JP2017115072A - Curable composition for three-dimensional molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a three-dimensional molded article by using an inkjet 3D printer or the like, which allows accurately producing a three-dimensional molded article with excellent workability even in the presence of oxygen.SOLUTION: The curable composition for three-dimensional molding according to the present invention contains a monomer component and an acid generator. The monomer component contains a vinyl ether compound (A) (including at least a vinyl ether compound (a) having a cyclic ether skeleton). The vinyl ether compound (a) having a cyclic ether skeleton is preferably a compound represented by formula (a-1) and/or a compound represented by formula (a-2).SELECTED DRAWING: None

Description

  The present invention relates to a curable composition for three-dimensional modeling, a cured product thereof, and a method for manufacturing a three-dimensional model using the composition.

  In recent years, using an ink jet 3D printer, ejecting ink to form a coating film, curing the coating film to obtain a thin film cured product, and further forming a coating film on the obtained thin film cured product A method of manufacturing a three-dimensional model by laminating thin film cured products by repeating the above is known. According to this method, since it is not necessary to create a metal mold, it is easy to change the shape, and the intended three-dimensional structure can be manufactured at low cost even in a small lot. Thus, for example, in the field of medical devices, this method is used to create products tailored to individual patients.

  An acrylic resin is known as an ink used in the inkjet 3D printer (Patent Document 1). However, radical curable compositions such as acrylic resins are easily inhibited by oxygen. In particular, in the ink jet method, ink is ejected in the form of small droplets, so that inhibition of curing by oxygen is significant, causing odor. The problem was that a large amount of unreacted monomer remained. Moreover, since the curing shrinkage is large and the cured product is likely to warp (that is, the dimensional stability is low), the accuracy of the obtained three-dimensional model is low, depolymerization is likely to proceed due to ultraviolet irradiation, light resistance, The problem was low weather resistance.

Japanese Patent Laying-Open No. 2015-038166

Accordingly, an object of the present invention is a composition for forming a three-dimensional structure using an ink jet 3D printer or the like, and can produce a three-dimensional structure with high accuracy and excellent workability even in the presence of oxygen. It is to provide a composition that can be made.
Another object of the present invention is a composition for forming a three-dimensional object using an ink jet 3D printer or the like, and the three-dimensional object is accurate and excellent even in the presence of oxygen and / or moisture. Another object of the present invention is to provide a composition that can be manufactured with excellent workability.

  As a result of intensive studies by the present inventors to solve the above problems, the cationic curable composition containing at least a vinyl ether compound having a cyclic ether skeleton as a monomer component is irradiated with ultraviolet rays and / or heat-treated even in the presence of oxygen. Can be quickly cured to form a cured product with excellent dimensional stability, and when the curable composition is used for forming a three-dimensional model using an inkjet 3D printer or the like. It has been found that a three-dimensional model can be manufactured with high accuracy, low cost, and excellent workability. The present invention has been completed based on these findings.

  That is, the present invention is a composition containing a monomer component and an acid generator, wherein the monomer component contains a vinyl ether compound (A) (including at least a vinyl ether compound (a) having a cyclic ether skeleton). A curable composition for modeling is provided.

In the present invention, the vinyl ether compound (a) having a cyclic ether skeleton is a compound represented by the following formula (a-1) and / or a compound represented by the formula (a-2): A curable composition is provided.

  In the present invention, the monomer component contains a vinyl ether compound (A), an oxetane compound (B), and an epoxy compound (C), and the compound represented by the formula (a-1) as the vinyl ether compound (A) And / or the compound represented by the formula (a-2) and the oxetane compound (B) include 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, and the formula (a-1) The total content of the compound represented by the compound represented by the formula (a-2) and the compound represented by the formula is 5% by weight or more and less than 30% by weight of the total amount of the monomer components.

  The present invention also provides the above-described curable composition for three-dimensional modeling, wherein the epoxy compound (C) includes an epoxy compound having a cyclohexene oxide group.

  The present invention also provides the above-described curable composition for three-dimensional modeling, wherein the content of the epoxy compound (C) is 5 to 80% by weight of the total amount of the monomer components.

  The present invention also provides the three-dimensional modeling curable composition, wherein the content of 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane is 5 to 80% by weight of the total amount of monomer components. .

（式中、Ｒ^cは１価の炭化水素基を示す） In the present invention, the monomer component contains a vinyl ether compound (A) and an oxetane compound (B), and the compound represented by the formula (a-1) and / or the formula (a) as the vinyl ether compound (A) -2) The said curable composition for three-dimensional model | molding containing the compound represented by following formula (b ') as an oxetane compound (B) is contained.

(Wherein R ^c represents a monovalent hydrocarbon group)

  The present invention also provides the above three-dimensional curable composition, wherein the compound represented by the formula (b ′) is 3-allyloxyoxetane and / or 3- (2-ethylhexyloxy) oxetane.

  The present invention also provides the curable composition for three-dimensional modeling, wherein the content of the compound represented by the formula (b ′) is 5 to 90% by weight of the total amount of the monomer components.

  In the present invention, the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 5% by weight or more and less than 30% by weight based on the total amount of the monomer components. The curable composition for three-dimensional modeling is provided.

  The present invention further provides the above-mentioned curable composition for three-dimensional structure containing an epoxy compound (C) containing a compound having a cyclohexene oxide group.

  The present invention also provides the above-described curable composition for three-dimensional modeling, wherein the content of the epoxy compound (C) is 5 to 80% by weight of the total amount of the monomer components.

  In the present invention, the monomer component contains a vinyl ether compound (A) and an epoxy compound (C), and the compound represented by the formula (a-1) and / or the formula (a-) as the vinyl ether compound (A) 2) The compound represented by 2) is contained in an amount of 5% by weight or more and less than 30% by weight of the total amount of the monomer components, and 1,2: 8,9-diepoxy limonene is used as the epoxy compound (C) in excess of 40% by weight of the total amount of the monomer components The above-mentioned curable composition for three-dimensional modeling is provided.

  The present invention also provides the above-described curable composition for three-dimensional modeling, wherein the monomer component further contains 5 to 50% by weight of the oxetane compound (B) based on the total amount of the monomer components.

  In the present invention, the monomer component contains a vinyl ether compound (A), an oxetane compound (B), and an epoxy compound (C), and the compound represented by the formula (a-1) as the vinyl ether compound (A) And / or a compound represented by the formula (a-2) containing at least 5% by weight and less than 30% by weight of the total amount of the monomer components, and 3-ethyl-3-[(2-ethylhexyloxy) as the oxetane compound (B) Methyl] Oxetane-containing monofunctional oxetane compound containing 10 to 85% by weight of the total amount of monomer components, and epoxy compound (C) containing 1,2: 8,9-diepoxy limonene of 10 to 40% by weight of the total amount of monomer components The above-mentioned curable composition for three-dimensional modeling is provided.

  In the present invention, the monomer component contains a vinyl ether compound (A) and an oxetane compound (B), and the compound represented by the formula (a-1) and / or the formula (a) as the vinyl ether compound (A) -2) and the divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton, and the monolithic oxetane compound as the oxetane compound (B). A sex composition is provided.

（式中、環Ｚは下記式（z-1）〜（z-5）

から選択される環であり、ｎ、ｎ’は同一又は異なって、０以上の整数を示す）
で表される化合物である前記の立体造形用硬化性組成物を提供する。 In the present invention, the divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton is represented by the following formula (a" -1):

(In the formula, ring Z represents the following formulas (z-1) to (z-5)

And n and n ′ are the same or different and represent an integer of 0 or more)
The said three-dimensional shaping | molding curable composition which is a compound represented by these is provided.

  The present invention also relates to a compound represented by formula (a-1) and / or a compound represented by formula (a-2) and a divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton. The curable composition for three-dimensional modeling is provided, wherein the total content is 10 to 80% by weight of the total amount of monomer components.

  In the present invention, the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 5% by weight or more and less than 30% by weight based on the total amount of the monomer components. The curable composition for three-dimensional modeling is provided.

  The present invention also provides the above-mentioned curable composition for three-dimensional modeling, wherein the content of the monofunctional oxetane compound is 10 to 70% by weight of the total amount of the monomer components.

  The present invention also provides the above three-dimensional curable composition containing an epoxy compound (C) containing an epoxy compound having a cyclohexene oxide group.

  The present invention also provides the above-described curable composition for three-dimensional modeling, wherein the content of the epoxy compound (C) is 5 to 80% by weight of the total amount of the monomer components.

  In the present invention, the monomer component contains the vinyl ether compound (A), the monofunctional monomer contains 20 to 70% by weight of the total amount of the monomer components, and the vinyl ether compound (a) having a cyclic ether skeleton and a chain hydrocarbon The vinyl ether compound (a ′) having a skeleton contains 10 to 40% by weight of the total amount of the monomer components, and the content of the vinyl ether compound (a) having the cyclic ether skeleton is 5% by weight or more and 30% by weight of the total amount of the monomer components The above-described curable composition for three-dimensional modeling is provided.

  The present invention also provides the above-mentioned curable composition for three-dimensional modeling, which further contains 1 to 50% by weight of the vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton as the vinyl ether compound (A) based on the total amount of monomer components. To do.

  The present invention also provides the above-mentioned curable composition for three-dimensional modeling, which further contains oxetane compound (B) in an amount of 5 to 80% by weight based on the total amount of monomer components.

  The present invention also provides the above-mentioned curable composition for three-dimensional modeling, which further contains the epoxy compound (C) in an amount of 5 to 80% by weight based on the total amount of the monomer components.

  The present invention also provides the above-mentioned curable composition for three-dimensional structure containing a pigment and / or a dye.

  The present invention also provides the above-described three-dimensional curable composition, which is an ink for an ink jet 3D printer.

  This invention also provides the hardened | cured material of the said curable composition for three-dimensional modeling.

  This invention also provides the manufacturing method of the three-dimensional molded item which manufactures a three-dimensional molded item using the said curable composition for three-dimensional modeling.

  Since the curable composition for three-dimensional modeling of the present invention has the above-described configuration, it is low in viscosity and excellent in dischargeability before being subjected to heat treatment or ultraviolet irradiation, and can be rapidly irradiated even in the presence of oxygen by performing ultraviolet irradiation or heat treatment. Can be cured to form a cured product having excellent dimensional stability. In addition, by adjusting the composition of the monomer component, fast curability can be exhibited even in the presence of moisture, and a cured product having a desired hardness can be formed. Furthermore, since the curable composition for three-dimensional modeling of the present invention is excellent in curability, it is possible to suppress the residual unreacted monomer and to significantly reduce the odor caused by the residual unreacted monomer. Furthermore, it can form a cured product with excellent light resistance and weather resistance, and can be yellowed and deteriorated (for example, brittle and fragile) even in places exposed to strong ultraviolet rays such as outdoors. Can be suppressed. Therefore, the curable composition for three-dimensional model | molding of this invention can be used suitably as an ink, when forming a three-dimensional model | molded object using an inkjet type 3D printer etc.

