JP6790692B2 - Active energy ray-polymerizable resin composition for optical three-dimensional modeling, and three-dimensional modeling - Google Patents

Description

The present invention provides an optical three-dimensional molding having a low viscosity in an uncured state, a high curing speed by irradiation with active energy rays, excellent molding accuracy, and excellent mechanical properties such as strength and heat resistance. The present invention relates to an active energy ray-polymerizable resin composition.

The active energy ray polymerization technology has various characteristics such as its high polymerization rate, good workability due to being solvent-free in general, and energy saving of extremely low energy requirement, and in recent years, due to environmental pollution problems, environmental pollution has been reduced. Since it has the advantage of being polymerized, its application fields are expanding in fields such as building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical devices, and displays.
These contain a resin that can be polymerized with active energy rays and a monomer having an α, β-unsaturated double bond group, but a solvent is required because the monomer also functions as a solvent. Therefore, there is an advantage that the solvent does not volatilize when forming a coating film or a molded product. Then, as the resin having this active energy ray-polymerizable property, α, β-unsaturated double bond groups are provided at the molecular ends of low molecular weight polyester resins, polyurethane resins, polyepoxy resins, polyacrylic resins and the like. Oligomers and monomers having α, β-unsaturated double bond groups are used.

In recent years, as a method for manufacturing resin molded products, a liquid photocurable resin composition is used as an ultraviolet laser, which is a kind of active energy ray, based on three-dimensional shape data designed by a three-dimensional design system (three-dimensional CAD) on a computer. An optical three-dimensional modeling method (stereolithography) is used in which a molded product is produced by selectively polymerizing and curing it with light.
Compared to conventional cutting, this optical molding method has various advantages such as being able to handle complicated shapes that are difficult to cut, being a fully automated process, easy to handle, short manufacturing time, and cost-effective. In addition to the production of resin products, it has come to be widely used in the production of prototype models and medical models for design studies, performance tests, advertisements, etc.
As a typical example of this three-dimensional modeling method, light, for example, a kind of active energy rays, so that a polymerization cured layer having a desired pattern can be obtained on the liquid surface of a liquid photocurable resin composition placed in a container. A polymerized and cured layer is obtained by selectively irradiating the ultraviolet laser light, which is the above, and then a liquid photocurable resin composition is supplied in a layer on the cured layer, and then light is selectively applied in the same manner as described above. Irradiation is performed to form a polymerization cured layer continuous with the cured layer. By repeating this laminating operation, a desired three-dimensional model is finally obtained. This three-dimensional modeling method is attracting attention because it is possible to easily obtain the target modeled object in a short time even when the shape of the modeled object to be manufactured is complicated.

As an optical three-dimensional modeling method, for example, as disclosed in Patent Document 1, energy required for a liquid photocurable resin composition is selectively supplied to form a three-dimensional model having a desired shape. The method. Such a method or an improved technique thereof is disclosed in Patent Documents 2 and 3.

The photocurable resin composition used for the above-mentioned stereolithography can quickly form a smooth liquid surface with low viscosity from the viewpoint of performing efficient stereolithography, and has transparency and good photocuring. It is required to have sex. In addition, there is a problem that the cured product deforms (warps, shrinks, lifts of the overhanging portion, etc.) over time due to residual strain caused by shrinkage (curing shrinkage) during polymerization curing by light. It is required that the deformation with time is small. Further, depending on the application, the polymerized cured product is required to have mechanical strength such as toughness, heat resistance, moisture resistance and water resistance.

Conventionally, as such a photocurable resin composition, radically polymerizable compounds such as urethane (meth) acrylate, epoxy (meth) acrylate, and photosensitive polyimide (for example, patents) have been used from the viewpoint of transparency, photocurability, and the like. Documents 4 and 5) and resin compositions containing cationically polymerizable compounds such as epoxy compounds and vinyl ether compounds (for example, Patent Document 6) are used. However, with the recent miniaturization and complexity of the target products, the requirements for dimensional accuracy have become more and more strict, and the requirements cannot be satisfied by the time-dependent deformation characteristics of the above resin composition.
Further, Patent Document 7 discloses a photocurable liquid composition containing microhollow spheres in which the absolute value of the difference in refractive index from an ethylene-based unsaturated monomer or a photoinitiator is not 0, and the photocuring It has been described that the transparency of the sex liquid composition is reduced. Further, Patent Document 8 discloses an irradiation-curable resin composition containing a color-developing agent, and a three-dimensional article produced from the irradiation-curable resin composition exhibits different colors before and after curing. Is described.
However, the current situation is that the cured resin product obtained by curing the above resin composition does not satisfy all the requirements of toughness, water resistance, physical property stability and suppression of deformation over time.

Japanese Unexamined Patent Publication No. 60-247515 Japanese Patent Application Laid-Open No. 62-035966 (US Pat. No. 4,575,330) Japanese Unexamined Patent Publication No. 62-101408 Japanese Unexamined Patent Publication No. 2-228312 Japanese Unexamined Patent Publication No. 5-279436 Japanese Unexamined Patent Publication No. 1-213304 Japanese Patent No. 2648222 Special Table 2005-510603

The present invention is to provide an active energy ray-curable resin composition for optical three-dimensional modeling, which can obtain a cured product having small deformation with time and excellent toughness and having an excellent curing rate. Another object of the present invention is to provide a cured product of the composition.

As a result of diligent studies to solve the above problems, the present inventors have found that the above target can be achieved by the following active energy ray-curable resin composition for three-dimensional modeling, and have completed the present invention. ..

That is, the present invention comprises a polymer (A) obtained by radical polymerization of a monomer (a-1) containing a cyclic carbonate group and a monomer (a-2) excluding (a-1). The present invention relates to an active energy ray-curable resin composition for optical three-dimensional modeling containing a radically polymerizable compound (B).

Further, in the present invention, the radically polymerizable compound (B) has an acryloyl group or a methacryloyl group-containing compound (B1) having one or more hydroxyl groups in the molecule.
The present invention relates to the above-mentioned active energy ray-curable resin composition for optical three-dimensional modeling, which comprises an acryloyl group or a methacryloyl group-containing compound (B2) having no hydroxyl group in the molecule.

Further, in the present invention, the acryloyl group or methacryloyl group-containing compound (B1) having one or more hydroxyl groups in the molecule has an acryloyl group or methacryloyl group-containing compound (b1) having a hydroxyl group and not having a cyclic structure. The present invention relates to the above-mentioned active energy ray-curable resin composition for optical three-dimensional modeling, which is characterized by containing.

Further, in the present invention, the acryloyl group or methacryloyl group-containing compound (B1) having one or more hydroxyl groups in the molecule contains an acryloyl group or methacryloyl group-containing compound (b2) having a hydroxyl group and having a cyclic structure. The present invention relates to the above-mentioned active energy ray-curable resin composition for optical three-dimensional modeling.

The present invention also relates to the above-mentioned active energy ray-curable resin composition for optical three-dimensional modeling, which is characterized by containing an oligomer (E).

Further, the present invention is characterized in that the polymer (A) is contained in an amount of 1 to 20% by mass in the total amount of the active energy ray-curable resin composition for optical three-dimensional modeling. Regarding the sex resin composition.

The present invention also relates to a cured product of the active energy ray-curable resin composition for optical three-dimensional modeling.

Furthermore, the present invention relates to a three-dimensional model made of the cured product.

According to the present invention, there is little deformation during molding such as warpage and swelling, it is possible to produce a highly accurate molded product by stereolithography, and the mechanical properties of the polymerized cured product are excellent. It has become possible to provide an active energy ray-curable resin composition for stereolithography, which can also be used as a mechanical component. Furthermore, since it has an excellent curing rate, it has become possible to obtain a three-dimensional model in a shorter time than before.

Hereinafter, embodiments of the present invention will be described.
In addition, in this application, when it is described as "(meth) acryloyl", "(meth) acrylic acid", "(meth) acrylate", and "(meth) acryloyloxy", unless otherwise specified, each It shall represent "acryloyl and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", and "acryloyloxy and / or methacryloyloxy".

The present invention is an active energy ray-curable resin composition for optical three-dimensional modeling, wherein the monomer (a-1) containing a cyclic carbonate group and the monomer (a-2) excluding (a-1) are excluded. ) Is radically polymerized, and the polymer (A) and the radically polymerizable compound (B) are contained.
Here, the "active energy ray" means an energy ray in a broad sense capable of providing the energy required for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams, and radiation. .. The active energy ray-curable resin composition for optical three-dimensional modeling of the present invention (hereinafter referred to as "resin composition") undergoes a polymerization reaction by irradiation with the above active energy rays to form a cured product. Although not particularly limited, in one embodiment of the present invention, the active energy ray is preferably light energy including ultraviolet rays.
Hereinafter, each component constituting the resin composition of the present invention will be described in detail.

<Polymer (A)>
First, the polymer (A) of the present invention will be described. The polymer (A) of the present invention is used to impart a function (chain transfer) of reactivating radicals whose activity has decreased due to polymerization inhibition by oxygen molecules during radical polymerization, and contains a cyclic carbonate group. For example, the structure is not limited.

The polymer (A) is a polymer formed by radical polymerization of a monomer (a-1) containing a cyclic carbonate group and a monomer (a-2) excluding (a-1).

As the monomer (a-1) containing a cyclic carbonate group, the cyclic carbonate group can be easily introduced, the amount of the cyclic carbonate group introduced can be easily controlled, and the curability is controlled by controlling the molecular weight and the copolymerization composition. The monomer having a (meth) acrylate group is preferable from the viewpoint that the physical properties of the cured film of the composition can be easily controlled, and the monomer represented by the following general formula (1) or the following general formula (2). Is even more preferable.

General formula (1)

In the formula, R ¹ represents a hydrogen atom or a methyl group.

General formula (2)

In the formula, R ² represents a hydrogen atom or a methyl group.

The monomer (a-2) other than (a-1) is not particularly limited as long as it has a structure capable of radical polymerization with the monomer (a-1) containing a cyclic carbonate group, but is not particularly limited. It is preferable that the monomer has a (meth) acrylate group as in the monomer (a-1) containing a radical.

The amount of the monomer (a-1) containing the cyclic carbonate group in the polymer (A) is preferably 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the total solid content. The amount is more preferable.

As the monomer (a-2) excluding (a-1), for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isobornyl ( Meta) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo- [5.2.1.0 (2,6)]-decanyl (meth) Acrylate, tricyclo- [5.2.1.0 (2,6)]-aliphatic monomers such as decanyloxyethyl (meth) acrylate;
Aromatic monomers such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and rosin acrylate;

2- (1,3-Dioxobutoxy) ethyl (meth) acrylate, 2- (1,3-dioxobutoxy) propyl (meth) acrylate, 3- (1,3-dioxo) (meth) acrylate Butoxy) propyl, 2- (1,3-dioxobutoxy) butyl (meth) acrylate, 3- (1,3-dioxobutoxy) butyl (meth) acrylate, 4- (1,3-dioxobutoxy) acrylate 3-Dioxobutoxy) A monomer containing an active methylene group such as butyl;

Oxetane (meth) acrylate, tetrahydrofurfreel (meth) acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, 1,4-dioxaspiro [4,5] Deca-2-yl) Methyl (meth) acrylate, 2-methacryloyloxy-γ-butyrolactone, 3-methacryloyloxy-γ-butyrolactone, 5-methacryloyloxy-2,6-norbornancarbolactone, β-methacryloyloxy-β- Methyl-δ-valerolactone, β-methacryloyloxy-β-methyl-γ-butyrolactone, 2- (1-methacryloyloxy) ethyl-4-butanolide, N- (meth) acryloyloxyethyl hexahydrophthalimide, etc. Monomer containing;

Polyalkylene glycols such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, and ethoxypolypropylene glycol (meth) acrylate. Monomer containing;

(Meta) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, isobutyl (meth) acrylamide, t-butyl Unsubstituted or N-substituted (meth) acrylamides such as (meth) acrylamide, t-octyl (meth) acrylamide, 2-hydroxyethyl acrylamide, diacetone (meth) acrylamide, and acryloylmorpholin;

Nitriles such as (meth) acrylonitrile;

Polymerizable oligomers such as one-ended methacryloylated polymethylmethacrylate oligomers, one-ended methacryloylated polystyrene oligomers, and one-ended methacryloylated polyethylene glycol;

Styrenes such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, vinyltoluene, inden;

Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether;

Fatty acid vinyls such as vinyl acetate and vinyl propionate;

N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide;

Examples of the hydroxyl group-containing monomer used for the monomer obtained by addition reaction of the carboxylic acid anhydride and the hydroxyl group-containing monomer include a hydroxyl group-containing monomer.

As a method for producing the monomer (a-1) containing a cyclic carbonate group having a (meth) acrylate group, an existing chemical reaction can be used, and the synthesis method thereof is not particularly limited.

One example is the reaction of glycerin carbonate with a (meth) acrylate having a carboxy group and the reaction of glycerin carbonate with a (meth) acrylate having an isocyanate group.

The polymerization step of the polymer (A) will be described.

Polymerization of the polymer (A) formed by radical polymerization of the monomer (a-1) containing a cyclic carbonate group and the monomer (a-2) excluding (a-1) is carried out by a known method. It can be carried out. That is, it can be carried out by optionally mixing the monomer (a-1) and the monomer (a-2) excluding (a-1) with a polymerization initiator and heating. The polymerization temperature is 40 to 150 ° C, preferably 50 to 120 ° C.

