JP2016098324A - 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 has little deformation in molding such as warpage and swelling and can give a cured product with high accuracy by optical three-dimensional molding process, and which can be polymerized and cured by irradiation with various active energy rays and give a resin cured product, and a three-dimensional molded object that is strong and robust.SOLUTION: The active energy ray-polymerizable resin composition for optical three-dimensional molding comprises: an α,β-unsaturated double bond group-containing compound (A) having a cyclic structure (Ca) containing a nitrogen atom; an α,β-unsaturated double bond group-containing compound (B) having a cyclic structure (cb) containing no hetero atom; and an α,β-unsaturated double bond group-containing compound (X) having no cyclic structure.SELECTED DRAWING: None

Description

  The present invention is an optical three-dimensional modeling active energy that gives a three-dimensional modeled article that has a low viscosity in an uncured state, a high curing rate by light irradiation, excellent molding accuracy, and excellent mechanical properties such as strength and heat resistance. The present invention relates to a linear 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 from 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 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 may be deformed over time (warping, shrinkage, lifting of the overhang 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 and the like, radically polymerizable compounds such as urethane (meth) acrylate, epoxy (meth) acrylate, and photosensitive polyimide (for example, patents) Documents 4 and 5), 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-A-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 optical three-dimensionally active energy ray-polymerizable resin composition that is small in deformation with time and that can provide a cured product having excellent 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 optical three-dimensional modeling active energy ray polymerizable resin composition shown below, and further completed the present invention by a three-dimensional modeling product. It came to do.
That is, the present invention relates to an α, β-unsaturated double bond group-containing compound (A) having a cyclic structure (ca) containing a nitrogen atom and an α, β having a cyclic structure (cb) not containing a hetero atom. -Active energy ray polymerizable resin composition for optical three-dimensional modeling containing unsaturated double bond group-containing compound (B) and α, β-unsaturated double bond group-containing compound (X) having no cyclic structure Related to things.

  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 object can provide an optical three-dimensional active energy ray-polymerizable resin composition 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 resin composition for optical three-dimensional modeling of the present invention includes an α, β-unsaturated double bond group-containing compound (A) having a cyclic structure (ca) containing a nitrogen atom, and a cyclic structure containing no heteroatom ( For optical three-dimensional modeling comprising an α, β-unsaturated double bond group-containing compound (B) having cb) and an α, β-unsaturated double bond group-containing compound (X) having no cyclic structure It is characterized by being an active energy ray polymerizable resin composition.

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 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.
<Α, β-unsaturated double bond group-containing compound (A) having a cyclic structure (ca) containing a nitrogen atom>
In the resin composition for optical three-dimensional modeling of the present invention (hereinafter referred to as a resin composition), the α, β-unsaturated double bond group-containing compound (A) having a cyclic structure (ca) containing a nitrogen atom is: In addition to the addition polymerization of α, β-unsaturated double bond groups on the three-dimensional structure after irradiation with active energy rays, since it has a cyclic structure (ca) containing nitrogen atoms, Due to the rigidity derived from the annular structure, the glass transition point (Tg) of the modeled object is improved, so that the internal cohesive force is further improved, and a three-dimensional modeled object having good heat resistance and water resistance is formed. It is possible to do. The cyclic structure (ca) containing such a nitrogen atom is a cyclic structure (ca1) containing only one or more nitrogen atoms in the ring, and contains both nitrogen and oxygen atoms in the ring. The cyclic structure (ca2), and the cyclic structure (ca3) containing both a nitrogen atom and a sulfur atom in the ring. Furthermore, the cyclic structure (ca1) is roughly classified into a ring structure (ca1-1) having only one nitrogen atom and a ring structure (ca1-2) having two or more nitrogen atoms.

Such a cyclic structure (ca) containing a nitrogen atom is not particularly limited, but contains one nitrogen atom such as ethyleneimine ring, azetidine ring, pyrrolidine ring, piperidine ring, azepane ring, quinuclidine ring, tropane ring, etc. Saturated monocycles (ca1-1); Saturated monodates (ca1-2) containing two or more nitrogen atoms such as piperazine rings and methenamine rings; azirine rings, azeto rings, pyrrole rings, pyridine rings, quinuclidine rings Unsaturated monocycles containing one nitrogen atom such as azepine ring (ca1-1); imidazole ring, indazole ring, imidazoline ring, pyrazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazole ring, triazine ring, Unsaturated monocyclic rings (ca1-2) containing two or more nitrogen atoms such as tetrazole ring; indole ring, isoindole ring Unsaturated polycycles containing one nitrogen atom such as quinoline ring, isoquinoline ring, carbazole ring, acridine ring (ca1-1); benzimidazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, cinnoline ring, pteridine ring, Represented by unsaturated polycyclic rings containing two or more nitrogen atoms such as naphthyridine ring, purine ring, benzotriazole ring, phenazine ring, benzodiazevin ring, benzo-o-cinnoline ring, porphyrin ring, chlorin ring, choline ring Heterocycles containing only nitrogen atoms (ca1-2);

  Nitrogen atoms such as morpholine, pyrrolidone, lactam, isatin, primidone, oxazine, oxazole, isoxazole, benzoxazine, phenoxazine, benzophenoxazine, phenazone, hydantoin and phthalocyanine And heterocycles containing both oxygen atoms (ca2);

Heterocycles containing both nitrogen and sulfur atoms (ca3) such as thiazol ring, isothiazol ring, thiazine ring, phenothiazine ring and the like can be mentioned, and can be used without particular limitation.

As the α, β-unsaturated double bond group-containing compound (A) having a cyclic structure (ca) containing these nitrogen atoms, a cyclic structure (ca1) containing only one or more nitrogen atoms in the ring. ), Compound (a2) having a cyclic structure (ca2) containing both nitrogen and oxygen atoms in the ring, and both nitrogen and sulfur atoms in the ring A cyclic structure (ca3) having a ring structure (ca1-1) having only one nitrogen atom, and a compound (a1). It is roughly classified into the compound (a1-2) having a ring structure (ca1-2) having two or more atoms.

The compound (A) can be used without particular limitation as long as it has a cyclic structure (ca) containing one or more nitrogen atoms in its structure, and can be used as an α, β-unsaturated double bond group. Conventionally, acryloyl group, methacryloyl group, vinyl group, vinyl ester group, vinylsilyl group, vinyl ether group, allyl group, methallyl group, etc. are known and can be used without particular limitation. Among the saturated double bond groups, vinyl group, vinyl ester group, vinylsilyl group, vinyl ether group, allyl group, methallyl group, etc. are inferior in radical polymerizability compared to acryloyl group or methacryloyl group, and compound (A) is Since it is likely to remain unreacted, it is preferable to use an acryloyl group or a methacryloyl group as the α, β-unsaturated double bond group. . In particular, an acryloyl group is particularly preferable because it has good polymerizability by active energy rays such as ultraviolet rays and electron beams.

In the present application, when “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” are expressed, 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 α, β-unsaturated double bond group-containing compound (a1-2) having only two nitrogen atoms in the ring, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyl) Oxypropylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-3′-) tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl) Le -5 '- (meth) acryloyloxyethyl phenyl) -5-chloro -2H- benzotriazole nitrogen-containing polycyclic (meth) acrylate;

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- (meta) Acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, It has a six-membered ring containing a nitrogen atom such as 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine (Meth) acrylic acid esters;

As the α, β-unsaturated double bond group-containing compound (a1-1) having only one nitrogen atom in the ring, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, Cyclic (meth) acrylic acid esters containing nitrogen atoms such as 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate;

  1-vinylpyrrole, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 1-vinyl-2-imidazoline, 2-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 4,5-dihydro-2-vinyl-1H-imidazole, 1-vinylimidazole, 2-vinyl-1H-imidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl-1H-pyrazole, 3 -Vinyl group-containing compounds having a five-membered ring containing a nitrogen atom such as methyl-5-phenyl-1-vinylpyrazole;

2-vinylpiperazine, 4-vinylpiperazine, 1-benzyl-2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 2-vinylpyridine, 3-vinylpyridine, 4 -Vinylpyridine, 6-methyl-2-vinylpyridine, 2-vinylpyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3-vinylpyrazine, 2-vinyl Pyrimidine, 2-vinylpyridazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl-1,3,5-dimethyl-2,4-diamine, 3-vinyl-1,2 Vinyl group-containing compounds having a nitrogen atom-containing six-membered ring, such as 1,4,5-tetrazine;

Vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, vinyl nicotinoyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, isonicotinoyl Vinyl group-containing compounds having an acyl group and a nitrogen atom-containing six-membered ring such as vinyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate ;

1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl -1H-benzimidazole, 1-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquinoline, 2-vinylisoxaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 1 -Nitrogen-containing polycyclic vinyl group-containing compounds such as vinylcarbazole;

1-methyl-4,5-divinyl-1H-imidazole, 1,1′-divinyl-2,2′-bi (1H-imidazole), 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5 -Compounds having a nitrogen atom-containing ring structure and two or more vinyl groups, such as divinylpyridine and 2,6-divinylpyridine;

1- (Meth) allyl-1H-imidazole [1-allyl-1H-imidazole and 1-methallyl-1H-imidazole are collectively referred to as “1- (meth) allyl-1H-imidazole”. The same applies below. ], 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazole-3-ium, 1- (meth) allyl-3-ethyl-1H-imidazole -3-ium, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5-bromo-1--1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 5- ( 1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5-isopropylpyrimidine, 1- (meth) allyl-5,5-diethylpyrimidine, 2- (meth) allylpyridine, 4- (Meth) allylpyridine, 3,6-dihydro-3- (meth) allylpyridine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6 Having a cyclic structure containing nitrogen atoms, such as dichloro -1,3-5- triazin-2-amine (meth) allyl group-containing compounds;

2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 1- (meth) allyl-1H-benzimidazole, 2- (meth) allylindazole, 1- (meth) allyl-3 -Methyl-1H-indazole, 1- (meth) allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 3-phenyl-4- (meth) (Meth) allyl group-containing compounds having a polycyclic structure containing nitrogen atoms, such as allylisoquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline, 9- (meth) allyl-9H-carbazole;

Examples of the α, β-unsaturated double bond group-containing compound (ca2) containing both a nitrogen atom and an oxygen atom in the ring include imide (meth) acrylate and 2- (4-oxazolin-3-yl ) Having a cyclic structure containing oxygen atoms in addition to nitrogen atoms such as ethyl (meth) acrylate, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone modified tris- (2-acryloyloxyethyl) isocyanurate (meth) Acrylic esters;

Cyclic acrylamides such as 4-acryloylmorpholine;

Cyclic amide group-containing compounds having both a nitrogen atom and an oxygen atom, such as N-vinyl-2-pyrrolidone and N-vinyl-ε-caprolactam;

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

2-vinyloxazole, 2-phenyl-4-vinyloxazole, 2-phenyl-5-vinyloxazole, 5-ethoxy-2-vinyloxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5-diphenyl Other than nitrogen atoms such as oxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, 2-vinylbenzoxazole, 1-vinylpyridin-2 (1H) -one An ethenyl group-containing compound having a cyclic structure containing an oxygen atom in

Examples of the α, β-unsaturated double bond group-containing compound (ca3) having both a nitrogen atom and a sulfur atom in the ring include 2-vinylthiazol, 4-methyl-5-vinylthiazole, 2 Other than nitrogen atoms such as -vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzothiazole, 1-vinyl-2 (1H) -pyridinethione Examples thereof include vinyl group-containing compounds having a cyclic structure containing a sulfur atom, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  In the α, β-unsaturated double bond group-containing compound (A) having a cyclic structure (ca) containing a nitrogen atom used in the present invention, the ring structure does not contain an oxygen atom or a sulfur atom. Is preferred. When the 6B group atom of the periodic table is contained in the ring in addition to the nitrogen atom, the basicity is lowered, the hydrogen bonding performance is lowered, and the internal cohesive force of the polymer irradiated with the active energy ray is lowered. In some cases, the strength of the three-dimensional model is reduced. The cyclic structure (ca) containing a nitrogen atom is preferably a 5-membered ring or more. A 3- or 4-membered ring is not preferable because it is likely to cause a ring-opening reaction by heat or active energy rays. Furthermore, it is preferable that there is one nitrogen atom in the ring. If there are multiple nitrogen atoms in the ring, the hydrogen bonding performance will also improve, but the yellowing derived from the nitrogen atoms will become noticeable, so the polymer irradiated with active energy rays will turn yellow in the presence of a small amount of oxygen, It is difficult to obtain a colorless and transparent model. Therefore, the α, β-unsaturated double bond group-containing compound (a1-1) containing a cyclic structure (ca1-1) containing only one nitrogen atom is most preferable.

