bifunctional radically polymerizable oligomers composed of two or more monomer units linked by carbonate, ester, or ether groups exhibit unexpectedly superior impact resistance and a high modulus of elasticity. To explain the reason for this, we consider multifunctional urethane oligomers, which are outside the scope of the present invention. Generally, multifunctional urethane oligomers have a structure consisting of hard and soft segments, and the urethane bonds interact with each other via hydrogen bonds. Therefore, they are ideally used as crosslinkers to impart impact resistance and a high modulus of elasticity to cured products. Meanwhile, the unique impact resistance achieved by a mixture of component (A) and component (D) is thought to be due in part to the flexibility of the main chain resulting from its unique molecular structure, which effectively transmits external stress to component (D) via the polymer network, resulting in stress relaxation. To maximize this effect, it is desirable to avoid interactions such as hydrogen bonding between urethane bonds within the crosslinked network. To overcome the reduced flexibility of the polymer network due to the urethane bond, it is conceivable to use a urethane oligomer with elongated soft segments, but this would pose a problem of reduced modulus due to a decrease in crosslink density. On the other hand, when the monomer unit is a bifunctional radically polymerizable oligomer formed by linking two or more monomer units via carbonate, ester, or ether groups, the interaction between the crosslinked networks is weak. Therefore, it is possible to improve the modulus of elasticity through crosslinking while maintaining the flexibility of the main chain due to component (A). Furthermore, when the monomer unit is a hydrocarbon group without a heteroatom, the interaction between the crosslinked networks is further reduced, resulting in higher impact resistance. It is also noteworthy that a mixture of component (A) and the oligomer of the present invention was found to maintain high impact resistance even when the oligomer has a low molecular weight and a relatively high crosslink density, specifically, even when the weight-average molecular weight is between 400 and 5,000. Note that impact resistance equivalent to that of the present invention is not achieved when the oligomer has three or more functional groups.The reason for this is thought to be that excessive cross-linking significantly reduces the flexibility of the polymer network, causing stress concentration in a part of the polymer network in response to an external force.

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

[0055] Examples of the monofunctional radically polymerizable compound 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] Examples of the 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, phenyl glycidyl (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 acrylate, 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 phthalic acid (meth)acrylate, EO-modified succinic acid (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 radically polymerizable compounds having an ethylenically unsaturated group other than a (meth)acryloyl group include styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; 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-vinylmorpholine, and N-vinylacetamide.

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

[0060] From the viewpoint of increasing the curing rate, 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, and particularly preferably contains a monofunctional acrylamide compound. Examples of polyfunctional radically polymerizable compounds having two or more radically polymerizable functional groups in the molecule, which are contained 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, dimethyloltricyclodecane 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 fluorine atoms, 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'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 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 hexavinyl ether. An example of the polyfunctional aromatic vinyl compound is divinylbenzene. These polyfunctional radical polymerizable compounds may be used alone or in combination of two or more.

[0061] The content of component (C) is not particularly limited, but is preferably 0 parts by mass or more but less than 30 parts by mass, more preferably 0 parts by mass or more but less than 25 parts by mass, and may even be 0 parts by mass, relative to 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 need to contain component (C). When the content of component (C) is within this range, the impact resistance improving effect attributable to component (A) is clearly manifested in the cured product.

[0062] <Component (D): Rubber particles> Component (D) is rubber particles. The addition of rubber particles to the curable resin composition of the present invention can improve the impact resistance of the cured product. The rubber particles used in the present invention are not particularly limited, but examples include butadiene rubber particles, styrene / butadiene copolymer rubber particles, and acrylonitrile / butadiene copolymer rubber particles. Other examples include 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, and silicone / acrylic composite rubber particles. These rubber particles may be used alone or in combination of two or more. From the standpoint of flexibility, at least one type of particle selected from butadiene rubber particles, crosslinked butadiene rubber particles, styrene / butadiene copolymer rubber particles, acrylic rubber particles, and silicone / acrylic composite rubber particles is preferred.

[0063] The rubber particles are preferably rubber particles having a multilayer structure (core-shell structure) consisting of a core portion having rubber elasticity and at least one shell layer covering the core portion.

