JP2014196453A - Radiation-curable liquid resin composition for optical three-dimensional molding, and optically molded product obtained by photocuring the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-curable liquid resin composition for optical three-dimensional molding, from which an optically molded product excellent in toughness and heat resistance can be obtained.SOLUTION: A radiation-curable liquid resin composition for optical three-dimensional molding comprises (A) a compound having a carbonate group, two or more (meth)acryloyl groups and no urethane bond, (B) a cation polymerizable compound, (C) a photocationic polymerization initiator, (D) a radical polymerizable compound, and (E) a photoradical polymerization initiator. A preferred example of the (A) component is a compound having two or more carbonate groups and three or more (meth)acryloyl groups. A preferred structural moiety included in the chemical structure of the (A) component is, for example, a branched structure and an aromatic structure.

Description

  The present invention relates to a radiation curable liquid resin composition for optical three-dimensional modeling, and an optical modeling object obtained by photocuring the same.

By repeating the process of selectively irradiating a radiation-curable liquid substance (liquid resin composition) to form a cured resin layer, a three-dimensional shape formed by integrally laminating the cured resin layer is formed. An optical three-dimensional modeling method is known (see Patent Document 1). A typical example of this optical three-dimensional modeling method will be described as follows.
First, a cured resin layer having a predetermined pattern is formed by selectively irradiating the surface of the radiation curable liquid resin composition contained in the container with light such as an ultraviolet laser. Next, a radiation curable liquid resin composition for one layer is supplied onto the cured resin layer, and the liquid surface is selectively irradiated with light to thereby form a layer on the previously formed cured resin layer. A new cured resin layer is integrally laminated so as to be continuous. Then, by repeating the above process a predetermined number of times while changing or not changing the pattern irradiated with light, a three-dimensional object formed by integrally laminating a plurality of cured resin layers is formed.
This optical three-dimensional modeling method can be obtained easily and in a short time even if the target three-dimensional object has a complicated shape. This technology is extremely useful in the trial production process of new product development in the automobile and home appliance industries, and is becoming an indispensable means for shortening the development period and reducing costs.

Moreover, the radiation-curable liquid resin composition used for the optical three-dimensional modeling method containing the cationically polymerizable compound which has an oxetane structure is also disclosed (refer patent documents 2-5). However, when an optically shaped article is manufactured using a conventional liquid resin composition, the obtained optically shaped article has a drawback that it is brittle and easily broken when mechanical stress is applied. There is also a problem that heat resistance is insufficient. For this reason, it was difficult to obtain an optically shaped article excellent in both toughness and heat resistance.
Further, it is described that a dendrimer obtained by repeating Michael type addition and condensation reaction using ammonia, methyl acrylate and ethylenediamine as starting materials is used for a stereoscopic image forming apparatus (Patent Document 6). However, a specific radiation curable liquid resin composition containing dendrimer is not disclosed.

JP 60-247515 A JP-A-10-168165 JP 2000-302964 A JP 2002-60463 A JP 2009-173781 A Japanese Patent Laid-Open No. 2005-14386

  The objective of this invention is providing the radiation-curable liquid resin composition for optical three-dimensional model | molding which can obtain the optical model | molding thing excellent in toughness and heat resistance.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has optical three-dimensional modeling radiation containing a compound having a carbonate group and two or more (meth) acryloyl groups and having no urethane bond. It has been found that by using a curable liquid resin composition, an optically shaped article excellent in toughness and heat resistance can be obtained, and the present invention has been completed.
That is, the present invention provides the following (1) to (6).
(1) (A) a compound having a carbonate group and two or more (meth) acryloyl groups and not having a urethane bond, (B) a cationic polymerizable compound, (C) a photocationic polymerization initiator, ( D) Radiation-curable liquid resin composition for optical three-dimensional modeling containing a radically polymerizable compound and (E) a photoradical polymerization initiator.
(2) The radiation curable liquid resin composition according to (1), wherein the component (A) has two or more carbonate groups and three or more (meth) acryloyl groups.
(3) The radiation curable liquid resin composition according to (1), wherein the component (A) has a branched structure.
(4) The radiation curable liquid resin composition according to (1), wherein the component (A) has an aromatic structure.
(5) The component (A) is a compound obtained by introducing a (meth) acryloyl group into one or more compounds selected from the following [1] and [2]. The radiation-curable liquid resin composition described.
[1] A compound having three or more hydroxyl groups obtained by reacting a compound represented by the following formula (1) with a compound represented by the following formula (3) [2] represented by the following formula (2) Compound having three or more hydroxyl groups obtained by reacting a compound with a compound represented by the following formula (4) R ^1- [O— (C═O) —X] _n1 (1)
^{R 2 - [(C = O} ) -X] n2 (2)
R ^3- (OH) _m1 (3)
_{^{R 4 - {[R 5 -O-}} (C = O) -O] m2 -R 6 -OH} m3 (4)
[In the formulas (1) to (4), R ¹ and R ² are each independently a monovalent organic group having an aliphatic, alicyclic or aromatic structure, and R ³ and R ⁴ are respectively Independently, it is a monovalent organic group having an aliphatic, alicyclic or aromatic structure, and R ⁵ and R ⁶ are each independently an alkylene group. n1 and n2 are each independently an integer of 2 or more, m1 and m3 are each independently an integer of 3 or more, and m2 is an integer of 1 to 3. However, at least one of R ¹ and R ³ or R ² and R ⁴ constituting one compound has an aromatic structure. ]
(6) An optically shaped article obtained by irradiating the radiation-curable liquid resin composition according to any one of (1) to (5) with light.

  According to the radiation curable liquid resin composition for optical three-dimensional modeling of the present invention (hereinafter, also referred to as “the composition of the present invention”), an optical modeled product having excellent toughness and heat resistance can be obtained.

It is a figure which shows the optical modeling thing manufactured using the composition described in the Example and the comparative example.

