JP2018100350A - Active energy ray polymerizable resin composition for optical stereoscopic molding, and stereoscopic molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cured product having less deformation during molding such as warpage and swelling and having excellent toughness, and an active energy ray-curable resin composition for optical three-dimensional molding having an excellent curing rate. Is to provide. Another object of the present invention is to provide a cured product of the composition. SOLUTION: A polymer (A) obtained by radically polymerizing a monomer (a-1) containing a sterol skeleton and a monomer (a-2) excluding (a-1) is contained in a molecule. Active energy ray for optical three-dimensional modeling containing an acryloyl group or methacryloyl group-containing compound (B1) having one or more hydroxyl groups and an acryloyl group or methacryloyl group-containing compound (B2) having no hydroxyl group in the molecule. Curable resin composition. [Selection diagram] None

Description

  The present invention is an optical three-dimensional modeling that provides a three-dimensional modeled article that has a low viscosity in an uncured state, a high curing rate by active energy ray irradiation, 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.

In addition to various characteristics such as fast polymerization rate, good workability due to the absence of solvent, energy saving of extremely low energy requirements, active energy ray polymerization technology has recently reduced environmental pollution due to environmental pollution problems. Therefore, the field of use is expanding in the fields of building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical devices, displays, and the like.
These contain only a resin that can be polymerized with active energy rays and a monomer having an α, β-unsaturated double bond group, and since the monomer also functions as a solvent, a coating film or a molded product is formed. This is because sometimes the solvent does not volatilize. And as this resin having active energy ray polymerizability, it has an α, β-unsaturated double bond group at the molecular terminal of a low molecular weight polyester resin, polyurethane resin, polyepoxy resin, polyacrylic resin, etc. Oligomers and monomers having an α, β-unsaturated double bond group are used.

In recent years, as a method for producing resin molded products, an ultraviolet laser, which is a kind of active energy ray, is obtained by using a liquid photocurable resin composition 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 (optical modeling method) for producing a molded product by selectively polymerizing and curing with light is used.
Compared to conventional cutting, this stereolithography method can deal with complex shapes that are difficult to cut, is a fully automated process, is easy to handle, has a short manufacturing time, and is advantageous in terms of cost. In addition to the production of resin products, it has come to be widely used in the manufacture of prototype models and medical models for design studies, performance tests, advertisements, and the like.
As a representative example of this three-dimensional modeling method, light, for example, a kind of active energy ray, is obtained so that a polymerization cured layer having a desired pattern is obtained on the liquid surface of the liquid photocurable resin composition placed in a container. Is selectively irradiated with ultraviolet laser light to obtain a polymerized cured layer, and then a liquid photocurable resin composition is supplied on the cured layer in a layered manner, and then the light is selectively irradiated as described above. Irradiation forms a cured polymer layer that is continuous with the cured layer. This is a method of finally obtaining a desired three-dimensional modeled object by repeating this lamination operation. This three-dimensional modeling method is attracting attention because even if the shape of a model to be manufactured is complicated, the target model can be easily obtained in a short time.

  As the optical three-dimensional modeling method, for example, as disclosed in Patent Document 1, the energy supply necessary for the liquid photocurable resin composition is selectively performed to form a three-dimensional modeled object having a desired shape. Is the method. Such a method or an improved technique thereof is disclosed in Patent Documents 2 and 3.

  As a photocurable resin composition used for the above-mentioned optical modeling, from the viewpoint of efficient optical modeling, it is possible to quickly form a smooth liquid surface with low viscosity, transparency and good photocuring. It is required to have sex. In addition, there is a problem that the cured product is deformed over time (warping, shrinkage, lifting of the protruding portion, etc.) due to residual distortion caused by shrinkage (curing shrinkage) during polymerization curing by light. Small deformation over time is required. Furthermore, 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, from the viewpoint of transparency, photocurability, etc., radically polymerizable compounds such as urethane (meth) acrylate, epoxy (meth) acrylate, photosensitive polyimide (for example, patents) 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 complication of target products, the demand for dimensional accuracy has become increasingly severe, and the temporal deformation characteristics of the resin composition cannot satisfy the demand.
Furthermore, Patent Document 7 discloses a photocurable liquid composition containing fine hollow spheres whose absolute value of the difference in refractive index from an ethylenically unsaturated monomer or photoinitiator is not 0. It is described that the transparency of the ionic liquid composition is reduced. Furthermore, Patent Document 8 discloses a radiation curable resin composition containing a color former, and a three-dimensional article produced from the radiation curable resin composition exhibits different colors before and after curing. Is described.
However, the cured resin obtained by curing the above resin composition does not satisfy all the requirements for toughness, water resistance, physical property stability, and suppression of deformation over time.

JP 60-247515 A JP 62-035966 (US Pat. No. 4,575,330) JP 62-101408 A JP-A-2-228312 JP-A-5-279436 JP-A-1-213304 Japanese Patent No. 2648222 JP 2005-510603 A

  The present invention makes it possible to obtain a cured product with less deformation during molding such as warping and swelling, and excellent toughness by utilizing the extremely high cohesive force of the sterol structure, and an excellent curing rate. It is providing the active energy ray-curable resin composition for optical three-dimensional modeling which has. Moreover, it aims at providing the hardened | cured material of this composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that the target can be achieved by the active energy ray-curable resin composition for optical three-dimensional modeling shown below. It came to be completed.

That is, the present invention relates to a monomer (a-1) containing a sterol skeleton, a polymer (A) obtained by radical polymerization of a monomer (a-2) excluding (a-1), a radical, An active energy ray-curable resin composition for optical three-dimensional modeling containing a polymerizable compound (B),
Active energy ray-curable resin composition for optical three-dimensional modeling, wherein the monomer (a-1) containing a sterol skeleton contains at least one of monomers represented by the following general formulas (1) to (4) About.

General formula (1)

General formula (2)

General formula (3)

[式中、実線と点線の二重線は、それぞれ独立に二重結合または単結合を表し、隣接する実線と点線の二重線が同時に二重結合となることはない。
Ｒ₁〜Ｒ₃は、水素原子またはメチル基を表し、
Ｌは、水素原子、炭素原子、酸素原子、窒素原子、および硫黄原子から選ばれる任意の組合せからなる分子量４００以下の連結基を表し、
Ｒ₄は、酸素原子、あるいは、水素原子、炭素原子、および酸素原子から選ばれる任意の組合せからなる分子量２００以下の置換基を表す。] General formula (4)

[In the formula, the solid and dotted double lines each independently represent a double bond or a single bond, and the adjacent solid and dotted double lines do not form a double bond at the same time.
R _{1 to} R ₃ represent a hydrogen atom or a methyl group,
L represents a linking group having a molecular weight of 400 or less composed of any combination selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom;
R ₄ represents an oxygen atom or a substituent having a molecular weight of 200 or less composed of any combination selected from a hydrogen atom, a carbon atom, and an oxygen atom. ]

  In the present invention, the radical polymerizable compound (B) contains an acryloyl group or methacryloyl group-containing compound (B1) having one or more hydroxyl groups in the molecule, and an acryloyl group or methacryloyl group having no hydroxyl groups in the molecule. The active energy ray-curable resin composition for optical three-dimensional modeling, comprising the compound (B2).

  Further, in the present invention, the proportion of the structural unit having a sterol skeleton in the polymer (A) is 25 to 100% by weight in 100% by weight of the polymer (A). The present invention relates to a functional resin composition.

  The present invention also provides an acryloyl group or methacryloyl group-containing compound (b1) having an acryloyl group or methacryloyl group having one or more hydroxyl groups in the molecule and having no hydroxyl group and no cyclic structure. It contains about the said active energy ray curable resin composition for optical three-dimensional modeling characterized by containing.

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

  Moreover, this invention relates to the said active-energy-ray-curable resin composition for optical three-dimensional model | molding characterized by containing oligomer (E) (except when becoming (A)).

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

  Furthermore, this invention relates to the three-dimensional molded item consisting of the said hardened | cured material.

  According to the present invention, there is little deformation at the time of molding such as warping and swelling, and it is possible to produce a highly accurate shaped article by an optical three-dimensional shaping method, and since the mechanical properties of the polymerized cured product are excellent, The shaped article can provide an active energy ray-curable resin composition for optical three-dimensional shaping that can 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 the present application, when expressed as `` (meth) acryloyl '', `` (meth) acrylic acid '', `` (meth) acrylate '', and `` (meth) acryloyloxy '', unless otherwise specified, It is intended to represent “acryloyl and / or methacryloyl”, “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, which includes a monomer (a-1) containing a sterol skeleton and a monomer (a-2) excluding (a-1) And a radically polymerizable compound (B).
Here, the “active energy ray” means an energy ray in a broad sense that can provide energy necessary 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 upon irradiation with the active energy ray to form a cured product. Although it does not specifically limit, In one Embodiment of this invention, it is preferable that the said active energy ray is light energy containing an ultraviolet-ray.
Hereinafter, each component which comprises the resin composition of this invention is explained in full detail.

<Polymer (A)>
First, the polymer (A) of the present invention will be described. The polymer (A) of the present invention has a sterol skeleton exhibiting a very high cohesive force and can incorporate monomers having different physical properties easily and with high purity. To produce a three-dimensional structure that is highly elastic and has excellent surface lubricity due to dimensional stability because it can maintain the balance of cohesive force (hardness and flexibility) and suppress polymerization hardening shrinkage. Can do.

  The polymer (A) of the present invention is not particularly limited as long as it is a resin containing a sterol skeleton, and examples of the resin form include acrylic resin, polyurethane resin, polyurea resin, polyester resin, polyamide resin, polyimide resin, polyolefin resin, and the like. And a resin structure in which a sterol skeleton is incorporated into a known resin skeleton or a composite resin skeleton thereof by a covalent bond. Among these, from the viewpoint of easy adjustment of the introduction amount of the sterol skeleton into the resin skeleton and compatibility with the radical polymerizable compound (B), it is preferable to contain at least an acrylic polymer incorporating the sterol skeleton.

  Examples of the sterol skeleton include, but are not limited to, for example, campesterol, β-sitosterol, stigmasterol, brassicasterol and phytosterol, which is a mixture of the four, cholesterol, lanosterol, ergosterol, and β-cholesteral. , A structure derived from a sterol compound such as dehydroepiandrosterone, coprostanol, pregnenolone, epicholestanol, and 7-dehydrocholesterol, and specific examples include structures represented by the following general formulas (5) to (9). Can be mentioned.