[Monomer component]
The curable composition for three-dimensional modeling of the present invention contains a vinyl ether compound (A) (including at least a vinyl ether compound (a) having a cyclic ether skeleton) as a monomer component.

  The monomer component in the present invention may contain other vinyl ether compounds in addition to the vinyl ether compound (a) having a cyclic ether skeleton. Moreover, monomers (for example, oxetane compound (B), epoxy compound (C), etc.) other than vinyl ether compound (A) may be contained.

(Vinyl ether compound (A))
The vinyl ether compound is a monomer having a vinyl ether group as a polymerizable group (particularly a cationic polymerizable monomer). The vinyl ether compound has a small cure shrinkage, and can be cured rapidly even in the presence of oxygen to suppress warpage and form a cured product having excellent dimensional stability. Further, a cured product having high hardness and excellent in transparency, heat resistance, light resistance, and weather resistance can be formed.

  In addition to the vinyl ether compound (a) having a cyclic ether skeleton, the vinyl ether compound includes a vinyl ether compound (a ′) having a chain hydrocarbon skeleton and a vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton. The vinyl ether compound includes a monofunctional vinyl ether compound and a polyfunctional vinyl ether compound.

The vinyl ether compound (a) having the cyclic ether skeleton is represented by, for example, the following formula (a).
R— (O—CH═CH ₂ ) _s (a)
(In the formula, R represents a group obtained by removing s hydrogen atoms from a heterocyclic structural formula containing an oxygen atom as a hetero atom, and s represents an integer of 1 or more)

Heterocycles containing oxygen atoms as heteroatoms include 3-membered rings such as oxirane rings; 4-membered rings such as oxetane rings; 5-membered rings such as furan rings, tetrahydrofuran rings, oxazole rings, isoxazole rings, and γ-butyrolactone rings 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring; hexahydrofuro [3,2-b] furan ring, benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring Condensed ring such as chroman ring and isochroman ring; 7-oxabicyclo [2.2.1] heptane ring, 3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one ring, 3 -A bridged ring such as an oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring.

The heterocycle containing an oxygen atom as the heteroatom has various substituents [eg, alkyl groups (eg, C _1-4 alkyl groups such as methyl group, ethyl group, etc.), cycloalkyl groups, aryl groups (eg, phenyl Group, naphthyl group, etc.), halogen atom, oxo group, hydroxyl group, substituted oxy group (for example, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group (alkoxycarbonyl group, Aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group and the like. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.

  s shows an integer greater than or equal to 1, for example, 1-10.

Examples of the vinyl ether compound (a) having a cyclic ether skeleton include compounds represented by the following formula (a-1), compounds represented by the following formula (a-2), tetrahydrofurfuryl vinyl ether, glycidyl vinyl ether, and the like. Can be mentioned. These can be used alone or in combination of two or more. In the present invention, among them, the use of a compound represented by the following formula (a-1) and / or a compound represented by the following formula (a-2) can exhibit fast curability. It is preferable in that it has low shrinkage and is excellent in dimensional stability and can form a cured product having high hardness.

The vinyl ether compound (a ′) having the chain hydrocarbon skeleton is represented by the following formula (a ′), for example.
R ′ — (O—CH═CH ₂ ) _t (a ′)
(Wherein R ′ represents a t-valent aliphatic hydrocarbon group or a t-valent group in which two or more aliphatic hydrocarbon groups are bonded via a linking group, and t represents an integer of 1 or more)

  Examples of the monovalent aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, decyl group, An alkyl group having about 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3) such as dodecyl group; vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group , 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 5-hexenyl group, etc., and 2-20 carbon atoms (preferably 2-10, especially Preferably an alkenyl group of about 2 to 3); an alkynyl group of about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3) such as an ethynyl group and a propynyl group. Can. Examples of the t-valent aliphatic hydrocarbon group include groups in which (t-1) hydrogen atoms have been removed from the structural formula of the monovalent aliphatic hydrocarbon group.

  The aliphatic hydrocarbon group may have various substituents [eg, halogen atom, oxo group, hydroxyl group, substituted oxy group (eg, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group etc.), carboxyl group, substituted Oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc.] You may have. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.

  Examples of the linking group include a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond. (-OCOO-) etc. can be mentioned.

  t represents an integer of 1 or more, and is 1 to 10, for example.

  Examples of the vinyl ether compound (a ′) having a chain hydrocarbon skeleton include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n- Pentyl vinyl ether, isopentyl vinyl ether, tert-pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl Vinyl ether, ethoxymethyl vinyl ether, -Methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether, 4-ethoxybutyl vinyl ether, 2- (2- Methoxyethoxy) ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol ethyl vinyl ether, triethylene glycol monovinyl ether, tetraethylene Glico Monovinyl ether, polyethylene glycol monovinyl ether, propylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, trimethylolpropane monovinyl ether, ethylene oxide-added trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, Ethylene oxide-added pentaerythritol monovinyl ether, diethylene glycol ethyl vinyl ether, triethylene glycol methyl vinyl ether, divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene Tylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol Divinyl ether, Trimethylolpropane divinyl ether, Ethylene oxide added trimethylolpropane divinyl ether, Pentaerythritol divinyl ether, Ethylene oxide added pentaerythritol divinyl ether, Trimethylolpropane trivinyl ether, Ethylene oxide added trimethylolpropane tribi Ether, pentaerythritol trivinyl ether, ethylene oxide adduct of pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, ditrimethylolpropane tetra vinyl ethers include dipentaerythritol hexa vinyl ether. These can be used alone or in combination of two or more.

The vinyl ether compound (a ″) having the cyclic hydrocarbon skeleton is represented by the following formula (a ″), for example.
R ″ − (O—CH═CH ₂ ) _u (a ″)
(Wherein R ″ represents a u-valent alicyclic hydrocarbon group or a u-valent group in which two or more alicyclic hydrocarbon groups are bonded via a single bond or a linking group, and u represents one or more Indicates an integer)

  The alicyclic ring constituting the alicyclic hydrocarbon group includes a monocyclic hydrocarbon ring and a polycyclic hydrocarbon ring (a spiro hydrocarbon ring, a ring assembly hydrocarbon ring, a bridged cyclic hydrocarbon ring, a condensed cyclic ring). Hydrocarbon ring, bridged condensed cyclic hydrocarbon ring). Examples of the u-valent alicyclic hydrocarbon group include groups in which u hydrogen atoms have been removed from the structural formula of the alicyclic ring.

Examples of the monocyclic hydrocarbon ring include C _5-12 cycloalkane rings such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane ring; C _5-12 cycloalkene rings such as cyclohexene ring, and the like. .

Examples of the spiro hydrocarbon ring include C _5-16 spiro hydrocarbon rings such as spiro [4.4] nonane, spiro [4.5] decane, and spirobicyclohexane rings.

Examples of the ring assembly hydrocarbon ring include a ring assembly hydrocarbon ring including two or more C _5-12 cycloalkane rings such as bicyclohexane.

Examples of the bridged cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, norbornene, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) and the like. A bicyclic hydrocarbon ring such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring.

  Examples of the condensed cyclic hydrocarbon ring include 5 to 8 such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene ring. A condensed ring in which a plurality of membered cycloalkane rings are condensed can be exemplified.

  Examples of the bridged condensed cyclic hydrocarbon ring include dimers of dienes (for example, dimers of cycloalkadiene such as cyclopentadiene, cyclohexadiene, cycloheptadiene), hydrogenated products thereof, and the like. it can.

  The alicyclic hydrocarbon group may have a substituent, and examples of the substituent include the same examples as the substituent that R ′ in the above formula (a ′) may have. .

  Examples of the linking group include a divalent hydrocarbon group (the same examples as those of X in the formula (c) described later), a carbonyl group (—CO—), an ether bond (— O-), a thioether bond (-S-), an ester bond (-COO-), an amide bond (-CONH-), a carbonate bond (-OCOO-), and the like.

  u represents an integer of 1 or more, and is 1 to 10, for example.

  Examples of the vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton include compounds represented by the following formula (a ″ -1) (specifically, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, hydrogenated) Divinyl ether compounds having a cyclic hydrocarbon skeleton such as bisphenol F type divinyl ether, hydrogenated biphenyl divinyl ether, hydrogenated bisphenol A type divinyl ether, and tricyclodecane dimethanol divinyl ether (a "- 1); 4-hydroxycyclohexyl vinyl ether, cyclohexyldimethanol monovinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, norbornenyl vinyl Ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether monovinyl ether compounds having a cyclic hydrocarbon skeleton such as (a "-2) is. These can be used alone or in combination of two or more.

（式中、環Ｚは下記式（z-1）〜（z-5）

から選択される環であり、ｎ、ｎ’は同一又は異なって、０以上の整数を示す）

(In the formula, ring Z represents the following formulas (z-1) to (z-5)

And n and n ′ are the same or different and represent an integer of 0 or more)

  N and n 'in the formula (a "-1) are the same or different and represent an integer of 0 or more, preferably an integer of 0 to 10, particularly preferably an integer of 0 to 3.

  Examples of the vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton include commercial products such as trade names “CHDVE” (manufactured by Nippon Carbide Industries Co., Ltd.) and “4CH-DVE” (manufactured by Daicel Corporation). Can be used.

  A vinyl ether compound can be manufactured using the manufacturing method of a well-known vinyl ether compound. For example, the compound represented by the above formula (a-1) includes 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane in the presence of a transition metal compound and a vinyl ester compound ( For example, it can be produced by reacting with vinyl propionate). The compound represented by the formula (a-2) is the same method as described above except that isosorbide is used instead of 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane. Can be manufactured.

(Oxetane compound (B))
The oxetane compound is a monomer having an oxetanyl group as a polymerizable group (particularly a cationic polymerizable monomer), and includes a monofunctional oxetane compound and a polyfunctional oxetane compound. One oxetane compound can be used alone, or two or more oxetane compounds can be used in combination.

  Oxetane compounds have fast curability and can form a cured product quickly even in the presence of oxygen.

（式中、Ｒ^aは１価の有機基を示し、Ｒ^bは水素原子又はエチル基を示す。ｍは０以上の整数を示す） As an oxetane compound, the compound represented by a following formula (b) can be mentioned, for example.

(In the formula, R ^a represents a monovalent organic group, R ^b represents a hydrogen atom or an ethyl group, and m represents an integer of 0 or more.)

The monovalent organic group in Ra includes ^a monovalent hydrocarbon group, a monovalent heterocyclic group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group). Etc.), substituted carbamoyl groups (N-alkylcarbamoyl groups, N-arylcarbamoyl groups, etc.), acyl groups (aliphatic acyl groups such as acetyl groups; aromatic acyl groups such as benzoyl groups), and two or more of these A monovalent group bonded through a single bond or a linking group is included.

  The monovalent hydrocarbon group includes a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group.

  Examples of the monovalent aliphatic hydrocarbon group include the same examples as the monovalent group for R ′ in the above formula (a ′). Examples of the monovalent alicyclic hydrocarbon group include the same examples as the monovalent group for R ″ in the above formula (a ″).

  Examples of the monovalent aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as a phenyl group and a naphthyl group.

