JP7799474B2 - Curable resin composition and method for producing article - Google Patents

Description

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

BACKGROUND ART Optical three-dimensional modeling (hereinafter referred to as photolithography) 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 a shaped object is produced by stacking the cured resin layers integrally.
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 complexly 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.

Japanese Patent Application Laid-Open No. 2004-051665 Special Publication No. 2020-505255

However, the curable resin composition disclosed in Patent Document 1 does not exhibit 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 exhibiting 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.

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): 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):

[wherein R ₁ 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 R ₃ and 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.
_R5 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),
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).
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):
[wherein R ₁ 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 R ₃ and 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.
_R5 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 no urethane bond and including 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 is characterized in that it is any one of 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 component (A) and the component (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).

The present invention provides a curable resin composition that can form a cured product with impact resistance and a high elastic modulus, and has low viscosity, making it suitable for three-dimensional modeling.

FIG. 1 is a diagram illustrating an example of the configuration of a photo-fabrication apparatus.

Embodiments of the present invention are described below. Please note that the embodiment described below is merely one embodiment of the present invention, and the present invention is not limited to these embodiments.

<Component (A): α-(Unsaturated Alkoxyalkyl)acrylic Acid or Ester thereof>
Component (A) is an α-(unsaturated alkoxyalkyl)acrylic acid or its ester represented by the following general formula (1):

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 a hydrocarbon 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.

Examples of hydrocarbon groups include chain saturated hydrocarbons with one or more carbon atoms, chain unsaturated hydrocarbons with three or more carbon atoms, alicyclic hydrocarbon groups with three or more carbon atoms, and aromatic hydrocarbon groups with six or more carbon atoms.

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.

For example, the chain saturated hydrocarbon group may be a linear or branched hydrocarbon group, and is not particularly limited. 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, and melissyl. Furthermore, at least a portion of the hydrogen atoms bonded to the carbon atoms constituting the chain saturated hydrocarbon group may be substituted with halogen atoms, cyano groups, trimethylsilyl groups, or the like.

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, and linolene.

The alicyclic hydrocarbon group may be any hydrocarbon group containing a saturated cyclic structure of three or more members, or a non-aromatic unsaturated cyclic structure, and is not particularly limited. Suitable examples include cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, tricyclodecanyl, isobornyl, adamantyl, dicyclopentanyl, and dicyclopentenyl.

The aromatic hydrocarbon group may be any hydrocarbon group containing an aromatic ring structure of six or more members, and is not particularly limited. Suitable examples include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-t-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, and anthranyl.

Monovalent organic groups consisting of a hydrocarbon skeleton containing an ether bond may be any group 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, and are not particularly limited. Examples 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.

_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. 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, an ether-containing ring structure having 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.

_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 interfere with 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.