General formula (5)

General formula (6)

General formula (7)

General formula (8)

[一般式（５）〜（９）中、Ｘは酸素原子または水素原子、炭素原子、酸素原子から選ばれる任意の組合せからなる分子量２００以下の置換基を、＊印は樹脂との連結点をそれぞれ表す。] General formula (9)

[In the general formulas (5) to (9), X represents a substituent having a molecular weight of 200 or less composed of any combination selected from an oxygen atom, a hydrogen atom, a carbon atom, and an oxygen atom, and * represents a connecting point with the resin. Represent each. ]

  X is not particularly limited as long as it is a substituent having a molecular weight of 200 or less and comprising any combination selected from an oxygen atom, a hydrogen atom, a carbon atom, and an oxygen atom. For example, straight chain or branched alkyl group, straight chain or branched alkenyl group Group, alkylcarbonyl group and the like.

  Examples of the polymer (A) containing at least an acrylic polymer include a resin composed only of an acrylic polymer and / or a composite resin in which an acrylic polymer and another resin are bonded. Examples of the resin composed only of an acrylic polymer include a copolymer of a monomer containing a monomer (a-1) containing a sterol skeleton, and an acrylic polymer obtained by modifying an acrylic polymer having no sterol skeleton with a sterol skeleton. Etc. These may be block resins or graft resins of an acrylic polymer having a sterol skeleton and an acrylic polymer not having a sterol skeleton. The composite resin in which the acrylic polymer and other resin are bonded is not particularly limited, but preferably has a sterol skeleton at the acrylic polymer site. Specifically, after introducing a reactive group at the initiation terminal or polymerization terminal of an acrylic polymer having a sterol skeleton using an initiator or a chain transfer agent having a reactive group such as a hydroxyl group or a carboxyl group, condensation is performed. Examples thereof include graft resins linked to other resins by reaction.

  As the proportion of the structural unit having a sterol skeleton (the proportion of the structure derived from the monomer (a-1) containing a sterol skeleton out of the structure derived from the monomer constituting the polymer), the polymer (A) is When it consists only of an acrylic polymer, Preferably it is 25 to 75 weight% in 100 weight% of acrylic polymers, More preferably, it is 30 to 70 weight%. It is possible to make compatible the high cohesion force derived from a sterol skeleton, and the compatibility with a radically polymerizable compound (B) as it is in the said range.

  When the polymer (A) is composed of a composite resin in which an acrylic polymer having a sterol skeleton and another resin are linked, the proportion of the structural unit having a sterol skeleton in the acrylic polymer is preferably 100% by weight of the acrylic polymer. It is preferably 25 to 100% by weight, and preferably contains 5 to 75% by weight of a structural unit having a sterol skeleton in 100% by weight of the composite resin.

  Further, the ratio of the composite resin is not particularly limited, but preferably, the acrylic polymer having a sterol skeleton is 5 to 75% by weight in 100% by weight of the composite resin. The other resin may contain a sterol skeleton, and is preferably 0 to 25% by weight in 100% by weight of the other resin.

A preferred specific example of the acrylic polymer having a sterol skeleton is a copolymer of the monomer (a-1) containing a sterol skeleton and the monomer (a-2) excluding (a-1). .
The monomer (a-1) containing a sterol skeleton has a sterol skeleton and an ethylenically unsaturated bond in the same compound, and is represented by any one of the general formulas (1) to (4) ( It contains at least one monomer having a (meth) acryloyl group or a styrene group.

General formula (1)

General formula (2)

General formula (3)

General formula (4)

In the general formulas (1) to (4), the solid and dotted double lines each independently represent a double bond or a single bond, R _{1 to} R ₃ are hydrogen atoms or methyl groups, L is a hydrogen atom, carbon A linking group having a molecular weight of 400 or less composed of an arbitrary combination selected from an atom, an oxygen atom, a nitrogen atom and a sulfur atom, R ₄ is a molecular weight of 200 selected from an oxygen atom, a hydrogen atom, a carbon atom and an oxygen atom. Each of the following substituents is represented.
Specific examples of R ₄ include an oxygen atom, a linear or branched alkyl group, a linear or branched alkenyl group, and an alkylcarbonyl group.
Specific examples of L include, for example, an alkylene group having 1 to 8 carbon atoms, an ethylene oxide group having 1 to 4 repeating units, a propylene oxide group having 1 to 4 repeating units, a urethane bond, or these substituents. Combinations are mentioned, and —CH ₂ CH ₂ NHCO— is particularly preferable from the viewpoint of synthesis.

  The monomer (a-1) containing a sterol skeleton can be obtained by introducing a (meth) acryloyl group or a styrene skeleton into a sterol compound. The introduction method is not limited to the following examples. For example, a sterol compound, (meth) acrylic acid chloride, (meth) acrylic acid 2-isocyanatoethyl, α, α-dimethyl-3-isopropenylbenzyl isocyanate And a method of condensing a (meth) acryloyl group-containing compound or a styrene group-containing compound having a functional group capable of reacting with a hydroxyl group in a sterol compound in a solvent.

  The monomer (a-2) other than the monomer (a-1) containing a sterol skeleton is not particularly limited as long as it is a monomer having a copolymerizable ethylenically unsaturated bond.

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl ( Alkyl (meth) acrylates such as (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate;
Carboxyalkyl (meth) acrylates such as 2-carboxylethyl (meth) acrylate;
Dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dibutylaminoethyl Aminoalkyl (meth) acrylates such as (meth) acrylate and dihydroxyethylaminoethyl (meth) acrylate;
Dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminobutyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminoethyl (meth) acrylamide, dibutylaminoethyl Aminoalkyl (meth) acrylamides such as (meth) acrylamide and dihydroxyethylaminoethyl (meth) acrylamide; having an alkylene oxide chain such as polyalkylene glycol mono (meth) acrylate and polyalkylene glycol mono (meth) acrylate monoalkyl ether (Meth) acrylates;
Lactone modified (meth) acrylates such as Plaxel FM5, Plaxel FA10L (above, manufactured by Daicel) under the product name;
By product name, polydimethylsiloxane (meth) acrylates such as Silaplane FM-0711 and Silaplane FM-0721 (above, manufactured by Chisso Corporation);
By product name, Cheminox FAAC-4, Cheminox FAAC-6, Cheminox FAMAC-4, Cheminox FAMAC-6 (above, manufactured by Unimatec), R-1110, R-1210, R-1420, R-1620, R-5210 R-5410, R-5610, M-1110, M-1210, M-1420, M-1620, M-5210, M-5410, M-5610 (manufactured by Daikin), light acrylate FA-108 ( Fluorine-containing (meth) acrylates such as Biscoat-3F, Biscoat-3FM, Biscoat-4F, Biscoat-8F, Biscoat-8FM (above, Osaka Organic Chemical Industry Co., Ltd.);
By product name, macromonomer AA-6 (methyl methacrylate macromonomer), macromonomer AB-6 (butyl (meth) acrylate macromonomer), macromonomer AW-6S (isobutyl (meth) acrylate macromonomer), macro Monomer AY-707S (2-ethylhexyl (meth) acrylate / hydroxyethyl (meth) acrylate macromonomer), macromonomer AS-6 (styrene macromonomer), macromonomer AN-6S (styrene / acrylonitrile macromonomer), Vinyl copolymer macromonomers such as macromonomer AK-5 (dimethylsiloxane macromonomer) (manufactured by Toagosei Co., Ltd.);
Acrylic acid multimer type (meth) acrylates such as biscoat # 150D (tetrahydrofurfuryl alcohol oligoacrylate) and biscoat # 190D (ethoxydiethylene glycol oligoacrylate) (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.);
Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethoxyethyl (meth) Various (meth) acrylates such as acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, styrene, maleic anhydride Etc.
These monomers (a-2) may be used individually by 1 type, and may be used in combination of 2 or more type.

  As a weight average molecular weight of an acrylic polymer, it is a standard polystyrene conversion value by gel permeation chromatography (GPC), Preferably it is 3,000-300,000, More preferably, it is 5,000-150,000. When the weight average molecular weight is 3,000 or more, good pigment dispersibility tends to be obtained. When the weight average molecular weight is 300,000 or less, the viscosity can be easily controlled.

  When the acrylic polymer has a carboxyl group or an amino group, an organic amine, an inorganic salt, an alkyl chloride, an inorganic acid, an organic acid, etc. may be used for the purpose of adjusting solubility in a solvent and pigment dispersibility. Can be used after neutralization or quaternary chlorination.

  Examples of organic amines include, but are not limited to, ammonia, dimethylaminoethanol, diethanolamine, triethanolamine, dibutylamine, triethylamine octylamine, dodecylamine, tetradecylamine, hexadecylamine, polyoxyalkyleneamine, and the like. It is done.

  Examples of the inorganic salt include, but are not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.

  Examples of the alkyl chloride include, but are not limited to, methyl chloride and ethyl chloride.

  As an inorganic acid, although not limited to the following examples, hydrochloric acid etc. are mentioned.

  Examples of the organic acid include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, acetic acid, formic acid, propionic acid, and the like.

  There is no restriction | limiting in particular as a manufacturing method of an acrylic polymer, For example, it can obtain by polymerizing said monomer by well-known radical polymerization reaction. Although the reaction may be carried out in the absence of a solvent, it is preferable to use a solvent from the viewpoint of synthesis stability and handling. From the viewpoint of molecular weight control, it is preferable to use a radical polymerization initiator (hereinafter sometimes abbreviated as “polymerization initiator”). In addition, you may use well-known additives, such as a chain transfer agent.

  Examples of the solvent include, but are not limited to, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, toluene, xylene, anisole, isopropanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like. Can be mentioned. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the polymerization initiator include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxydicarbonate. Tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, Organic peroxides such as diacetyl peroxide,
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis ( Azo compounds such as 4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Can be mentioned. These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.

Furthermore, a chain transfer agent may be used for the purpose of adjusting the molecular weight of the acrylic polymer. Examples of the chain transfer agent include thioglycerol, alkyl mercaptans such as octyl mercaptan, nonyl mercaptan, decyl mercaptan, dodecyl mercaptan,
Thioglycolic acid esters such as octyl thioglycolate, nonyl thioglycolate, 2-ethylhexyl thioglycolate, 2,4-diphenyl-4-methyl-1-pentene, 1-methyl-4-isopropylidene-1- Examples include cyclohexene, α-pinene, and β-pinene.
Among these, thioglycerol can be preferably used when it is combined with another resin because it can introduce two reactive hydroxyl groups at the starting end of the acrylic polymer.

  Although it does not specifically limit as other resin compounded with an acrylic polymer, A polyurethane resin, a polyurea resin, a polyester resin etc. are mentioned as a preferable specific example among the resin illustrated above. There are no particular restrictions on the method of conjugating the acrylic polymer with a different resin form, and any known conjugation method can be used. For example, a reactive hydroxyl group is formed at the starting end obtained by polymerizing thioglycerol with a chain transfer agent. A method of condensing a diisocyanate and a polyol to form a urethane acrylic composite resin, or having two reactive hydroxyl groups at the starting terminal obtained by polymerization using thioglycerol as a chain transfer agent Examples thereof include a method in which an acrylic polymer, a polyfunctional acid anhydride, and a polyester resin are subjected to a condensation reaction.