  The monovalent hydrocarbon group may have a substituent, and examples of the substituent include the same examples as the substituent which R ′ in the above formula (a ′) may have. .

Examples of the heterocyclic ring constituting the heterocyclic group include a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a 4-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, γ- 5-membered ring such as butyrolactone ring; 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring; benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, isochroman ring 3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8 ] nonane-2- A bridged ring such as an on-ring), a heterocyclic ring containing a sulfur atom as a hetero atom (for example, a 5-membered ring such as a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring; 4-oxo; 6-membered ring such as 4H-thiopyran ring; condensed ring such as benzothiophene ring), heterocycle containing nitrogen atom as a hetero atom (for example, pyrrole ring, pyrrolidine ring, pyrazole ring, imidazole ring, triazole ring, etc.) Ring: 6-membered ring such as pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring; condensed ring such as indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring, purine ring, etc. And the like. Examples of the monovalent heterocyclic group include groups in which one hydrogen atom has been removed from the above structural formula of the heterocyclic ring.

In addition to the substituents that the hydrocarbon group may have, the heterocyclic group may be an alkyl group (for example, a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group It may have a substituent such as a phenyl group or a naphthyl group.

  Examples of the linking group include a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond. (-OCOO-), a silyl bond (-Si-), and a group in which a plurality of these are linked.

  Said m shows an integer greater than or equal to 1, for example 1-20, Preferably it is 1.

A preferred example of the compound represented by the formula (b) is a compound represented by the following formula (b ′). In the following formula, R ^c represents a monovalent hydrocarbon group, and examples similar to the examples for R ^a in formula (b) can be given. The compound represented by the following formula (b ′) can exhibit fast curability even in the presence of oxygen and / or moisture, and when the curable composition for three-dimensional modeling of the present invention contains this, It is preferable at the point from which the effect which reduces the hardening inhibition in presence is acquired.

  Specific examples of the compound represented by the formula (b ′) include 3-methoxyoxetane, 3-ethoxyoxetane, 3-propoxyoxetane, 3-isopropoxyoxetane, 3- (n-butoxy) oxetane, 3-isobutoxy. Oxetane, 3- (s-butoxy) oxetane, 3- (t-butoxy) oxetane, 3-pentyloxyoxetane, 3-hexyloxyoxetane, 3- (2-ethylhexyloxy) oxetane, 3-heptyloxyoxetane, 3- Octyloxyoxetane, 3- (1-propenyloxy) oxetane, 3-cyclohexyloxyoxetane, 3- (4-methylcyclohexyloxy) oxetane, 3-[(2-perfluorobutyl) ethoxy] oxetane, 3-phenoxyoxetane, 3- (4-Methylphenoxy) ) Oxetane, 3- (3-chloro-1-propoxy) oxetane, 3- (3-bromo-1-propoxy) oxetane, 3- (4-fluorophenoxy) oxetane, 3-allyloxyoxetane and the like. .

Other examples of the compound represented by the formula (b) include compounds represented by the following formulas (b-1) to (b-13).

  Examples of oxetane compounds include “Aron oxetane OXT-101”, “Aron oxetane OXT-121”, “Aron oxetane OXT-212”, “Aron oxetane OXT-211”, “Aron oxetane OXT-213”, “Aron oxetane”. Commercial products such as “OXT-221” and “Aron oxetane OXT-610” (manufactured by Toagosei Co., Ltd.) can be used.

  In terms of improving the light resistance and weather resistance of the resulting cured product, it is preferable to use an oxetane compound having no aromatic ring.

(Epoxy compound (C))
The epoxy compound is a monomer having an epoxy group as a polymerizable group (particularly a cationic polymerizable monomer), and includes a monofunctional epoxy compound and a polyfunctional epoxy compound. An epoxy compound can be used individually by 1 type or in combination of 2 or more types.

  Epoxy compounds have fast curability and can form a cured product quickly even in the presence of oxygen.

  Examples of the epoxy compound (C) include an aromatic glycidyl ether-based epoxy compound; an alicyclic glycidyl ether-based epoxy compound (eg, hydrogenated bisphenol A diglycidyl ether); an aliphatic glycidyl ether-based epoxy compound; An epoxy compound; a glycidylamine epoxy compound; an epoxy compound having a cyclohexene oxide group (hereinafter sometimes referred to as “alicyclic epoxy compound”); an epoxy-modified siloxane compound;

  The epoxy compound (C) in the present invention preferably contains at least an alicyclic epoxy compound, and in particular, contains at least 30% by weight of the total epoxy compound contained in the monomer component. More preferably, it is 50% by weight or more, and particularly preferably 80% by weight or more. The alicyclic epoxy compound can exhibit fast curability even in the presence of oxygen and / or moisture, and when the curable composition for three-dimensional modeling of the present invention contains this, it inhibits curing in the presence of moisture. It is preferable at the point from which the effect to reduce is acquired. Moreover, since it has low shrinkage, a cured product excellent in dimensional stability can be formed. Furthermore, it can form a cured product that has high hardness, is less likely to be colored or deteriorated by light, and is excellent in light resistance and weather resistance.

As said alicyclic epoxy compound, the compound represented by a following formula (c) can be mentioned, for example.

In the above formula (c), R ^{1 to} R ¹⁸ are the same or different and are a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may contain a halogen atom, or an alkoxy which may have a substituent. Indicates a group.

As a halogen atom in R < ¹ > -R < ¹⁸ >, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. can be mentioned, for example.

Examples of the hydrocarbon group in R ^{1 to} R ¹⁸ include the same examples as R ^a in the formula (b).

Examples of the hydrocarbon group that may contain an oxygen atom or a halogen atom in R ^{1 to} R ¹⁸ include a group in which at least one hydrogen atom in the above-described hydrocarbon group is substituted with a group having an oxygen atom or a halogen atom, etc. Can be mentioned. Examples of the group having an oxygen atom include hydroxyl group; hydroperoxy group; C _1-10 alkoxy group such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy group; C _2-10 such as allyloxy group. An alkenyloxy group; a C _6-14 aryloxy group optionally having a substituent selected from a C _1-10 alkyl group, a C _2-10 alkenyl group, a halogen atom, and a C _1-10 alkoxy group (for example, C _7-18 aralkyloxy groups such as benzyloxy and phenethyloxy groups; C _1-10 acyloxy groups such as acetyloxy, propionyloxy, (meth) acryloyloxy and benzoyloxy groups; methoxy carbonyl, ethoxycarbonyl, propoxycarbonyl, C _1-10 aralkyl such as a butoxycarbonyl group Alkoxycarbonyl group; C _1-10 alkyl group, C _2-10 alkenyl group, a halogen atom, and C _1-10 may have a substituent group selected from an alkoxy group C _6-14 aryloxycarbonyl group ( For example, phenoxycarbonyl, tolyloxycarbonyl, naphthyloxycarbonyl group, etc.); C _7-18 aralkyloxycarbonyl group such as benzyloxycarbonyl group; epoxy group-containing group such as glycidyloxy group; oxetanyl group such as ethyloxetanyloxy group Groups: C _1-10 acyl groups such as acetyl, propionyl and benzoyl groups; isocyanate groups; sulfo groups; carbamoyl groups; oxo groups; two or more of these are bonded via a single bond or a C _1-10 alkylene group Groups and the like.

Examples of the alkoxy group in R ^{1 to} R ¹⁸ include C _1-10 alkoxy groups such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, and isobutyloxy groups.

Examples of the substituent that the alkoxy group may have include, for example, a halogen atom, a hydroxyl group, a C _1-10 alkoxy group, a C _2-10 alkenyloxy group, a C _6-14 aryloxy group, a C _1-10 Acyloxy group, mercapto group, C _1-10 alkylthio group, C _2-10 alkenylthio group, C _6-14 arylthio group, C _7-18 aralkylthio group, carboxyl group, C _1-10 alkoxycarbonyl group, C _{6- 14} aryloxycarbonyl group, C _7-18 aralkyloxycarbonyl group, amino group, mono or di C _1-10 alkylamino group, C _1-10 acylamino group, epoxy group-containing group, oxetanyl group-containing group, C _1-10 And an acyl group, an oxo group, and a group in which two or more of these are bonded through a single bond or a C _1-10 alkylene group.

  In said formula (c), X shows a single bond or a coupling group. Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group (—CO—), an ether bond (—O—), Examples thereof include an ester bond (—COO—), a carbonate group (—O—CO—O—), an amide group (—CONH—), and a group in which a plurality of these are linked.

  Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms. . Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, and a 1,2-cyclohexylene group. And cycloalkylene groups (including cycloalkylidene groups) such as 1,3-cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

Representative examples of the compound represented by the above formula (c) include (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2- Epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, 1,2-bis (3,4- And epoxycyclohexane-1-yl) ethane and compounds represented by the following formulas (c-1) to (c-8). In the following formulas (c-5) and (c-7), n ¹ and n ² each represent an integer of 1 to 30. L in the following formula (c-5) is a linear or branched alkylene group having 1 to 8 carbon atoms.

  In addition to the compound represented by the above formula (c), the alicyclic epoxy compound includes an intramolecular compound such as 1,2: 8,9-diepoxy limonene represented by the following formula (c-9). Also included are compounds having an alicyclic ring and two or more epoxy groups, and one of the two or more epoxy groups being a cyclohexene oxide group.

The alicyclic epoxy compound further includes an alicyclic epoxy compound having three or more cyclohexene oxide groups represented by the following formulas (c-10) and (c-11), and the following formula (c-12): The cycloaliphatic epoxy compound which has one cyclohexene oxide group represented by-(c-15) and does not have an epoxy group is also included. In the following formulas (c-10) and (c-11), n ^{3 to} n ⁸ are the same or different and represent an integer of 1 to 30, and R ¹⁹ and R ^{20 in the following} formula (c-14). Are the same or different and represent a C1-C31 linear or branched alkyl group.

  The epoxy compound (C) in the present invention preferably contains at least a compound represented by the above formula (c) and having two cyclohexene oxide groups in one molecule. In particular, the above formula (c-1) 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate represented by the formula, exhibits rapid curability even in the presence of oxygen and / or moisture, and is excellent in dimensional stability, And it is preferable at the point which can form the hardened | cured material which has high hardness.

  Moreover, when high hardness and heat resistance are desired for the cured product, an epoxy-modified siloxane compound is preferably contained as the epoxy compound (C).

  Examples of the epoxy-modified siloxane compound include epoxy-modified polyorganosilsesquioxane and epoxy-modified silicone. These can be used alone or in combination of two or more.

  Examples of the epoxy-modified polyorganosilsesquioxane include compounds having structural units represented by the following formulas (c-16) and (c-17) (random structure, cage structure, and ladder structure compounds). Include).

The epoxy-modified silicone includes a compound having a cyclic structure and a chain structure. The epoxy-modified silicone having a cyclic structure is represented, for example, by the following formula (c-18). Moreover, the epoxy-modified silicone having a chain structure is represented by, for example, the following formula (c-19).

