JP6543974B2 - Active energy ray polymerizable resin composition for optical three-dimensional shaping, and three-dimensional shaped article - Google Patents

Description

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

Active energy ray polymerization technology has reduced environmental pollution in recent years due to environmental pollution problems, in addition to various characteristics such as high polymerization rate, good workability with no solvent in general, energy saving of extremely low energy requirement, etc. In the fields of construction materials, packaging materials, printing materials, display materials, electric and electronic component materials, optical devices, displays and the like, their application fields tend to be expanded.
These contain only a resin that can be polymerized by active energy rays and a monomer having an α, β-unsaturated double bond group, and since the monomer also functions as a solvent, it forms a coating film or a molded article It is because there is an advantage that the solvent does not volatilize sometimes. And, as a resin having this active energy ray polymerization property, it has an α, β-unsaturated double bond group at the molecular terminal of 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, ultraviolet laser, which is a kind of active energy ray, is 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 article by selective polymerization curing with light is used.
This stereolithography method can cope with complex shapes that are difficult to cut, compared with conventional cutting, etc. It is a fully automated process, easy to handle, has a short manufacturing time, has advantages such as cost advantages, etc. In addition to the production of resin products, they are widely used in design studies, performance tests, manufacturing of prototype models for medical use, etc.
As a representative example of this three-dimensional modeling method, light, for example, a type of active energy ray, is obtained so that a polymerization cured layer of a desired pattern can be 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 and cured layer, and then a liquid photocurable resin composition is supplied in layers on the cured layer, and then light is selectively selected in the same manner as described above. It irradiates and forms a polymerization hardening layer continuous with the above-mentioned hardening layer. It is a method of finally obtaining a desired three-dimensional object by repeating this lamination operation. This three-dimensional modeling method is drawing attention because it can easily obtain a target object in a short time even if the shape of the object to be produced is complicated.

  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 article having a desired shape. It is a method. Such methods or their improved techniques are disclosed in Patent Documents 2 and 3.

  As a photocurable resin composition used for the above-mentioned photofabrication, while being able to form a smooth liquid level with a low viscosity rapidly from a viewpoint of performing efficient photofabrication, transparency and favorable photocuring are made. It is required to have sex. In addition, there is a problem that the cured product is deformed (warped, pulled out, raised in the overhang portion, etc.) over time due to residual strain caused by shrinkage (curing shrinkage) at the time of polymerization curing by light. It is required that the deformation over time be small. Furthermore, depending on the application, the cured product is required to have mechanical strength such as toughness, heat resistance, moisture resistance, water resistance and the like.

Conventionally, as such a photocurable resin composition, radically polymerizable compounds such as urethane (meth) acrylate, epoxy (meth) acrylate, photosensitive polyimide and the like from the viewpoint of transparency, photocurability, etc. Documents 4, 5) and resin compositions containing cationically polymerizable compounds such as epoxy compounds and vinyl ether compounds (eg, Patent Document 6) are used. However, with the miniaturization and complexity of the target products in recent years, the demand for dimensional accuracy is becoming more and more severe, and the demand can not be satisfied with the time-dependent deformation characteristics of the resin composition.
Furthermore, Patent Document 7 discloses a photocurable liquid composition containing micro hollow spheres in which the absolute value of the difference in refractive index between an ethylenically unsaturated monomer and a photoinitiator is not 0, and the photocuring It is stated that the transparency of the sexual liquid composition is reduced. Furthermore, Patent Document 8 discloses a radiation curable resin composition containing a color former, and the three-dimensional article produced from the radiation curable resin composition exhibits a different color before and after curing. Is described.
However, at present the cured resin product obtained by curing the above resin composition has not been able to satisfy all the requirements for toughness, water resistance, physical property stability and suppression of temporal deformation.

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

  An object of the present invention is to provide an active energy ray polymerizable resin composition for optical three-dimensional shaping, which is capable of obtaining a cured product which is less deformed with time and which is excellent in toughness and stability with time. Another object of the present invention is to provide a cured product of the composition.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnestly examining that the present inventors should solve the said subject, it discovers that the said goal can be achieved by the active energy ray polymeric resin composition for optical three-dimensional modeling shown below, Furthermore, this invention It came to complete.
That is, the present invention is an aromatic ring possess two or more in the molecule, an average number of moles added of alkylene oxide linking group 1-40 does not contain a cyclic structure (ca) containing nitrogen atoms, alpha A compound (A) containing two β-unsaturated double bond groups,
And α, β-unsaturated double bond group-containing compound (B) having a 2,2,6,6-tetramethylpiperidine skeleton as a cyclic structure (ca) containing a nitrogen atom,
A photopolymerization initiator (C),
And the α, β-unsaturated double bond group of the compound (A) and the compound (B) is an acryloyl group and / or a methacryloyl group. ,
60 to 90.9 wt% of the compound (A), 9 to 20 wt% of the compound (B), and 0.1 to 20 wt parts of the photopolymerization initiator (C) in the total amount of the resin composition, and The compound (A) is an active energy ray polymerizable resin composition for optical three-dimensional modeling, containing 12 to 22% by weight of a compound having an average addition mole number of alkylene oxide bonding group of 4 with respect to the total amount of the resin composition. About.

  Furthermore, the present invention relates to the above active energy ray polymerizable resin composition for optical three-dimensional modeling, wherein the α, β-unsaturated double bond group of the compound (A) is a methacryloyl group.

  Furthermore, the present invention relates to the above active energy ray polymerizable resin composition for optical three-dimensional modeling, wherein the α, β-unsaturated double bond group of the compound (B) is a methacryloyl group.

  Furthermore, the present invention relates to the active energy ray polymerizable resin composition for optical three-dimensional modeling described above, wherein the compound (C) is a phosphorus-containing compound.

  Furthermore, the present invention relates to a resin cured product obtained by polymerizing and curing the above-mentioned active energy ray polymerizable resin composition with active energy rays.

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

  According to the present invention, it is possible to produce a high-precision shaped object by optical three-dimensional shaping method with little deformation at the time of molding such as warpage and swelling, and also excellent in mechanical properties of the polymerized and cured material. It has become possible to provide an active energy ray polymerizable resin composition for optical three-dimensional modeling that can also be used as a mechanical component.