Hereinafter, the present invention will be described in detail.
I. Radiation curable liquid resin composition for optical three-dimensional modeling The composition of the present invention contains components (A), (B), (C), (D) and (E) described below as essential components. Moreover, as an arbitrary component, the (F), (G), (H) component etc. which are mentioned later can further be contained.
Hereinafter, each component will be described.

[(A) component]
The component (A) used as a component of the composition of the present invention is a compound having a carbonate group and two or more (meth) acryloyl groups and having no urethane bond. Since the component (A) has a carbonate group, an optically shaped article having excellent toughness can be obtained, and since it has two or more (meth) acryloyl groups, an optically shaped article having excellent heat resistance can be obtained. it can.
Since the component (A) does not have a urethane bond, urethane (meth) acrylate does not correspond to the component (A). The composition for optical three-dimensional modeling of the present invention is a combined system of a radical polymerization system and a cationic polymerization system, and has a feature that can reduce distortion of an optical modeling object due to crosslinking shrinkage compared to the case of a radical polymerization system alone. Compared to the case of the polymerization system alone, there is an advantage that the curing rate is large. When urethane (meth) acrylate is blended in a combined system of radical polymerization and cationic polymerization, urethane (meth) acrylate tends to inhibit cationic polymerization.

When the urethane (meth) acrylate is blended as a component that is not the component (A), the content is preferably 10% by mass or less, more preferably 3% by mass or less, based on the total amount of the composition. It is especially preferable to set it as 0 mass%.
The component (A) preferably has 2 or more carbonate groups and 3 or more (meth) acryloyl groups. Since the component (A) has a plurality of carbonate groups, the mechanical characteristics of stereolithography can be improved.
The component (A) preferably has a branched structure. By having a branched structure, it is possible to obtain an optically shaped article having excellent toughness. Although the branched structure which (A) component has is not specifically limited, For example, it can obtain by making the compound which has a bivalent or more halogenated formyl group react with trivalent or more alcohol.
The component (A) preferably has an aromatic structure. By having an aromatic structure, an optically shaped object having excellent rigidity can be formed.

  The number average molecular weight of the component (A) is preferably 500 to 50000, and more preferably 2000 to 30000. When the number average molecular weight of the component (A) is in the range of 500 to 50,000, the viscosity of the composition is suitable for use in an optical modeling apparatus, and an optical molded article excellent in heat resistance and toughness can be obtained. . Here, the number average molecular weight is a polystyrene-equivalent number average molecular weight measured by a gel permeation chromatography method.

The component (A) can be obtained, for example, by introducing a (meth) acryloyl group into one or more compounds selected from the following [1] and [2].
[1] A compound having three or more hydroxyl groups obtained by reacting a compound represented by the following formula (1) with a compound represented by the following formula (3).
[2] A compound having three or more hydroxyl groups obtained by reacting a compound represented by the following formula (2) with a compound represented by the following formula (4).
R ^1- [O— (C═O) —X] _n1 (1)
^{R 2 - [(C = O} ) -X] n2 (2)
R ^3- (OH) _m1 (3)
_{^{R 4 - {[R 5 -O-}} (C = O) -O] m2 -R 6 -OH} m3 (4)

In formulas (1) to (4), R ¹ and R ² are each independently a monovalent organic group having an aliphatic, alicyclic or aromatic structure, and R ³ and R ⁴ are each independently Furthermore, it is a monovalent organic group having an aliphatic, alicyclic or aromatic structure, and R ⁵ and R ⁶ are each independently an alkylene group. n1 and n2 are each independently an integer of 2 or more, m1 is an integer of 3 or more, m3 is an integer of 2 or more, and m2 is an integer of 1 to 3. However, at least one of R ¹ and R ³ or R ² and R ⁴ constituting one compound has an aromatic structure.

Specific examples of the compound represented by the above formula (1) include a compound represented by the following formula (5).

Specific examples of the compound represented by the above formula (2) include a compound represented by the following formula (6).

Specific examples of the compound represented by the above formula (3) include a compound represented by the following formula (7).

［式（８）において、ｍ、ｎ、ｐ、ｑ、ｒは、式（８）で表される化合物の分子量が５００〜３０００となるよう適宜選択される。］ Specific examples of the compound represented by the above formula (4) include compounds represented by the following formula (8) or (9).

[In Formula (8), m, n, p, q, and r are appropriately selected such that the molecular weight of the compound represented by Formula (8) is 500 to 3000. ]

HO— [R ⁷ —O— (C═O) —O—] _s —R ⁷ —OH (9)
[In Formula (9), R ⁷ is an alkylene group or a divalent organic group having an alicyclic structure, and s is appropriately selected so that the molecular weight of the compound represented by Formula (9) is 500 to 3000. Selected. ]

  Specific examples of the compound represented by the above formula (9) include polybutadiene hydrogenated diol, 1,9-nonanediol 1,4-cyclohexanedimethanol carbonate diol, 1,4-cyclohexanedimethanol / 1,6-hexane. Diol, 1,4-cyclohexanedimethanol / 1,6-hexanediol, 1,4-cyclohexanedimethanol / 1,6-hexanediol, 1,6-hexanediol carbonate diol, 1,6-hexanediol carbonate diol, 1,6-hexanediol carbonate diol, 1,6-hexanediol / 1,5-pentanediol carbonate diol, 1,6-hexanediol / 1,5-pentanediol carbonate diol, 1,6-hexanediol / 1, 5-Pentangio Carbonate diol, 1,6 hexanediol carbonate diol, 1,5 pentanediol / 1,6 hexanediol = 5/5 carbonate diol, 1,4-butanediol / 1,6-hexanediol = 7/3 carbonate diol, 1,4-butanediol / 1,6-hexanediol = 9/1 carbonate diol, 2-methyl-1,3-propanediol / 1,4-butanediol = 5/5 carbonate diol, and the like.

Specific examples of the reaction product of the compound represented by the above formula (1) as the component (A) and the compound represented by the above formula (3) include the following formulas described in JP-A-2008-274239 ( The compound etc. which have the repeating structure represented by 10) can be mentioned.

Specific examples of the reaction product of the compound represented by the above formula (2) as the component (A) and the compound represented by the above formula (4) are represented by the following formulas (11) and (12). Examples include compounds having a structure.