[0064] The glass transition temperature of the polymer constituting the core portion of the rubber particle 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. By adjusting the glass transition temperature of the polymer to 0°C or lower, the impact resistance of the cured product tends to be improved. The glass transition temperature of the polymer constituting the core portion means 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 that makes up the core (unit: K) W i : Weight fraction of monomer i relative to the total amount of monomers constituting the polymer that constitutes the core portion Tg i : Glass transition temperature of homopolymer of monomer i (unit: K)

[0065] Glass transition temperature Tg of homopolymer i For the glass transition temperature not described in the literature, the glass transition temperature measured by differential scanning calorimetry of a homopolymer obtained by polymerizing a monomer by a conventional method can be used.

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

[0067] The polymer constituting the shell layer of the rubber particle is preferably a different polymer from the polymer constituting the core portion.

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

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

[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 is 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 shell layer tends to disperse well in the composition. The glass transition temperature of the shell layer is a calculated value calculated using the Fox formula above.

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

[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 impact resistance improvement effect of adding the rubber particles is clearly apparent. Furthermore, when the average particle size is 2,000 nm or less, it is easy to obtain a cured product that is well-balanced in terms of impact resistance, elastic modulus, and heat resistance.

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

[0074] <Component (E): Radical Polymerization Initiator> Component (E) is a radical polymerization initiator. The radical polymerization initiator may be a photoradical 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, upon absorbing light of a specific wavelength, bonds at specific sites are cleaved, generating radicals at the cleaved sites, which act as polymerization initiators and initiate the polymerization of ethylenically unsaturated compounds containing (meth)acryloyl groups. On the other hand, hydrogen abstraction type photoradical polymerization initiators absorb light of a specific wavelength and become excited, and these excited species undergo a hydrogen abstraction reaction from surrounding hydrogen donors, generating radicals, which act as polymerization initiators and initiate 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 types in which the bond adjacent to the carbonyl group undergoes α-cleavage to generate radical species. Examples of alkylphenone-based photoradical polymerization initiators include benzyl methyl ketal-based photoradical polymerization initiators, α-hydroxyalkylphenone-based photoradical polymerization initiators, and aminoalkylphenone-based photoradical polymerization initiators. Specific compounds include, for example, benzyl methyl ketal-based photoradical polymerization initiators such as 2,2'-dimethoxy-1,2-diphenylethan-1-one (OMNIRAD (registered trademark) 651, manufactured by IGM RESINS BV), and α-hydroxyalkylphenone-based photoradical polymerization initiators such as 2-hydroxy-2-methyl-1-phenylpropan-1-one (OMNIRAD (registered trademark) 1173, manufactured by IGM RESINS BV), 1-hydroxycyclohexyl phenyl ketone (OMNIRAD (registered trademark) 184, manufactured by IGM RESINS BV), and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (OMNIRAD (registered trademark) 2959, manufactured by IGM RESINS BV). Examples of the aminoalkylphenone-based photoradical polymerization initiator include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (OMNIRAD (registered trademark) 907, IGM RESINS BV) and 2-benzylmethyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (OMNIRAD (registered trademark) 369, IGM RESINS BV), but are not limited thereto.Examples of acylphosphine oxide-based photoradical polymerization initiators include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO, manufactured by BASF) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (OMNIRAD (registered trademark) 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 trade 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 alone or in combination of two or more, and may also be used in combination with a thermal radical polymerization initiator, which will be described later.

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

[0080] The thermal radical polymerization initiator is not particularly limited as long as it generates radicals upon heating, and conventionally known compounds can be used. Examples of preferred compounds include azo compounds, peroxides, and persulfates. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 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 the thermal radical polymerization initiator added is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total of Components (A), (B), and (C). When the amount of the polymerization initiator is 15 parts by mass or less, the molecular weight increases 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 the objects and effects of the present invention are not impaired.