In the above formula, R ^{21 to} R ³⁷ are the same or different and each represents a hydrogen atom or a hydrocarbon group optionally having an oxirane ring. Examples of the hydrocarbon group include the same examples as R ^a in the formula (b). Moreover, m ¹ in the above formula (c-18) and m ² in the above formula (c-19) are the same or different and are an integer of 1 or more. When m ¹ and m ² are integers of 2 or more, m ¹ R ²⁶ and R ²⁷ in (c-18) may be the same or different. M ² R ³² and R ^{33 in} (c-19) may be the same or different. However, it is included in at least one of R ^{21 to} R ²³ contained in polyorganosilsesquioxane, at least one of R ^{24 to} R ²⁹ contained in silicone having a cyclic structure, and silicone having a chain structure. At least one of R ^{30 to} R ³⁷ is a hydrocarbon group having an oxirane ring (for example, a hydrocarbon group having a cyclohexene oxide group or a hydrocarbon group having a glycidyl group).

  The content of the epoxy-modified siloxane compound is, for example, 1 to 100% by weight of the total epoxy compound contained in the monomer component, and the upper limit is preferably 80% by weight, particularly preferably 70% by weight, and most preferably 60% by weight. It is. The lower limit is preferably 5% by weight, particularly preferably 10% by weight, most preferably 20% by weight.

  The three-dimensional shaping curable composition of the present invention contains at least a vinyl ether compound (A) (including at least a vinyl ether compound (a) having a cyclic ether skeleton) as a monomer component. Therefore, it has a low viscosity and excellent dischargeability. In addition, a cured product having fast curability, high hardness, and excellent dimensional stability can be formed.

  Although the curable composition for three-dimensional modeling of the present invention may contain only the vinyl ether compound (a) having a cyclic ether skeleton as a monomer component, in that case, it quickly cures in the absence of moisture. Although a cured product having excellent dimensional stability and extremely high hardness can be formed, the progress of curing is inhibited in the presence of moisture, and the cured product tends to be difficult to obtain. For this reason, it is preferable to use a vinyl ether compound (a) having a cyclic ether skeleton in combination with another monomer from the viewpoint of suppressing curing inhibition due to moisture while maintaining fast curability. Moreover, it is preferable at the point which can adjust the hardness of the hardened | cured material obtained by mix | blending another monomer in the range of 6B-4H, for example. Furthermore, by blending other monomers, the degree of crosslinking of the resulting cured product is improved, depolymerization caused by ultraviolet irradiation can be suppressed, and light resistance and weather resistance are also improved.

  As the other monomer, it is possible to use at least one cationically polymerizable monomer selected from a vinyl ether compound other than the vinyl ether compound (a) having a cyclic ether skeleton, an oxetane compound (B), and an epoxy compound (C). preferable.

Preferred combinations of the monomer components in the three-dimensional modeling curable composition of the present invention include the following modes of the monomer component (Type 1) to the monomer component (Type 6).
[Monomer component (Type 1)]
The vinyl ether compound (A), the oxetane compound (B), and the epoxy compound (C) are contained, and the compound represented by the formula (a-1) and / or the formula (a-2) is represented as the vinyl ether compound (A). The compound represented by the above formula (a-1) and 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane as the oxetane compound (B) and the formula (a-2) Is 5% by weight or more and less than 30% by weight of the total amount of the monomer components.
[Monomer component (Type 2)]
A vinyl ether compound (A) and an oxetane compound (B) are contained, and the vinyl ether compound (A) contains a compound represented by the formula (a-1) and / or a compound represented by the formula (a-2). And an oxetane compound (B) containing a compound represented by the formula (b ′).
[Monomer component (Type 3)]
A monomer component containing a vinyl ether compound (A) and an epoxy compound (C), a compound represented by the formula (a-1) and / or a compound represented by the formula (a-2) as the vinyl ether compound (A) 5% by weight or more and less than 30% by weight of the total amount, and 1,2: 8,9-diepoxy limonene as the epoxy compound (C) is contained more than 40% by weight of the total amount of the monomer components.
[Monomer component (Type 4)]
The vinyl ether compound (A), the oxetane compound (B), and the epoxy compound (C) are contained, and the compound represented by the formula (a-1) and / or the formula (a-2) is represented as the vinyl ether compound (A). A monofunctional oxetane compound containing 5% by weight or more and less than 30% by weight of the total amount of the monomer components and containing 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane as the oxetane compound (B) 10 to 85% by weight of the total amount of the components, and 10: 40% by weight of 1,2: 8,9-diepoxy limonene as the epoxy compound (C) based on the total amount of the monomer components.
[Monomer component (Type 5)]
A vinyl ether compound (A) and an oxetane compound (B), the vinyl ether compound (A) represented by the formula (a-1) and / or the compound represented by the formula (a-2), and a ring The divinyl ether compound (a "-1) which has a formula hydrocarbon skeleton is contained, and a monofunctional oxetane compound is contained as an oxetane compound (B).
[Monomer component (Type 6)]
A vinyl ether compound (A), a monofunctional monomer containing 20 to 70% by weight of the total amount of monomer components, a vinyl ether compound (a) having a cyclic ether skeleton, and a vinyl ether compound (a ′) having a chain hydrocarbon skeleton. The content of the vinyl ether compound (a) containing 10 to 40% by weight of the total amount of the monomer components and having the cyclic ether skeleton is 5% by weight or more and less than 30% by weight of the total amount of the monomer components.

(Monomer component (Type 1))
The monomer component (Type 1) contains a vinyl ether compound (A) containing at least a compound represented by the above formula (a-1) and / or a compound represented by the formula (a-2). In addition to the compound represented by the formula (a-1) and the compound represented by the formula (a-2), other vinyl ether compounds may be contained, but the above-mentioned total amount of vinyl ether compounds contained in the monomer component The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is, for example, 50% by weight or more, preferably 70% by weight or more, particularly preferably 85% by weight or more. is there.

  The total content of the compound represented by the above formula (a-1) and the compound represented by the formula (a-2) is the total amount of monomer components (the monomer contained in the three-dimensional curable composition of the present invention). 5% by weight or more and less than 30% by weight, preferably 10% by weight or more and less than 30% by weight, particularly preferably 10 to 25% by weight. When the curable composition for three-dimensional modeling of the present invention contains the compound represented by the above formula (a-1) and / or the compound represented by the formula (a-2) in the above range, oxygen and / or moisture It can be cured quickly even in the presence of a cured product with excellent dimensional stability. When the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) exceeds the above range, a cured product having higher hardness is obtained in the absence of moisture. However, the progress of curing tends to be inhibited in the presence of moisture. On the other hand, when the total content is less than the above range, the curing rate is lowered, and a cured product having excellent dimensional stability tends to be hardly obtained.

  The monomer component (Type 1) contains at least 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane as the oxetane compound (B). In addition, other oxetane compounds may be contained, but the proportion of 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane in the total oxetane compound contained in the monomer component is, for example, 50 wt. % Or more, preferably 70% by weight or more, particularly preferably 85% by weight or more.

  The content of 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane is preferably, for example, 5 to 80% by weight, particularly preferably 10%, based on the total amount of the monomer components, in that it can exhibit fast curability. -70 wt%, most preferably 20-60 wt%.

  The monomer component (Type 1) contains an epoxy compound (C) including an epoxy compound having a cyclohexene oxide group, and forms a cured product having fast curability, high hardness and excellent dimensional stability. The content of the epoxy compound (C) is preferably 5 to 80% by weight, particularly preferably 10 to 70% by weight, and most preferably 20 to 60% by weight of the total amount of the monomer components.

  When the curable composition for three-dimensional modeling of the present invention contains the monomer component (Type 1) having the above-described configuration, the cured product is rapidly cured even in the presence of oxygen and / or moisture, and has excellent dimensional stability. Can be formed.

(Monomer component (Type 2))
The monomer component (Type 2) contains a vinyl ether compound (A) containing at least a compound represented by the above formula (a-1) and / or a compound represented by the formula (a-2). The monomer component (Type 2) may contain other vinyl ether compounds in addition to the compound represented by the formula (a-1) and the compound represented by the formula (a-2). The total content of the compound represented by the above formula (a-1) and the compound represented by the formula (a-2) in the total amount of the vinyl ether compound contained in is, for example, 30% by weight or more, preferably 50% by weight or more, Especially preferably, it is 80 weight% or more.

  The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is, for example, about 5 wt% or more and less than 30 wt% of the total amount of the monomer components, It is 5 to 25% by weight, particularly preferably 10 to 25% by weight. When the curable composition for three-dimensional modeling of the present invention contains the compound represented by the above formula (a-1) and / or the compound represented by the formula (a-2) in the above range, oxygen and / or moisture It can be cured quickly even in the presence of a cured product with excellent dimensional stability. When the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) exceeds the above range, a cured product having higher hardness is obtained in the absence of moisture. However, the progress of curing tends to be inhibited in the presence of moisture. On the other hand, when the total content is less than the above range, the curing rate is lowered, and a cured product having excellent dimensional stability tends to be hardly obtained.

  The content of the total vinyl ether compound (A) including the compound represented by the formula (a-1) and / or the compound represented by the formula (a-2) is, for example, 5 to 80% by weight of the total amount of the monomer components. Degree, preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight.

  The monomer component (Type 2) contains at least the compound represented by the formula (b ′) as the oxetane compound (B). As the compound represented by the formula (b ′), 3-allyloxyoxetane and / or 3- (2-ethylhexyloxy) oxetane is particularly preferable.

  In addition to the compound represented by the above formula (b ′), other oxetane compounds may be contained, but the compound represented by the above formula (b ′) in all the oxetane compounds contained in the monomer component (particularly , 3-allyloxyoxetane and / or 3- (2-ethylhexyloxy) oxetane) is, for example, 10% by weight or more in that it can exhibit rapid curability even in the presence of oxygen and / or moisture. More preferably, it is 40% by weight or more, and particularly preferably 70% by weight or more.

  The content of the total oxetane compound (B) including the compound represented by the formula (b ′) is preferably about 10 to 70% by weight of the total amount of the monomer components in that it can exhibit fast curability. The amount is preferably 20 to 70% by weight, particularly preferably 30 to 60% by weight.

  Further, the content of the compound represented by the formula (b ′) (the total amount in the case where two or more compounds are contained) is a monomer that can exhibit fast curability even in the presence of oxygen and / or moisture. For example, about 5 to 70% by weight of the total amount of the components is preferable. The lower limit is preferably 20% by weight, more preferably 30% by weight, particularly preferably 40% by weight, and most preferably 45% by weight. The upper limit is preferably 60% by weight.

  The monomer component (Type 2) may contain an epoxy compound (C) including an epoxy compound having a cyclohexene oxide group, and the content of the epoxy compound (C) (particularly, the alicyclic epoxy compound) is oxygen And / or in the presence of moisture, it can exhibit fast curability, and can form a cured product with high hardness and excellent dimensional stability, for example, about 5 to 80% by weight of the total amount of monomer components. More preferably, it is 10 to 70% by weight, and particularly preferably 20 to 60% by weight.