In the above formulas (11) and (12), preferably R ³ is a divalent organic group having an aromatic structure, R ⁴ is a trivalent aliphatic group, and R ⁵ is independently selected. And R ⁶ is a trivalent organic group having an aromatic structure, and R ⁷ is independently a divalent organic group having an alkylene group or an alicyclic structure. n is appropriately selected so that the compound represented by the formula (11) or the formula (12) has a molecular weight suitable as the component (A).

  Since the component (A) having the structure represented by the formulas (10) to (12) has a branched structure in the repeating structure, the structure of a polymer having a large number of branched structures (also referred to as dendrimers). It can also be taken. By taking a polymer structure having a large number of branched structures, it is possible to obtain an optically shaped article that is more excellent in heat resistance and toughness.

  The synthesis of the component (A), which is a reaction product of the compound represented by the formula (1) and the compound represented by the formula (3), is performed by a method described in JP-A-2008-274239. be able to. Specifically, the compound represented by the formula (1), the compound represented by the formula (3), and a basic catalyst such as pyridine are dissolved in an organic solvent, and the reaction is performed at room temperature for 1 to 6 hours, for example Thus, a compound having three or more hydroxyl groups as a precursor of the component (A) is obtained. Subsequently, the compound which is a component (A) can be obtained by making the hydroxyl group of this precursor compound, for example, an anhydrous (meth) acrylic acid etc. react.

The synthesis of the component (A) that is a reaction product of the compound represented by the formula (2) and the compound represented by the formula (4) can be performed by, for example, the following method 1 or method 2.
[Method 1]
A method in which the compound represented by the formula (2), the compound represented by the formula (4), and a (meth) acryloyl ester having a hydroxyl group are mixed and reacted in the presence of a basic catalyst [Method 2].
A reaction product of the compound represented by the formula (2) and the compound represented by the formula (4) (a compound having three or more hydroxyl groups as a precursor of the component (A)) was synthesized, and the above formula was separately prepared. After synthesizing a reaction product of the compound represented by (2) and a (meth) acryloyl ester having a hydroxyl group (a compound for introducing a (meth) acryloyl group), the hydroxyl group which is a precursor of the component (A) is synthesized. Method of reacting compound having 3 or more and compound for introducing (meth) acryloyl group

  The content of the component (A) in the composition of the present invention is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and particularly preferably 5 to 20% by mass with respect to the total amount of the composition. . When the content of the component (A) is 1 to 40% by mass, the toughness of the optically shaped article can be further increased.

[Component (B)]
The component (B) used as a component of the composition of the present invention is a cationic polymerizable compound.
The component (B) is preferably a compound having one or two or more epoxy groups. In this specification, an epoxy group means a group in which an oxygen atom is bonded to two carbon atoms in the same molecule, such as a 3-membered ring such as a glycidyl group, a 4-membered ring such as an oxetanyl group, and a 5-membered ring. The group of is mentioned. It is preferable that the epoxy group which (B) component has is a glycidyl group or an oxetanyl group.

Specific examples of the cation polymerizable compound having a glycidyl group (hereinafter also referred to as component (B1)) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and brominated bisphenol A diglycidyl ether. , Brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxy Cyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 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, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxyl , Β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), di (3,4-ethylene glycol) Epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, di-2-ethylhexyl epoxycyclohexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ethers; ethylene glycol, propylene glycol, glycerin, etc. Polyether obtained by adding one or more alkylene oxides to the aliphatic polyhydric alcohol Polyglycidyl ethers of polyols; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide Mention may be made of ethers; glycidyl esters of higher fatty acids; epoxidized soybean oil; butyl epoxy stearate; octyl epoxy stearate; epoxidized linseed oil;
These can be used alone or in combination of two or more.

  Examples of commercially available (B1) components include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, and Celoxide. 2081, Celoxide 2083, Celoxide 2085, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide 401, Epolide 403 (above, manufactured by Daicel Chemical Industries), KRM-2100, KRM-2110 KRM-2199, KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2200, KRM-2720, KRM-2750 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Rapi-c re DVE-3, CHVE, PEPC (above, ISP) Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, Japan Epoxy Resin), POX, EHOX (above, Toagosei Co., Ltd.) , VECOMER 2010, 2020, 4010, 4020 (manufactured by Allied Signal).

  Specific examples of the cation polymerizable compound having an oxetanyl group (hereinafter also referred to as the component (B2)) include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (XDO), A compound having two or more oxetanyl groups such as di [2- (3-oxetanyl) butyl] ether (DOX), 3-ethyl-3- (phenoxymethyl) oxetane (POX), 3-ethyl-3-hydroxymethyl A compound having one oxetanyl group such as oxetane (OXA) can be given.

  Content of (B) component in the composition of this invention is 30-90 mass% with respect to the composition whole quantity, Preferably it is 40-80 mass%, More preferably, it is 50-75 mass%. When the content of the component (B) is 30 to 90% by mass, the mechanical and thermal characteristics of the optically shaped article are improved.

[Component (C)]
(C) component used as a component of the composition of this invention is a photocationic polymerization initiator. The component (C) serves as a photocationic polymerization initiator in the polymerization of the cationic polymerizable compound (component (B)).
Examples of the component (C) include diphenyl (phenylthiophenyl) sulfonium salts containing a structure represented by the following formula (3).

Specific examples of the component (C) include more specifically salts containing antimony atoms such as diphenyl (phenylthiophenyl) sulfonium hexafluoroantimonate, diphenyl (phenylthiophenyl) sulfonium hexafluorophosphate, diphenyl ( And salts containing no antimony atom, such as phenylthiophenyl) sulfonium tris (pentafluoroethyl) trifluorophosphate. Among these, a salt containing no antimony atom is preferable from the viewpoint of safety.
Examples of the commercially available component (C) include CPI-100A, CPI-101A, CPI-110A, CPI-200K (manufactured by San Apro).