Here, since the synthesis process of the polymer (A) is generally carried out in the absence of oxygen such as in a nitrogen atmosphere, many of the cyclic carbonate groups of the monomer (a-1) containing the cyclic carbonate groups Is not involved in chain transfer, and many cyclic carbonate groups remain in the polymer (A).

On the other hand, as described later, the step of applying and curing the active energy ray-curable resin composition for optical three-dimensional modeling, which is the present invention, containing the polymer (A) and the radically polymerizable compound (B). Since it is carried out in the atmosphere, it is subjected to polymerization inhibition by oxygen molecules, but the presence of cyclic carbonate groups regenerates active radicals by chain transfer and promotes curing.

At the time of polymerization, 0.001 to 15 parts by weight of the polymerization is optionally started with respect to 100 parts by weight of the total of the monomer (a-1) and the monomer (a-2) excluding (a-1). Agents can be used.

As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), and 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) , 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl)) Propane] and the like. Examples of organic peroxides are benzoyl peroxide, t-butylperbenzoate, cumenehydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxy. Examples thereof include dicarbonate, t-butylperoxyneodecanoate, t-butylperoxyvivarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like. These polymerization initiators can be used alone or in combination of two or more.

At the time of polymerization, a chain transfer agent may be used for the purpose of adjusting the molecular weight. A chain transfer agent of 0.001 to 15 parts by weight is optionally used with respect to a total of 100 parts by weight of the monomer (a-1) and the monomer (a-2) excluding (a-1). can do.

The chain transfer agent is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and a known chain transfer agent can be used. For example, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioapple. Mercaptans such as acids, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, butylthioglycolate; dimethylxanthogen disulfide, diethylxantogen disulfide, diisopropylxanthigen disulfide, tetramethylthiuram disulfide, tetraethylthiuram Disulfides such as disulfides and tetrabutylthiuram disulfides; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, carbon tetrabromide, ethylene bromide; secondary alcohols such as isopropanol and glycerin; bisulfite Acids, hypophosphates, and salts thereof (sodium bisulfite, potassium hypophosphate, etc.), sulfites, hydrogen sulfites, dithionic acids, metabisulfites, and salts thereof (sodium bisulfite, sulfites, etc.) Lower oxides and salts thereof, such as potassium hydrogen hydrogen, sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite, etc.; and allyl alcohol, 2-ethylhexylthioglycolate, α-methyl Examples thereof include styrene dimer, turpinolene, α-terpinene, γ-terpinene, dipentene, and anisole. These may be used alone or in combination of two or more.

Further, at the time of polymerization, an organic solvent can be used as the polymerization solvent.

As the organic solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethoxydiethylene glycol and the like are used, but are particularly limited thereto. It's not a thing. Two or more kinds of these polymerization solvents may be mixed and used, but the solvent used in the final use is preferable.

<Radical polymerizable compound (B)>
In the present invention, the component (B) is a monomer containing at least one acryloyl group or methacryloyl group in the molecule. The component (B) is divided into a compound (B1) having at least one hydroxyl group in the molecule and a compound (B2) having no hydroxyl group in the molecule.
The hydroxyl group in the compound (B1) is preferable in terms of improving the reaction rate and suppressing polymerization curing shrinkage. By having a hydroxyl group, hydrogen bonds between molecules work, and the cohesive force and degree of cross-linking of the resin composition can be improved, which is effective in improving heat resistance, moisture heat resistance, and thermal dimensional stability as a three-dimensional model. Shown.

On the other hand, by containing the compound (B2) in the resin composition, it is easy to improve the efficiency and sensitivity of the copolymerization reaction with the compound (B1), and the cohesive force is increased after irradiation with active energy rays. A highly cured product can be formed. In addition, the viscosity of the resin composition can be easily reduced, and workability during modeling can be easily improved.
By timely blending so that both the compound having a hydroxyl group (B1) and the compound having no hydroxyl group (B2) are contained, the polymerization curability by activation energy ray irradiation, the curing shrinkage of the three-dimensional model, and A resin composition having good durability such as heat resistance, moisture heat resistance, and water resistance can be obtained.

As the compound (B1), any compound containing one or more hydroxyl groups and one or more acryloyl group or methacryloyl group in its structure can be used without particular limitation. The compound (B1) is divided into a compound (b1) having a hydroxyl group and not having a cyclic structure and a compound (b2) having a hydroxyl group and having a cyclic structure, both of which are polymerized by having a hydroxyl group. It has a great effect on reducing curing shrinkage associated with the reaction.

[Compound having a hydroxyl group and not having a cyclic structure (b1)]
Among the acryloyl group or methacryloyl group-containing compounds (B1) having one or more hydroxyl groups in the molecule, the compound (b1) having a hydroxyl group and not having a cyclic structure is, for example, (meth) acrylic acid 2-. Hydroxyethyl, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) Acrylic acid ester, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl-α- (hydroxymethyl) (meth) acrylate, glycerol monofunctional (meth) acrylate, or 2 A (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to an acryloyl group or methacryloyl group-containing compound having the hydroxyl group such as − (acryloyloxy) ethyl 6-hydroxyhexanonate. , Containing hydroxyl groups such as alkylene oxide-added (meth) acrylic acid ester in which alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide are repeatedly added to the hydroxyl group-containing α, β-ethylenically unsaturated double-bonding group-containing compound. Acrylic (meth) acrylic acid esters;

For example, it contains hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, and N-hydroxyoctyl (meth) acrylamide. (Meta) acrylamides;, etc., but are not particularly limited thereto. Only one of these may be used, or a plurality of types may be used in combination.

The compound (b1) includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and ε-caprolactone from the viewpoint of adhesion between cured products. A hydroxyl group-containing (meth) acrylic acid alkyl ester having 2 to 18 carbon atoms, such as 2-hydroxyethyl (meth) acrylate having 1 to 2 mol added, is particularly preferable.

[Compound having a hydroxyl group and having a cyclic structure (b2)]
Among the compounds (B1), the compound (b2) having a hydroxyl group and having a cyclic structure can be used without particular limitation as long as it has both a hydroxyl group and a cyclic structure. Since the compound (b2) has one or more ring structures in the molecule, it is preferable in terms of water resistance and the like in addition to durability such as heat resistance and moisture heat resistance even if it has a hydroxyl group.

Examples of the compound (b2) include (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, and (meth). ) 2-Hydroxy-3-phenoxymethyl acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3 (meth) acrylate -Phenoxybutyl, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, monohydroxyethylphthalate (meth) acrylate, 2-(meth) acrylate (Meth) acrylic acid esters having a cyclic structure other than a hydroxyl group such as 4-benzoyl-3-hydroxyphenoxy) ethyl and a heterocycle;

For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2'-dihydroxy-4- {2- Hydroxy group-containing benzophenone-based (meth) acrylic acid esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4'-(2-hydroxyethoxy) benzophenone;

For example, 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-Chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy Hydroxy-containing benzotriazole-based (meth) acrylic acid esters such as -3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole;

For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}] -S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}] -S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy} }] -S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}] -S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}] -S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) Acryloyloxyethoxy}]-S-triazine, and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine Hydroxy group-containing triazine (meth) acrylic acid esters such as, etc.;, etc., but are not particularly limited thereto. Only one of these may be used, or a plurality of types may be used in combination.

The compound (b2) includes acrylic acid 1,2-cyclohexanedimethanol and acrylic acid 1,3-cyclohexanedim from the viewpoint of compatibility with the compound (B2) described later and durability such as heat resistance and water resistance. Particularly preferred are methanol, 1,4-cyclohexanedimethanol acrylate, 2-hydroxy-3-phenoxypropyl acrylate and the like.

As described above, by using the above compound (B1), it becomes easy to have a preferable crosslink density and suppress curing shrinkage. Along with this, when the above resin composition is used as a material for optical three-dimensional modeling, it is easy to impart not only excellent heat resistance and moist heat resistance but also surface slipperiness to the three-dimensional model made of the resin composition. It becomes.

[Acryloyl group or methacryloyl group-containing compound (B2) having no hydroxyl group in the molecule]
In the present invention, the compound (B2) is a monomer of an acryloyl group or a methacryloyl group-containing compound having no hydroxyl group in the molecule, and by containing the compound (B2) in the resin composition, the compound (B1) It is easy to improve the efficiency and sensitivity of the copolymerization reaction with the compound, and it is possible to form a cured resin product having a high cohesive force after irradiation with active energy rays. In addition, the viscosity of the resin composition can be easily reduced, and workability during modeling can be easily improved. Although not particularly limited, examples of the compound that can be used as the component (B2) include the following.

Examples of the compound (B2) include (meth) acrylic acid, 2-carboxyethyl (meth) acrylic acid, 2-carboxypropyl (meth) acrylic acid, 3-carboxypropyl (meth) acrylic acid, and (meth) acrylic acid. 4-carboxybutyl, (meth) acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconic acid, sorbic acid, silicic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid , Itaconic acid, tigric acid, angelic acid, senecioic acid, crotonic acid, isoccrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, acrylic acid, penicic acid, gelanic acid, citronellic acid, 4-acrylamide butanoic acid, 6 Polylactone-based (meth) having a carboxyl group at the end due to ring-opening addition of the lactone ring, such as −acrylamide hexanoic acid, 2- (meth) acryloyloxyethyl succinate, mono (meth) acrylic acid ω-carboxypolycaprolactone ester. Acrylic acid ester, alkylene oxide-added succinic acid having a carboxyl group at the end, to which alkylene oxides such as ethylene oxide and propylene oxide are repeatedly added, and a carboxyl group-containing aliphatic such as an ester of (meth) acrylic acid. Acrylic acid group or methacryloyl group-containing carboxylic acids and their acid anhydrides;

For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropylphthalate, 2- (meth) acryloyloxybutylphthalate, 2- (meth) acryloyl. Acryloyl group or acryloyl group-containing carboxylic acids having a carboxyl group-containing alicyclic or aromatic ring such as oxyhexylphthalate, 2- (meth) acryloyloxyoctylphthalate, 2- (meth) acryloyloxydecylphthalate and their acid anhydrides ;

For example, (meth) acrylic acid hydrazide, 2- (2-furyl) -3- (5-nitro-2-furyl) (meth) acrylic acid hydrazide, β- (2-furanyl) (meth) acrylic acid N ² , N ² -bis (2-chloroethyl) hydrazide, p-vinylbenzhydrazide, N- (m-vinylphenyl) acrylohydrazide, 4-vinylbenzenesulfonic acid hydrazide, 2- [2- (5-nitro-2-furyl) ) Vinyl] -4--quinolin Carbohydrazide (meth) acrylic acid esters having a hydrazino group;

For example, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N-propylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate, (meth) acrylic. (Meta) acrylic acid esters having primary and / or secondary amino groups such as N-tributylaminoethyl acid, tetramethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl acrylate;

For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidine). -2-Il) Piperazin-1-yl (meth) Acrylic acid esters having a tertiary amino group such as acrylate;

For example, it has a primary and / or secondary amino group such as monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, and monoethylaminopropyl (meth) acrylamide. (Meta) acrylamides;

For example, (meth) acrylamides having a tertiary amino group such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide;

Heterocyclic acryloyl groups of maleimide derivatives having both nitrogen and oxygen atoms, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Or maleimide group-containing compounds;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth). ) 1-Methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate , (Meta) benzyl acrylate, (meth) acrylate iso-bornyl, (meth) acrylate phenyl, (meth) acrylate 2-phenoxyethyl, (meth) acrylate 2-oxo-1,2-phenylethyl, 2-Oxo-1,2-diphenylethyl (meth) acrylic acid, 1-naphthyl (meth) acrylic acid, 2-naphthyl (meth) acrylic acid, 1-naphthylmethyl (meth) acrylic acid, 1 (meth) acrylic acid -Anthryl, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, (meth) acrylic Dicyclopentanyl acid, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyl (meth) acrylate Adamanthyl-2-yl, 2-isopropyl (meth) acrylate, adamantyl-2-yl, 1- (meth) acrylate-1- (adamantan-1-yl) -1-methylethyl, 1- (meth) acrylate 1- (adamantan-) 1-Il) -1-ethylethyl, 1- (meth) acrylate 1- (adamantan-1-yl) -1-methylpropyl, (meth) acrylate 1- (adamantan-1-yl) -1-ethylpropyl, ( Meta) Acrylic Acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] Nona-2-yl, (Meta) Acrylic Acid-5-oxo-4-oxa-tricyclo [5. 2.1.0 ^3,8 ] Deca-2-yl, dihydro-α-terpinyl (meth) acrylic acid, -6-oxo-7-oxa-bicyclo (meth) acrylic acid [3.2.1] octa- 2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] octa-2-yl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyp Lopilphthalate, 2- (meth) acryloyloxybutylphthalate, 2- (meth) acryloyloxyhexylphthalate, 2- (meth) acryloyloxyoctylphthalate, 2- (meth) acryloyloxydecylphthalate, 2- (meth) acryloyl Oxyethyl hexahydrophthalate, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o-2-propenylphenyl, (meth) acrylic acid cyclohexylglycidyl ether, (meth) acrylic acid phenylglycidyl (Meta) acrylic acid cyclic esters such as ether;

For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl). (Meta) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3-( Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meta) acrylamides containing cyclic structures such as (meth) acrylamide

For example, (meth) acrylic acid cyclic esters containing a sulfonyl group such as sulfophenoxyethyl (meth) acrylate, sulfocyclohexyl (meth) acrylate, sulfobenzyl (meth) acrylate;

