JP2002060463A - Photocurable resin composition and three-dimensionally shaped article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photocurable resin composition which has substantially unchanging molding characteristics even when stored/used for a long time in a normal use environment and which can stably molded into a three- dimensionally shaped article having desired properties under the same molding conditions. SOLUTION: The resin composition for three-dimensional molding contains (A) an oxetane compound, (B) an epoxy compound, and (C) a photoinduced acid generator and has a water content of 0.3-1.5 wt.% when just prepared.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition used for an optical three-dimensional molding method, and a three-dimensional product obtained by photocuring the same.

[0002]

2. Description of the Related Art In recent years, by repeating a process of forming a cured resin layer by selectively irradiating a photocurable liquid resin composition with light, a three-dimensional object is formed by integrally laminating the cured resin layers. There has been proposed an optical three-dimensional molding method for forming (JP-A-60-247515, JP-A-62-35966).
JP, JP-A-62-101408 and JP-A-5-24119). The photocurable resin composition used in such a three-dimensional molding method has a low viscosity and can immediately form a smooth liquid surface from the viewpoint of performing efficient photolithography, and has a photocurable property. Be superior,
That is, it is required that the resin be rapidly cured by light irradiation. Further, the photocurable resin composition,
It is required that the amount of deformation including warping due to curing shrinkage during light curing be small. Since the three-dimensional objects obtained by the optical three-dimensional molding method are used as models for studying designs and prototypes of mechanical parts, etc., they have excellent molding accuracy, that is, fine processing that is faithful to the design drawing Is required to be performed with high accuracy, sufficient mechanical strength capable of withstanding use conditions, and such mechanical properties being stable without changing over time.

[0003] In view of the above points, the present inventors have proposed a resin composition for stereolithography containing an oxetane compound and an epoxy compound as a cationically polymerizable organic compound (Japanese Patent Application Laid-Open No. 10-168165). reference). This resin composition is excellent in photocurability, and according to the resin composition, a three-dimensional object having high dimensional accuracy and high mechanical strength can be formed in a short time.

[0004] A photocurable resin composition for optical three-dimensional modeling is sometimes housed in the same container and used for several months to several years. And the environmental conditions (temperature and humidity) under which the resin composition is stored and used.
Is not always constant. For this reason, the photocurable resin composition for optical three-dimensional modeling has good storage stability, and even after being stored in such an environment for a long period of time, its modeling characteristics do not change. It is desirable that a three-dimensional object having the performance (interlayer adhesion and modeling accuracy) can be stably formed.

[0005] However, the above resin composition containing an oxetane compound and an epoxy compound is subjected to a normal use environment (for example, a temperature of 10 to 30 ° C and a relative humidity of 20 to 8).
(0%) for several months, there is a problem that the resin composition absorbs (absorbs moisture) with time, and its molding characteristics are greatly changed. In this case, even if molding under the same conditions as the molding conditions in the resin composition before storage,
It is not possible to obtain a three-dimensional object having the expected performance.

Here, when the above resin composition containing an oxetane compound and an epoxy compound is stored and used under a standard use environment (temperature 23 ° C., relative humidity 50%), the resin composition becomes Absorb water over a long period of time until the equilibrium water content in the environment is reached. Then, due to the difference between the water content of the resin composition before storage and the water content of the resin composition after storage, the molding characteristics of the resin composition, for example, when receiving a certain irradiation energy Of the cured layer (thickness of the cured layer formed by light irradiation) greatly changes.

[0007] When molding is performed for a long period of time under the optimal molding conditions for the resin composition (resin composition having a low moisture content) before storage, the curing depth decreases as the moisture content increases with time. In a three-dimensional object obtained after a certain period of time (after storage or during a storage period), interlayer adhesion is reduced and peeling occurs. On the other hand, when the molding is performed under the optimal molding conditions for the resin composition (resin composition having a high water content) after storage, the curing depth of the resin composition in the initial stage becomes larger than the design value, and the molding in the laminating direction is performed. Accuracy decreases. Such inconvenience is more remarkable as the humidity of the storage / use environment is higher. Therefore, it is extremely difficult to set optimal conditions for stably forming a three-dimensional object having the expected performance. Was.

[0008]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances. It is an object of the present invention to provide a device in a normal use environment (temperature: 10 to 30 ° C., relative humidity: 20 to 8).
0%), even when stored and used for a long time, the shaping characteristics (hardening depth) do not substantially change,
It is an object of the present invention to provide a photocurable resin composition that can stably form a three-dimensional object having desired performance (layer adhesion and molding accuracy) under the same molding conditions.

[0009]

The photocurable resin composition of the present invention comprises a photocurable resin for three-dimensional molding, comprising (A) an oxetane compound, (B) an epoxy compound, and (C) a photoacid generator. A composition having a water content of 0.3 to
It is characterized by being 1.5% by weight. Here, the “moisture content at the time of preparation” refers to the moisture content measured within 48 hours after the preparation of the resin composition.

The photocurable resin composition of the present invention is a photocurable resin composition for three-dimensional modeling, comprising (A) an oxetane compound, (B) an epoxy compound, and (C) a photoacid generator. Water is added so that the water content is 0.3 to 1.5% by weight.

In the photocurable resin composition of the present invention,
The following forms are preferred. [1] (D) Elastomer particles having a number average particle size of 10 to 700 nm are contained. [2] 10 to 80 parts by weight of (A) oxetane compound,
(B) 10 to 80 parts by weight of an epoxy compound, (C) 0.1 to 10 parts by weight of a photoacid generator, and (D) number average particle diameter of 10 to 10.
The composition contains 0 to 35 parts by weight of 700 nm elastomer particles, and comprises component (A), component (B), component (C) and component (D).
The total of the components is 100 parts by weight. [3] Water is added so that the water content is 0.5 to 1.5 times the equilibrium water content at a temperature of 23 ° C. and a relative humidity of 50%. [4] A mixture obtained by defoaming a mixture of component (A), component (B), component (C), component (D) and water.

The three-dimensionally shaped article of the present invention is obtained by photocuring the photocurable resin composition of the present invention.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the resin composition of the present invention will be described in detail. The resin composition of the present invention includes an oxetane compound as the component (A), an epoxy compound as the component (B), a photoacid generator as the component (C), and water added at the time of preparation. It may be contained as a component, and may contain elastomer particles as the component (D).

<Component (A)> The oxetane compound as the component (A) has one oxetane ring represented by the following formula (1).
It is a compound having one or more.

[0015]

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The oxetane compound undergoes a polymerization reaction or a crosslinking reaction when irradiated with light in the presence of a cationically polymerizable photopolymerization initiator. As such an oxetane compound, various compounds can be used as long as the compound has one or more oxetane rings in the molecule. Examples are given below.

The compound having one oxetane ring in the molecule includes a compound represented by the following formula (2).