Hereinafter, embodiments of the present invention will be described.
<Configuration of Active Energy Ray Polymerizable Resin Composition for Optical Three-Dimensional Sizing>
The active energy ray polymerizable resin composition for optical three-dimensional modeling of the present invention comprises an α, β-unsaturated double bond group-containing compound (A) having two or more aromatic rings in the molecule,
An α, β-unsaturated double bond group-containing compound (B) having a cyclic structure containing a nitrogen atom,
A photopolymerization initiator (C),
Contains

  Here, "active energy ray" means a broad energy ray capable of providing energy necessary for activation to cause a chemical reaction, including ultraviolet light, visible light, infrared light, electron beam, and radiation. . The polymerization reaction of the active energy ray polymerizable resin composition for optical three-dimensional modeling (hereinafter referred to as “resin composition”) of the present invention proceeds by the irradiation of the active energy ray to form a cured product. Although not particularly limited, in the embodiment of the present invention, the active energy ray is preferably light energy including ultraviolet light.

Hereinafter, the components of the resin composition will be specifically described.
<Compound (A)>
The resin composition of this invention WHEREIN: The (alpha), (beta)-unsaturated double bond group containing compound (A) which has 2 or more of aromatic rings in a molecule | numerator is demonstrated.

  In the present invention, the compound (A) is a monomer which is a compound having at least two aromatic rings in the molecule and containing at least one α, β-unsaturated double bond group. The above-mentioned compound (A) has an aromatic ring, and the three-dimensional object produced by irradiation with active energy rays becomes non-aqueous, and therefore, it is possible to suppress a decrease in water resistance and moisture resistance. Furthermore, it is preferable because it can be expected to improve the hardness and durability of the shaped article derived from the cyclic structure.

  As the aromatic ring of the present invention, for example, a benzene ring;

For example, aromatic fused bicyclics such as naphthalene ring, pentalene ring, indene ring, indane ring, tetralin ring, azulene ring and the like;

For example, carbon-fused tricycles such as as-indacene ring, s-indacene ring, biphenylene ring, acenaphthylene ring, acenaphthene ring, fluorene ring, phenalene ring, perinaften ring, phenanthrene ring, anthracene ring and the like;

  For example, a trindane ring, a trindane ring, a fluoranthene ring, an acephenanthrylene ring, an acephenanthrene ring, an aceanthrylene ring, an aceanthrene ring, a triphenylene ring, a pyrene ring, a chrysene ring, a tetraphen ring, a tetraphen ring, a tetracene ring, a naphthacene ring, rubrene Carbon-fused tetracycles such as a ring, a preadine ring, a benzoanthrone ring and a chrysene ring;

  For example, carbon-fused pentacycles such as picene ring, perylene ring, pentaphen ring, pentacene ring, tetraphenylene ring, cholanthrene ring, cholanthrene ring;

For example, corannulene ring, phuromine ring, anthantrene ring, zethrene ring, hexahelicene ring, hexaphene ring, hexacene ring, rubene ring, coronene ring, trinaphthylene ring, heptaphene ring, heptacene ring, pyrantrene ring, octaphene ring, octacene ring, terrylene Ring, naphthaenonaphthacene ring, nonaphen ring, nonacene ring, biolanthrene ring, biolanthrone ring, isobiolanthrene ring, isobiolanthrone ring, ovalene ring, decaphen ring, decacene ring, decacyclene ring, pentasenopentacene ring, quaterylene A ring structure such as a fused carbon ring having 6 or more rings such as a ring, a hexasenohexacene ring, a helicene ring and the like can be mentioned without particular limitation.

  As the aromatic ring of the present invention, a benzene ring is also preferable for the availability of the material, compatibility with the compound (B) and the compound (C), and suppression of the viscosity of the resin composition.

  In the present application, in particular, when it is described as “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl”, in particular 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. It represents ".

  The compound (A) can be used without particular limitation as long as it is a compound containing two or more aromatic rings and one or more α, β-unsaturated double bond groups in the structure. Although not particularly limited, the following compounds may be mentioned as specific examples.

(Meth) acrylic acid cyclic esters such as (meth) acrylic acid 2-oxo-1,2-diphenylethyl;

Tetraethylene oxide adduct of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane, tetraethylene oxide adduct of di (meth) acrylic acid 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid ) Tetraethylene oxide adduct of acrylic acid-4,4'-sulfonyldiphenol, tetraethylene oxide adduct of di (meth) acrylic acid-hydrogenated 2,2-bis (hydroxyphenyl) propane, di (meth) acrylic acid Acid-hydrogenated tetraethylene oxide adduct of 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) Difunctional (meta) such as tetraethylene oxide adduct of dioxy (meth) oxyloxypropane-dicaprolactone, and tetraethylene oxide adduct of di (meth) acrylic acid-2, 2-bis (hydroxyphenyl) methane-dicaprolactone ) Acrylic acid cyclic esters;

For example, (meth) acrylamides such as N-phenyl-N- (3-methoxyphenyl) (meth) acrylamide, N-phenyl-N- (3-methoxyphenyl) (meth) acrylamide and the like;

For example, hydroxyl group-containing alicyclic or aromatic ring-containing cyclic (meth) acrylamides such as N- (2-phenylethyl) -3- (3-methoxy-4-hydroxyphenyl) (meth) acrylamide;

For example, 2,2-bis {4- (meth) acryloyloxyethoxyphenyl} propane, 2,2-bis {4- (meth) acryloyloxypropoxyphenyl} propane, 2,2-bis {4- (meth) acrylic acid Roxydiethoxyphenyl} propane, 2,2-bis {4- (meth) acryloyloxypolyethoxyphenyl} propane, (meth) acrylic acid 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 9, 9, (Meth) acrylic esters having a bisphenol skeleton such as 9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, or these C 2 -C 4 alkylene oxide adducts [average addition mole of alkylene oxide Several 0 to 30 moles (especially about 1 to 10 moles)]; for example, bisphenol A jig Additives of acrylic acid of bisphenol type epoxy such as acrylic acid adduct of syl ether and acrylic acid adduct of bisphenol F; (meth) acrylic esters having biphenyl skeleton such as bi (di) (meth) acrylic acid, for example Or these alkylene oxide adducts of 2 to 4 carbon atoms [average addition mole number of alkylene oxide: about 0 to 30 moles (especially about 1 to 10 moles)]; for example, 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, tri (meth) acrylic Acid 1,1 '-((4-hydroxycyclohexyl) methylene) -bis (2-methyl-4-hydroxycyclohexane), tri (meth) acrylic acid 1,1'-((2-methyl-4-hydroxycyclohexyl) (Meth) acrylic acid esters having a hydrogenated bisphenol skeleton such as methylene) -bis (3-methyl-4-hydroxycyclohexyl) and tri (meth) acrylic acid 1,1,1-tris (4-hydroxycyclohexyl) methane Or these alkylene oxide adducts of 2 to 4 carbon atoms [about 0 to 30 moles (especially about 1 to 10 moles) of the average addition mole number of the alkylene oxide] and the like.