For example, (meth) acryloyloxyethyl dimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate, phenyl-2-( Metal salts and ammonium salts of (meth) acrylic acid cyclic esters containing a sulfonyl group such as acryloyloxyethyl phosphate;

For example, di (meth) acrylic acid tricyclodecanedihydroxymethyl, di (meth) acrylic acid tricyclodecanedihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantandiol, di (meth) acrylic acid 1 , 3-adamantandiol, di (meth) acrylate 1,4-adamantandiol, di (meth) acrylate tricyclodecanyl dimethylol, di (meth) acrylate dicyclopentanyl, di (meth) acrylate di Cyclopentenyl, dicyclopentenyloxyethyl di (meth) acrylate ,, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxy) di (meth) acrylate Tetraethylene oxide adduct of propyl) benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane, tetraethylene oxide adduct of di (meth) acrylic acid 2,2-bis (hydroxyphenyl) methane , Di (meth) acrylic acid-4,4'-sulfonyl diphenol tetraethylene oxide adduct, di (meth) acrylic acid-hydrated 2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct, di (Meta) acrylic acid-hydrated 2,2-bis (hydroxyphenyl) methane tetraethylene oxide adduct, di (meth) acrylic acid-hydrated 2,2-bis (hydroxyphenyl) propane, di (2-methyl) ) Propenic acid-hydrated 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct-dicaprolactonate, di (meth) Bifunctional (meth) acrylic acid cyclic esters such as tetraethylene oxide adduct of acrylic acid-2,2-bis (hydroxyphenyl) methane-dicaprolactonate;

Heterocyclic (meth) acrylic acid esters containing nitrogen atoms, such as pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidine-2-yl) piperazin-1-yl (meth) acrylate;

For example, imide (meth) acrylate, 2- (4-oxazoline-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone. A heterocyclic structure containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, and tri (meth) acrylic acid isocyanuric acid ethylene oxide modification. Has (meth) acrylic acid esters;

For example, 4-acryloyl morpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2). -Heterocyclic acrylamides such as ylmethoxymethyl) (meth) acrylamide;

For example, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ( -2-oxotetrahydropyran-4-yl acrylate, (meth) -4-methyl-2-oxotetrahydropyran-4-yl acrylate, -4-ethyl-2-oxotetrahydropyran (meth) acrylate -4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxo tetrahydrofuran-3-yl, (meth) acrylic acid-2,2- Dimethyl-5-oxo tetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetra-3-yl, (meth) acrylic acid-2-oxotetra-3-yl, (meth) Acrylic acid-4,4-dimethyl-2-oxo tetrahydrofuran-3-yl, (meth) acrylic acid-5,5-dimethyl-2-oxotetra-3-yl, (meth) acrylic acid-2-oxo tetrahydrofuran- 3-Il, (meth) acrylic acid-5-oxo tetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3,3-dimethyl-5-oxo tetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4- Heterocycle-containing (meth) acrylic acid esters having an oxygen atom such as dimethyl-5-oxo tetrahydrofuran-2-ylmethyl;

For example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec- (meth) acrylate. Butyl, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-Ethylhexyl acrylate, n-octyl (meth) acrylate, iso-octyl acrylate, n-nonyl (meth) acrylate, iso-nonyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Alkyl esters of (meth) acrylic acid such as dodecyl acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;

For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-Butenyl, 2-Chlor 2-propenyl (meth) acrylate, 3-Chlor 2-propenyl (meth) acrylate, 2- (2-propenyloxy) ethyl (meth) acrylate, 2-2-propenyl (meth) acrylate Propenyl lactyl, (meth) acrylic acid 3,7-dimethylocta-6-ene-1-yl, (meth) acrylic acid (E) -3,7-dimethylocta-2,6-dien-1-yl, (Meta) acrylic acid esters containing further unsaturated groups such as (meth) acrylateyl, cinnamyl (meth) acrylate, and (meth) vinyl acrylate;

For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-per (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, (meth) acrylic propenic acid (Meta) acrylic acid perfluoroalkyl esters such as 2-perfluorodecylethyl, 2-perfluorohexadecylethyl (meth) acrylic acid;

For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate. Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylic acid, and 4-butoxyethyl (meth) acrylic acid;

For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic. Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meta) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Butyl, (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Hexyl, (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Octyl, (Meta) Acrylic Acid 2- (Propoxycarbonyloxy) ethyl, (meth) acrylate 2- (butoxycarbonyloxy) ethyl, (meth) acrylate 2- (butoxycarbonyloxy) butyl, (meth) acrylate 2- (octyloxycarbonyloxy) ethyl, (Meta) Acrylic Acid 2- (Octyloxycarbonyloxy) An aliphatic (meth) acrylic acid ester having one carbonyl group such as butyl;

For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, 2-oxobutanoyloctyl (meth) acrylate, 2-oxobutanoyldecyl (meth) acrylate, 2-oxobutanoyldodecyl (meth) acrylate, 3-oxobutanoylethyl (meth) acrylate, (meth) ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylic acid, 4-cyanooxobutanoylethyl (meth) acrylic acid, 4-cyanooxobutanoylpropyl (meth) acrylic acid, (meth) acrylic Acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoylhexyl, (meth) acrylic acid 4-cyanooxobutanoyloctyl, (meth) acrylic acid 2,3-di (oxobutanoyl) Propyl, 2,3-di (oxobutanoyl) butyl (meth) acrylic acid, 2,3-di (oxobutanoyl) hexyl (meth) acrylic acid, 2,3-di (oxobutanoyl) (meth) acrylic acid ) An aliphatic (meth) acrylic acid ester having two carbonyl groups such as octyl;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] nona-2-yl, (meth) acrylic acid-10-methoxycarbonyl -5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] nona-2-yl, (meth) acrylic acid-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3] .2.1] It has a carbonyl group such as octa-2-yl, (meth) acrylate-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] octa-2-yl ( Meta) Acrylic acid cyclic esters;

For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N-( (Meta) acrylamides having carbonyl groups such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

For example, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxybutyl (meth) acrylate, -3-chloro-2-acid phosphooxyethyl (meth) acrylate, ( Meta) Acrylic acid-3-chloro-2-acid Phosphonoxypropyl, (Meta) Acrylic acid-3-chloro-2-acid Phosphonoxybutyl, (Meta) Acrylic acid Acid Phosphonoxyethylene oxide (Number of moles of ethyleneoxide added: Phosphonate group-containing (meth) acrylic acid esters such as 4 to 10), (meth) acrylic acid acid phosphooxypropylene oxide (number of moles added with propylene oxide: 4 to 10);

For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysisilane. , 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (Meta) acryloyloxypropylethyl dipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, (Meth) acrylic acid esters containing alkoxysilyl groups such as 3- (meth) acryloyloxypropyltripropoxysilane;

For example, metal salts and ammonium of (meth) acrylic acid esters containing a sulfonyl group such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, and (meth) acryloylaminopropyltriethylammonium sulfate. salt;

For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di. Dipropylene oxide of (meth) acrylic acid, tripropylene oxide of di (meth) acrylic acid, polypropylene oxide of di (meth) acrylic acid, butene oxide of di (meth) acrylic acid, penten oxide of di (meth) acrylic acid, di (meth) 2,2-Dimethylpropyl Acrylic Acid, Di (Meta) Acrylic Acid Hydroxypivalyl hydroxypivalate, Di (Meta) Acrylic Acid Hydroxy Pivalyl Hydroxypivalate Dicaprolactonate, Di (Meta) Acrylic Acid 1,6-hexane Diol, di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7 -Heptanediol, di (meth) acrylic acid 1,8-octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol, di (meth) acrylic acid 1 , 2-Decandiol, Di (meth) acrylic acid 1,10-decanediol, Di (meth) acrylic acid 1,2-decanediol, Di (meth) acrylic acid 1,12-dodecanediol, Di (meth) acrylic Acid 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) acrylic acid 1,16-hexadecanediol, di (meth) ) Acrylic acid 1,2-hexadecanediol, di (meth) acrylic acid 2-methyl-2,4-pentanediol, di (meth) acrylic acid 3-methyl-1,5-pentanediol, di (meth) acrylic acid 2-Methyl-2-propyl-1,3-propanediol, di (meth) acrylic acid 2,4-dimethyl-2,4-pentanediol, di (meth) acrylic acid 2,2-diethyl-1,3- Propanediol, di (meth) acrylic acid 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane di (meth) acrylic acid, 2-ethyl-1,3-hexanediol di (meth) acrylic acid , Di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylic acid 2-methi Lu-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di 2-Methyl-2-propyl-1,3-propanediol (meth) acrylic acid, 2,4-dimethyl-2,4-pentanediol di (meth) acrylic acid, 2,2-diethyl di (meth) acrylic acid -1,3-Propanediol, di (meth) acrylate 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane di (meth) acrylate, 2-ethyl-1 di (meth) acrylate , 3-Hexanediol, di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylate 2-butyl-2-ethyl-1,3-propanediol, di (meth) Bifunctional (meth) acrylic acid esters such as 2,4-diethyl-1,5-pentanediol acrylic acid and 1,1,1-trishydroxymethylethane di (meth) acrylic acid;

For example, tri (meth) acrylic acid 1,2,3-propanetriol, tri (meth) acrylic acid 2-methylpentane-2,4-diol, tri (meth) acrylic acid 2-methylpentane-2,4-diol. Tricaprolactonate, tri (meth) acrylic acid 2,2-dimethylpropane-1,3-diol, tri (meth) acrylic acid trimethylol hexane, tri (meth) acrylic acid trimethylol octane, tri (meth) acrylic acid 2,2-Bis (hydroxymethyl) 1,3-propanediol, tri (meth) acrylic acid 1,1,1-trishydroxymethylethane, tri (meth) acrylic acid 1,1,1-trishydroxymethylpropane, etc. Trifunctional (meth) acrylic acid esters;

For example, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxylated tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetra (meth) acrylate 2, 2-Bis (Hydroxymethyl) 1,3-Propanediol, Tetra (Meta) Acrylic Acid 2,2-Bis (Hydroxymethyl) 1,3-Propandiol Tetracaprolactonate, Tetra (Meta) Acrylic Acid Di1, 2,3-Propanetriol, di2-methylpentane tetra (meth) acrylate-2,4-diol, di2-methylpentane tetra (meth) acrylate-2,4-diol tetracaprolactonate, tetra ( Di2,2-dimethylpropane-1,3-diol (meth) acrylate, ditrimethylolbutane tetra (meth) acrylate, ditrimethylolhexane tetra (meth) acrylate, ditrimethylol octane tetra (meth) acrylate, tetra (meth) Di 2,2-bis (hydroxymethyl) 1,3-propanediol meta) acrylic acid, di-2,2-bis (hydroxymethyl) 1,3-propanediol hexa (meth) acrylic acid, hexa (meth) acrylic acid Tri 2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meth) acrylate Tri 2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylate tri 2,2 -Polyfunctional (meth) acrylic acid esters such as bis (hydroxymethyl) 1,3-propanediol and hepta (meth) acrylic acid di2,2-bis (hydroxymethyl) 1,3-propanediol polyalkylene oxide;

For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl. (Meta) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecil (Meta) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleeamide, Fumalamide, Mesaconamide, Citraconamide, Itaconamide, 2-Methylpropa-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N', N' -Dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethaneamide, N-vinylacetamide and other aliphatic (meth) acrylamides;

For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy. Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide , N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-iso Propoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxyoctyl (meth) acrylamide, N-butoxy Methyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide, N-butoxyoctyl (meth) acrylamide , N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide , N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl-2-methoxyethyl (meth) acrylamide, N, N-di (methoxymethyl) meta) acrylamide , N-alkoxy group-containing (meth) acrylamides such as N, N-di (ethoxymethyl) (meth) acrylamide;

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;

Examples thereof include, but are not limited to, acryloyl group or methacryloyl group-containing compounds having a nitrile group such as (meth) acrylonitrile and 2-cyanoethyl (meth) acrylate.

Further, for example, o-di (meth) allyl bisphenol A, hydrogenated bisphenol A having an aromatic ring structure, and the like are also included in the compound (B2) if they have an acryloyl group or a methacryloyl group. Only one of these may be used, or a plurality of types may be used in combination.

When the resin composition of the present invention is used as a photothree-dimensional modeling material, the compound (B2) preferably contains bifunctional or higher (meth) acrylic acid esters from the viewpoint of the activation energy ray polymerization rate. From the viewpoint of durability such as heat resistance and water resistance, 4-acryloyl morpholine, neopentyl glycol di (meth) acrylate, isocyanuric acid ethoxylated di (meth) acrylate, and isocyanuric ethoxylated tri (meth) acrylate. Acids and dicyclopentanyl diacrylate are preferred.

<Cationopolymerizable compound (D)>
In one embodiment of the resin composition of the present invention, the resin composition may contain the cationically polymerizable compound (D) in addition to the above-mentioned essential components. By using the cationically polymerizable compound (D), when the resin composition is used as a three-dimensional model, heterogeneous polymerization curing by irradiation with active energy rays becomes possible, so that the cured product forms a phase-separated structure and is elastic. It is easy to control stress relaxation properties and creep characteristics, and it is possible to further improve appropriate elasticity and flexibility maintenance and hardening shrinkage suppression. Further, it becomes easy to improve the heat resistance or the moisture heat resistance of the resin layer.

The cationically polymerizable compound (D) contains at least one functional group that is cationically polymerized by an acid catalyst, and these can be used without particular limitation. As the cationically polymerizable compound (D), the cyclic hetero compound (d) is preferable from the viewpoint of reactivity with active energy rays, and among the cyclic hetero compounds, a compound having one or more cyclic ether groups is particularly preferably used.