[0018]

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[In the formula (2), Z represents an oxygen atom or
Indicates a sulfur atom. R¹Is hydrogen atom; fluorine atom; methyl
Group, ethyl group, propyl group, butyl group, etc.
~ 6 alkyl groups; trifluoromethyl group, perful
Number of carbon atoms in oloethyl group, perfluoropropyl group, etc.
1 to 6 fluoroalkyl groups; phenyl group, naphthyl
An aryl group having 6 to 18 carbon atoms such as a group; a furyl group or
Represents a thienyl group. R ^TwoIs a hydrogen atom; methyl group, d
1 to 6 carbon atoms such as tyl, propyl, butyl, etc.
An alkyl group of 1-propenyl group, 2-propenyl group,
2-methyl-1-propenyl group, 2-methyl-2-pro
Phenyl, 1-butenyl, 2-butenyl, 3-butene
An alkenyl group having 2 to 6 carbon atoms such as a phenyl group;
Group, naphthyl group, antonyl group, phenanthryl group, etc.
An aryl group having 6 to 18 carbon atoms; benzyl group, full
Orobenzyl group, methoxybenzyl group, phenethyl group,
Substitution of styryl group, cinnamyl group, ethoxybenzyl group, etc.
A substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms;
Arylo such as phenoxymethyl group and phenoxyethyl group
Groups having other aromatic rings such as xyalkyl; ethyl
Carbonyl group, propylcarbonyl group, butyl carbonyl
An alkylcarbonyl group having 2 to 6 carbon atoms such as an alkyl group;
Ethoxycarbonyl, propoxycarbonyl, buto
Alkoxy having 2 to 6 carbon atoms such as xycarbonyl group
Carbonyl group; ethylcarbamoyl group, propylcarba
Moyl group, butylcarbamoyl group, pentylcarbamoy
N-alkylcarbamoy having 2 to 6 carbon atoms such as
And the like. ]

The compound having two oxetane rings in the molecule includes a compound represented by the following formula (3).

[0021]

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[In the formula (3), Z represents an oxygen atom or a sulfur atom, and R ¹ is the same as defined in the above formula (2). R ³ is a linear or branched alkylene group having 1 to 20 carbon atoms such as an ethylene group, a propylene group or a butylene group; a linear or branched alkylene group such as a poly (ethyleneoxy) group or a poly (propyleneoxy) group; A branched poly (alkyleneoxy) group having 1 to 120 carbon atoms; a linear or branched unsaturated hydrocarbon group such as a propenylene group, a methylpropenylene group, a butenylene group; a carbonyl group; An alkylene group containing a carboxyl group in the middle of a molecular chain; and an alkylene group containing a carbamoyl group in the middle of a molecular chain. R ³ may be a polyvalent group selected from the groups represented by the following formulas (4), (5) and (6). ]

[0023]

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[In the formula (4), R ⁴ is a hydrogen atom;
An alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group; a methoxy group, an ethoxy group,
A alkoxy group having 1 to 4 carbon atoms such as a propoxy group and a butoxy group; a halogen atom such as a chlorine atom and a bromine atom; a nitro group; a cyano group; a mercapto group; a lower alkylcarboxyl group; a carboxyl group or a carbamoyl group; x is an integer of 1 to 4. ]

[0025]

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[In the formula (5), R ⁵ is an oxygen atom,
Sulfur atom, a methylene group, -NH -, - SO -, - SO 2
—, —C (CF ₃ ) ₂ — or —C (CH ₃ ) ₂ —. ]

[0027]

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[In the formula (6), R ⁶ represents a methyl group,
1-4 carbon atoms such as ethyl group, propyl group and butyl group
Alkyl groups; an aryl group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group. y is an integer of 0 to 200. R ⁷ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; an aryl group having 6 to 18 carbon atoms such as a phenyl group or a naphthyl group;
Or a group represented by the following formula (7). ]

[0029]

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[In the formula (7), R ⁸ is a methyl group,
1-4 carbon atoms such as ethyl group, propyl group and butyl group
Alkyl groups; an aryl group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group. z is an integer of 0 to 100. ]

Specific examples of the compound having two oxetane rings in the molecule represented by the above formula (3) include compounds represented by the following formulas (8) and (9).

[0032]

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[0033]

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Specific examples of the compound other than the above formula (3) having two oxetane rings in the molecule include a compound represented by the following formula (10).

[0035]

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[In the formula (10), R ¹ is the same as the definition in the above formula (2). ]

The compound having three or more oxetane rings in the molecule includes a compound represented by the following formula (11).

[0038]

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[In the formula (11), Z represents an oxygen atom or a sulfur atom, and R ¹ is the same as defined in the above formula (2). R ⁹ represents a trivalent to divalent organic group, for example, a branched or linear alkylene group having 1 to 30 carbon atoms such as a group represented by the following formulas (12) to (14); And a branched poly (alkyleneoxy) group such as a group represented by 15) or a linear or branched polysiloxane-containing group represented by the following formula (16) or (17). j is an integer of 3 to 10 equal to the valence of R ⁹ . ]

[0040]

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[In the formula (12), R ¹⁰ is a methyl group,
It represents an alkyl group having 1 to 6 carbon atoms such as an ethyl group and a propyl group. ]

[0042]

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[0043]

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[0044]

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[In the formula (15), L is the same or a different integer from 1 to 10. ]

[0046]

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[0047]

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Specific examples of the compound having three or more oxetane rings in the molecule include a compound represented by the following formula (18).

[0049]

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The compound represented by the following formula (19) may have 1 to 10 oxetane rings.

[0051]

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[In the formula (19), R ¹ is the same as defined in the above formula (2), and R ⁸ is the same as the formula (7)
Is the same as the definition in R ¹¹ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group or a trialkylsilyl group (where the alkyl groups are the same or different, and an alkyl group having 3 to 12 carbon atoms) Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, and a tributylsilyl group.), And r is an integer of 1 to 10. ]

Further, as the oxetane compound constituting the component (A), in addition to the above exemplified compounds, the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) is 1,000 to 5,000.
Compounds having a high molecular weight are also included. Examples of such a compound include compounds represented by the following formulas (20), (21), and (22).

[0054]

Embedded image (Here, p is an integer of 20 to 200.)

[0055]

Embedded image (Here, q is an integer of 15 to 100.)

[0056]

Embedded image (Here, s is an integer of 20 to 200.)

Specific examples of the oxetane compound having one oxetane ring in the molecule include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3 -Oxetanylmethoxy) methylbenzene, 4-fluoro- [1
-(3-ethyl-3-oxetanylmethoxy) methyl]
Benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-
Ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl- 3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether , Dicyclopentenyloxyethyl (3
-Ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl)
Ether, tetrahydrofurfuryl (3-ethyl-3-
Oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2
-Tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3
-Ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3 -Ethyl-3-oxetanylmethyl)
Ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl -3-oxetanylmethyl) ether and the like.

Specific examples of oxetane compounds having two or more oxetane rings in the molecule include 3,7-bis (3-
Oxetanyl) -5-oxa-nonane, 3,3'-
(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane),
1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-
3-oxetanylmethoxy) methyl] ethane, 1,3-
Bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-
3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycolbis (3-ethyl-3- Oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-
3-oxetanylmethyl) ether, trimethylolpropanetris (3-ethyl-3-oxetanylmethyl)
Ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-
Oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-
3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3) -Oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3 -Ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-
Oxetanylmethyl) ether, ethylene oxide (E
O) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (P
O) Modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3) -Oxetanylmethyl) ether and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

These exemplified compounds may be used alone or
The component (A) can be constituted by combining two or more kinds.

Of these, oxetane compounds which can be suitably used as component (A) are those having 1 to 10, more preferably 1 to 4, and particularly preferably 2 oxetane rings in the molecule. . Specifically, the following equation (2)
(3-ethyl-3-oxetanylmethoxy) methylbenzene represented by 3), 1,4 represented by the following formula (24)
-Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis (3-ethyl-3-oxetanylmethoxy) ethane represented by the following formula (25),
Trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether represented by the following formula (26),
And a compound represented by the above formula (19).