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, n-hexyl α-allyloxymethylacrylate, s-hexyl α-allyloxymethylacrylate, n-heptyl α-allyloxymethylacrylate, n-octyl α-allyloxymethylacrylate, and α-allyloxymethyl. s-octyl acrylate, t-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, capryl α-allyloxymethyl acrylate, nonyl α-allyloxymethyl acrylate, decyl α-allyloxymethyl acrylate, undecyl α-allyloxymethyl acrylate, lauryl α-allyloxymethyl acrylate, tridecyl α-allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, nonadecyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate Cosyl, seryl α-allyloxymethylacrylate, melissyl 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, linolene α-allyloxymethylacrylate, cyclopentyl α-allyloxymethylacrylate, cyclopentylmethyl α-allyloxymethylacrylate, α-allyloxymethyl acrylate Cyclohexyl 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 α-allyloxymethyl acrylate, phenyl α-allyloxymethyl acrylate, methylphenyl α-allyloxymethyl acrylate, dimethylphenyl α-allyloxymethyl acrylate, trimethylphenyl α-allyloxymethyl acrylate, 4-t-allyloxymethyl acrylate Butylphenyl, benzyl α-allyloxymethylacrylate, diphenylmethyl α-allyloxymethylacrylate, diphenylethyl α-allyloxymethylacrylate, triphenylmethyl α-allyloxymethylacrylate, 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, α-allyl Cyclopentoxyethyl α-allyloxymethylacrylate, cyclohexyloxyethyl α-allyloxymethylacrylate, 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-oxetanetriol α-allyloxymethylacrylate methyl 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, dioxanyl α-allyloxymethylacrylate, α-methallyloxymethylacrylic acid, methyl α-methallyloxymethylacrylate, ethyl α-methallyloxymethylacrylate, n-propyl α-methallyloxymethylacrylate, i-propyl α-methallyloxymethylacrylate, n-butyl α-methallyloxymethylacrylate, α-methallyl n-Amyl α-methallyloxymethylacrylate, s-Amyl α-methallyloxymethylacrylate, t-Amyl α-methallyloxymethylacrylate, neopentyl α-methallyloxymethylacrylate, n-Hexyl α-methallyloxymethylacrylate, 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, α-Methallyloxymethylacrylic Acid undecyl, lauryl α-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, linoleic α-methallyloxymethyl acrylate, linolene α-methallyloxymethyl acrylate, cyclopentyl α-methallyloxymethyl acrylate, cyclopentylmethyl α-methallyloxymethyl acrylate, cyclohexyl α-methallyloxymethyl acrylate, cyclohexylmethyl α-methallyloxymethyl acrylate, 4-methylcyclohexyl α-methallyloxymethyl acrylate, 4-t-butylcyclohexyl α-methallyloxymethyl acrylate, α-methallyloxymethyl acrylate tricyclodecanyl acrylate, isobornyl α-methallyloxymethylacrylate, adamantyl α-methallyloxymethylacrylate, 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, triphenyl α-methallyloxymethylacrylate phenylmethyl, cinnamyl α-methallyloxymethyl acrylate, naphthyl α-methallyloxymethyl acrylate, anthranyl α-methallyloxymethyl acrylate, methoxyethyl α-methallyloxymethyl acrylate, methoxyethoxyethyl α-methallyloxymethyl acrylate, methoxyethoxyethoxyethyl α-methallyloxymethyl acrylate, 3-methoxybutyl α-methallyloxymethyl acrylate, ethoxyethyl α-methallyloxymethyl acrylate, ethoxyethoxyethyl α-methallyloxymethyl acrylate, cyclopentoxyethyl α-methallyloxymethyl acrylate, cyclohexyloxyethyl α-methallyloxymethyl acrylate, cyclopentoxyethoxyethyl α-methallyloxymethyl acrylate, Cyclohexyloxyethoxyethyl methallyloxymethyl acrylate, dicyclopentenyloxyethyl α-methallyloxymethyl acrylate, phenoxyethyl α-methallyloxymethyl acrylate, phenoxyethoxyethyl α-methallyloxymethyl acrylate, 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, ... tetrahydrofuranyl α-methallyloxymethylacrylate, 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(tricyclodecanilic) di(isobornyl)-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.

Of these, compounds that contain an ether structure in the main chain and polymerize while forming a five- or six-membered ring are preferred, with methyl α-allyloxymethylacrylate, ethyl α-allyloxymethylacrylate, methyl α-methallyloxymethylacrylate, and dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate being more preferred. Of these, methyl α-allyloxymethylacrylate, which forms a ring structure such as that shown in structural formula (2) below during polymerization, is most preferred from the standpoint of impact resistance and elastic modulus of the cured product.

The reason why this structure provides particularly high impact resistance is that the ether bond in the tetrahydrofuran ring and the methylene group adjacent to the tetrahydrofuran ring contribute to improving the flexibility of the main chain. Meanwhile, the incorporation of a ring structure into the main chain provides not only impact resistance but also a high elastic modulus. Note that commercially available α-allyloxymethyl methyl acrylate can be used; for example, it is available from Nippon Shokubai Co., Ltd. under the name AOMA.

The content of component (A) is not particularly limited, but from the perspective of the impact resistance of the cured product, it is preferably more than 70 parts by mass and less than 100 parts by mass, and more preferably 75 parts by mass or more and less 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 keeping the content within the above range, the impact resistance-improving effect of component (A) is clearly manifested.

