WO2020162475A1

WO2020162475A1 - Curable resin composition

Info

Publication number: WO2020162475A1
Application number: PCT/JP2020/004231
Authority: WO
Inventors: 恭平和田; 卓之平谷
Original assignee: キヤノン株式会社
Priority date: 2019-02-08
Filing date: 2020-02-05
Publication date: 2020-08-13

Abstract

This curable resin composition is characterized by containing: monofunctional 2-(aryloxymethyl)acrylic acid or an ester thereof as component (A); a polyfunctional radical-polymerizable compound having an isocyanurate ring as component (B); a radical-polymerizable compound as component (C); rubber particles as component (D); and an initiator of radical polymerization as component (E), wherein component (C) is a radical-polymerizable compound different from component (A) and component (B), the contained amounts of component (B) and component (C) are 20-80 parts by mass and 0-40 parts by mass, respectively, when the total amount of component (A), component (B), and component (C) is defined as 100 parts by mass.

Description

Curable resin composition

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

An optical three-dimensional modeling method for obtaining a three-dimensional model by curing a liquid curable resin layer by layer with energy active light such as ultraviolet rays and stacking the layers has been studied. Optical three-dimensional objects can now be used not only for prototypes for rapid shape confirmation (rapid prototyping), but also for mold production (rapid tooling) and service parts (production of actual products, rapid manufacturing). Is coming.
Along with this, the demand for material properties (impact resistance, heat resistance, flexural modulus, etc.) for three-dimensional molded objects has become more advanced, and in recent years, physical properties equivalent to engineering plastics have been required. There is.
A three-dimensional molded object made of a curable resin is required to have a certain degree of heat resistance and impact resistance, especially high impact resistance. Patent Document 1 discloses a curable resin composition containing a specific radical-polymerizable compound and a polyfunctional radical-polymerizable compound in order to achieve both high impact resistance and heat resistance. Further, Patent Document 2 discloses a curable resin composition comprising a radically polymerizable compound and rubber particles.

JP, 2014-040585, A JP, 2015-110772, A

However, from the curable resin compositions disclosed in Patent Document 1 and Patent Document 2, although a cured product exhibiting high heat resistance has been obtained, a cured product exhibiting sufficient impact resistance cannot be obtained. ..
An object of the present invention is to provide a curable resin composition capable of obtaining a cured product having excellent heat resistance, impact resistance and flexural modulus.

The curable resin composition according to the present embodiment,
Component (A): monofunctional 2-(allyloxymethyl)acrylic acid or its ester,
Component (B): a polyfunctional radically polymerizable compound having an isocyanurate ring,
Component (C): radically polymerizable compound,
Component (D): rubber particles,
Component (E): radical polymerization initiator,
Containing
The component (A) is represented by the following general formula (1),

[In general formula (1), R is a hydrogen atom or a hydrocarbon group. The hydrocarbon group may have an ether bond, and the hydrocarbon group may have a substituent. ]
The component (B) is represented by the following general formula (2),

[In the general formula (2), two or more of X ₁ , X ₂ , and X ₃ each independently have a radically polymerizable group. ]
The component (C) is a radically polymerizable compound different from the components (A) and (B),
When the total of the component (A), the component (B) and the component (C) is 100 parts by mass, the component (B) is 20 parts by mass or more and 80 parts by mass or less, and the component (C ) Is 0 parts by mass or more and 40 parts by mass or less.

According to the present invention, it is possible to form a cured product having excellent heat resistance, impact resistance and flexural modulus, and it is possible to provide a curable resin composition suitable for three-dimensional modeling.

An embodiment of the present invention will be described below. The embodiment described below is just one of the embodiments of the present invention, and the present invention is not limited to these embodiments.

The components (A) to (E) contained in the curable resin composition according to this embodiment will be described in detail below.
<Component (A): monofunctional 2-(allyloxymethyl)acrylic acid or its ester (A)>
The monofunctional 2-(allyloxymethyl)acrylic acid or its ester which is the component (A) is represented by the following general formula (1).

In the general formula (1), R is a hydrogen atom or a hydrocarbon group. The hydrocarbon group may have an ether bond, and the hydrocarbon group may have a substituent.

Examples of the substituent of the hydrocarbon group represented by R include a halogen atom, a cyano group, a trimethylsilyl group and the like. The hydrocarbon group may have a straight chain structure, a branched chain structure, or a cyclic structure.

Examples of the hydrocarbon group include a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group having 2 or more carbon atoms, an alicyclic hydrocarbon group having 3 or more carbon atoms, and an aromatic hydrocarbon group having 6 or more carbon atoms. Are listed. Preferably, a chain saturated hydrocarbon group having 1 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 or more carbon atoms It is an aromatic hydrocarbon group having 20 or less, preferably a chain saturated hydrocarbon group having 1 to 20 carbon atoms, and more preferably a saturated hydrocarbon having 1 to 10 carbon atoms.

The chain saturated hydrocarbon group is not particularly limited as long as it is a linear or branched hydrocarbon group. For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, s-pentyl, t-pentyl, neopentyl, n-hexyl, s-hexyl, n-heptyl, n-octyl, s- Preferred examples include groups such as octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl, ceryl and melysyl. Further, the chain saturated hydrocarbon group may have an aromatic group as a substituent, and preferable examples thereof include groups such as a benzyl group and a phenethyl group.