Of the α, β-unsaturated double bond group-containing compound (A) having a cyclic structure (ca) containing a nitrogen atom, an α, β-unsaturated double bond group having only one nitrogen atom in the ring The containing compound (a1-1), particularly, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, and 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate are particularly preferred. Preferably used.

<Α, β-unsaturated double bond group-containing compound (B) having a cyclic structure (cb) containing no hetero atom>
Next, the α, β-unsaturated double bond group-containing compound (B) having a cyclic structure (cb) containing no hetero atom will be described.
In the resin composition of the present invention, the α, β-unsaturated double bond group-containing compound (B) having a cyclic structure (cb) not containing a heteroatom is different from the compound (A) in that a heteroatom (N, It is a compound having both a cyclic structure not containing atoms such as O and S and an α, β-unsaturated double bond group. The compound (B) has a cyclic structure (cb) that does not contain a heteroatom, so that the three-dimensional structure created by irradiation with active energy rays becomes non-aqueous, thereby suppressing a decrease in water resistance and moisture resistance. Is possible. Furthermore, it is preferable because it can be expected to improve the hardness and durability of the shaped product derived from the annular structure.

Although it does not specifically limit as such a cyclic structure (cb) which does not contain a hetero atom, A ring structure can be divided roughly into bridged polycyclic structure (cb1) and other ring structures (cb2). The bridged polycyclic structure (cb1) includes a bicyclo [1.1.1] pentane ring, a (1r, 4r) -bicyclo [2.1.1] hexane ring, and a (1s, 4s) -bicyclo [2.2. .1] heptane ring (also known as norbornane ring), bicyclo [2.2.2] octane ring, (1r, 5r) -bicyclo [3.1.1] heptane ring, (1R, 5S) -bicyclo [3. 2.1] octane ring, (1R, 5S) -bicyclo [3.3.1] nonane ring, bicyclo [3.3.2] decane ring, bicyclo [3.3.3] undecane ring, (1r, 6r ) -Bicyclo [4.2.2] decane ring, (1r, 6r) -bicyclo [4.3.2] undecane ring, (1r, 6r) -bicyclo [43.3] dodecane ring, (1R, 6S) -bicyclo [4.2.1] nonane ring, (1R, 6S) -bicyclo [4.3.1] decane ring, (3aR, 4R, 7S, 7aS) -Octahydro-1H-4,7-methanoindene ring (also known as dicyclopentanyl ring), (1R, 4S, 4as, 5R, 8S) -decahydro-1,4: 5,8-medimethanonaphthalene Ring (alias: tetracyclododecanyl ring), tricyclo [1.1.0.0 ^2,4 ] butane ring, pentacyclo [2.1.0.0 ^1,3 . 0 ^2,4 . 0 ^2,5 ] pentane ring, tetracyclo [2.1.0 ^1,3 . 0 ^2,5 ] pentane ring, heptacyclo [2.2.0.0 ^1,3 . 0 ^2,5 . 0 ^2,6 . 0 ^3,5 . 0 ^4,6 ] hexane ring, adamantane ring, (1s, 4s) -bicyclo [2.2.1] hept-2-ene ring (also known as norbornene ring), (3aR, 4R, 7R, 7aR) -hexahydro- 1H-4,7-methanoindene ring (also known as dicyclopentenyl ring), (1R, 4S, 5S, 8R, 8aR) -1,2,3,4,4a, 5,8,8a-octahydro-1,4 : 5,8-methanonaphthalene ring (also known as tricyclododecanyl ring), [1,1] paracyclophane ring, [2,2] paracyclophane ring, [2,2] metacyclophane ring, [2 , 2, 2, 2] (1, 2, 4, 5) cyclophane ring, 9,10-dihydro-9,10- [1,2] benzenezenanthracene ring, and the like.

  Ring structures other than the bridged polycyclic structure (cb2) include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cyclododecane ring, cyclohexadecane ring , (1s, 3s) -bicyclo [1.1.0] butane ring, (1R, 4S) -bicyclo [2.1.0] pentane ring, (1R, 5s) -bicyclo [3.1.0] hexane Ring, (1R, 5s) -bicyclo [3.2.0] heptane ring, (3as, 6as) -octahydropentalene ring, (1R, 6S) -bicyclo [4.1.0] heptane ring, (1R , 6S) -bicyclo [4.2.0] octane ring, (3aR, 7aS) -octahydro-1H-indene ring, (4as, 8as) -decahydronaphthalene ring, (4ar, 8ar - decahydronaphthalene ring, decahydronaphthalene ring, a cycloalkane such as tetra-decahydronaphthalene ring;

Cyclopropene ring, cyclobutene ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, cyclobutadiene ring, cyclopentadiene ring, cyclohexadiene ring, cycloheptadiene ring, cyclooctadiene ring, octahydronaphthalene ring, dodecahydroanthracene Cycloalkenes such as

  [4n + 2] annulene having 3 or more carbon atoms constituting a ring such as a benzene ring, a cyclooctatetraene ring, a cyclotetradecaheptaene ring and a cyclooctadecanaene ring;

Aromatic condensed bicycles such as naphthalene ring, pentalene ring, indene ring, indane ring, tetralin ring, azulene ring;

carbon-fused tricyclic rings such as as-indacene ring, s-indacene ring, biphenylene ring, acenaphthylene ring, acenaphthene ring, fluorene ring, phenalene ring, perinaphthene ring, phenanthrene ring, anthracene ring;

  Tridene ring, trindane ring, fluoranthene ring, acephenanthrylene ring, acephenanthrene ring, aceantolylene ring, aceanthrene ring, triphenylene ring, pyrene ring, chrysene ring, tetraphen ring, tetracene ring, naphthacene ring, rubrene ring, Carbon condensed tetracycles such as preaden ring, benzoanthrone ring, chrysene ring;

  Carbon-fused pentacycles such as a picene ring, a perylene ring, a pentaphen ring, a pentacene ring, a tetraphenylene ring, a coranthrylene ring, a coranthrene ring;

Corannulene ring, fluorene ring, anthanthrene ring, zetrene ring, hexahelicene ring, hexaphen ring, hexacene ring, rubicene ring, coronene ring, trinaphthylene ring, heptaphen ring, heptacene ring, pyrantrene ring, octaphen ring, octacene ring, terylene ring, Naphthacenonaphthacene ring, nonaphene ring, nonacene ring, violanthrene ring, violanthrone ring, isoviolanthrene ring, isoviolanthrone ring, ovalene ring, decaphene ring, decacene ring, decacyclene ring, pentasenopentacene ring, quaterrylene ring, Examples thereof include ring structures such as carbon condensed rings having 6 or more rings such as a hexacenohexacene ring and a helicene ring, which can be used without particular limitation.

In the α, β-unsaturated double bond group-containing compound (B) having a cyclic structure (cb) containing no hetero atom in the present invention, the cyclic structure (cb) containing no hetero atom is the ring structure (cb). It can be roughly divided into a compound (b2) having one and a compound (b1) containing two or more.

In the case of having two or more ring structures (cb), a bridged ring such as (1S, 1 ′S, 4R, 4′R) -2,2′-bi (bicyclo [2.2.1] heptane) Polycycles having two or more structures (cb1);

An alicyclic polycyclic ring having two or more ring structures (cb2) other than a bridged structure such as a dicyclohexylmethane ring and a tricyclohexylmethane ring;

Examples thereof include alicyclic polycyclic rings having two or more ring structures (cb2) other than a bridged structure such as a dicyclohexylmethane ring and a tricyclohexylmethane ring.

Thus, since the cyclic structure (cb) containing no hetero atom is divided into the above-mentioned bridged ring structure (cb1) and the other ring structure (cb2), the compound (B) is a bridged ring. Α, β-unsaturated double bond group-containing compound (b2-1) having one structure (cb1), α, β-unsaturated double bond group containing one ring structure (cb2) other than bridged Compound (b2-2), α, β-unsaturated double bond group-containing compound (b1-1) having two or more bridged ring structures (cb1), and two ring structures (cb2) other than bridged The α, β-unsaturated double bond group-containing compound (b1-2) is classified into four types.

In the present invention, the α, β-unsaturated double bond group-containing compound (b2-1) having one bridged ring structure (cb1) includes norbornyl (meth) acrylate and iso-bonyl (meth) acrylate. , Iso-bonyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dimethylol di (meth) acrylate Cyclopentane, (meth) acrylic acid tricyclodecane dimethanol, (meth) acrylic acid tetracyclo [4.4.0.12.5.17.10] dodecane, (meth) acrylic acid 3-hydroxy-1-adamantyl, 2- (1-adamantyl) propyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate (Meth) acrylic acid 2-ethyladamantyl-2-yl, (meth) acrylic acid 2-n-propyladamantyl-2-yl, (meth) acrylic acid 2-isopropyladamantyl-2-yl, (meth) acrylic acid 1 -(Adamantan-1-yl) -1-methylethyl, 1- (adamantan-1-yl) -1-ethylethyl (meth) acrylate, 1- (adamantan-1-yl) -1- (meth) acrylate Methylpropyl, (meth) acrylic acid 1- (adamantan-1-yl) -1-ethylpropyl, (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-6-oxo-7 - (Meth) acrylic acid such as sub-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl Cyclic esters;

Iso-bonyl di (meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentenyl di (meth) acrylate, dicyclopentenyloxyethyl di (meth) acrylate, di (meth) acrylate di Cyclopentanyl dimethylene, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meta ) Bifunctional (meth) acrylic acid cyclic esters such as 1,3-adamantanediol acrylate, 1,4-adamantanediol di (meth) acrylate, and tricyclodecanyl dimethylol di (meth) acrylate;

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-containing cyclic compounds containing alkenyl groups, and the like.

