JP5012462B2 - Photocurable composition for stereolithography, carbonized article, and method for producing the same - Google Patents

Description

  The present invention relates to a photocurable composition for producing a carbonized article using an optical modeling method, a three-dimensional article manufactured using the composition, and a carbonized article formed by firing the three-dimensional article. Related to things.

It has hitherto been known to manufacture a modeled object having a complicated three-dimensional shape using an optical modeling method.
The stereolithography method involves irradiating a thin layer liquid surface of a photocurable resin liquid with light to form a cured product (cross-section cured layer) having a desired pattern cross section, and then on the cross-section cured layer. 1 layer of a photo-curable resin layer is supplied, irradiated with light to further form a cross-section hardened layer, and thereafter, by repeating this operation, a plurality of cross-section hardened layers are laminated and integrated. A method of modeling a three-dimensional model having a shape is representative.
Moreover, forming the modeling object which consists of ceramics using such an optical modeling method is also performed. For example, a ceramic model having a complicated three-dimensional shape can be manufactured by blending ceramic fine particles in a photocurable resin liquid, manufacturing a three-dimensional model by an optical modeling method, and then firing the three-dimensional model. (For example, Patent Document 1).

On the other hand, molded articles made of carbon materials are used in various fields such as fuel cell electrodes, but are molded using a mold or the like (for example, Patent Document 2). It was difficult to give shape.
JP 2006-348214 A JP-A-8-2979

If a carbonized model (in other words, a cured product made of a carbon material having a desired three-dimensional shape) can be formed instead of the ceramic model described in Patent Document 1, an electrode for a fuel cell, an electromagnetic shield, etc. In addition, the optical modeling technique can be applied not only to semiconductor processes such as carbon wiring, but also to fields such as MEMS (microelectromechanical systems). In particular, if the carbonization yield during carbonization (residual carbon ratio; mass ratio remaining as charcoal without being burned and lost) is high, a fine shaped object can be formed with high accuracy.
Then, an object of this invention is to provide the photocurable composition which can manufacture the carbonized modeling thing which has a fine three-dimensional shape easily with high precision.

The present inventors have made study in order to solve the above problems, an epoxy compound 40-90 wt% having two or more (A) a main chain Yes vital epoxy group an aromatic ring structure, (B) cationic 0.01 to 10% by mass of a photopolymerization initiator, (D) 5 to 45% by mass of a phosphoric ester compound having two or more ethylenically unsaturated groups, and (E) a radical photopolymerization initiator of 0.1 to 0.1%. According to the photocurable composition containing 8% by mass, the inventors have found that the above object of the present invention can be achieved and completed the present invention.

（式中、Ｒ^１は水素原子又は１価の有機基である。）

（式中、ｎは１以上の整数である。）

（式中、ｎは１以上の整数である。）
［５］ 上記［１］〜［４］のいずれかに記載の光硬化性組成物を光硬化させてなる立体造形物。
［６］ 上記［１］〜［４］のいずれかに記載の光硬化性組成物に光を照射して、前記組成物の硬化層を形成した後、該硬化層の上に、前記組成物を再度供給し、光を照射して、前記組成物の硬化層をさらに形成し、以後、これを繰り返すことにより、複数の硬化層が積層し一体化してなる立体造形物を造形する立体造形物の製造方法。
［７］ 上記［５］に記載の立体造形物を焼成してなる、炭素化収率が３０質量％以上である炭化造形物。
［８］ 上記［１］〜［４］のいずれかに記載の光硬化性組成物に、光を照射し、前記組成物の硬化層を形成した後、該硬化層の上に、前記組成物を再度供給し、光を照射して、前記組成物の硬化層をさらに形成し、以後、これを繰り返すことにより、複数の硬化層が積層し一体化してなる立体造形物を得る造形工程と、該立体造形物を焼成し、炭素化収率が３０質量％以上である炭化造形物を得る焼成工程を含むことを特徴とする炭化造形物の製造方法。 That is, the present invention provides the following [1] to [ 8 ].
[1] (A) a main chain Yes vital epoxy group an aromatic ring structure in an epoxy compound having two or more 40 to 90 wt%, (B) a cationic photopolymerization initiator 0.01 to 10 wt%, (D ) 5 to 45% by mass of a phosphoric acid ester compound having two or more ethylenically unsaturated groups, and (E) 0.1 to 8% by mass of a radical photopolymerization initiator (however, the blending ratio of each of the above components is light When the curable composition contains a solvent, it is a ratio when the total amount of the photocurable composition excluding the solvent is 100% by mass)). object.
[2] (C) 3 to 30% by mass of monomers other than the above component (D) having two or more ethylenically unsaturated groups (however, the proportion of the component (C) is determined by the photocurable composition being the solvent) In the case where the total amount of the photocurable composition excluding the solvent is 100% by mass.), The photocurable composition according to the above [1].
[ 3 ] The component (A) is at least one selected from the group consisting of a naphthalene skeleton type epoxy resin, a biphenyl skeleton type epoxy resin, an anthraquinone skeleton type epoxy resin, a phenol novolak skeleton type epoxy resin, and a cresol novolak skeleton type epoxy resin. The photocurable composition according to the above [1] or [2] , which is a seed.
[ 4 ] The component (A) is represented by the naphthalene skeleton type epoxy resin represented by the following formula (1), the phenol novolak skeleton type epoxy resin represented by the following formula (3), and the following formula (4). The photocurable composition according to the above [ 3 ], which is at least one selected from the group consisting of cresol novolac skeleton type epoxy resins.