The chain unsaturated hydrocarbon group is not particularly limited as long as it is a straight chain or branched hydrocarbon group containing at least one non-aromatic carbon-carbon unsaturated bond. For example, crotyl, 1,1-dimethyl-2-propenyl, 2-methyl-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 2-methyl-3-butenyl, oleyl, linole, linolene, Groups such as are preferred.

The alicyclic hydrocarbon group is not particularly limited as long as it is a hydrocarbon group containing a saturated cyclic structure having three or more membered rings or an unsaturated cyclic structure that is not aromatic. Preferred examples include groups such as cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, tricyclodecanyl, isobornyl, adamantyl, dicyclopentanyl and dicyclopentenyl. ..

The aromatic hydrocarbon group is not particularly limited as long as it is a hydrocarbon group containing a 6-membered or more aromatic ring structure, and examples thereof include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-t- Suitable examples include groups such as butylphenyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, anthranyl and the like.

The hydrocarbon group containing an ether bond is a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, an alicyclic hydrocarbon group, or an oxygen atom in at least one carbon-carbon bond constituting an aromatic hydrocarbon group. There is no particular limitation as long as it has a structure in which is inserted. For example, chain ether groups such as methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, ethoxyethoxyethyl: cyclopentoxyethyl, cyclohexyloxyethyl, cyclopentoxyethoxyethyl, cyclohexyloxy. Group having both alicyclic hydrocarbon group such as ethoxyethyl and dicyclopentenyloxyethyl and a chain ether group: group having both aromatic hydrocarbon group and chain ether group such as phenoxyethyl, phenoxyethoxyethyl: glycidyl, β -Methylglycidyl, β-ethylglycidyl, 3,4-epoxycyclohexylmethyl, 2-oxetanemethyl, 3-methyl-3-oxetanemethyl, 3-ethyl-3-oxanemethyl, tetrahydrofuranyl, tetrahydrofurfuryl, tetrahydropyranyl, Preferred examples include cyclic ether groups such as dioxazolanyl and dioxanyl.

Examples of the component (A) include 2(allyloxymethyl)acrylic acid, 2-(allyloxymethyl)methyl acrylate, 2-(allyloxymethyl)ethyl acrylate, and 2-(allyloxymethyl)acrylic acid n. -Propyl, i-propyl 2-(allyloxymethyl)acrylate, n-butyl 2-(allyloxymethyl)acrylate, n-pentyl 2-(allyloxymethyl)acrylate, 2-(allyloxymethyl)acrylic Acid s-Pentyl, 2-(allyloxymethyl)acrylic acid t-pentyl, 2-(allyloxymethyl)acrylic acid neopentyl, 2-(allyloxymethyl)acrylic acid n-hexyl,2-(allyloxymethyl)acrylic acid Acid s-hexyl, 2-(allyloxymethyl)acrylic acid n-heptyl, 2-(allyloxymethyl)acrylic acid n-octyl, 2-(allyloxymethyl)acrylic acid s-octyl, 2-(allyloxymethyl) ) T-octyl acrylate, 2-ethylhexyl 2-(allyloxymethyl)acrylate, capryl 2-(allyloxymethyl)acrylate, nonyl 2-(allyloxymethyl)acrylate, 2-(allyloxymethyl)acryl Decyl acid, undecyl 2-(allyloxymethyl)acrylate, lauryl 2-(allyloxymethyl)acrylate, tridecyl 2-(allyloxymethyl)acrylate, myristyl 2-(allyloxymethyl)acrylate, 2-( Allyloxymethyl) pentadecyl acrylate, 2-(allyloxymethyl) cetyl acrylate, heptadecyl 2-(allyloxymethyl) acrylate, stearyl 2-(allyloxymethyl) acrylate, 2-(allyloxymethyl) acrylate Nonadecyl, eicosyl 2-(allyloxymethyl)acrylate, ceryl 2-(allyloxymethyl)acrylate, melicyl 2-(allyloxymethyl)acrylate, crotyl 2-(allyloxymethyl)acrylate, 2-(allyl (Oxymethyl)acrylic acid 1,1-dimethyl-2-propenyl, 2-(allyloxymethyl)acrylic acid 2-methylbutenyl, 2-(allyloxymethyl)acrylic acid 3-methyl-2-butenyl, 2-(allyloxy) Methyl)acrylic acid 3-methyl-3-butenyl, 2-(allyloxymethyl)acrylic acid 2-methyl-3-butenyl, 2-(allyloxymethyl)acrylic acid oleyl, 2-(allyloxymethyl)acrylic acid Linole, linolene 2-(allyloxymethyl)acrylate, cyclopentyl 2-(allyloxymethyl)acrylate, cyclopentylmethyl 2-(allyloxymethyl)acrylate, cyclohexyl 2-(allyloxymethyl)acrylate, 2-( Cyclohexylmethyl allyloxymethyl)acrylate, 4-methylcyclohexyl 2-(allyloxymethyl)acrylate, 4-t-butylcyclohexyl 2-(allyloxymethyl)acrylate, tricyclo-2-(allyloxymethyl)acrylate Decanyl, isobornyl 2-(allyloxymethyl) acrylate, adamantyl 2-(allyloxymethyl) acrylate, dicyclopentanyl 2-(allyloxymethyl) acrylate, dicyclo 2-(allyloxymethyl) acrylate Pentenyl, phenyl 2-(allyloxymethyl)acrylate, methylphenyl 2-(allyloxymethyl)acrylate, dimethylphenyl 2-(allyloxymethyl)acrylate, trimethylphenyl 2-(allyloxymethyl)acrylate, 2 4-(t-butylphenyl)-(allyloxymethyl)acrylate, benzyl 2-(allyloxymethyl)acrylate, diphenylmethyl 2-(allyloxymethyl)acrylate, diphenylethyl 2-(allyloxymethyl)acrylate, Triphenylmethyl 2-(allyloxymethyl)acrylate, cinnamyl 2-(allyloxymethyl)acrylate, naphthyl 2-(allyloxymethyl)acrylate, anthranyl 2-(allyloxymethyl)acrylate, 2-(allyl Oxymethyl) methoxyethyl acrylate, 2-(allyloxymethyl) methoxyethoxyethyl acrylate, 2-(allyloxymethyl) methoxyethoxyethoxyethyl acrylate, 2-(allyloxymethyl) 3-methoxybutyl acrylate, Ethoxyethyl 2-(allyloxymethyl)acrylate, ethoxyethoxyethyl 2-(allyloxymethyl)acrylate, cyclopentoxyethyl 2-(allyloxymethyl)acrylate, cyclohexyloxy 2-(allyloxymethyl)acrylate Ethyl, cyclopentoxyethoxyethyl 2-(allyloxymethyl)acrylate, cyclohexyloxyethoxyethyl 2-(allyloxymethyl)acrylate, dicyclopentenyloxyethyl 2-(allyloxymethyl)acrylate, 2-(allyl Oxymethyl) Phenoxyethyl acrylate, phenoxyethoxyethyl 2-(allyloxymethyl)acrylate, glycidyl 2-(allyloxymethyl)acrylate, β-methylglycidyl 2-(allyloxymethyl)acrylate, 2-(allyloxymethyl) Β-ethylglycidyl acrylate, 3,4-epoxycyclohexylmethyl 2-(allyloxymethyl)acrylate, 2-oxetanemethyl 2-(allyloxymethyl)acrylate, 3-methyl 2-(allyloxymethyl)acrylate -3-Oxetanemethyl, 3-ethyl-3-oxetanemethyl 2-(allyloxymethyl)acrylate, tetrahydrofuranyl 2-(allyloxymethyl)acrylate, tetrahydrofurfuryl 2-(allyloxymethyl)acrylate, 2 Examples thereof include tetrahydropyranyl-(allyloxymethyl)acrylate, dioxazolanyl, and dioxanyl 2-(allyloxymethyl)acrylate.