[0061]

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[0062]

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[0063]

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[0064]

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The content ratio of the component (A) in the resin composition of the present invention is from 10 to 10 parts by weight when the total of the components (A), (B), (C) and (D) is 100 parts by weight.
It is preferably 80 parts by weight, more preferably 20 parts by weight.
To 60 parts by weight. When the content ratio of the component (A) is too small, the cationic polymerization reaction rate (curing rate) of the obtained resin composition becomes small, and a long time is required for modeling, and the resolution tends to be reduced. . On the other hand, (A)
When the content ratio of the components is excessive, the toughness of the cured product (three-dimensional product) of the obtained resin composition tends to decrease, and the curing speed tends to decrease.

<Component (B)> The epoxy compound as the component (B) refers to a compound having a three-membered ethylene oxide structure and does not include a compound having a structure of four or more members such as an oxetane group. The number of ethylene oxide structures in one molecule of the epoxy compound is one or more,
The number is preferably 2 to 15, more preferably 2 to 8. By using the component (B) together with the component (A) as the cationically polymerizable organic compound, the obtained resin composition has a higher photocuring reaction rate than the resin composition containing only the component (A). And photocurability is improved.

Epoxy compounds suitable as component (B) include (i) compounds having an epoxycyclohexyl group in the molecule (epoxycyclohexyl group-containing compounds),
(Ii) Compounds having a glycidyl group in the molecule (glycidyl group-containing compounds). Epoxycyclohexyl group-containing compounds have excellent cationic polymerizability. Further, the glycidyl group-containing compound can impart flexibility to the polymer, increase the mobility of the polymerization system, and further improve the curability.

(I) Specific examples of the compound containing an epoxycyclohexyl group include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 2- (3,4-epoxycyclohexyl-
5,5-spiro-3,4-epoxy) cyclohexane-
Meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6)
-Methylcyclohexylmethyl) adipate, 3,4-
Epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate,
Methylenebis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), 3,4-epoxycyclohexylmethyl modified with ε-caprolactone 3 ',
4′-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4'-
Epoxy cyclohexane carboxylate and the like can be mentioned.

Of these, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone-modified 3,4
-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-
3 ′, 4′-Epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate is preferred, and 3,4-epoxycyclohexylmethyl-3 ', 4'-Epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate is particularly preferred.

Commercially available epoxycyclohexyl group-containing compounds which can be suitably used as component (B) include UVR-6100, UVR-6105, and UVR-6105.
6110, UVR-6128, UVR-6200, UV
R-6216 (all manufactured by Union Carbide Co.), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2
085, EPOLID GT-300, EPOLID GT-3
01, Eporide GT-302, Eporide GT-40
0, Eporide 401, Eporide 403 (all manufactured by Daicel Chemical Industries Ltd.), KRM-2100, KRM-
2110, KRM-2199 (above, Asahi Denka Kogyo Co., Ltd.)
Manufactured).

(Ii) Specific examples of the glycidyl group-containing compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S
Diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl Ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether,
Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; polyglycidyl of polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Ethers; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of phenol, cresol, butylphenol or polyether alcohols obtained by adding alkylene oxide thereto; Glycidyl esters of higher fatty acids and the like can be mentioned.

Of these, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Preferred are diol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.

Commercially available glycidyl group-containing compounds which can be suitably used as component (B) include UVR
-6216 (all manufactured by Union Carbide Co.), glycidol, AOEX24, Cyclomer A200, (all manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828,
Epicoat 812, Epicoat 1031, Epicoat 8
72, Epikote CT508 (both Yuka Shell Co., Ltd.)
KRM-2400, KRM-2410, KRM-
2408, KRM-2490, KRM-2720, KR
M-2750 (all manufactured by Asahi Denka Kogyo KK) and the like.

Further, as the epoxy compound constituting the component (B), in addition to the above-mentioned compounds, a polystyrene-equivalent number average molecular weight of 1,000 to 20,000 as measured by GPC is used.
0 is preferably contained, whereby
It is possible to improve the toughness of the cured product of the obtained resin composition.

Such a compound can be obtained by (1) epoxidizing a carbon-carbon double bond of a corresponding compound having an ethylenically unsaturated bond group with a suitable oxidizing agent such as hydrogen peroxide or peracid. Epoxy-modified compound; (2) Epoxy group-containing polymer obtained by polymerizing a radical polymerizable monomer having an epoxy group in the molecule; (3) Reaction of a compound having a functional group such as a hydroxyl group with epichlorohydrin Examples thereof include epoxy group-containing compounds obtained by a production method known per se such as a method.

The number average molecular weight in terms of polystyrene is 1,0
In order to obtain a compound having a number average molecular weight of 1,000 in the case of the epoxy-modified compound (1), the compound having an ethylenically unsaturated bond group as a raw material has a number average molecular weight of 1,1 in terms of polystyrene. 000 or more and 20,000
What is necessary is just to use the thing below, and in the case of the said epoxy group containing polymer of (2), what is necessary is just to adjust by a well-known method so that the polymer of a desired degree of polymerization may be obtained. In the case of the epoxy group-containing compound (3), a compound having a number average molecular weight in terms of polystyrene of 1,000 or more and less than 20,000 is used as a compound having a functional group such as a hydroxyl group as a raw material. Good. Commercial products of the epoxy-modified compound of the above (1) include Poly bd R-45EP
I (Idemitsu Petrochemical Co., Ltd.), R-15EPI, R-4
5EPI (above, manufactured by Nagase Kasei Kogyo Co., Ltd.), Eporide PB3600, PB4700 (above, manufactured by Daicel Chemical Industries, Ltd.) and the like.

The above-mentioned epoxy compounds can be used alone or in combination of two or more to constitute the component (B).

The content of the component (B) in the resin composition of the present invention is 10 to 10 parts by weight based on 100 parts by weight of the total of the components (A), (B), (C) and (D).
It is preferably 80 parts by weight, more preferably 20 parts by weight.
To 70 parts by weight. When the content ratio of the component (B) is too small, the photocurability of the obtained resin composition decreases. On the other hand, when the content ratio of the component (B) is excessive,
There is a tendency that the viscosity of the obtained resin composition increases and the molding time becomes longer.

<Component (C)> The photoacid generator, which is the component (C), receives energy rays such as light,
A compound capable of releasing a substance that initiates cationic polymerization of the component (A) and the component (B). here,
Energy rays such as light include visible light, ultraviolet light, infrared light,
X-rays, α-rays, β-rays, γ-rays and the like are included.

As a suitable compound constituting the component (C), an onium salt having a structure represented by the following formula (27) can be given. This onium salt is a compound that emits a Lewis acid upon receiving light.

[0081]

Embedded image [R ¹² _a R ¹³ _b R ¹⁴ _c R ¹⁵ _d Z] ^{+ m} [MX _{n + m} ] ^−m (27)

Wherein the cation is an onium ion
Z is S, Se, Te, P, As, Sb, Bi, O,
Represents I, Br, Cl or N≡N;¹², R¹³, R¹⁴
And R ^FifteenRepresents the same or different organic groups. a,
b, c and d are each an integer of 0 to 3,
(A + b + c + d) is equal to the valence of Z. M is a haloge
Complex [MX_{n + m}The metal constituting the central atom of
Represents a metalloid, for example, B, P, As, Sb, F
e, Sn, Bi, Al, Ca, In, Ti, Zn, S
c, V, Cr, Mn, Co and the like. X is F,
A halogen atom such as Cl or Br, and m is a halide
Is the net charge of the complex ion, and n is the valence of M
You. ]

In the above formula (27), specific examples of the onium ion include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecyl) Phenyl) iodonium, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4
- (di (4- (2-hydroxyethyl) phenyl) sulfonio) - phenyl] sulfide, η ⁵ -2, 4- (cyclopentadienyl) [1, 2, 3, 4, 5, 6-η]
-(Methylethyl) -benzene] -iron (1+).