Among the cyclic heterocompounds (d), an epoxy group-containing compound (d1) which is a cyclic heterocompound having a 3-membered cyclic ether group, an oxetanyl group-containing compound (d2) which is a 4-membered ring ether, and a cyclic ether having a 5-membered ring or more. There is a compound (d3) and a compound (d4) having two or more oxygen or a heterogroup other than oxygen.

[Epoxy group-containing compound (d1), which is a cyclic heterocompound having a 3-membered cyclic ether group]
Examples of the epoxy group-containing compound (d1) include oxylan, methyloxylan, phenyloxylan, 1,2-diphenyloxylan, methylideneoxylan, oxylanylmethyl, oxylanylmethanol, oxylancarboxylic acid, and (chloromethyl) oxylan. , (Bromomethyl) oxylane, oxylanyl acetonitrile, 2,2'-(dimethylmethylene) bis [(p-phenylene) oxymethylene] bisoxylane, 2,2'-[methylenebis (2,1-phenyleneoxymethylene)] Oxylan compounds such as bisoxylan, or epoxy group-containing compounds in which the hydrogen atom of the oxylan ring such as glycidyl ether, glycidyl ester, and glycidylamine is substituted with a methylene group or a methine group;

For example, 2- (cyclohexylmethyl) oxylane, 2-ethoxy-3- (cyclohexylmethyl) oxylane, [(cyclohexyloxy) methyl] oxylan, 1,4-bis (oxylanylmethoxymethyl) cyclohexane, 2,2'-. [(1-Methylethylidene) bis (4,1-cyclohexanediyloxymethylene)] Bisoxylan, 2-[{4- (oxylan-2-ylmethoxy) cyclohexyl} methoxy] Contains an epoxy group having a cycloalkane ring such as oxylan Compounds;

For example, 7-oxabicyclo [4.1.0] heptane, 3-methyl-7-oxabicyclo [4.1.0] heptane, 7-oxabicyclo [4.1.0] heptane-3-ylmethanol, 7-Oxabicyclo [4.1.0] heptane-3-methoxymethyl, 3-{(2-ethylhexyl) oxy} -2-hydroxypropyl 7-oxabicyclo [4.1.0] heptane 3-carboxylate, 7-Oxabicyclo [4.1.0] heptane-1-olacetate, 5,8,8-trimethyl-3-oxatricyclo [5.1.0.0 ^2,4 ] octane, α, α, 6 -Trimethyl-7-oxabicyclo [4.1.0] heptane-3-methanol acetate, β, 6-dimethyl-7-oxabicyclo [4.1.0] heptane-3-ethanol acetate, piperitone oxide, 3 -Calene oxide, α-terpineol oxide, 3- (tyran-2-yl) -7-oxabicyclo [4.1.0] heptane, 6-methyl-3-isopropyl-7-oxabicyclo [4.1.0] ] Heptane-3-ol, 3,4-oxylancyclohexylmethyl 3,4-oxylancyclohexanecarboxylate, 3,4-oxylan-6-methylcyclohexylmethyl 3,4-oxylan-6-methylcyclohexanecarboxylate, (1s, 4s) -7-oxabicyclo [2.2.1] heptane, (1R, 4S) -2-methyl-7-oxabicyclo [2.2.1] heptane, (1R, 2S, 4S, 5S)- 3-Oxabicyclo [3.2.1.0 ^2,4 ] octane, ethylenebis (3,4-oxylancyclohexanecarboxylate), bis (3,4-oxylancyclohexylmethyl) adipate, bis (7-oxabicyclo [7-oxabicyclo] 4.1.0] Heptane-3-ylmethyl) adipate, bis (3,4-oxylan-6-methylcyclohexylmethyl) adipate, bis (7-oxabicyclo [4.1.0] heptane-3-ylmethyl) carbonate , Diethylene glycol bis (3,4-oxylancyclohexylmethyl ether), ethylene glycol bis (3,4-oxylancyclohexylmethyl ether), 2,3,14,15-dioxylan-7,11,18,21-tetraoxatrispyro -[5.2.2.5.2.2] Henikosan (also 3,4-oxylancyclohexanespiro-2', 6'- Dioxane spiro-3'', 5''-dioxan spiro-3''', 4'''-a compound that can also be called oxylancyclohexane), 4- (3,4-oxylancyclohexyl) -2,6-dioxa-8 , 9-Oxylance Spiro [5.5] Undecane, 4-Vinylcyclohexendioxide, Bis-2,3-Oxylancyclopentyl ether, and Dicyclopentadiendioxide, which are alicyclic epoxy group-containing compounds having no aromatic ring. Kind;

For example, 3-phenyl-7-oxabicyclo [4.1.0] heptane-3-carboxylate, 4-ethylphenyl7-oxabicyclo [4.1.0] heptane, benzyl7-oxabicyclo [4.1] .0] Heptane-3-carboxylate, 4-ethylphenyl7-oxabicyclo [4.1.0] Heptane-3-carboxylate, 2-hydroxy-3-phenoxypropyl 7-xabicyclo [4.1.0] ] Heptane-3-carboxylate, 1,2-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), 1,3-phenylenebis (methylene) bis (7) −Oxabicyclo [4.1.0] heptane-3-carboxylate), 1,4-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), 1- phenylethane-1,2-diyl bis (7-oxabicyclo [4.1.0] ^{heptane-3-carboxylate), O '3, O 3} -1,4- phenylenebis (methylene) 4- dibutylbis (7- Oxabicyclo [4.1.0] heptane-3,4-dicarboxylate), bis (7-oxabicyclo [4.1.0] heptane-3-ylmethyl) isophthalate, bis [2-{(7-) Oxabicyclo [4.1.0] heptane-3-carbonyl) oxy} ethyl] terephthalate, 1,2-bis {(7-oxabicyclo [4.1.0] heptane-3-ylmethoxy) methyl} benzene, 1 , 3-bis {(7-oxabicyclo [4.1.0] heptane-3-ylmethoxy) methyl} benzene, 1,4-bis {(7-oxabicyclo [4.1.0] heptane-3-ylmethoxy) ) Methyl} Benzene, [{Propane-2,2-diylbis (4,1-phenylene)} bis (oxy)] bis (ethane-2,1-diyl) bis (7-oxabicyclo [4.1.0] Examples thereof include alicyclic epoxy group-containing compounds having an aromatic ring such as heptane-3-carboxylate).

The epoxy group-containing compounds exemplified here may be used alone, or a plurality of epoxy group-containing compound compounds may be mixed and used, and the present invention is not particularly limited thereto.

[Oxetanyl group-containing compound (d2) which is a 4-membered ring ether]
Examples of the oxetanyl group-containing compound (d2) include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, and di (1-ethyl-3-3). Oxetanyl) methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, 3-ethyl-{(3-triethoxysilylpropoxy) Methyl} oxetane and the like can be mentioned. The oxetanyl group-containing compound (d2) may be used alone or in combination of two or more.

[Cyclic ether compound with 5 or more membered rings (d3)]
Examples of the cyclic ether compound (d3) having a 5-membered ring or more include 2-methyltetrahydrofuran, 2,5-diethoxytetrahydrofuran, tetrahydrofuran-2,2-dimethanol 3-methyl-2,4 (3H, 5H)-. Frangion, 2,4-dioxotetrahydropyran-3-carboxylate, 1,5-di (tetrahydropyran-2-yl) pentan-3-yl propanoate, 4- (2,5-dioxotetrahydropyran-3-yl) ) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, methoxytetrahydropyran, 2- (propadienyloxy) tetrahydro-2H-pyran, 2- (tetrahydrofuryloxy) tetrahydropyran , N- (2,6-dioxotetrahydro-2H-pyran-3-yl) phthalimide, 3- [3-hydroxypropyl] oxy] oxepan, (2R, 3R) -2-methyl-3- (benzyloxymethyl) ) Oxepan-3-ol, 5-chloro-2- (2-phenylethyl) oxepan and the like may be mentioned, and they may be used alone or in combination of two or more.

[Compound having two or more oxygens or heterogroups other than oxygen (d4)]
Examples of the compound (d4) having two or more oxygen or a heterogroup other than oxygen include a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, and a fluorine-containing cyclic compound. The cyclic ester compound is preferably a lactone. More preferably, the cyclic formal compound is a compound selected from dioxolanes, dioxanes and trioxanes.
Industrially, propiolactone, butyrolactone, valerolactone, caprolactone, 1,3-dioxolane, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 1,3,5-trioxane, ethylene carbonate , Propylene carbonate, glycerin carbonate and the like are preferably used in terms of reactivity.

Examples of the cationically polymerizable compound (D) include (d1), (d2), (d3) and (d4), and the cation-polymerizable compound (D) is not particularly limited, but is an epoxy group-containing compound (d1) or an oxetanyl group-containing compound ( d2) is preferable. Further, the epoxy group-containing compound (d1) or the oxetanyl group-containing compound (d2) has a large steric strain and is likely to cause a nucleophilic ring-opening reaction. Therefore, since the crosslink density can be improved at the time of modeling, the cohesive force is easily improved, which is industrially preferable. These may be used alone or in combination of two or more depending on the purpose of use.

As described above, by using the cationically polymerizable compound (D) in combination with the resin composition of the present invention, it is easy to suppress the curing shrinkage of the three-dimensional molded product which has been polymerized and cured by irradiating with active energy rays. It is possible to improve the poor appearance of the three-dimensional model due to its large size.

In the present invention, when the total amount of the polymer (A) and the compound (B) is 100 parts by mass, the amount of the cationically polymerizable compound (D) is preferably 1 to 350 parts by mass. More preferably, it is 1 to 150 parts by mass. By setting the amount of the cationically polymerizable compound (D) to 1 part by mass or more, the lack of cohesive force can be improved, and the properties such as heat resistance and moisture heat resistance can be easily improved. On the other hand, when the amount of the cationically polymerizable compound (D) is 350 parts by mass or less, it becomes easy to obtain an effect of reducing the curing shrinkage when the resin composition is used as a modeling material.

<Oligomer (E)>
In one embodiment of the resin composition of the present invention, the resin composition may contain an oligomer (E) in addition to the above essential components. By using the oligomer (E), when the resin composition is used as a stereolithography material, the formability and the curing shrinkage can be further improved. Further, it becomes easy to improve the heat resistance or the moisture heat resistance of the resin layer.

The oligomer (E) is a compound obtained by adding an α, β-unsaturated double bond group to a polymer of a monomer having at least an α, β-unsaturated double bond group and / or various compounds. , Has one or more acryloyl or methacryloyl groups in the molecule. However, those contained in the above compound (A) or the above compound (B) are excluded. The oligomer may have various functional groups in addition to the acryloyl group or the methacryloyl group. In one embodiment of the present invention, the oligomer (E) is selected from the group consisting of polyester-based oligomers (e1), polyurethane-based oligomers (e2), polyepoxy-based oligomers (e3), and polyacrylic oligomers (e4). At least one of them is included, and these can be used without particular limitation.

Polyester-based oligomer (e1);
As the polyester-based oligomer (e1), the terminal of the polyester obtained by polycondensing a polybasic acid and a polyhydric alcohol on the main chain skeleton or the hydroxyl group in the polyester chain and the molecule of (meth) acrylic acid, maleic acid, etc. A compound obtained by esterification with an α, β-ethylene unsaturated double bond group-containing compound having one or more carboxyl groups, or a carboxyl group at the end of a polyester or in a polyester chain and (meth) acrylic acid 2-. It is a compound obtained by esterification with the above-mentioned compound (B1) such as hydroxyethyl and 2-hydroxypropyl (meth) acrylate. In addition, a polyester oligomer obtained from an acid anhydride, glycidyl (meth) acrylate, and a compound having at least one hydroxyl group can also be used as the polyester oligomer (e1).

Examples of the above-mentioned polybasic acid include aliphatic type, alicyclic group type, and aromatic type, and each of them can be used without particular limitation. More specifically, the aliphatic polybasic acid includes, for example, succinic acid, malonic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, and dodecanedi. Examples thereof include acids, pimeric acid, citraconic acid, glutaric acid, itaconic acid, succinic acid anhydride, maleic anhydride and the like, and these aliphatic dicarboxylic acids and their anhydrides can be used. Derivatives of succinic anhydride (methyl anhydride, 2,2-dimethylanhydride, butylanhydride, isobutyl anhydride, hexyl anhydride, octyl anhydride, dodecenyl anhydride, phenylanhydride Succinic acid, etc.), derivatives of glutaric anhydride (glutaric anhydride, 3-allyl maleic anhydride, 2,4-dimethyl maleic anhydride, 2,4-diethyl anhydride, butyl anhydride, hexyl anhydride, etc. ), Derivatives of maleic anhydride (2-methyl maleic anhydride, 2,3-dimethyl maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl Anhydrous derivatives such as maleic anhydride, 2,3-dichloromaleic anhydride, phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, etc.) can also be used. ..