  Content of (C) component in the composition of this invention is 0.1-15 mass% with respect to the composition whole quantity, Preferably it is 0.5-10 mass%, More preferably, it is 1-7 mass%. is there. When the content of the component (C) is less than 0.1% by mass, the radiation curability of the liquid resin composition is lowered, and it becomes difficult to form a three-dimensional object having sufficient mechanical strength. . On the other hand, when the content of the component (C) exceeds 15% by mass, when the liquid resin composition is subjected to an optical three-dimensional modeling method, an appropriate light transmittance cannot be obtained, and the curing depth is reduced. Control becomes difficult and the modeling accuracy of the obtained three-dimensional shaped object tends to be lowered.

[(D) component]
(D) component used as a component of the composition of this invention is a radically polymerizable compound. Specifically, it is a compound having an ethylenically unsaturated bond (C = C), a monofunctional monomer having one ethylenically unsaturated bond in one molecule, and two or more ethylenic in one molecule. Mention may be made of polyfunctional monomers having an unsaturated bond.
A monofunctional monomer and a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types, respectively. Further, at least one monofunctional monomer and at least one polyfunctional monomer may be used in combination.

  In the component (D), a polyfunctional monomer having three or more functional groups, that is, three or more ethylenically unsaturated bonds in one molecule is a ratio of 60% by mass or more, with the total amount of the component (D) being 100% by mass. It is preferable that it is contained. The content ratio of the trifunctional or higher polyfunctional monomer is more preferably 70% by mass or more, further preferably 80% by mass or more, and most preferably 100% by mass. When the content ratio is 60% by mass or more, the radiation curability of the obtained resin composition is further improved, and the three-dimensional product to be shaped tends not to be deformed with time.

  Specific examples of the monofunctional monomer as component (D) include, for example, acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, and isobornyl. Oxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene 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) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetra Bromophenoxyethyl (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 ( Data) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyl triethylene diglycol (meth) acrylate.

  Specific examples of the polyfunctional monomer as component (D) include, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. , Tricyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) ) Isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter also referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, pro Renoxide (hereinafter also referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, both end (meth) acrylic of bisphenol A diglycidyl ether Acid adduct, 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 Rate, dipentaerythritol monohydroxypenta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (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, EO-modified bisphenol F di (meth) acrylate, phenol novolak Examples thereof include (meth) acrylates of polyglycidyl ether.

  Among these, the tri (meth) acrylate compound, tetra (meth) acrylate compound, penta (meth) acrylate compound, hexa (meth) acrylate compound, and the like exemplified above corresponding to a polyfunctional monomer having three or more functions are contained. It is preferable. Among them, tris (acryloyloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate and dipentaerythritol monohydroxypenta (meth) acrylate are more preferred.

  As a commercial item of the monofunctional monomer which is (D) component, for example, Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, Toagosei) KAYARAD TC-110S, R-564, R-128H (manufactured by Nippon Kayaku Co., Ltd.), biscoat 192, biscoat 220, biscoat 2311HP, biscoat 2000, biscoat 2100, biscoat 2150, biscoat 8F, biscoat 17F ( As mentioned above, Osaka Organic Chemical Industry Co., Ltd.) can be mentioned.

  Commercially available products of the polyfunctional monomer (D) include, for example, SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, and biscoat 300. Biscoat 360, biscoat GPT, biscoat 400, biscoat 700, biscoat 540, biscoat 3000, biscoat 3700 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R -712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA- 0, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M-309, M-310, M-315, M-325, M-400, M-6200, M-6400 (manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (above, Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 (above, new Sakai Chemical Co., Ltd.), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above Showa Polymer Co., Ltd.), NK ester A-BPE-4 (above, Shin Nakamura Chemical Co., Ltd.).

  Content of (D) component in the composition of this invention is 1-50 mass% with respect to the composition whole quantity, Preferably it is 5-40 mass%, More preferably, it is 10-30 mass%. By adding the component (D), the radiation curability of the liquid resin composition is improved, and the three-dimensional object to be shaped tends not to be deformed with time.

[(E) component]
The component (E) used as a component of the composition of the present invention is a radical photopolymerization initiator. The component (E) is a compound that decomposes upon receiving radiation such as light and initiates the radical polymerization reaction of the component (E) by the generated radicals.
Specific examples of the component (E) include 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, thioxanthone compound, 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-methylpentylphosphine oxide, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl Ether, benzophenone, Michler ketone, 3-methylacetophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB), and BTTB and xanthene, thioxanthene, coumarin, ketocoumarin and other dye enhancements The combination with a sensitizer etc. can be mentioned.
Among these, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- ON is preferred.
Said radical photopolymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  Content of (E) component in the composition of this invention is 0.01-10 mass% with respect to the composition whole quantity, Preferably it is 0.1-5 mass%, More preferably, it is 1-4 mass%. is there. When the content of the component (E) is less than 0.01% by mass, the radical polymerization reaction rate (curing rate) of the liquid resin composition is lowered and time is required for modeling, or the resolution is reduced. Tend to. On the other hand, when the content of the component (E) exceeds 10% by mass, an excessive amount of the polymerization initiator deteriorates the curing characteristics of the liquid resin composition, or adversely affects the moisture resistance and heat resistance of the three-dimensional shape. May have an effect.

The composition of this invention can contain an elastomer particle as (F) component within the range which does not inhibit the effect of this invention.
Specific examples of the component (F) include polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer. Base components include polymers, ethylene / α-olefin / polyene copolymers, acrylic rubber, butadiene / (meth) acrylic acid ester copolymers, styrene / butadiene block copolymers, styrene / isoprene block copolymers, etc. An elastomer particle etc. can be mentioned.

Other specific examples of the component (F) include core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like. Here, the ratio of the core radius to the shell thickness (core radius / shell thickness) is usually 1/2 to 1000/1, preferably 1/1 to 200/1. For example, when the core radius is 350 nm and the shell thickness is 10 nm, the ratio of the core radius to the shell thickness is 35/1.
In the case of core / shell type particles, among the above-mentioned elastomer particles, polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, butadiene / (meth) acrylate copolymer, styrene / butadiene An elastomer particle coated with a methyl methacrylate polymer or an elastomer particle coated with a methyl methacrylate / glycidyl methacrylate copolymer on a core obtained by partially crosslinking a block copolymer, a styrene / isoprene block copolymer, or the like is preferable.