In the above formula (27), the anion [MX
_{n + m} ] is tetrafluoroborate (B
F ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ), and the like.

Further, the general formula [MX _n An onium salt having an anion represented by (OH) ^- ] can be used. Furthermore, perchlorate ion (ClO ₄ ⁻ ), trifluoromethanesulfonic acid ion (CF ₃ SO ₃ ⁻ ), fluorosulfonic acid ion (FSO ₃ ⁻ ), toluenesulfonic acid ion, trinitrobenzenesulfonic acid anion, trinitrotoluenesulfonic acid Onium salts with other anions, such as anions, can also be used.

Among such onium salts, a photoacid generator particularly effective as the component (C) is an aromatic onium salt. For example, JP-A-50-151996 and JP-A-5-151996
Aromatic halonium salts described in JP-A-158680, JP-A-50-151997, JP-A-52-3
No. 0899, JP-A-56-55420, JP-A-55-125105 and the like, and VA-group aromatic onium salt as described in JP-A-50-158698 and the like. JP-A-56-8428
JP, JP-A-56-149402, JP-A-57-149402
Preferred are oxosulfoxonium salts described in JP-A-192429 and the like, aromatic diazonium salts described in JP-A-49-17040 and the like, and thiobrillium salts described in U.S. Pat. No. 4,139,655. . Further, an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator and the like can also be mentioned.

Commercially available photoacid generators that can be suitably used as component (C) include UVI-6950,
UVI-6970, UVI-6974, UVI-699
0 (all manufactured by Union Carbide Co., Ltd.), Adeka Optomer SP-150, SP-151, SP-170, SP-
172 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacur
e 261 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI
-2639, CI-2064 (Nippon Soda Co., Ltd.)
Manufactured), CD-1010, CD-1011, CD-101
2, DTS-102, DTS
-103, NAT-103, NDS-103, TPS-
103, MDS-103, MPI-103, BBI-1
03 (all manufactured by Midori Kagaku Co., Ltd.), PCI-061
T, PCI-062T, PCI-020T, PCI-0
22T (all manufactured by Nippon Kayaku Co., Ltd.) and the like. Among them, UVI-6970, UVI-6
974, Adeka Optomer SP-170, SP-17
2, CD-1012 and MPI-103 are particularly preferable because a resin composition containing them can exhibit high photocuring sensitivity.

The photoacid generators described above can be used alone or in combination of two or more to form the component (C).

The content ratio of the component (C) in the resin composition of the present invention is 0.1% when the total of the components (A), (B), (C) and (D) is 100 parts by weight. 1
The amount is preferably from 10 to 10 parts by weight, more preferably from 0.2 to 6 parts by weight, particularly preferably from 0.3 to 4 parts by weight. When the content ratio of the component (C) is too small,
The photocurability of the obtained resin composition is reduced, and a three-dimensional article having sufficient mechanical strength cannot be formed. On the other hand, when the content ratio is excessively large, when the obtained resin composition is subjected to an optical three-dimensional molding method, it is not possible to obtain an appropriate light transmittance, and it is difficult to control the curing depth, so that There is a tendency that the modeling accuracy of the three-dimensional object to be formed is reduced.

<Component (D)> The resin composition of the present invention comprises:
As the component (D), elastomer particles having a number average particle size of 10 to 700 nm may be contained. The resin composition containing the component (D) has improved impact resistance as compared with a resin composition not containing the component, and can provide a cured product having high toughness. As the elastomer particles constituting the component (D), for example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α- Olefin copolymer, ethylene / α-olefin / polyene copolymer, acrylic rubber, butadiene / (meth) acrylate copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer, etc. Particles may be mentioned.

The elastomer forming the elastomer particles may have a crosslinked structure. Crosslinking of the elastomer can be carried out by a conventionally known method. Examples of the crosslinking agent used for crosslinking the elastomer include divinylbenzene, ethylene glycol di (meth)
Examples include acrylate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane triacrylate, allyl methacrylate and the like.

The elastomer particles constituting the component (D) are core / shell particles obtained by coating the surface of particles (core particles) made of the above elastomer with polymethyl methacrylate, a copolymer of methyl methacrylate / glycidyl methacrylate, or the like. It may be.

The elastomer particles which can be suitably used as the component (D) include, for example, polybutadiene, polyisoprene, styrene / butadiene copolymer,
Styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / α-olefin / polyene copolymer, acrylic rubber, butadiene / (meth) acrylate copolymer, Elastomer particles having a styrene / butadiene block copolymer, a styrene / isoprene block copolymer or the like as a base component can be exemplified.

The core / shell type elastomer particles which can be suitably used as the component (D) include polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer. Polymer, ethylene / α-olefin copolymer, ethylene / α-olefin / polyene copolymer, acrylic rubber, butadiene / (meth) acrylate copolymer, styrene / butadiene block copolymer, styrene / isoprene Elastomer particles in which a coating layer (shell) made of polymethyl methacrylate is formed on the surface of core particles obtained by partially cross-linking a block copolymer or the like; methyl methacrylate / glycidyl methacrylate copolymer on the surface of the core particles Forming a shell layer made of Examples of the obtained elastomer particles can be given. In the core / shell type elastomer particles, the ratio (t / R) of the shell thickness (t) to the radius (R) of the core particle is usually 1/1000 to 100/100.
2/1, preferably 1/200 to 1/1.

Among these elastomer particles, polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, butadiene /
A coating layer (shell) composed of polymethyl methacrylate is formed on the surface of a core particle composed of a partially crosslinked product such as a (meth) acrylate copolymer, a styrene / butadiene block copolymer, and a styrene / isoprene block copolymer. Elastomer particles; methyl methacrylate /
Elastomer particles having a coating layer (shell) made of a glycidyl methacrylate copolymer are particularly preferred.

These elastomer particles can be produced by a conventionally known method such as an emulsion polymerization method. Emulsion polymerization methods for obtaining elastomer particles include a method in which all of the monomer components are charged at once and a polymerization is performed, and a method in which a part of the monomer components is polymerized and the remaining portion is added continuously or intermittently. A method of continuously adding a monomer component from the beginning of polymerization, a method of using seed particles, and the like can be employed.

The number average particle diameter of the elastomer particles constituting the component (D) is from 10 to 700 nm, preferably from 3 to 700 nm.
0 to 300 nm. When the number average particle diameter of the elastomer particles is less than 10 nm, a three-dimensional article formed by the obtained resin composition may not have sufficient impact resistance, and the obtained resin composition May increase, and may affect the production efficiency and the modeling accuracy of the three-dimensional object. On the other hand, when the number average particle diameter of the elastomer particles exceeds 700 nm, the surface smoothness of a three-dimensional object formed by the obtained resin composition tends to be impaired, or the molding accuracy tends to be reduced.

Commercially available core / shell type elastomer particles which can be suitably used as the component (D) include, for example, Reginas Bond RKB (Reginas Chemical Co., Ltd.)
And Techno MBS-61 and MBS-69 (all manufactured by Techno Polymer Co., Ltd.).

These elastomer particles can be used alone or in combination of two or more to constitute the component (D).

