JP2016160372A - Active energy ray-polymerizable resin composition for optical three-dimensional molding, and three-dimensional molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-polymerizable resin composition for optical three-dimensional molding, which shows little deformation such as warpage or swell during molding and can give a cured product having high accuracy by an optical three-dimensional molding process, and which can give a resin cured product allowing fast polymerization curing by irradiation with various active energy rays, and to provide a strong and robust three-dimensional molded object.SOLUTION: A resin composition for optical three-dimensional molding is provided, which contains a coloring material (A) and a photopolymerizable oligomer (E) in a liquid photocurable resin composition comprising a photopolymerizable compound and a photopolymerizable initiator, the coloring material (A) incorporated by 0.2 wt.% or less based on the weight of the photocurable resin composition. However, a coloring material with dispersion of carbon black, as a pigment, is excluded.SELECTED DRAWING: 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 has not yet satisfied 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

  An object of the present invention is to provide an active energy ray-polymerizable resin composition for optical three-dimensional modeling, which is capable of obtaining a cured product having small deformation with time and excellent in toughness and stability over time. 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 polymerizable resin composition for optical three-dimensional modeling shown below, and further the present invention by a three-dimensional molded product. It came to be completed.
That is, the present invention provides a liquid photocurable resin composition containing a photopolymerizable compound and a photopolymerizable initiator based on the weight of the photocurable resin composition,
0.2% by weight or less of color material (A),
A photopolymerizable oligomer (E);
It is related with the resin composition for optical three-dimensional modeling characterized by containing.
However, a color material in which carbon black is dispersed as a pigment is excluded.

Furthermore, the present invention provides a liquid photocurable resin composition containing a photopolymerizable compound and a photopolymerizable initiator based on the weight of the photocurable resin composition,
0.2% by weight or less of color material (A),
A photopolymerizable oligomer (E);
An α, β-unsaturated double bond group-containing compound (B) having one or more hydroxyl groups in the molecule;
An α, β-unsaturated double bond group-containing compound (C) having no hydroxyl group in the molecule;
It is related with the resin composition for optical three-dimensional modeling characterized by containing.
However, a color material in which carbon black is dispersed as a pigment is excluded.

  Furthermore, this invention relates to the resin cured material formed by superposing | polymerizing and hardening the said active energy ray polymeric resin composition with an active energy ray.

  Furthermore, this invention relates to the three-dimensional molded item which consists of the said resin 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 modeled object by the optical three-dimensional modeling method, and the mechanical properties of the polymerized cured product are excellent. The product can provide an active energy ray-polymerizable resin composition for optical three-dimensional modeling that can also be used as a mechanism part.

Hereinafter, embodiments of the present invention will be described.
<Configuration of Active Energy Ray Polymerizable Resin Composition for Optical Stereolithography>
The active energy ray polymerizable resin composition for optical three-dimensional modeling of the present invention is based on the weight of the photocurable resin composition.
0.2% by weight or less of color material (A),
A photopolymerizable oligomer (E);
Containing.
However, a color material in which carbon black is dispersed as a pigment is excluded.

  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 polymerizable 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, the constituent components of the resin composition will be specifically described.
<Coloring material (A)>
In the resin composition of the present invention, the color material (A) will be described.

In the present invention, when a three-dimensional model is formed by using the color material (A), various functions such as thermal characteristics, electrical characteristics, optical characteristics, etc., as well as design properties, depending on the dyes and pigments contained. It becomes possible to impart sex.
The coloring material (A) 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 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 colorant (A), a general acrylic resin is used as the dispersion resin, and in some cases, a surfactant, the following compound (B), compound (C), compound (D), or photopolymerization is used. The functional oligomer (E) is also used in combination. In order to stabilize the hue, it is preferable to use these compounds (B), (C), (D) or photopolymerizable oligomer (E) in combination.
The dispersion resin is preferably used in the range of 10 to 60 parts by weight in terms of nonvolatile content with respect to 100 parts by weight of the dye or pigment. Moreover, when using together a compound (B), a compound (C), a compound (D), or a photopolymerizable oligomer (E), it is 100-800 weight in conversion of a non volatile matter with respect to 100 weight part of dyes and pigments. It is preferable to use within the range of parts.
If the dispersion resin, compound (B), compound (C), compound (D), or photopolymerizable oligomer (E) is less than this range, the dispersion stability is lowered, and the dispersion stability and storage of the resin composition are reduced. Stability may deteriorate. 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 copolymers such as maleic acid copolymer and polyitaconic acid;
resin;

For example, a polyester resin obtained by a polycondensation reaction of a polyvalent carboxylic acid and a polyol, and the entire resin is balanced in polarity / nonpolarity 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 a polar resin is used for the color material (A) of the present invention, the polar resin is preferably 0.1 to 80% by weight in the total amount of the color material (A). If the concentration is less than 0.1% by weight, the dispersion and stabilization of the dye or pigment cannot be expected. On the other hand, when it exceeds 80% by weight, even if the modeling performance is remarkably reduced or the modeling is completed, the durability such as water resistance and heat-and-moisture resistance of the three-dimensional model is likely to decrease.
<Compound (B)>
The α, β-unsaturated double bond group-containing compound (B) having one or more hydroxyl groups in the molecule in the resin composition of the present invention will be described.

  In the present invention, the component (B) is a monomer of a compound having at least one hydroxyl group in the molecule and containing at least one α, β-unsaturated double bond group. The hydroxyl group in the compound (B) is preferable in terms of improving the reaction rate and suppressing polymerization curing shrinkage. By having a hydroxyl group, intermolecular hydrogen bonding works, the cohesive strength and crosslinking degree of the resin composition can be improved, and the effect of improving heat resistance, moist heat resistance and thermal dimensional stability as a laminate is shown. . The compound (B) 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.