  Furthermore, the component (F) may have a crosslinked structure inside the particles, and can be crosslinked by a commonly used means. Examples of the crosslinking agent used in this case include divinylbenzene, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane triacrylate, allyl methacrylate, etc. Is mentioned.

  These elastomer particles can be produced by a commonly used method. Examples of the usually used method include an emulsion polymerization method. Examples of the emulsion polymerization method include, for example, a method in which all monomer components are charged and polymerized in a lump, a method in which a part of the monomer component is polymerized, and then the remainder is added continuously or intermittently. A method of continuously adding components from the beginning of polymerization, a method using seed particles, or the like can be employed.

The number average particle diameter of the elastomer particles obtained by these methods is preferably 10 to 1,000 nm, more preferably 10 to 700 nm. When the number average particle diameter is less than 10 nm, the impact resistance and fracture toughness of the resulting three-dimensional shaped product are lowered, and the viscosity of the resin liquid is increased, thereby affecting the productivity and modeling accuracy of the three-dimensional shaped product. The On the other hand, when the number average particle diameter exceeds 1,000 nm, a three-dimensional object having a sufficiently smooth surface cannot be obtained, or the modeling accuracy is lowered.
The number average particle diameter of the elastomer particles is measured as a number average particle diameter in terms of polystyrene particles based on the light scattering method or the dynamic light scattering method.

Examples of commercially available core / shell type elastomer particles as described above include Resin Bond RKB (manufactured by Resin Chemicals), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like. be able to.
These elastomer particles (F) can be used alone or in combination of two or more.

  The content of the component (F) in the composition of the present invention is preferably 1 to 35% by mass, more preferably 3 to 30% by mass, and particularly preferably 5 to 20% by mass with respect to the total amount of the composition. . When the content is less than 1% by mass, impact resistance and fracture toughness are lowered. On the other hand, when the content exceeds 35% by mass, the modeling accuracy of the obtained three-dimensional object tends to be lowered.

[(G) component]
The composition of this invention can contain the compound which has a phenolic hydroxyl group and / or a phosphite group as (G) component within the range which does not inhibit the effect of this invention.
(G) As a component, a well-known antioxidant etc. can be mentioned. Among these, a hindered phenol compound or a phosphorus compound is preferable. By adding the component (G), it is possible to effectively reduce the time-dependent coloring (yellowing) of the three-dimensional structure, and therefore, maintaining the high transparency of the three-dimensional structure for a long time after molding. Can do.

Specific examples of the component (G) include the following compounds. In addition, what was written together with the parenthesis after the following compound name is an example of a brand name.
Examples of hindered phenol compounds include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010), thiodiethylene-bis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1035FF), benzenepropanoic acid-3,5-bis (1,1-dimethylethyl) -4-hydroxy, ethylenebis (oxyethylene) bis [3- ( 5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245), octadecyl-3- (3,5-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076), 3,3 ′, 3 ″ , 5,5 ', 5 "-hexa-t-butyl- , A ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol (Irganox 1330), 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Irganox 3114), 4,6-bis (octylthiomethyl) -o-cresol (Irganox 1520L), 9-bis [2 -{3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (Sumilizer GA-80), 2,6-di-t-butyl-4-methylphenol (Sumilizer BHT) and the like.
In the above, Irganox is a registered trademark of Ciba Specialty Chemicals, and Sumilizer is a registered trademark of Sumitomo Chemical.

Examples of phosphorus compounds include tris (2,4-di-t-butylphenyl) phosphite (Irgafos 168) and bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester. Phosphorous acid (Irgafos38), 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propoxy] -2,4,8,10-tetra-tert-butylbenz [d, f] And [1,3,2] -dioxaphosphine (Sumilyzer GP).
In the above, Irgafos is a registered trademark of Ciba Specialty Chemicals, and Sumilizer is a registered trademark of Sumitomo Chemical.

  As described above, commercially available products of the hindered phenol (G) component include Irganox 1010, 1035FF, 245, 1076, 1330, 3114, 1520L, 3125 (manufactured by Ciba Specialty Chemicals), Sumizer BHT, GA- 80 (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytec Co., Ltd.) and the like.

  As described above, commercially available phosphorus-based (G) component Irgafos 168, 12, 38 (above, manufactured by Ciba Specialty Chemicals), ADK STAB 329K, PEP36, PEP-8 (above, Asahi Denka Kogyo Co., Ltd.) Product), Sandstab P-EPQ (manufactured by Clariant), Weston 618, 619G, Ultranox 626 (manufactured by General Electric), Sumizer GP (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Among the components (G) mentioned above, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], benzenepropanoic acid-3,5-bis (1,1- Dimethylethyl) -4-hydroxy, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], 4,6-bis (octylthiomethyl) -o-cresol Bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl)- Propoxy] -2,4,8,10-tetra-t-butylbenz [d, f] [1,3,2] -dioxaphosphine is long after forming the transparency of the three-dimensional shape Preferable in that it maintained over between. Among these, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is particularly preferable.

  The content of the component (G) in the composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 1 to 4% with respect to the total amount of the composition. % By mass. When the content of the component (G) is less than 0.01% by mass or exceeds 10% by mass, problems such as a decrease in the transparency of the optically shaped article occur with time, which is not preferable.

[(H) component]
The composition of this invention can contain water as (H) component within the range which does not inhibit the effect of this invention.
By adding water, the radiation curability of the liquid resin composition can be improved. In addition, since the mechanical properties of the cured product obtained by irradiating light to the liquid resin composition, particularly the elastic modulus, is improved, the temporal change in the shape and mechanical properties of the three-dimensional modeled product obtained by optical modeling is suppressed. be able to.
The content of water in the composition of the present invention is preferably 0.1 to 2% by mass, more preferably 0.2 to 1% by mass, based on the total amount of the composition.
When the water content is less than 0.1% by mass, the sensitivity of the resin tends to change with time, and it tends to be difficult to perform stable modeling. On the other hand, even when the content of water exceeds 2% by mass, the elastic modulus of the three-dimensional object obtained by optical modeling tends to decrease.