[0083] For example, physical property modifiers for imparting desired physical properties to the cured product include resins such as epoxy resins, polyurethanes, polychloroprene, polyesters, polysiloxanes, petroleum resins, xylene resins, ketone resins, and cellulose resins, as well as polycarbonates, modified polyphenylene ethers, polyamides, polyacetals, polyethylene terephthalates, polybutylene terephthalates, ultra-high molecular weight polyethylenes, polyphenylsulfones, polysulfones, polyarylates, polyetherimides, polyetheretherketones, and polyphenylenes. Other examples of the additives that may be added include engineering plastics such as polystyrene sulfide, polyethersulfone, polyamideimide, liquid crystal polymers, polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride, fluorine-based oligomers, silicone-based oligomers, and polysulfide-based oligomers, soft metals such as gold, silver, and lead, and layered crystal structure substances such as graphite, molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, calcium fluoride, barium fluoride, lithium fluoride, silicon nitride, and molybdenum selenide.

[0084] Furthermore, as a photosensitizer, a polymerization inhibitor such as phenothiazine or 2,6-di-t-butyl-4-methylphenol, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, or a xanthone compound may be added.

[0085] Examples of other additives include polymerization initiation aids, leveling agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, silane coupling agents, inorganic fillers, pigments, dyes, antioxidants, flame retardants, thickeners, and antifoaming agents.

[0086] <Curable resin composition> The composition of the present invention can be produced by charging appropriate amounts of components (A), (B), (C), (D), and (E), or, if component (C) is not included, components (A), (B), (D), and (E), as well as other optional components as necessary, into a stirring vessel and stirring the mixture at a temperature generally between 20° C. and 120° C., preferably between 40° C. and 100° C. Then, as necessary, dispersion treatment using ultrasound, removal of volatile solvents, and the like can be carried out.

[0087] The curable resin composition of the present invention can be suitably used as a modeling material for stereolithography. Specifically, a modeled object having a desired shape can be produced by selectively irradiating the curable resin composition of the present invention with active energy rays such as ultraviolet or visible light, electron beams, X-rays, or radioactive rays to supply the energy required for curing. When the curable resin composition of the present invention is used as a modeling material for stereolithography, the viscosity at 25°C is preferably 10 mPa·s or more and 10,000 mPa·s or less, more preferably 10 mPa·s or more and 5,000 mPa·s or less, even more preferably 10 mPa·s or more and 1,000 mPa·s or less, and most preferably 10 mPa·s or more and 200 mPa·s or less.

[0088] <Cured product> The cured product of the present invention can be obtained by curing the 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 radioactive rays. Among these, ultraviolet / visible light having a wavelength of 300 nm to 450 nm is preferred due to its easy availability and compatibility with photoradical polymerization initiators. Examples of light sources that can be used for ultraviolet / visible light include ultraviolet / visible lasers (e.g., Ar lasers, He-Cd lasers, etc.), mercury lamps, xenon lamps, halogen lamps, and fluorescent lamps. Laser light sources are particularly preferred because they can increase the energy level, shorten the molding time, and provide excellent light-focusing capabilities to achieve high molding accuracy. The curing method can be appropriately selected depending on the type of radical polymerization initiator contained in the curable resin composition. Furthermore, the curing methods may be used alone or in combination.

[0089] <Article creation method> The curable resin composition according to the present embodiment can be suitably used in a method for manufacturing an article by a stereolithography method (stereolithography). Hereinafter, a method for manufacturing an article using the curable resin composition according to the present embodiment will be described.

[0090] As the stereolithography method, a conventionally known method can be used. That is, the method for manufacturing an article of 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 the article is manufactured by laminating cured layers of the curable resin composition cured to a predetermined thickness.

[0091] FIG. 1 shows an example of the configuration 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 drivable in the vertical direction by a drive shaft 13. The active energy rays 15 emitted from a light source 14 for curing the photocurable resin composition 10 are scanned over the surface of the tank 11, with the irradiation position changed by a galvanometer mirror 16 controlled by a control unit 18 in accordance with slice data for the three-dimensional model to be created. In FIG. 1, the scanning range is indicated by a thick dashed line.