<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.

Component (B) can be, for example, 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 be composed of a hydrocarbon group. Here, the monomer unit refers to the oligomer in question 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 a linear saturated hydrocarbon or alicyclic hydrocarbon is particularly preferred.

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.

Polycarbonate diol can be represented by the following general formula (3):

(In the formula, n is a number of 2 or more. R is any group, and the Rs may be the same or different.)

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.

Diol compounds that can be used as raw materials for polycarbonate diol are not particularly limited, and examples thereof include diols without side chains 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-1,8-octanediol. Examples of suitable diols include diols with side chains 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 with aromatic rings 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.

Carbonate esters used as raw materials for polycarbonate diol 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 is easy to obtain polycarbonate diols with a specific primary terminal OH ratio by adjusting conditions such as the feed ratio of diol to carbonate. Furthermore, from the viewpoints of ease 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.

Commercially available polycarbonate diols may also be suitably selected. Products suitable for the present invention may be appropriately selected from among 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.).

Polyester diol can be represented by the following general formula (4):

(In the formula, n is a number of 2 or more. R is any group, and the Rs may be the same or different.)

The polyester diol represented by 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.

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

Dicarboxylic acids used as raw materials for polyester diols are not particularly limited, and examples 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 of these dicarboxylic acids can be used as raw materials. Additionally, the above-mentioned dicarboxylic acids can also be subjected to the reaction in the form of acid anhydrides, in which case they will react with water in the reaction system to produce the dicarboxylic acid.

Commercially available polyester diols may also be suitably selected. Examples include Polylite® (DIC Corporation) diols, Maximol® RDK-133, RDK-142 (Kawasaki Chemical Industries, Ltd.), Nipporan® 4002, 4040, 4009, 4010, 3027, 164, 4073, 136, 1004, 141, 4042, 5018, 5035 (Tosoh Corporation), Adeka New Ace® (ADEKA Corporation) diols, 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.), and CN2203, CN2254, CN2270, CN2271, CN2273, CN2274 manufactured by SATOMER Co., Ltd., etc.

Polyether diol can be represented by the following general formula (5):

(In the formula, n is a number of 2 or more. R is any group, and the Rs may be the same or different.)

The polyether diol represented by general formula (5) may be produced by any method, but can be obtained, for example, by addition polymerization of the ring-opening polymerization of a cyclic ether. Alternatively, a copolymer 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 the cyclic ether raw material can be used as a reaction initiator for ring-opening polymerization.

The diol compounds used as raw materials for polyether diols can be the same as the diol compounds used as raw materials for polycarbonate diols.

The cyclic ether used as a raw material for polyether diol is not particularly limited, and examples 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. Furthermore, one or more of these cyclic ethers can be used as raw materials.

Commercially available polyether diols can also be suitably selected. Products suitable for the present invention can be selected from among 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.), and TOHO POLYOL (manufactured by Toho Chemical Industry Co., Ltd.).

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 to standard polystyrene molecular weight and is measured using a high performance liquid chromatography (Tosoh Corporation, high-speed GPC apparatus "HLC-8220GPC") with two Shodex GPCLF-804 columns (exclusion limit molecular weight: 2 × 10 ⁶ , separation range: 300 to 2 × 10 ⁶ ) in series.

The content of component (B) is not particularly limited, but it is preferably 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.

The 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), 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 this 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 between the crosslinked networks, such as hydrogen bonds between urethane bonds. 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 of elasticity due to a reduced 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 mixed system of component (A) and the oligomer of the present invention can 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 400 to 5,000. Note that when the oligomer has three or more functional groups, impact resistance equivalent to that of the present invention is not achieved. The reason for this is thought to be that excessive cross-linking significantly reduces the flexibility of the polymer network, causing stress concentration in parts of the polymer network in response to external forces.

<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, more than 75 parts by mass of the monofunctional radically polymerizable compound is contained 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 25 parts by mass or more of the polyfunctional radically polymerizable compound is contained per 100 parts by mass of the total of component (C), sufficient impact resistance cannot be exhibited. Examples of the radically polymerizable functional group include an ethylenically unsaturated group. Specific examples of the ethylenically unsaturated group include a (meth)acryloyl group and a vinyl group.