More specifically, as the alicyclic polybasic acid, for example, as the alicyclic dicarboxylic acid, for example, dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclopropane-1α, 2β-dicarboxylic acid. , Cyclopropane-1β, 2α-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, cyclobutane-1α, 2β-dicarboxylic acid, cyclobutane-1α, 3β-dicarboxylic acid, cyclobutane-1α, 3α-dicarboxylic acid, (1R) -Cyclopentane-1β, 2α-dicarboxylic acid, trans-cyclopentane-1,3-dicarboxylic acid, (1β, 2β) -cyclopentane-1,3-dicarboxylic acid, (1β, 3β) -cyclopentane-1, 3-dicarboxylic acid, (1S, 2S) -1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptane Saturated alicyclic dicarboxylic acids such as dicarboxylic acid, cuban-1,4-dicarboxylic acid, 2,3-norbornandicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and 1- Cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1,2- Dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,3-dicarboxylic acid, 2,5-hexadien-1α, 4α-dicarboxylic acid, etc. Examples thereof include unsaturated alicyclic dicarboxylic acids having one or two unsaturated double bonds in the ring, and these alicyclic dicarboxylic acids and their anhydrides can be used.

In addition, derivatives of hexahydrophthalic anhydride (3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), derivatives of tetrahydrophthalic anhydride (1,2,3,6-tetrahydrophthalic anhydride, 3- Methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) A hydrogenated phthalic anhydride derivative can also be used as an alicyclic dicarboxylic acid anhydride.

More specifically, as the aromatic polybasic acid, for example, as the aromatic dicarboxylic acid, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, 2,5-dimethylterephthalic acid, 2 , 2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornenedicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindandandicarboxylic acid , 1,2-azurange carboxylic acid, 1,3-azurange carboxylic acid, 4,5-azurange carboxylic acid, (-)-1,3-acenaftendicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,5- Aromatic dicarboxylic acids such as anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracene dicarboxylic acid, 1,2-phenanthrange carboxylic acid, 4,5-phenanthrange carboxylic acid, and 3,9-perylene dicarboxylic acid , Aromatic dicarboxylic acid anhydrides such as phthalic acid anhydride and 4-methylphthalic anhydride, and these aromatic dicarboxylic acids and their anhydrides can be used.

In addition, chlorendic anhydride, hetic anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3 , 6-Tetrahydro phthalic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used as polybasic acid.

Further, as the polyhydric alcohol, a relatively low molecular weight polyol having a number average molecular weight (Mn) of about 50 to 500 and a relatively high molecular weight polyol having a number average molecular weight (Mn): 500 to 30,000 are used. Each of them can be used without any particular limitation.

More specifically, as the polyols having a relatively low molecular weight, for example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2, 4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptan, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (Additional moles of 10 or less), Polyoxypropylene glycol (Additional moles of 10 or less), Propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , 1,9-Nonandiol, Neopentyl glycol, Octanediol, Butylethylpentanediol, 2-Ethyl-1,3-hexanediol, Cyclohexanediol, Cyclohexanedimethanol, Tricyclodecanedimethanol, Cyclopentadiene dimethanol, Dimer Aliphatic or alicyclic diols such as diols;

For example, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4'-methylenediphenol, Addition of 4,4'-(2-norbornenilidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropyridenephenol, bisphenol with alkylene oxide added Examples thereof include aromatic diols such as type bisphenol.

Examples of the raw material bisphenol of the addition type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.
More specific examples of the relatively high molecular weight polyols include high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. The high molecular weight polycarbonate polyol is obtained by reacting the above-mentioned relatively low molecular weight diol with a carbonic acid ester or phosgene.

Examples of commercially available products of the high molecular weight polyester polyol include the Byron series manufactured by Toyobo Co., Ltd., the Kuraray polyol P series manufactured by Kuraray Co., Ltd., and the Kyowa Pole series manufactured by Kyowa Hakko Chemical Co., Ltd.
As a commercially available product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd. or the like can be used.
Examples of commercially available products of the high molecular weight polycarbonate polyol include Oxymer N112 manufactured by Perstop, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray polyol PMHC series manufactured by Kuraray, and Kuraray polyol C series.

Examples of commercially available high molecular weight polyurethane polyols include Byron UR series manufactured by Toyo Spinning Co., Ltd., Takelac E158 (hydroxyl value = 20, acid value <3) manufactured by Mitsui Chemicals Polyurethane Co., Ltd., and Takelac E551T (hydroxyl value = 30,). Examples thereof include an acid value <3) and Takelac Y2789 (hydroxyl value = 10, acid value <2).
In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diols, poly (β-methyl-γ-valerolactone) diols, and polyvalerolactone diols can also be used as the high molecular weight polyols. Included in polyol.

Polyurethane-based oligomer (e2):
The polyurethane-based oligomer (e2) is a compound obtained by reacting a compound having at least one or more isocyanate groups with the compound (B1), or a compound having at least one isocyanate group and the above-mentioned polyhydric alcohol. A compound obtained by reacting a urethane prepolymer having a terminal isocyanate group obtained by reacting with the compound (B1), or a compound obtained by reacting a compound having at least one isocyanate group with a polyhydric alcohol. It is a compound obtained by reacting a terminal isocyanate group urethane prepolymer obtained by reacting an isocyanate group urethane prepolymer with a compound having at least one amino group and the compound (B1). Further, the polyurethane-based oligomer (e2) also contains a urea-bonding group obtained by reacting an isocyanate group with an amino group.

Examples of the compound having at least one isocyanate group include monofunctional polyisocyanate and polyfunctional isocyanate, and aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate and the like, respectively. Can be mentioned. More specifically, the monofunctional polyisocyanate includes, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, and p-chlorophenyl. Isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methyl Benzyl isocyanate, (S)-(-)-α-methylbenzylisocyanate, (R)-(-)-1-(1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethylisocyanate, ( Examples thereof include S)-(-)-1-phenylethyl isocyanate and p-toluenesulfonyl isocyanate.

Among the polyfunctional isocyanates, more specifically, examples of the aromatic polyisocyanate include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, and 4,4'-diphenylmethane diisocyanate ( Also known as: 4,4'-MDI), 2,4-tolylene diisocyanate (also known as 2,4-TDI), 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-tri Examples thereof include isocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate and the like.

Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca. Examples thereof include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1, , 4-Tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate (also known as IPDI), 1,3-cyclopentanediisocyanate, 1,3-cyclohexanediisocyanate, and 1,4-cyclohexanediisocyanate. Examples thereof include methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4′-methylenebis (cyclohexylisocyanate), and 1,4-bis (isocyanatemethyl) cyclohexane.

Further, as a part of the component (e2), the above-mentioned 2-methylpentane-2,4-diol adduct of polyisocyanate, trimer having an isocyanurate ring and the like can also be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, and modified products of these polyisocyanates can be used. As the polyisocyanate modified product, a carbodiimide group, a uretdione group, a uretonimine group, a bullet group reacted with water, an isocyanurate group, or a modified product having two or more of these groups can be used. The reaction product of polyol and diisocyanate can also be used as a compound having at least two isocyanate groups.
Examples of amines having an amino group include aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane and 3-aminopentane. , Isoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane (laurylamine), 1-aminotridecane, 1-amino Hexadecane, 1-aminotetradecane (myristylamine), 1-aminopentadecane, cetylamine, oleylamine, cocoalkylamine, beef alkylamine, hardened beef alkylamine, allylamine, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane , Aminocyclohexane, Aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino-1-propene, 3-aminomethylheptane, 3 -Isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine, 3-myristyloxypropylamine, 2 -Aminomethyl tetrahydrofuran, aniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1- Aminoanthracene, 2-aminoanthracene, 5-aminoisoquinolin, o-aminodiphenyl, 4-aminodiphenyl ether, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine , Α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine and other primary amines;

For example, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, din-propylamine, din-butylamine, disec-butylamine, N-ethyl-1,2 -Dimethylpropylamine, piperidine, 2-pipecholine, 3-pipecholine, 4-pipecholine, 2,4-lupetidine, 2,6-rupetidine, 3,5-lupetidine, 3-piperidin methanol, 2-piperidinethanol, 4-piperidin Ethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidin, 3-pyrrolidinol, diamilamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkylamine, di-cured beef fat alkylamine, distearylamine, etc. Secondary amines;

For example, ethylene diamine, propylene diamine [alias: 1,2-diaminopropane or 1,2-propanediamine], trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias : 1,4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylenediamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], diethylenetriamine, Triaminopropane, 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine, dimerdiamine, dicyclohexylmethane-4,4'-diamine, diethylene glycol bis (3-amino) Propyl) ether, phenylenediamine, xylylene diamine, dicyclohexylmethane-4,4'-diamine, 2,4-tolylene diamine, 2,6-tolylene diamine, diethyltoluenediamine, 3,3'-dichloro-4 , 4'-diaminodiphenylmethane, 4,4'-bis- (sec-butyl) diphenylmethane, glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid, diaminobenzenesulfonic acid, etc. Diamine having two primary amino groups Kind;

For example, diamines having two secondary amino groups such as N, N-dimethylethylenediamine, N, N-diethylethylenediamine, and N, N'-di-tert-butylethylenediamine, piperazine;

For example, N-methylethylenediamine [also known as methylaminoethylamine], N-ethylethylenediamine [also known as ethylaminoethylamine], N-methyl-1,3-propanediamine [also known as N-methyl-1,3-diaminopropane or Methylaminopropylamine], N,2-methyl-1,3-propanediamine, N-isopropylethylenediamine [also known as isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [also known as N-isopropyl-1, 3-Propanediamine or Isopropylaminopropylamine], and N-lauryl-1,3-propanediamine [also known as N-lauryl-1,3-diaminopropane or laurylaminopropylamine], triethyltetramine, diethylenetriamine, 2-hydroxy Ethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethyl) Polyamines having primary and secondary amino groups such as propylene) diamine, (2-hydroxypropylethylene) diamine, and (di-2-hydroxypropylethylene) diamine;

For example, dihydrazide oxalic acid, dihydrazide malonic acid, dihydrazide succinic acid, dihydrazide glutaric acid, dihydrazide adipic acid, dihydrazide sebacic acid, dihydrazide dodecane diacid, hexadecandiohydrazide, dihydrazide dihydric acid, dihydrazid maleate, dihydrazide maleate. Hydrazides such as dihydrazide, phthalic acid dihydrazide, carbonate dihydrazide, carbodihydrazide, thiocarbodihydrazide, oxalyl dihydrazide, polyacrylic acid hydrazide;

For example, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine, N, N-dimethylbenzylamine, N-methylmorpholin, diazabicycloundecene (also known as DBU). , 1,5-Diazabicyclo- [4.3.0] -5-nonen and other tertiary amines;

For example, in addition, pyridine, morpholine, N-methylmorpholine, pyrrolidine, piperidine, N-methylpiperidine, dimethyloxazoline, imidazole, N-methylimidazole, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethylisopropanolamine, N-methyldiethanolamine and the like can be used.

Polyepoxy oligomer (e3):
The polyepoxy oligomer (e3) is a compound having a glycidyl group and α, β-non having one or more hydroxyl groups or carboxyl groups in the molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, and maleic acid. It is a compound obtained by reacting with a saturated double bond group-containing compound, and is an acryloyl group or methacryloyl group-containing compound having substantially no glycidyl group. Typical examples include bisphenol type, epoxidized oil type, phenol novolac type, and alicyclic type. As the bisphenol type polyepoxy oligomer, α, β-unsaturated having one or more carboxyl groups in the molecule such as bisphenol type diglycidyl ether obtained by reacting bisphenols with epichlorohydrin and (meth) acrylic acid. It is obtained by reacting with a compound containing a double bond group.

Epoxy oil Polyepoxy oligomers include epoxidized oils such as soybean oil and having one or more hydroxyl groups or carboxyl groups in molecules such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, and maleic acid. Those obtained by reaction with α, β-unsaturated double bond group-containing compounds can be used. Novolac-type polyepoxy oligomers include novolac-type epoxy resins and α, β-unsaturated compounds having one or more hydroxyl groups or carboxyl groups in molecules such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, and maleic acid. Those obtained by reaction with a double bond group-containing compound can be used. The alicyclic polyepoxy oligomer includes an alicyclic epoxy resin and α, β- having one or more hydroxyl groups or carboxyl groups in molecules such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, and maleic acid. Those synthesized by reaction with an unsaturated double bond group-containing compound can be used.

Polyacrylic oligomer (e4):
In the present invention, an acrylic oligomer (e4) can also be used as the oligomer (E). Specific examples of the compounds that can be used include acryloyl group or methacryloyl group-containing modified polyethers, amine-modified acryloyl group or methacryloyl group-containing compounds, and alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins and polyhydric alcohols. It is possible to use an oligomer or a prepolymer of one or more compounds selected from the group consisting of compounds in which an acryloyl group or a methacryloyl group is added to various compounds such as.

From the viewpoint of obtaining excellent properties in addition to the aggregation density, compatibility with other components forming a modeled product by polymerization, and durability such as heat resistance and moisture heat resistance, the mass average molecular weight of the oligomer (E) (hereinafter referred to as the above). , Mw) is preferably in the range of 300 to 50,000, preferably in the range of 400 to 50,000, in terms of compatibility, good durability (heat resistance, moisture heat resistance), and aggregation density of the three-dimensional model. It is preferably in the range of 000. By using an oligomer having an Mw of 50,000 or less, it is possible to easily provide a resin composition having excellent fluidity and excellent compatibility with the above components (A), (B) and (D). Can be done. Further, along with this, problems such as deterioration of the formability of the resin composition, deterioration of durability such as curing shrinkage of the cured product, and whitening of the cured product can be easily suppressed. On the other hand, by using an oligomer having Mw of 300 or more, when the resin composition is used as a stereolithography material, cohesive failure in the three-dimensional model is less likely to occur.