  In addition, the compound (A) of the present invention may be a commercially available one. For example, “ethylene oxide diadduct bisphenol A dimethacrylate (trade name: FA-320M)” manufactured by Hitachi Chemical Co., Ltd. Ethylene oxide 10 adduct bisphenol A dimethacrylate (trade name: FA-321M), "ethylene oxide 18 adduct bisphenol A dimethacrylate (trade name: FA-3218M)", "ethylene oxide 10 adduct bisphenol A diacrylate ( Trade name: FA-321A) "and" Ethylene oxide tetraadduct bisphenol A diacrylate (trade name: FA-324A) ";" Ethylene oxide 2-adduct bisphenol A dimethacrylate (trade name: SR348) "manufactured by SARTOMER , “Ethylene oxide 4-adduct Phenol A dimethacrylate (trade name: SR540), "ethylene oxide 10 adduct bisphenol A dimethacrylate (trade name: SR480)", "ethylene oxide triadduct bisphenol A acrylate (trade name: SR 349)", "ethylene oxide 4-adduct bisphenol A diacrylate (trade name: SR601) and "ethylene oxide 10 adduct bisphenol A diacrylate (trade name: SR602)"; "Ethylene oxide tri-adduct bisphenol A manufactured by Shin-Nakamura Chemical Co., Ltd." Diacrylate (trade name: ABE-300), "ethylene oxide 10 adduct bisphenol A diacrylate (trade name: A-BPE-10)", "ethylene oxide 20 adduct bisphenol A diacrylate (trade name: A- BPE-20 "", "Ethylene oxide tetraadduct bisphenol A diacrylate (trade name: A-BPE-4)", "Ethylene oxide 2.3 adduct bisphenol A dimethacrylate (trade name: BPE-80N)", "ethylene oxide 2.6 adduct bisphenol A dimethacrylate (trade name: BPE-100), "ethylene oxide tetraadduct bisphenol A dimethacrylate (trade name: BPE-200)", "ethylene oxide 10 adduct bisphenol A dimethacrylate ( Trade name: BPE-500), "Ethylene oxide 17 adduct bisphenol A dimethacrylate (trade name: BPE-900)", "Ethylene oxide 30 adduct bisphenol A dimethacrylate (trade name: BPE-1300N)", " Propylene oxide triadduct bis HENOL A diacrylate (trade name: A-BPP-3), "Ethoxylated-R-phenylphenol acrylate (trade name: A-LEN-10)", "2-hydroxy-R-phenylphenol propyl acrylate (trade) Name: 401P), "fluorene acrylate (trade name: A-BPEF)" and "ethylene oxide 17 adduct bisphenol A dimethacrylate (trade name: BPE-900)"; "Ethylene" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Oxide tetraadduct bisphenol A diacrylate (trade name: BPE-4), "ethylene oxide 20 adduct bisphenol A diacrylate (trade name: BPE-20)" and "ethylene oxide 10 adduct bisphenol A dimethacrylate (trade Name: BPEM-10) ";" Ethylene oxide "manufactured by Toagosei Co., Ltd. De 4-adduct bisphenol A diacrylate (trade name: M-211B); "Propylene oxide tetra-adduct bisphenol A diacrylate (trade name: HPP-A)" manufactured by Kyoeisha Chemical Co., Ltd .;

  Moreover, these may use only 1 type, or may use multiple types together.

  The compound (A) of the present invention preferably has an alkylene oxide bonding group. Among them, in terms of viscosity, photosensitivity and polymerization rate, ethylene oxide units are preferable as the alkylene oxide bonding group. These alkylene oxide bonding groups may be present singly or in combination of two or more. Moreover, the preferable range of the average added mole number of an alkylene oxide bonding group is 1-40, and 2-30 are more preferable. When the average addition mole number of the alkylene oxide bonding group is smaller than this range, the action to lower the viscosity of the resin composition, the action to improve the photosensitivity, the action to improve the flexibility of the three-dimensional object, etc. are insufficient. It becomes. Moreover, if it is larger than this range, the viscosity of the resin composition is rather increased, and the crosslink density is lowered too much by the lengthening of the alkylene oxide chain, so that the strength of the shaped article is lowered.

  As the α, β-unsaturated double bond group of the compound (A) of the present invention, acryloyl group, methacryloyl group, vinyl group, vinyl ester group, vinyl silyl group, vinyl silyl group, vinyl ether group, allyl group, methallyl group etc. Among these α, β-unsaturated double bond groups, vinyl group, vinyl ester group, vinyl silyl group, vinyl ether group, allyl group, methallyl group and the like are known to be used without particular limitation. As the α, β-unsaturated double bond group is an acryloyl group or methacryloyl group, the compound (A) is likely to be left unreacted as the radical polymerization property is inferior to the group or methacryloyl group. Is preferred. In particular, a methacryloyl group is particularly preferable in order to suppress deformation and distortion due to warpage of the photofabricated product and to suppress deterioration in appearance defect and dimensional accuracy and formation accuracy because curing shrinkage at the time of light curing is small.

<Compound (B)>
In the resin composition of the present invention, the α, β-unsaturated double bond group-containing compound (B) having a cyclic structure (ca) containing a nitrogen atom has a cyclic structure (ca) containing a nitrogen atom In addition, in addition to the addition polymerization of α, β-unsaturated double bond groups, the glass transition point of the shaped article due to hydrogen bond formation accompanied by a nitrogen atom and the rigidity derived from the cyclic structure in a three-dimensional shaped article after active energy ray irradiation. By improving (Tg), it is possible to further improve the internal cohesive force, and to form a three-dimensional object having good resistance such as heat resistance and water resistance. The cyclic structure (ca) containing such a nitrogen atom means a cyclic structure (ca1) containing only one or more nitrogen atoms in the ring, and contains both a nitrogen atom and an oxygen atom in the ring And cyclic structures (ca3) containing both nitrogen atoms and sulfur atoms in the ring. Further, the cyclic structure (ca1) is roughly classified into a cyclic structure (ca1-1) having only one nitrogen atom and a cyclic structure (ca1-2) having two or more nitrogen atoms.