A commercially available product can be used as the component (A), and examples thereof include AOMA (manufactured by Nippon Shokubai Co., Ltd.).

The component (A) has a structure in which the carbon-carbon double bond at the α-position of the carbonyl group in the ester structure is sterically crowded as compared with the methacrylic acid ester, but is radical polymerized at least as good as the acrylic acid ester. Have activity. The component (A) is a main chain skeleton having a 5-membered ring ether structure in which a carbon-carbon double bond at the α-position and a terminal double bond are polymerized while cyclizing, and methylene groups are arranged on both sides as a repeating unit. To form. Further, the polymer obtained from the polymerizable composition containing the component (A) has a characteristic of being excellent in tough mechanical properties due to the unique main chain skeleton generated by the polymerization.

The content of the component (A) is preferably 20 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more based on 100 parts by mass of the total of the components (A), (B) and (C). It is 75 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less. If the component (A) is 20 parts by mass or more, the impact resistance of the cured product will be sufficient, and if it is 80 parts by mass or less, the heat resistance of the cured product will be sufficient.

<Component (B): polyfunctional radically polymerizable compound having isocyanurate ring>
The polyfunctional radically polymerizable compound having an isocyanurate ring, which is the component (B), is represented by the following general formula (2).

In general formula (2), two or more of X ₁ , X ₂ , and X ₃ are each independently a radically polymerizable group. Preferably, X ₁ , X ₂ , and X ₃ are each independently a radically polymerizable group. Examples of the radically polymerizable group include an allyl group, a (meth)acryloyl group, a (meth)acryloyloxyalkyl group, and the like. Here, in this specification, “(meth)acryloyl (group)” means acryloyl (group) or methacryloyl (group). When _{two of} X ₁ , X ₂ , and X ₃ are radically polymerizable groups, the remaining one is a condensable group such as a hydroxy group, an amino group, a carboxyl group, a sulfonyl group, or an aromatic group such as a phenyl group. Groups, and the like.

As the component (B), triallyl isocyanurate, diallyl isocyanurate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid diacrylate, ε-caprolactone modified tris-(2-acryloxyethyl) isocyanurate, ε-caprolactone modified Bis-(2-acryloxyethyl) isocyanurate can be preferably used. A commercial item can be used as a component (B). For example, A-9300 (Shin Nakamura Chemical Co., Ltd.), A-9200 (Shin Nakamura Chemical Co., Ltd.), A-9300-1CL (Shin Nakamura Chemical Co., Ltd.), FA-731A (Hitachi Chemical Co., Ltd.) Company manufactured), TAIC (TM) (manufactured by Mitsubishi Chemical Co., Ltd.), TMAIC (TM) (manufactured by Mitsubishi Chemical Co., Ltd.) and the like.