In the present invention, the α, β-unsaturated double bond group-containing compound (b2-2) having one ring structure (cb2) other than bridged is cyclohexyl (meth) acrylate, (meth) acrylic acid 1 -Methyl-1-cyclopentyl, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, 1-methyl-1-cyclohexyl (meth) acrylate, (meth) acryl 1-ethyl-1-cyclohexyl acid, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylic acid 2-phenoxyethyl, (meth) acrylic acid 2-oxo-1,2-phenylethyl, (meth) a 2-oxo-1,2-diphenylethyl crylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, (Meth) acrylic acid 2-anthryl, (meth) acrylic acid 9-anthryl, (meth) acrylic acid 9-anthrylmethyl, (meth) acrylic acid dihydro-α-terpinyl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (Meth) acryloyloxyethyl Sahydrophthalate, (meth) acrylic (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o-2-propenylphenyl, (meth) acrylic acid cyclohexyl glycidyl ether, (meth) acrylic acid phenylglycidyl ether, etc. (Meth) acrylic acid cyclic esters;

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

(Meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate-containing (meta) ) Metal salts and ammonium salts of acrylic acid cyclic esters;

Di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct, di (meth) acrylic acid 2,2-bis (hydroxyphenyl) methane tetraethylene oxide adduct, di (meta) ) A tetraethylene oxide adduct of acrylic acid-4,4'-sulfonyldiphenol, a diethylene (ethylene) adduct of di (meth) acrylic acid-hydrogenated 2,2-bis (hydroxyphenyl) propane, di (meth) acryl Tetraethylene oxide adduct of acid-hydrogenated 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-hydrogenated 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid- Hydrogenated 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-2,2-bis (hydride) Roxyphenyl) propane tetraethylene oxide adduct-dicaprolactonate, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane tetraethylene oxide adduct-dicaprolactonate ) Acrylic acid cyclic esters;

2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid, cyclohexyl vinyl ether, cyclohexyl Alkenyl group-containing cyclic compounds such as maleimide and vinylcyclohexene monooxirane;

Benzoyl vinyl formate, benzoyl vinyl acetate, benzoyl vinyl propionate, vinyl benzoyl butyrate, vinyl benzoyl valerate, vinyl benzoyl hexanoate, vinyl benzoyl dodecanoate, 1-naphthoyl vinyl acetate, 1-naphthoyl vinyl propionate, 1-naphthoyl butyric acid Vinyl, 1-naphthoyl vinyl valerate, 1-naphthoyl vinyl hexanoate, 2-naphthoyl vinyl acetate, 2-naphthoyl vinyl propionate, 2-naphthoyl butyrate, 2-naphthoyl vinyl valerate, 2-naphthoyl Vinyl hexanoate, vinyl anthraniloyl acetate, vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, anthraniloyl vinyl hexanoate, anthraniloyl decanoate , Vinyl anthraniloydodecanoate, 4- (2-t-ethoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylpropyloxy) styrene Aromatic vinyl compounds having an acyl group such as

Benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoyl propionate (meth) allyl, benzoyl butyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoate (meth) allyl, benzoyldodecanoic acid (meta ) Allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexanoic acid ( (Meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoylhexanoic acid Aromatic (meth) allyl compounds having an acyl group such as (meth) allyl

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- (1- Aromatic vinyl monomers such as ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

Vinyl phenylpentyl 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 tetra Decyl 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 docosyl ether , Vinyl phenyl methyl butyl ether, vinyl phenyl methyl pen Ether, vinyl phenylmethyl 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 phenyl methyl 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 heneicosyl ether, vinyl phenyl Aromatic vinyl ether-based monomers having a long-chain alkyl groups such as chilled stiffness ether;

Hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate, 4 -Octadecyl vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenylbenzoic acid Decyl, dodecyl 4-isopropenylbenzoate, tetradecyl 4-isopropenylbenzoate, hexadecyl 4-isopropenylbenzoate, octadecyl 4-isopropenylbenzoate, eicosyl 4-isopropenylbenzoate, docosyl 4-isopropenylbenzoate, etc. Head of Vinyl benzoate ester or isopropenyl benzoic acid ester monomers having alkyl group;

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) vinylphenyl ether, n-penta Citetra (propylene oxide) 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 Vinyl phenyl ether monomers having a long-chain polyalkylene oxide moiety such as (propylene oxide) vinyl phenyl ethyl ether, ethyl poly (propylene oxide) vinyl phenyl ethyl ether;

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 Phenylmethylundecyl ether, isopropenyl phenylmethyl dodecyl ether, isopropenyl phenylmethyl tridecyl ether, isopropenyl phenylmethyl tetradecyl ether, isopropenyl phenylmethyl pentadecyl ether, isopropenyl phenylmethyl hexadecyl ether, isopropenyl phenyl methyl hepta Decyl ether, isopropyl Isopropenyl phenyl having a long-chain alkyl group such as phenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl henecosyl ether, isopropenyl phenyl methyl docosyl ether Type monomers;

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) isoprop Isopropenyl-based monomers having a polyalkylene oxide moiety, such as Le benzyl ether;

Mono-long chain alkyl ester cyclic monomers of dicarboxylic acids such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

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;

Alkenyl group-containing cyclic sulfonic acids such as styrenesulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid;

Styrene ammonium 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 ammonium styrene sulfonate, Ammonium styrene sulfonates such as tetraethyl ammonium styrene sulfonate, propyl ammonium styrene sulfonate, dipropyl ammonium styrene sulfonate, tripropyl ammonium styrene sulfonate, butyl ammonium styrene sulfonate, pentyl ammonium styrene sulfonate or hexyl ammonium styrene sulfonate salts;

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;

(Meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid 2-hydroxy-3- Phenoxymethyl, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, (meth) acrylic acid 2-hydroxy-3-phenoxydecyl, (meth) acrylic acid 2-hydroxy-3-phenoxyoctadecyl, (meth) acrylic acid monohydroxyethyl phthalate, (meth) acrylic acid 2- (4-benzoyl-3-hydroxyphenoxy) Ethyl, 1,4-bis (2) di (meth) acrylate Hydroxypropyl) benzene, di (meth) acrylate 1,3-bis (2-hydroxypropyl) hydroxyl group-containing annular benzene (meth) acrylic acid esters;

2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- (meta ) Hydroxyl-containing benzophenone-based (meth) acrylic esters such as acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

1,2-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 2-hydroxy-3-phenoxymethyl monovinyl ether, 2-hydroxy-3-phenoxyethyl mono Vinyl ether, 2-hydroxy-3-phenoxypropyl monovinyl ether, 2-hydroxy-3-phenoxybutyl monovinyl ether, 2-hydroxy-3-phenoxydecyl monovinyl ether, 2-hydroxy-3-phenoxyoctadecyl monovinyl ether, 2- (4 -Vinyl ethers having a hydroxyl group-containing alicyclic ring or aromatic ring such as benzoyl-3-hydroxyphenoxy) ethyl monovinyl ether;

2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, 2-methyl-3-hydroxystyrene 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6- Hydroxyl-containing aromatic ethenyl compounds such as trihydroxystyrene and 2-hydroxy-6-vinylnaphthalene;

1,2-cyclohexanedimethanol mono (meth) allyl ether, 1,3-cyclohexanedimethanol mono (meth) allyl ether, 1,4-cyclohexanedimethanol mono (meth) allyl ether, o- (meth) allylphenol, m- (meth) allylphenol, p- (meth) allylphenol, 2-hydroxy-3-phenoxymethyl mono (meth) allyl ether, 2-hydroxy-3-phenoxyethyl mono (meth) allyl ether, 2-hydroxy- 3-phenoxypropyl mono (meth) allyl ether, 2-hydroxy-3-phenoxybutyl mono (meth) allyl ether, 2-hydroxy-3-phenoxydecyl mono (meth) allyl ether, 2-hydroxy-3-phenoxyoctadecyl mono (Meth) allyl ether 2- (4-benzoyl-3-hydroxyphenoxy) Echirumono (meth) having an alicyclic or aromatic ring of the hydroxyl group-containing and allyl ether (meth) allyl ethers;

N- (2-methoxyphenyl) (meth) acrylamide, N- (4-methoxyphenyl) (meth) acrylamide, N- (2-ethoxyphenyl) (meth) acrylamide, N- (4-ethoxyphenyl) (meth) Acrylamide, N-phenyl-N- (3-methoxyphenyl) (meth) acrylamide, N-phenyl-N- (3-methoxyphenyl) (meth) acrylamide, (Z) -3- [4-methoxyphenyl] (meta ) Cyclic (meta) containing alkoxy groups such as acrylamide, (E) -N-cyclohexyl-3- (4-methoxyphenyl) (meth) acrylamide, (E) -N, N-diethyl-3-cyclohexyl (meth) acrylamide, etc. ) Acrylamides;

N- (2-hydroxyphenyl) (meth) acrylamide, N- (4-hydroxyphenyl) (meth) acrylamide, N- (2-phenylethyl) -3- (3-methoxy-4-hydroxyphenyl) (meth) Acrylamide, N-[(3,5-di-tert-butyl-4-hydroxybenzyl) oxymethyl] (meth) acrylamide, N- (4-hydroxy3,5-dimethylbenzyl) (meth) acrylamide, 2- [ (S) -alpha-hydroxybenzyl] (meth) acrylamide, N- (2-hydroxyethyl) -N- [2- (benzyloxyimino) ethyl] (meth) acrylamide, N-cyclohexyl-2-[(S) -Β-hydroxyphenethyl] (meth) acrylamide-containing alicyclic ring or aromatic ring-containing cyclic (meth) Acrylamide and the like, and the like, but not particularly limited thereto. Moreover, these may use only 1 type or may use multiple types together.

In the present invention, the α, β-unsaturated double bond group-containing compound (b1-1) having two or more bridged ring structures (cb1) is (1R, 1′R, 2R, 2 ′S, 4R). , 4′R) 5,5′-divinyl-2,2′-bi (bicyclo [2.2.1] heptane) and other alkenyl compounds having a bridge structure.

In the present invention, the α, β-unsaturated double bond group-containing compound (b1-2) having two or more ring structures (cb2) other than the bridged ring structure is 2,2-bis {4- (meta ) Acryloyloxyethoxyphenyl} propane, 2,2-bis {4- (meth) acryloyloxypropoxyphenyl} propane, 2,2-bis {4- (meth) acryloxydiethoxyphenyl} propane, 2,2-bis {4- (Meth) acryloyloxypolyethoxyphenyl} propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) ) Phenyl] fluorene and other (meth) acrylic acid esters having a bisphenol skeleton, or alkyleneoxy having 2 to 4 carbon atoms thereof Adduct [average addition mole number of 0 to 30 moles of alkylene oxide (especially 1 to 10 mol) of about];

Adducts of acrylic acid of bisphenol type epoxy such as acrylic acid adduct of bisphenol A diglycidyl ether and acrylic acid adduct of bisphenol F;

(Meth) acrylic acid esters having a biphenyl skeleton such as biphenyl di (meth) acrylate, or their alkylene oxide adducts having 2 to 4 carbon atoms [average addition mole number of alkylene oxide of 0 to 30 mol (especially 1 to About 10 mol)];

Di (meth) acrylic acid 2,2′-bis (4-hydroxycyclohexyl) propane, di (meth) acrylic acid bis (4-hydroxycyclohexane) methane, tri (meth) acrylic acid 1- (α-methyl-α- (4′-hydroxycyclohexyl) ethyl) -4- (α, α′-bis (4 ″ -hydroxycyclohexyl) ethyl) benzene, 1,1 ′-((4-hydroxycyclohexyl) methylene) tri (meth) acrylate -Bis (2-methyl-4-hydroxycyclohexane), tri (meth) acrylic acid 1,1 '-((2-methyl-4-hydroxycyclohexyl) methylene) -bis (3-methyl-4-hydroxycyclohexyl), Has a hydrogenated bisphenol skeleton such as 1,1,1-tris (4-hydroxycyclohexyl) methane tri (meth) acrylate (Meth) acrylic acid esters or their alkylene oxide adducts having 2 to 4 carbon atoms [average addition mole number of alkylene oxide of about 0 to 30 mol (particularly about 1 to 10 mol)] and the like. These can be used alone or in combination of two or more.