[0092] The active energy rays 15 irradiated onto the curable resin composition are not particularly limited as long as they are active energy rays capable of curing the curable resin composition according to this embodiment. Specific examples of the active energy rays 15 include ultraviolet rays, visible light, infrared rays, electromagnetic waves such as X-rays, gamma rays, and laser beams, and particle rays such as alpha rays, beta rays, and electron beams. Of these, ultraviolet rays are most preferred in terms of the absorption wavelength of the curing agent used and the cost of introducing equipment. The exposure dose is not particularly limited, but is preferably 0.001 J / cm. 2 More than 10J / cm 2 It is less than 0.001J / cm 2 If the curable resin composition is cured sufficiently, the curable resin composition will be cured sufficiently. 2 If it is less than this, the irradiation time is appropriate and is preferable from the viewpoint of productivity.

[0093] The method of irradiating the curable resin composition with active energy rays is not limited to the configuration shown in FIG. 1. When irradiating light energy as active energy rays, the following methods can be used, for example. The first method, as shown in FIG. 1, is to use light focused into a point shape, such as laser light, and two-dimensionally scan this light onto the curable resin composition. In this case, the two-dimensional scanning may be a pointillist method or a line drawing method. The second method is a surface exposure method in which light is irradiated in the shape of cross-sectional data using a projector or the like. In this case, the active energy rays may be irradiated planarly through a surface drawing mask formed by arranging multiple micro-optical shutters, such as liquid crystal shutters or digital micromirror 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 made when the slice data was generated, and affects the accuracy (reproducibility of the shape data of the object to be molded) of the resulting molded object 17. The thickness d is achieved by the control unit 18 controlling the drive amount 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 to a thickness d onto the modeling stage 12. The liquid curable resin composition on the modeling stage 12 is selectively irradiated with active energy rays based on slice data to form a cured layer having the desired pattern. Next, the modeling stage 12 is moved in the direction of the white arrow, and uncured curable resin composition is supplied to a thickness d onto the surface of the cured layer. Then, active energy rays 15 are irradiated based on the slice data, forming 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.

[0096] The object obtained by the stereolithography method described above is subjected to post-processing as necessary to obtain an article. The post-processing may involve, for example, cleaning the surface of the object with a cleaning agent such as an organic solvent. The object may also be subjected to post-curing, in which unreacted components that may remain on the surface or inside the object are cured by further irradiating the object with light or heat treating it. Furthermore, mechanical processing, such as polishing the surface to smooth out surface irregularities or drilling screw holes, may also be performed. A combination of these processes may also be performed. [Example]

[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. [Component (A)] A-1: α-allyloxymethyl methyl acrylate (AOMA, manufactured by Nippon Shokubai Co., Ltd.)

[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: approximately 760, manufactured by Toagosei Co., Ltd.) B-6: Polyester diacrylate; "M-6250" (weight average molecular weight: approximately 660, manufactured by Toagosei Co., Ltd.) B-7: Polyester diacrylate; "M-6500" (weight average molecular weight: approximately 740, manufactured by Toagosei Co., Ltd.) B-8: Polyester diacrylate; "CN2254-NS" (weight average molecular weight: approximately 3800, manufactured by SARTOMER)

[0100] [Component (B'): Bifunctional radically polymerizable oligomer other than component (B)] B'-1: Bifunctional 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 compound C1-1: Acryloylmorpholine; "ACMO" (KJ Chemicals) C1-2: 4-tert-butylcyclohexyl acrylate; "TBCHA" (KJ Chemicals)

[0102] (2) Polyfunctional radical polymerizable compound C2-1: 1,6-hexanediol diacrylate C2-2: Tricyclodecane dimethanol diacrylate C2-3: Trimethylolpropane triacrylate

[0103] [Component (D)] D-1: Core-shell rubber particles; "Kane Ace(R) M-511" (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] <Production of Curable Resin Composition> Components (A) to (C) were blended in the ratios shown in Tables 1 and 2 and mixed uniformly. Component (D), a secondary particle powder, was added to this blend in the ratio shown in Tables 1 and 2. A stirring bar was then placed in the mixture, and the mixture was stirred with a magnetic stirrer at 750 rpm for 1 hour to obtain a gel-like mixture. The mixture was then dispersed twice for 10 minutes with a 2-minute interval using a Tomy Seiko ultrasonic homogenizer "UD-200" at 60 W to obtain a uniform mixture. Component (E) was then added in the ratio shown in Tables 1 and 2 and mixed uniformly to obtain the curable resin composition shown in Tables 1 and 2.