In order to exhibit the effect of the present invention, the content of the component (B) in the curable resin composition is 20 parts by weight with respect to 100 parts by weight of the total of the components (A), (B) and (C). Parts or more and 80 parts by mass or less, preferably 25 parts by mass or more and 80 parts by mass or less, more preferably 30 parts by mass or more and 80 parts by mass or less. When the amount of the component (B) is less than 20 parts by mass, the crosslinked density of the cured product is insufficient, and thus the cured product may not have sufficient heat resistance. Furthermore, in the process of changing from a curable resin composition to a cured product, if the crosslinking density is low, a sufficient curing rate cannot be obtained, and there is a possibility that it cannot be applied to three-dimensional modeling. Therefore, if the amount of the component (B) is less than 20 parts by mass, the effects of the present invention may be impaired, which is not preferable. On the other hand, when the amount of the component (B) exceeds 80 parts by mass, the cross-linking density of the cured product becomes excessive and the plastic deformation of the rubber particles (component (D)) is hindered, so that the effect of improving the impact resistance of the cured product is difficult to obtain. There is a tendency that the effects of the present invention may be impaired, which is not preferable.

<Component (C): radically polymerizable compound>
A radical polymerizable compound (component (C)) different from the component (A) and the component (B) can be added to the curable resin composition according to the present embodiment. Examples of the component (C) include, but are not limited to, commonly used monofunctional and polyfunctional radically polymerizable compounds, (meth)acrylates, compounds having polyrotaxane, and the like. The component (C) can be appropriately added according to the desired properties of the cured product. Here, in this specification, “(meth)acrylate” means acrylate or methacrylate.

(Meth)acrylate is a radically polymerizable compound having at least one (meth)acryloyl group, and is polymerized by radicals generated by a radical polymerization initiator (component (E)) described later. The component (C) may be composed of one kind or plural kinds.

The number of (meth)acryloyl groups contained in (meth)acrylate is not particularly limited. Examples of the (meth)acrylate include monofunctional (meth)acrylates having one (meth)acryloyl group in the molecule, bifunctional (meth)acrylates having two (meth)acryloyl groups in the molecule, and Include, but are not limited to, a trifunctional (meth)acrylate having three (meth)acryloyl groups, and a tetrafunctional or more (meth)acrylate having four or more (meth)acryloyl groups in the molecule. is not. As the (meth)acrylate, urethane (meth)acrylate having a urethane structure in the molecular structure, polyester (meth)acrylate having a polyester structure in the molecular structure, or the like may be used.

Specific examples of the (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, and n-(meth)acrylate. -Butyl, i-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic Acid n-heptyl, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate , Isodecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid 2-methoxyethyl, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, ( Monofunctional (meth)acrylates such as (meth)acrylic acid (3-ethyloxetane-3-yl)methane; 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1, 9-nonanediol di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, bisphenol A(poly)ethoxydi(meth)acrylate, bisphenol A(poly)propoxydi(meth)acrylate, bisphenol F(poly)ethoxydi(meth) ) Acrylate, bifunctional (meth)acrylate such as ethylene glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylate, trimethyloloctanetri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, trimethylol Propane(poly)propoxytri(meth)acrylate, trimethylolpropane(poly)ethoxy(poly)propoxytri(meth)ac Trilate, pentaerythritol tri(meth)acrylate and other trifunctional (meth)acrylates; ditrimethylolpropane tetra(meth)acrylate, pentaerythritol polyethoxytetra(meth)acrylate, pentaerythritol polyethoxytetra(meth)acrylate, pentaerythritol( Poly)propoxy tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. (Meth)acrylate; and the like, but are not limited thereto.

Specific examples of the urethane (meth)acrylate include polycarbonate-based urethane (meth)acrylate, polyester-based urethane (meth)acrylate, polyether-based urethane (meth)acrylate, and caprolactone-based urethane (meth)acrylate. , But not limited to these. These urethane (meth)acrylates can be obtained by reacting an isocyanate compound obtained by reacting a polyol with a diisocyanate, and a (meth)acrylate monomer having a hydroxyl group. Here, specific examples of the polyol include polycarbonate diol, polyester polyol, polyether polyol, and polycaprolactone polyol.

The polyester (meth)acrylate is obtained, for example, by condensing a polycarboxylic acid and a polyol to obtain a polyester oligomer having a hydroxyl group at the terminal, and then esterifying the hydroxyl group at the terminal with acrylic acid.

Further, a cyclic molecule having a (meth)acryloyl group, a linear molecule penetrating the plurality of cyclic molecules in a skewered shape, and elimination of the plurality of cyclic molecules arranged at both ends of the linear upper molecule A blocking group that prevents the polyrotaxane can be included. Examples of commercially available polyrotaxanes that can be used as the polyrotaxane having a (meth)acryloyl group according to the present embodiment include SeRM SM3405P, SeRM SA3405P, SeRM SM3400C, SeRM SA3400C, SeRM SA2400C (all of which are Advanced Soft Materials). (Manufactured by KK).

The addition amount of the component (C) is 0 parts by mass or more and 40 parts by mass or less, preferably 0 parts by mass or more and 30 parts by mass, based on 100 parts by mass of the total of the components (A), (B) and (C). Below the section. When the amount of the component (C) is 40 parts by mass or more, the structure derived from the component (A) cannot exhibit sufficient impact resistance (toughness) in the cured product.