Examples of monofunctional radically polymerizable compounds having a (meth)acryloyl group include monofunctional acrylamide compounds and monofunctional (meth)acrylate compounds.

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.

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-adamantyl (meth)acrylate, 3,5-dihydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate. 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, 2,2,2-trifluoroethyl (meth)acrylate, Examples include 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,N-diethylaminoethyl (meth)acrylate, morpholino (meth)acrylate, EO-modified phosphate (meth)acrylate, (meth)acrylates with imide groups (product name: M-140, manufactured by Toagosei Co., Ltd.), and monofunctional (meth)acrylates with siloxane structures.

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, and 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-vinylmorpholine, and N-vinylacetamide.

These monofunctional radically polymerizable compounds may be used alone or in combination of two or more.

From the viewpoint of increasing the curing rate, the monofunctional radically 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 the polyfunctional radically polymerizable compound having two or more radically polymerizable functional groups in the molecule, which is 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.

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 evident in the cured product.

<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 viewpoint 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.

Preferred rubber particles are those having a multilayer structure (core-shell structure) consisting of a core portion having rubber elasticity and at least one shell portion covering the core portion.

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 favorably. 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=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...+W _n /Tg _n
Tg: glass transition temperature of the polymer constituting the core portion (unit: K)
W _i : weight fraction of monomer i relative to the total amount of monomers constituting the polymer constituting the core portion Tg _i : glass transition temperature of the homopolymer of monomer i (unit: K)

The glass transition temperature _Tg of the homopolymer can be a value described in a literature. For a value not described in a literature, the glass transition temperature of a homopolymer obtained by polymerizing a monomer by a conventional method, measured by differential scanning calorimetry, can be used.

The polymer that makes up the core portion is not particularly limited, but is preferably made from any of butadiene rubber, cross-linked butadiene rubber, styrene/butadiene copolymer rubber, acrylic rubber, and silicone/acrylic composite rubber.

It is preferable that the polymer constituting the shell layer of the rubber particle is a different polymer from the polymer constituting the core portion.

The polymer that constitutes the shell layer can be, but is not limited to, (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, maleimide, styrene, α-(unsaturated alkoxyalkyl)acrylic acid or its ester (component (A)), etc.

The polymer constituting the shell layer, like the core portion, may contain, in addition to the above-mentioned monomers, 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, as other monomer components.

The glass transition temperature of the polymer that constitutes 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, there is no increase in viscosity 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.

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 applying the shell layer to the core portion and grafting the shell layer onto the surface of the core portion, but grafting the shell layer onto the surface of the core portion is preferred.

The average particle size of the rubber particles is not particularly limited, but is preferably 20 nm or more and 2,000 nm or less, more preferably 20 nm or more and 900 nm or less, and even more preferably 30 nm or more and 800 nm or less. When the average particle size of the rubber particles is 20 nm or more, the impact resistance improvement effect of adding rubber particles is clearly evident. 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.

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

<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.

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 enter an excited state, 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.

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 examples of the compounds include 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 B.V.), 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 B.V.), 1-hydroxycyclohexyl phenyl ketone (OMNIRAD (registered trademark) 184, manufactured by IGM RESINS B.V.), and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (OMNIRAD (registered trademark) 2959, manufactured by IGM RESINS B.V.). Examples of the photopolymerization initiator include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (OMNIRAD (registered trademark) 127, IGM Resins B.V.), and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one. Examples of the aminoalkylphenone photoradical polymerization initiator include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (OMNIRAD (registered trademark) 907, IGM Resins B.V.) and 2-benzylmethyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (OMNIRAD (registered trademark) 369, IGM Resins B.V.), 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® TPO H, manufactured by IGM RESINS B.V.). 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.

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.

These photoradical polymerization initiators may be used alone or in combination of two or more. They may also be used in combination with the thermal radical polymerization initiators described below.

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. 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 will be obtained.

Thermal radical polymerization initiators are not particularly limited as long as they generate radicals upon heating, and conventionally known compounds can be used. Preferred examples 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.