  In addition, the total content of the vinyl ether compound (A) and the epoxy compound (C) in the total amount of the monomer components is, for example, from 5 to 5 in that it can exhibit fast curability and form a cured product having high hardness. About 90% by weight is preferable, more preferably 10 to 80% by weight, particularly preferably 20 to 80% by weight, and most preferably 40 to 75% by weight.

  When the curable composition for three-dimensional modeling of the present invention contains the monomer component (Type 2) having the above-described configuration, the cured product is rapidly cured even in the presence of oxygen and / or moisture, and has excellent dimensional stability. Can be formed.

(Monomer component (Type 3))
The monomer component (Type 3) contains a vinyl ether compound (A) containing at least a compound represented by the above formula (a-1) and / or a compound represented by the formula (a-2).

  The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 5% by weight or more and less than 30% by weight, preferably 10% by weight based on the total amount of the monomer components. % Or more and less than 30% by weight, particularly preferably 10 to 25% by weight. When the curable composition for three-dimensional modeling of the present invention contains the compound represented by the above formula (a-1) and / or the compound represented by the formula (a-2) in the above range, oxygen and / or moisture It can be cured quickly even in the presence of a cured product with excellent dimensional stability. When the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) exceeds the above range, a cured product having higher hardness is obtained in the absence of moisture. However, the progress of curing tends to be inhibited in the presence of moisture. On the other hand, when the total content is less than the above range, the curing rate is lowered, and a cured product having excellent dimensional stability tends to be hardly obtained.

  The monomer component (Type 3) contains one or more other vinyl ether compounds in addition to the compound represented by the formula (a-1) and the compound represented by the formula (a-2). The content of the other vinyl ether compound is, for example, about 1 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, based on the total amount of the monomer components. Among them, a vinyl ether compound (a ′) having a chain hydrocarbon skeleton [for example, a compound represented by the formula (a ′), particularly a divinyl ether compound] and / or a vinyl ether compound having a cyclic hydrocarbon skeleton (a ″) ) [For example, a compound represented by the formula (a ″), particularly a divinyl ether compound] is preferable in that it exhibits fast curability and can form a cured product having high hardness. The sum of the content of the vinyl ether compound (a ′) having a chain hydrocarbon skeleton and the vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton is, for example, 10 to 70% by weight of the total vinyl ether compound contained in the monomer component. , Preferably 20 to 60% by weight, particularly preferably 30 to 50% by weight.

  The monomer component (Type 3) may or may not contain the oxetane compound (B). When the oxetane compound (B) is contained, the oxetane compound (B) may be either a monofunctional oxetane compound or a polyfunctional oxetane compound. The content of the oxetane compound (B) is about 50% by weight or less, preferably 5 to 50% by weight, particularly preferably 5 to 20% by weight, based on the total amount of the monomer components.

  The monomer component (Type 3) contains 1,2: 8,9-diepoxy limonene in excess of 40% by weight of the total amount of the monomer component (preferably more than 40% by weight and 80% by weight or less, particularly preferably 40% by weight). % To 60% by weight or less, most preferably 45 to 60% by weight). Therefore, it can be quickly cured even in the presence of oxygen and / or moisture to form a cured product having excellent dimensional stability.

  The monomer component (Type 3) may contain other epoxy compounds in addition to 1,2: 8,9-diepoxy limonene, and the content of the other epoxy compounds is, for example, 1 to 50 of the total amount of the monomer components. It is about 5% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight.

  When the curable composition for three-dimensional modeling of the present invention contains the monomer component (Type 3) having the above-described configuration, the cured product is rapidly cured even in the presence of oxygen and / or moisture, and has excellent dimensional stability. Can be formed.

(Monomer component (Type 4))
The monomer component (Type 4) contains a vinyl ether compound (A) containing at least a compound represented by the above formula (a-1) and / or a compound represented by the formula (a-2).

  The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 5% by weight or more and less than 30% by weight, preferably 10% by weight based on the total amount of the monomer components. % Or more and less than 30% by weight, particularly preferably 10 to 25% by weight. When the curable composition for three-dimensional modeling of the present invention contains the compound represented by the above formula (a-1) and / or the compound represented by the formula (a-2) in the above range, oxygen and / or moisture It can be cured quickly even in the presence of a cured product with excellent dimensional stability. When the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) exceeds the above range, a cured product having higher hardness is obtained in the absence of moisture. However, the progress of curing tends to be inhibited in the presence of moisture. On the other hand, when the total content is less than the above range, the curing rate is lowered, and a cured product having excellent dimensional stability tends to be hardly obtained.

  The monomer component (Type 4) contains one or more other vinyl ether compounds in addition to the compound represented by the formula (a-1) and the compound represented by the formula (a-2). The content of the other vinyl ether compound is, for example, about 1 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, based on the total amount of the monomer components. Among them, a vinyl ether compound (a ′) having a chain hydrocarbon skeleton [for example, a compound represented by the formula (a ′), particularly a divinyl ether compound] and / or a vinyl ether compound having a cyclic hydrocarbon skeleton (a ″) ) [For example, a compound represented by the formula (a ″), particularly a divinyl ether compound] is preferable in that a cured product having high hardness can be obtained by exhibiting fast curability, The sum of the content of the vinyl ether compound (a ′) having a chain hydrocarbon skeleton and the vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton is, for example, 10 to 70% by weight of the total vinyl ether compound contained in the monomer component, Preferably it is 20-60 weight%, Most preferably, it is 30-50 weight%.

  The monomer component (Type 4) is a monofunctional oxetane compound containing 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane as the oxetane compound (B) in an amount of 10 to 85% by weight (preferably 10%). -60 wt%, particularly preferably 20-40 wt%).

  The content of 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane is, for example, about 5 to 50% by weight, preferably 10 to 40% by weight, particularly preferably 20 to 40% by weight of the total amount of the monomer components. %. Therefore, quick curability can be exhibited.

  The monomer component (Type 4) contains 1,2: 8,9-diepoxy limonene in an amount of 10 to 40% by weight (preferably 20 to 30% by weight) based on the total amount of the monomer components. Therefore, it can be quickly cured even in the presence of oxygen and / or moisture to form a cured product having excellent dimensional stability.

  The monomer component (Type 4) may contain other epoxy compounds in addition to 1,2: 8,9-diepoxy limonene, and the content of the other epoxy compounds is, for example, 1 to 50 of the total amount of the monomer components. It is about 5% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight.

  Furthermore, the sum of the contents of 1,2: 8,9-diepoxylimonene and 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane may be 50% by weight or more of the total amount of monomer components. Preferably, it is 50-80 weight%, Most preferably, it is 50-60 weight%.

  When the curable composition for three-dimensional modeling of the present invention contains the monomer component (Type 4) having the above-described configuration, the cured product is rapidly cured even in the presence of oxygen and / or moisture, and has excellent dimensional stability. Can be formed.

(Monomer component (Type 5))
The monomer component (Type 5) includes a compound represented by the above formula (a-1) and / or a compound represented by the formula (a-2) and a vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton. contains.

  The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is, for example, about 5% by weight or more and less than 30% by weight, preferably 10% of the total amount of the monomer components. % By weight or more and less than 30% by weight, particularly preferably 10 to 25% by weight. When the curable composition for three-dimensional modeling of the present invention contains the compound represented by the above formula (a-1) and / or the compound represented by the formula (a-2) in the above range, oxygen and / or moisture It can be cured quickly even in the presence of a cured product with excellent dimensional stability. When the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) exceeds the above range, a cured product having higher hardness is obtained in the absence of moisture. However, the progress of curing tends to be inhibited in the presence of moisture. On the other hand, when the total content is less than the above range, the curing rate is lowered, and a cured product having excellent dimensional stability tends to be hardly obtained.

  As the divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton, among them, the use of the compound represented by the formula (a" -1) exhibits fast curability, It is preferable at the point which can form the hardened | cured material which has high hardness.

  The total content of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton has a fast curing property. For example, it is preferably 10 to 80% by weight, more preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight, based on the total amount of the monomer components, in that it can form a cured product having high hardness. Most preferably, it is 30 to 60% by weight.

  The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2), and the content of the divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton The ratio (weight ratio, former: latter) is, for example, about 90:10 to 10:90, preferably 80:20 to 20:80, more preferably 75:25 to 30:70, and particularly excellent in dimensional stability. 75:25 to 40:60 is preferable in that a cured product can be obtained.

  The monomer component (Type 5) is a compound represented by the above formula (a-1), a compound represented by the above formula (a-2), and a divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton. In addition to the above, other vinyl ether compounds may be contained, but the above formula (a- The total content of the compound represented by 1), the compound represented by formula (a-2) and the divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton is, for example, 50% by weight or more, preferably It is 70% by weight or more, particularly preferably 85% by weight or more.

  The monomer component (Type 5) contains at least a monofunctional oxetane compound as the oxetane compound (B). The content of the monofunctional oxetane compound is, for example, about 10 to 70% by weight, preferably 20 to 60% by weight, particularly preferably 20 to 50% by weight, based on the total amount of the monomer components.

  The monomer component (Type 5) includes a monofunctional oxetane compound and a polyfunctional oxetane compound [eg, 1,4-bis ([(3-ethyl-3-oxetanyl) methoxy] methyl) benzene, bis [(3-ethyloxetane- 3-yl) methyl] ether and the like] may be contained, but the proportion of the monofunctional oxetane compound in the total oxetane compound contained in the monomer component is, for example, 50% by weight or more, preferably 70% by weight or more, Preferably it is 85 weight% or more.

  The monomer component (Type 5) contains an epoxy compound (C) containing an epoxy compound having a cyclohexene oxide group, so that it cures quickly even in the presence of oxygen and / or moisture and has excellent dimensional stability. The content of the epoxy compound (C) is, for example, from 5 to 80% by weight, preferably from 10 to 70% by weight, particularly preferably from 20 to 60% by weight, based on the total amount of the monomer components. Preferably it is 20 to 50 weight%, More preferably, it is 20 to 40 weight%.

  Furthermore, the total content of the monofunctional oxetane compound and the epoxy compound (C) is preferably, for example, about 15 to 80% by weight, more preferably 30 to 70%, based on the total amount of the monomer components, from the viewpoint that rapid curability can be exhibited. % By weight, particularly preferably 40 to 70% by weight, most preferably 45 to 70% by weight.

  When the curable composition for three-dimensional modeling of the present invention contains the monomer component (Type 5) having the above-described configuration, the cured product is rapidly cured even in the presence of oxygen and / or moisture, and has excellent dimensional stability. Can be formed.

(Monomer component (Type 6))
The monomer component (Type 6) contains a monofunctional monomer (particularly a monofunctional cation polymerizable monomer) in an amount of 20 to 70% by weight, preferably 20 to 60% by weight, particularly preferably 20 to 50% by weight, based on the total amount of the monomer components. .