  Examples of the diisocyanate include, but are not limited to, aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and the like, for example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (also known as: MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane -1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhe Samethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate , Norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis-chloromethyl-diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride and dicarboxylic acid carboxyl groups as isocyanate groups Examples thereof include converted dimer isocyanate. These diisocyanates may be used individually by 1 type, and may be used in combination of 2 or more type.

  The polyol is not limited to the following examples, but known polymer diols such as polyether polyol, polyester polyol, polycarbonate polyol, etc., as well as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol. 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, , 3-alkanediol, 1-mono Riseraido, 2-monoglyceride, 1 monoglycerol ether, 2-mono-glycerol ether, dimer diol, include low molecular diols such as hydrogenated dimer diol.

  Examples of the polyether polyol include, but are not limited to, the following examples: polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polyoxytetramethylene glycol, and copolymerized polyether diols thereof.

  The polyester polyol or polyester resin is not limited to the following examples. For example, a condensate obtained by an esterification reaction between a dibasic acid and the low molecular diol, and caprolactone obtained using the low molecular diol as an initiator. Examples thereof include a polymer, a valerolactone polymer, a methyl valerolactone polymer, a lactic acid polymer, and a castor oil fatty acid polymer.

  The dibasic acid is not limited to the following examples. For example, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid And dibasic acids such as sebacic acid, suberic acid, glutaric acid, 1,4-cyclohexyl dicarboxylic acid, dimer acid and hydrogenated dimer acid.

  The polyfunctional acid anhydride is not particularly limited as long as it is a compound having two or more carboxylic anhydride groups generated by dehydration condensation of two carboxyl groups in the molecule. For example, pyromellitic anhydride, benzophenone tetra Carboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic acid Dianhydride, naphthalenetetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA-10", "Ricacid MTA-15", "Ricacid TMEG series", "Ricacid TDA", etc. Is mentioned.

<Radically 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 bonding between molecules works, and the cohesive strength and cross-linking degree of the resin composition can be improved, which is effective for improving heat resistance, heat and humidity resistance, and thermal dimensional stability as a three-dimensional model. Show.

On the other hand, by containing the compound (B2) in the resin composition, it is easy to increase the efficiency and sensitivity of the copolymerization reaction with the compound (B1). A high cured product can be formed. In addition, the viscosity of the resin composition can be easily reduced, and the workability during modeling can be easily improved.
By blending in a timely manner so that both the compound (B1) having a hydroxyl group and the compound (B2) not having a hydroxyl group are contained, polymerization curability by irradiation with active energy rays, cure shrinkage of a three-dimensional structure, and It can be set as a resin composition favorable in durability, such as heat resistance, heat-and-moisture resistance, and water resistance.

  As the compound (B1), any compound containing one or more hydroxyl groups and one or more acryloyl groups or methacryloyl groups in the structure thereof 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. It shows a great effect in reducing cure shrinkage associated with the reaction.

[Compound (b1) having a hydroxyl group and no cyclic structure]
Of the acryloyl group or methacryloyl group-containing compound (B1) having one or more hydroxyl groups in the molecule, examples of the compound (b1) having a hydroxyl group and not having a cyclic structure include (meth) acrylic acid 2- Hydroxyethyl, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-methacrylic acid 2- Hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) Acrylic acid ester, (meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12-hydroxyl An acryloyl group having the hydroxyl group such as ryl, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional (glycerol) methacrylate, or 2- (acryloyloxy) ethyl 6-hydroxyhexanoate, or (Meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the methacryloyl group-containing compound, or ethylene to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound Hydroxyl group-containing aliphatic (meth) acrylic acid esters such as alkylene oxide addition (meth) acrylic acid esters obtained by repeatedly adding alkylene oxides such as oxide, propylene oxide, butylene oxide;

  For example, hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. (Meth) acrylamides; and the like, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

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

[Compound (b2) having a hydroxyl group and a cyclic structure]
Of 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, even if it has a hydroxyl group, it is preferable from the viewpoint of water resistance in addition to durability such as heat resistance and moist heat resistance.

  Examples of the compound (b2) include (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, ) 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, monohydroxyethyl phthalate (meth) acrylate, 2- (meth) acrylic acid 2- ( 4-benzoyl-3-hydroxyphenoxy) having a cyclic structure other than a hydroxyl group such as ethyl and a heterocyclic ring (Meth) acrylic acid esters;

  For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Hydroxyl-containing benzophenone-based (meth) acrylic 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 -3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole Triazole (meth) acrylic acid esters;

  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) acryloyloxyate Xyl}]-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 and other hydroxyl group-containing triazine-based (meth) acrylic acid esters However, it is not particularly limited to these. These may use only 1 type or may use multiple types together.

  As the compound (b2), 1,2-cyclohexanedimethanol acrylate, 1,3-cyclohexanediacrylate, in view 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.

  Thus, by using the compound (B1), it becomes easy to have a preferable crosslink density and suppress cure shrinkage. Accordingly, when the resin composition is used as a material for optical three-dimensional modeling, the three-dimensional modeled product made of the resin composition is not only excellent in heat resistance and heat-and-moisture resistance, but also easy to impart surface lubricity. It becomes.

[Acryloyl or methacryloyl group-containing compound having no hydroxyl group in the molecule (B2)]
In the present invention, the compound (B2) is a monomer of an acryloyl group or methacryloyl group-containing compound that does not have a hydroxyl group in the molecule, and the compound (B1) is contained in the resin composition by containing the compound (B2). It is easy to increase the efficiency and sensitivity of the copolymerization reaction, and it is possible to form a cured resin having a high cohesion after irradiation with active energy rays. In addition, the viscosity of the resin composition can be easily reduced, and the workability during modeling can be easily improved. Although it does not specifically limit, The following is mentioned as a compound which can be used as a component (B2).

  Examples of the compound (B2) include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, and (meth) acrylic acid. 4-carboxybutyl, (meth) acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid , Itaconic acid, tiglic acid, angelic acid, senetic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4-acrylamidobutanoic acid, 6 Acrylamide hexanoic acid, 2- (meth) acryloyloxyethyl succine , Mono (meth) acrylic acid ω-carboxypolycaprolactone ester, etc., polylactone-based (meth) acrylic acid ester having a terminal carboxy group by ring-opening addition of lactone ring, alkylene oxide such as ethylene oxide and propylene oxide Carboxyl group-containing aliphatic acryloyl group or methacryloyl group-containing carboxylic acid such as an ester of alkylene oxide addition-type succinic acid having a carboxyl group at the terminal and (meth) acrylic acid, which has been repeatedly added, and acid anhydrides thereof Kind;

  For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, and other carboxyl group-containing alicyclic and aromatic acryloyl or methacryloyl group-containing carboxylic acids and acid anhydrides thereof ;

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-quinolinecarbohydrazide and other (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) acryl (Meth) acrylic acid esters having primary and / or secondary amino groups such as N-tributylaminoethyl acid, tetramethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl acrylate, etc .;

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

  For example, it has primary and / or secondary amino groups such as monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide and the like. (Meth) acrylamides;

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

  For example, heterocyclic acryloyl group of maleimide derivatives having both nitrogen atom and oxygen atom such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Or methacryloyl 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 Benzyl (meth) acrylate, iso-bornyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, 2-Oxo-1,2-diphenylethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, (meth ) 2-methyladamantyl-2-yl acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethyl (meth) acrylate Adamantyl-2-yl, 2-n-propyladamantyl-2-yl (meth) acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, 1- (adamantan-1-yl) (meth) acrylate -1-methylethyl, 1- (adamantan-1-yl) -1-ethylethyl (meth) acrylate, 1- (adamantan-1-yl) -1 (meth) acrylate -Methylpropyl, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] Non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] dec-2-yl, (meth) acrylic acid dihydro-α-terpinyl , (Meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1]. ] Oct-2-yl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- ( (Meta) acrylo Ruoxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o- (Meth) acrylic acid cyclic esters such as 2-propenylphenyl, (meth) acrylic acid cyclohexyl glycidyl ether, (meth) acrylic acid phenyl glycidyl ether;

  For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (Meth) 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) (Meth) 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) acryloyloxyethyldimethylbenzylammonium-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 (meth) acryloyloxyethyl phosphate;

  For example, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meth) acrylic acid 1 , 3-adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 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 Propyl) benzene, tetraethylene oxide addition of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane , Tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, tetraethylene oxide adduct of di (meth) acrylic acid-4,4′-sulfonyldiphenol, di (meth) Tetraethylene oxide adduct of acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, tetraethylene oxide adduct of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) methane, (Meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-2,2 -Tetraethylene oxide adduct of bis (hydroxyphenyl) propane-Dicaprolactonate, di (meth) acrylic acid-2,2-bis (hydroxy) Bifunctional (meth) acrylic acid cyclic esters such as tetraethylene oxide adduct of diphenyl) -dicaprolactonate;

  For example, heterocyclic (meth) acrylic acid esters containing nitrogen atoms such as pentamethylpiperidinyl (meth) acrylate and 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate;

  For example, imide (meth) acrylate, 2- (4-oxazolin-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone Heterocyclic structures containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification (Meth) acrylic acid esters having;

  For example, 4-acryloylmorpholine, 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, ( (Meth) acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran -4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2- Dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid 2-Oxotetrahydrofuran-3-yl lylate, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5,5-dimethyl-2-oxotetrahydrofuran 3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran Heterocycle-containing (meth) acrylic acid esters having an oxygen atom, such as 2-ylmethyl and (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl;

  For example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec- (meth) acrylic acid 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 (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic iso-nonyl, decyl (meth) acrylate, (meth) ) Alkyl (meth) acrylates 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-chloro-2-propenyl (meth) acrylate, 3-chloro-2-propenyl (meth) acrylate, 2- (2-propenyloxy) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, (Meth) acrylic acid esters further containing an unsaturated group such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) 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-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, tripperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, (meth) acrylpropenoic acid 2-perfluorodecylethyl, 2- (perfluorohexadecyl) (meth) acrylate (Meth) acrylic acid perfluoroalkyl esters and the like;

  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 esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  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 , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, 2- (ethoxycarbonyloxy) ethyl (meth) acrylate, 2- (ethoxycarbonyloxy) propyl (meth) acrylate , (Meth) acrylic acid 2- (ethoxycarbonyloxy) butyl, (meth) acrylic acid 2- ( (Toxycarbonyloxy) hexyl, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, 2- (butoxycarbonyloxy) ethyl (meth) acrylate, (meth ) Fatty acid having one carbonyl group such as 2- (butoxycarbonyloxy) butyl acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxycarbonyloxy) butyl (meth) acrylate Family (meth) acrylic acid esters;