Although not particularly limited, in the present invention, it is preferable to include the polyurethane-based oligomer (e2). When the resin composition is used for applications such as stereolithography materials, the elasticity and flexibility of the cured product tend to change depending on the binding group in the oligomer (E). When the binding group is an ester or ether group, it is easy to obtain excellent flexibility. However, it tends to have low elasticity and hydrolysis resistance. On the other hand, when the above component (e2) is used, it is easy to balance elasticity and flexibility based on the urethane bond. Further, since the above component (e2) has good hydrolysis resistance, water resistance and moisture heat resistance can be easily improved.

In the present invention, when the total amount of the polymer (A) and the compound (B) is 100 parts by mass, the blending amount of the oligomer (E) is preferably 1 to 250 parts by mass. More preferably, it is 1 to 100 parts by mass. By setting the oligomer (E) to 1 part by mass or more, the lack of cohesive force can be improved, and the properties such as heat resistance and moisture heat resistance can be easily improved. On the other hand, when the oligomer (E) is 250 parts by mass or less, it becomes easy to highly suppress curing shrinkage when the resin composition is used as a modeling material.

<Active energy ray polymerization initiator (F)>
The resin composition of the present invention can be cured by advancing the polymerization reaction by irradiation with various activation energy rays. However, the resin composition may contain an active energy ray polymerization initiator (F) if necessary. The polymerization reaction can be promoted by using the active energy ray polymerization initiator (F). In one embodiment of the present invention, the activation energy is preferably ultraviolet rays, and when the polymerization reaction is allowed to proceed by irradiation with ultraviolet rays, the resin composition preferably contains an active energy ray polymerization initiator (F). ..

In the present invention, as the initiator (F), a compound arbitrarily selected from known compounds as an active energy ray polymerization initiator can be used.

Among the initiators (F), the photoradical generator (f1) includes, for example, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-. Chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2 Examples thereof include −methyl-1-phenylpropan-1-one, 4-thioxanthone, camphorquinone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one.

As commercially available products, for example, Irgacure 184,907,651,1700,1800,819,369, and 261 (manufactured by BASF), DAROCUR-TPO (manufactured by BASF, 2,4,6-trimethylbenzoyl-). Diphenyl-phosphine oxide), DaroCure-1173 (manufactured by Merck & Co., Ltd.), EzaCure KIP150, and TZT (manufactured by Nippon Kayaku Hegner), KayaCure BMS, and KayaCure DMBI (manufactured by Nippon Kayaku Co., Ltd.).

It is also possible to use a photopolymerization initiator having at least one (meth) acryloyl group in the molecule.

In addition, as compound (B2), glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) acrylate (3-methyl-3-oxetanyl) methyl, (meth) acrylate-3 , 4-Epoxycyclohexylmethyl or other heterocyclic-containing (meth) acrylic acid esters having 3- or 4-membered oxygen atoms, or cationically polymerizable compound (D) or epoxy-modified vegetable oil is used as the cationically polymerizable compound. If so, it is preferable to contain the photoacid generator (f2) among the initiators (F). Examples of the photoacid generator (f2) include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec) and CPI-110P (manufactured by San-Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), and WPI-113 (manufactured by Ciba Specialty Chemicals). Examples include iodonium salts such as Wako Junyaku Co., Ltd.) and RP-2074 (Rhodia Japan Co., Ltd.), and when used in combination, polymerization cross-linking progresses and curing with excellent durability against heat and humidity It is preferable because it forms an object.

In the present invention, the above-mentioned compounds can be used alone or in combination of two or more as the initiator (F). From the viewpoint of reactivity, the blending ratio of the initiator (F) is preferably in the range of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, with the total amount of the resin composition being 100 parts by mass. The range.

The resin composition of the present invention is substantially free of organic solvents. The resin composition preferably does not contain any organic solvent, but the active energy ray polymerization initiator (F) is often poorly soluble in the polymerizable component. Therefore, a small amount of organic solvent may be contained in order to dissolve the active energy ray polymerization initiator (F). The content of the organic solvent in the resin composition is preferably 5% by mass or less.

Further, in order to improve the performance of the active energy ray polymerization initiator (F), an active energy ray sensitizer may be used in combination. Examples of active energy ray sensitizers include benzophenone derivatives, unsaturated ketone derivatives such as chalcone derivatives and dibenzalacetone, and benzyl and camphorquinone. Polymethine dyes such as 2-diketone derivative, benzoin derivative, fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, thioxanthene derivative, xantone derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, merocyanine derivative, oxonoal derivative, etc. , Acridine derivatives, azine derivatives, thiadine derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, Phthalocyanin derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrrium derivative, tetraphyllin derivative, anulene derivative, spiropyrane derivative, spiroxazine derivative, thiospiropyrane derivative, metal Alene complexes, organic ruthenium complexes, etc. are mentioned, and more specific examples are Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, Sea). The pigments and sensitizers described in "Special Functional Materials" (1986, CMC), edited by MC), Chuzaburo Ikemori et al., Are not limited to these, and are not limited to these, and are also used in the ultraviolet to near-infrared region. Examples thereof include dyes and sensitizers that absorb the light of the above, and two or more of these may be used in any ratio as required.

Among the sensitizers described above, the thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-bis. Examples of coumarins include (diethylamino) benzophenone, and examples of coumarins include coumarin 1, coumarin 338, and coumarin 102. Examples of coumarins include 3,3'-carbonylbis (7-diethylaminocoumarin) and the like. However, it is not limited to these.

<Silane compound (G)>
The resin composition of the present invention preferably contains a silane compound (G). As the silane compound (G), a known silane compound can be used, and is not particularly limited as long as it improves the strength of the three-dimensional model described later. For example, alkyl-based alkoxysilane, aryl-based alkoxysilane, vinyl-based alkoxysilane, amino-based alkoxysilane, epoxy-based alkoxysilane, halogen-based alkoxysilane, (meth) acryloyl-based alkoxysilane, mercapto-based alkoxysilane, cationic-based alkoxysilane, Examples thereof include alkoxysilanes having an alkoxyl group such as isocyanate-based alkoxysilanes, and / or organic silanes having a reactivity in which a hydrogen atom is directly bonded to a silicon atom. More specifically, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, methyltris (methoxyethoxy) silane, methyltris ( Methoxypropoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxy Silane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxy Silane, dimethyldiacetoxysilane, dimethylbis (methoxyethoxy) silane, dimethylbis (methoxypropoxy) silane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxysilane, methylethyldimethoxysilane, methylethyl Alkyl alkoxysilanes such as diethoxysilane, methylethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, methylpropyldiisopropoxysilane, methylpropyldiacetoxysilane;

For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, triltrimethoxysilane, trilltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldi. Aryl-based alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, and methylphenyldiacetoxysilane;

For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltris (methoxypropoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, divinyldimethoxysilane. , Divinyldiethoxysilane, divinyldiisopropoxysilane, divinyldiacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldiisopropoxysilane, methylvinyldiacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, Vinyl-based alkoxysilanes such as diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxysilane, and methylallyldiacetoxysilane;

For example, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminomethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , N- (2-Aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3-aminopyropyrtrimethoxysilane hydrochloride and other amino acids. Alkoxysilanes;

For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2-( Epoxy alkoxysilanes such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane;

For example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxy. Halogen-based alkoxysilanes such as silane, 3,3,3-trifluoropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, and 3,3,3-trifluoropropylmethyldimethoxysilane. Kind;

For example, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- (Meta) acryloyl-based alkoxysilanes such as acryloxipropylmethyldimethoxysilane;

For example, mercapto-based alkoxysilanes such as 3-mercaptopropyltrimethoxylane, 3-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane;

For example, alkoxysilanes typified by isocyanate-based alkoxysilanes such as γ-isocyanatepropyltriethoxysilane can be mentioned.

Furthermore, methylsilane, ethylsilane, dimethylsilane, diethylsilane, diethylmethylsilane, butyldimethylsilane, di-t-butylmethylsilane, triethylsilane, trihexylsilane, butyldimethylsilane, cyclohexyldimethylsilane, n-hexylsilane, n- Octylsilane, tri-n-octylsilane, tripropylsilane, triisopropylsilane, triisobutylsilane, trihexylsilane, n-octadecylsilane, phenylsilane, methylphenylsilane, dimethylphenylsilane, methylphenylvinylsilane, dimethylbenzylsilane, Diphenylsilane, triphenylsilane, (phenylethynyl) dimethylsilane, methyldichlorosilane, ethyldichlorosilane, dimethylchlorosilane, bis (2-chloroethoxy) methylsilane, tris (2-chloroethoxy) silane, n-hexyldichlorosilane, diisopropyl Chlorosilane, dichlorosilane, di-t-butylchlorosilane, trichlorosilane, chloromethylsilane, methylphenylchlorosilane, phenyldichlorosilane, diphenylchlorosilane, chloroisopropylsilane, dichloromethylsilane, dichloroethylsilane, methyldimethoxysilane, dimethoxymethylsilane, Methyldiethoxysilane, dimethylethoxysilane, diethoxysilane, trimethoxysilane, triethoxysilane, tripentyloxysilane, tris (trimethylsiloxy) silane, methylphenylethenylsilane, allyldimethylsilane, 1,1,2-trimethyl Disilane, 1,1,2,2-tetraphenyldisilane, 1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylsilyl) benzene, methyltris (dimethylsiloxy) silane, tris (trimethylsiloxy) Silane, phenyltris (dimethylsiloxy) silane, tetrakis (dimethylsiloxy) silane, tetramethyldisilazane, dimethylsilyldimethylamine, bis (dimethylamino) methylsilane, tris (dimethylamino) silane, tris (dimethylsilyl) amine, N, N-dimethylaminomethylethoxysilane, diacetoxymethylsilane, N, O-bis (dimethylsilyl) acetamido, 2- (dimethylsilyl) pyridine, tetrakis (dimethylsilyl) silane, allyldimethylsilane, mercaptodimethylsilane, cyclopropanesilane , Tris (trimethylsilyl) silane, 1,1,4,4-tetramethyldisilylethene, cyclohexanesilane, pentamethyldisiloxane, tetramethylcyclotetrasiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, pentamethyl Disiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetrax (trimethylsiloxy) disiloxane, 1,1,3 , 3,-Tetramethyldisilazane, 1,2-bis (dimethylsilyl) benzene, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7 , 7-Octamethyltetrasiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,1, 3,5,7,7,7-Octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,2,3 , 4, 5, 6-Hexamethylcyclotrisilazane, α, ω-bis (hydrodiene) polydimethylsiloxane, oil-like or wax-like organic silanes having a silyl group with a long-chain dimethylsiloxane oligomer, and the like. ..

Further, as the silane compound (G), a commercially available product can be used, and it is also possible to use an oligomeric silane obtained by hydrolyzing and condensing a mixture of two or more kinds of silanes to form an oligomer. )include. The silane compound (G) can also be used alone or as a mixture of two or more kinds.

The resin composition of the present invention preferably contains 0.01 to 10 parts by mass of the silane compound (G), more preferably 0.1 to 5 parts by mass. If it is less than 0.01 parts by mass, the effect of improving heat resistance and moisture heat resistance may be small.
On the other hand, if it exceeds 10 parts by mass, the cohesive force is insufficient and foaming is likely to occur in the polymerized cured product in durability tests such as heat resistance and moist heat resistance. The hardness for the cured product may decrease.

<Antioxidant (H)>
The resin composition in the present invention may further contain an antioxidant. By containing the antioxidant (H), it is possible to suppress the coloration of the cured product over time after the active energy ray polymerization.
Examples of the antioxidant include phenolic antioxidants such as Adekastab AO-50 and Adekastab AO-80 (manufactured by Adeca), and phosphorus such as Adekastab PEP-8 (manufactured by BASF) and IRGAFOS168 (manufactured by BASF). Commercially available products such as sulfur-based antioxidants and sulfur-based antioxidants such as IRGANOX-PS-800FD (manufactured by BASF) can be mentioned, but are not limited thereto.
The blending ratio of the antioxidant (H) is 0.01 to 20 parts by mass, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the resin composition of the present invention. If it is less than 0.01 parts by mass, it will be consumed early by the active energy rays, and the polymerization rate may decrease. On the contrary, when it is more than 20 parts by mass, the polymerization rate is increased, but the molecular weight of the cured product is decreased, and the cohesive force as a three-dimensional model is decreased, so that the durability may be decreased.

<Color material (J)>
The resin composition of the present invention may contain a coloring material (J) in addition to the above components. By using the coloring material (J), when a three-dimensional model is formed, not only the design but also various functionalities such as thermal properties, electrical properties, and optical properties are imparted depending on the dyes and pigments contained. It becomes possible.

The coloring material (J) is used by dispersing dyes and pigments in a dispersion resin at a high concentration. As such dyes and pigments, for example, achromatic pigments such as carbon black, titanium oxide and calcium carbonate, or chromatic organic pigments and dyes can be used.
For example, organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, hanza ero, benzidine ero, and pyrazolone red.
Soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet, Permanent Red 2B,
Derivatives from vat dyes such as alizarin, indigo maroon, thioindigo maroon,
Phthalocyanine-based organic pigments such as phthalocyanine blue and phthalocyanine green,
Quinacridone organic pigments such as quinacridone red and quinacridone magenta,
Perylene-based organic pigments such as perylene red and perylene scarlet,
Isoindolinone-based organic pigments such as Isoindolinone Yellow and Isoindolinone Orange,
Pyranthron organic pigments such as Pyranthron red and Pyranthron orange, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments,
Kinophthalone-based organic pigments such as quinophthalone yellow,
Isoindoline organic pigments such as isoindoline yellow,
Examples of other pigments include organic pigments such as flavanthrone ero, acylamide ero, nickel azo ero, copper azomethine ero, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet.