  The cyclic structure (ca) containing such a nitrogen atom is not particularly limited, but more specifically, for example, ethyleneimine ring, azetidine ring, pyrrolidine ring, piperidine ring, azepane ring, quinuclidine ring, tropane ring and the like Saturated monocyclic compounds containing one nitrogen atom (ca1-1); saturated monocycles containing two or more nitrogen atoms such as piperazine ring and methenamine ring (ca1-2); azirine ring, azeto ring, pyrrole Unsaturated monocyclic compounds (ca1-1) containing one nitrogen atom such as ring, pyridine ring, quinuclidine ring and azepine ring (imidazole ring, indazole ring, imidazoline ring, pyrazole ring, pyrazine ring, pyrimidine ring, pyridazine ring) Unsaturated monocyclic rings (ca1-2) containing two or more nitrogen atoms such as triazole ring, triazine ring and tetrazole ring; Unsaturated polycyclic compounds (ca1-1) containing one nitrogen atom such as ring, isoindole ring, quinoline ring, isoquinoline ring, carbazole ring and acridine ring; benzoimidazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, Unsaturated multiple containing two or more nitrogen atoms such as cinnoline ring, pteridine ring, naphthyridine ring, purine ring, benzotriazole ring, phenazine ring, benzodiazebin ring, benzo-o-cinnoline ring, porphyrin ring, chlorin ring, choline ring Heterocycles containing only nitrogen atoms represented by rings (ca1-2);

  For example, morpholine ring, pyrrolidone ring, lactam ring, isatin ring, primidone ring, oxazine ring, oxazole ring, oxazole ring, isoxazole ring, benzoxazine ring, phenoxazine ring, benzophenoxazine ring, phenazone ring, hydantoin ring, phthalocyanine ring, etc. Heterocycles (ca2) containing both nitrogen and oxygen atoms;

Examples thereof include heterocycles (ca3) containing both a nitrogen atom and a sulfur atom, such as thiazole ring, isothiazole ring, thiazine ring, phenothiazine ring and the like, which can be used without particular limitation.

  As the α, β-unsaturated double bond group-containing compound (B) having a cyclic structure (ca) containing these nitrogen atoms, a cyclic structure (ca1 containing only one or more nitrogen atoms in the ring) And a compound (b2) having a cyclic structure (ca2) containing both a nitrogen atom and an oxygen atom in the ring, and containing both a nitrogen atom and a sulfur atom in the ring And the compound (b1), and the compound (b1) is a compound (b1-1) having a ring structure (ca1-1) having only one nitrogen atom and the nitrogen The compound is roughly classified into a compound (b1-2) having a ring structure (ca1-2) having two or more atoms.

  The compound (B) can be used without particular limitation as long as it has a cyclic structure (ca) containing one or more nitrogen atoms in the structure, and it can be used as an α, β-unsaturated double bond group The acryloyl group, methacryloyl group, vinyl group, vinyl ester group, vinyl silyl group, vinyl silyl group, vinyl ether group, allyl group or methallyl group are conventionally 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 or methallyl group is inferior in radical polymerizability compared to acryloyl group or methacryloyl group, and compound (B) is It is preferable to use an acryloyl group or methacryloyl group as the α, β-unsaturated double bond group because it tends to remain unreacted. . In particular, a methacryloyl group is particularly preferable in order to suppress deformation and distortion due to warpage of the photofabricated product and to suppress deterioration in appearance defect and dimensional accuracy and formation accuracy because curing shrinkage at the time of light curing is small.

  More specific examples of the α, β-unsaturated double bond group-containing compound (b1-2) having two or more nitrogen atoms in the ring are, for example, 2- (2′-hydroxy-5 ′-(b) (Meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-) 5 '-(Meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2) '-Hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy) Nitrogen atom-containing polycyclic (meth) acrylic acid esters such as cis-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole;

For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy] } -S-Triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- (Meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S -Membered nitrogen-containing six-membered such as -triazine and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine (Meth) acrylic esters having a ring;

More specifically, examples of the α, β-unsaturated double bond group-containing compound (b1-1) having only one nitrogen atom in the ring include, for example, pentamethyl piperidinyl (meth) acrylate and tetramethyl pi Nitrogen-containing cyclic (meth) acrylates such as peridinyl (meth) acrylate and 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate;

  For example, 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 And vinyl group-containing compounds having a nitrogen atom-containing five-membered ring such as 3-methyl-5-phenyl-1-vinylpyrazole;

For example, 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-vinyl pyridazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl-1,3,5-dimethyl-2,4-diamine, 3-vinyl-1 , Vinyl group-containing compounds having a nitrogen-containing six-membered ring such as 2,4,5-tetrazine;

For example, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, vinyl nicotinoyl didecanoate, vinyl isonicotinoyl vinyl acetate, vinyl isonicotinoyl propionate , Vinyl group containing an acyl group such as vinyl isonicotinoyl vinylbutyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl didecanoate and a six-membered ring containing a nitrogen atom Compounds;

For example, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzoimidazole, 2-vinyl-1H-benzoimidazole, 2-vinyl-5, 6 -Dimethyl-1H-benzoimidazole, 1-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquinoline, 2-vinylisoxaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline And nitrogen-containing polycyclic vinyl-containing compounds such as 1-vinylcarbazole;

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

For example, 1- (meth) allyl-1H-imidazole [1-allyl-1H-imidazole and 1-methallyl-1H-imidazole are collectively referred to as "1- (meth) allyl-1H-imidazole". Same below. 1- (Meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazol-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) allyl piperazine, 5- (5-) 1-methylpropyl) -5- (meth) allyl pyrimidine, 5- (meth) allyl-5-isopropyl pyrimidine, 1- (meth) allyl-5,5-diethyl pyrimidine, 2- (meth) allyl pyridine, 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;