The amount of thermal radical polymerization initiator added is preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total of components (A), (B), and (C). If 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.

<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.

For example, physical property modifiers for imparting desired physical properties to the cured product include resins such as epoxy resin, polyurethane, polychloroprene, polyester, polysiloxane, petroleum resin, xylene resin, ketone resin, and cellulose resin, as well as polycarbonate, modified polyphenylene ether, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, ultra-high molecular weight polyethylene, polyphenylsulfone, polysulfone, polyarylate, polyetherimide, polyether ether ketone, and polyphenylene Other materials 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 crystalline structure materials such as graphite, molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, calcium fluoride, barium fluoride, lithium fluoride, silicon nitride, and molybdenum selenide.

Photosensitizers such as polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds may also be added.

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

<Curable resin composition>
The composition of the present invention can be produced by charging 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, if necessary, other optional components, into a stirring vessel and stirring the mixture at a temperature generally from 20° C. to 120° C., preferably from 40° C. to 100° C. Then, if necessary, dispersion treatment using ultrasonic waves, removal of volatile solvents, and the like may be carried out.

The curable resin composition of the present invention can be suitably used as a modeling material for stereolithography. Specifically, 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 necessary for curing, a modeled object of a desired shape can be produced. 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.

<Cured product>
The cured product of the present invention can be obtained by curing the curable resin composition described above 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 or more and 450 nm or less is preferred due to its ease of availability and compatibility with the photoradical polymerization initiator. 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 preferred because they can increase the energy level, shorten the molding time, and have excellent light-gathering properties, resulting in 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.

<Method for forming an article>
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.

A conventionally known method can be used as the stereolithography method. 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. The step of curing the curable resin composition to a predetermined thickness is then carried out multiple times, and the article is manufactured by laminating cured layers of the curable resin composition that have been cured to a predetermined thickness.

Figure 1 shows an example of the configuration of a modeling device using stereolithography. The stereolithography device 100 has a vat 11 filled with a liquid photocurable resin composition 10. Inside the vat 11, a modeling stage 12 is provided that can be driven vertically by a drive shaft 13. The active energy rays 15 emitted from the light source 14 for curing the photocurable resin composition 10 are scanned across the surface of the vat 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 Figure 1, the scanning range is indicated by a thick dashed line.

The active energy rays 15 irradiated to 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, X-rays, gamma rays, laser beams, and other electromagnetic waves, as well as 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 or more and 10 J/cm ² or less. If the exposure dose is 0.001 J/cm ² or more, the curable resin composition will be sufficiently cured, and if the exposure dose is 10 J/cm ² or less, the exposure time will be appropriate, which is preferred from the viewpoint of productivity.

The method of irradiating the curable resin composition with active energy rays is not limited to the configuration shown in Figure 1. When irradiating light energy as active energy rays, the following methods can be used, for example. The first method, as shown in Figure 1, is to use light focused into a point shape, such as laser light, and scan this light two-dimensionally over 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 the 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 microscopic optical shutters, such as liquid crystal shutters or digital micromirror shutters.

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 of the resulting molded object 17 (the reproducibility of the shape data of the object being molded). The thickness d is achieved by the control unit 18 controlling the drive amount of the drive shaft 13.

First, the control unit 18 controls the drive shaft 13 based on the settings, and 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 with 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. Active energy rays 15 are then 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.

The object obtained by the above-mentioned stereolithography method is subjected to post-processing as necessary to obtain an article. Post-processing may involve, for example, cleaning the surface of the obtained object with a cleaning agent such as an organic solvent. Post-processing may also involve further irradiating the obtained object with light or subjecting it to heat treatment, thereby post-curing any unreacted components that may remain on the surface or inside the object. Furthermore, mechanical processing such as polishing the surface to smooth out any surface irregularities or drilling screw holes may also be used. A combination of these processes may also be used.

The present invention will be described in detail below using examples, but the present invention is not limited to these examples.