The content of the component (D) in the resin composition of the present invention is from 0 to 100 parts by weight when the total of the components (A), (B), (C) and (D) is 100 parts by weight. 3
It is preferably 5 parts by weight, more preferably 0 to 3 parts by weight.
0 parts by weight, particularly preferably 0 to 20 parts by weight.
If the content ratio of the component (D) is too large, the modeling accuracy of the finally obtained three-dimensionally shaped article tends to decrease.

<Water> The resin composition according to the first aspect is characterized in that the water content at the time of preparation is 0.3 to 1.5% by weight. The water content is 0.
It is characterized by being prepared by adding water so as to be 3 to 1.5% by weight. The water constituting the resin composition of the present invention (hereinafter, also referred to as component (E)) is not particularly limited as long as it does not contain impurities that inhibit three-dimensional modeling, and is ion-exchanged water or distilled water. Is preferred.

According to the resin composition having a water content in the range of 0.3 to 1.5% by weight at the time of preparation, even when the resin composition is stored and used for a long period of time under the use environment, the water content can be reduced. Does not change significantly. As a result, the shaping characteristics depending on the water content of the resin composition (for example,
The curing depth when receiving a certain amount of irradiation energy) does not substantially change, and therefore, without changing the molding conditions,
A three-dimensional object having the expected performance can be stably formed. Further, by adding water at the time of preparation, a defoaming treatment described later can be easily performed.

The water content at the time of preparing the resin composition of the present invention is usually 0.3 to 1.5% by weight, preferably 0.5 to 1.0% by weight.

When the water content at the time of preparation is less than 0.3% by weight, when stored and used for a long period of time in a normal use environment, especially in a high humidity environment, an equilibrium water content over time may be reached. As the moisture content increases, the curing depth greatly decreases. When the molding is performed under the optimal conditions in the initial stage (the moisture content of the resin composition <0.3% by weight), peeling between the cured layers occurs, and the intended three-dimensional shape is obtained. I can't shape things.

In this case, water is added to the resin composition (water content <equilibrium water content) accommodated in a container attached to a molding device at the start of molding during the storage and use period of the resin composition. However, it is extremely difficult and impractical to determine an appropriate addition amount in consideration of environmental conditions (humidity) and the like. Further, it is difficult to make water uniformly contained in the resin composition contained in the container.

On the other hand, if the water content at the time of preparation exceeds 1.5% by weight, the hardening depth increases as the water content decreases over time to reach the equilibrium water content when stored and used for a long period of time. If it is increased and the molding is performed under the optimal conditions in the initial stage (water content of the resin composition> 1.5% by weight), the molding accuracy in the laminating direction is reduced, and the desired three-dimensional object cannot be formed.

The water content at the time of preparing the resin composition of the present invention is in the range of 0.3 to 1.5% by weight,
In addition, a standard use environment of a temperature of 23 ° C. and a relative humidity of 5
It is preferably 0.5 to 1.5 times the equilibrium water content at 0%, and most preferably the same as the equilibrium water content. This makes it possible to reduce the change over time of the water content that reaches the equilibrium water content, and does not affect the modeling characteristics.

<Other Components> The photocurable resin composition of the present invention contains the above components (A), (B), (C), and so forth as long as the effects of the present invention are not impaired.
Components other than the component (D) and the component (E) can be contained as necessary.

The photocurable resin composition of the present invention has a photocurability of the resin composition, a shape stability (performance for suppressing temporal deformation) and a shape stability (mechanical stability) of a three-dimensional object obtained by stereolithography. A polyol can be contained in order to exhibit the property of suppressing the characteristic change over time. The polyol to be used preferably has two or more hydroxyl groups in one molecule, more preferably 2 to 6 hydroxyl groups in one molecule. When a polyol having less than 2 hydroxyl groups in one molecule is used, the effect of improving photocurability is not sufficient, and the mechanical properties, particularly elastic modulus, of the obtained three-dimensional object tend to decrease. . On the other hand, when more than 6 polyols are contained in one molecule, there is a tendency that elongation of the obtained three-dimensionally shaped product is reduced and there is a tendency that a problem is caused in moisture resistance.

Examples of such polyols include polyether polyols, polycaprolactone polyols,
Examples thereof include polyester polyols obtained by modification with a polyester comprising a basic acid and a diol.

Among the above polyols, polyether polyols are preferred. For example, trimethylolpropane,
Polyether obtained by modifying a polyhydric alcohol having a valency of 3 or more such as glycerin, pentaerythritol, sorbitol, sucrose, and quadrol with a cyclic ether compound such as ethylene oxide (EO), propylene oxide (PO), butylene oxide, and tetrahydrofuran. Polyols can be mentioned. Specifically, EO-modified trimethylolpropane, PO-modified trimethylolpropane, tetrahydrofuran-modified trimethylolpropane, EO-modified glycerin, PO-modified glycerin, tetrahydrofuran-modified glycerin, EO-modified pentaerythritol, PO-modified pentaerythritol, tetrahydrofuran-modified pentaerythritol, EO-modified sorbitol, PO-modified sorbitol, EO-modified sucrose, PO-modified sucrose, EO-modified sucrose, EO
Examples thereof include modified quadol, polyoxyethylene diol, polyoxypropylene diol, polyoxytetramethylene diol, polyoxybutylene diol, and polyoxybutylene-oxyethylene copolymer diol. Of these, EO-modified trimethylolpropane, PO-modified trimethylolpropane, PO-modified glycerin, and PO-modified sorbitol are preferred.

Commercially available polyether polyols which can be used include Sanix TP-400, Sanix GP-600, and Sanix GP-100.
0, Sanix SP-750, Sanix GP-2
50, Sannics GP-400, Sannics GP-
600 (manufactured by Sanyo Chemical Co., Ltd.), TMP-3Gly
col, PNT-4Glycol, EDA-P-4, E
DA-P-8 (all manufactured by Nippon Emulsifier Co., Ltd.), G-30
0, G-400, G-700, T-400, EDP-4
50, SP-600 and SC-800 (all manufactured by Asahi Denka Kogyo KK).

Specific examples of the polycaprolactone polyol include caprolactone-modified trimethylolpropane, caprolactone-modified glycerin, caprolactone-modified pentaerythritol, caprolactone-modified sorbitol, and the like.

Commercially available polycaprolactone polyols include TONE0301, TONE0305, TON
E0310 (above, Union Carbide) and commercially available polyester polyols include Plaxel 303,
Praxel 305 and Praxel 308 (all from Daicel Chemical Industries, Ltd.) and the like.

The above-mentioned polyols can be used alone or in combination of two or more.

The molecular weight of the polyol used is from 100 to
It is preferably 50,000, more preferably 1
60 to 20,000. If a polyol having an excessively low molecular weight is used, it may be difficult to obtain a three-dimensional product having shape stability and physical property stability depending on the obtained resin composition. On the other hand, when a polyol having an excessively high molecular weight is used, the viscosity of the obtained resin composition becomes excessively high, and the elastic modulus of the three-dimensional object obtained by stereolithography may decrease.

In the resin composition of the present invention, an ethylenically unsaturated monomer which is a radically polymerizable compound can be used in combination to improve the mechanical strength of the obtained molded article and to shorten the molding time. The ethylenically unsaturated monomer is a compound having an ethylenically unsaturated bond (C = C) in a molecule, a monofunctional monomer having one ethylenically unsaturated bond in one molecule, and a compound having two ethylenically unsaturated bonds in one molecule. Examples include polyfunctional monomers having at least two ethylenically unsaturated bonds.