<Component (D): rubber particles>
The curable resin composition according to the present embodiment can improve the impact resistance of the cured product by adding rubber particles (component (D)). The component (D) is not particularly limited, but for example, butadiene rubber particles, styrene/butadiene rubber copolymer particles, acrylonitrile/butadiene copolymer rubber particles and the like can be used. Further, saturated rubber particles obtained by hydrogenating or partially hydrogenating these diene rubbers, crosslinked butadiene rubber particles, isoprene rubber particles, chloroprene rubber particles, natural rubber particles, silicone rubber particles, ethylene/propylene/diene monomer terpolymer rubber particles. , Acrylic rubber particles, acrylic/silicone composite rubber particles, and the like. These rubber particles may be used alone or in combination of two or more kinds. Among them, the curable resin composition is selected from butadiene rubber particles, crosslinked butadiene rubber particles, styrene/butadiene copolymer rubber particles, acrylic rubber particles and silicone/acrylic composite rubber particles from the viewpoint of improving the impact resistance of the cured product. It is preferable to include at least one kind of particles that are
The addition amount of the rubber particles in the curable resin composition is preferably 0.1 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the total of the components (A), (B) and (C). , And more preferably 5 parts by mass or more and 40 parts by mass or less. When the content of the rubber particles (D) is within the above range, the cured product can have both good heat resistance and good impact resistance (toughness).

The component (D) is preferably a rubber particle having a multilayer structure (core-shell structure) having the above-mentioned rubber particles as a core portion and at least one shell layer covering the core portion.

The glass transition temperature of the polymer constituting the core portion is not particularly limited, but is preferably lower than 0°C, more preferably lower than -20°C, and further preferably -40°C or lower. By setting the glass transition temperature of the polymer forming the core portion to 0° C. or lower, the impact resistance of the cured product tends to be favorably improved.

The glass transition temperature of the polymer constituting the core portion means a calculated value calculated by the following Fox equation (see Bull. Am. Phys. Soc., 1(3)123 (1956)). The following Fox formula shows the formula in the case where the polymer constituting the core portion is a copolymer of monomer i (monomer 1, monomer 2,..., And monomer n). ..
1/Tg=W1/Tg1+W2/Tg2+... +Wn/Tgn
Tg: Glass transition temperature of polymer constituting core part (unit: K)
Wi: Mass fraction of monomer i with respect to the total amount of monomers constituting the polymer constituting the core portion Tgi: Glass transition temperature of homopolymer of monomer i (unit: K)

As the glass transition temperature (Tgi) of the homopolymer, the value described in various documents can be adopted, and for example, the value described in “POLYMER HANDBOOK 3rd edition” (published by John Wiley & Sons, Inc.) can be adopted. .. For those not described in the literature, the value of the glass transition temperature of the homopolymer obtained by polymerizing a monomer by a usual method and measured by the DSC method can be adopted.

The polymer forming the shell layer is preferably different from the polymer forming the core portion. Examples of the monofunctional monomer component of the polymer constituting the shell layer include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, maleimide, styrene, 2-( Allyloxymethyl)acrylic acid ester and the like can be used, but not limited thereto. Use of divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc. as the polyfunctional monomer component of the polymer constituting the shell layer. You can

The glass transition temperature of the polymer forming the shell layer is not particularly limited, but is preferably 0° C. or higher, more preferably 15° C. or higher, and further preferably 30° C. or higher. When the glass transition temperature of the shell layer is 0° C. or higher, the viscosity of the composition does not increase, and the composition tends to be well dispersed in the composition. The glass transition temperature of the shell layer is a calculated value calculated by the Fox equation.

Rubber particles having a core-shell structure are obtained by coating the core part with a shell layer. Examples of the method of coating the core portion with the shell layer include a method of coating the core portion with the shell layer and a method of graft-polymerizing the shell layer on the surface of the core portion, but preferably the shell is coated on the surface of the core portion. It is a method of graft-polymerizing a layer.

The average particle size of component (D) is not particularly limited, but is preferably 10 nm to 1000 nm, more preferably 20 nm to 900 nm, and further preferably 30 nm to 800 nm. When the average particle size of the component (D) is 10 nm or more, the effect of improving the impact resistance of the cured product can be easily obtained. If the average particle size is 1000 nm or less, the heat resistance of the cured product will be sufficient.

<Component (E): radical polymerization initiator>
The curable resin composition according to the present embodiment is obtained by adding a radical polymerization initiator (component (E)) such as a photoradical polymerization initiator to irradiate the composition with active energy rays to obtain a cured product. You can

Photo-radical polymerization initiators are mainly classified into intramolecular cleavage type and hydrogen abstraction type. In the intramolecular cleavage type radical polymerization initiator, by absorbing light of a specific wavelength, the bond at a specific site is cleaved, and a radical is generated at the cleaved site, which becomes a polymerization initiator and becomes radically polymerizable. Polymerization of the compound begins. On the other hand, in the case of the hydrogen abstraction type, it absorbs light of a specific wavelength to be in an excited state, and the excited species cause a hydrogen abstraction reaction from the surrounding hydrogen donor to generate a radical, which becomes a polymerization initiator and becomes a radical. Polymerization of the polymerizable compound begins.