  The sum of the contents of the vinyl ether compound (a) having a cyclic ether skeleton and the vinyl ether compound (a ′) having a chain hydrocarbon skeleton contained in the vinyl ether compound (A) is 10 to 40% by weight of the total amount of the monomer components. , Preferably 15 to 40% by weight, particularly preferably 20 to 40% by weight. When the curable composition for three-dimensional modeling of the present invention contains the vinyl ether compound (a) having a cyclic ether skeleton and the vinyl ether compound (a ′) having a chain hydrocarbon skeleton within the above range, it exhibits fast curability. A cured product having high hardness can be formed.

  Further, the content of the vinyl ether compound (a) having a cyclic ether skeleton (the total amount when two or more are included) is 5 wt% or more and less than 30 wt%, preferably 10 to 30 wt% of the total amount of the monomer components. %, Particularly preferably 15 to 30% by weight. When the curable composition for three-dimensional modeling of the present invention contains the vinyl ether compound (a) having a cyclic ether skeleton in the above range, it cures quickly even in the presence of oxygen and / or moisture, and has excellent dimensional stability. Things can be formed. When the content of the vinyl ether compound (a) having a cyclic ether skeleton exceeds the above range, a cured product having higher hardness can be obtained in the absence of moisture, but the progress of curing tends to be inhibited in the presence of moisture. There is. On the other hand, when the total content is less than the above range, the curing rate is lowered, and a cured product having excellent dimensional stability tends to be hardly obtained.

  The vinyl ether compound (a) having a cyclic ether skeleton is preferably a compound represented by the formula (a-1) and / or a compound represented by the formula (a-2).

  The content of the vinyl ether compound (a ′) having a chain hydrocarbon skeleton (the total amount when two or more types are contained) exhibits fast curability and can form a cured product having high hardness. For example, about 5 to 35% by weight of the total amount of the monomer components is preferable, more preferably 5 to 25% by weight, and particularly preferably 10 to 20% by weight.

  Moreover, the ratio (the former: latter, weight ratio) of the content of the vinyl ether compound (a) having a cyclic ether skeleton and the vinyl ether compound (a ′) having a chain hydrocarbon skeleton is, for example, about 10:90 to 90:10 The ratio is preferably 30:70 to 80:20, and particularly preferably 50:50 to 70:30 in that a cured product having excellent dimensional stability can be obtained.

  The monomer component (Type 6) may contain other vinyl ether compounds in addition to the vinyl ether compound (a) having a cyclic ether skeleton and the vinyl ether compound (a ′) having a chain hydrocarbon skeleton.

  The monomer component (Type 6) further contains a vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton as the vinyl ether compound (A), thereby exhibiting fast curability and a cured product having high hardness. The content of the vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton is preferably, for example, about 1 to 50% by weight, preferably 5 to 50% by weight, and particularly preferably 5 to 30% by weight, most preferably 5 to 20% by weight.

  The monomer component (Type 6) is a vinyl ether other than the vinyl ether compound (a) having a cyclic ether skeleton, a vinyl ether compound (a ′) having a chain hydrocarbon skeleton, and a vinyl ether compound (a ″) having a cyclic hydrocarbon skeleton. A compound may be contained, but the content of the other vinyl ether compound is about 20% or less, preferably 10% by weight or less of the total vinyl ether compound contained in the monomer component.

  The monomer component (Type 6) preferably contains the oxetane compound (B) from the viewpoint of exhibiting fast curability, and the content of the oxetane compound (B) is, for example, about 5 to 80% by weight of the total amount of the monomer components. , Preferably 10 to 70% by weight, particularly preferably 15 to 60% by weight.

  It is preferable that the monomer component (Type 6) further contains an epoxy compound (C) in that it can exhibit fast curability, and the content of the epoxy compound (C) is, for example, 5 to 5% of the total amount of the monomer components. About 80% by weight, preferably 10 to 60% by weight, particularly preferably 10 to 40% by weight.

  When the curable composition for three-dimensional modeling of the present invention contains the monomer component (Type 6) having the above-described configuration, the cured product is rapidly cured even in the presence of oxygen and / or moisture, and has excellent dimensional stability. Can be formed.

  The monomer components (Type 1) to (Type 6) may contain other monomers in addition to the above cationic polymerizable monomers, but the content of other monomers (when two or more types are contained, the total amount) Is about 30% by weight or less, preferably 20% by weight or less of the total amount of the monomer components. If the content of other monomers exceeds the above range, the effects of the present invention tend to be difficult to obtain.

(Acid generator)
The curable composition for three-dimensional model | molding of this invention contains an acid generator with the said monomer component. The acid generator includes a photoacid generator and a thermal acid generator. These can be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a photoacid generator because a cured product can be rapidly formed by light irradiation.

(Photoacid generator)
A photoacid generator is a compound that generates an acid upon irradiation with light, and is also referred to as a photocationic polymerization initiator. The photoacid generator is composed of a cation moiety that absorbs light and an anion moiety that is a source of acid. For example, a diazonium salt compound, an iodonium salt compound, a sulfonium salt compound, a phosphonium salt compound, and a selenium salt compound Oxonium salt compounds, ammonium salt compounds, bromine salt compounds, metallocene complexes, iron arene complexes, and the like. These can be used alone or in combination of two or more.

  Examples of the cation moiety of the sulfonium salt compound include (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and tri-p-tolylsulfonium ion. An arylsulfonium ion (especially a triarylsulfonium ion) can be mentioned.

Examples of the anion portion of the photoacid generator include BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ C ₆ H ₄ SO ₃ ⁻ , CH ₃ (NO ₂ ) C ₆ H ₄ SO ₃ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , [(Rf) _t PF _6−t ] ⁻ (Rf: an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, t: an integer of 1 to 5), AsF Examples thereof include ₆ ⁻ , SbF ₆ ⁻ , SbF ₅ OH ⁻ , halogen anion, sulfonic acid anion, carboxylic acid anion, and sulfate anion.

As a photo-acid generator, the compound represented by a following formula can be mentioned, for example.

  In the present invention, for example, trade names “Syracure UVI-6970”, “Syracure UVI-6974”, “Syracure UVI-6990”, “Syracure UVI-950” (manufactured by Union Carbide, USA), “Irgacure 250”. "Irgacure 261", "Irgacure 264", "Irgacure 270", "Irgacure 290" (manufactured by BASF), "CG-24-61" (Ciba Geigy), "Adekaoptomer SP-150", “Adeka optomer SP-151”, “Adeka optomer SP-170”, “Adeka optomer SP-171” (manufactured by ADEKA Corporation), “DAICAT II” (manufactured by Daicel Corporation), “UVAC1590” "" UVAC1591 "(above, Daicel-Cytec Corporation) Manufactured), "CI-2064", "CI-2439", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758" “CIT-1682” (manufactured by Nippon Soda Co., Ltd.), “PI-2074” (manufactured by Rhodia, tetrakis (pentafluorophenyl) borate toluylcumyliodonium salt), “FFC509” (manufactured by 3M), “BBI-102”, “BBI-101”, “BBI-103”, “MPI-103”, “BDS-105”, “TPS-103”, “MDS-103”, “MDS-105”, “MDS” -203 "," MDS-205 "," DTS-102 "," DTS-103 "," NAT-103 "," NDS-103 "," BMS-105 "," TMS 105 "(above, manufactured by Midori Chemical Co., Ltd.)," CD-1010 "," CD-1011 "," CD-1012 "(above, manufactured by Sartomer, USA)," CPI-100P "," CPI-101A " "," CPI-110P "," CPI-110A "," CPI-210S "(manufactured by San Apro Co., Ltd.)," UVI-6992 "," UVI-6976 "(manufactured by Dow Chemical) Commercial products can be used.

[Curable composition for three-dimensional modeling]
The three-dimensional shaping curable composition of the present invention contains at least the monomer component and the acid generator.

  The content of the monomer component in the total amount (100% by weight) of the three-dimensional curable composition of the present invention is, for example, about 50 to 99.9% by weight, and preferably 70 to 99.5% by weight.

  Content of the said acid generator in the curable composition for three-dimensional model | molding of this invention is about 0.1-20 weight part with respect to 100 weight part of monomer components, Preferably it is 0.5-10 weight part. .

  Since the curable composition for three-dimensional model | molding of this invention has the said structure, it has a viscosity suitable for use as an ink for inkjet 3D printers, without diluting with a solvent. Therefore, the curable composition for three-dimensional modeling of the present invention is a solvent-free system, that is, containing no solvent can improve the drying property, and prevent the generation of odor due to the volatilization of the solvent. It is preferable at the point which can do. Accordingly, the content of the solvent is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less of the total amount (100% by weight) of the three-dimensional curable composition.

  The three-dimensional shaping curable composition of the present invention may contain one or more other components as required in addition to the monomer component and the acid generator. For example, pigments, dyes, dispersants, Well-known and commonly used sensitizers, sensitization aids, antioxidants, stabilizers and the like can be mentioned. Moreover, although the curable composition for three-dimensional model | molding of this invention may contain the polymer and the oligomer, the total content of a polymer and an oligomer is the total amount of the curable composition for three-dimensional model | molding of this invention from a dischargeable viewpoint. For example, 10% by weight or less, preferably 5% by weight or less, most preferably 3% by weight or less, and particularly preferably 1% by weight or less.

  The three-dimensional shaping curable composition of the present invention may contain a pigment and / or a dye, and these contents (the total amount when containing two or more kinds) are the total amount of the three-dimensional shaping curable composition. For example, it is about 1 to 25% by weight.

  Usable pigments include, for example, earthen pigments (eg, ocher, amber, etc.), lapis lazuli, azurite, chalk, pepper, lead white, vermilion, ultramarine, viridan, cadmium red, carbon pigments (eg, carbon black, Carbon refined, carbon nanotubes, etc.), metal oxide pigments (eg, iron black, cobalt blue, zinc oxide, titanium oxide, chromium oxide, iron oxide, etc.), metal sulfide pigments (eg, zinc sulfide, etc.), metal sulfuric acid Inorganic pigments such as salts, metal carbonates (eg, calcium carbonate, magnesium carbonate, etc.), metal silicates, metal phosphates, metal powders (eg, aluminum powder, bronze powder, zinc powder, etc.); insoluble azo pigments ( For example, monoazo yellow, monoazo red, monoazo violet, disazo yellow, di Azo orange, pyrazolone pigments, etc.), soluble azo pigments (eg, azo yellow lake, azo lake red, etc.), benzimidazolone pigments, β-naphthol pigments, naphthol AS pigments, condensed azo pigments, quinacridone pigments (eg, quinacridone red, Quinacridone magenta, etc.), perylene pigments (eg, perylene red, perylene scarlet, etc.), perinone pigments (eg, perinone orange, etc.), isoindolinone pigments (eg, isoindolinone yellow, isoindolinone orange, etc.), isoindoline. Pigment (eg, isoindoline yellow), dioxazine pigment (eg, dioxazine violet), thioindigo pigment, anthraquinone pigment, quinophthalone pigment (eg, quinophthalone yellow), metal complex pigment, diketopi Examples thereof include organic pigments such as pyrrolopyrrole pigments, phthalocyanine pigments (for example, phthalocyanine blue and phthalocyanine green), dye lake pigments; fluorescent pigments such as inorganic phosphors and organic phosphors.