Examples of the monofunctional monomer having one ethylenically unsaturated bonding group in one molecule include acrylamide, (meth) acryloylmorpholine, 7-amino-
3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamidotetrachlorophenyl (meth) acrylate, 2-tetrac B phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-
Tetrabromophenoxyethyl (meth) acrylate,
2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth)
Acrylate, butoxyethyl (meth) acrylate,
Pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylenediglycol (meth)
Acrylates and compounds represented by the following formulas (28) to (30) can be exemplified, and these can be used alone or in combination of two or more.

[0119]

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[0120]

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[0121]

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[In the formulas (28) to (30), R ¹⁶ represents a hydrogen atom or a methyl group, and R ¹⁷ has 2 to 2 carbon atoms.
6, preferably an alkylene group having 2 to 4 carbon atoms, R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms, and R ¹⁹ has 2 to 8 carbon atoms, preferably 2 carbon atoms. Represents an alkylene group of 1 to 5; e is an integer of 0 to 12, preferably 1 to 8, and f is 1 to 8, preferably 1 to 8.
4 is an integer. Of these monofunctional monomers, preferred are isobornyl (meth) acrylate, lauryl (meth) acrylate, and phenoxyethyl (meth) acrylate, but are not limited thereto.

Commercial products of these monofunctional monomers include, for example, Aronix M-101, M-102, M-
111, M-113, M-117, M-152, TO-
1210 (Toagosei Co., Ltd.), Kayarad TC-
110S, R-564, R-128H (Nippon Kayaku Co., Ltd.), Biscoat 192, Biscoat 220, Biscoat 2311HP, Biscoat 2000, Biscoat 2100, Biscoat 2150, Biscoat 8F, Biscoat 17F (Osaka Organic Chemical Industry) Co., Ltd.).

Examples of the polyfunctional monomer having two or more ethylenically unsaturated bonding groups in one molecule include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, and the like. Tetraethylene glycol di (meth)
Acrylate, tricyclodecanediyl dimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxy Ethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, Neopentyl glycol di (meth)
Acrylate, both-terminal (meth) acrylic acid adduct of bisphenol A diglycidyl ether, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropante La (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, Examples include EO-modified bisphenol F di (meth) acrylate and (meth) acrylate of phenol novolak polyglycidyl ether, and these can be used alone or in combination of two or more.

Among these polyfunctional monomers, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO
Modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipenta Erythritol penta (meth) acrylate and ditrimethylolpropanetetra (meth) acrylate are preferred,
It is not limited to these examples.

Commercial products of these polyfunctional monomers include, for example, SA1002 (above, Mitsubishi Chemical Corporation), Biscoat 195, Biscoat 230, Biscoat 26
0, Bis coat 215, Bis coat 310, Bis coat 214HP, Bis coat 295, Bis coat 300, Bis coat 360, Bis coat GPT, Bis coat 40
0, Viscoat 700, Viscoat 540, Viscoat 3000, Viscoat 3700 (above, Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPG
DA, TPGDA, MANDA, R-551, R-71
2, R-604, R-684, PET-30, GPO-
303, TMPTA, THE-330, DPHA, DP
HA-2H, DPHA-2C, DPHA-2I, D-3
10, D-330, DPCA-20, DPCA-30,
DPCA-60, DPCA-120, DN-0075,
DN-2475, T-1420, T-2020, T-2
040, TPA-320, TPA-330, RP-10
40, RP-2040, R-011, R-300, R-
205 (Nippon Kayaku Co., Ltd.), Aronix M-2
10, M-220, M-233, M-240, M-21
5, M-305, M-309, M-310, M-31
5, M-325, M-400, M-6200, M-64
00 (Toagosei Co., Ltd.), Light Acrylate B
P-4EA, BP-4PA, BP-2EA, BP-2P
A, DCP-A (Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, TEICA, BR-42M, G
X-8345 (above, Daiichi Kogyo Seiyaku Co., Ltd.), ASF-
400 (Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1
506, SP-1507, SP-1509, VR-7
7, SP-4010, SP-4060 (shown by Showa Polymer Co., Ltd.), NK Ester A-BPE-4 (both manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like. it can.

As the polyfunctional monomer, the tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds and hexa (meth) acrylate compounds exemplified above are preferable. Particularly preferred are methylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and ditrimethylolpropanetetra (meth) acrylate. It is not limited to these examples.

When the ethylenically unsaturated monomer is contained in the resin composition, a radical photopolymerization initiator is usually added to initiate the radical polymerization reaction. A radical photopolymerization initiator is a compound that is decomposed by receiving energy rays such as light and initiates a radical polymerization reaction of an ethylenically unsaturated monomer by generated free radicals. Can be used.

As the radical photopolymerization initiator, an ordinary radical photopolymerization initiator can be used. For example, acetophenone, acetophenone benzyl ketal,
Anthraquinone, 1- (4-isopropylphenyl)-
2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone,
4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthones, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Propan-2-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-
Tri-methylbentylphosphine oxide, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene,
Benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3-methylacetophenone, 3,3 ', 4,4'-
Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and a combination of BTTB with xanthene, thioxanthene, coumarin, ketocoumarin and other dye sensitizers. Among them, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- On and the like are particularly preferred, but are not limited to these examples.

The photocurable resin composition of the present invention may contain a photosensitizer (polymerization accelerator), a reactive diluent and the like as long as the effects of the present invention are not impaired. Examples of the photosensitizer include amine compounds such as triethanolamine, methyldiethanolamine, triethylamine, and diethylamine; thioxanthone, thioxanthone derivatives, anthraquinone, anthraquinone derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, benzophenone, and benzoin. Photosensitizers such as isopropyl ether can be used. The reactive diluent is preferably a cationic polymerizable substance copolymerizable with the component (A) and the component (B), which lowers the solution viscosity of the obtained resin composition.

The photocurable resin composition of the present invention includes
Various additives may be contained as long as the effects of the present invention are not impaired. Examples of such additives include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene-styrene block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, and fluorine-based resins. Polymers or oligomers such as oligomers, silicone-based oligomers and polysulfide-based oligomers; phenothiazine, 2,6-di-
polymerization inhibitors such as t-butyl-4-methylphenol; polymerization initiation aids; antioxidants; leveling agents; wetting improvers; surfactants; plasticizers; ultraviolet absorbers; silane coupling agents; Pigments and dyes.

<Method for Preparing Resin Composition> The photocurable resin composition of the present invention comprises the components (A), (B),
It can be prepared by uniformly mixing the component (C) and the component (E) (water), and if necessary, the component (D) and various optional components.

<Defoaming Treatment> In preparing the photocurable resin composition of the present invention, it is preferable to remove foreign substances by filtration after mixing the components and to further perform defoaming treatment. By performing the defoaming treatment, it is possible to prevent the remaining of the air bubbles that cause a reduction in modeling accuracy and a poor appearance in a cured product (three-dimensional shape) of the obtained resin composition. As a method of the defoaming treatment, a method of forcibly removing air bubbles in the resin composition by reducing the pressure, a method of reducing the viscosity by heating the resin composition, and reducing the air bubbles collected on the surface of the resin composition There is no particular limitation on the method of removal.

<Viscosity of Resin Composition> The viscosity (25 ° C.) of the photocurable resin composition of the present invention is 50 to 2,000 mPa · s.
s, more preferably 70 to 1.5.
00 mPa · s.