For example, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 1- (meth) allyl-1H-benzoimidazole, 2- (meth) allyl indazole, 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- (4) (Meth) allyl group-containing compounds having a nitrogen atom-containing polycyclic structure such as meta) allylisoquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline, 9- (meth) allyl-9H-carbazole and the like Kind;

More specifically, examples of the α, β-unsaturated double bond group-containing compound (b2) containing both a nitrogen atom and an oxygen atom in the ring include, for example, imide (meth) acrylate, 2- (2) It contains an oxygen atom other than nitrogen atoms such as 4-oxazolin-3-yl) ethyl (meth) acrylate, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone modified tris- (2-acryloyloxyethyl) isocyanurate, etc. (Meth) acrylic esters having a cyclic structure;

For example, cyclic acrylamides such as 4-acryloyl morpholine;

For example, 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;

For example, maleimide derivatives having both a nitrogen atom and an oxygen atom such as maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide and the like;

For example, 2-vinyloxazole, 2-phenyl-4-vinyloxazole, 2-phenyl-5-vinyloxazole, 5-ethoxy-2-vinyloxazole, 3-vinyl-5-nitrosooxazole, 2-vinyl-4,5 Nitrogen such as -diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, 2-vinylbenzoxazole, 1-vinylpyridine-2 (1H) -one, etc. Ethenyl group-containing compounds having a cyclic structure containing an oxygen atom in addition to the atom;

More specifically, examples of the α, β-unsaturated double bond group-containing compound (b3) having both a nitrogen atom and a sulfur atom in the ring include, for example, 2-vinylthiazole, 4-methyl -5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzothiazole, 1-vinyl-2 (1H)- Although vinyl group containing compounds etc. which have a cyclic structure containing a sulfur atom other than nitrogen atoms, such as pyridinethion, are mentioned, It is not limited in particular in these. These may be used alone or in combination of two or more.

  In the α, β-unsaturated double bond group-containing compound (B) having a nitrogen atom-containing cyclic structure (ca) used in the present invention, the ring structure does not contain an oxygen atom or a sulfur atom Is preferred. When atoms of group 6B of the periodic table are contained in the ring in addition to nitrogen atoms, the basicity is lowered, so the hydrogen bonding performance is lowered and the internal cohesive force of the polymer irradiated with active energy rays is lowered. The strength of the three-dimensional object may be reduced. The cyclic structure (ca) containing a nitrogen atom is preferably a 5- or more-membered ring. A three- or four-membered ring is not preferable because it is likely to cause a ring-opening reaction by heat or active energy rays. Furthermore, it is preferred that there be one nitrogen atom in the ring. If there are multiple nitrogen atoms in the ring, hydrogen bonding performance is also improved, but yellowing due to nitrogen atoms becomes remarkable, so the polymer irradiated with active energy rays yellows in the presence of a trace amount of oxygen, It is difficult to obtain a colorless and transparent shaped article. Therefore, an α, β-unsaturated double bond group-containing compound (b1-1) containing a cyclic structure (ca1-1) containing only one nitrogen atom is most preferable.

  Among the α, β-unsaturated double bond group-containing compounds (B) having a cyclic structure (ca) containing a nitrogen atom, an α, β-unsaturated double bond group having only one nitrogen atom in the ring In particular, pentamethyl piperidinyl (meth) acrylate, tetramethyl piperidinyl (meth) acrylate, 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate which is the compound (b1-1) containing It is preferably used.

<Compound (C)>
In the resin composition of the present invention, the photopolymerization initiator (C) is used to promote the polymerization reaction by irradiation of activation energy rays. In one embodiment of the present invention, the activation energy is preferably ultraviolet light, and when the polymerization reaction is advanced by irradiation of ultraviolet light, the resin composition absorbs the ultraviolet light to be contained in the resin composition α, It is preferable that it is a compound which can start superposition | polymerization of (beta)-unsaturated double bond group containing compound.

  As a specific example, for example, the following may be mentioned. 2,2-Dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl Dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-thioxanthone, camphorquinone, and Photoradical generators such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

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

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

  In the present invention, as the photopolymerization initiator (C), the above-mentioned compounds can be used alone or in combination of two or more.

  As the compound (C) of the present invention, it is possible to use ultraviolet light having a wavelength of 380 nm or more which is easy to handle, to be able to form a colored material, and to be less susceptible to coloring when producing clear shaped objects. Therefore, it is preferable to use DAROCUR-TPO (manufactured by BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) and Irgacure 819, which are compounds of an acylphosphine type.

The resin composition in the present invention comprises 60 to 99.8% by weight of the compound (A) and 0.1 to 20% by weight of the compound (B) in the total amount of the active energy ray polymerizable resin composition for optical three-dimensional modeling, It is preferable to contain 0.1 to 20% by weight of the compound (C), 75 to 99% by weight of the compound (A), 0.5 to 15% by weight of the compound (B), and 0.5 for the compound (C). It is more preferable to contain 10 wt%.
If the compound (B) and the compound (C) in the total amount of the resin composition are each 0.1% by weight or more, curing is carried out by suppressing curing inhibition due to dissolved oxygen in the resin composition during photocuring, etc. An improvement in speed can be expected, and a sufficient cohesive force can be easily obtained, and an effect of improving heat resistance and moist heat resistance can be expected. Further, if the compound (A) is 60% by weight or more, it has sufficient cohesion, leading to improvement in heat resistance and moisture and heat resistance. Furthermore, when a resin composition is used as an optical shaping material, the cure shrinkage of a three-dimensional object can be reduced, and the flexibility is improved. On the other hand, when the compound (B) exceeds 20% by weight or the compound (C) exceeds 20% by weight in the total amount of the resin composition, the curing rate decreases or the three-dimensional object decreases due to the problem of yellowing and the increase of compounds not contributing to polymerization. If the compound (A) is less than 60% by weight, there is a concern that the strength of the three-dimensional object may be reduced and the heat and moisture resistance may be reduced.