  Examples of the dye include nitroaniline, phenyl monoazo, pyridone azo, quinophthalone, styryl, anthraquinone, naphthalimide azo, benzothiazolyl azo, phenyl disazo, thiazolyl azo dyes, and the like. Can do.

  The curable composition for three-dimensional modeling of the present invention may contain a dispersant in order to improve the dispersibility of the pigment or dye, and the content of the dispersant is based on 100 parts by weight of the pigment and / or dye. For example, about 1 to 50 parts by weight, preferably 3 to 30 parts by weight.

  When the curable composition for three-dimensional modeling of the present invention is used for the purpose of curing by irradiating a UV-LED, it is possible to contain a sensitizer and, if necessary, a sensitization aid to generate acid. It is preferable in that the ultraviolet light absorption rate of the agent (particularly, the photoacid generator) can be improved and the curability can be improved, and the content thereof is the total amount (100% by weight) of the three-dimensional curable composition. For example, about 0.05 to 10% by weight, preferably 0.1 to 5% by weight.

  The curable composition for three-dimensional modeling of the present invention includes the above-mentioned monomer component, acid generator, and other components as necessary, such as a self-revolving stirring deaerator, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It can manufacture by mixing uniformly using the mixing apparatus generally known. Each component may be mixed simultaneously or sequentially.

  The surface tension (at 25 ° C. under 1 atm) of the three-dimensional modeling curable composition of the present invention is, for example, about 10 to 50 mN / m, preferably 15 to 40 mN / m, and particularly preferably 15 to 30 mN / m. . Moreover, the viscosity [at 25 ° C., shear rate 10 (1 / s)] of the curable composition for three-dimensional modeling of the present invention is, for example, about 1 to 1000 mPa · s, preferably 3 to 500 mPa · s, and particularly preferably 5 It is -100 mPa * s, Most preferably, it is 5-50 mPa * s, More preferably, it is 8-30 mPa * s. Therefore, when the three-dimensional modeling curable composition of the present invention is used as an ink for an ink jet 3D printer, the discharge property is excellent.

  Further, the three-dimensional curable composition of the present invention can be used even in the presence of oxygen (when the content of the vinyl ether compound (a) having a cyclic ether skeleton is in a specific range, even in the presence of oxygen and / or moisture). By performing ultraviolet irradiation and / or heat treatment, the monomer can be quickly cured without remaining unreacted, and a cured product having excellent dimensional stability can be formed. Therefore, it can be suitably used as an ink for an ink jet 3D printer (particularly, when the three-dimensional modeling curable composition of the present invention contains a pigment and / or a dye, an ink jet 3D printer color ink). A highly accurate three-dimensional model can be formed at high speed while suppressing the generation of odor in an air atmosphere.

In the case of curing by applying ultraviolet irradiation, the light source used for ultraviolet irradiation may be any light source that can generate an acid in the three-dimensional curable composition by irradiating light. For example, UV -LEDs, mercury lamps such as low, medium and high pressure mercury lamps, mercury xenon lamps, metal halide lamps, tungsten lamps, arc lamps, excimer lamps, excimer lasers, semiconductor lasers, YAG lasers, lasers combined with nonlinear optical crystals A laser system, a high frequency induced ultraviolet ray generator or the like can be used. The ultraviolet irradiation amount (integrated light amount) is, for example, about 10 to 1000 mJ / cm ² .

  After irradiation with ultraviolet rays, heat treatment may be further performed. By performing the heat treatment, the degree of curing can be further improved. When performing heat processing, heating temperature is about 40-200 degreeC, and heating time is about 1 minute-15 hours. The degree of curing can also be improved by leaving the composition at room temperature (1 to 30 ° C.) for about 1 to 48 hours after irradiation with ultraviolet rays.

  When curing by heat treatment, the heating temperature is, for example, 40 to 200 ° C., and the heating time is, for example, about 1 minute to 15 hours.

[Method of manufacturing a three-dimensional model]
The manufacturing method of the three-dimensional model | molding of this invention uses the said curable composition for three-dimensional model | molding, especially uses the said curable composition for three-dimensional model | mold as an ink for inkjet 3D printers, and manufactures a three-dimensional model | molded object. It is characterized by that. According to the method for producing a three-dimensional structure of the present invention, when the content of the vinyl ether compound (a) having a cyclic ether skeleton is in a specific range in an air atmosphere, the generation of odor is suppressed without limiting the humidity condition. However, a highly accurate three-dimensional model can be manufactured at high speed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Example (1-1)
Mixing 25 parts by weight of ONB-DVE, 25 parts by weight of Celoxide 2021P, 50 parts by weight of OXT-212 as a monomer component, and 5 parts by weight of CPI-110P as a photoacid generator, Tension (at 25 ° C. under 1 atm): 19.5 mN / m, viscosity (at 25 ° C., shear rate 10 (1 / s)): 12 mPa · s].

Examples (1-2) to (1-28)
Except having changed the monomer component into the prescription of following Table 1, it carried out like Example (1-1) and obtained the curable composition for three-dimensional modeling.

Example (2-1)
As a monomer component, 25 parts by weight of ONB-DVE, 25 parts by weight of Celoxide 2021P, 50 parts by weight of ALOX, and 5 parts by weight of CPI-110P as a photoacid generator were mixed, and a curable composition for three-dimensional modeling (surface tension ( 19.6 mN / m, viscosity [at 25 ° C., shear rate 10 (1 / s): 15.1 mPa · s)].

Examples (2-2) to (2-21)
Except having changed the monomer component into the prescription of the following Table 2, it carried out like Example (2-1) and obtained the curable composition for three-dimensional modeling.

Example (3-1)
Mixing 25 parts by weight of ONB-DVE as a monomer component, 25 parts by weight of 4CH-DVE, 50 parts by weight of Celoxide 3000, and 5 parts by weight of CPI-110P as a photoacid generator, a three-dimensional curable composition [surface Tension (at 25 ° C. under 1 atm): 24.1 mN / m, viscosity (at 25 ° C., shear rate 10 (1 / s)): 15.5 mPa · s].

Examples (3-2) to (3-14)
Except having changed the monomer component into the prescription of following Table 3, it carried out like Example (3-1) and obtained the curable composition for three-dimensional model | molding.

Example (4-1)
Three-dimensional modeling by mixing 25 parts by weight of ONB-DVE, 25 parts by weight of 4CH-DVE, 20 parts by weight of Celoxide 2021P, 30 parts by weight of OXT-212 and 5 parts by weight of CPI-110P as a photoacid generator as monomer components Curable composition [surface tension (at 25 ° C., under 1 atm): 20.1 mN / m, viscosity (at 25 ° C., shear rate 10 (1 / s)): 14 mPa · s].

Examples (4-2) to (4-22)
Except having changed the monomer component into the prescription of the following Table 4, it carried out like Example (4-1) and obtained the curable composition for three-dimensional model | molding.

Example (5-1)
As a monomer component, 25 parts by weight of ISB-DVE, 15 parts by weight of TEGDVE, 20 parts by weight of Celoxide 2021P, 40 parts by weight of OXT-212, and 5 parts by weight of CPI-110P as a photoacid generator are mixed and cured for three-dimensional modeling. Composition [surface tension (at 25 ° C., under 1 atm): 21.1 mN / m, viscosity (at 25 ° C., shear rate 10 (1 / s)): 14 mPa · s].

Examples (5-2) to (5-11)
A curable composition for three-dimensional modeling was obtained in the same manner as in Example (5-1) except that the monomer component was changed to the formulation shown in Table 5 below.

Comparative Example 1
As a monomer component, 70 parts by weight of IB-XA, 30 parts by weight of APG-200, and 2 parts by weight of Irgacure 184 as a radical photopolymerization initiator were mixed to obtain a three-dimensional curable composition.

Comparative Example 2
A curable composition for three-dimensional modeling was obtained in the same manner as in Comparative Example 1 except that the monomer component was changed to the formulation shown in Table 6 below.

(Curability evaluation)
Apply a three-dimensional curable composition to a glass plate (film thickness: 5 μm) and irradiate it with ultraviolet rays using a mercury xenon lamp (product “LC8 LIGHTNINGCURE L9588”, manufactured by Hamamatsu Photonics Co., Ltd.) as a light source. , Integrated light quantity (= not containing water) until tack disappears (specifically, when the surface of the coating film is not sticky or peeled off from the glass plate when rubbed with Kimwipe (registered trademark)) The accumulated light amount required for curing of the three-dimensional modeling curable composition: mJ / cm ² ) was measured to evaluate curability.

(Evaluation of curability in the presence of moisture)
5 parts by weight of water was added to 100 parts by weight of the three-dimensional curable composition and stirred to prepare a water-containing three-dimensional curable composition.
The integrated light amount (mJ / cm ² ) until tack disappears was measured in the same manner as in the above (curability evaluation) except that the water-containing three-dimensional modeling curable composition was used instead of the three-dimensional modeling curable composition. From the following formula, the increase rate of the integrated light quantity by adding water was calculated, and the curability in the presence of moisture was evaluated according to the following criteria.
Increase rate of integrated light quantity (%) = {(integrated light quantity required for curing water-containing three-dimensional curable composition / integrated light quantity required for curing water-free three-dimensional curable composition) -1} × 100
Criteria for evaluation of curability in the presence of moisture Increase rate of accumulated light quantity is 150% or more: Poor curability (x)
Increase rate of integrated light quantity is 20% or more and less than 150%: Slightly poor curability (△)
Increase rate of integrated light quantity is 10% or more and less than 20%: Good curability (○)
Increase rate of integrated light quantity is less than 10%: very good curability (◎)

(Dimensional stability evaluation)
The curable compositions for three-dimensional modeling obtained in the examples and comparative examples were applied to a 100 μm PET film with a thickness of 100 μm, and in an air atmosphere, a mercury xenon lamp (product “LC8 LIGHTNINGCURE L9588”, Hamamatsu Photonics Co., Ltd.) )) Was used for irradiation with ultraviolet rays to obtain a cured product. In addition, the curable composition for three-dimensional model | molding obtained by the comparative example performed light irradiation in nitrogen atmosphere.
A test piece (length × width = 2 cm × 10 cm) is prepared from the obtained cured product, and one side (one side of 2 cm) of the test piece is fixed to the substrate surface using cello tape (registered trademark). The dimensional stability was evaluated according to the following criteria from the degree of warpage (distance from the substrate surface) of the other side of the 2 cm side.
Evaluation criteria A: Warpage is less than 5 mm B: Warpage is 5 mm or more and less than 10 mm X: Warpage is 10 mm or more

(Hardness evaluation)
About the hardened | cured material obtained by the method similar to (dimensional stability evaluation), according to JISK5600-5-4: 1999, the pencil hardness test was done and hardness was evaluated.