<Optical three-dimensional molding method> The photocurable resin composition of the present invention is suitably used as a photocurable liquid resin composition in an optical three-dimensional molding method. That is, the resin composition of the present invention, visible light, ultraviolet light, by repeating the process of selectively irradiating light such as infrared light to form a cured resin layer, the cured resin layer integrally A three-dimensional object having a desired shape can be manufactured by being laminated.

The means for selectively irradiating light to the photocurable resin composition of the present invention is not particularly limited, and various means can be employed. For example,
Means for irradiating the composition while scanning laser light or convergent light obtained using a lens, a mirror, or the like; using a mask having a light transmitting portion of a predetermined pattern, forming non-convergent light through this mask Means for irradiating an object, means for using a light guide member formed by bundling a large number of optical fibers, and means for irradiating light to the composition through optical fibers corresponding to a predetermined pattern in the light guide member, and the like can be adopted. . In the means using a mask, a mask that electro-optically forms a mask image including a light-transmitting region and a light-impermeable region according to a specified pattern according to the same principle as that of the liquid crystal display device is used. Can also. In the above, when the target three-dimensional object has a fine partial shape or when high dimensional accuracy is required, the spot diameter is used as a means for selectively irradiating the composition with light. It is preferable to employ means for scanning with a laser beam having a small value.

The light irradiation surface (for example, the scanning plane of the convergent light) of the resin composition contained in the container is the liquid surface of the resin composition and the contact surface of the transparent container with the container wall. Any one may be used. When the liquid surface of the resin composition or the contact surface with the container wall is used as the light irradiation surface, the light can be irradiated directly from the outside of the container or through the container wall.

In the above-mentioned optical three-dimensional molding method, usually, after a specific portion of the resin composition is cured, a light irradiation position (irradiation surface) is continuously or stepwise changed from a cured portion to an uncured portion. By moving the hardened parts, the hardened portions are laminated to form a desired three-dimensional shape. Here, the irradiation position can be moved by various methods, for example, by moving any one of a light source, a container for storing the resin composition, and a cured portion of the resin composition, or additionally supplying the resin composition to the container. And the like.

[0139] A typical example of the optical three-dimensional molding method will be described. A supporting stage provided so as to be able to move up and down in a container is lowered (settled) by a very small amount from the liquid surface of the resin composition. The thin layer (1) is formed by supplying the resin composition thereon. Next, the thin layer (1) is selectively irradiated with light to form a solid cured resin layer (1). Next, a resin composition is supplied on the cured resin layer (1) to form a thin layer (2), and the thin layer (2) is selectively irradiated with light, whereby the cured resin layer is formed. (1) A new cured resin layer (2) is formed thereon so as to be continuously and integrally laminated thereon. This process is repeated a predetermined number of times while changing or not changing the pattern to be irradiated with light, whereby a three-dimensional object formed by integrally laminating a plurality of cured resin layers (n) is formed.

The thus obtained three-dimensionally shaped object is taken out of the container, and after removing the resin composition remaining on the surface thereof, washing is performed if necessary. Here, as the cleaning agent, alcohol-based organic solvents represented by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents represented by acetone, ethyl acetate, and methyl ethyl ketone; aliphatics represented by terpenes System organic solvent; low-viscosity thermosetting resin and photocurable resin.

In the case of producing a three-dimensional object having good surface smoothness, it is preferable to wash using the above-mentioned thermosetting resin or photo-setting resin. Depending on the type of the curable resin, post-curing by heat irradiation or light irradiation needs to be performed. In addition,
The post cure not only cures the resin on the surface but also cures the unreacted resin composition that may remain inside the three-dimensional object. Is preferably performed.

Further, in order to improve the surface strength and heat resistance of the three-dimensional object, it is preferable to use a thermosetting or photocurable hard coat material after performing a cleaning treatment. As such a hard coat material, an organic coat material made of an acrylic resin, an epoxy resin, a silicone resin, or the like, or an inorganic hard coat can be used. These hard coat materials can be used alone or in combination.
It can be used in combination of more than one species.

[0143]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “%” and “parts” mean “% by weight” and “parts by weight” unless otherwise specified.

Example 1 According to the formulation shown in Table 1 below, 1,4-bis [(3-ethyl-3-oxetanyl) was added as a component (A) in a separable flask having a capacity of 10 liters equipped with a stirring blade. Methoxy) methyl] benzene 300
0 g (30 parts), as component (B), 4000 g (40 parts) of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1.6
-Hexanediol diglycidyl ether 1000 g
(10 parts), epoxy-modified polybutadiene “Eporide PB3600” (manufactured by Daicel Chemical Industries, Ltd.) 1000
g (10 parts), triallylsulfonium hexafluoroantimonate “UVI-6974” as the component (C)
100 g (1 part) (manufactured by Union Carbide), (D)
Core / shell type elastomer particles “Regina's Bond RKB” in which a coating layer (shell) made of a methyl methacrylate / glycidyl methacrylate copolymer is formed on the surface of a core particle made of a partially crosslinked styrene / butadiene copolymer as a component. (Reginasu Kasei Co., Ltd.
900 g (9 parts) of a number average particle size (200 nm) was charged, and the system was stirred at 60 ° C. for 3 hours. After allowing this system to cool to 25 ° C., 60 g (0.6 g) of distilled water was used as the component (E).
And the mixture was stirred at 25 ° C. for 2 hours. After the thus obtained mixture was subjected to a filtration treatment, the mixture was subjected to a defoaming treatment under reduced pressure to prepare a photocurable resin composition of the present invention.

The water content of the photocurable resin composition thus obtained immediately after preparation was measured by the Karl Fischer method to find that it was 0.68% (temperature: 23
1.0% relative to the equilibrium water content at 50 ° C and 50% relative humidity.
). The measurement of the water content by the Karl Fischer method was carried out using a Karl Fischer-type trace moisture analyzer "AQ-7" (manufactured by Hiranuma Sangyo Co., Ltd.), using "Aqualight RS" (manufactured by the company) as an electrolyte. The test was performed using "Aqualight CN" (manufactured by the company) as the liquid.

Example 2 According to the recipe shown in Table 1 below, the amount of component (A) charged was changed to 5000 g (50 parts), and component (B) 3,4-epoxycyclohexylmethyl-3 ′, The charge of 4′-epoxycyclohexanecarboxylate was changed to 2900 g (29 parts),
A photocurable resin composition of the present invention was prepared in the same manner as in Example 1 except that the component (D) was not charged. When the water content of the obtained photocurable resin composition immediately after preparation was measured by the Karl Fischer method, it was found to be 0.69%
Met.

Comparative Example 1 According to the recipe shown in Table 1 below, the amount of the component (C) charged was changed to 200 g (2 parts).
A comparative photocurable resin composition was prepared in the same manner as in Example 1 except that the charge amount of the component (D) was changed to 800 g (8 parts) and distilled water was not added. The water content of the resulting photocurable resin composition immediately after preparation was measured by the Karl Fischer method to find that it was 0.08% (temperature 2
0.1 at equilibrium water content at 3 ° C and 50% relative humidity.
(Corresponding to 1 time).

Comparative Example 2 A photocurable resin composition for comparison was prepared in the same manner as in Example 1 except that the amount of distilled water was changed to 300 g (3 parts) in accordance with the formulation shown in Table 1 below. Prepared. About the obtained photocurable resin composition,
The water content immediately after the preparation was measured by the Karl Fischer method and found to be 3.01% (corresponding to 4.6 times the equilibrium water content at a temperature of 23 ° C. and a relative humidity of 50%).