  Moreover, the radiation-curable liquid resin composition for optical modeling of the present invention may contain various additives as other optional components within a range not impairing the object and effects of the present invention. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; Plasticizers; UV absorbers; silane coupling agents; inorganic fillers; pigments; dyes and the like.

The composition of the present invention is charged with an appropriate amount of the above-mentioned essential components (A), (B), (C), (D) and (E) and other optional components as required, and usually 30 to It can be produced by stirring at a temperature of 70 ° C., preferably 50 to 60 ° C., usually for 1 to 6 hours, preferably for 1 to 2 hours.
The viscosity at 25 ° C. of the composition of the present invention is preferably 50 to 2,000 mPa · s, more preferably 70 to 1,500 mPa · s.

The composition of the present invention obtained as described above is suitably used as a radiation curable liquid resin composition in an optical three-dimensional modeling method. That is, for the radiation curable liquid resin composition of the present invention, an optical three-dimensional modeling method that selectively irradiates light such as visible light, ultraviolet light, and infrared light to supply energy necessary for curing, A three-dimensionally shaped object (optically shaped object) having a desired shape can be manufactured.
If the composition of this invention is used, the optical modeling thing excellent in toughness, heat resistance, and transparency can be obtained.

II. Stereolithography The stereolithography of the present invention can be obtained by irradiating the composition of the present invention with radiation such as light.
The means for selectively irradiating the composition of the present invention with light is not particularly limited, and various means can be employed. For example, a laser beam or means for irradiating the composition while scanning convergent light obtained using a lens, mirror, etc., and a mask having a light transmission part of a predetermined pattern are used, and non-convergence is performed through this mask. Use a means for irradiating the composition with light, a light guide member formed by bundling a large number of optical fibers, and a means for irradiating the composition with light via an optical fiber corresponding to a predetermined pattern in the light guide member. Can do.
In the means using a mask, a mask that electro-optically forms a mask image composed of a light transmission region and a light non-transmission region according to a predetermined pattern according to a principle similar to that of a liquid crystal display device is used. You can also.
When the target three-dimensional object has fine portions or high dimensional accuracy is required, a laser beam with a small spot diameter is scanned as a means for selectively irradiating the composition with light. It is preferable to adopt means.
In addition, the light irradiation surface (for example, the scanning plane of convergent light) in the resin composition housed in the container is either the liquid surface of the resin composition or the contact surface with the vessel wall of the translucent container. There may be. 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 modeling method, usually, after curing a specific part of the resin composition, the light irradiation position (irradiation surface) is moved continuously or stepwise from the already cured part to the uncured part. By doing so, the cured portion is laminated to obtain a desired three-dimensional shape.
Here, the irradiation position can be moved by various methods. For example, either the light source, the container for the resin composition, or the cured part of the resin composition is moved, or the resin composition is added to the container. The method of supply etc. can be mentioned.
A typical example of the optical three-dimensional modeling method will be described as follows.
First, the resin composition is supplied onto the support stage by lowering (sinking) a small amount of the support stage provided in the container so as to be movable up and down from the liquid level of the resin composition. ).
Next, the thin cured layer (1) is formed by selectively irradiating the thin layer (1) with light.
Next, the radiation curable liquid resin composition is supplied onto the cured resin layer (1) to form the thin layer (2), and the thin layer (2) is selectively irradiated with light, A new cured resin layer (2) is formed on the cured resin layer (1) so as to be continuously laminated integrally therewith.
A three-dimensional structure in which a plurality of cured resin layers (1, 2,... N) are integrally laminated by repeating this step a predetermined number of times with or without changing the pattern irradiated with light. A shaped object is formed.

The three-dimensionally shaped product thus obtained is taken out from the container, and after removing the unreacted resin composition remaining on the surface, the solid shaped product is washed as necessary. Here, as the cleaning agent, alcohol-based organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents typified by acetone, ethyl acetate, methyl ethyl ketone, etc .; aliphatics typified by terpenes Organic solvents; low viscosity thermosetting resins and radiation curable resins.
In addition, after washing | cleaning with a cleaning agent, you may post-cure by heat irradiation or light irradiation as needed. Post-cure can cure unreacted resin composition that may remain on the surface and inside of the three-dimensional object, and can suppress the stickiness of the surface of the object, and improve the initial strength of the object. Can be made.

  The stereolithography object of the present invention is excellent in toughness and heat resistance.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[Synthesis Example 1: Synthesis of component (A)]
A 500 ml three-necked eggplant flask was charged with 2.48 g (0.008 mol) of 1,1,1-tris (4-hydroxyphenyl) ethane (THE) and 2.24 g (0.028 mol) of pyridine as a base, and 160 ml Was dissolved in tetrahydrofuran (THF) to obtain a THE solution. While stirring the THE solution, a BABC solution in which 4.24 g (0.012 mol) of bisphenol A bischloroformate (BABC) was dissolved in 24 ml of THF was added dropwise over 1 hour and reacted for 1 hour. .
After completion of the reaction, the reaction solution was diluted with 160 ml of chloroform, and washed with chloroform using a Kiriyama funnel to separate the gel portion and the chloroform soluble portion. Concentrate the chloroform soluble part using an evaporator, and then perform reprecipitation purification by using chloroform as a good solvent and methanol as a poor solvent, followed by drying under reduced pressure to obtain a hydroxyl group consisting of white powder at a yield of 80%. 4.63 g of polymer having was obtained.