As the α, β-unsaturated double bond group-containing compound (B) having a cyclic structure (cb) containing no hetero atom, a compound having a (meth) acryloyl group is preferable from the viewpoint of reactivity. When used as an active energy ray polymerizable resin composition for optical three-dimensional modeling, it is preferable that bifunctional or higher functional (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 (B) having a cyclic structure (cb) containing no hetero atom in the present invention, as described above, when irradiated with photoactive energy rays such as ultraviolet rays, When it has a ring structure, since the glass transition temperature (Tg) of the resin cured product is improved and the cohesive force is increased, it is preferable because the hardness of the resin is improved. The superiority of the compound (B) in terms of polymerization curability by irradiation with active energy rays, strength of the three-dimensional structure, and durability such as heat resistance, moist heat resistance and water resistance is (b1-1)> (b2- 1) Although it is ≧ (b1-2)> (b2-2), industrial production of an α, β-unsaturated double bond group-containing compound (b1-1) having two or more bridged ring structures (cb1) Therefore, the advantage based on the industrially usable point is (b2-1) ≧ (b1-2)> (b2-2). Moreover, these can be set as a favorable three-dimensional molded item by mix | blending timely so that the cyclic structure (cb) which does not contain a hetero atom may be contained according to the objective.

In particular, from the viewpoint of price and industrial availability, iso-bonyl (meth) acrylate, iso-bonyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate Bridged ring structures such as dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentenyl di (meth) acrylate, dicyclopentenyloxyethyl di (meth) acrylate (B1-2), 2,2-bis {4- (meth) acryloyloxyethoxyphenyl} propane, 2,2-bis {4- (meth) acryloyloxypropoxyphenyl} propane, 2,2- Bis {4- (meth) acryloxydiethoxyphenyl} propane, di (meth) acrylic acid 2,2 ′ Ring structures such as -bis (4-hydroxycyclohexyl) propane, bis (4-hydroxycyclohexane) methane di (meth) acrylate, 1,1,1-tris (4-hydroxycyclohexyl) methane tri (meth) acrylate A compound (b1-2) having two or more is preferably used.

<Α, β-unsaturated double bond group-containing compound (X) having no cyclic structure>
Next, the α, β-unsaturated double bond group-containing compound (X) having no cyclic structure will be described.
In the present invention, the α, β-unsaturated double bond group-containing compound (X) having no cyclic structure (hereinafter referred to as compound (X)) does not have a cyclic structure in the molecule, and has one or more It is a compound containing an α, β-unsaturated double bond group and does not include compounds corresponding to the compound (A) and the compound (B). By using the compound (X) of the present invention, it is possible to suppress the increase in viscosity of the optical three-dimensional active energy ray polymerizable resin composition and improve the durability such as heat resistance while improving the active energy ray polymerizability. While maintaining, the hardness and viscosity of the below-mentioned resin cured product, or three-dimensional modeling property can be maintained.

In particular, any compound containing one or more α, β-unsaturated double bond groups can be used without any limitation, but the structure contains an alkylene oxide bond group having an addition mole number of 1 or more. It is preferable to contain an α, β-unsaturated double bond group-containing compound (x1). By containing an alkylene oxide bonding group in the compound (x1), it becomes possible to impart flexibility while maintaining the hardness of a three-dimensional structure to be described later. Moreover, the compound (x2) which does not contain alkylene oxide coupling groups other than a compound (x1) can also be contained.
By adding the compound (X) to the resin composition, it becomes easy to increase the efficiency and sensitivity of the copolymerization reaction with the compound (A), the compound (B), and the compound (X). . In addition, the viscosity of the resin composition can be easily reduced, and the workability during modeling can be easily improved. Although it does not specifically limit, The following is mentioned as a compound which can be used as a component (X).

  Among the compounds (X), the α, β-unsaturated double bond group-containing compound (x1) containing one or more alkylene oxide bond groups in its structure is the hydroxyl group of the hydroxyl group-containing compound (x1-1). It has a structure in which a part or all of them are converted to α, β-unsaturated double bond groups such as (meth) acryloyl groups via a spacer composed of ethylene oxide, propylene oxide, butylene oxide, or a plurality of these. doing. Among these, from the viewpoint of viscosity, photosensitivity, and polymerization rate, an alkylene oxide bonding group is preferably an ethylene oxide unit. These alkylene oxide bonding groups may be present alone or in combination of two or more. Moreover, the preferable ranges of the average added mole number of an alkylene oxide coupling group are 1-40, and 3-30 are more preferable. If the average number of added moles of the alkylene oxide bonding group is smaller than this range, the effect of reducing the viscosity of the resin composition, the effect of improving the photosensitivity, or the effect of improving the flexibility of the three-dimensional structure are insufficient. It becomes. On the other hand, if it is larger than this range, the viscosity of the resin composition increases, and the crosslink density decreases too much as the alkylene oxide chain becomes longer, so that the strength of the molded article decreases. Furthermore, in the structure of the compound (x1), one or more hydroxyl groups not having an α, β-unsaturated double bond group may remain. Since it can contribute to strength improvement, there is no particular problem.

The alkylene oxide modification method using the hydroxyl group-containing compound (x1-1) as a raw material can be arbitrarily selected. As a general method, in addition to a method using an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, a cyclic ether compound such as oxetane, furan, pyran, dioxolane, dioxane, trioxane, or bucrown ether was used. Examples thereof include a method, a method using a cyclic carbonate compound such as ethylene carbonate and propylene carbonate, and a method using ethylene chlorohydrin.
As a general method for introducing an α, β-unsaturated double bond group in producing the compound (x1), it corresponds to a target structure such as methyl acrylate and methyl methacrylate described later (meth). Transesterification method using acrylic acid ester, acid chloride method using (meth) acrylic acid chloride, N, N′-dicyclohexylcarbodiimide, 2-chloro-1,3-dimethylimidazolium chloride, propanephosphonic acid anhydride, Examples include a method using a condensing agent such as carbonyldiimidazole (CDI) and WSCD (water-soluble carbodiimide), and a dehydration esterification method in which azeotropic and dehydration with (meth) acrylic acid is performed in the presence of an acid catalyst. It is not limited.

Although it does not specifically limit as a hydroxyl-containing compound (x1-1), In addition to general alcohol and phenols, it is using the (alpha), (beta)-unsaturated double bond group containing compound containing the below-mentioned hydroxyl group. it can. An α, β-unsaturated double bond group-containing compound having an alkylene oxide bond group in the molecule in advance can also be used as the hydroxyl group-containing compound (x1-1). Common alcohols include monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, 1-octanol, 1-nonanol, and benzyl alcohol;

Ethylene glycol, propylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-di Methylol heptane, 2-butyl-2-ethyl-1,3-propanediol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, dimer diol, etc. Dihydric alcohol ;

  Trihydric or higher polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, quadrol, dipentaerythritol;

  Common phenols include phenol, 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, 4, , 4'-sulfonyldiphenol, phenols such as bisphenol A, bisphenol F, and the like, but are not limited thereto.

  As the α, β-unsaturated double bond group-containing compound (x1) containing an alkylene oxide bond group of the present invention, (meth) acrylic acid ester having a hydroxyl group at the terminal, vinyl phenyl ether, isopropenyl ether, vinyl benzoate Alkylene oxide addition by repeating alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, etc. to hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compounds such as acid ester or isopropenyl benzoate Examples of the compound include an α, β-unsaturated double bond group, but are not limited thereto. These may use only 1 type or may use multiple types together.

  As a commercial item of the compound (x1) of the present invention, Blemmer PME-1000, Blemmer PME-4000, Blemmer 50POEP-800B, Blemmer PLE-1300, Blemmer PSE-1300, Blemmer PDE-600, Blemmer PDBE-450, Blemmer ADE -600, Bremer AP800 (above, manufactured by NOF Chemical Co., Ltd.), New Frontier BPE-10, New Frontier PE-600, New Frontier TMP-15 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), SR-415, SR-602 SR-9035 (above, manufactured by Sartomer), Aronix M-260, Aronix M-270 (above, manufactured by Toagosei Co., Ltd.), Denacol Acrylate DA-931 (above, manufactured by Nagase Kasei Co., Ltd.), NK Ester AM-130G , NK S AM-230G, NK ester A-600, NK ester A-1000, NK ester APG-700, NK ester A-1206PE, NK ester A-0612PE, NK ester A-04-12PE, NK ester A-1000PER, NK ester A -3000PER, NK ester A-BPE-10, NK ester A-BPE-20, NK ester A-BPE-30, NK ester AT-20E, NK ester AT-30E, NK ester A-GLY-20E, NK ester A -BPE-10, NK ester ATM-35E, NK ester ATM-10P, NK ester A-DPH-12E, NK ester A-DPH-12EL, NK economy A-PG5027E, NK economy A-PG5054E, NK ester M-13 G, NK ester M-230G, NK ester S-20E, NK ester S-12E, NK ester 14G, NK ester 23G, NK ester 1206PE, NK Economer 1000PER, NK ester BPE-500, NK ester BPE-900, NK ester BPE-1300N, NK Ester GLY-20E, NK Ester TM-35E, NK Ester TM-10P, NK Ester M-DPH-12E, NK Economer M-PG5027E, NK Economer M-PG5054E (manufactured by Shin-Nakamura Chemical Co., Ltd.) However, it is not particularly limited to these. Moreover, these may use only 1 type or may use multiple types together.

Among the compounds (X) of the present invention, the α, β-unsaturated double bond group-containing compound (x2) that does not contain an alkylene oxide bond group includes neither the above-mentioned cyclic structure nor an alkylene oxide bond group. It is. The compound (x2) is preferably used because it controls the strength, flexibility, shrinkage rate, durability and the like of the molded article in addition to the viscosity, photosensitivity, and polymerization rate of the resin composition. Among the compounds (x2), the α, β-unsaturated double bond group-containing compound containing a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, and (meth) acrylic. 2-hydroxypropyl acid, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) acrylic 4-hydroxybutyl acid, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (meth) acryl Ethyl-α- (hydroxymethyl), monofunctional (meth) acrylic acid glycerol, Or (meth) acrylic acid glycidyl lauric acid ester, (meth) acrylic acid glycidyl oleic acid ester, (meth) acrylic acid glycidyl stearic acid ester-based (meth) acrylic acid ester, or ring-opening addition of lactone ring Hydroxyl-containing aliphatic (meth) acrylates such as Placcel FA2D (manufactured by Daicel Chemical Co., Ltd.) and other polylactone-based (meth) acrylic acid esters, (meth) acrylic acid 2-hydroxyethyl phosphate, etc. ;

N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl ( Hydroxyl-containing aliphatic (meth) acrylamides such as (meth) acrylamide and 3-hydroxy (meth) acrylamide;

Hydroxyethyl-containing aliphatic vinyl ethers such as 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 and the like. Kind;

(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, hydroxy Aliphatic (meth) allyl having a hydroxyl group at the terminal, such as octyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether Alcohols or (meth) allyl ethers;

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

  Monomers having a hydroxyl group and a vinyl group, such as vinyl alcohol, can be mentioned, but the invention is not particularly limited thereto. These may use only 1 type or may use multiple types together.

  As the hydroxyl group-containing α, β-unsaturated double bond group-containing compound, 2-hydroxyethyl (meth) acrylate, from the viewpoint of reactivity with the above-mentioned alkylene oxide bond group and the reduction in shrinkage of the molded article, Α, β- having 2 to 18 carbon atoms such as 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-hydroxymethyl (meth) acrylamide, Plaxel FA2D (manufactured by Daicel Chemical) An unsaturated double bond group-containing compound is particularly preferred.