  In the present application, particularly when expressed as `` (meth) acryloyl '', `` (meth) acrylic acid '', `` (meth) acrylate '', `` (meth) acryloyloxy '', and `` (meth) allyl '', Unless otherwise stated, “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyloxy and / or methacryloyloxy”, and “allyl and / or methallyl”, respectively. ".

  As the compound (B), any compound containing one or more hydroxyl groups and one or more α, β-unsaturated double bond groups in its structure can be used without particular limitation. Although it does not specifically limit, the following compounds are mentioned as a specific example.

  Of the α, β-ethylenically unsaturated double bond group-containing compound (B) containing one or more hydroxyl groups, the compound (b1) having a hydroxyl group and not having a cyclic structure includes a hydroxyl group in the structure. Is not particularly limited as long as it does not have a cyclic structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , (Meth) acrylate 3-hydroxypropyl, (meth) acrylate 1-hydroxybutyl, (meth) acrylate 2-hydroxybutyl, (meth) acrylate 3-hydroxybutyl, (meth) acrylate 4-hydroxybutyl , 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, (meth) acrylate 10-hydroxydecyl laurate, 12-hydroxy lauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional glycerol (meth) acrylate, or glycidyl laurate (meth) acrylate , (Meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate and other fatty acid ester-based (meth) acrylic acid ester, or 2- (acryloyloxy) ethyl 6-hydroxyhexanonate A (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, or the hydroxyl group-containing α, β-ethylenic group Ethylene oxide and propylene oxide for unsaturated double bond group-containing compounds Id, alkylene oxide addition was repeated adding an alkylene oxide such as butylene oxide (meth) aliphatic hydroxyl group-containing acrylic acid ester (meth) acrylate;

For example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, triethylene glycol Hydroxyl-containing aliphatic vinyl ethers such as methylolpropane monovinyl ether, pentaerythritol monovinyl ether, or alkylene oxide-added vinyl ether having a hydroxyl group at the terminal where alkylene oxide such as ethylene oxide or propylene oxide is repeatedly added;

For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide A hydroxyl group-containing aliphatic (meth) allyl alcohol or (meth) allyl ether, such as an alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal of repeating addition;

  For example, α, β-ethylenically unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;

  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. Of (meth) acrylamides;

Examples thereof include monomers having a hydroxyl group and a vinyl group such as vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.
As the compound (b1), from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε-caprolactone An α, β-ethylenically unsaturated double bond group-containing compound having 2 to 18 carbon atoms, such as 1-2 mol-added (meth) acrylic acid 2-hydroxyethyl, is particularly preferable.

Among the compounds (B), 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.

The compound (b2) is not particularly limited as long as it has both a hydroxyl group and a cyclic structure in its structure, and examples thereof include (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1, 3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (meth) acrylate, 2-hydroxy-3-phenoxymethyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, (meth) 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy-3- (meth) acrylate Phenoxyoctadecyl, (meth) acrylic acid monohydroxyethyl phthalate, (meth) acrylic acid 2- (4-benzoyl-3) (Meth) acrylic acid esters having a cyclic structure other than a hydroxyl group and a heterocyclic ring such as -hydroxyphenoxy) ethyl;

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 These may be used, and these may be used alone or in combination of two or more.

As the compound (b2), in view of compatibility with the compound (C) and durability such as heat resistance and water resistance, 1,2-cyclohexanedimethanol acrylate, 1,3-cyclohexanedimethanol acrylate, acrylic Particularly preferred are acid 1,4-cyclohexanedimethanol, 2-hydroxy-3-phenoxypropyl acrylate and the like.

Thus, by using the compound (B), it is easy to obtain 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.

<Compound (C)>
The α, β-unsaturated double bond group-containing compound (C) having no hydroxyl group in the molecule in the resin composition of the present invention will be described. In the present invention, the compound (C) is a monomer of a compound containing an α, β-unsaturated double bond group having no hydroxyl group in the molecule, and the component (C) is added to the resin composition. By containing, it is easy to improve the efficiency and sensitivity of the copolymerization reaction with the compound (B). In addition, the viscosity of the resin composition can be easily reduced, and the workability during modeling can be easily improved. In addition, it is possible to improve the glass transition point (Tg) of the modeled object to develop a high cohesive force or to form a three-dimensional modeled article having good heat resistance and water resistance. Although it does not specifically limit, The following can be mentioned as a compound which can be used as a component (C).

Examples of the compound (C) 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 succinate , Mono (meth) acrylic acid ω-carboxypolycaprolactone ester, etc., repeating a lactone ring by ring-opening addition of a lactone ring, polylactone type (meth) acrylic acid ester, alkylene oxide such as ethylene oxide and propylene oxide are repeated A carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxylic acid such as an ester of an alkylene oxide-added succinic acid having a carboxyl group at the terminal and (meth) acrylic acid, Its acid anhydrides;

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, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Carboxylic acids such as cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid and the like, and carboxylic acids containing alicyclic and aromatic rings containing aromatic groups and aromatic rings, and acid anhydrides thereof Etc .;

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, (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, 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, vinylamine, methylvinylamine, ethylvinylamine, propylvinylamine, butylvinylamine, 2-vinylimidazole, 2-vinylpiperazine, 4-vinylpiperazine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 2-vinylpyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3-vinylpyrazine, 2-vinylpyrimidine, 2-vinylpyridazine, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl-1H-benzimidazole, 2-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquino Phosphorus, 2-vinylisoxaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine, 2,6- Vinyl compounds having primary and / or secondary amino groups such as divinylpyridine;

For example, (meth) allylamine, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5- (1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5- (Meth) having primary and / or secondary amino groups such as isopropylpyrimidine, 2- (meth) allylpyridine, 4- (meth) allylpyridine, 3,6-dihydro-4- (meth) allylpyridine, etc. Allyl compounds;