In a 100-ml eggplant flask, 2.50 g of the obtained polymer having a hydroxyl group was dissolved in 30 ml of pyridine, and 3.70 g (0.024 mol) of methacrylic anhydride was stirred under a nitrogen atmosphere at −5 ° C. Was slowly added dropwise and reacted at room temperature for 6 hours. After completion of the reaction, the reaction solution is subjected to reprecipitation purification by using methanol as a poor solvent twice and dried under reduced pressure, whereby a polymer comprising a white powder (a component having a repeating structure represented by the formula (10) ( A)) was obtained with a yield of 85%.
When the molecular weight and molecular weight distribution of this polymer were measured by gel permeation chromatography (GPC), the number average molecular weight Mn was 14000 in terms of polystyrene, and the molecular weight distribution Mw / Mn was 5.3.

[Synthesis Example 2: Synthesis of Component (A)]
In a three-necked eggplant flask having a volume of 500 ml, 12.18 g (0.06 mol) of o-phthalic acid chloride (OPC manufactured by Ihara Nikkei Chemical Industry) was dissolved in 270 ml of ethyl acetate to obtain an OPC solution. While stirring the OPC solution at 5.degree.-10.degree. C., 7.81 g (0.06 mol) of 2-hydroxyethyl methacrylate (HEMA) and 5.62 g (0.07 mol) of pyridine as a base in 30 ml of ethyl acetate. The HEMA solution obtained by dissolution was dropped over 1 hour and reacted for 2 hours.
Thereafter, 2.48 g (0.008 mol) of polycarbonate triol (PCTL: manufactured by Kuraray (CF-1000)) and 5.62 g (0.07 mol) of pyridine as a base were dissolved in 30 ml of ethyl acetate in this reaction solution. The obtained PCTL solution was added dropwise over 1 hour and allowed to react for 1 hour.
The reaction mother liquor was filtered, separated, dehydrated, and concentrated using an evaporator. Thereafter, reprecipitation purification was performed by using ethyl acetate as a good solvent and methanol as a poor solvent, followed by drying under reduced pressure to obtain a polymer composed of a viscous liquid at a yield of 60%.
When the molecular weight and molecular weight distribution of this polymer were measured by gel permeation chromatography (GPC), the number average molecular weight Mn was 2400 in terms of polystyrene, and the molecular weight distribution Mw / Mn was 2.2.

[Synthesis Example 3: Compound having three or more hydroxyl groups obtained by reacting the compound represented by the formula (2) and the compound represented by the formula (4), which is a precursor of the component (A) Synthesis]
In a 500 ml three-necked eggplant flask, 1.71 g (0.0084 mol) of p-phthalic acid chloride (TPC manufactured by Ihara Nikkei Chemical Industry) was dissolved in 100 ml of ethyl acetate to obtain a TPC solution. While stirring in this TPC solution, at 5 to 10 ° C., 2.40 g (0.0024 mol) of polycarbonate triol (PCTL) and 0.67 g (0.0084 mol) of pyridine as a base were dissolved in 100 ml of ethyl acetate. The obtained PCTL solution 1 was added dropwise over 1 hour and allowed to react for 1 hour.
Thereafter, 9.60 g (0.0096 mol) of polycarbonate triol (PCTL) and 0.78 g (0.0098 mol) of pyridine as a base were dissolved in 100 ml of ethyl acetate in PCTL solution 1 for 1 hour. The mixture was added dropwise and reacted for 1 hour to obtain a component (A) precursor having three or more hydroxyl groups.

[Synthesis Example 4: Synthesis of a compound for introducing a (meth) acryloyl group into the precursor of the component (A) obtained in Synthesis Example 3]
In a 200 ml three-necked eggplant flask, 4.87 g (0.0024 mol) of p-phthalic acid chloride (OPC) was dissolved in 50 ml of ethyl acetate to obtain an OPC solution. While stirring the OPC solution at 5.degree.-10.degree. C., 3.15 g (0.0242 mol) of 2-hydroxyethyl methacrylate (HEMA) and 1.94 g (0.0242 mol) of pyridine as a base in 50 ml of ethyl acetate. The HEMA solution obtained by dissolving was dropped over 1 hour and reacted for 1 hour to obtain a solution of a compound for introducing a (meth) acryloyl group.

[Synthesis Example 5: Synthesis of Component (A)]
To the precursor solution of component (A) obtained in Synthesis Example 3, the compound solution obtained in Synthesis Example 4 and 1.94 g (0.0242 mol) of pyridine were added dropwise over 30 minutes and reacted for 1 hour.
The reaction mother liquor was filtered, separated, dehydrated, and concentrated using an evaporator. Thereafter, reprecipitation purification was performed by using ethyl acetate as a good solvent and methanol as a poor solvent, followed by drying under reduced pressure to obtain a polymer (component (A)) composed of a viscous liquid in a yield of 44%.
When the molecular weight and molecular weight distribution of this polymer were measured by gel permeation chromatography (GPC), the number average molecular weight Mn was 7000 in terms of polystyrene, and the molecular weight distribution Mw / Mn was 1.7.

[Preparation of liquid resin composition]
The liquid resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared by charging each component in a stirring vessel according to the formulation shown in Table 1 and stirring at 60 ° C. for 3 hours. The unit of the numerical values in the formulation of Table 1 is parts by mass.

[Evaluation]
Using each of the liquid resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4, the cured film was evaluated for Young's modulus, film impact value, glass transition temperature (Tg), and color tone. The evaluation results are shown in Table 1.
The evaluation method is as follows.
[Young's modulus of cured film]
(1) Preparation of test piece The liquid resin composition was applied in a glass plate shape to a thickness of 200 μm, and a cured film was obtained by irradiating 1 J / cm ² using a metal halide lamp. Then, it was left still for 24 hours in a constant temperature and humidity room with a temperature of 23 ° C. and a humidity of 50%.
(2) Measurement A test piece having a size of 8 cm × 0.6 cm was cut out from the cured film thus prepared. The Young's modulus of the test piece was measured according to JIS K7127 using a tensile measurement tester AGS-50G manufactured by Shimadzu Corporation. At this time, the tensile speed was 1 mm / min, and the distance between marked lines was 2.5 cm (the gripping distance on both ends was 2.75 cm).