Among the compounds (x2), the α, β-unsaturated double bond group-containing compound not containing a hydroxyl group includes methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, ( 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n (meth) acrylate -Amyl, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, (meta ) N-nonyl acrylate, (meth) acrylic iso-nonyl, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl esters such as octadecyl acid, lauryl (meth) acrylate, stearyl (meth) acrylate;

  Perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) acrylic acid Trifluoromethylmethyl, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoromethyl (meth) acrylate 2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, ( (Meth) acrylic propenoic acid 2-perfluorode Ruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

(Meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth) acryl 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-acrylamidohexanoic acid, 2- (meta ) Acrylyloxyethyl succinate, is Is an aliphatic α, β- containing a carboxyl group such as a polylactone (meth) acrylate having a carboxyl group at the terminal by ring-opening addition of a lactone ring such as mono (meth) acrylic acid ω-carboxypolycaprolactone ester. Unsaturated double bond group-containing carboxylic acids and acid anhydrides thereof;

  N-methylaminoethyl (meth) acrylate, N-tributylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (meth) Amino group-containing (meth) acrylic acid esters such as N, N-diethylaminomethyl acrylate;

  (Meth) acrylic acid glycidyl, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid-2-oxotetrahydropyran-4-yl, (meta ) 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-oxotetrahydro Lan-3-yl, (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-2-ylmethyl, (Meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl-containing heterocyclic ring-containing (meth) acrylic acid esters;

(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, ( 2- (Ethoxycarbonyl) methacrylic acid (Oxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) acryl 2- (Butoxycarbonyloxy) ethyl acid, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxycarbonyl) (meth) acrylic acid Aliphatic (meth) acrylic acid esters having one carbonyl group such as oxy) butyl;

(Meth) acrylic acid 2-oxobutanoylethyl, (meth) acrylic acid 2-oxobutanoylpropyl, (meth) acrylic acid 2-oxobutanoylbutyl, (meth) acrylic acid 2-oxobutanoylhexyl, ) 2-oxobutanoyl octyl acrylate, 2-oxobutanoyl decyl (meth) acrylate, 2-oxobutanoyl dodecyl (meth) acrylate, 3-oxobutanoylethyl (meth) acrylate, (meth) acryl 3-oxobutanoylpropyl (meth) acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic acid 3 -Oxobutanoyldecyl (meth) acrylate 3-oxobutanoyldodecyl (meth) 4-cyanooxobutanoylethyl acrylate, 4-cyanooxobutanoylpropyl (meth) acrylate, 4-cyanooxobutanoylbutyl (meth) acrylate, 4-cyanooxobutanoylhexyl (meth) acrylate, ( 4-Cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, (meth) acryl Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl acid and 2,3-di (oxobutanoyl) octyl (meth) acrylate;

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 Emissions, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

(Meth) acrylic acid sulfomethyl, (meth) acrylic acid 2-sulfoethyl, (meth) acrylic acid 2-sulfopropyl, (meth) acrylic acid 3-sulfopropyl, (meth) acrylic acid 2-sulfobutyl, (meth) acrylic acid 4-sulfobutyl, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulfolauryl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl esters containing a sulfonyl group such as acid sulfostearyl;

Metal salts and ammonium salts of (meth) acrylic acid esters containing sulfonyl groups such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate;

(Meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, (meth) Contains phosphonic acid groups such as acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, phenyl-2- (meth) acryloyloxyethyl phosphate (meta ) Acrylic esters;

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

(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, fuma Amide, Mesaconamide, Citraconamide, Itaconamide, 2-Methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N ′ -(Dimethylamino) propyl]-(meth) acrylamide, aliphatic (meth) acrylamides such as N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxyoctyl ( (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-isopropoxy Methyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (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) acryl Amide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- 2-methoxyethyl (meth) acrylamide, N- (oxetane-2-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N, N-di (methoxymethyl) Alkoxy group-containing aliphatic (meth) acrylamides such as (meth) acrylamide and N, N-di (ethoxymethyl) (meth) acrylamide;

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

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

Vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, vinyl acetodecanoate , 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, propa Noyl vinyl valerate, vinyl butyryl valerate, isobutyryl valerate, palmitoyl valerate, stearoyl valerate, pyruvyl valerate Vinyl, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, 2-acetoacetoxyethyl vinyl compounds of aliphatic having an acyl group such as octyl vinyl ether;

  Ethyl vinyl ether, 1-propyl vinyl ether, 2-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, n-hexyl, 2-ethylhexyl vinyl ether, n-octyl Aliphatic vinyl ethers such as vinyl ether, iso-octyl vinyl ether, n-nonyl vinyl ether, iso-nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether;

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

Alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, vinyl sulfuric acid;

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;

  Nitrile group-containing α, β-non, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itacononitrile, 2-propenenitrile, 2-cyanoethyl (meth) acrylate Saturated double bond group-containing compounds;

  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;

  Of 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;

  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-ethylhexane 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, acetocapric 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, stearoyl acetate (Meth) allyl, (meth) allylaldehyde, etc. Aliphatic (meth) allyl compounds having an acyl group;

  (Meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxyvinylsilane, Alkoxysilyl group-containing alkenyl group-containing compounds such as vinyltris (2-methoxyethoxy) silane;

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

Halogenated vinyl esters such as vinyl chloride, vinylidene chloride and allyl chloride;

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-hexacosene, 1-octacosene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetracontene etc. Alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1 and the like

(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-propenyl (meth) acrylate Lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (E) -3,7-dimethyloct-2,6-dien-1-yl (meth) acrylic acid, ( (Meth) acrylic acid esters further containing an unsaturated group such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;

Di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid propylene oxide, di (meth) acrylic acid dipropylene oxide, di ( (Meth) acrylic acid tripropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid penten oxide, di (meth) acrylic acid 2,2-dimethylpropyl, di (meth) acrylic acid hydroxypivalyl hydroxypi Valate, di (meth) acrylic acid hydroxypivalyl hydroxypivalate dicaprolactonate, di (meth) acrylic acid 1,6-hexanediol, di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic 1,5-hexanediol diacid, (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, 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-hexadecanediol, di ( T) 2-methyl-2,4-pentanediol acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1,3-di (meth) acrylate Propanediol, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol di (meth) acrylate, 2,2 di (meth) acrylic acid , 4-Trimethyl-1,3-pentanediol, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl di (meth) acrylate -2,5-hexanediol, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, (Meth) acrylic acid 2,4-diethyl-1,5-pentanediol, di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate, 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 1,2-tetradecanediol (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4 di (meth) acrylate -Pentane, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4 di (meth) acrylic acid -Dimethyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, Dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2 di (meth) acrylate 5-Hexanediol, Di (meth) acrylate 2-butyl-2-ethyl-1,3-propanediol, Di (meth) acrylate 2,4-diethyl-1,5-pentanediol, Di (meth) acryl Bifunctional (meth) acrylic acid esters such as acid 1,1,1-trishydroxymethylethane;

Tri (meth) acrylic acid 1,2,3-propanetriol, tri (meth) acrylic acid 2-methylpentane-2,4-diol, tri (meth) acrylic acid 2-methylpentane-2,4-diol tricapro Lactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, 2, tri (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tri (meth) acrylic acid 1,1,1-trishydroxymethylethane, tri (meth) acrylic acid 1,1,1-trishydroxymethylpropane, tri ( Trifunctional (meth) acrylic acid esters such as (meth) acrylic acid pentaerythritol;

Tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 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, tetra (meth) Di2,2-dimethylpropane-1,3-diol acrylate Tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3- Propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (Meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meth) acrylic Di2,2-bis (hydroxymethyl) 1,3-propanediol polyal acid Polyfunctional (meth) acrylic acid esters such as alkylene oxide;

Dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, vinyl (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9,12, Examples include α, β-unsaturated double bond group-containing compounds containing a polyfunctional unsaturated bond such as vinyl 15-trienoate. In particular, it is not limited to these. These may use only 1 type or may use multiple types together.

In the optical three-dimensional modeling active energy ray polymerizable resin composition of the present invention, 0.1 to 40% by weight of the compound (A) and 0.5 to 40% of the compound (B) in the total amount of the active energy ray polymerizable composition. It is preferable to contain 20% to 99.4% by weight of compound (X), 1 to 20% by weight of compound (A), 1 to 40% by weight of compound (B), and compound ( More preferably, X) is contained in a proportion of 40 to 98% by weight. Other than this ratio, the cohesive force is insufficient and the effect of improving heat resistance and moist heat resistance cannot be expected so much, or when the resin composition is polymerized and cured with active energy rays, shrinkage during polymerization curing and deformation during molding This is not preferable because the cured product tends to be brittle due to an increase in the thickness.

  In the resin composition of the present invention, as described above, when irradiated with photoactive energy rays such as ultraviolet rays, the hydrogen bonding performance associated with the nitrogen atom is increased if the resin has a cyclic structure (ca) containing a nitrogen atom, and the resin Since the Tg of the cured product is improved and the cohesive force is increased, the hardness of the resin is improved. Moreover, when it has the cyclic structure (cb) which does not contain a hetero atom, since not only Tg of a resin hardened | cured material will improve, but the hydrophobization performance will increase, the water resistance and heat-and-moisture resistance of resin will improve. Moreover, when it has an alkylene oxide bond group, the shrinkage rate in polymerization curing can be reduced, and further, the brittleness of the cured resin can be reduced. Thus, by compounding compound (A), compound (B), and compound (X) in a well-balanced manner, it is possible to provide a cured resin obtained by irradiation with active energy rays as the best three-dimensional model. It becomes.

<Oligomer (C)>
Next, the oligomer (C) will be described.
In one embodiment of the resin composition of the present invention, the resin composition may contain an oligomer (C) in addition to the essential components. By using the oligomer (C), when the resin composition is polymerized and cured by irradiating active energy rays, it is possible to further improve the formability and curing shrinkage. Moreover, it becomes easy to improve the heat resistance or heat-and-moisture resistance of a three-dimensional molded item.

The oligomer (C) is a compound obtained by adding an α, β-unsaturated double bond group to a polymer of monomers and / or various compounds having at least an α, β-unsaturated double bond group. , One or more α, β-unsaturated double bond groups in the molecule. However, the oligomer (C) is not included in the compound (A) and the compound (B). The oligomer may have various functional groups in addition to the α, β-unsaturated double bond group. In one embodiment of the present invention, the oligomer (C) is selected from the group consisting of a polyester oligomer (c1), a polyurethane oligomer (c2), a polyepoxy oligomer (c3), and a polyacrylic oligomer (c4). Including at least one kind, these can be used without any particular limitation.

<Polyester oligomer (c1)>
As the polyester-based oligomer (c1), the terminal of the polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol on the main chain skeleton, or a hydroxyl group in the polyester chain and a molecule such as (meth) acrylic acid or maleic acid A compound obtained by esterification with an α, β-ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups, or a carboxyl group in the terminal or polyester chain of polyester and (meth) acrylic acid 2- It is a compound obtained by esterification with the aforementioned hydroxyl group-containing α, β-unsaturated double bond group-containing compound such as hydroxyethyl and 2-hydroxypropyl (meth) acrylate. In addition, a polyester oligomer obtained from an acid anhydride, glycidyl (meth) acrylate, and a compound having at least one hydroxyl group can also be used as the polyester oligomer (c1).

Examples of the polybasic acid include aliphatic, alicyclic, and aromatic acids, which can be used without any particular limitation. Aliphatic polybasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, Examples include 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.), glutaric anhydride derivatives (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, phenyl maleic anhydride Phosphate, also anhydride derivative of 2,3-diphenyl maleic anhydride, etc.) and the like can be used. .