(In the formula, R ¹ is a hydrogen atom or a monovalent organic group.)

(In the formula, n is an integer of 1 or more.)

(In the formula, n is an integer of 1 or more.)
[ 5 ] A three-dimensional structure formed by photocuring the photocurable composition according to any one of [1] to [ 4 ].
[ 6 ] The photocurable composition according to any one of [1] to [ 4 ] above is irradiated with light to form a cured layer of the composition, and then the composition is formed on the cured layer. Is again applied, and irradiated with light to further form a cured layer of the composition, and thereafter, by repeating this, a three-dimensional structure that forms a three-dimensional structure formed by laminating and integrating a plurality of cured layers Manufacturing method.
[ 7 ] A carbonized article having a carbonization yield of 30% by mass or more, which is obtained by firing the three-dimensional article described in [ 5 ] above.
[ 8 ] After irradiating the photocurable composition according to any one of [1] to [ 4 ] with light to form a cured layer of the composition, the composition is formed on the cured layer. , By irradiating with light, further forming a cured layer of the composition, and thereafter repeating this, a modeling step of obtaining a three-dimensional model formed by laminating and integrating a plurality of cured layers; A method for producing a carbonized molded article, comprising a firing step of firing the three-dimensional molded article to obtain a carbonized molded article having a carbonization yield of 30% by mass or more.

According to the photocurable composition of the present invention, carbonization modeling is performed by a simple process of forming a three-dimensional model using an optical modeling method such as an optical layered modeling method or a micro optical modeling method, and firing the three-dimensional model. Can be manufactured.
Since the three-dimensional shaped product before firing is made of the cured product of the photocurable composition of the present invention and contains a specific component, a high carbonization yield can be achieved at the time of firing. While maintaining the fine three-dimensional shape of the three-dimensional model, the carbonized model can be formed.
The obtained carbonized shaped article is excellent in physical properties such as electrical conductivity (conductivity) and thermal conductivity.
The carbonized model can be suitably used for semiconductor processes such as carbon wiring, MEMS (Micro Electro Mechanical Systems), and the like.

First, the photocurable composition for optical modeling of the present invention will be described.
The compositions of the present invention, (A) a main chain epoxy compound 40-90 wt% with an aromatic ring structure Yu vital two or more epoxy groups, (B) 0.01 to 10 weight cationic photopolymerization initiator % , (D) 5 to 45% by mass of a phosphoric acid ester compound having two or more ethylenically unsaturated groups, (E) 0.1 to 8% by mass of a radical photopolymerization initiator Is a ratio when the total amount of the photocurable composition excluding the solvent is 100% by mass when the photocurable composition contains a solvent.), And other components blended as necessary It contains optional components.
Hereinafter, each component will be described.

[(A) component]
Component (A) used in the photocurable composition of the present invention is a backbone organic vital epoxy group an aromatic ring structure in epoxy compound having two or more.
In the present invention, by using an epoxy compound having an aromatic ring structure in the main chain, a high carbonization yield of 30% by mass or more can be achieved to form a carbonized shaped article having a desired fine three-dimensional shape. it can. (A) instead of the components, no aromatic ring structure in the main chain, in the case of using a compound having an aromatic ring structure in a side chain is reduced carbonization yield to obtain a good carbide shaped object I can't.
The number of epoxy groups in one molecule of the epoxy compound as the component (A) is 2 or more, preferably 3 or more, more preferably 4 or more.