<Materials>
The materials used in the examples and comparative examples are listed below.
[Component (A)]
A-1: Methyl α-allyloxymethylacrylate (manufactured by Nippon Shokubai Co., Ltd., AOMA)

[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 Dai-ichi 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)

[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)

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

(2) Polyfunctional radical polymerizable compound C2-1: 1,6-hexanediol diacrylate C2-2: tricyclodecane dimethanol diacrylate C2-3: trimethylolpropane triacrylate

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

[Component (E)]
E-1: Photoradical generator; "Omnirad 819" (manufactured by IGM RESINS B.V.)

<Production of Curable Resin Composition>
Components (A) to (C) were blended at the blending ratios shown in Tables 1 and 2 and mixed uniformly. Component (D) secondary particle powder was added to this blend at the blending ratios shown in Tables 1 and 2. A stirrer was then placed in the mixture, and the mixture was stirred at 750 rpm with a magnetic stirrer 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 output to obtain a uniform mixture. Component (E) was then added at the blending ratios shown in Tables 1 and 2 and mixed uniformly to obtain the curable resin compositions shown in Tables 1 and 2.

<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 ultraviolet light at 5 mW/cm ² using an ultraviolet irradiator (manufactured by HOYA CANDEO OPTRONICS, product name "LIGHT SOURCE EXECURE 3000"). The obtained cured product was subjected to post-curing, such as additional ultraviolet irradiation or heating, as necessary, within the range that did not damage 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.

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

[Charpy impact strength]
In accordance with JIS K 7111, a 2 mm deep, 45° notch was made in the center of the test piece using a notch forming machine (manufactured by Toyo Seiki Seisakusho, trade name "Notching Tool A-4"). Using an impact tester (manufactured by Toyo Seiki Seisakusho, trade name "IMPACT TESTER IT"), the test piece was broken with an energy of 2 J from the back of the notch. The energy required for breakage was calculated from the angle at which a hammer swung up to 150° swung up after the test piece 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): 15 kJ/ ^m2 or more.
B (good): 10 kJ/m ² or more and less than 15 kJ/m ² .
C (poor): Less than 10 kJ/ ^m2 .

[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 piece 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): 2 GPa or more and less than 2.4 GPa.
C (poor): Less than 2 GPa.

[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 adjusted to 20°C. The value obtained under the condition of a shear rate of 5 s ^-1 was taken 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): 1000 mPa·s or more.

In Tables 1 and 2, each part by mass is calculated based on a total of 100 parts by mass of 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 measurements are shown to evaluate the elastic modulus, and the results of viscosity measurements are shown 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.

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

[Effectiveness of component (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.

[Effectiveness of component (C)]
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 the monofunctional polymerizable compound relative to 100 parts by mass of the total of component (C). On the other hand, it was confirmed that when component (C) contained 25 parts by mass or more of the polyfunctional polymerizable compound relative to 100 parts by mass of the total of component (C), the same performance in terms of impact resistance could not be achieved.

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

These results demonstrate that the composition of the present invention has low viscosity and can be suitably used for optical three-dimensional modeling, and that the cured product can achieve both impact resistance and a high elastic modulus.

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 (19)

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):
[wherein R ₁ 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 R ₃ and 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.
_R5 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). The curable resin composition according to claim 1, characterized in that component (A) is a compound that contains an ether structure in its main chain and polymerizes while forming a five- or six-membered ring. The curable resin composition according to claim 1 or 2, wherein component (A) is methyl α-allyloxymethylacrylate or ethyl α-allyloxymethylacrylate. 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. 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. 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. The curable resin composition according to claim 1, wherein the monomer unit of the component (B) is a hydrocarbon group. 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. The curable resin composition according to any one of claims 1 to 8 , characterized in that the component (C) contains at least one of a monofunctional acrylamide-based compound, a monofunctional N-vinyl-based compound, and a monofunctional (meth)acrylate-based compound. 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). 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. 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. 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. 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):
[wherein R ₁ 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 R ₃ and 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.
_R5 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) . 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):
[wherein R ₁ 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 R ₃ and 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.
_R5 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) . A cured product obtained by curing the curable resin composition according to any one of claims 1 to 15 . 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 . The method for manufacturing an article according to claim 17 , further comprising a step of processing the shaped object. 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.