[0106] <Creating test specimens> A cured product was produced from the prepared curable resin composition by the following method. First, a mold measuring 80 mm in length, 10 mm in width, and 4 mm in thickness was sandwiched between two pieces of quartz glass, and the curable resin composition was poured into the mold. The poured curable resin composition was irradiated with an ultraviolet ray irradiator (manufactured by HOYA CANDEO OPTRONICS, product name "LIGHT SOURCE EXECURE3000") at 5 mW / cm. 2 The resulting cured product was subjected to post-curing such as additional UV irradiation or heating as necessary, within the scope of not damaging the shape of the test piece, to obtain a test piece measuring 80 mm in length, 10 mm in width, and 4 mm in thickness.

[0107] <Evaluation> [Weight average molecular weight] A gel permeation chromatography (GPC) apparatus (Tosoh Corporation, HLC-8220GPC) was fitted with a Shodex GPC LF-804 column (Showa Denko K.K., exclusion limit molecular weight: 2 × 10 6 Separation range: 300 to 2 × 10 6 Two HPLC columns were arranged in series, and measurements were taken with an RI (Refractive Index) detector at 40°C using THF as a developing solvent. The weight-average molecular weight obtained is a value converted into a standard polystyrene equivalent.

[0108] [Charpy impact strength] In accordance with JIS K 7111, a 2 mm deep, 45° notch was made in the center of the test specimen using a notch-making machine (manufactured by Toyo Seiki Seisakusho, product name "Notching Tool A-4"). Using an impact tester (manufactured by Toyo Seiki Seisakusho, product name "IMPACT TESTER IT"), the test specimen was broken from the back of the notch with an energy of 2 J. The energy required for fracture was calculated from the angle at which the hammer, raised to 150°, swung back after the specimen broke, and this was taken as the Charpy impact strength, which was used as an index of impact resistance. Impact resistance was evaluated as follows: A (very good): 15kJ / 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 (conditions: test speed 2 mm / min, distance between supports 64 mm, indenter radius 5 mm, support table radius 5 mm) was performed on the test specimen using a tension-compression testing machine (manufactured by A&D, product name "Tensilon Universal Material Testing Machine RTF-1250C"), and the bending modulus was calculated from the measured stress gradient in the strain range from 0.05% to 0.25%. The bending modulus was evaluated as follows: A (very good): 2.4 GPa or more. B (Good): 2GPa or more and less than 2.4GPa. C (poor): Less than 2GPa.

[0110] [viscosity] The obtained curable resin composition was measured as follows using a viscoelasticity measuring device (MCR302 manufactured by Anton Paar). Approximately 0.5 mL of sample was filled into the measuring device equipped with a cone-plate type measuring jig (25 mm diameter, 2°), and the temperature was adjusted to 20°C. The shear rate was 5 s -1 The value obtained under the above conditions was taken as the viscosity. The viscosity was evaluated as follows: A (very good): Less than 200 mPa·s. B (Good): 200 mPa·s or more but 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 based on 100 parts by mass of the radical polymerizable compounds. The results of a Charpy impact test are shown to evaluate the impact resistance of the cured resin compositions prepared at the mixing ratios shown in Tables 1 and 2, the results of flexural modulus measurement are shown to evaluate the elastic modulus, and the results of viscosity measurement are shown to evaluate the moldability. The effectiveness of the present invention will be explained with reference to Examples and Comparative Examples using Tables 1 and 2.

[0114] [Effectiveness of ingredient (A)] Comparing Example 1 and Comparative Example 9, it can be seen that the presence of component (A) significantly contributes to the impact resistance and low viscosity of the cured product.

[0115] [Effectiveness of ingredient (B)] Comparing Examples 1 to 8 with Comparative Examples 1, 2, and 11, it can be seen that the presence of component (B) contributes significantly to the impact resistance of the cured product, and that because component (B) is a bifunctional radically polymerizable oligomer consisting of an oligomer moiety 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, it also exhibits a higher elastic modulus, and that urethane oligomers outside the scope of the present invention cannot exhibit equivalent performance in terms of elastic modulus.