As the intramolecular cleavage type photoradical polymerization initiator, an alkylphenone type photoradical polymerization initiator, an acylphosphine oxide type photoradical polymerization initiator, and an oxime ester type photoradical polymerization initiator are known. These are types in which a bond adjacent to a carbonyl group is cleaved to generate a radical species. Examples of the alkylphenone-based photoradical polymerization initiator include a benzylmethylketal-based photoradical polymerization initiator, an α-hydroxyalkylphenone-based photoradical polymerization initiator, and an aminoalkylphenone-based photoradical polymerization initiator. Specific compounds include, for example, benzylmethyl ketal-based photoradical polymerization initiators such as 2,2′-dimethoxy-1,2-diphenylethan-1-one (Irgacure (R)651, manufactured by BASF). As the α-hydroxyalkylphenone-based photoradical polymerization initiator, 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur (R) 1173, manufactured by BASF), 1-hydroxycyclohexylphenyl ketone (Irgacure (R) 184, manufactured by BASF), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure (R) 2959, BASF) 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Irgacure (R) 127, BASF) Examples of aminoalkylphenone-based photoradical polymerization initiators include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Irgacure (R) 907, manufactured by BASF), 2 -Benzylmethyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (Irgacure (R)369, manufactured by BASF) and the like, but not limited thereto. Examples of the acylphosphine oxide-based photoradical polymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucillin(R)TPO, manufactured by BASF), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. (Irgacure (R) 819, manufactured by BASF Corporation) and the like, but not limited thereto. Examples of the oxime ester-based photoradical polymerization initiator include (2E)-2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octane-1-one (Irgacure (R) OXE-01, manufactured by BASF Corporation. ) And the like, but not limited thereto.

Examples of hydrogen abstraction type radical polymerization initiators include 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. Examples include, but are not limited to:

The photo radical polymerization initiator may be used in combination of two or more kinds, or may be used alone.

The addition amount of the photoradical polymerization initiator is preferably 0.1 parts by mass or more and 15 parts by mass or less, and more preferably 100 parts by mass of the total of the components (A), (B) and (C). It is 0.1 part by mass or more and 10 parts by mass or less. When the addition amount of the radical photopolymerization initiator is 0.1 part by mass or more, the curable resin composition is sufficiently polymerized and the cured product has sufficient heat resistance. When the amount of the photo-radical polymerization initiator added is 15 parts by mass or less, the molecular weight becomes large and the impact resistance of the cured product becomes sufficient.

Also, a thermal radical polymerization initiator may be contained in order to promote the polymerization reaction in the heat treatment after shaping. The thermal radical polymerization initiator is not particularly limited as long as it generates a radical by heating, and conventionally known compounds can be used. For example, azo compounds, peroxides and persulfates are preferable. It can be mentioned as a thing. Azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- Examples thereof include azobis(1-acetoxy-1-phenylethane). Examples of peroxides include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate and di(4-t-butylcyclohexyl)peroxydicarbonate. Examples of persulfates include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

The addition amount of the thermal radical polymerization initiator is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 100 parts by mass of the component (A), the component (B) and the component (C). It is 0.1 part by mass or more and 10 parts by mass or less. When the amount of the thermal radical polymerization initiator is 15 parts by mass or less, the molecular weight is extended and sufficient physical properties can be obtained.

<Additive>
The curable resin composition according to the present embodiment may contain various additives as other optional components as long as the objects and effects of the present invention are not impaired. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Silicone-based oligomers, polysulfide-based oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiation aids; leveling agents; wettability improvers; surfactants; plasticizers; Examples thereof include ultraviolet absorbers, silane coupling agents, inorganic fillers, pigments, dyes and the like.

<How to create a three-dimensional object>
The curable resin composition according to the present embodiment can be suitably used in a method for producing a cured product by an optical three-dimensional modeling method (stereolithography method). Hereinafter, a method for producing a cured product using the curable resin composition according to this embodiment will be described.

A conventionally known method can be used as the stereolithography method. That is, the cured product includes a step of selectively irradiating the curable resin composition of the present embodiment layer by layer with an active energy ray such as light to perform curing such as photocuring, and repeating this to obtain a cured product. Is a method of manufacturing.

In the step of curing the curable resin composition layer by layer, the curable resin composition is selectively irradiated with active energy rays based on the slice data of the cured product to be prepared. The active energy ray with which the curable resin composition is irradiated is not particularly limited as long as it is an active energy ray capable of curing the curable resin composition according to the present embodiment. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays, and particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays are most preferable from the viewpoint of the absorption wavelength of the radical polymerization initiator (component (E)) used and the cost of introducing equipment. The exposure of the active energy ray is not particularly limited, preferably not 0.001J / cm ² or more 10J / cm ² or less. When it is less than 0.001 J/cm ² , the curable resin composition may not be sufficiently cured, and when it exceeds 10 J/cm ² , the irradiation time becomes long and the productivity is lowered.

The method of irradiating the curable resin composition with active energy rays is not particularly limited. For example, when irradiating light as active energy rays, the following method can be adopted. As a first method, there is a method in which a point-shaped light such as a laser beam is used and the curable resin composition is two-dimensionally scanned with the light. At this time, the two-dimensional scanning may be performed by a point drawing method or a line drawing method. A second method is a surface exposure method in which a projector or the like is used to irradiate the shape of the cross-section data with light. In this case, the active energy rays may be irradiated in a planar manner through a planar drawing mask formed by arranging a plurality of minute optical shutters such as a liquid crystal shutter or a digital micromirror shutter.