  The resin composition of the present invention is a polymerization cure shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement as long as the effects of the present invention are not impaired. It is possible to mix | blend various additives suitably from a viewpoint of toughness improvement, coloring improvement, etc. For example, an α, β-unsaturated double bond group-containing compound represented by (meth) acrylic acid esters not corresponding to the compound (A) or compound (B) of the present invention, an epoxy group-containing compound, an oxetanyl group-containing compound A cationically polymerizable compound represented by the formula, a polymer of a monomer having an .alpha.,. Beta.-unsaturated double bond group and / or a compound obtained by adding an .alpha.,. Beta.-unsaturated double bond group to various compounds Yes, oligomers represented by polyesters, polyurethanes, polyepoxys and polyacrylics, cationic photopolymerization initiators, sensitizers, silane compounds, sulfur based antioxidants, coloring materials represented by dyes and pigments, Organic / inorganic fillers such as polymers, ceramics, metals, metal oxides, metal salts and the like can be mentioned. The shape of the filler is not particularly limited, such as particulate or fibrous. In addition, when compounding the above-mentioned polymer, as a softener, a plasticizer, a flame retardant, a storage stabilizer, a thixotropy imparting agent, a dispersion stabilizer, a fluidity imparting agent, an antifoamer, etc., as a filler It is also possible to dissolve, semi-dissolve or micro-disperse in a resin composition for optical stereolithography as a polymer blend or polymer alloy.

<Properties of Active Energy Ray Polymerizable Resin Composition for Optical Three-Dimensional Modeling>
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 is produced by using the above compound (A), compound (B) and compound (C) as essential components, and further blending various additives as required, and uniformly mixing them. Can.
When stirring and mixing, it may be prepared by stirring and mixing using a general-purpose apparatus such as a single-shaft or multi-shaft extruder, a kneader, and a dissolver equipped with a pressure reduction device. It is preferable that the temperature at the time of stirring and mixing is usually set to 10 to 60 ° C. If the set temperature at preparation is less than 10 ° C., the viscosity may be too high to make uniform stirring and mixing work difficult, and conversely, if the temperature at preparation exceeds 60 ° C., a curing reaction due to heat will occur In some cases, it is not preferable because a normal resin composition may not be obtained.

The resin composition of the present invention can be used in any form of liquid, paste and film.
In addition, although it is preferable that the resin composition in this invention does not contain an organic solvent substantially, it is also possible to contain an organic solvent. For example, water, and organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbon solvents, and water are further added, The viscosity of the resin composition for optical three-dimensional model formation can also be adjusted, and the resin composition for optical three-dimensional model formation can also 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 of 25 ° C. of 1 to 2000 mPa · s, preferably 10 to 1500 mPa · s, and 20 to 1000 mPa · s. More preferable. When the viscosity is higher than 2000 mPa · s, in the case of a cured resin, three-dimensional shaping can not be performed and the hardness is deteriorated. On the other hand, when the viscosity is lower than 1 mPa · s, it becomes difficult to control the dimensional stability of the cured 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 can be controlled by controlling these viscosities in the range of 1 to 100,000 mPa · s. Management is also possible.

<Forming process of active energy ray polymerizable resin composition for optical three-dimensional shaping>
Next, the shaping process (optical three-dimensional modeling method) of the resin cured product 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 shaping method (hereinafter also referred to as an optical shaping method). That is, the resin composition of the present invention is selectively irradiated with active energy rays such as ultraviolet rays to supply energy necessary for polymerization and curing, thereby producing a desired three-dimensional resin cured product. be able to.

The resin composition of the present invention is suitably used as a curable liquid material in optical stereolithography. That is, by selectively irradiating light such as visible light, ultraviolet light, infrared light and the like to specific places of this resin composition to supply active energy necessary for polymerization and curing, a three-dimensional object having a desired shape is obtained. You can get it.
The irradiation light source of active energy ray mainly comprises light in the 150 to 550 nm wavelength region, and is a low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, chemical lamp, black light lamp, microwave excitation mercury lamp, LED Other than a lamp, a xenon lamp, a metal halide lamp, etc., a semiconductor laser beam, an electron beam or the like can be used as an active energy ray for exposure. An ultraviolet laser beam is preferable in terms of cost, directivity, and convergence.
The irradiation intensity of the active energy ray is preferably 0.1 to 500 mW / cm ² . When the light irradiation intensity is less than 0.1 mW / cm ² , curing takes a long time, and when it exceeds 500 mW / cm ² , the uncured resin composition may be degraded by the heat radiated from the lamp. Unfavorable because of the nature. The integrated irradiation dose represented as the product of the irradiation intensity and the irradiation time is preferably ¹ to 5,000 mJ / cm ² . If the cumulative irradiation amount is less than 1 mJ / cm ² , a long time is required for polymerization and curing, and if it is more than 5,000 mJ / cm ² , the irradiation time becomes very long and productivity is poor, which is not preferable.

  The method of selectively irradiating the light which is the active energy ray for such polymerization curing to a specific part 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 using a laser beam, a lens, a mirror or the like to a specific place, a method of irradiating non-focused light through a mask of a predetermined pattern, 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, and in such a case, it is preferable to use a laser beam. Furthermore, the specific portion 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 bottom wall of the container, or a liquid. In order to irradiate light to the liquid surface of the resin composition or the contact surface with the container wall, light may be irradiated from the outside directly or through a transparent vessel wall, and in the case of irradiating a specific location in the liquid, an optical fiber Irradiation may be performed using a light guide such as

  In the above-described optical three-dimensional modeling method, usually, after specific portions of the resin composition are polymerized and cured, the irradiated position is continuously or stepwise moved from the already cured portion to the uncured portion. Thus, the hardened portion can be grown into a desired three-dimensional shape. The movement of the irradiated position can be performed by various methods, for example, moving at least one of a light source, a container containing the resin composition, and a cured portion of the resin composition, and the container is not yet cured. It can be carried out by a method such as adding a resin composition (liquid curable substance) of the above.

<Three-dimensional object>
Next, a three-dimensional object will be described.
As a representative method of obtaining a three-dimensional object by using the resin composition of the present invention, light is applied so that a cured layer having a desired pattern can be obtained from the resin composition for optical three-dimensional formation of the present invention which is liquid. Selectively to form a hardened layer, and then the unhardened composition layer adjacent to the hardened layer is similarly irradiated with light to form a new hardened layer continuous with the previously formed hardened layer. By repeating the laminating operation to finally form a three-dimensional shaped object of interest. As more specific embodiments of this method, the following exemplified methods can be mentioned.