[0116] [Effectiveness of ingredient (C)] Comparing Examples 9 to 11 with Comparative Examples 3 to 8, it was found that when component (C) contained more than 75 parts by mass of a monofunctional polymerizable compound per 100 parts by mass of component (C), the impact resistance of the cured product was good. On the other hand, when component (C) contained 25 parts by mass or more of a polyfunctional polymerizable compound per 100 parts by mass of component (C), it was found that the same impact resistance performance could not be achieved.

[0117] [Effectiveness of ingredient (D)] Comparing Example 1 and Comparative Example 10, it can be seen that the presence of component (D) contributes greatly to the impact resistance of the cured product.

[0118] The above results demonstrate that the composition of the present invention has a low viscosity and can be suitably used for optical three-dimensional modeling, and furthermore, the cured product can have both impact resistance and a high elastic modulus. [Explanation of symbols]

[0119] 10: Photocurable resin composition, 11: Tank, 12: Modeling stage, 13: Drive shaft, 14: Light source, 15: Active energy rays, 16: Galvanometer mirror, 17: Modeled object, 18: Control unit, 100: Optical modeling device

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 component (A) and the component (B); may contain The component (A) is an α-(unsaturated alkoxyalkyl)acrylic acid or its ester 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 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 containing 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, and does not contain a urethane bond; 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 relative to 100 parts by mass of the total of the component (A), the component (B), and the component (C); the content of the component (A) is more than 70 parts by mass and 100 parts by mass or less, relative to 100 parts by mass of the total of the components (A) and (C), the content of the component (D) is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the total of the components (A), (B), and (C), a curable resin composition, characterized in that, when the component (C) is contained, the content of the monofunctional radical polymerizable compound contained in the component (C) is 80 parts by mass or more per 100 parts by mass of the total of the components (C).

2. 2. The curable resin composition according to claim 1, wherein the component (A) is a compound that contains an ether structure in its main chain and that polymerizes while forming a five-membered ring or a 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. 4. The curable resin composition according to claim 1, wherein the content of the component (A) is 75 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the total of the component (A) and the component (C).

5. 5. The curable resin composition according to claim 1, wherein the content of the component (B) is more than 10 parts by mass relative to 100 parts by mass of the total of the components (A), (B), and (C).

6. 6. 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.

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

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

9. The curable resin composition according to any one of claims 1 to 8, 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.

10. 10. The curable resin composition according to claim 1, 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).

11. The curable resin composition according to any one of claims 1 to 10, wherein all of the components (C) are monofunctional radically polymerizable compounds.

12. 12. 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.

13. 13. The curable resin composition according to claim 1, wherein 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.

14. 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 its ester represented by the following general formula (1): 【Chemistry 2】 [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 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 containing 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, and does not contain a urethane bond; Component (C): a radical polymerizable compound other than the component (A) and the component (B); Does not contain The content of the component (A) is more than 70 parts by mass and less than 90 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B), A curable resin composition characterized in that the content of the component (D) is 5 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the total of the components (A) and (B).

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 its ester represented by the following general formula (1): 【Chemistry 2】 [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 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 containing 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, and does not contain a urethane bond; moreover, Component (C): A radical polymerizable compound other than the components (A) and (B). Contains 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 relative to 100 parts by mass of the total of the component (A), the component (B), and the component (C); the content of the component (A) is more than 70 parts by mass and 100 parts by mass or less, relative to 100 parts by mass of the total of the components (A) and (C), the content of the component (D) is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the total of the components (A), (B), and (C), A curable resin composition, characterized in that the content of the monofunctional radically polymerizable compound contained in the component (C) is 80 parts by mass or more per 100 parts by mass of the total of the components (C).

16. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 15.

17. A method for manufacturing an article using a stereolithography method, a step of disposing a photocurable resin composition in a layer; a step of irradiating the layered photocurable resin composition with light energy to cure it based on slice data of a model to form a modeled object; Including, A method for producing an article, wherein the photocurable resin composition is the curable resin composition according to any one of claims 1 to 15.

18. The method for manufacturing an article according to claim 17, further comprising a step of processing the shaped object.

19. 19. The method for manufacturing an article according to claim 18, wherein the step of processing the shaped object includes performing at least one process selected from the group consisting of cleaning, post-cure, and mechanical processing.

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