For example, vinyl compounds containing tertiary amino groups such as N-ethyl-N-nitrosovinylamine;

For example, maleic derivatives of maleimide derivatives having both nitrogen and oxygen atoms, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, β-unsaturated double bond 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, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 1-allyladamantane, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinyl Cyclic compounds containing alkenyl groups such as benzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid, cyclohexyl vinyl ether, cyclohexylmaleimide, vinylcyclohexene monooxirane ;

  For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( Aromatic vinyl monomers such as 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

For example, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, tetrahydrofurfuryl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 1-naphthyl vinyl ether, 2- Cyclic vinyl ethers such as naphthyl vinyl ether;

For example, vinyl phenyl pentyl ether, vinyl phenyl hexyl ether, vinyl phenyl heptyl ether, vinyl phenyl octyl ether, vinyl phenyl nonyl ether, vinyl phenyl decyl ether, vinyl phenyl undecyl ether, vinyl phenyl dodecyl ether, vinyl phenyl tridecyl ether, vinyl Phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eicosyl ether, vinyl phenyl henecosyl ether, vinyl phenyl doco Sil ether, vinyl phenyl methyl butyl ether, vinyl phenyl Rupentyl ether, vinyl phenyl methyl hexyl ether, vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl Tridecyl ether, vinyl phenylmethyl tetradecyl ether, vinyl phenyl methyl pentadecyl ether, vinyl phenyl methyl hexadecyl ether, vinyl phenyl methyl heptadecyl ether, vinyl phenyl methyl octadecyl ether, vinyl phenyl methyl nonadecyl ether, vinyl phenyl methyl eicosyl Ether, vinyl phenyl methyl henecosyl ether, vinyl Aromatic vinyl ether-based monomers having a long-chain alkyl groups such as E methylpropenylmethyl docosyl ether;

For example, hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate , Octadecyl 4-vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenyl Decyl benzoate, 4-isopropenylbenzoic acid dodecyl, 4-isopropenylbenzoic acid tetradecyl, 4-isopropenylbenzoic acid hexadecyl, 4-isopropenylbenzoic acid octadecyl, 4-isopropenylbenzoic acid eicosyl, 4-isopropenylbenzoic acid Docosil How long vinylbenzoic acid ester having a chain alkyl group or isopropenyl benzoic acid ester monomers;

For example, tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether , N-pentyltetra (ethylene oxide) vinyl phenyl ether, tetra (propylene oxide) vinyl phenyl ether, methyl tetra (propylene oxide) vinyl phenyl ether, ethyl tetra (propylene oxide) vinyl phenyl ether, propoxy tetra (propylene oxide) vinyl phenyl ether , N-butyltetra (propylene oxide) vinyl phenyl ether, n-pentaxytetra (propylene Xylose) vinyl phenyl ether, poly (ethylene oxide) vinyl phenyl ether, methyl poly (ethylene oxide) vinyl phenyl ether, ethyl poly (ethylene oxide) vinyl phenyl ether, poly (propylene oxide) vinyl phenyl ether, methyl poly (propene oxide) vinyl phenyl ether , Ethyl poly (propylene oxide) ethenyl phenyl ether, poly (ethylene oxide) vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene oxide) ethenyl benzyl ether, poly (propylene oxide) vinyl benzyl ether, methyl vinyl Poly (propylene oxide) vinyl benzyl ether, ethyl poly (propylene oxide) vinyl benzyl ether , Poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether, methyl poly (propylene oxide) vinyl phenyl ethyl ether Vinyl phenyl ether monomers having a long-chain polyalkylene oxide moiety such as ethyl poly (propylene oxide) vinyl phenyl ethyl ether;

For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether Type monomers;

For example, poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (propylene oxide) isopropenyl phenyl ether, methyl poly (propylene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethylene oxide) isopropenyl benzyl ether, methyl poly (ethylene oxide) isopropenyl benzyl ether, ethyl poly (ethylene oxide) isopropenyl benzyl ether, poly (propylene oxide) isopropenyl benzyl Ether, methyl poly (propylene oxide) isopropenyl benzyl ether Isopropenyl monomers having any polyalkylene oxide moiety;

For example, mono-long chain alkyl ester cyclic monomers of dicarboxylic acid such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

For example, monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate;
Polyalkylene oxides such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl polyvinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropylenylbenzoate poly (propylene oxide) Vinyl benzoate or isopropenyl benzoate monomers having a moiety;

For example, alkenyl group-containing cyclic sulfonic acids such as styrenesulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid;

For example, ammonium styrene sulfonate, monomethyl ammonium styrene sulfonate, dimethyl ammonium styrene sulfonate, trimethyl ammonium styrene sulfonate, tetramethyl ammonium styrene sulfonate, ethyl ammonium styrene sulfonate, diethyl ammonium styrene sulfonate, triethyl styrene sulfonate Styrenesulfonic acid such as ammonium, tetraethylammonium styrenesulfonate, propylammonium styrenesulfonate, dipropylammonium styrenesulfonate, tripropylammonium styrenesulfonate, butylammonium styrenesulfonate, pentylammonium styrenesulfonate or hexylammonium styrenesulfonate Ammonium salts of
Metal salts of styrene sulfonic acid such as sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, magnesium styrene sulfonate, zinc styrene sulfonate, iron styrene sulfonate;
Metal salts and ammonium salts of alkenyl group-containing vinyloxybenzenesulfonic acid such as ammonium vinyloxybenzenesulfonate, sodium vinyloxybenzenesulfonate, potassium vinyloxybenzenesulfonate, etc .;
2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonate sodium, 2-methyl-2-propenyloxybenzenesulfonate potassium and the like 2-methyl-2-propenyloxybenzenesulfonate Metal salts and ammonium salts of acids;