Examples of the component (A) include naphthalene skeleton type epoxy resins, biphenyl skeleton type epoxy resins, anthraquinone skeleton type epoxy resins, phenol novolac skeleton type epoxy resins, cresol novolak skeleton type epoxy resins and the like.
Among these, a naphthalene skeleton type epoxy resin is preferable from the viewpoint of obtaining a high carbonization yield.
In addition, the phenol novolac skeleton type epoxy resin and the cresol novolac skeleton type epoxy resin can obtain a high carbonization yield, and it is not necessary to add a solvent to the photocurable composition. It is preferable in terms of improvement.

（式中、Ｒ^１は水素原子又は１価の有機基である。）
このようなエポキシ樹脂としては、ジヒドロキシナフタレンジグリシジルエーテル、メチレンビス（ジヒドロキシナフタレンジグリシジルエーテル）等が挙げられる。 The naphthalene skeleton type epoxy resin may be any one having at least one naphthalene ring in the main chain and at least two epoxy groups, and a preferred example thereof is represented by the following formula (1). The epoxy resin which has a structure is mentioned.

(In the formula, R ¹ is a hydrogen atom or a monovalent organic group.)
Examples of such an epoxy resin include dihydroxy naphthalene diglycidyl ether, methylene bis (dihydroxy naphthalene diglycidyl ether), and the like.

The naphthalene skeleton type epoxy resin preferably has two or more naphthalene rings in the main chain. Moreover, it is preferable to have an epoxy group in each of two benzene rings which comprise a naphthalene ring. Examples of the epoxy resin corresponding to these include methylene bis (dihydroxynaphthalenediglycidyl ether).
Examples of commercially available naphthalene skeleton-type epoxy resins include EPICLON HP-4700 (manufactured by Dainippon Ink & Chemicals, Inc .; methylenebis (dihydroxynaphthalenediglycidyl ether; compound represented by the following formula (2)) and the like.

（式中、ｎは１以上の整数である。）

（式中、ｎは１以上の整数である。）
式（３）、（４）中、ｎは１〜５の整数であることが好ましく、１〜３の整数であることがより好ましい。
フェノールノボラック骨格型エポキシ樹脂の市販品としては、ＹＤＰＮ−６３８（東都化成社製；式（３）で表されるエポキシ樹脂）等が挙げられる。クレゾールノボラック骨格型エポキシ樹脂の市販品としては、ＹＤＣＮ−７０１（東都化成社製；下記式（５）で表されるエポキシ樹脂）等が挙げられる。

（式中、ｎは１以上の整数である。）
式（５）中、ｎは１〜５の整数であることが好ましく、１〜３の整数であることがより好ましい。 Examples of the phenol novolac skeleton type epoxy resin include an epoxy resin represented by the following formula (3). Examples of the cresol novolak skeleton type epoxy resin include an epoxy resin represented by the following formula (4).

(In the formula, n is an integer of 1 or more.)

(In the formula, n is an integer of 1 or more.)
In the formulas (3) and (4), n is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
As a commercial item of a phenol novolak skeleton type epoxy resin, YDPN-638 (manufactured by Toto Kasei Co., Ltd .; epoxy resin represented by formula (3)) and the like can be mentioned. As a commercial item of a cresol novolak skeleton type epoxy resin, YDCN-701 (manufactured by Tohto Kasei Co., Ltd .; epoxy resin represented by the following formula (5)) and the like can be mentioned.

(In the formula, n is an integer of 1 or more.)
In formula (5), n is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

  Examples of the biphenyl skeleton type epoxy resin include 4,4′-bis (2,3-epoxypropoxy) biphenyl, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetra. Methylbiphenyl, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetraethylbiphenyl, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′ , 5,5′-tetrabutylbiphenyl and the like.

The blending ratio of the component (A) is 40 to 90% by mass, more preferably 45%, where the total amount of the photocurable composition of the present invention (however, when the solvent is included, the total amount excluding the solvent) is 100% by mass. It is -85 mass%. If the blending ratio is less than 30% by mass, the carbonization yield decreases, which is not preferable.

[Component (B)]
The component (B) used in the photocurable composition of the present invention is a cationic photopolymerization initiator.
The cationic photopolymerization initiator of component (B) is a compound that initiates cationic polymerization of component (A) by receiving energy rays such as light.