As the alicyclic polybasic acid, the alicyclic dicarboxylic acid includes dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclopropane-1α, 2β-dicarboxylic acid, cyclopropane-1β, 2α-dicarboxylic acid. , Cyclobutane-1,2-dicarboxylic acid, cyclobutane-1α, 2β-dicarboxylic acid, cyclobutane-1α, 3β-dicarboxylic acid, cyclobutane-1α, 3α-dicarboxylic acid, (1R) -cyclopentane-1β, 2α-dicarboxylic acid , Trans-cyclopentane-1,3-dicarboxylic acid, (1β, 2β) -cyclopentane-1,3-dicarboxylic acid, (1β, 3β) -cyclopentane-1,3-dicarboxylic acid, (1S, 2S) -1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, Saturated alicyclic dicarboxylic acids such as 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. Or Two unsaturated alicyclic dicarboxylic acids having cited, such as those 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.

Among aromatic polybasic acids, aromatic dicarboxylic acids include 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-azudienedicarboxylic acid, 1, 3-azulene dicarboxylic acid, 4,5-azulene dicarboxylic acid, (-)-1,3-acenaphthene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,5-anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid 2,3-anthracene dicarboxylic acid, 1,2-phenanthrene Aromatic dicarboxylic acids such as acid, 4,5-phenanthrene dicarboxylic acid, 3,9-perylene dicarboxylic acid, and aromatic dicarboxylic anhydrides such as phthalic anhydride and 4-methylphthalic anhydride. Aromatic dicarboxylic acids and their anhydrides 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.

Polyhydric alcohols 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.

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 (added mole number of 10 or less), Polyoxypropylene glycol (added mole number of 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, Neopentyl glycol, octanediol, butyl Aliphatic or alicyclic diols such as ethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol;

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-type bisphenol obtained by adding alkylene oxide to bisphenol Aromatic diols and the like.

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.
Examples of 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.

Examples of commercially available high molecular weight polyester polyols include Byron series manufactured by Toyobo Co., Ltd., Kuraray polyol P series manufactured by Kuraray Co., Ltd., and Kyowapol series manufactured by Kyowa Hakko Chemical Co., Ltd.
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 manufactured by Kuraray, and Kuraray polyol C series.

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

<Polyurethane oligomer (c2)>
The polyurethane oligomer (c2) is a compound obtained by reacting a compound having at least one isocyanate group with the hydroxyl group-containing α, β-unsaturated double bond group-containing compound, or at least one isocyanate group. A compound obtained by reacting a urethane prepolymer of a terminal isocyanate group obtained by reacting a compound having a hydroxyl group with the above-mentioned polyol and the above-mentioned compound containing an α, β-unsaturated double bond group containing a hydroxyl group, or at least 1 Terminal isocyanate group urethane prepolymer obtained by reacting a compound having a plurality of isocyanate groups with polyols, and further a terminal isocyanate group urethane prepolymer obtained by reacting a compound having at least one amino group. Polymer and said hydroxyl-containing α, β-unsaturated double bond It is a compound obtained by reacting the containing compound. Moreover, what contains the urea bond group obtained by making an isocyanate group and an amino group react is also contained in a polyurethane-type oligomer (c2).

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. Monofunctional polyisocyanates include 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-methylbenzyl isocyanate, (S) — (−)-Α-methylbenzyl isocyanate, (R)-(−) Examples include -1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(−)-1-phenylethyl isocyanate, p-toluenesulfonyl isocyanate, and the like.

Among the polyfunctional isocyanates, aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (also known as 4,4′- MDI), 2,4-tolylene diisocyanate (also known as 2,4-TDI), 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3, Examples include 5-triisocyanatebenzene, 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 HMDI), 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.

  As the aromatic aliphatic polyisocyanate, 2,4-diisocyanate-1-methyl-benzene (alias: 2,4-TDI), 2,6-diisocyanate-1-methyl-benzene (alias: 2,6-TDI), 1,3-phenylene bismethylene diisocyanate (alias: m-XDI), 1,4-phenylene bismethylene diisocyanate (alias: p-XDI), 2,2′-diphenylmethane diisocyanate (alias: 2,2- MDI), 4,4'-diphenylmethane diisocyanate (alias: 4,4-MDI), 1,3-naphthalenediyl diisocyanate (alias: 1,3-NDI), 1,5-naphthalenediyl diisocyanate (alias: 1,5) -NDI) and the like.

As 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, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) (also known as hydrogenated MDI), 1,4-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate, etc. Can be mentioned.

In addition, as part of the component (c2), the adducts of polyisocyanates such as 2-methylpentane-2,4-diol and polyols such as trimethylolpropane, trimers having an isocyanurate ring, and the like are also used. be able to. Polyphenylmethane polyisocyanate (also known as PAPI), and these polyisocyanate-modified products 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, 3-aminopentane, and isoamyl. Amine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane (laurylamine), 1-aminotridecane, 1-aminohexadecane, 1-aminotetradecane (myristylamine), 1-aminopentadecane, cetylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, allylamine, stearylamine, aminocyclopropane, aminocyclobutane, amino Clopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, aniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1 − Minoanthracene, 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;

Dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethyl Propylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkylamine, di-cured tallow alkylamine, Secondary amines such as stearylamine;

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, triamino Propane, 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine, dimer diamine, dicyclohexylmethane-4,4'-diamine, diethylene glycol bis (3-aminopropyl) Ether, poly Oxyalkylene glycol diamine (the number of added moles of alkylene glycol is an arbitrary integer of 2 to 50), phenylenediamine, xylylenediamine, dicyclohexylmethane-4,4'-diamine, 2,4-tolylenediamine, 2,6 -Tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-bis- (sec-butyl) diphenylmethane, glutamine, asparagine, lysine, diaminopropionic acid, ornithine, Diamines having two primary amino groups such as diaminobenzoic acid and diaminobenzenesulfonic acid;

Diamines having two secondary amino groups such as N, N-dimethylethylenediamine, N, N-diethylethylenediamine, and N, N′-di-tert-butylethylenediamine, piperazine;

N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylamino Propylamine], 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-hydroxy Ethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethyl) Polyamines having primary and secondary amino groups such as propylene) diamine, (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine;

Oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, hexadecandiodiohydrazide, eicosanedioic acid dihydrazide, maleic acid dihydrazide dihydrazide diacid Hydrazides such as phthalic acid dihydrazide, carbonic acid dihydrazide, carbodihydrazide, thiocarbodihydrazide, oxalyl dihydrazide, polyacrylic acid hydrazide;

In addition, pyridine, morpholine, N-methylmorpholine, pyrrolidine, piperidine, N-methylpiperidine, dimethyloxazoline, imidazole, N-methylimidazole, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N- Dimethylisopropanolamine, N-methyldiethanolamine and the like can be used.

A catalyst can also be used to promote the production of the polyurethane oligomer (c2). The use of a catalyst as appropriate is preferable because the interaction can proceed more smoothly. Catalysts used include ammonia, tertiary amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, Lewis acids, tin, lead, titanium, iron, zinc , Zirconium, cobalt, and other organometallic compounds, metal halides, and the like.

<Polyepoxy oligomer (c3)>
The polyepoxy oligomer (c3) is a compound having a glycidyl group and an α, β-invalid 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 saturated double bond group-containing compound, and is a compound having substantially 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. As the bisphenol type polyepoxy oligomer, α, β-unsaturation having one or more carboxyl groups in the molecule such as bisphenol type diglycidyl ether obtained by reacting bisphenols and epichlorohydrin and (meth) acrylic acid It is obtained by reacting with a double bond group-containing compound.

The epoxidized oil polyepoxy oligomer has at least one hydroxyl group or carboxyl group in the molecule such as epoxidized oil such as soybean oil and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. Those obtained by reaction with an α, β-unsaturated double bond group-containing compound can be used. As the novolak type polyepoxy oligomer, α, β-unsaturation having novolak type epoxy resin and one or more hydroxyl groups or carboxyl groups in the molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. What is obtained by reaction with a double bond group containing compound can be used. Examples of the alicyclic polyepoxy oligomer include α, β- having one or more hydroxyl groups or carboxyl groups in the molecule such as alicyclic epoxy resin and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid and the like. What was synthesize | combined by reaction with an unsaturated double bond group containing compound can be used.

<Polyacrylic oligomer (c4)>
In the present invention, an acrylic oligomer (c4) can also be used as the oligomer (C). 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. Oligomers or prepolymers of one or more compounds can be used.

In addition to the aggregation density, the weight average molecular weight of the oligomer (C) from the viewpoint of obtaining excellent properties in terms of compatibility with other components that form a cured coating film by polymerization, and durability such as heat resistance and moist heat resistance ( (Hereinafter referred to as Mw) is preferably in the range of 300 to 50,000 in terms of the compatibility of the cured product, good durability (heat resistance, moist heat resistance) and agglomeration density, and 400 to 30,000. It is preferable that it is the range of these. 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 (X). Can do. In addition, it is possible to easily suppress problems such as a decrease in polymerization curability of the resin composition, a decrease in durability such as curing shrinkage of the cured product, and 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 a modeling material, cohesive failure inside the three-dimensional modeled object is less likely to occur.
In addition, the measuring method of a number average molecular weight (Mn), a weight average molecular weight (Mw), an acid value (AV), and a hydroxyl value (OHV) is mentioned later.

Although it does not specifically limit, In preferable one Embodiment of this invention, it is preferable that the said oligomer (C) contains a polyurethane-type oligomer (c2) at least. When using the said resin composition for uses, such as modeling material, there exists a tendency for the elasticity and softness | flexibility of hardened | cured material to change depending on the coupling group in the said oligomer (C). 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 (c2) is used, it is easy to balance elasticity and flexibility based on the urethane bond. Moreover, since the said component (c2) also has favorable hydrolysis resistance, it can improve water resistance and heat-and-moisture resistance easily.
However, even when an oligomer component other than the component (c2) is used in the present invention, desired characteristics can be easily obtained by appropriately blending other constituent components.

In one embodiment of the resin composition of the present invention, the total amount of components (A), (B) and (X) is 100 parts by weight, and the amount of oligomer (C) is preferably 1 to 250 parts by weight. . More preferably, it is the range of 1-100 weight part. By setting the oligomer (C) to 1 part by weight or more, deficiency in cohesive force can be improved, and characteristics such as heat resistance and moist heat resistance can be easily improved. On the other hand, by setting the oligomer (C) to 250 parts by weight or less, when the resin composition is used as a modeling material, it becomes easy to highly suppress curing shrinkage.

<Cationically polymerizable compound (D)>
Next, the cationic polymerizable compound (D) will be described.
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 cationically polymerizable compound (D), when the resin composition is used as a three-dimensional modeled object, it is possible to perform different polymerization curing by irradiation with active energy rays, so that the cured product forms a phase separation 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 wet heat resistance of the cured resin.

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 among the cyclic hetero compounds is particularly preferably used.