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, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl- 1H-pyrazole, 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 1 -Vinylindazole, 1-vinylquinoline, 1-vinylisoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1-vinylcarbazole, 1,1'-divinyl-2,2'-bi (1H-imidazole) N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, 1-bi Le -2 (IH) - vinyl group-containing compounds having a heterocyclic nitrogen-containing, such as pyridinethione;

For example, 1- (meth) allyl-1H-imidazole, 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazol-3-ium, 1- ( (Meth) allyl-3-ethyl-1H-imidazol-3-ium, 5-bromo-1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 1- (meth) allyl-5,5- Diethylpyrimidine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5-triazine-2-amine, 1-benzyl 2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl-1, 3,5-dimethyl- , 4-diamine, 3-vinyl-1,2,4,5-vinyl group-containing compounds having a six-membered ring nitrogen-containing, such as tetrazine;

For example, 1-vinyl-1H-benzimidazole, 1-vinyl-5,6-dimethyl-1H-benzimidazole, 1-vinylindazole, 1-vinylquinoline, 1-vinylquinoline, 1-vinylisoquinoline, 1-vinyliso Xaline, 1-vinylquinoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1- (meth) allyl-1H-benzimidazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meta Nitrogen atoms such as allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline Containing heteropolycyclic ethenyl group-containing compounds;

For example, compounds having a nitrogen atom-containing heterocyclic structure and two or more vinyl groups such as 1-methyl-4,5-divinyl-1H-imidazole;

For example, 1- (meth) allyl-3,5-dimethyl-1H-pyrazole, 1- (1-methylpropyl) -5- (meth) allylpyrimidine, 1- (meth) allyl-5-isopropylpyrimidine, 1- (Meth) allyl group-containing compounds having a nitrogen atom-containing heterocyclic structure such as (meth) allylpyridine, 1- (meth) allylpyridine, 3,6-dihydro-1- (meth) allylpyridine;

For example, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meth) allylindazole, 3-phenyl-4- (meth) allylisoquinoline, 9- (meth) allyl (Meth) allyl group-containing compounds having a heteropolycyclic structure containing a nitrogen atom, such as -9H-carbazole;

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, maleimide derivatives having both nitrogen and oxygen atoms, such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

For example, 2-vinyl oxazole, 2-phenyl-4-vinyl oxazole, 2-phenyl-5-vinyl oxazole, 5-ethoxy-2-vinyl oxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5 -It has a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, 2-vinylbenzoxazole Vinyl group-containing compounds;

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, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

For example, 2-vinylthiazol, 4-methyl-5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzo Examples thereof include vinyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom such as thiazole, and these may be used alone or in combination of two or more.

From the viewpoint of durability such as heat resistance and water resistance, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl methacrylate, 4-acryloylmorpholine, 1-vinylimidazole, N-vinyl-ε-caprolactam 1-vinylpyridin-2 (1H) -one, di (meth) acrylic acid ethoxylated isocyanuric acid, and tri (meth) acrylic acid ethoxylated isocyanuric acid are preferred.

In addition, there is no particular limitation as long as it has an α, β-ethylenically unsaturated double bond group in its structure,

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, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perfluorodecylethyl, (meth) acrylic acid 2 (Meth) acrylic acid such as perfluoro hexadecyl ethyl perfluoroalkyl esters;

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, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acid, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;

  For example, vinyl benzoylformate, vinyl benzoyl acetate, vinyl benzoylpropionate, vinyl benzoylbutyrate, vinyl benzoylvalerate, vinyl benzoylhexanoate, vinyl benzoyldodecanoate, 1-naphthoylvinyl acetate, 1-naphthoylpropionate, 1- Naphthoyl vinyl butyrate, 1-naphthoyl vinyl valerate, 1-naphtho vinyl hexanoate, 2-naphtho vinyl acetate, 2-naphtho vinyl propionate, 2-naphtho vinyl butyrate, 2-naphtho vinyl butyrate, 2- Vinyl naphthoyl hexanoate, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotine Vinyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl Vinyl acetate, vinyl 2-furoylpropionate, vinyl 2-furoylbutyrate, vinyl 2-furoylvalerate, vinyl 2-furoylhexanoate, vinyl 2-furoyldecanoate, vinyl 2-furoyldodecanoate, 3-furoyl Vinyl acetate, vinyl 3-furoylpropionate, vinyl 3-furoylbutyrate, vinyl 3-furoylvalerate, vinyl 3-furoylhexanoate, vinyl 3-furoyldecanoate, vinyl 3-furoyldodecanoate, vinyl anthraniloyl acetate , Vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, 4- (2-t-ethoxycarbonylethyl Aromatic vinyl compounds having an acyl group, such as oxy) styrene, 4- (2-t-butoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylpropyloxy) styrene;

  For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Aliphatic (meth) allyl compounds having an acyl group such as stearoyl acetate (meth) allyl and (meth) allylaldehyde

  For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoyl propionate (meth) allyl, benzoyl butyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexane Acid (meth) allyl, 2-naphthoyl acetate (meth) allyl, 2-naphthoyl propionate (meth) allyl, 2-naphthoyl butyrate (meth) allyl, 2-naphthoylvalerate (meth) allyl, 2-naphthoyl Α, β-unsaturated double bonds containing carbonyl groups such as aromatic (meth) allyl compounds having acyl groups such as (meth) allyl hexanoate Compound containing compounds;

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, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Trifunctional (meth) acrylic esters such as pentaerythritol tri (meth) acrylate;

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, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

  For example, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert -Pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexanedecyl vinyl ether , Octa Sil vinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether, 4-ethoxy Butyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol ethyl vinyl ether, diethylene glycol butyl vinyl ether, etc. The aliphatic vinyl Ruethers;