After the cured product is obtained by the above method, the surface of the obtained cured product may be washed with a cleaning agent such as an organic solvent. Moreover, you may perform the post cure which hardens the unreacted residual component which remained on the surface or inside of a hardened|cured material by performing light irradiation or heat processing with respect to the obtained hardened|cured material.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

<<Examples 1 to 3>>
The components used in the examples are as follows.
[Component (A)]
A-1: 2-(allyloxymethyl)methyl acrylate (AOMA, manufactured by Nippon Shokubai Co., Ltd.)
[Component (B)]
B-1: Ethoxylated isocyanuric acid triacrylate (Shin Nakamura Chemical Co., Ltd., A-9300)
[Component (C)]
Urethane acrylate (Nippon Kayaku Co., Ltd., KAYARAD UX-6101)

[Component (D)]
Rubber particles produced by the following method An acetone dispersion of rubber particles having a core-shell structure was produced. First, 370 parts by mass of latex (Nipol (R) LX111A2 manufactured by Nippon Zeon Co., Ltd., 200 parts by mass of polybutadiene rubber particles) and 630 parts by mass of deionized water were charged into a 2 L glass container, and the mixture was purged with nitrogen at 60° C. It was stirred for 60 minutes. After adding 0.0096 parts by mass of EDTA, 0.0024 parts by mass of iron sulfate, 0.48 parts by mass of sodium formaldehyde sulfoxylate, 35.28 parts by mass of a graft monomer (methyl methacrylate (MMA), 3-methyl-3-oxetanyl). -Methyl methacrylate (OXMA) 35.28 parts by mass) and cumene hydroperoxide (CHP) 0.119 parts by mass were continuously added dropwise over 2 hours to carry out graft polymerization. After the dropping was completed, the reaction was further stirred for 2 hours to complete the reaction, and rubber particles having a core-shell structure were produced. 1000 parts by mass of acetone was introduced into a 2 L mixing bath, and the obtained rubber particles were added while stirring. After the addition was completed, a slurry liquid consisting of an aqueous layer containing a part of floating aggregates and an organic solvent was obtained. The obtained slurry liquid was packed in a 250 mL centrifuge tube, centrifuged at a rotation speed of 12000 rpm and a temperature of 10° C. for 30 minutes, and then the supernatant was removed. Acetone was added to the precipitated rubber particles to redisperse them, and the mixture was centrifuged again at a rotation speed of 12000 rpm for 30 minutes at a temperature of 10° C., and the supernatant was removed to obtain an acetone dispersion of rubber particles. Since the rubber particles maintain the dispersibility in the acetone dispersion liquid, it was confirmed that MMA and OXMA were graft-polymerized on the surface of the rubber particles. Rubber particles obtained from the maximum value of the particle size distribution curve (particle diameter-scattering intensity) of the obtained acetone dispersion of rubber particles, which was measured using a dynamic light scattering device (Zetasizer Nano ZS manufactured by Malvern Instruments Ltd.). Had an average particle size of 0.32 μm.
[Component (E)]
Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure (R)819, manufactured by BASF)

<Production of curable resin composition>
Component (A), component (B) and component (E) or component (A), component (B), component (C) and component (E) are blended in the blending ratio shown in Table 1 and uniformly mixed. Mixed. A curable resin composition was obtained by mixing an acetone dispersion liquid of the component (D) in this formulation and removing acetone which is a volatile component by using a rotary evaporator.

<Production of cured product for test piece>
A cured product was prepared by the following method using the prepared curable resin composition. First, a mold having a length of 80 mm, a width of 10 mm and a thickness of 4 mm was sandwiched between two pieces of quartz glass, and a curable resin was poured therein. The curable resin composition that had been cast was irradiated with 5 mW/cm ² of ultraviolet light from both sides of the mold for 360 seconds using an ultraviolet irradiation device (EXECURE 3000 manufactured by HOYA CANDEO OPTRONICS Co., Ltd.) to obtain a cured product ( 3600 mJ/cm ² as total energy). Further, the obtained cured product was placed in a heating oven at 50° C. for 1 hour, and then placed in a heating oven at 100° C. for 2 hours to perform heat treatment to obtain a cured product.

<Evaluation of impact resistance>
Regarding the obtained test piece, according to JIS K 7111, a notch forming machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "Notching Tool A-4") is used to form a notch with a depth of 2 mm and a 45° in the central portion. I put it in. Then, using an impact tester (trade name “IMPACT TESTER IT” manufactured by Toyo Seiki Seisaku-sho, Ltd.), the test piece is broken with energy of 2 J from the back surface of the notch. The energy required for breaking was calculated from the angle at which the hammer swung up to 150° swung up after breaking the test piece, and this Charpy impact strength was used as an index of impact resistance. The impact resistance was evaluated according to the following criteria.
A (very good): Charpy impact strength is 6 kJ/m ² or more.
B (good): Charpy impact strength is 5 kJ/m ² or more and less than 6 kJ/m ² .
C (defective): Charpy impact strength is less than 5 kJ/m ² .