  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 5 or more members. There exists a compound (d4) which has a hetero group other than a compound (d3) 2 or more oxygen or 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, oxiranyl acetonitrile, 2,2 ′-(dimethylmethylene) bis [(p-phenylene) oxymethylene] bisoxirane, 2,2 ′-[methylenebis (2,1-phenyleneoxymethylene)] bisoxirane Or epoxy group-containing compounds in which a hydrogen atom of an oxirane ring such as glycidyl ether, glycidyl ester, glycidylamine or the like is substituted with a methylene bond group or a methine bond group;

2- (cyclohexylmethyl) oxirane, 2-ethoxy-3- (cyclohexylmethyl) oxirane, [(cyclohexyloxy) methyl] oxirane, 1,4-bis (oxiranylmethoxymethyl) cyclohexane, 2,2 ′-[( Epoxy group-containing compounds having a cycloalkane ring such as 1-methylethylidene) bis (4,1-cyclohexanediyloxymethylene)] bisoxirane, 2-[{4- (oxiran-2-ylmethoxy) cyclohexyl} methoxy] oxirane ;

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, piperitone oxide, 3-caret Oxide, α-terpineol oxide, 3- (thiilan-2-yl) -7-oxabicyclo [4.1.0] heptane, 6-methyl-3-isopropyl-7-oxabicyclo [4.1.0] heptane -3-ol, 3,4-oxiranecyclohexylmethyl 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-oxirane-6-methylcyclohexanecarboxylate, (1s, 4s) -7-oxabicyclo [2.2.1] heptane, (1R, 4S) -2-methyl-7-oxabicyclo [2.2.1] heptane, (1R, 2S, 4S, 5S) -3- oxabicyclo [3.2.1.0 ^2,4] octane, ethylene bis (3,4-oxirane-cyclohexane carboxylate), bis (3 4-oxiranecyclohexylmethyl) adipate, bis (7-oxabicyclo [4.1.0] heptan-3-ylmethyl) adipate, bis (3,4-oxirane-6-methylcyclohexylmethyl) adipate, bis (7-oxa Bicyclo [4.1.0] heptan-3-ylmethyl) carbonate, diethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), ethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), 2,3,14,15 -Dioxirane-7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] henicosane (also 3,4-oxirane cyclohexane spiro-2 ', 6'-dioxane spiro- 3 ″, 5 ″ -Dioxanespiro-3 ′ ″, 4 ′ ″-oxiranci A compound that can also be named rhohexane), 4- (3,4-oxiranecyclohexyl) -2,6-dioxa-8,9-oxiranespiro [5.5] undecane, 4-vinylcyclohexenedioxide, bis-2,3- Alicyclic epoxy group-containing compounds having no aromatic ring, such as oxirane cyclopentyl ether and dicyclopentadiene dioxide;

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-oxa Bicyclo [4.1.0] heptane-3-carboxylate), 1,4-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane- 3-carboxylate), 1-phenylethane-1,2-diylbis (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] heptane-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] Ptan-3-ylmethoxy) methyl} benzene, [{propane-2,2-diylbis (4,1-phenylene)} bis (oxy)] bis (ethane-2,1-diyl) bis (7-oxabicyclo [4 .1.0] heptane-3-carboxylate) and the like, and alicyclic epoxy group-containing compounds having an aromatic ring.

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, and 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} And oxetane. The oxetanyl group-containing compound (f2) may be used alone or in combination of two or more.

  As the cyclic ether compound (d3) having 5 or more members, 2-methyltetrahydrofuran, 2,5-diethoxytetrahydrofuran, tetrahydrofuran-2,2-dimethanol 3-methyl-2,4 (3H, 5H) -flange-on 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. May be used alone or in combination of two or more.

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.

Among the cationically polymerizable compounds (D), vinyl ethers can be selected and used from the above-mentioned compound (X) in a timely manner.

Examples of the cationically polymerizable compound (D) include (d1), (d2,) (d3), and (d4), and are not particularly limited, but include an epoxy group-containing compound (d1) or an 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 model 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 one embodiment of the resin composition of the present invention, the total amount of the compound (A), the compound (B) and the compound (X) is 100 parts by weight, and the amount of the cationic polymerizable compound (D) is 1 to 350 parts by weight. It is preferable that More preferably, it is 1-150 weight part. By setting the cationic polymerizable compound (D) to 1 part by weight or more, deficiency of cohesive force can be improved, and improvement of characteristics such as heat resistance and moist heat resistance is facilitated. 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 is easy to obtain an effect for reducing the curing shrinkage.

<Active energy ray polymerization initiator (E)>
Next, the active energy ray polymerization initiator (E) will be described.
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 (E) as necessary in addition to the essential components (A), (B), and (X). By using the active energy ray polymerization initiator (E), 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 includes an active energy ray polymerization initiator (E). .

The active energy ray polymerization initiator (E) used in the present invention can be arbitrarily selected from known ones, and specific examples thereof include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, Xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy 2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxanthone, camphorquinone, and 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropane 1-one, and the like. Commercially available products include Irgacure 184,907,651,1700,1800,819,369,261, DAROCUR-TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF), Darocur 1173 (Merck) Ezacure KIP150, TZT (made by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI (made by Nippon Kayaku Co., Ltd.) and the like. Moreover, the radical polymerization initiator which has at least 1 (meth) acryloyl group in a molecule | numerator can be used as the radical polymerization initiator (e1) of this invention.

In addition, sulfonium salt cationic initiators such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by BASF), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), and Rp- Photoacid generators such as iodonium salt-based cationic initiators such as 2074 (manufactured by Rhodia Japan) can be used as the cationic polymerization initiator (e2) of the present invention.
I can get lost.

The active energy ray polymerization initiator (E) can be used alone or in combination of two or more, and is preferably 0.01 to 30 parts by weight, more preferably 0 to 100 parts by weight of the resin composition. It can be used in an amount of 5 to 20 parts by weight. If the initiator (E) is added in an amount exceeding 30 parts by weight, migration may occur due to the remaining initiator or odor may be generated. If it is less than 0.01 parts by weight, the progress of polymerization is poor and the curing is poor. It may become.

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 (E) 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 (E). 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 (E), 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 other specific examples include Okawara Shin et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Chemicals of Functional Dye” (1981, CMC), Ikemori Chusaburo et al., “Special Functional Materials” (1986, CMC) And sensitizers, but are not limited to these, and other dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region, and these are optional. Two or more kinds may be used in a ratio.

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). However, it is not limited to these.

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 (E). Although it can be preferably used, it is more preferable not to use at all from the viewpoint of yellowing.

<Silane compound (F)>
Next, the silane compound (F) will be described.
The resin composition of the present invention preferably contains a silane compound (F). As a silane compound (F), a well-known silane compound can be used and will not be specifically limited if the intensity | strength of the below-mentioned three-dimensional molded item improves.

Specifically, alkyl alkoxysilane, aryl alkoxysilane, vinyl alkoxysilane, amino alkoxysilane, epoxy alkoxysilane, halogen alkoxysilane, (meth) acryloyl alkoxysilane, mercapto alkoxysilane, cationic Examples thereof include alkoxysilanes having an alkoxyl group such as alkoxysilanes and isocyanate-based alkoxysilanes, and / or organic silanes having reactivity by directly bonding a hydrogen atom to a silicon atom. Tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, methyltris (methoxyethoxy) silane, methyltris (methoxypropoxy) silane, ethyltri Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, Octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, cyclohexane Siltrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiacetoxysilane, dimethylbis (methoxyethoxy) silane, dimethylbis (methoxypropoxy) silane, diethyldimethoxysilane, Diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane Alkyl-based alkoxysilanes such as methylpropyldiisopropoxysilane and methylpropyldiacetoxysilane;

  Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldiacetoxysilane Aryl-based alkoxysilanes such as methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, and methylphenyldiacetoxysilane;

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltris (methoxypropoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, divinyldimethoxysilane, divinyl Diethoxysilane, divinyldiisopropoxysilane, divinyldiacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldiisopropoxysilane, methylvinyldiacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldi Isopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxysilane Vinyl-based alkoxysilanes such as methylallyldiacetoxysilane;

N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminomethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N Amino alkoxy such as-(2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3-aminopyrrolyltrimethoxysilane hydrochloride Silanes;

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

Chloromethyltrimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, Halogen-based alkoxysilanes such as 3,3,3-trifluoropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane;

3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxy (Meth) acryloyl alkoxysilanes such as propylmethyldimethoxysilane;

Mercapto-based alkoxysilanes such as 3-mercaptopropyltrimethoxylane, 3-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane;

Examples include alkoxysilanes typified by isocyanate alkoxysilanes such as γ-isocyanatopropyltriethoxysilane.

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-chloro Ethoxy) 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-teto Phenyldisilane, 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, diacetoxymethyl Silane, N, O-bis (dimethylsilyl) acetamide, 2- (dimethylsilyl) pyridine, tetrakis (dimethylsilyl) silane, allyldimethylsilane, mercaptodimethylsilane, cyclopropanesilane, tris (Trimethylsilyl) silane, 1,1,4,4-tetramethyldisilylethene, cyclohexanesilane, pentamethyldisiloxane, tetramethylcyclotetrasiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, pentamethyldi Siloxane, 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-hepta Tiltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-penta Methylcyclopentasiloxane, 1,2,3,4,5,6-hexamethylcyclotrisilazane, α, ω-bis (hydrodiene) polydimethylsiloxane or long-chain dimethylsiloxane oligomer with oily state or Examples thereof include waxy organosilanes.

In addition, as the silane compound (F), 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 (F) 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 (F) 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 (G)>
Next, the antioxidant (G) will be described.
The resin composition in the present invention may further contain an antioxidant. By containing the antioxidant (G), coloring of the cured resin after active energy ray polymerization with time can be suppressed.
Antioxidants include phenolic antioxidants such as ADK STAB AO-50 and ADK STAB AO-80 (manufactured by ADEKA), and phosphorous oxidations such as ADK STAB PEP-8 (manufactured by ADEKA) and IRGAFOS 168 (manufactured by BASF). Commercial products such as inhibitors, sulfur antioxidants such as IRGANOX-PS-800FD (BASF), hindered amine light stabilizers such as TINUBIN 622LD, TINUBIN 144, and TINUBIN 765 (all three types are manufactured by BASF) However, it is not limited to these.

  The mixture ratio of antioxidant (G) 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.

<Coloring material (H)>
The resin composition of the present invention may contain a color material (H) in addition to the above components. By using the coloring material (H), when used as a three-dimensional model, 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 (H) is used by dispersing a dye or pigment (h1) at a high concentration with a dispersing resin. As such a dye or pigment (h1), an achromatic pigment such as carbon black, titanium oxide, calcium carbonate, or a chromatic organic pigment or dye can be used.
Examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, Benzidine Yellow, and pyrazolone red,
Soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, Permanent Red 2B,
Derivatives from vat dyes such as alizarin, indanthrone, thioindigo maroon,
Phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green,
Quinacridone organic pigments such as quinacridone red and quinacridone magenta;
Perylene organic pigments such as perylene red and perylene scarlet,
Isoindolinone organic pigments such as isoindolinone yellow and isoindolinone orange;
Pyranthrone organic pigments such as pyranthrone red and pyranthrone orange, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments,
Quinophthalone organic pigments such as quinophthalone yellow,
Isoindoline organic pigments such as isoindoline yellow,
Other pigments include organic pigments such as Flavanthrone Yellow, Acylamide Yellow, Nickel Azo Yellow, Copper Azomethine Yellow, Perinone Orange, Anthrone Orange, Dianthraquinonyl Red, Dioxazine Violet.

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

Of the coloring material (H), a general acrylic resin is used as the dispersion resin. In some cases, a surfactant, the above-described compound (A), compound (B), compound (X), oligomer (C ) Or compound (D) or the like is also used in combination. In order to stabilize the hue, it is preferable to use these compounds (A), compounds (B), compounds (X), oligomers (C), or compounds (D) 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 (h1). Moreover, when using together a compound (A), a compound (B), a compound (X), an oligomer (C), or a compound (D), it is non-volatile matter conversion with respect to 100 weight part of dyes and pigments (h1). It is preferable to use in the range of 100 to 800 parts by weight.