  For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol Divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, 1,4-cyclohexanediol divinyl ether (CHODVE), 1,4-cyclohexanedimethanol divinyl ether ( CHD E), trimethylolpropane trivinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether (TMPEOTVE), epentaerythritol tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol hexavinyl ether, etc. Vinyl ethers of

For example, fluorine-containing vinyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;

  For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing α, β-unsaturated double bond group-containing compounds such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;

For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

For example, mono- or di-alkylaminoalkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

  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;
For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itaconnitrile, 2-propenenitrile, 2-methacrylic acid (meth) acrylate, β-unsaturated double bond group-containing compounds;

  For example, saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate, (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of acids;

  For example, vinyl halides such as vinyl chloride, vinylidene chloride and allyl chloride;

  For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

  For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, vinyl (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

  For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, and the like. In particular, it is not limited to these.

Further, for example, o-di (meth) allylbisphenol A, hydrogenated bisphenol A in which an aromatic ring structure is hydrogenated, and the like are also included in compound (C) if they have an α, β-unsaturated double bond group. . These may use only 1 type or may use multiple types together.

As the other α, β-ethylenically unsaturated double bond group-containing compound (C), a compound having a (meth) acryloyl group is preferable from the viewpoint of reactivity, and the resin composition of the present invention is used as an optical three-dimensional modeling material. When used as, it is preferable that bifunctional or higher (meth) acrylic acid esters are included from the viewpoint of the active energy ray polymerization rate.

  In the α-, β-unsaturated double bond group-containing compound (C) that does not have a hydroxyl group in the molecule of the present invention, polymerization curability by irradiation with active energy rays, cure shrinkage of a molded article described later, and In terms of durability such as heat resistance, moist heat resistance and water resistance, a good resin can be obtained by blending in a timely manner so that both the hydroxyl group and the cyclic structure of compound (B) and the cyclic structure of compound (C) are contained. It can be a composition.

The compound (C) preferably has a viscosity of 0.5 to 2,000 mPa · s, more preferably 1 to 1,000 mPa · s. By using such a compound (C), it is possible to maintain the active energy ray polymerizability while suppressing the increase in viscosity of the resin composition and improving the formability.

As described above, the α, β-unsaturated double bond group-containing compound (C) having at least a hydroxyl group in the molecule of the present invention is an α, β-unsaturated double bond group having a hydroxyl group. By coexisting with the compound (B), a cured resin having high cohesive strength can be formed after irradiation with active energy rays.
The compound (C) of the present invention is improved in the copolymerization reactivity with the α, β-unsaturated double bond group-containing compound (B) having a hydroxyl group in the molecule and the cohesive strength of the cured product after the copolymerization reaction. Taking this point into consideration, the α, β-unsaturated double bond group contained in the compound (C) is preferably an acryloyl group or a methacryloyl group. Furthermore, the curing shrinkage of the three-dimensional model to be described later can be reduced, and the flexibility can be improved.

<Photopolymerizable oligomer (E)>
In the resin composition of the present invention, the photopolymerizable oligomer (E) will be described.

The photopolymerizable 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. And having one or more α, β-unsaturated double bond groups in the molecule. The photopolymerizable oligomer may have various functional groups in addition to the α, β-unsaturated double bond group. In one embodiment of the present invention, the photopolymerizable oligomer (E) comprises a polyester photopolymerizable oligomer (e1), a polyurethane photopolymerizable oligomer (e2), a polyepoxy photopolymerizable oligomer (e3) and a polyepoxy photopolymerizable oligomer (e3). It contains at least one selected from the group consisting of acrylic photopolymerizable oligomers (e4), and these can be used without particular limitation.

Polyester-based photopolymerizable oligomer (e1);
Examples of the polyester photopolymerizable oligomer (e1) include a terminal of a polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol on a main chain skeleton or a hydroxyl group in a polyester chain and (meth) acrylic acid, maleic acid, etc. A compound obtained by esterification with an α, β-ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule, or a carboxyl group in the terminal or polyester chain of the polyester and (meth) acrylic It is a compound obtained by esterification with the aforementioned compound (B) such as 2-hydroxyethyl acid 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-based photopolymerizable 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 dicarbo 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 acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used as 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 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-based photopolymerizable oligomer (e2):
The polyurethane-based photopolymerizable oligomer (e2) is a compound obtained by reacting at least one compound having an isocyanate group with the compound (B), or a compound having at least one isocyanate group and the above-mentioned many compounds. A compound obtained by reacting a urethane prepolymer of a terminal isocyanate group obtained by reacting a monohydric alcohol with the compound (B), or a compound having at least one isocyanate group and a polyhydric alcohol are reacted. Compound obtained by reacting urethane prepolymer of terminal isocyanate group obtained by reacting the obtained urethane prepolymer of terminal isocyanate group with a compound having at least one amino group and said compound (B) It is. Also included in the polyurethane photopolymerizable 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, disec-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-piperidine Ethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkylamine, di-cured tallow alkyl Min, 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′- Diamines having two primary amino groups such as diaminodiphenylmethane, 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 photopolymerizable oligomer (e3):
The polyepoxy photopolymerizable oligomer (e3) is a compound having a glycidyl group and α, having at least one hydroxyl group or carboxyl group in the molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid and maleic acid. It is a compound obtained by a reaction with a β-unsaturated double bond group-containing compound, and is a compound substantially having no glycidyl group and having an α, β-unsaturated double bond group-containing compound. Representative examples include bisphenol type, epoxidized oil type, phenol novolac type, and alicyclic type. The bisphenol-type polyepoxy photopolymerizable oligomer includes α, β 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. -Obtained by reacting with an unsaturated double bond group-containing compound.