  For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylate 2-oxobutanoyloctyl, (meth) acrylate 2-oxobutanoyldecyl, (meth) acrylate 2-oxobutanoyldodecyl, (meth) acrylate 3-oxobutanoylethyl, (meth) ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyl decyl acid, 3-oxobutanoyl dodecyl (meth) acrylate, 4-cyanooxobutane (meth) acrylate Ylethyl, 4-cyanooxobutanoylpropyl (meth) acrylate, 4-cyanooxobutanoylbutyl (meth) acrylate, 4-cyanooxobutanoylhexyl (meth) acrylate, 4-cyanooxo (meth) acrylate Butanoyloctyl, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, 2,3-di (oxo) (meth) acrylate Aliphatic (meth) acrylic acid esters having two carbonyl groups such as butanoyl) hexyl and 2,3-di (oxobutanoyl) octyl (meth) acrylate;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-10-methoxycarbonyl -5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] non-2-yl, (meth) acrylic acid-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3 2.1] having a carbonyl group such as octa-2-yl, (meth) acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ( (Meth) acrylic acid cyclic esters;

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

  For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, (meth) acrylic acid phosphooxyethylene oxide (ethylene oxide addition moles: 4-10), (meth) acrylic acid acid phosphooxypropylene oxide (propylene oxide addition mole number: 4-10) and other phosphonic acid group-containing (meth) acrylic acid esters;

  For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyl dipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acrylic Yl trimethoxy silane, 3- (meth) acryloyloxy propyl trimethoxy propoxy alkoxysilyl group-containing (meth) acrylic acid esters such as silane;

  For example, metal salts and ammonium of sulfonyl group-containing (meth) acrylic acid esters such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (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 (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate, hydroxypivalylhydroxypivalate hydroxypivalate dicaprolactonate, 1,6-hexane di (meth) acrylate Diol, di (meth) acrylic acid 1,2-hexane All, 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-decanediol, 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-hexadecane All, di (meth) acrylate 2-methyl-2,4-pentanediol, di (meth) acrylate 3-methyl-1,5-pentanediol, di (meth) acrylate 2-methyl-2-propyl- 1,3-propanediol, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol di (meth) acrylate, di (meth) acryl Acid 2,2,4-trimethyl-1,3-pentanediol, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) acrylate, di (meth) acrylic acid 2 , 5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, Di (meth) acrylic 2,4-diethyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-di (meth) acrylate Pentanediol, 2,2-diethyl-1,3-propanediol di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, di (meth) acrylate di Methyloloctane, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2 di (meth) acrylate -Bifunctional such as ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate ( (Meta) Acry Esters;

  For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, 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, tetra (meth) acrylate pentaerythritol, tetra (meth) acrylate ethoxylated pentaerythritol, tetra (meth) acrylate ditrimethylolpropane, hexa (meth) acrylate dipentaerythritol, tetra (meth) acrylate 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, Di, 2-dimethylpropane-1,3-diol, meth) acrylic acid, tetra (meth) acrylic acid Trimethylol butane, tetra (meth) acrylate ditrimethylol hexane, tetra (meth) acrylate ditrimethylol octane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate, tri 2,2-bis (hydroxymethyl) 1,3-propanediol hexa (meth) acrylate, trimethyl hepta (meth) acrylate 2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meth) acrylate di-2,2- Polyfunctional (meth) acrylic acid esters such as 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 (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleinamide, Fumaramide, Mesaconamide, Citraconami , Itaconamide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N′-dimethylamino) propyl] -Aliphatic (meth) acrylamides such as (meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

  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 Isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxyoctyl (meth) acrylamide, N- Butoxymethyl (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-isobutoxyhex Sil (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl-2-methoxyethyl (meth) acrylamide, N, N-di (methoxy) N-alkoxy group-containing (meth) acrylamides such as methyl) meth) acrylamide and 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 of the compound include acryloyl group or methacryloyl group-containing compounds having a nitrile group such as (meth) acrylonitrile and 2-cyanoethyl (meth) acrylate, but are not particularly limited thereto.

  In addition, for example, o-di (meth) allylbisphenol A, hydrogenated bisphenol A in which an aromatic ring structure is hydrogenated, and the like have an acryloyl group or a methacryloyl group, and are included in the compound (B2). These may use only 1 type or may use multiple types together.

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

<Cationically polymerizable compound (D)>
In one embodiment of the resin composition of the present invention, the resin composition may contain a cationically polymerizable compound (D) in addition to the essential components. By using the cationic polymerizable compound (D), when the resin composition is used as a three-dimensional modeled object, heterogeneous polymerization curing by active energy ray irradiation becomes possible, so the cured product forms a phase separation structure and is elastic. In addition, it is easy to control stress relaxation properties and creep characteristics, and appropriate elasticity and flexibility can be maintained, and curing shrinkage suppression can be further improved. Moreover, it becomes easy to improve the heat resistance or heat-and-moisture 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 any particular limitation. As the cationic polymerizable compound (D), a cyclic hetero compound (d) is preferable from the viewpoint of reactivity by active energy rays, and a compound having one or more cyclic ether groups is particularly preferably used among the cyclic hetero compounds.

  Among the cyclic hetero compounds (d), an epoxy group-containing compound (d1) which is a cyclic hetero compound having a 3-membered cyclic ether group, an oxetanyl group-containing compound (d2) which is a 4-membered cyclic ether, and a cyclic ether having a 5-membered ring or more. There exists a compound (d4) which has a hetero group other than a compound (d3) 2 or more oxygen or oxygen.

[Epoxy group-containing compound (d1) which is a cyclic hetero compound having a 3-membered cyclic ether group]
Examples of the epoxy group-containing compound (d1) include oxirane, methyloxirane, phenyloxirane, 1,2-diphenyloxirane, methylideneoxirane, oxiranylmethyl, oxiranylmethanol, oxiranecarboxylic acid, (chloromethyl) oxirane. , (Bromomethyl) oxirane, oxiranylacetonitrile, 2,2 ′-(dimethylmethylene) bis [(p-phenylene) oxymethylene] bisoxirane, 2,2 ′-[methylenebis (2,1-phenyleneoxymethylene)] Oxirane compounds such as bisoxirane, or epoxy group-containing compounds in which a hydrogen atom of an oxirane ring such as glycidyl ether, glycidyl ester or glycidylamine is substituted with a methylene bond group or a methine bond group;

  For example, 2- (cyclohexylmethyl) oxirane, 2-ethoxy-3- (cyclohexylmethyl) oxirane, [(cyclohexyloxy) methyl] oxirane, 1,4-bis (oxiranylmethoxymethyl) cyclohexane, 2,2′- Contains an epoxy group having a cycloalkane ring such as [(1-methylethylidene) bis (4,1-cyclohexanediyloxymethylene)] bisoxirane, 2-[{4- (oxirane-2-ylmethoxy) cyclohexyl} methoxy] oxirane Compounds;

For example, 7-oxabicyclo [4.1.0] heptane, 3-methyl-7-oxabicyclo [4.1.0] heptane, 7-oxabicyclo [4.1.0] heptan-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] heptan-1-ol acetate, 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, piperiton oxide, 3 - Ren oxide, α-terpineol oxide, 3- (thiilan-2-yl) -7-oxabicyclo [4.1.0] heptane, 6-methyl-3-isopropyl-7-oxabicyclo [4.1.0] Heptane-3-ol, 3,4-oxiranecyclohexylmethyl 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-oxirane-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, ethylene bis (3,4-oxirane-cyclohexane carboxylate), bis (3,4-Okishira Cyclohexylmethyl) adipate, bis (7-oxabicyclo [4.1.0] heptan-3-ylmethyl) adipate, bis (3,4-oxirane-6-methylcyclohexylmethyl) adipate, bis (7-oxabicyclo [4 .1.0] Heptane-3-ylmethyl) carbonate, diethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), ethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), 2,3,4,15-dioxirane- 7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] henicosane (also 3,4-oxiranecyclohexanespiro-2 ′, 6′-dioxanespiro-3 ″ , 5 ″ -Dioxanespiro-3 ′ ″, 4 ′ ″-Compound that can also be named oxirane cyclohexane ), 4- (3,4-oxiranecyclohexyl) -2,6-dioxa-8,9-oxiranespiro [5.5] undecane, 4-vinylcyclohexenedioxide, bis-2,3-oxiranecyclopentyl ether, and Alicyclic epoxy group-containing compounds having no aromatic ring such as dicyclopentadiene dioxide;

For example, 3-phenyl-7-oxabicyclo [4.1.0] heptane-3-carboxylate, 4-ethylphenyl 7-oxabicyclo [4.1.0] heptane, benzyl 7-oxabicyclo [4.1. .0] heptane-3-carboxylate, 4-ethylphenyl 7-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-carba Bokishireto), 1-phenyl-ethane-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] heptan-3-ylmethyl) isophthalate, bis [2 -{(7-oxabicyclo [4.1.0] heptane-3-carbonyl) oxy} ethyl] terephthalate, 1,2-bis {(7-oxabicyclo [4.1.0] heptan-3-ylmethoxy) Methyl} benzene, 1,3-bis {(7-oxabicyclo [4.1.0] heptan-3-ylmethoxy) methyl} benzene, 1,4-bis {(7-oxabicyclo [4.1.0] Heptane-3-ylmethoxy) Benzene, [{propane-2,2-diylbis (4,1-phenylene)} bis (oxy)] bis (ethane-2,1-diyl) bis (7-oxabicyclo [4.1.0] heptane And alicyclic epoxy group-containing compounds having an aromatic ring such as (-3-carboxylate).

  The epoxy group-containing compounds exemplified here may be used alone or in combination with a plurality of epoxy group-containing compound compounds, and are not particularly limited thereto.

[Oxetanyl group-containing compound which is a 4-membered ring ether (d2)]
Examples of the oxetanyl group-containing compound (d2) include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, di (1-ethyl-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. The oxetanyl group-containing compound (d2) may be used alone or in combination of two or more.

[Cyclic ether compound having five or more members (d3)]
Examples of the cyclic ether compound (d3) having 5 or more members include 2-methyltetrahydrofuran, 2,5-diethoxytetrahydrofuran, tetrahydrofuran-2,2-dimethanol 3-methyl-2,4 (3H, 5H)- Frangionone, 2,4-dioxotetrahydrofuran-3-carboxylate, 1,5-di (tetrahydrofuran-2-yl) pentan-3-yl propanoate, 4- (2,5-dioxotetrahydrofuran-3-yl) ) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, methoxytetrahydropyran, 2- (propadienyloxy) tetrahydro-2H-pyran, 2- (tetrahydrofurfuryloxy) tetrahydropyran N- (2,6-dioxotetrahydro-2H-pyran-3-yl) phthalimide, 3- [3 Hydroxypropyl] oxy] oxepane, (2R, 3R) -2-methyl-3- (benzyloxymethyl) oxepane-3-ol, 5-chloro-2- (2-phenylethyl) oxepane, etc. You may use, and may use two or more types together.