  The formed three-dimensional object is removed from the vessel used for the reaction, and after removing the unreacted compound remaining on the surface of the object, 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, and aliphatics represented by terpenes and glycol ether esters. It is possible to use a liquid resin having a low viscosity of a system organic solvent, thermosetting or light curing (meaning polymerization curing by light which is an active energy ray). When it is desired to impart transparency to a three-dimensional object, it is desirable to use the above-mentioned thermosetting or photocurable liquid resin as a cleaning agent. In this case, depending on the type of resin used for washing, it is necessary to carry out drying with heat or light (also referred to as post cure) after washing. 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 object, so cleaning with an organic solvent is possible. It is preferable to carry out in the case of

  The resin cured product of the active energy ray polymerizable resin composition for optical three-dimensional shaping of the present invention is various three-dimensional shaped articles such as electronic products requiring complicated and fine processing; for design study of new products, for presentation It can be preferably used as a three-dimensional object such as a model for advertising or display; a prototype for development for performance test or production aptitude confirmation; a medical model for simulation of surgery or the like.

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

[Composition Examples 1 to 15]
The compound (A), the compound (B) and the compound (C) are charged in the ratio shown in Table 1 into a light-shielded 300 ml mayonnaise bottle having an oxygen concentration of 10% or less, and sufficiently stirred with a stirrer. After sufficient defoaming, the resin composition shown in the formulation example was obtained.

  The appearance and viscosity (mPa · s) of the resin compositions of the formulation examples shown in Table 1 were determined according to the following method, and the results were shown.

"appearance"
The liquid appearance of the resin composition obtained in each formulation example was visually evaluated. In addition, methods for measuring molecular weight, hydroxyl value, acid value, and glass transition temperature were also described.

"viscosity"
About 1.2 ml is used as a measurement sample with an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) at 23 ° C. under an atmosphere of 23 ° C., and the rotational speed is 0.5 to 0.5. It measured on conditions of 100 rpm and rotation for 1 minute, and was set as solution viscosity (mPa * s).

Molecular weight
The measurement of a number average molecular weight (Mn) and a weight average molecular weight (Mw) used Showa Denko GPC (gel permeation chromatography) "ShodexGPC System-21." GPC is a liquid chromatography that separates and quantifies a substance dissolved in a solvent based on the difference in molecular size, and the solvent is tetrohydrofuran, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

<< OH 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. Furthermore, 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, add phenolphthalein test solution as an indicator and hold for 30 seconds. It is then titrated with 0.1 N alcoholic potassium hydroxide solution until the solution is pinkish.
The hydroxyl value was determined by the following formula. The hydroxyl value is a numerical value of the dry state of the resin (unit: mg KOH / g).
Hydroxyl value (mg KOH / g) = [{(b-a) × F × 28.25} / S] / (nonvolatile content concentration / 100) + D
However, S: amount of sample collected (g)
a: Consumption of 0.1 N alcoholic potassium hydroxide solution (ml)
b: Consumption of empty 0.1 N alcoholic potassium hydroxide solution (ml)
F: titer of 0.1 N alcoholic potassium hydroxide solution
D: Acid value (mg KOH / g)

<< Acid number (AV)
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask, and dissolved by adding 100 ml of a mixture of toluene / ethanol (volume ratio: toluene / ethanol = 2/1). To this was added phenolphthalein test solution as an indicator, held for 30 seconds, and then titrated with 0.1 N alcoholic potassium hydroxide solution until the solution turned pink.
The acid value (mg KOH / g) was determined by the following equation as the value of the resin in a dry state.
Acid value (mg KOH / g) = {(5.611 × a × F) / S} / (nonvolatile content concentration / 100)
However, S: amount of sample collected (g)
a: Consumption of 0.1 N alcoholic potassium hydroxide solution (ml)
F: titer of 0.1 N alcoholic potassium hydroxide solution

<< Glass transition temperature (Tg) >>
“SSC 5200 disc station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC 220” manufactured by Seiko Instruments Inc.) and used for measurement.
The resin composition of Table 1 is coated on a release-treated polyester film, irradiated with active energy rays, polymerized and cured, and scraped about 10 mg, put in an aluminum pan as a sample, weighed, and a differential scanning calorimeter And heated for 5 minutes at a temperature of 100.degree. C. using the same type of aluminum pan as a reference without samples and then quenched to -120.degree. 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 rise.

  Exemplary compounds are specifically shown in Table 1 below, but are not limited thereto. In Table 1, the symbol "-" means no blending.

・ Compound (A)
BPE 100: Shin-Nakamura Chemical Co., Ltd. Ethylene oxide 2.6 adduct bisphenol A dimethacrylate (trade name: BPE-100)
SR540: SARTOMER ethylene oxide tetraadduct bisphenol A dimethacrylate (trade name: SR540)
SR480: SARTOMER ethylene oxide 10 adduct bisphenol A dimethacrylate (trade name: SR480)
BPE 900: Shin-Nakamura Chemical Co., Ltd. Ethylene oxide 17 adduct bisphenol A dimethacrylate (trade name: BPE-900)
・ Compound (B)
PMPMA: pentamethyl piperidinyl methacrylate TMPMA: tetramethyl piperidinyl 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 · Compound (C)
TPO: 2,4,6-trimethyl benzoyl-diphenyl- phosphine oxide (BASF, DAROCUR TPO)
819: bis (2,4,6-trimethyl benzoyl) -phenyl-phosphine oxide (manufactured by BASF, Irgacure 819)
・ Others 4HBA: 4-hydroxybutyl acrylate 168: product of BASF Phosphorus antioxidant product made of BASF antioxidant (trade name: IRGAFOS 168)
Indicates

[Examples 1 to 12] [Comparative Examples 1 to 3]
About the resin composition for optical three-dimensional model | molding shown in Table 1, hardening speed and a mechanical property were measured with the following method, and the shaping | molding test was done. The results are shown in Table 2.
In the present specification, examples other than Examples 1, 4 to 7, 11 and 12 are reference examples.