(Light resistance evaluation)
The cured product obtained by the same method as in (Dimensional stability evaluation) is irradiated with ultraviolet rays (308 MJ / m ² ) corresponding to the amount of light for one year, visually confirmed for yellowing, and in accordance with the following criteria: Light resistance was evaluated.
Evaluation criteria ○: No yellowing ×: Yellowing

The compounds used in Examples and Comparative Examples are as follows.
<Vinyl ether compound>
ONB-DVE: Compound represented by formula (a-1), trade name “ONB-DVE”, manufactured by Daicel Corporation ISB-DVE: Compound represented by formula (a-2), trade name “ISB- DVE ", manufactured by Daicel Corporation TEGDVE: triethylene glycol divinyl ether, trade name" TEGDVE ", manufactured by Nippon Carbide Industries Co., Ltd. 4CH-DVE: cyclohexanediol divinyl ether, trade name" 4CH-DVE ", manufactured by Nippon Carbide Industries ( Co., Ltd. CHDMDVE: cyclohexane dimethanol divinyl ether, trade name “CHDMDVE”, Nippon Carbide Industries Co., Ltd. TCDDVE: tricyclodecane dimethanol divinyl ether HBisF-DVE: hydrogenated bisphenol F type divinyl ether HBisA-DVE: hydrogenated Bisphenol A divinyl A Teru HBP-DVE: hydrogenated biphenyl divinyl ether CHVE: cyclohexyl vinyl ether, trade name “CHVE”, manufactured by Nippon Carbide Industries Co., Ltd. 2-EHVE: 2-ethylhexyl vinyl ether, trade name “EHVE”, manufactured by Nippon Carbide Industries Co., Ltd. <Epoxy compound>
CEL2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, trade name “Celoxide 2021P”, manufactured by Daicel Corporation CEL3000: 1,2: 8,9-diepoxy limonene, trade name “Celoxide” 3000 ", manufactured by Daicel Corporation X-22-163: both ends epoxy-modified silicone, epoxy group equivalent: 200 g / mol, trade name" X-22-163 ", manufactured by Shin-Etsu Chemical KF-105: both Terminal epoxy-modified silicone, epoxy group equivalent: 490 g / mol, trade name “KF-105”, manufactured by Shin-Etsu Chemical Co., Ltd. CHOX: 1,2-epoxycyclohexane, manufactured by Wako Pure Chemical Industries, Ltd. EP0408: epoxy (= 3,4-epoxycyclohexylmethyl) modified polyorganosilsesquio Sun, molecular weight 1418.20, trade name “EP0408”, manufactured by Toyotsu Chemiplus Co., Ltd. EP0409: epoxy (= glycidyloxyethyl) modified polyorganosilsesquioxane, molecular weight 1337.88, trade name “EP0409”, Toyotsu EP0419 manufactured by Chemiplus Co., Ltd .: Epoxy (= glycidyloxypropyl) modified polyorganosilsesquioxane, molecular weight 13224.37, trade name “EP0419”, manufactured by Toyotsu Chemiplus Co., Ltd. E-PS: Epoxy hexahydrophthalic acid di 2-Ethylhexyl, trade name “Sunsocizer E-PS”, manufactured by Shin Nippon Rika Co., Ltd. <Oxetane compound>
OXT-212: 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, trade name “Aron Oxetane OXT-212”, manufactured by Toagosei Co., Ltd. OXT-221: Bis [(3-ethyloxetane-3 -Yl) methyl] ether, trade name "Aron oxetane OXT-221", manufactured by Toagosei Co., Ltd. ALOX: 3-allyloxyoxetane EHOX: 3- (2-ethylhexyloxy) oxetane <photoacid generator>
CPI-110P: Diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate and thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluorophosphate) mixture (99.5 / 0.5), trade name “CPI-110P”, manufactured by San Apro Co., Ltd. <acrylate>
IB-XA: Isobornyl acrylate, trade name “Light acrylate IB-XA”, manufactured by Kyoeisha Chemical Co., Ltd. APG-200: Tripropylene glycol diacrylate, trade name “APE-200”, Shin-Nakamura Chemical Co., Ltd. FA-513AS: dicyclopentanyl acrylate, trade name “FA-513AS”, Hitachi Chemical Co., Ltd. DCP-A: dicyclopentane dimethylol diacrylate, trade name “light acrylate DCP-A”, Kyoeisha Chemical ( Co., Ltd. Photomer 6010: urethane acrylate oligomer, trade name “Photomer 6010”, manufactured by Cognis <Radical photopolymerization initiator>
Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, trade name “Irgacure 184”, manufactured by Ciba Japan Co., Ltd.

Claims (30)

  A composition containing a monomer component and an acid generator, wherein the monomer component contains a vinyl ether compound (A) (including at least a vinyl ether compound (a) having a cyclic ether skeleton). . The curability for three-dimensional modeling according to claim 1, wherein the vinyl ether compound (a) having a cyclic ether skeleton is a compound represented by the following formula (a-1) and / or a compound represented by the formula (a-2). Composition.

  The monomer component contains a vinyl ether compound (A), an oxetane compound (B), and an epoxy compound (C), and the compound represented by the formula (a-1) and / or the formula (a) as the vinyl ether compound (A) -2), the compound represented by the formula (a-1) and the formula containing 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane as the oxetane compound (B) The curable composition for three-dimensional modeling according to claim 2, wherein the total content of the compound represented by (a-2) is 5% by weight or more and less than 30% by weight of the total amount of the monomer components.   The curable composition for three-dimensional model | molding of Claim 3 in which an epoxy compound (C) contains the epoxy compound which has a cyclohexene oxide group.   The curable composition for three-dimensional modeling according to claim 3 or 4, wherein the content of the epoxy compound (C) is 5 to 80% by weight of the total amount of the monomer components.   The curability for three-dimensional modeling according to any one of claims 3 to 5, wherein the content of 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane is 5 to 80% by weight of the total amount of monomer components. Composition. The monomer component contains a vinyl ether compound (A) and an oxetane compound (B), and is represented by the compound represented by the formula (a-1) and / or the formula (a-2) as the vinyl ether compound (A). The curable composition for three-dimensional model | molding of Claim 2 containing the compound represented by following formula (b ') as an oxetane compound (B).

(Wherein R ^c represents a monovalent hydrocarbon group)   The curable composition for three-dimensional modeling according to claim 7, wherein the compound represented by the formula (b ') is 3-allyloxyoxetane and / or 3- (2-ethylhexyloxy) oxetane.   The curable composition for three-dimensional modeling according to claim 7 or 8, wherein the content of the compound represented by the formula (b ') is 5 to 90% by weight of the total amount of the monomer components.   The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 5% by weight or more and less than 30% by weight of the total amount of the monomer components. The curable composition for three-dimensional model | molding of any one.   Furthermore, the curable composition for three-dimensional model | molding of any one of Claims 7-10 containing the epoxy compound (C) containing the compound which has a cyclohexene oxide group.   The curable composition for three-dimensional modeling according to claim 11, wherein the content of the epoxy compound (C) is 5 to 80% by weight of the total amount of the monomer components.   The monomer component contains a vinyl ether compound (A) and an epoxy compound (C), and is represented by the compound represented by the formula (a-1) and / or the formula (a-2) as the vinyl ether compound (A). The compound is contained in an amount of 5% by weight or more and less than 30% by weight based on the total amount of the monomer components, and 1,2: 8,9-diepoxy limonene as the epoxy compound (C) is contained in an amount exceeding 40% by weight of the total amount of the monomer components. The curable composition for three-dimensional modeling described.   The curable composition for three-dimensional modeling according to claim 13, wherein the monomer component further contains 5 to 50% by weight of the oxetane compound (B) based on the total amount of the monomer components.   The monomer component contains a vinyl ether compound (A), an oxetane compound (B), and an epoxy compound (C), and the compound represented by the formula (a-1) and / or the formula (a) as the vinyl ether compound (A) -2) a compound containing 5% by weight or more and less than 30% by weight of the total amount of the monomer components and containing 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane as the oxetane compound (B). The functional oxetane compound is contained in an amount of 10 to 85% by weight based on the total amount of the monomer components, and 1,2: 8,9-diepoxy limonene is contained as the epoxy compound (C) in an amount of 10 to 40% by weight based on the total amount of the monomer components. Curable composition for three-dimensional modeling.   The monomer component contains a vinyl ether compound (A) and an oxetane compound (B), and is represented by the compound represented by the formula (a-1) and / or the formula (a-2) as the vinyl ether compound (A). And a divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton, and the monofunctional oxetane compound as the oxetane compound (B). object. A divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton is represented by the following formula (a" -1)

(In the formula, ring Z represents the following formulas (z-1) to (z-5)

And n and n ′ are the same or different and represent an integer of 0 or more)
The curable composition for three-dimensional model | molding of Claim 16 which is a compound represented by these.   The total content of the compound represented by the formula (a-1) and / or the compound represented by the formula (a-2) and the divinyl ether compound (a "-1) having a cyclic hydrocarbon skeleton is a monomer. The curable composition for three-dimensional modeling according to claim 16 or 17, which is 10 to 80% by weight of the total amount of the components.   The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 5% by weight or more and less than 30% by weight based on the total amount of the monomer components. The curable composition for three-dimensional model | molding of any one.   The curable composition for three-dimensional modeling according to any one of claims 16 to 19, wherein the content of the monofunctional oxetane compound is 10 to 70% by weight of the total amount of the monomer components.   Furthermore, the curable composition for three-dimensional model | molding of any one of Claims 16-20 containing the epoxy compound (C) containing the epoxy compound which has a cyclohexene oxide group.   The curable composition for three-dimensional modeling according to claim 21, wherein the content of the epoxy compound (C) is 5 to 80% by weight of the total amount of the monomer components.   The monomer component contains the vinyl ether compound (A), the monofunctional monomer contains 20 to 70% by weight of the total amount of the monomer components, the vinyl ether compound (a) having a cyclic ether skeleton, and the vinyl ether compound having a chain hydrocarbon skeleton ( a ′) is contained in an amount of 10 to 40% by weight of the total amount of the monomer components, and the content of the vinyl ether compound (a) having the cyclic ether skeleton is 5% by weight or more and less than 30% by weight of the total amount of the monomer components. The curable composition for three-dimensional modeling according to claim 1 or 2.   Furthermore, the curable composition for three-dimensional model | molding of Claim 23 which contains 1-50 weight% of vinyl ether compounds (a '') which have cyclic hydrocarbon frame | skeleton as a vinyl ether compound (A) of a monomer component whole quantity.   Furthermore, the curable composition for three-dimensional model | molding of Claim 23 or 24 which contains 5 to 80 weight% of oxetane compounds (B) of monomer component whole quantity.   Furthermore, the curable composition for three-dimensional model | molding of any one of Claims 23-25 which contains 5 to 80weight% of epoxy compound (C) with respect to the monomer component whole quantity.   Furthermore, the curable composition for three-dimensional model | molding of any one of Claims 1-26 containing a pigment and / or dye.   It is an ink for inkjet 3D printers, The curable composition for three-dimensional modeling of any one of Claims 1-27.   Hardened | cured material of the curable composition for three-dimensional model | molding of any one of Claims 1-28.   The manufacturing method of the three-dimensional molded item which manufactures a three-dimensional molded item using the curable composition for three-dimensional modeling of any one of Claims 1-28.