<Evaluation of heat resistance>
The obtained test piece was subjected to a heat resistance test in accordance with JIS K 7191-2 using a deflection temperature tester under load (manufactured by Toyo Seiki Seisakusho, trade name "No. 533 HDT tester 3M-2"). .. The bending stress was 1.80 MPa and the temperature was raised from 25° C. to 2° C. per minute. The temperature at which the amount of deflection of the test piece reached 0.34 mm was taken as the deflection temperature under load and used as an index of heat resistance. The heat resistance was evaluated according to the following criteria.
A (very good): Deflection temperature under load is 150°C or higher.
B (good): The deflection temperature under load is 80°C or higher and lower than 150°C.
C (defective): Deflection temperature under load is less than 80°C.
<Evaluation of flexural modulus>
The flexural modulus of the obtained test piece was measured using a tensile/compression tester (manufactured by A&D Co., Ltd., trade name "Tensilon Universal Material Testing Machine RTF-1250") according to JIS K 7171. I went. The flexural modulus was calculated from the stress gradient in the specified strain section (0.05 to 0.25%) under the condition of 2 mm·min. The flexural modulus was evaluated according to the following criteria.
A (very good): Bending elastic modulus of 2.0 GPa or more B (good): Bending elastic modulus of 1.6 GPa or more and less than 2.0 GPa.
C (poor): Flexural modulus is less than 1.6 GPa.

<<Comparative Examples 1 to 5>>
A curable resin composition was produced in the same manner as in Example except that the following components were used in the compounding ratio shown in Table 1 in place of the component (A) or the component (B), and evaluated in the same manner as in the example.
A-2: Methyl methacrylate (Tokyo Chemical Industry Co., Ltd., MMA)
A-3: 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd., light ester HO-250(N))
B-2: Pentaerythritol tetraacrylate (Kyoeisha Chemical Co., Ltd., light acrylate PE-4A)
B-3: Trimethylolpropane trimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-4: Bisphenol A dimethacrylate (manufactured by Sigma-Aldrich)

From Table 1, comparing Example 1 using A-1 as the component (A) with Comparative Examples 1 and 2 using A-2 or A-3 instead of A-1, the curing of Example 1 It was found that the product is a curable composition that gives a cured product having high impact resistance (fracture toughness). In addition, comparing Examples 1 to 3 using B-1 as the component (B) with Comparative Examples 3 to 5 using B-2, B-3 or B-4 in place of B-1, comparison was made. It was found that the cured products of Examples 1 to 3 are curable compositions that give high impact resistance (fracture toughness). Only when the polyfunctional radically polymerizable compound having an isocyanurate ring (component (B)) and the rubber particles (component (D)) are combined, the high fracture toughening effect of the rubber particles (component (D)) is exhibited. However, it was revealed that, contrary to expectations, the cured product exhibited very good impact resistance.

From the above results, monofunctional 2-(allyloxymethyl)acrylic acid or its ester (component (A)), a polyfunctional radically polymerizable compound having an isocyanurate ring (component (B)), and rubber particles (component) In the case of a composition containing (D)) and a radical polymerization initiator (component (E)), a cured product having a high balance of high impact resistance (toughness), high heat resistance, and high flexural modulus is obtained. It became clear that it can be used suitably for optical three-dimensional modeling.

The present invention is not limited to the above embodiments, and various changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, the following claims are attached to open the scope of the present invention.

This application claims priority based on Japanese Patent Application No. 2019-021783 filed on February 8, 2019 and Japanese Patent Application No. 2020-007357 filed on January 21, 2020, The entire contents of the description are incorporated herein.

Claims

Component (A): monofunctional 2-(allyloxymethyl)acrylic acid or its ester,
Component (B): a polyfunctional radically polymerizable compound having an isocyanurate ring,
Component (C): radically polymerizable compound,
Component (D): rubber particles,
Component (E): radical polymerization initiator,
Containing
The component (A) is represented by the following general formula (1),

[R is a hydrogen atom or a hydrocarbon group. The hydrocarbon group may have an ether bond, and the hydrocarbon group may have a substituent. ]
The component (B) is represented by the following general formula (2),

[Two or more of X 1 , X 2 , and X 3 each independently have one or more radically polymerizable groups. ]
The component (C) is a radically polymerizable compound different from the components (A) and (B),
When the total of the component (A), the component (B) and the component (C) is 100 parts by mass, the component (B) is 20 parts by mass or more and 80 parts by mass or less, and the component (C ) Is 0 parts by mass or more and 40 parts by mass or less, a curable resin composition.
The curable resin composition according to claim 1, wherein R is a saturated hydrocarbon group having 1 to 20 carbon atoms.
The curable resin composition according to claim 1 or 2, wherein the component (A) is methyl 2-(allyloxymethyl)acrylate or ethyl 2-(allyloxymethyl)acrylate.
The curable resin composition according to any one of claims 1 to 3, wherein the component (D) has a core-shell structure.
The curable resin composition according to claim 4, wherein the shell layer having the core-shell structure is graft-polymerized on the surface of the core portion of the core-shell structure.
The curable resin composition according to any one of claims 1 to 5, wherein the component (E) is a photoradical polymerization initiator.
A cured product obtained by curing the curable resin composition according to any one of claims 1 to 6.
A method for producing a cured product, which comprises a step of forming a cured product by photocuring a curable resin composition for each layer based on slice data,
The method for producing a cured product, wherein the curable resin composition is the curable resin composition according to any one of claims 1 to 6.
The method for producing a cured product according to claim 8, further comprising the step of subjecting the cured product to a heat treatment.