Epoxidized oil Polyepoxy-based photopolymerizable oligomer includes epoxidized oil such as soybean oil and one or more hydroxyl groups or carboxyl groups in a molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. Those obtained by reaction with an α, β-unsaturated double bond group-containing compound having a group can be used. As the novolak type polyepoxy photopolymerizable oligomer, α, β having one or more hydroxyl groups or carboxyl groups in the molecule such as novolak type epoxy resin and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. -What can be obtained by reaction with an unsaturated 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 photopolymerizable oligomer (e4):
In the present invention, an acrylic photopolymerizable oligomer (e4) can also be used as the photopolymerizable oligomer (E). Specific examples of usable compounds include modified polyethers having α, β-unsaturated double bond groups, amine-modified α, β-unsaturated double bond group-containing compounds, alkyd resins, and spiroacetal resins. Selected from the group consisting of a modified α, β-unsaturated double bond group-containing compound obtained by adding an α, β-unsaturated double bond group to various compounds such as polybutadiene resin, polythiol polyene resin and polyhydric alcohol. Photopolymerizable oligomers or prepolymers of one or more compounds can be used.

In addition to the agglomeration density, compatibility with other components that form a molded article by polymerization, and durability such as heat resistance and moist heat resistance, from the viewpoint of obtaining excellent characteristics, the weight average of the photopolymerizable oligomer (E) The molecular weight (hereinafter referred to as “Mw”) is preferably in the range of 300 to 50,000 in terms of the compatibility of the three-dimensional structure, good durability (heat resistance, heat and humidity resistance), and aggregation density. It is preferable to be in the range of ˜30,000. By using an oligomer having an Mw of 50,000 or less, it is possible to easily provide a resin composition having excellent fluidity and compatibility with the components (A), (B) and (C). 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 adhesive, cohesive failure in the three-dimensional modeled object hardly occurs.
The method for measuring the number average molecular weight (Mn), the weight average molecular weight (Mw), the acid value (AV) and the hydroxyl value (OHV) will be described later.

Although it does not specifically limit, in this invention, it is preferable that a polyurethane-type polymerizable oligomer (e2) is included. When the resin composition is used for applications such as an adhesive, the elasticity and flexibility of the cured product tends 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, it tends to have low elasticity and low hydrolysis resistance. 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 compound (A), the compound (B) and the compound (C) is 100 parts by weight, the amount of the photopolymerizable oligomer (E) is preferably 1 to 250 parts by weight. . More preferably, it is 1 to 100 parts by weight. By setting the photopolymerizable oligomer (E) to 1 part by weight or more, deficiency in cohesive force can be improved, and characteristics such as heat resistance and heat and humidity resistance can be easily improved. On the other hand, by setting the photopolymerizable oligomer (E) to 250 parts by weight or less, it becomes easy to highly suppress curing shrinkage when the resin composition is used as a modeling material.

The resin composition in the present invention is composed of 0.2% by weight or less of compound (A), 0.5 to 50% by weight of compound (B), and compound in the total amount of the active energy ray polymerizable resin composition for optical three-dimensional modeling. It is preferable to contain 20 to 99.4% by weight of (C) and 20 to 99.4% by weight of photopolymerizable oligomer (E), 0.15% by weight or less of compound (A), and compound (B). More preferably, it contains 1 to 40% by weight, compound (C) 40 to 98% by weight, and photopolymerizable oligomer (E) 30 to 90% by weight.
By containing 0.2% by weight or less of compound (A) and 30 to 90% by weight of photopolymerizable oligomer (E) in the total amount of the resin composition, sufficient cohesive force and dispersibility of pigments and dyes can be obtained. Easy to improve heat resistance and moist heat resistance. 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, when the compound (A) exceeds 0.2% by weight in the total amount of the resin composition, there is a concern about a decrease in the curing rate due to an increase in the compound that does not contribute to the polymerization and a decrease in the strength of the three-dimensional structure.

<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 model, since different types of polymerization curing by active energy ray irradiation is possible, the cured product forms a phase-separated structure, and is elastic. Since stress relaxation properties and creep characteristics can be easily controlled, moderate elasticity and flexibility maintenance and cure 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 is compound (d3), compound (d4) having two or more oxygen or hetero groups other than oxygen.

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 [5.1.0.02,4] 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 Karen 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, ethylenebis (3,4-oxiranecyclohexanecarboxylate), bis (3,4-oxy) Silanecyclohexylmethyl) 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' It can also be named as', 5 ''-Dioxanespiro-3 ''',4'''-oxirane cyclohexane Compound), 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 compound compounds exemplified herein may be used alone or in combination with a plurality of epoxy group-containing compound compounds, and are not particularly limited thereto.

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 (c2) may be used alone or in combination of two or more.

  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 it may use it in combination of 2 or more types.

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

<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.
Specific examples include the following. 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl Dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-thioxanthone, camphorquinone, and Photo radical generator (f1) such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

  Moreover, as a commercial item, the following is mentioned, for example. Irgacure 184,907,651,1700,1800,819,369, and 261 (manufactured by BASF), DAROCUR-TPO (manufactured by BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), Darocur-1173 Photoradical generators such as (Merck), Ezacure KIP150, and TZT (Nihon Shibel Hegner), Kayacure BMS, and Kayacure DMBI (Nippon Kayaku).

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

Further, as the α, β-ethylenically unsaturated double bond group-containing compound (C), glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) acrylic acid (3-methyl- (3-oxetanyl) methyl, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, and other heterocycle-containing (meth) acrylates having a 3-membered or 4-membered oxygen atom, or cationically polymerizable compounds ( When D) or an epoxy-modified vegetable oil is used as the cationic polymerizable compound, it is preferable to contain a known photoacid generator (e2) as the active energy ray polymerization initiator, if necessary. 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 because it forms 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 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, with the total amount of the resin composition being 100 parts by weight, 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 weight.