If the amount of the dispersion resin, compound (A), compound (B), compound (X), oligomer (C), or compound (D) is less than this range, the dispersion stability decreases, and the dispersion stability of the resin composition. , Storage 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 the dye or pigment (h1), a polar resin 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 copolymer, styrene-maleic acid copolymer, styrene. -Maleic acid- (meth) acrylic acid alkyl ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate- (meth) acrylic acid copolymer, polystyrene sulfonic acid, sodium polystyrene sulfonate, styrene sulfonic acid-maleic Hydrophilic vinyl copolymers such as acid copolymers and polyitaconic acid;

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 polar groups;

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;

Examples include salts of long-chain polyaminoamides and polar acid esters, salts of long-chain polyaminoamides and high-molecular-weight acid esters, naphthalenesulfonic acid formalin condensate salts, amide ester salts such as stearylamine acetate, and the like. It is not something. 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)”, and “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 (polymer 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 Kazusan polycarboxylic acid and silicon) "can be mentioned.

Also, “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 polyvalent carboxylic acid), # 7004 (polyether ester type) ” That.

When using a polar resin for the coloring material (H) of this invention, it is preferable that a polar resin is 0.1 to 80 weight% in the coloring material (H) whole quantity. 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, if the amount exceeds 80% by weight, the modeling performance is remarkably deteriorated, or even if the modeling is completed, the durability of the three-dimensional modeled object such as water resistance and heat-and-moisture resistance tends to decrease.

<Various additives (Q)>
If the resin composition of the present invention is within the range not impairing the effects of the present invention, various additives (Q) can be appropriately blended in addition to the above-described components. Organic or inorganic fillers can be blended from the viewpoints of polymerization curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement and the like. 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 compound (A), the compound (B) and the compound (X) as essential components, and further, if necessary, the compound (C), the compound (D), and a photopolymerization initiator. (E), a silane compound (F), an antioxidant (G), and other various additives (Q) can be mixed and then mixed 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 fat 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 is also possible to contain an organic solvent. Add organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbon solvents, and add water to optically The viscosity of the three-dimensional modeling resin composition can be adjusted, or the optical three-dimensional modeling resin composition can be heated to reduce the viscosity.

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 (A) and the compound (B), 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 ¹ to 500 mW / cm ² . If the light irradiation intensity is less than 1 mW / cm ² , a long time is required for curing, and if it exceeds 500 mW / cm ² , the uncured resin composition may be deteriorated due to heat radiated from the lamp. This is not preferable. 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 material) 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. 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, depending on the type of resin used for cleaning, it is necessary to dry (also referred to as post-cure) with heat or light after cleaning. 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 optical three-dimensional modeling active energy ray-polymerizable resin composition of the present invention includes various three-dimensional modeling products for electronic products that require complicated and fine processing; It can be preferably used as a three-dimensional model such as a model for advertisement or exhibition; a prototype for development such as performance test or production aptitude confirmation; or a medical model for simulation of surgery.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<Manufacture of coloring material (H)>
[Production Examples 1 and 2]
After stirring the compound (B) and the dispersion resin and confirming that the dispersion resin is completely dissolved, the dye or the pigment (f1) is added, and after stirring with a high speed mixer or the like, it is obtained. The mill base was prepared by dispersing in a horizontal sand mill for about 2 hours. Table 1 shows the composition of the produced coloring material (H) (pigment dispersion).

The details of the color material (H) shown in Table 1 are as follows. In Table 1, the symbol “no mark” means no blending.
・ Dye or pigment (f1)
E5B02: Clariant's quinacridone pigment “Hostaperm Red E5B02”
E4GN: Lanxess nickel complex azo pigment "YELLOW PIGMENT E4GN"
Dispersing resin 24000: Pigment dispersant “Solspers 24000” manufactured by Avicia
33000: Pigment dispersant “Solspers 33000” manufactured by Avicia
Compound (B)
PhA: 2-phenoxyethyl acrylate In the present invention, an aqueous dispersion of a coloring material excellent in various properties can be provided without being limited to the above-described components.

[Composition Examples 1-42]
In a light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less, compound (A), compound (B), and compound (X) as essential components, and if necessary, oligomer (C), The ratio of the cationically polymerizable compound (D), the active energy ray polymerization initiator (E), the silane compound (F), the antioxidant (G), the coloring material (H) and various additives (Q) shown in Table 2. After charging and sufficiently stirring with a stirrer and sufficiently defoaming, the resin compositions shown in the formulation examples were obtained.

About the resin composition of the compounding example shown in Table 2, it calculated | required according to the following method and the result was shown in Table 3.

"appearance"
The liquid appearance of the resin composition obtained in each formulation example was visually evaluated. Moreover, the assumption method of molecular weight, a hydroxyl value, an acid value, and a glass transition temperature was also described.

"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.) under an atmosphere of 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》
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Showa Denko GPC (gel permeation chromatography) “Shodex GPC System-21”. 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 (Mn) 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, exactly 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 was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile 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 empty 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 precisely 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 1 is applied to a release-treated polyester film, irradiated with active energy rays, polymerized and cured, and placed in 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.

・ Ingredient (A)
PMPMA: Pentamethylpiperidinyl methacrylate TMPMA: Tetramethylpiperidinyl methacrylate TZMA: 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- {2-methacryloyloxyethoxy}]-S -Triazine OxV: 2-phenyl-4-vinyloxazole ThV: 4-methyl-5-vinylthiazole, component (B)
DIBA: (1R, 1′R, 2R, 2 ′S, 4R, 4′R) 5,5′-divinyl-2,2′-bi (bicyclo [2.2.1] heptane)
BSDA: 2,2-bis {4- (meth) acryloyloxyethoxyphenyl} propane DCPA: dicyclopentanyl acrylate ADCP: dicyclopentanyl diacrylate CHA: cyclohexyl acrylate-component (X)
SR602: “SR-602” manufactured by Sartomer (additional mole number of alkylene oxide linking group: 10)
AT30E: “NK Ester AT-30E” manufactured by Shin-Nakamura Chemical Co., Ltd. (number of added alkylene oxide linking groups: 30)
4HBA: 4-hydroxybutyl acrylate, NPGDA: neopentyl glycol diacrylate TMPTA: 1,2,3-propanetriol triacrylate, component (C)
811: Daicel Cytec Polyester Acrylate “Ebecryl 811”
3000B: Polyurethane oligomer (urethane acrylate) “Shikou UV3000B” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
600: Polyepoxy oligomer (epoxy acrylate) “Ebecryl 600” manufactured by Daicel Cytec Co., Ltd.
・ Ingredient (D)
2021P: 3,4-oxiranecyclohexylmethyl-3,4-oxiranecyclohexanecarboxylate (Daicel)
DOME: Di (1-ethyl-3-oxetanyl) methyl ether GC: Glycerin carbonate component (E)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, DAROCUR TPO)
CPI-110P: p-phenylthiophenyldiphenylsulfonium PF6 salt / component (F)
A-174: Silane coupling agent / component (G) manufactured by Tanak
168: Antioxidant “IRGAFOS168” manufactured by BASF
・ Ingredient (H)
See creation example in Table 1.
・ Ingredient (Q)
DIDP: diisodecyl phthalate (plasticizer)
Indicates.

[Examples 1 to 34] [Comparative Examples 1 to 8]
About the resin composition for optical three-dimensional model | molding shown to Table 2 and 3, the mechanical characteristic was measured with the following method and the molding test was done. The results are shown in Table 4.

"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 1 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-described 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 (one lamination thickness 0.2mm x 100 times lamination). 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 active energy ray polymerizable resin composition for optical three-dimensional modeling of the present invention was polymerized and cured with active energy rays, as shown in Table 3, in Examples 1, 2, 7, 8, and 11-30 No problem in particular. In Examples 3 to 6, 9, 10, 31 to 34, although Young's modulus, swelling degree, warpage, and surface slipperiness are slightly inferior, they can be used. On the other hand, in Comparative Examples 1-8, it turns out that all of Young's modulus, swelling degree, and curvature have difficulty, and it is difficult to use it.

As a result of intensive studies to solve the above problems, the present inventors have found that the target can be achieved by the optical three-dimensional modeling active energy ray polymerizable resin composition shown below, and further completed the present invention by a three-dimensional modeling product. It came to do.
That is, the present invention is a cyclic structure containing a nitrogen atom having a (ca), acryloyl or methacryloyl group-containing compound (A), having a cyclic structure containing no hetero atoms (cb), containing acryloyl group or a methacryloyl group An active energy ray-polymerizable resin composition for optical three-dimensional modeling comprising a compound (B) and an acryloyl group or methacryloyl group-containing compound (X) having no cyclic structure ,
The acryloyl group or methacryloyl group-containing compound (A) has a cyclic structure (ca1-1) containing one nitrogen atom, no oxygen atom, and no sulfur atom. It is related with the active energy ray polymeric resin composition for optical three-dimensional modeling characterized by being a1-1).

[Examples 1 to 34] [Comparative Examples 1 to 8] [Reference Examples 1 to 3]
About the resin composition for optical three-dimensional model | molding shown to Table 2 and 3, the mechanical characteristic was measured with the following method and the molding test was done. The results are shown in Table 4.

When the active energy ray-polymerizable resin composition for optical three-dimensional modeling of the present invention was polymerized and cured with active energy rays, as shown in Table 4 , in Examples 1, 2, 7, 8, and 11-30 No problem in particular. In Examples 3, 9, 10 , 31 to 34, although Young's modulus, swelling degree, warpage, and surface slipperiness are slightly inferior, they can be used. On the other hand, in Comparative Examples 1-8, it turns out that there are difficulty in any of a Young's modulus, a swelling degree, and curvature, and it is difficult to use it.

Claims (10)

An α, β-unsaturated double bond group-containing compound (A) having a cyclic structure (ca) containing a nitrogen atom;
An α, β-unsaturated double bond group-containing compound (B) having a cyclic structure (cb) containing no hetero atom;
An active energy ray polymerizable resin composition for optical three-dimensional modeling, comprising an α, β-unsaturated double bond group-containing compound (X) having no cyclic structure. In the total amount of the active energy ray polymerizable composition,
0.1 to 40% by weight of compound (A),
0.5 to 40% by weight of compound (B),
20 to 99.4% by weight of compound (X)
The optical three-dimensional modeling active energy ray polymerizable resin composition according to claim 1, which is contained. The active energy ray-polymerizable resin composition for optical three-dimensional modeling according to claim 1, wherein the cyclic structure (ca) containing a nitrogen atom is a cyclic structure (ca1) containing no oxygen atom or sulfur atom. object. The active energy ray-polymerizable resin composition for optical three-dimensional modeling according to claim 3, wherein the cyclic structure (ca1) containing a nitrogen atom is a cyclic structure (ca1-1) containing one nitrogen atom. object. The compound (B) is a compound (b1) containing two or more cyclic structures (cb) not containing a hetero atom, The active energy ray for optical three-dimensional modeling according to any one of claims 1 to 4 Polymerizable resin composition. 6. The active energy ray-polymerizable resin composition for optical three-dimensional modeling according to claim 1, wherein the cyclic structure (cb) containing no hetero atom is a bridged polycyclic structure (cb1). Compound (X) is an α, β-unsaturated double bond group-containing compound (x1) containing an alkylene oxide bond group, The activity for optical three-dimensional modeling according to any one of claims 1 to 6 Energy ray polymerizable resin composition. The resin material for optical three-dimensional model | molding using the optical three-dimensional model | formation active energy ray polymeric resin composition in any one of Claims 1-7.   A resin cured product obtained by polymerizing and curing the resin material for optical three-dimensional modeling according to claim 8 with active energy rays.   A three-dimensional structure made of the resin cured product according to claim 9.