[Film impact value]
(1) Preparation of test piece A cured film was prepared under the same conditions as the preparation of a test piece of Young's modulus of the cured film.
(2) Measurement The test piece prepared in this manner was allowed to stand in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and then a test piece having a size of 10 cm × 10 cm was cut out. The film impact value was measured using a film impact tester manufactured by Yasuda Seiki Co., Ltd. The impact sphere was a 12 mm diameter plastic sphere.
[Glass transition temperature (Tg)]
Using a 15 mil applicator bar (corresponding to a coating thickness of about 200 μm), a radiation curable resin composition was applied onto a glass plate, and this was cured by irradiating with ultraviolet rays having an energy of 1000 mJ / cm 2 in air. A film was obtained. A test piece of 3 mm × 35 mm was cut out from the film for measurement, and the dynamic viscoelasticity was measured with RHEOVIBRON DDV-01FP manufactured by ORIENTEC. The temperature showing the maximum value of the loss tangent (tan δ) at the vibration frequency of 3.5 Hz was defined as the glass transition temperature, and the glass transition temperature was evaluated.

[Manufacture of stereolithography]
Using a solid creator SCS-300P (manufactured by Sony Manufacturing Systems Co., Ltd.), each liquid resin composition under the conditions of a laser power of 100 mW on the irradiated surface (liquid surface) and a scanning speed with a curing depth of 0.2 mm in each composition. By repeating the process of selectively irradiating the object with laser light to form a cured resin layer (thickness of 0.10 mm), a shaped object having a fitting shape shown in FIG. 1 (convex shape) The size was 62 × 34 × 11 mm, and the concave size was 52 × 34 × 11 mm).
In all the examples and comparative examples, the target optically shaped object could be manufactured.

Each component in Table 1 is as follows.
[Component (B)]
2021P: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (manufactured by Daicel Chemical Industries)
EXA850CRP: Bisphenol A type diglycidyl ether (Dainippon Ink Chemical Co., Ltd.)
EXA830CRP: Bisphenol F type diglycidyl ether (manufactured by Dainippon Ink & Chemicals, Inc.)
OXIPA: bis [(3-ethyl-3-oxetanyl) methyl] ester isophthalate (manufactured by Ube Industries)
OXA: 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd.)
[Component (C)]
CPI-200K: Diphenyl (phenylthiophenyl) sulfonium (pentafluoroethyl) trifluorophosphate (manufactured by San Apro)
[(D) component]
DPHA: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
[(E) component]
Irgacure 184: 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals)

[(F) component]
Elastomer particles: RKB5610CP-60 (manufactured by Resinas Kasei)
[(G) component]
Irganox 1010: hindered phenol type antioxidant (manufactured by Ciba Japan Co., Ltd.)
[Others]
DOX: Bis [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Toagosei Co., Ltd.)
XDO: 1,4-bis {[(3-ethyl-oxetane-3-yl) methoxy] methyl} benzene (manufactured by Toagosei Co., Ltd.)
[Others; (A) compounds that do not fall under component]
Polycarbonate diol: Duranol G3452 (Asahi Kasei Chemicals Corporation, molecular weight 2000)
Hydroxyl terminal-reactive polycarbonate dendrimer: reaction product obtained by reacting bisphenol A bischloroformate (BABC) and 1,1,1-tris (4-hydroxyphenylethane) ethane (THE) Hydroxyl-terminated polyester dendrimer: Boltorn H2004 (Perstorp)

From the results in Table 1, it can be seen that according to the compositions of Examples 1 to 6 that satisfy the conditions of the component composition defined in the present invention, an optically shaped article excellent in toughness and heat resistance can be obtained.
On the other hand, in the comparative example 1 which did not mix | blend a component (A), a film impact value and Tg are inferior. In Comparative Examples 2 to 4 using polycarbonate diol or dendrimer not corresponding to Component (A) instead of Component (A), Young's modulus and Tg are inferior in Comparative Example 2, and Young's modulus and film impact are in Comparative Example 3. The value is inferior, and in Comparative Example 4, the Young's modulus and Tg are inferior.

Claims (6)

(A) a compound having a carbonate group and two or more (meth) acryloyl groups and having no urethane bond,
(B) a cationically polymerizable compound,
(C) a photocationic polymerization initiator,
A radiation curable liquid resin composition for optical three-dimensional modeling, comprising (D) a radical polymerizable compound, and (E) a photo radical polymerization initiator.   The radiation-curable liquid resin composition according to claim 1, wherein the component (A) has two or more carbonate groups and three or more (meth) acryloyl groups.   The radiation curable liquid resin composition according to claim 1, wherein the component (A) has a branched structure.   The radiation curable liquid resin composition according to claim 1, wherein the component (A) has an aromatic structure. The radiation according to claim 1, wherein the component (A) is a compound obtained by introducing a (meth) acryloyl group into one or more compounds selected from the following [1] and [2]. A curable liquid resin composition.
[1] A compound having three or more hydroxyl groups obtained by reacting a compound represented by the following formula (1) with a compound represented by the following formula (3) [2] represented by the following formula (2) Compound having three or more hydroxyl groups obtained by reacting a compound with a compound represented by the following formula (4) R ^1- [O— (C═O) —X] _n1 (1)
^{R 2 - [(C = O} ) -X] n2 (2)
R ^3- (OH) _m1 (3)
_{^{R 4 - {[R 5 -O-}} (C = O) -O] m2 -R 6 -OH} m3 (4)
[In the formulas (1) to (4), R ¹ and R ² are each independently a monovalent organic group having an aliphatic, alicyclic or aromatic structure, and R ³ and R ⁴ are respectively Independently, it is a monovalent organic group having an aliphatic, alicyclic or aromatic structure, and R ⁵ and R ⁶ are each independently an alkylene group. n1 and n2 are each independently an integer of 2 or more, m1 and m3 are each independently an integer of 3 or more, and m2 is an integer of 1 to 3. However, at least one of R ¹ and R ³ or R ² and R ⁴ constituting one compound has an aromatic structure. ]   The optical modeling thing obtained by irradiating light to the radiation-curable liquid resin composition of any one of Claims 1-5.

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