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.

The sensitizer is preferably used in an amount of 0.01 to 100 parts by weight, more preferably in the range of 0.1 to 60 parts by weight, with respect to 100 parts by weight of the active energy ray polymerization initiator (F). Although it can be preferably used, it is more preferable not to use at all from the viewpoint of yellowing.

<Silane compound (G)>
Next, the silane compound (G) will be described.
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 weight part of silane compounds (G) in 100 weight part of resin compositions of this invention, and it is more preferable to contain 0.1-5 weight part. If the amount is less than 0.01 parts by weight, the effect of improving heat resistance and moist heat resistance cannot be expected. On the other hand, when the amount exceeds 10 parts by weight, 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. Since the hardness with respect to hardened | cured material falls, it is not preferable.

<Antioxidant (H)>
Next, the antioxidant (H) will be described.
The resin composition in the present invention may further contain an antioxidant. By containing the antioxidant (H), coloring of the cured resin after active energy ray polymerization with time 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 weight part with respect to 100 weight part of resin compositions for optical three-dimensional modeling, and it is preferable that it is 0.01-10 weight part. If it is less than 0.01 parts by weight, it will be consumed early by the active energy rays, so the polymerization rate will decrease. Conversely, if it exceeds 20 parts by weight, the polymerization rate will increase, but the molecular weight of the cured resin will decrease, Since the cohesive force as a three-dimensional modeled object falls, durability falls.

<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.

<Properties of Active Energy Ray Polymerizable Resin Composition for Optical Stereolithography>
Next, the properties of the active energy ray polymerizable resin composition for optical three-dimensional modeling will be described.
The resin composition of the present invention comprises the above-described coloring material (A) and photopolymerizable oligomer (E) as essential components, and further, if necessary, compound (B), compound (C), compound (D), light It can be produced by mixing the polymerization initiator (F), the silane compound (G), the antioxidant (H) and other various additives (Q) and then mixing them uniformly.
When stirring and mixing, it 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.

It is important that the resin composition for optical three-dimensional modeling in the present invention has a viscosity at 25 ° C. of 1 to 2000 mPa · s, preferably 10 to 1500 mPa · s, and 20 to 1000 mPa · s. More preferred. 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 (B) and the compound (C), 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 an active energy ray polymerizable resin composition for optical three-dimensional modeling>
Next, a modeling process (optical three-dimensional modeling method) of the cured resin and the active energy ray polymerizable resin composition for optical three-dimensional modeling will be described.
The resin composition of the present invention is suitably used as a photocurable liquid resin material in an optical three-dimensional modeling method (hereinafter also referred to as an optical modeling method). That is, a resin cured product having a desired three-dimensional shape is produced by an optical modeling method that selectively irradiates active energy rays such as ultraviolet rays to the resin composition of the present invention to supply energy necessary for polymerization and curing. be able to.

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 three-dimensional shaped object with a desired shape is obtained. 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 , it takes a long time for curing, and when it exceeds 500 mW / cm ² , the uncured resin composition may be deteriorated by the heat radiated from the lamp. It is not preferable because of its properties. 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 is 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. Thus, 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>
Next, a three-dimensional molded item will be described.
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. In addition, 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-curing 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 resin cured product of the active energy ray-polymerizable resin composition for optical three-dimensional modeling of the present invention is a variety of three-dimensional modeling products for electronic products that require complex and fine processing; It can be preferably used as a three-dimensional model such as a model for advertising or exhibition; a prototype for development such as performance testing 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 following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<Manufacture of coloring material (A)>
[Production Examples 1 and 2]
After stirring the compound (C) and the dispersion resin and confirming that the dispersion resin is completely dissolved, a dye or a pigment is added, and 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 1 shows the composition of the produced colorant (A) (pigment dispersion).

Details of the color material (A) shown in Table 1 are as follows. In Table 1, the symbol “no mark” means no blending.
-Dye or pigment E5B02: Quinacridone pigment "Hostaperm Red E5B02" manufactured by Clariant
E4GN: Lanxess nickel complex azo pigment "YELLOW PIGMENT E4GN"
R-550: manufactured by Ishihara Sangyo Co., Ltd. Titanium oxide pigment "Taipeke R-550"
-Dispersing resin 24000: Pigment dispersant "Solsperse 24000" manufactured by Avicia
33000: Pigment dispersant “Solsperth 33000” manufactured by Avicia
・ Compound (C)
PEA: 2-phenoxyethyl acrylate In the present invention, it is possible to provide a dispersion of a color material excellent in various properties without being limited to the above-described components.

[Formulation Examples 1 to 28]
Into a light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less, compound (A) and photopolymerizable oligomer (E) as essential components, and further, if necessary, compound (B), compound (C ), Compound (D), Active Energy Ray Polymerization Initiator (F), Silane Compound (G), Antioxidant (H) and Various Additives (Q) are charged in the ratios shown in Table 2 and sufficiently stirred. After stirring and sufficiently defoaming, the resin composition shown in the formulation example was obtained.

For the resin compositions of the formulation examples shown in Table 2, 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. Also described are methods for measuring molecular weight, hydroxyl value, acid value, and glass transition temperature.

"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.

《Molecular weight》
For the measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw), GPC (gel permeation chromatography) “Shodex GPC System-21” manufactured by Showa Denko KK was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and weight average molecular weight (Mw) is determined in terms of polystyrene.