<Evaluation of Resin Composition> The curing depth of each of the resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was measured before and after the resin compositions were allowed to stand in a certain environment. In addition, for the three-dimensional object formed by the resin composition before and after standing, the interlayer adhesion and the modeling accuracy in the laminating direction were evaluated. The measuring method and the evaluation method are shown below.

The resin compositions according to Example 1 and Comparative Example 1 were left at a temperature of 23 ° C., a relative humidity of 50%, and a standing time of 60 days. In the resin composition according to Comparative Example 2, the temperature was 23 ° C., the relative humidity was 20%, and the standing time was 60 days.
In addition, as a container for storing the resin composition, an open container having a width of 32 cm, a depth of 43 cm, and a depth of 6.5 cm, which is attached to an optical shaping apparatus “Solid Creator SCS-1000HD” (manufactured by Sony Corporation) was used. The leaving of the resin composition was started from the day when the resin composition was prepared.

(1) Method of measuring curing depth: A He-Cd laser (wavelength: 325 nm) was mounted as a light source for irradiation.
Open container (32cm wide x 43cm deep x 6.5c deep)
m) equipped with a stereolithography machine "Solid Creator SCS"
-1000HD "(manufactured by Sony Corporation), and the laser spot diameter on the liquid surface (irradiation surface) of the resin composition contained in the open container was 100 µm, and the laser power was 1
0 mW, and the scanning speed shown in Table 1 below (200 mm / s in Examples 1 and 2 and Comparative Example 1, 160 mm in Comparative Example 2)
(mm / s), the liquid surface was irradiated with a laser beam to form a cured layer having a wedge-shaped cross section, and the thickness (cured depth) of the cured layer was measured.

(2) Evaluation method of interlayer adhesion of three-dimensional object: Stereolithography apparatus “Solid Creator SCS-100”
0HD "(manufactured by Sony Corporation) with a laser spot diameter of 100 μm, laser power of 10 mW, and a laser beam selectively irradiated to the resin composition at a scanning speed shown in Table 1 below to obtain a thickness. By repeating the process of forming a 100 μm cured resin layer, a three-dimensional object as shown in FIG. 1 was formed. Next, the obtained three-dimensionally shaped object was taken out of the optical shaping apparatus, the resin composition adhering to the outer surface was wiped off, and the excess resin composition was washed and removed with a terpene-based solvent. The side surface (laminated cross section) of this three-dimensional object was observed, and the case where no delamination was observed was evaluated as “○”, and the case where delamination was observed in all or part of the side surface was evaluated as “x”.

(3) Method for evaluating the modeling accuracy of a three-dimensional object:
Whether or not there is a surplus growth portion (a hardened portion not in the design data) that should not be hardened under the overhang portion (A, B in FIG. 1) of the three-dimensional object formed by the above (2). Observe that there is no excess growth part, the case where the lower surface of the overhang part has smoothness is `` ○ '', the case where the excess growth part exists and the smoothness of the lower surface of the overhang part is impaired. “×” was assigned.

The above measurement and evaluation were carried out under the same conditions as the environment in which the resin composition was left (temperature: 23 ° C., relative humidity: 5).
0%). The above results were compared before and after standing (0 days /
The results are shown in Table 1 below together with the water content of the resin composition at (60 days).

[0155]

[Table 1]

As is clear from the results shown in Table 1, the resin compositions according to Examples 1 and 2 showed a small difference in water content between before and after standing, and no change was observed in the curing depth. Further, according to the resin compositions according to Examples 1 and 2, even when the resin composition before and after standing was formed under the same irradiation conditions (scanning speed), a three-dimensional object excellent in interlayer adhesion and modeling accuracy was obtained. Could be shaped.

On the other hand, in the resin composition according to Comparative Example 1 in which the water content at the time of preparation was as small as 0.08% by weight, the difference (increase) in water content between before and after standing was large, and The depth decreased greatly from 150 μm to 125 μm. As a result, the three-dimensional article formed with the resin composition according to Comparative Example 1 after standing was poor in interlayer adhesion.

Also, the resin composition according to Comparative Example 2, which had an excessively large water content of 3.01% by weight at the time of preparation, had a large difference in water content between before and after standing (decrease amount) and a curing depth of 1%.
It increased greatly from 50 μm to 220 μm. As a result, the three-dimensional object formed with the resin composition according to Comparative Example 2 after standing was inferior in modeling accuracy in the laminating direction. When it is attempted to form a three-dimensional object having excellent interlayer adhesion and molding accuracy using the resin compositions according to Comparative Example 1 and Comparative Example 2, the irradiation conditions are changed each time molding is performed during the standing period. Have to do,
Such an operation can be said to be extremely complicated and impractical.

[0159]

According to the resin composition of the present invention, it can be used under normal use environment (temperature: 10 to 30 ° C., relative humidity: 20 to 80%).
Even when stored and used over a long period of time, the three-dimensional object having the expected performance (interlayer adhesion and molding accuracy) without substantially changing the molding characteristics (depth of cure) Depending on the molding conditions, the molding can be performed stably.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing the shape and dimensions of a three-dimensional object for evaluating interlayer adhesion and modeling accuracy, (1)
Is a plan view, and (2) is a side view.

[Explanation of symbols]

 A, B Overhang part

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/02 C08L 71/02 101/00 101/00 (72) Inventor Tetsuya Yamamura Tsukiji 2, Chuo-ku, Tokyo No. 11-24, JSR Co., Ltd. (72) Inventor Takashi Ukaji 2-11-24, Tsukiji, Chuo-ku, Tokyo F-term in JSR Co., Ltd. 4F213 AA44 WA25 WA86 WA87 WB01 WL02 WL12 WL24 WL25 WL92 WL95 4J002 AC02Y AC03Y AC06Y AC07Y AC08Y BB15Y BG03Y BG04Y BG05Y BN06Y BN12Y BN14Y BP01Y CD01W CD02W CD04W CD05W CD08W CD11W CD12W CD17W CD19W CH05X CP05X EA067 AEB EB117 AB EB117 EL056 EV 237 GA22 GA24 GA25 HA02

Claims (7)

[Claims] 1. A three-dimensionally shaped photocurable resin composition containing (A) an oxetane compound, (B) an epoxy compound, and (C) a photoacid generator, wherein the water content at the time of preparation is 0.3. 0.1 to 1.5% by weight. 2. A photocurable resin composition for three-dimensional modeling, comprising (A) an oxetane compound, (B) an epoxy compound, and (C) a photoacid generator, wherein the water content is 0.3 to 1. A photocurable resin composition, wherein water is added so as to be 5% by weight. 3. The photocurable resin composition according to claim 1, comprising (D) elastomer particles having a number average particle diameter of 10 to 700 nm. 4. An oxetane compound of 10 to 80 parts by weight, (B) an epoxy compound of 10 to 80 parts by weight,
(C) 0.1 to 10 parts by weight of a photoacid generator, (D) 0 to 35 parts by weight of elastomer particles having a number average particle diameter of 10 to 700 nm, component (A), component (B), The photocurable resin composition according to any one of claims 1 to 3, wherein the total of component (D) and component (D) is 100 parts by weight. 5. The method according to claim 1, wherein water is added so that the amount of water is 0.5 to 1.5 times the equilibrium water amount at a temperature of 23 ° C. and a relative humidity of 50%. The photocurable resin composition according to claim 2. 6. A component (A), a component (B), a component (C),
The photocurable resin composition according to any one of claims 3 to 5, which is obtained by defoaming a mixture of the component (D) and water. 7. A three-dimensional object obtained by photo-curing the photo-curable resin composition according to any one of claims 1 to 6.