Curing speed
The resin composition is applied to a thickness of 10 μm on a glass plate using an applicator, and the light of a mercury-xenon lamp UXM-200YA made by Ushio Inc. selectively transmits only the light of 405 nm to this coating film It irradiated with 0.1 J / cm < ² > through the band pass filter and ND filter for light quantity adjustment. The tack of the film after light irradiation was evaluated by palpation.
○: no tack △: some tack ×: some tack

"Young's modulus"
The resin composition was applied to a thickness of 250 μm on a glass plate using an applicator and irradiated with ultraviolet light 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 at 23 ° C. and 50% relative humidity for 24 hours 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 a relative humidity of 50% under the conditions of a pulling speed of 1 mm / min and a distance between marked lines of 25 mm. Further, the elongation at break and the breaking strength of the test piece at 23 ° C. were measured under the conditions of a tensile speed of 50 mm / min and a distance between marked lines of 25 mm.
This Young's modulus was evaluated in four steps. In the case of "以上" evaluation or more, there is no particular problem in actual use.
◎: 120 (kg / mm ² ) or more. There is no problem at all.
○: not less than 100 (kg / mm ² ) and less than 120 (kg / mm ² ). Slightly weak, but no problem.
Δ: 80 (kg / mm ² ) or more and less than 100 (kg / mm ² ). Practically usable.
X: less than 80 (kg / mm ² ). There is a problem in practical use.

<< Measurement of swelling degree >>
Using an optical forming device (Solid Creator JSC-2000: made by Sony Corporation) using Ar ion laser (wavelength 351, 385 nm) as a light source, molding at a laser power of 40 mW at the liquid surface and a scanning speed of 100 cm / min A test piece [(width 50 × length 50 × height 1 mm): laminating thickness 0.2 mm × five times at one time] was used.
After carefully wiping off the adhering resin liquid, the weight W ₁ of the plate was measured. Subsequently, the test piece was immersed in a resin solution at 25 ° C. for 24 hours, and after wiping off the adhered resin solution, the weight W ₂ was measured.
The degree of swelling was calculated by the following equation and evaluated in three steps. In the case of "以上" evaluation or more, there is no particular problem in actual use.
Swelling degree (%) = [(W ₂ −W ₁ ) / W ₁ ] × 100
○: less than 2 (%). There is no problem at all.
Δ: 2 (%) or more and less than 5 (%). Practically usable.
X: 5 (%) or more. There is a problem in practical use.

<< Measurement of warpage >>
Using the above-mentioned optical shaping apparatus, it is molded at a laser power of 40 mW at the liquid surface and at a scanning speed of 100 cm / min and a test piece [(width 50 × length 50 × height 40 mm): lamination thickness of 0.2 mm × 100 times lamination].
It shape | molded using the optical shaping | molding apparatus mentioned above (single lamination thickness 0.2 mm x 100 times lamination | stacking). After wiping off the adhered resin solution, 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 table, and the warpage was evaluated by the lifting amount Δh (mm) of the other end.
This warp was evaluated in four steps.
◎: less than 0.2 (mm). There is no problem at all. In the case of "以上" evaluation or more, there is no particular problem in actual use.
○: 0.2 (mm) or more and less than 0.5 (mm). There are a few, but no problem.
Δ: 0.5 (mm) or more and less than 1.0 (mm). Practically usable.
X: 1.0 (mm) or more. There is a problem in practical use.

"Surface smoothness"
The resin composition is applied to a thickness of 250 μm on a glass plate using an applicator and irradiated with ultraviolet light of 0.5 J / cm ² (wavelength: 350 nm) to obtain a cured glass laminated film, 23 ° C., relative humidity 50% The sample was conditioned for 24 hours to prepare a test piece.
The surface of the cured film was rubbed 10 times with a steel wool of # 0000 under a load of 250 g / cm ² in a constant temperature and humidity chamber of measurement 23 ° C. and relative humidity 50%, and a scratch resistance test was performed. The The occurrence of scratches and the degree of scratches were visually observed and used as an index of surface activity.
The evaluation was performed in four stages. In the case of "以上" evaluation or more, there is no particular problem in actual use.
◎: no occurrence of scratches. There is no problem at all.
○: Less than 5 scratches occur. There are a few, but no problem.
Fair: 6 to 10 scratches occur. Practically usable.
X: Innumerable scratches occur. There is a problem in practical use.

  When the resin composition for optical three-dimensional modeling of the present invention is polymerized and cured by active energy rays, as shown in Table 2, it exhibits excellent curing speed, and has Young's modulus, swelling degree, warpage, and surface lubricity. Excellent results were shown for all items (Examples 1 to 12). On the other hand, when the resin composition for optical three-dimensional modeling other than the present invention is polymerized and cured by active energy rays, it is difficult for any of the curing speed, Young's modulus, swelling degree, warpage, and surface lubricity. Yes, it proves difficult to use.

Claims (6)

The aromatic ring possess two or more in the molecule, an average number of moles added of alkylene oxide linking group 1-40 does not contain a cyclic structure (ca) containing nitrogen atoms, alpha, beta-unsaturated double A compound (A) containing two heavy bonding groups,
An α, β-unsaturated double bond group-containing compound (B) having a 2,2,6,6-tetramethylpiperidine skeleton as a cyclic structure (ca) containing a nitrogen atom,
A photopolymerization initiator (C),
And the α, β-unsaturated double bond group of the compound (A) and the compound (B) is an acryloyl group and / or a methacryloyl group. ,
60 to 90.9 wt% of the compound (A), 9 to 20 wt% of the compound (B), and 0.1 to 20 wt parts of the photopolymerization initiator (C) in the total amount of the resin composition, and The compound (A) is an active energy ray polymerizable resin composition for optical three-dimensional modeling, containing 12 to 22% by weight of a compound having an average addition mole number of alkylene oxide bonding group of 4 with respect to the total amount of the resin composition. . Compounds of (A) alpha, beta-unsaturated double bond group, for stereolithography active energy ray-polymerizable resin composition according to claim 1, wherein the methacryloyl group. 3. The active energy ray polymerizable resin composition for optical stereolithography according to claim 1 or 2 , wherein the α, β-unsaturated double bond group of the compound (B) is a methacryloyl group. The compound (C) is a phosphorus-containing compound, The active energy ray polymerizable resin composition for optical three-dimensional model formation in any one of the Claims 1-3 characterized by the above-mentioned. A cured resin obtained by polymerizing and curing the active energy ray polymerizable resin composition according to any one of claims 1 to 4 with an active energy ray. A three-dimensional object made of the resin cured product according to claim 5 .