<< Hydroxyl value (OHV) >>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula. The hydroxyl value is a numerical value of the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Nonvolatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the blank experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

《Acid Value (AV)
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<< Glass transition temperature (Tg) >>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
About 10 mg of the resin composition shown in Table 2 coated on a peeled polyester film, irradiated with active energy rays, polymerized and cured, scraped into an aluminum pan as a sample, weighed, and a differential scanning calorimeter The sample was heated for 5 minutes at a temperature of 100 ° C. using an aluminum pan of the same type without a sample as a reference, and then rapidly cooled to −120 ° C. using liquid nitrogen. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained during the temperature elevation.

Illustrative compounds are specifically shown in Table 2 below, but are not limited thereto. In Table 2, the symbol “-” means no blending.

・ Coloring material (A)
See creation example in Table 1.
・ Compound (B)
4HBA: 4-hydroxybutyl acrylate 2HEA: 2-hydroxyethyl acrylate CHDMA: 1,4-cyclohexanedimethanol acrylate HPPA: 2-hydroxy-3-phenoxypropyl acrylate / compound (C)
IBXA: Isobornyl acrylate M-315: Nuacrylate ring-containing triacrylate ADCP: Dicyclopentanyl diacrylate ACMO: 4-acryloylmorpholine GMA: Glycidyl mesylate NPGDA: Neopentyl glycol diacrylate Compound (D)
2021P: 3,4-oxiranecyclohexylmethyl-3,4-oxiranecyclohexanecarboxylate (Daicel)
DOME: di (1-ethyl-3-oxetanyl) methyl ether,
GC: Glycerin carbonate / photopolymerizable oligomer (E)
811: Polyester acrylate “Ebecryl 811” manufactured by Daicel Cytec Co., Ltd.
3000B: Made by Nippon Synthetic Chemical Industry Co., Ltd. Polyurethane oligomer (urethane acrylate) "Purple light UV3000B"
600: Polyepoxy oligomer (epoxy acrylate) “Ebecryl 600” manufactured by Daicel Cytec Co., Ltd.
・ Initiator (F)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, DAROCUR TPO)
CPI-110P: p-phenylthiophenyldiphenylsulfonium PF ₆ salt / silane coupling agent (G)
A-174: Silane coupling agent / antioxidant (H) manufactured by Tanac Corporation
168: Antioxidant “IRGAFOS168” manufactured by BASF
・ Antioxidant (Q)
DIDP: Diisodecyl phthalate (plasticizer)
Indicates.

[Examples 1 to 25] [Comparative Examples 1 to 3]
About the resin composition for optical three-dimensional model | molding shown in Table 2, the hardening rate and the mechanical characteristic were measured with the following method, and the molding test was done. The results are shown in Table 3.

《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 by palpation.
○: No tack △: There is some tack ×: There is tack

"Young's modulus"
The applicator was used to apply a resin composition to a thickness of 250 μm on a glass plate, and irradiated with ultraviolet rays of 0.5 J / cm ² (wavelength: 350 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.
Measurement The Young's modulus of the test piece was measured in a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity under the conditions of a tensile speed of 1 mm / min and a gap between marked lines of 25 mm. Further, the breaking elongation and breaking strength of the test piece at 23 ° C. were measured under the conditions of a tensile speed of 50 mm / min and a gap between marked lines of 25 mm.
This Young's modulus was evaluated in four stages. In the case of “△” evaluation or higher, 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.

<Measurement of 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 × length 50 × height 1 mm): laminated thickness of one time 0.2 mm × 5 times of lamination].
After the attached resin solution was carefully wiped off, the weight 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 weight W ₂ was measured.
The degree of swelling was calculated according to the following formula and evaluated in three stages. In the case of “△” evaluation or higher, 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.

<Measurement of warpage>
Using the above-mentioned stereolithography apparatus, a test piece [(width 50 × length 50 × 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].
It shape | molded using the optical modeling apparatus mentioned above (1 time of lamination | stacking thickness 0.2mm x 100 times lamination | stacking). After the adhered resin solution was wiped off, post-curing was performed using a UV lamp (irradiation dose 5 J / cm ² ).
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.
A: Less than 0.2 (mm). No problem at all. In the case of “△” evaluation or higher, there is no problem in actual use.
○: 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 and irradiated with ultraviolet rays of 0.5 J / cm ² (wavelength: 350 nm) to obtain a glass laminated cured film at 23 ° C. and 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. In the case of “△” evaluation or higher, there is no problem in actual use.
(Double-circle): There is no generating 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.

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 3, and has a Young's modulus, swelling degree, warpage, and surface lubricity. Excellent results were shown in all items (Examples 1 to 25). On the other hand, when the resin composition for optical three-dimensional modeling other than the present invention is polymerized and cured with active energy rays, there are difficulties in any of curing speed, Young's modulus, swelling degree, warpage, and surface lubricity. Yes, it is difficult to use.

Claims (4)

In a liquid photocurable resin composition containing a photopolymerizable compound and a photopolymerizable initiator, based on the weight of the photocurable resin composition,
0.2% by weight or less of color material (A),
A photopolymerizable oligomer (E);
The resin composition for optical three-dimensional modeling characterized by containing.
However, a color material in which carbon black is dispersed as a pigment is excluded. In a liquid photocurable resin composition containing a photopolymerizable compound and a photopolymerizable initiator, based on the weight of the photocurable resin composition,
0.2% by weight or less of color material (A),
A photopolymerizable oligomer (E);
An α, β-unsaturated double bond group-containing compound (B) having one or more hydroxyl groups in the molecule;
An α, β-unsaturated double bond group-containing compound (C) having no hydroxyl group in the molecule;
The resin composition for optical three-dimensional modeling characterized by containing.
However, a color material in which carbon black is dispersed as a pigment is excluded. A cured resin obtained by polymerizing and curing the active energy ray-polymerizable resin composition according to claim 1 or 2 with active energy rays.   A three-dimensional structure made of the cured resin according to claim 3.