[Compound (d4) having two or more oxygen or hetero groups other than oxygen]
Examples of the compound (d4) having two or more oxygen or hetero groups 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 are not particularly limited. However, the epoxy group-containing compound (d1) or the oxetanyl group-containing compound ( d2) is preferred. In addition, the epoxy group-containing compound (d1) or the oxetanyl group-containing compound (d2) has a large steric distortion and tends to cause a nucleophilic ring-opening reaction. Therefore, since the crosslinking 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 cationic 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 structure that is polymerized and cured by irradiating active energy rays. It is also possible to improve the appearance defect of the three-dimensional structure resulting from the large size.

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

<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 essential components. By using the oligomer (E), when the resin composition is used as an optical modeling material, it is possible to further improve the moldability and curing shrinkage. Moreover, it becomes easy to improve the heat resistance or heat-and-moisture 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 monomers having at least an α, β-unsaturated double bond group and / or various compounds. , Have one or more acryloyl or methacryloyl groups in the molecule. However, those included in the compound (A) and the 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 a polyester oligomer (e1), a polyurethane oligomer (e2), a polyepoxy oligomer (e3) and a polyacrylic oligomer (e4). Including at least one kind, these can be used without any particular limitation.

Polyester oligomer (e1);
As the polyester oligomer (e1), the end of the polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol on the main chain skeleton, or a hydroxyl group in the polyester chain and a molecule such as (meth) acrylic acid or maleic acid A compound obtained by esterification with an α, β-ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups, or a carboxyl group in the terminal or polyester chain of polyester and (meth) acrylic acid 2- It is a compound obtained by esterification with the aforementioned 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 polybasic acid include aliphatic, alicyclic, and aromatic acids, which can be used without any particular limitation. More specifically, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, and dodecanedioic acid. Examples thereof include acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used. Derivatives of succinic anhydride (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl anhydride Succinic acid, etc.), derivatives of glutaric anhydride (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc. ), Maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecyl Maleic anhydride, 2,3-dichloromaleic anhydride, phenylmaleic anhydride Anhydride derivative of 2,3-diphenyl maleic anhydride, etc.) and the like 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-si Rhohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexa Saturated alicyclic dicarboxylic acids such as hydrophthalic acid and tetrahydrophthalic acid, 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-hexadiene-1α, 4α-dicarboxylic acid, etc. Unsaturated double bonds include one or two unsaturated alicyclic dicarboxylic acids having within, etc. These alicyclic dicarboxylic acids and anhydrides thereof 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.) Hydrogenated phthalic anhydride derivatives can also be used as alicyclic dicarboxylic acid anhydrides.

  More specifically, examples of the aromatic polybasic acid include, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, 2 , 2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindanedicarboxylic acid 1,2-azulene dicarboxylic acid, 1,3-azulene dicarboxylic acid, 4,5-azulene dicarboxylic acid, (−)-1,3-acenaphthene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,5- Anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracene dicarboxylic acid Aromatic dicarboxylic acids such as acid, 1,2-phenanthrene dicarboxylic acid, 4,5-phenanthrene dicarboxylic acid, 3,9-perylene dicarboxylic acid, and aromatic dicarboxylic anhydrides such as phthalic anhydride and 4-methylphthalic anhydride These aromatic dicarboxylic acids and anhydrides thereof can be used.

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

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

  More specific examples of relatively low molecular weight polyols include 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′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (Addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol, oct Njioru, butyl ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadiene engine methanol, aliphatic or alicyclic diols and dimer diol;

  For example, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, addition of bisphenol with alkylene oxide And aromatic diols such as type bisphenol.

Examples of the raw material bisphenol of 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 carbonate or phosgene.

As a commercial item of the said high molecular weight polyester polyol, the Byron series by Toyobo Co., Ltd., the Kuraray polyol P series by Kuraray, and the Kyowapol series by Kyowa Hakko Chemical Co., Ltd. are mentioned, for example.
As a commercial product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd. can be used.
Examples of commercially available high molecular weight polycarbonate polyols include Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray polyol PMHC series, and Kuraray polyol C series manufactured by Kuraray.

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

Polyurethane oligomer (e2):
The polyurethane oligomer (e2) is a compound obtained by reacting a compound having at least one isocyanate group with the compound (B1), or a compound having at least one isocyanate group and the polyhydric alcohol described above. A terminal isocyanate group obtained by reacting a urethane prepolymer of a terminal isocyanate group obtained by reacting the compound with the compound (B1), or a compound having at least one isocyanate group and a polyhydric alcohol. This is a compound obtained by reacting a urethane prepolymer having a terminal isocyanate group obtained by reacting an isocyanate group urethane prepolymer with a compound having at least one amino group and the compound (B1). Also included in the polyurethane oligomer (e2) are those containing a urea bond group obtained by reacting an isocyanate group with an amino group.

  Examples of the compound having at least one isocyanate group include monofunctional polyisocyanates and polyfunctional isocyanates, and aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, etc., respectively. Can be mentioned. More specifically, as monofunctional polyisocyanate, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, 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-methylbenzyl isocyanate, (R )-(−)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(−)-1-phenylethyl isocyanate, p-toluenesulfonyl isocyanate, etc. Is mentioned.

  Among the polyfunctional isocyanates, the aromatic polyisocyanate is more specifically, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate ( Alias: 4,4′-MDI), 2,4-tolylene diisocyanate (alias: 2,4-TDI), 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-tri Examples 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, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  As the alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

Moreover, as a part of (e2) component, the above-mentioned 2-methylpentane-2,4-diol adduct of polyisocyanate, trimer having an isocyanurate ring, etc. can be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, and polyisocyanate-modified products thereof can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretonimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a 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 tallow alkylamine, cured tallow alkylamine, allylamine, stearylamine, aminocyclopropane, aminocyclobutane, amino Nocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino-1-propene, 3-aminomethyl Heptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine, 3-myristoxypropyl Amine, 2-aminomethyltetrahydrofuran, aniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonanaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone 1 Aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine Primary amines such as α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine;

  For example, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, di-sec-butylamine, N-ethyl- 1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkylamine, di-cured tallow Kiruamin, secondary amines such as di-stearylamine;

  For example, ethylenediamine, propylenediamine [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, dimer diamine, dicyclohexylmethane-4,4′-diamine, diethylene glycol bis (3-amino Propyl) ether Phenylenediamine, xylylenediamine, dicyclohexylmethane-4,4'-diamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diamino Diamines having two primary amino groups such as diphenylmethane, 4,4′-bis- (sec-butyl) diphenylmethane, glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid, diaminobenzenesulfonic acid;

  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 [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or Methylaminopropylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1, 3-propanediamine or isopropylaminopropylamine], and N-lauryl-1,3-propanediamine [alias: N-lauryl-1,3-diaminopropane or laurylaminopropylamine], triethyltetramine, diethylenetriamine, 2- Droxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2- Polyamines having primary and secondary amino groups, such as hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine;

  For example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, hexadecanediohydrazide, eicosanedioic acid dihydrazide, maleic acid dihydrazide acid, maleic acid dihydrazide acid, Hydrazides such as dihydrazide, phthalic acid dihydrazide, carbonic acid dihydrazide, carbodihydrazide, thiocarbodihydrazide, oxalyl dihydrazide, polyacrylic acid hydrazide;

  For example, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU) , Tertiary amines such as 1,5-diazabicyclo- [4.3.0] -5-nonene;

  For example, 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 an α, β-invalid 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 reaction with a saturated double bond group-containing compound, and is an acryloyl group or methacryloyl group-containing compound that has substantially no glycidyl group. Representative examples include bisphenol type, epoxidized oil type, phenol novolac type, and alicyclic type. As the bisphenol type polyepoxy oligomer, α, β-unsaturation having one or more carboxyl groups in the molecule such as bisphenol type diglycidyl ether obtained by reacting bisphenols and epichlorohydrin and (meth) acrylic acid It is obtained by reacting with a double bond group-containing compound.

  The epoxidized oil polyepoxy oligomer has one or more hydroxyl groups or carboxyl groups in the molecule such as epoxidized oil such as soybean oil and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. Those obtained by reaction with an α, β-unsaturated double bond group-containing compound can be used. As the novolak type polyepoxy oligomer, α, β-unsaturation having novolak type epoxy resin and one or more hydroxyl groups or carboxyl groups in the molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. What is obtained by reaction with a double bond group containing compound can be used. As the alicyclic polyepoxy oligomer, α, β- having at least one hydroxyl group or carboxyl group in the molecule such as alicyclic epoxy resin and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. What was synthesize | combined 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 usable compounds include acryloyl group or methacryloyl group-containing modified polyether, amine-modified acryloyl group or methacryloyl group-containing compound, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol polyene resin and polyhydric alcohol. An oligomer or a prepolymer of one or more compounds selected from the group consisting of compounds obtained by adding an acryloyl group or a methacryloyl group to various compounds such as can be used.

  In addition to the agglomeration density, compatibility with other components that form a shaped article by polymerization, and durability such as heat resistance and moist heat resistance, from the viewpoint of obtaining excellent characteristics, the mass average molecular weight of the oligomer (E) (below) Mw.) Is preferably in the range of 300 to 50,000 in terms of the compatibility of the three-dimensional modeled object, good durability (heat resistance, moist heat resistance), and agglomeration density. A range of 000 is preferred. 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 compatibility with the components (A), (B) and (D). Can do. Along with this, it is possible to easily suppress problems such as a decrease in formability of the resin composition, a decrease in durability such as curing shrinkage of the cured product, and a whitening of the cured product. On the other hand, when an oligomer having an Mw of 300 or more is used, when the resin composition is used as an optical modeling material, cohesive failure in the three-dimensional modeled object hardly occurs.

  Although it does not specifically limit, In this invention, it is preferable that a polyurethane-type oligomer (e2) is included. When the resin composition is used for applications such as an optical modeling material, the elasticity and flexibility of the cured product tend to change depending on the bonding group in the oligomer (E). When the bonding group is an ester or ether group, it is easy to obtain excellent flexibility. However, elasticity and hydrolysis resistance tend to be low. On the other hand, when the component (e2) is used, it is easy to balance elasticity and flexibility based on the urethane bond. Moreover, since the said component (e2) also has favorable hydrolysis resistance, it can improve water resistance and heat-and-moisture resistance easily.

  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 1-100 mass parts. By setting the oligomer (E) to 1 part by mass or more, a lack of cohesive force can be improved, and characteristics such as heat resistance and heat-and-moisture resistance can be easily improved. On the other hand, by setting the oligomer (E) to 250 parts by mass or less, when the resin composition is used as a modeling material, it becomes easy to highly suppress curing shrinkage.