For example, examples of the dye include an azo dye, a rhodamine dye, a quinoline dye, a thiazine dye, a thiazole dye, a xanthene dye, and a niglosin dye.
Any of these dye derivatives can be used without any particular problem.

Among the coloring materials (J), a general acrylic resin is used as the dispersion resin, and in some cases, a surfactant, the above-mentioned polymer (A), compound (B), compound (D), or oligomer. (E) and the like are also used in combination. For hue stabilization, it is preferable to use these polymers (A), compound (B), compound (D), or oligomer (E) in combination.
The dispersed resin is preferably used in the range of 10 to 60 parts by mass in terms of non-volatile content with respect to 100 parts by mass of the dye or pigment. When the polymer (A), the compound (B), the compound (D), or the oligomer (E) is used in combination, 100 to 800 parts by mass of the non-volatile content is equivalent to 100 parts by mass of the dye or pigment. It is preferable to use it within the range.
If the amount of the dispersed resin, the polymer (A), the compound (B), the compound (D), or the oligomer (E) is less than this range, the dispersion stability is lowered, and the dispersion stability and storage stability of the resin composition are reduced. May worsen. On the other hand, if it exceeds this range, the viscosity of the resin composition increases remarkably, which may adversely affect the storage stability of the resin composition, cause molding defects of the cured resin product, or affect the surface of the three-dimensional modeled product. Since migration occurs, the formability and strength of the three-dimensional model may also decrease.

If necessary, a polar resin can be used to stabilize the dispersion of dyes and pigments.
Examples of such polar resins include polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, poly (meth) acrylic acid, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, and styrene-maleic acid copolymer. , Styrene-maleic acid- (meth) acrylic acid alkyl ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate- (meth) acrylic acid copolymer, polystyrene sulfonic acid, sodium polystyrene sulfonate, styrene sulfonic acid -A hydrophilic vinyl-based copolymer resin such as maleic acid copolymer and polyitaconic acid;

For example, a polyester resin obtained by a polycondensation reaction of a polyvalent carboxylic acid and a polyol, in which the entire resin has a polar / non-polar balance due to the introduction of polar groups;
Cellulose derivatives such as methyl cellulose, ethyl cellulose, propyl cellulose, ethyl methyl cellulose, hydroxyalkyl cellulose, hydroxypropyl methyl cellulose, carboxymethyls cellulose, alkali metal carboxymethyl cellulose, alkali metal cellulose sulfate, cellulose graft polymer;
Polypeptides such as polyglutamic acid and polyaspartic acid;
Long-chain polyaminoamide and polar acid ester salt, long-chain polyaminoamide and high-molecular-weight acid ester salt, naphthalene sulfonic acid formarin condensate salt, stearylamine acetate and other amide ester salts;
Etc., but are not particularly limited to these. These can be used alone or in combination of two or more.

Examples of the polar resin commercially available as the dispersion resin include "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-203 / 204 (high molecular weight polycarboxylic acid salt)" manufactured by Abyssia. Disperbyk-101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl-containing carboxylic acid ester), 110, 111 (acid group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (high molecular weight copolymer) "," 400 "," Bykuman "(high molecular weight unsaturated acid ester)," BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) "," P104S, 240S (High molecular weight unsaturated acid polycarboxylic acid and silicon type) "," Lactimon (long-chain amine, unsaturated acid polycarboxylic acid and silicon) ".
In addition, "Fuka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766", "Fuka Polymer 100 (modified polyacrylate), 150 (aliphatic)" manufactured by Efka CHEMICALS. System-modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine), Kyoeisha Chemical Co., Ltd. "Floren TG-710 (urethane oligomer)," Fronon SH-290, SP-1000 "," Polyflow No. 50E, No. 300 (acrylic copolymer) ", Kusumoto Kasei Co., Ltd." Disparon KS-860, 873SN, 874 (polymer dispersant), # 2150 ( (Acrylic polyvalent carboxylic acid), # 7004 (polyether ester type) ”.

When a polar resin is used for the coloring material (J) of the present invention, the polar resin is preferably 0.1 to 80% by mass in the total amount of the coloring material (J). If the concentration is less than 0.1% by mass, it may not be possible to expect dispersion stabilization of the dye or pigment. On the other hand, if it is used in excess of 80% by mass, the modeling performance may be significantly reduced, or even if modeling is possible, the durability such as water resistance and moisture heat resistance of the three-dimensional model may be reduced.

<Additive (Q)>
In the resin composition of the present invention, various additives (Q) can be appropriately blended in addition to the above-mentioned components as long as the effects of the present invention are not impaired. For example, an organic or inorganic filler is blended from the viewpoints of reduction of polymerization curing shrinkage rate, reduction of coefficient of thermal expansion, improvement of dimensional stability, improvement of elastic modulus, viscosity adjustment, improvement of thermal conductivity, improvement of strength, improvement of toughness, improvement of coloring, etc. it can. As such a filler, a polymer, ceramics, metal, metal oxide, metal salt or the like can be used, and the shape is not particularly limited such as particulate or fibrous. In addition, when blending the above polymer, as a filler such as a flexibility imparting agent, a plasticizer, a flame retardant agent, a storage stabilizer, a thixotropy imparting agent, a dispersion stabilizer, a fluidity imparting agent, and a defoaming agent, It is also possible to dissolve, semi-dissolve or micro-disperse in the resin composition for optical three-dimensional modeling as a polymer blend or polymer alloy.

<Manufacturing of active energy ray-polymerizable resin composition>
The resin composition of the present invention contains the above-mentioned polymer (A) and compound (B) as essential components, and further, if necessary, compound (D), oligomer (E), photopolymerization initiator (F), and silane. It can be produced by blending the compound (G), the antioxidant (H), the colorant (J) and various other additives (Q), and then uniformly mixing them.

The active energy ray-curable resin composition for optical three-dimensional modeling in the present invention contains 1 to 20% by mass of the polymer (A) and 0.5 to 50% by mass of the compound (B1) in the total amount of the resin composition. It preferably contains 20 to 98.5% by mass of (B2), 1 to 15% by mass of the polymer (A), 1 to 40% by mass of the compound (B1), and 40 to 98% by mass of the compound (B2). It is more preferable to contain it. If the polymer (A) is 1% by mass or more in the total amount of the resin composition, it imparts a function (chain movement) of activating radicals whose activity has decreased due to polymerization inhibition by oxygen molecules during radical polymerization during light irradiation. By doing so, the curing rate is improved and the activated carbonate group is crosslinked (chemically bonded) with the compound (B), so that the curing shrinkage of the three-dimensional model can be reduced, and the flexibility and toughness are improved. Furthermore, the reactivation of radicals reduces the amount of photoinitiator (F) used, leading to a low yellow change in the three-dimensional model. Further, when the compound (B1) is 1% by mass or more, the curing speed can be expected to be improved by suppressing the curing inhibition due to the dissolved oxygen in the resin composition during photocuring, and sufficient cohesive force can be obtained. It is easy to be used, and the effect of improving heat resistance and moisture heat resistance can be expected. Further, when the resin composition is used as a stereolithography material, the curing shrinkage of the three-dimensional model can be reduced and the flexibility is improved. On the other hand, if the polymer (A) exceeds 20% by mass in the total amount of the resin composition, the viscosity of the resin composition is too high, and there is a concern that the strength and dimensional stability of the three-dimensional model may be lowered. .. If the compound (B1) exceeds 50% by mass, there may be a concern that the strength of the three-dimensional model and the moisture and heat resistance are lowered.

When the resin composition is stirred and mixed, it may be prepared by stirring and mixing using a general-purpose device such as a uniaxial or multiaxial extruder equipped with a decompression device, a kneader, and a solver. The temperature at the time of stirring and mixing is usually preferably set to 10 to 60 ° C. If the set temperature at the time of preparation is less than 10 ° C, the viscosity may be too high and uniform stirring / mixing work may be difficult. On the contrary, if the temperature at the time of preparation exceeds 60 ° C, a curing reaction due to heat occurs. In some cases, a normal resin composition may not be obtained.

The resin composition of the present invention can be used in any of liquid, paste and film forms.
The resin composition in the present invention preferably contains substantially no organic solvent, but it can also contain an organic solvent. For example, organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbon solvents, and water are further added. The viscosity of the resin composition for optical three-dimensional modeling can be adjusted, or the viscosity of the resin composition for optical three-dimensional modeling can be lowered by heating.

It is important that the resin composition in the present invention has a viscosity at 25 ° C. of 1 to 2000 mPa · s, preferably 10 to 1500 mPa · s, and more preferably 20 to 1000 mPa · s. If the viscosity is higher than 2000 mPa · s, when a cured resin product is formed, three-dimensional modeling cannot be performed and the hardness deteriorates. On the other hand, if the viscosity is lower than 1 mPa · s, it becomes difficult to control the dimensional stability of the cured wood resin.
Since the viscosity of the resin composition is mostly determined by the viscosities of the compound (B1) and the compound (B2), the viscosity of the resin composition can be controlled by controlling these viscosities in the range of 1 to 100,000 mPa · s. Can also be managed.

<Forming process of active energy ray-curable resin composition>
The resin composition of the present invention is suitably used as a curable liquid material in an optical three-dimensional modeling method. That is, by selectively irradiating a specific portion of this resin composition with light such as visible light, ultraviolet light, infrared light, etc. and supplying the active energy required for polymerization curing, a resin cured product having a desired shape can be obtained. A three-dimensional model can be obtained.
The light source for irradiating active energy rays is mainly light in the wavelength range of 150 to 550 nm. Low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, LED In addition to lamps, xenon lamps, metal halide lamps, and the like, semiconductor laser beams, electron beams, and the like can also be used as active energy rays for exposure. An ultraviolet laser beam is preferable in terms of cost, directivity, and convergence.
The irradiation intensity of the active energy ray is preferably 0.1 to 500 mW / cm ² . If the light irradiation intensity is less than 0.1 mW / cm ² , it takes a long time to cure, and if it exceeds 500 mW / cm ² , the uncured resin composition deteriorates due to the heat radiated from the lamp. There is. The integrated irradiation amount expressed as the product of the irradiation intensity and the irradiation time is preferably ¹ to 5,000 mJ / cm ² . If the cumulative irradiation amount is less than 1 mJ / cm ² , it takes a long time for polymerization curing, and if it is larger than 5,000 mJ / cm ² , the irradiation time becomes very long and the productivity may be deteriorated.

The method of selectively irradiating a specific portion of the resin composition with light, which is an active energy ray for such polymerization curing, is not particularly limited, and various methods can be used. For example, a method of irradiating a specific portion with focused light obtained by using a laser beam, a lens, a mirror, or the like, a method of irradiating unfocused light through a mask having a constant pattern, or the like can be adopted. However, when microfabrication or processing accuracy is required, it is desirable to minimize the magnitude of focused light, and in such a case, it is preferable to use laser light. Further, the specific portion of the resin composition to be irradiated with light may be the liquid surface of the resin composition placed in the container, the surface of the resin composition in contact with the side wall or the bottom wall of the container, or the liquid. To irradiate the liquid surface of the resin composition or the contact surface with the container wall, the light may be radiated directly from the outside or through a transparent vessel wall. When irradiating a specific part in the liquid, an optical fiber is used. Irradiation may be performed using a light guide body such as.

Further, in the above-mentioned stereolithography method, usually, after polymerizing and curing a specific portion of the resin composition, the irradiated position is continuously or stepwise moved from the already cured portion to the uncured portion. As a result, the cured portion can be grown into a desired three-dimensional shape. The irradiation position can be moved by various methods, for example, at least one of a light source, a container containing the resin composition, or a cured portion of the resin composition can be moved, or uncured in the container. It can be carried out by a method such as adding a resin composition (liquid curable substance) of.

<Three-dimensional model>
As a typical method for obtaining a three-dimensional model using the resin composition of the present invention, light is applied so that a cured layer having a desired pattern can be obtained on the liquid resin composition for optical three-dimensional modeling of the present invention. To form a cured layer by selectively irradiating the cured layer, and then irradiating the uncured composition layer adjacent to the cured layer with light in the same manner to form a new cured layer continuous with the previously formed cured layer. By repeating this laminating operation, a method of finally producing a desired three-dimensional shaped object can be mentioned. As a more specific aspect of this method, the following methods can be mentioned.

The formed three-dimensional model is taken out from the container used for the reaction, the unreacted compound remaining on the surface of the model is removed, and then washed if necessary. Examples of this cleaning agent include organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol, organic solvents typified by acetone, ethyl acetate, methyl ethyl ketone and the like, terpenes, and aliphatic typified by glycol ether esters. A low-viscosity liquid resin of an organic solvent, thermocurable or photocurable (meaning polymerization curability by light which is an active energy ray) can be used. Further, when it is desired to impart transparency to a three-dimensional model, it is desirable to use the thermosetting or photocurable liquid resin as a cleaning agent. In this case, depending on the type of resin used for cleaning, it is necessary to dry with heat or light (also referred to as post-cure) after cleaning. Since post-cure has the effect of not only curing the resin on the surface but also curing the unreacted resin composition that may remain inside the three-dimensional model, it is washed with an organic solvent. It is also preferable to carry out this case.

The cured product of the active energy ray-curable resin composition for optical three-dimensional modeling of the present invention is various three-dimensional modeling products such as for electronic products that require complicated and fine processing; for design examination of new products, for presentations, Models for advertising and exhibition; Development prototypes for performance testing and production aptitude confirmation; Can be preferably used as three-dimensional objects such as medical models for surgical simulation.

Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. Further, in Examples and Comparative Examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

Further, in the following examples, the molecular weight of the resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography), and a column using tetrahydrofuran as the eluent by GPC-8020 manufactured by Tosoh Corporation. Was measured using three TSKgel SuperHM-M (manufactured by Tosoh Corporation) at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.

The IR measurement was performed using a Spectrum One manufactured by PerkinElmer.

The NMR measurement was performed using JNM-ECX400 manufactured by JEOL Ltd.

<Production of Monomer Containing Cyclic Carbonate Group 1>
Put 10 parts of glycerin carbonate, 13 parts of triethylamine, 0.01 part of 4-methoxyphenol and 100 parts of tetrahydrofuran in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a gas introduction tube, and while injecting dry air into the vessel. After cooling to 0 ° C., 12 parts of acrylate chloride was added dropwise over 1 hour at the same temperature. After the completion of the dropping, NMR measurement was performed to confirm that the target product was produced. After cooling to room temperature, the precipitate was filtered, and tetrahydrofuran was distilled off and dried under reduced pressure to obtain Monomer 1 which is a monomer (a-1) containing a cyclic carbonate group.

<Production of Monomer Containing Cyclic Carbonate Group 2>
Put 25 parts of glycerin carbonate and 0.1 part of dibutyltin dilaurate in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube, and heat to 60 ° C. while injecting dry air into the vessel. At the same temperature, 30 parts of 2-isocyanatoethyl acrylate was added dropwise over 1 hour. After the completion of the dropping, IR measurement was performed to confirm that the peak derived from isocyanate was burnt out. After cooling to room temperature, it was taken out without dilution to obtain a monomer 2 which is a monomer (a-1) containing a cyclic carbonate group.

<Production of polymer solution A-1>
Place 150 parts of methyl ethyl ketone in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, and heat to 60 ° C. while injecting nitrogen gas into the container, and 90 parts of methyl methacrylate at the same temperature. A mixture of 10 parts of monomer 1 and 2.7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 60 ° C. for 1 hour, and then 0.3 part of 2,2'-azobis (2,4-dimethylvaleronitrile) dissolved in 3 parts of methyl ethyl ketone was added, followed by 3 hours. , Stirring was continued at the same temperature to obtain polymer A-1. By GPC measurement, the weight average molecular weight was 18,000. In addition, a peak around 1810 cm ^-1 derived from cyclic carbonate was observed by IR measurement.

<Production of polymer A-2>
Polymer A-2 was obtained in the same manner as in the production of polymer A-1, except that monomer 2 was used instead of monomer 1. By GPC measurement, the weight average molecular weight was 17,000. In addition, a peak around 1810 cm ^-1 derived from cyclic carbonate was observed by IR measurement.

<Production of polymer A-3>
Polymer A-3 was obtained in the same manner as in the production of polymer A-2, except that the amount of monomer 2 was 30 parts and the amount of methyl methacrylate was 70 parts. By GPC measurement, the weight average molecular weight was 16000. In addition, a peak around 1810 cm ^-1 derived from cyclic carbonate was observed by IR measurement.

<Production of polymer A-4>
Polymer A-4 was obtained in the same manner as in the production of polymer A-2, except that the amount of monomer 2 was 5 parts and the amount of methyl methacrylate was 95 parts. By GPC measurement, the weight average molecular weight was 19000. In addition, a peak around 1810 cm ^-1 derived from cyclic carbonate was observed by IR measurement.

<Manufacturing of polymer A-5>
Put 150 parts of methyl ethyl ketone in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, and heat to 60 ° C. while injecting nitrogen gas into the container, and 100 parts of methyl methacrylate at the same temperature. A mixture of 2.7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 60 ° C. for 1 hour, and then 0.3 part of 2,2'-azobis (2,4-dimethylvaleronitrile) dissolved in 3 parts of methyl ethyl ketone was added, followed by 3 hours. , Stirring was continued at the same temperature to obtain a polymer A-5 containing no carbonate group. By GPC measurement, the weight average molecular weight was 20000.

<Manufacturing of colored material (J) dispersion>
[Manufacturing Examples 1 and 2]
The compound (B2) and the dispersed resin are stirred, and after confirming that the dispersed resin is completely dissolved, a dye or a pigment is added, and the mixture is stirred with a high-speed mixer or the like until uniform, and then the obtained mill base is used. It was produced by dispersing in a horizontal sand mill for about 2 hours. Table 1 shows the composition (numerical values represent parts) of the produced color material (J) dispersion (pigment dispersion). In Table 1, blanks mean no compounding.

<Manufacturing of resin composition>
[Examples 1 to 35, Comparative Examples 1 to 3]
Compound (A), compound (B1) and compound (B2) are added as essential components in a light-shielded 300 ml mayonnaise bottle in which the oxygen concentration is substituted to 10% or less, and compound (D) and oligomer are added as necessary. (E), active energy ray polymerization initiator (F), silane compound (G), antioxidant (H), coloring material (J) and various additives (Q) were charged in the ratios shown in Table 2 and placed in a stirrer. The resin compositions of Examples 1 to 35 and Comparative Examples 1 to 3 were obtained by sufficiently stirring and sufficiently defoaming.

<Appearance and viscosity of resin composition>
The appearance and viscosity (mPa · s) of the obtained resin composition were determined according to the following method, and the results are shown in Table 2.
"appearance"
The liquid appearance of the resin composition was visually evaluated.
"viscosity"
Using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) in an atmosphere of 23 ° C., about 1.2 ml of the resin composition was used as a measurement sample, and the rotation speed was 0.5 to 100 rpm for 1 minute. Was measured and used as the solution viscosity (mPa · s).

The details of the abbreviations in Table 2 are as follows. In addition, the symbol "-" means no compounding.

<Evaluation of resin composition for optical three-dimensional modeling>
[Examples 36 to 70, Comparative Examples 4 to 6]
The obtained resin composition was subjected to a molding test by measuring the curing rate, Young's modulus, swelling degree, warpage, and surface slipperiness by the following methods. The results are shown in Table 4.

《Curing speed》
Using an applicator, a resin composition is applied to a glass plate to a thickness of 10 μm, and the light of a mercury-xenon lamp UXM-200YA manufactured by Ushio Electric Co., Ltd. is selectively transmitted to this coating film only to light of 405 nm. Irradiation was performed at 0.1 J / cm ² through a band pass filter and an ND filter for adjusting the amount of light. The tack of the membrane after light irradiation was evaluated by palpation on a three-point scale. If the evaluation is other than "x", there is no particular problem in actual use.
○: No tack △: Slightly tacky ×: Tacky

"Young's modulus"
The resin composition was applied to a glass plate to a thickness of 250 μm using an applicator, and irradiated with ultraviolet rays of 0.3 J / cm ² (wavelength: 405 nm) to obtain a cured film. Next, the cured film was peeled off from the glass plate, and the state was adjusted at 23 ° C. and 50% relative humidity for 24 hours to prepare a test piece. The measurement was performed in a constant temperature and humidity chamber at 23 ° C. and a relative humidity of 50%. The Young's modulus of the test piece was measured under the conditions of a tensile speed of 1 mm / min and a distance between marked lines of 25 mm.
This Young's modulus was evaluated on a 4-point scale. If the evaluation is other than "x", there is no particular problem in actual use.
⊚: 120 (kg / mm ² ) or more. No problem at all.
◯: 100 (kg / mm ² ) or more and less than 120 (kg / mm ² ). Slightly weak, but no problem.
Δ: 80 (kg / mm ² ) or more and less than 100 (kg / mm ² ). Practically usable.
X: Less than 80 (kg / mm ² ). There is a problem in practical use.

《Swelling degree》
Using a stereolithography device (Solid Creator JSC-2000: manufactured by Sony Corporation) using an Ar ion laser (wavelength 351 and 385 nm) as a light source, molding is performed at a laser power of 40 mW at the liquid surface and a scanning speed of 100 cm / min. A test piece [(width 50 mm × length 50 mm × height 1 mm): one-time lamination thickness 0.2 mm × five-time lamination] was used. After carefully wiping off the adhering resin liquid, the mass W ₁ of the plate was measured. Next, the test piece was immersed in a resin solution at 25 ° C. for 24 hours, the adhered resin solution was wiped off, and then the mass W ₂ was measured.
The degree of swelling was calculated by the following formula and evaluated in three stages. If the evaluation is other than "x", there is no particular problem in actual use.
Swelling degree (%) = [(W _2- W ₁ ) / W ₁ ] x 100
◯: Less than 2 (%). No problem at all.
Δ: 2 (%) or more and less than 5 (%). Practically usable.
×: 5 (%) or more. There is a problem in practical use.

"warp"
Using the above-mentioned stereolithography apparatus, the test piece is molded at a laser power of 40 mW at the liquid surface and a scanning speed of 100 cm / min [(width 50 mm × length 50 mm × height 40 mm): one-time stacking thickness 0.2 mm. × 100 times laminated]. After wiping off the adhered resin solution, post-cure was performed using a UV lamp (irradiation dose: 5 J / cm ² , wavelength: 365 nm). Next, one of the test pieces was fixed to a horizontal table, and the warp was evaluated by the lift amount Δh (mm) of the other end.
This warpage was evaluated on a 4-point scale. If the evaluation is other than "x", there is no particular problem in actual use.
⊚: Less than 0.2 (mm). No problem at all.
◯: 0.2 (mm) or more and less than 0.5 (mm). There are some, but there is no problem.
Δ: 0.5 (mm) or more and less than 1.0 (mm). Practically usable.
X: 1.0 (mm) or more. There is a problem in practical use.

《Surface slipperiness》
The resin composition was applied to a glass plate to a thickness of 250 μm using an applicator, and irradiated with ultraviolet rays of 0.3 J / cm ² (wavelength: 405 nm) to obtain a glass laminated cured film, 23 ° C., 50% relative humidity. The condition was adjusted for 24 hours with a test piece. A scratch resistance test was conducted by rubbing the test piece with # 0000 steel wool 10 times while applying a load of 250 g / cm ² in a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity. It was. The presence or absence of scratches and the degree of scratches were visually observed and used as an index of surface activity.
The evaluation was performed in 4 stages. If the evaluation is other than "x", there is no particular problem in actual use.
⊚: No scratches. No problem at all.
◯: 5 or less scratches occur. There are some, but there is no problem.
Δ: 6 to 10 scratches occur. Practically usable.
X: Innumerable scratches occur. There is a problem in practical use.

In Table 4, "curing rate" evaluates the rate of polymerization rate. If the reaction rate is slow and there are residual double bonds, tack remains on the membrane even after light irradiation. "Young's modulus" evaluates the strength and hardness of the cured product. "Swelling degree" evaluates the degree of cross-linking of the resin. When the degree of cross-linking of the resin is high, the resin is suppressed from entering the cured product, resulting in a low degree of swelling. "Warp" evaluates the curing shrinkage rate. The smaller the warp, the more the resin composition suppresses curing shrinkage. "Surface slipperiness" evaluates the surface hardness of the cured product.

When the resin composition for optical three-dimensional modeling of the present invention is polymerized and cured with active energy rays, it exhibits an excellent curing rate as shown in Table 4, and has Young's modulus, swelling degree, warpage, and surface slipperiness. Excellent results were shown in all items (Examples 36 to 70). In particular, the best results were shown when the compositions of Examples 5, 6, 25, 28-31 were used (Examples 40, 41, 60, 63-66). On the other hand, when a resin composition for optical three-dimensional modeling other than the present invention is polymerized and cured by an active energy ray, there is a difficulty in any one of curing speed, Young's modulus, swelling degree, warpage, and surface slipperiness. It turns out that it is difficult to use. Among them, in Comparative Examples 4 to 6 to which the polymer A was not added, the effect of promoting curing by regenerating the active radical by the chain transfer of the cyclic carbonate group and the toughness by the three-dimensional cross-linking utilizing the carbonate group. No effect such as granting can be obtained, and a satisfactory result cannot be obtained.

Claims (6)

A polymer (A) obtained by radical polymerization of a monomer (a-1) containing a cyclic carbonate group and a monomer (a-2) excluding (a-1), and a radically polymerizable compound (B). ) And an active energy ray-curable resin composition for optical three-dimensional modeling. The radically polymerizable compound (B) comprises an acryloyl group or a methacryloyl group-containing compound (B1) having one or more hydroxyl groups in the molecule.
The active energy ray-curable resin composition for optical three-dimensional modeling according to claim 1, which contains an acryloyl group or a methacryloyl group-containing compound (B2) having no hydroxyl group in the molecule. The acryloyl group or methacryloyl group-containing compound (B1) having one or more hydroxyl groups in the molecule is characterized by containing an acryloyl group or methacryloyl group-containing compound (b1) having a hydroxyl group and having no cyclic structure. The active energy ray-curable resin composition for optical three-dimensional modeling according to claim 2. The acryloyl group or methacryloyl group-containing compound (B1) having one or more hydroxyl groups in the molecule is characterized by containing an acryloyl group or methacryloyl group-containing compound (b2) having a hydroxyl group and having a cyclic structure. The active energy ray-curable resin composition for optical three-dimensional modeling according to claim 2 or 3. The active energy ray-curable resin composition for optical three-dimensional modeling according to any one of claims 1 to 4, further comprising an oligomer (E). The optical three-dimensional modeling according to any one of claims 1 to 5, wherein the polymer (A) is contained in an amount of 1 to 20% by mass in the total amount of the active energy ray-curable resin composition for optical three-dimensional modeling. Active energy ray curable resin composition for use.