<Active energy ray polymerization initiator (F)>
The resin composition of the present invention can be cured by a polymerization reaction that proceeds by irradiation with various activation energy rays. However, the resin composition may contain an active energy ray polymerization initiator (F) as necessary. By using the active energy ray polymerization initiator (F), the polymerization reaction can be promoted. In one embodiment of the present invention, the activation energy is preferably ultraviolet light, and when the polymerization reaction proceeds by irradiation with ultraviolet light, 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 compounds known as active energy ray polymerization initiators can be used.

  Among the initiators (F), examples of the photo radical generator (f1) include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthfluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4- Chlorobenzophenone, 4,4′-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 4-thioxanthone, camphorquinone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like.

  Examples of commercially available products include 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), Darocur-1173 (manufactured by Merck), Ezacure KIP150, and TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  A photopolymerization initiator having at least one (meth) acryloyl group in the molecule can also be used.

  Further, as the compound (B2), glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid-3 Heterocycle-containing (meth) acrylic acid esters having 3-membered or 4-membered oxygen atoms such as 1,4-epoxycyclohexylmethyl, or cationically polymerizable compounds (D) or epoxy-modified vegetable oils are used as cationically polymerizable compounds In this case, it is preferable that the photoacid generator (f2) is contained in the initiator (F). Examples of the photoacid generator (f2) include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), WPI-113 ( Examples include iodonium salts such as Wako Pure Chemical Industries, Ltd., RP-2074 (Rhodia Japan Co., Ltd.), etc. This is preferable for forming a product.

  In this invention, the above-mentioned compound can be used individually or in combination of 2 or more types as an initiator (F). The blending ratio of the initiator (F) is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.5 to 10 parts by mass, with the total amount of the resin composition being 100 parts by mass from the viewpoint of reactivity. It is a range.

  The resin composition of the present invention does not substantially contain an organic solvent. The resin composition preferably contains no organic solvent, but the active energy ray polymerization initiator (F) is often poorly soluble in the polymerizable component. Therefore, a small amount of an organic solvent may be included to dissolve the active energy ray polymerization initiator (F). The content of the organic solvent in the resin composition is preferably within 5% by mass.

  Furthermore, in order to improve the performance of the active energy ray polymerization initiator (F), an active energy ray sensitizer may be used in combination. As typical examples of the active energy ray sensitizer, benzophenone derivatives, unsaturated ketone derivatives typified by chalcone derivatives and dibenzalacetone, benzyl and camphorquinone, etc. Polymethine dyes such as 2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives , Acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphy Derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives , Tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes and the like. Other specific examples include Okawara Shin et al., “Dye Handbook” (1986, Kodansha), Nobu Okawara et al., "Chemicals of Functional Dyes" (1981, CMC), Chusaburo Ikemori et al., "Special Functional Materials" (1986, CMC) However, it is not limited to these, and other dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region are included, and these may be used in any ratio as necessary. The above may be used.

  Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). Raised Although it is Rukoto, but is not limited thereto.

<Silane compound (G)>
The resin composition of the present invention preferably contains a silane compound (G). As a silane compound (G), a well-known silane compound can be used and will not be specifically limited if the intensity | strength of the three-dimensional molded item mentioned later improves. For example, alkyl alkoxysilane, aryl alkoxysilane, vinyl alkoxysilane, amino alkoxysilane, epoxy alkoxysilane, halogen alkoxysilane, (meth) acryloyl alkoxysilane, mercapto alkoxysilane, cationic alkoxysilane, Examples thereof include alkoxysilanes having an alkoxyl group such as isocyanate-based alkoxysilanes, and / or organic silanes having reactivity by directly bonding a hydrogen atom 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, decyltriethoxy Silane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiacetoxysilane, dimethylbis (methoxyethoxy) silane, dimethylbis (methoxypropoxy) silane, diethyldimethoxy Silane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldi Alkyl alkoxysilanes such as ethoxysilane, methylpropyldiisopropoxysilane, methylpropyldiacetoxysilane, etc. Orchids;

  For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldi Aryl alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, 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, Diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxysilane Emissions, vinyl alkoxysilane such as methyl allyl diacetoxy silane;

  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-aminopropyltrimethoxysilane hydrochloride, etc. Alkoxysilanes;

  For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- ( Epoxy-based 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, 3,3,3-trifluoropropylmethyldimethoxysilane Kind;

  For example, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- (Meth) acryloyl alkoxysilanes such as acryloxypropylmethyldimethoxysilane;

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

  For example, alkoxysilanes represented by isocyanate-based alkoxysilanes such as γ-isocyanatopropyltriethoxysilane are exemplified.

  Further, 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-c Loethoxy) methylsilane, tris (2-chloroethoxy) silane, n-hexyldichlorosilane, diisopropylchlorosilane, 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-trimethyldisilane, 1,1,2,2-tetraphenyl Nyldisilane, 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) acetamide, 2- (dimethylsilyl) pyridine, tetrakis (dimethylsilyl) silane, allyldimethylsilane, mercaptodimethylsilane, cyclopropanesilane, tris (trimethylsilyl) silane, 1,1, , 4-tetramethyldisilylethene, cyclohexanesilane, pentamethyldisiloxane, tetramethylcyclotetrasiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, pentamethyldisiloxane, 1,1,3,3- Tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetrakis (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-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,2,3,4,5, Examples thereof include 6-hexamethylcyclotrisilazane, α, ω-bis (hydrodiene) polydimethylsiloxane, and long-chain dimethylsiloxane oligomers and oily or waxy organic silanes having a silyl group.

  In addition, as the silane compound (G), a commercially available product can be used, and it is also possible to use an oligomeric silane obtained by oligomerizing a mixture of two or more silanes by hydrolysis and condensation. )include. The silane compound (G) can be used alone or as a mixture of two or more.

It is preferable to contain 0.01-10 mass parts of silane compounds (G) in 100 mass parts of resin compositions of this invention, and it is more preferable to contain 0.1-5 mass parts. If the amount is less than 0.01 parts by mass, the effect of improving heat resistance and moist 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 with respect to the cured product may decrease.

<Antioxidant (H)>
The resin composition in the present invention may further contain an antioxidant. By containing the antioxidant (H), coloring over time of the cured product after active energy ray polymerization can be suppressed.
Examples of the antioxidant include phenolic antioxidants such as ADK STAB AO-50 and ADK STAB AO-80 (manufactured by ADEKA), phosphorus such as ADK STAB PEP-8 (manufactured by ADEKA) and IRGAFOS 168 (manufactured by BASF). Commercially available products such as sulfur-based antioxidants such as sulfur-based antioxidants and IRGANOX-PS-800FD (manufactured by BASF) are not limited thereto.
The mixture ratio of antioxidant (H) is 0.01-20 mass parts with respect to 100 mass parts of resin compositions of this invention, and it is preferable that it is 0.01-10 mass parts. If the amount is less than 0.01 parts by mass, the active energy rays are consumed at an early stage, so that the polymerization rate may decrease. On the other hand, when the amount exceeds 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 modeled product is decreased.

<Coloring material (J)>
The resin composition of the present invention may contain a color material (J) in addition to the above components. By using the coloring material (J), when it is a three-dimensional modeled object, various functionalities such as thermal characteristics, electrical characteristics, optical characteristics, etc. are imparted by the contained dyes and pigments as well as design characteristics. It becomes possible.

The coloring material (J) is used by dispersing a dye or pigment in a high concentration with a dispersing resin. 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.
Examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, Benzidine Yellow, and pyrazolone red,
Soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, Permanent Red 2B,
Derivatives from vat dyes such as alizarin, indanthrone, thioindigo maroon,
Phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green,
Quinacridone organic pigments such as quinacridone red and quinacridone magenta;
Perylene organic pigments such as perylene red and perylene scarlet,
Isoindolinone organic pigments such as isoindolinone yellow and isoindolinone orange;
Pyranthrone organic pigments such as pyranthrone red and pyranthrone orange, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments,
Quinophthalone organic pigments such as quinophthalone yellow,
Isoindoline organic pigments such as isoindoline yellow,
Other pigments include organic pigments such as Flavanthrone Yellow, Acylamide Yellow, Nickel Azo Yellow, Copper Azomethine Yellow, Perinone Orange, Anthrone Orange, Dianthraquinonyl Red, Dioxazine Violet.

Examples of the dye include azo dyes, rhodamine dyes, quinoline dyes, thiazine dyes, thiazole dyes, xanthene dyes, and nigrosine dyes.
These dye derivatives can be used without any particular problem.

Of the coloring material (J), a general acrylic resin is used as the dispersion resin, and in some cases, a surfactant, the above polymer (A), compound (B), compound (D), or oligomer is used. (E) is also used in combination. In order to stabilize the hue, it is preferable to use these polymer (A), compound (B), compound (D), or oligomer (E) in combination.
The dispersion 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. Moreover, when using together a polymer (A), a compound (B), a compound (D), or an oligomer (E), it is 100-800 mass parts in conversion of a non volatile matter with respect to 100 mass parts of dyes and pigments. It is preferable to use within a range.
If the dispersion resin, polymer (A), compound (B), compound (D), or oligomer (E) is less than this range, the dispersion stability is lowered, and the dispersion stability and storage stability of the resin composition. May get worse. On the other hand, if this range is exceeded, the viscosity of the resin composition will increase significantly, which may adversely affect the storage stability of the resin composition, may cause molding defects in the resin cured product, Since migration may occur, the formability and strength of the three-dimensional structure may also decrease.

In order to stabilize the dispersion of dyes and pigments, polar resins can be used as necessary.
Examples of such polar resins include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, poly (meth) acrylic acid, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymers, and styrene-maleic acid copolymers. , 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 -Hydrophilic vinyl copolymer resins 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, and the entire resin is balanced between polar and nonpolar by introducing a polar group;
Cellulose derivatives such as methyl cellulose, ethyl cellulose, propyl cellulose, ethyl methyl cellulose, hydroxyalkyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, alkali metal carboxymethyl cellulose, alkali metal cellulose sulfate, cellulose graft polymer;
Polypeptides such as polyglutamic acid and polyaspartic acid;
Amide ester salts such as salts of long chain polyaminoamides and polar acid esters, salts of long chain polyaminoamides and high molecular weight acid esters, naphthalenesulfonic acid formalin condensates, stearylamine acetate, etc .;
However, it is not particularly limited to these. These can be used alone or in combination of two or more.

Examples of polar resins that are commercially available as dispersion resins include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)” manufactured by Avicia, Disperbyk-101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (high molecular weight copolymer) "," 400 "," Bykumen "(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 system) ”,“ Lactimon (long chain amine and unsaturated acid polycarboxylic acid) Silicon) ", and the like.
Further, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine system) "," Floren TG-710 (urethane oligomer), "Flownon manufactured by Kyoeisha Chemical Co., Ltd. “SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150, manufactured by Enomoto Kasei Co., Ltd. Aliphatic polycarboxylic acid), # 7004 (polyether ester type) ”.

  When using polar resin for the coloring material (J) of this invention, it is preferable that polar resin is 0.1-80 mass% in coloring material (J) whole quantity. If the concentration is less than 0.1% by mass, the dispersion and stabilization of the dye or pigment may not be expected. On the other hand, when it exceeds 80 mass%, even if modeling performance falls remarkably, even if it can model, durability, such as water resistance of a three-dimensional molded item, and heat-and-moisture resistance, may fall.

<Additive (Q)>
If the resin composition of the present invention is within a range not impairing the effects of the present invention, various additives (Q) can be appropriately blended in addition to the above-described components. For example, blending organic or inorganic fillers from the viewpoints of polymerization cure shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. it can. As such a filler, polymers, ceramics, metals, metal oxides, metal salts, and the like can be used, and the shape is not particularly limited, such as particles and fibers. In addition, in the blending of the above polymer, as a filler, such as a flexibility imparting agent, a plasticizer, a flame retardant, a storage stabilizer, a thixotropy imparting agent, a dispersion stabilizer, a fluidity imparting agent, an antifoaming agent, etc. Alternatively, it can be dissolved, semi-dissolved, or micro-dispersed in the resin composition for optical three-dimensional modeling as a polymer blend or polymer alloy.

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

  The active energy ray-curable resin composition for optical three-dimensional modeling in the present invention is 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 is preferable to contain 20 to 98.5% by mass of (B2), 1 to 15% by mass of polymer (A), 1 to 40% by mass of compound (B1), and 40 to 98% by mass of compound (B2). It is more preferable to contain. If the polymer (A) is 1% by mass or more in the total amount of the resin composition, sufficient cohesive force can be easily obtained, and an effect of improving heat resistance and moist heat resistance can be expected. Further, when the compound (B1) is 0.5% by mass or more, an improvement in the curing rate can be expected by suppressing curing inhibition due to dissolved oxygen in the resin composition during photocuring, and sufficient cohesive force Can be obtained, and an effect of improving heat resistance and heat-and-moisture resistance can be expected. Further, when the resin composition is used as an optical modeling 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 modeled product may be reduced. . When the compound (B1) exceeds 50% by mass, there is a possibility that the strength of the three-dimensional structure is lowered or the heat and humidity resistance is lowered.

  When the resin composition is stirred and mixed, the resin composition may be prepared by stirring and mixing using a general-purpose device such as a uniaxial or multiaxial extruder, a kneader, or a dissolver equipped with a decompression device. Usually, the temperature at the time of stirring and mixing is 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 to make uniform stirring / mixing work difficult. Conversely, 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 form of liquid, paste, and film.
In addition, although it is preferable that the resin composition in this invention does not contain an organic solvent substantially, it can also contain an organic solvent. For example, further adding 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, water, The viscosity of the resin composition for optical three-dimensional modeling can be adjusted, or the viscosity can be lowered by heating the resin composition for optical three-dimensional modeling.

The resin composition in the present invention has an important viscosity at 25 ° C. of 1 to 2000 mPa · s, preferably 10 to 1500 mPa · s, and more preferably 20 to 1000 mPa · s. When the viscosity is higher than 2000 mPa · s, when the resin cured product is used, 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 resin resin.
Since the viscosity of the resin composition is almost determined by the viscosity of the compound (B1) and the compound (B2), the viscosity of the resin composition is controlled by managing these viscosities in the range of 1 to 100,000 mPa · s. Can also be managed.

<Modeling 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 the resin composition with light such as visible light, ultraviolet light, infrared light, etc., and supplying active energy necessary for polymerization and curing, a resin cured product having a desired shape or A three-dimensional model can be obtained.
The active energy ray irradiation light source mainly consists of 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 excitation 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. In view of cost, directivity, and convergence, an ultraviolet laser beam is preferable.
The irradiation intensity of the active energy ray is preferably 0.1 to 500 mW / cm ² . When the light irradiation intensity is less than 0.1 mW / cm ² , a long time is required for curing, and when it exceeds 500 mW / cm ² , the uncured resin composition is deteriorated due to heat radiated from the lamp. There is. The integrated dose expressed as a product of irradiation intensity and irradiation time is preferably ¹ to 5,000 mJ / cm ² . When the integrated irradiation amount is less than 1 mJ / cm ² , it takes a long time for polymerization and curing, and when it is larger than 5,000 mJ / cm ² , the irradiation time becomes very long and the productivity may be inferior.

  A method for selectively irradiating light, which is an active energy ray for polymerization and curing, to a specific portion of the resin composition is not particularly limited, and can be performed by various methods. For example, a method of irradiating focused light or the like obtained by using a laser beam, a lens, a mirror, or the like to a specific portion, a method of irradiating non-focused light through a fixed pattern mask, or the like can be employed. However, when fine processing or processing accuracy is required, it is desirable to minimize the size of the focused light. In such a case, it is preferable to use laser light. Furthermore, the specific part of the resin composition that is 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. In order to irradiate the liquid surface of the resin composition or the contact surface with the container wall, the light may be irradiated directly from the outside or through a transparent vessel wall. Irradiation may be performed using a light guide such as the above.

  Further, in the above-described optical three-dimensional modeling method, usually, after a specific portion of the resin composition is polymerized and cured, the irradiated position is moved continuously or stepwise from an already cured portion to an uncured portion. As a result, the cured portion can be grown into a desired three-dimensional shape. This irradiation position can be moved by various methods, for example, moving at least one of a light source, a container containing the resin composition, or a cured portion of the resin composition, or uncured in the container. The resin composition (liquid curable substance) can be added.

<3D objects>
As a typical method for obtaining a three-dimensional structure using the resin composition of the present invention, light is used so that a cured layer having a desired pattern is obtained in the liquid resin composition for optical three-dimensional structure of the present invention. To form a cured layer, and then irradiate light to the uncured composition layer adjacent to the cured layer in the same manner to form a new cured layer continuous with the previously formed cured layer. By repeating this lamination operation, a method for finally obtaining a three-dimensional shaped object can be mentioned. As a more specific embodiment of this method, the following method can be exemplified.

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

  The cured product of the active energy ray-curable resin composition for optical three-dimensional modeling of the present invention is a variety of three-dimensional modeling products for electronic products that require complicated and fine processing; It can be preferably used as a three-dimensional model such as a model for advertisement or exhibition; a prototype for development such as performance test or production aptitude confirmation; or a medical model for simulation of surgery.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the examples and comparative examples, “parts” and “%” represent “parts by mass” and “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 GPC-8020 manufactured by Tosoh Corporation uses tetrahydrofuran as the eluent. Used three TSKgel SuperHM-M (manufactured by Tosoh Corporation) and measured at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.

<Manufacture 1 of a monomer having a sterol skeleton>
A polymerization reaction apparatus equipped with a reaction tank, a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen introduction tube was prepared. The reaction vessel is charged with 63.3 parts of phytosterol (product name: phytosterol CO, manufactured by Tama Seikagaku Co., Ltd.), 20.5 parts of triethylamine, and 200 parts of chloroform, and 16.2 parts of acrylic acid chloride and 50 parts of chloroform are added to the dropping layer. Then, the mixed solution of the dropping layer was dropped into the reaction layer over 1 hour at 0 ° C. in a nitrogen stream, and the mixture was reacted at 50 ° C. for 3 hours after the dropping. After completion of the reaction, the solution was separated with 1N hydrochloric acid, and the organic layer was dried under reduced pressure until a white powder precipitated. Then, methanol was added to form a slurry, and the precipitated solid was filtered and washed with methanol. The monomer (a-1-1) was obtained.

<Manufacture 2 of a monomer having a sterol skeleton>
A polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was prepared. A reaction vessel was charged with 84.4 parts of phytosterol (product name: phytosterol CO, manufactured by Tama Seikagaku Co., Ltd.), 32.2 parts of 2-isocyanatoethyl acrylate, and 233.3 parts of chloroform. Reacted for hours. After completion of the reaction, 50 parts of methanol was added and dried by drying under reduced pressure until a white powder was precipitated. Then, methanol was added to form a slurry, and the precipitated solid was filtered and washed with methanol to give a monomer having a sterol skeleton (a -1-2) was obtained.

<Production of monomer having sterol skeleton 3>
A polymerization reaction apparatus equipped with a reaction tank, a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen introduction tube was prepared. The reaction vessel was charged with 62.1 parts of cholesterol, 21.1 parts of triethylamine, and 200 parts of chloroform, and 16.7 parts of acrylic acid chloride and 50 parts of chloroform were respectively added to the dropping layer. Was added dropwise to the reaction layer over 1 hour, and reacted at 50 ° C. for 3 hours. After completion of the reaction, the solution was separated with 1N hydrochloric acid, and the organic layer was dried under reduced pressure until a white powder precipitated. Then, methanol was added to form a slurry, and the precipitated solid was filtered and washed with methanol. The monomer (a-1-3) was obtained.

The structure of the sterol compound used in the production 1 to 3 of the monomer having a sterol skeleton is shown below.
Phytosterol: A mixture of β-sitosterol, campesterol, stigmasterol, and brassicasterol represented by formulas (10) to (13)

Formula (10)

Formula (11)

Formula (12)

Formula (13)

cholesterol:
Formula (14)

<Production of polymer A-1>
A polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was prepared. In the reaction layer, 50 parts of monomer (a-1-1) having a sterol skeleton synthesized above, 50 parts of Blemmer LMA (product name, general name: lauryl methacrylate, manufactured by NOF Corporation), azobisisobuty 2.0 parts of nitrile and 238 parts of cyclohexanone were charged and reacted at 90 ° C. for 3 hours under a nitrogen stream. Furthermore, 1.0 part of azobisisobutyronitrile was added and reacted for 5 hours to obtain a polymer A-1. The weight average molecular weight was 13,000 by GPC measurement.

<Production of Polymers A-2 to A-14 and Acrylic Polymers K-1 to K-2>
Except having changed into the monomer seed | species of Table 1, and a weight part, operation similar to manufacture of the polymer A-1 was performed. Table 1 shows the weight average molecular weights of the obtained polymers A-2 to A-14 and acrylic polymers K-1 to K-2.

The compounds listed in Table 1 are shown below.
・ Placcel FM5: manufactured by Daicel, polycaprolactone monoacrylate, Blemmer AP800: manufactured by NOF Corporation, polypropylene glycol monoacrylate, silaplane FA0711, manufactured by Chisso Corporation, dimethylsiloxane macromonomer, macromonomer AN-6S: manufactured by Toagosei Co., Ltd. Styrene / acrylonitrile macromonomer / light acrylate IBX: Kyoeisha Chemical Co., Ltd., isobornyl acrylate

<Production of polymer A-15>
A polymerization reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was prepared. The reaction layer was charged with 100 parts of the monomer (a-1-1) having a sterol skeleton synthesized above, 2.5 parts of thioglycerol, and 466.6 parts of cyclohexanone, and heated to 100 ° C. in a nitrogen stream. After 0.02 part of azobisisobutyronitrile was added and reacted 36 times every 30 minutes, it was cooled to 70 ° C., and Adekapolyol PP-2000 (product name, general name: polypropylene glycol, manufactured by ADEKA) 86 0.7 part, 12.3 parts of isophorone diisocyanate, 64.5 parts of cyclohexanone, and 0.02 g of dibutyltin dilaurate were added and reacted at 70 ° C. for 24 hours to obtain a polymer A-15. The weight average molecular weight of the obtained polymer A-15 was 27,000.

<Manufacture of colorant (J) dispersion>
[Production Examples 1 and 2]
The compound (B2) and the dispersion resin are stirred, and after confirming that the dispersion resin is completely dissolved, a dye or a pigment is added. After stirring with a high speed mixer or the like, the resulting mill base is stirred. It was produced by dispersing for about 2 hours in a horizontal sand mill. Table 2 shows the composition of the dispersion (pigment dispersion) of the produced coloring material (J) (numerical values represent parts). In Table 2, a blank means no blending.

<Manufacture of resin composition>
[Examples 1-45, Comparative Examples 1-3]
Compound (A), compound (B1) and compound (B2) as essential components in a light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less, and if necessary, compound (D), oligomer (E), active energy ray polymerization initiator (F), silane compound (G), antioxidant (H), colorant (J) and various additives (Q) are charged in the ratios shown in Table 3 and charged into a stirrer. After sufficiently stirring and sufficiently defoaming, the resin compositions shown in the formulation examples were obtained. In Table 3, the symbol “-” means no blending.

The compounds listed in Table 3 are shown below.
4HBA: 4-hydroxybutyl acrylate 2HEA: 2-hydroxyethyl acrylate CHDMA: 1,4-cyclohexanedimethanol acrylate HPPA: 2-hydroxy-3-phenoxypropyl acrylate IBXA: isobornyl acrylate M-315: ethoxylated isocyanuric acid triacrylate, ADCP: dicyclopentanyl diacrylate, ACMO: 4-acryloylmorpholine, GMA: glycidyl methacrylate, NPGDA: neopentyl glycol diacrylate, 2021P: 3,4-oxiranecyclohexyl Methyl-3,4-oxirane cyclohexanecarboxylate / DOME: Di (1-ethyl-3-oxetanyl) methyl ether / GC: Glycerin carbonate / 811: Daicel citite Company, Ltd., polyester acrylate "Ebecryl 811"
3000B: manufactured by Nippon Synthetic Chemical Industry Co., Ltd., polyurethane oligomer (urethane acrylate) "Purple light UV3000B"
600: manufactured by Daicel Cytec Co., Ltd., polyepoxy oligomer (epoxy acrylate) “Ebecryl 600”
TPO: manufactured by BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide CPI-110P: p-phenylthiophenyldiphenylsulfonium PF6 salt A-174: manufactured by Tanac Co., silane coupling agent : Antioxidant “IRGAFOS168” manufactured by BASF
DIOP: diisodecyl phthalate

<Appearance and viscosity of resin composition>
For the resin compositions of the formulation examples shown in Table 3, the appearance and viscosity (mPa · s) were determined according to the following method, and the results were shown.
"appearance"
The liquid appearance of the resin composition obtained in each formulation example was visually evaluated.
"viscosity"
About 1.2 ml of the resin composition obtained in each blending example was measured with an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) in an atmosphere at 23 ° C., and a rotation speed of 0.5 to The solution viscosity (mPa · s) was measured at 100 rpm for 1 minute.

<Evaluation of resin composition>
[Examples 46 to 90, Comparative Examples 4 to 6]
About the resin composition for optical three-dimensional model | molding shown in Table 3, the hardening rate, the Young's modulus, the swelling degree, curvature, and surface slipperiness were measured with the following method, and the molding test was done. The results are shown in Table 4.

《Curing speed》
Using an applicator, the resin composition is applied to a glass plate to a thickness of 10 μm, and the light from a mercury-xenon lamp UXM-200YA manufactured by Ushio Electric Co., Ltd. is selectively transmitted through this coating film. Irradiation was 0.1 J / cm ² through a band pass filter and an ND filter for light intensity adjustment. The film tack after light irradiation was evaluated in three stages by palpation. Other than the evaluation “x”, there is no problem in actual use.
○: No tack △: There is some tack ×: There is tack

"Young's modulus"
A resin composition was applied to a glass plate with 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 conditioned for 24 hours at 23 ° C. and 50% relative humidity to obtain 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 gap between marked lines of 25 mm.
This Young's modulus was evaluated in four stages. Other than the evaluation “x”, there is no problem in actual use.
A: 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 ). Can be used practically.
X: Less than 80 (kg / mm ² ). There is a problem in practical use.

《Swelling degree》
Using a stereolithography apparatus (solid creator JSC-2000: manufactured by Sony Corporation) using an Ar ion laser (wavelength 351, 385 nm) as a light source, molding was performed at a laser power of 40 mW on the liquid surface and a scanning speed of 100 cm / min. A test piece [(width 50 mm × length 50 mm × height 1 mm): laminated thickness 0.2 mm × 5 times laminated]. After carefully wiping off the adhering resin solution, 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, and the adhered resin solution was wiped off, and then the mass W ₂ was measured.
The degree of swelling was calculated according to the following formula and evaluated in three stages. Other than the evaluation “x”, there is no problem in actual use.
Swelling degree (%) = [(W ₂ −W ₁ ) / W ₁ ] × 100
○: Less than 2 (%). No problem at all.
Δ: 2 (%) or more and less than 5 (%). Can be used practically.
X: 5 (%) or more. There is a problem in practical use.

"warp"
Using the above-mentioned stereolithography apparatus, a test piece [(width 50 mm × length 50 mm × height 40 mm): one layer thickness 0.2 mm is molded at a laser power of 40 mW on the liquid surface and a scanning speed of 100 cm / min. × 100 times lamination]. After the adhered resin liquid was wiped off, post-curing 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 base, and the warpage was evaluated by the lift amount Δh (mm) at the other end.
This warpage was evaluated in four stages. Other than the evaluation “x”, there is no problem in actual use.
A: Less than 0.2 (mm). No problem at all.
○: 0.2 (mm) or more and less than 0.5 (mm). There are some, but no problem.
Δ: 0.5 (mm) or more and less than 1.0 (mm). Can be used practically.
X: 1.0 (mm) or more. There is a problem in practical use.

《Surface smoothness》
A resin composition is applied to a glass plate with a thickness of 250 μm using an applicator, 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 test piece was conditioned for 24 hours. Measurement In a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity, the test piece was rubbed 10 times with # 0000 steel wool while applying a load of 250 g / cm ² to conduct a scratch resistance test. It was. The presence or absence of scratches and the extent of the scratches were visually observed and used as an index of surface activity.
Evaluation was performed in four stages. Other than the evaluation “x”, there is no problem in actual use.
(Double-circle): There is no generation | occurrence | production of a crack. No problem at all.
○: 5 or less scratches occur. There are some, but no problem.
Δ: 6 to 10 scratches are generated. Can be used practically.
X: Innumerable scratches occur. There is a problem in practical use.

  In Table 4, “curing speed” evaluates the speed of polymerization speed. When the reaction rate is slow and there are residual double bonds, tack remains on the film even after light irradiation. “Young's modulus” evaluates the strength and hardness of the cured product. “Swelling degree” evaluates the degree of crosslinking of the resin. When the degree of cross-linking of the resin is high, entry of the resin into the cured product is suppressed, resulting in a low degree of swelling. “Warpage” evaluates the cure shrinkage. The one where warpage is smaller is a resin composition in which curing shrinkage is suppressed. “Surface lubricity” 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 a Young's modulus, swelling degree, warpage, and surface lubricity. Excellent results were shown in all items (Examples 46 to 90). In particular, when the compositions of Examples 5, 10-12, 15, 16, 38-41 were used, the most excellent results were shown (Examples 50, 55-57, 60, 61, 83-86). . On the other hand, when the resin composition for optical three-dimensional modeling other than the present invention is polymerized and cured with an active energy ray, there is difficulty in any of curing speed, Young's modulus, swelling degree, warpage, and surface lubricity. Yes, it is difficult to use. Among them, in Comparative Examples 4 to 6 in which the polymer A is not added, the balance of cohesive force (hardness and flexibility) is maintained and the polymerization curing shrinkage is reduced by forming a microphase separation structure in the polymer cured product derived from the sterol skeleton. The inhibitory effect cannot be obtained, and satisfactory results cannot be obtained.

Claims (8)

A monomer (a-1) containing a sterol skeleton, a polymer (A) obtained by radical polymerization of a monomer (a-2) excluding (a-1), and a radical polymerizable compound (B) An active energy ray-curable resin composition for optical three-dimensional modeling,
Active energy ray-curable resin composition for optical three-dimensional modeling, wherein the monomer (a-1) containing a sterol skeleton contains at least one of monomers represented by the following general formulas (1) to (4) .
General formula (1)

General formula (2)

General formula (3)

General formula (4)

[In the formula, the solid and dotted double lines each independently represent a double bond or a single bond, and the adjacent solid and dotted double lines do not form a double bond at the same time.
R _{1 to} R ₃ represent a hydrogen atom or a methyl group,
L represents a linking group having a molecular weight of 400 or less composed of any combination selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom;
R ₄ represents an oxygen atom or a substituent having a molecular weight of 200 or less composed of any combination selected from a hydrogen atom, a carbon atom, and an oxygen atom. ]   The radical polymerizable compound (B) comprises an acryloyl group or methacryloyl group-containing compound (B1) having one or more hydroxyl groups in the molecule, and an acryloyl group or methacryloyl group-containing compound (B2) having no hydroxyl groups in the molecule. The active energy ray-curable resin composition for optical three-dimensional modeling according to claim 1, which is contained.   The active energy ray for optical three-dimensional modeling of Claim 1 or 2 whose ratio of the structural unit which has a sterol skeleton in a polymer (A) is 25 to 100 weight% in 100 weight% of polymers (A). Curable resin composition.   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 (b1) having a hydroxyl group and having no cyclic structure. The active energy ray-curable resin composition for optical three-dimensional modeling according to any one of claims 1 to 3.   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 a cyclic structure. Item 5. The active energy ray-curable resin composition for optical three-dimensional modeling according to any one of Items 1 to 4.   Furthermore, oligomer (E) (except the case where it becomes (A)) is contained, The active energy ray curable resin composition for optical three-dimensional modeling of any one of Claims 1-5 characterized by the above-mentioned.   Hardened | cured material of the active energy ray-curable resin composition for optical three-dimensional modeling of any one of Claims 1-6.   A three-dimensional structure made of the cured product according to claim 7.