Preferable examples of the cationic photopolymerization initiator include onium salts having a structure represented by the following formula (6). This onium salt is a compound that releases a Lewis acid by receiving light.
_{^{[R 2 a R 3 b R}} 4 c R 5 d W] + m [MX n + m] -m (6)
(Wherein the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or N≡N, and R ² , R ³ , R ⁴ and R ⁵ is the same or different organic group, a, b, c, and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W + m, M is a halide complex [MX _{n + m} The metal or metalloid constituting the central atom of, for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is a halogen atom such as F, Cl, Br, etc., m is the net charge of the halide complex ion, and n is the valence of M.)
Specific examples of the onium ion in the formula (6) include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, tri Phenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide , Η ⁵ -2,4- (cyclopentagenyl) [1,2,3,4,5,6-η)-(methylethyl) -benzene] -iron (1+) and the like.
Of these, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, and bis [4- (diphenylsulfonio) -phenyl] sulfide are preferable.

Specific examples of the anion [MX _{n + m} ] in the formula (6) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate. (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.
Further, as an onium salt that can be used as a cationic photopolymerization initiator, in the above formula (6), instead of [MX _{n + m} ], a general formula [MX _n (OH) ⁻ ] (where M, X and n is as defined in relation to the general formula (6).) anion, perchlorate ion (ClO ₄ ⁻ ), trifluoromethanesulfonate ion (CF ₃ SO ³⁻ ), fluorosulfonate ion ( Examples include onium salts having other anions such as FSO ₃ ⁻ ), toluenesulfonate ion, trinitrobenzenesulfonate ion, and trinitrotoluenesulfonate ion.
These cationic photopolymerization initiators can be used alone or in combination of two or more.

Examples of commercially available cationic photopolymerization initiators include UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide), Adekaoptomer SP-151, SP-170, SP- 150, SP-171 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (above, manufactured by Ciba Geigy), CI-2481, CI-2624, CI-2638, CI-2039 (above, manufactured by Nippon Soda Co., Ltd.), CD -1010, CD-1011, CD-1012 (manufactured by Sartomer), DTS-102, DTS-103, NAT-103, NDS-103, TPS-102, TPS-103, MDS-103, MPI-103, BBI-101, BBI-102, BBI-103 (manufactured by Midori Chemical Co., Ltd.), Degacu re K126 (manufactured by Degussa), CPI-100A, CPI-101A, CPI-110A (above, San Apro) and the like.
Of these, CPI-100A, CPI-101A, and CPI-110A (manufactured by San Apro) are preferable.

  The blending ratio of the component (B) is 0.01 to 10% by mass, preferably 100% by mass, preferably 0.01 to 10% by mass, preferably 100% by mass of the total amount of the photocurable composition of the present invention. It is 0.1-8 mass%, More preferably, it is 0.3-5 mass%. When the blending ratio is less than 0.01% by mass, the polymerization reaction rate (curing rate) of the composition becomes small, so that it may take time to form a three-dimensional structure or the resolution may be lowered. When the said mixture ratio exceeds 10 mass%, an excessive amount of (B) component may reduce the hardening characteristic of a composition, or may reduce the intensity | strength of a three-dimensional molded item.

[Component (C)]
In the photocurable composition of the present invention, a monomer having two or more ethylenically unsaturated groups (component (C)) can be blended as necessary. Examples of the monomer having two or more ethylenically unsaturated groups (C═C) (also referred to as bifunctional or higher monomer) include bifunctional or higher (meth) acrylic monomers.

  Among the above monomers, examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and triethylene glycol. Both cyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and bisphenol A diglycidyl ether Terminal (meth) acrylic acid adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol Cold di (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified bisphenol A di (meth) acrylate, propylene oxide (hereinafter referred to as “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, (meth) acrylate of phenol novolac polyglycidyl ether, and the like.

Among the above monomers, examples of the tri- or higher functional monomer include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Methylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate (hereinafter also referred to as “ethoxylated trimethylolpropane tri (meth) acrylate”), PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, triacryloyloxyethyl A phosphate etc. are mentioned.
Commercially available products of tri- or higher functional monomers include Aronix M305, M309, M310, M315, M320, M350, M360, M408 (above, manufactured by Toagosei Co., Ltd., Biscoat # 295, # 300, # 360, GPT, 3PA , # 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK ester TMPT, A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) , Light acrylate TMP-A, TMP-6EO-3A, PE-3A, PE-4A, DPE-6A (above, manufactured by Kyoeisha Chemical Co., Ltd., KAYARAD PET-30, GPO-303, TMPTA, TPA-320, DPHA , D-310, DPCA-20, DPCA-60 (above, manufactured by Nippon Kayaku Co., Ltd.) and the like.

Of the above monomers, bifunctional monomers are preferable, and EO-modified bisphenol A di (meth) acrylate is particularly preferable.
Monomers having two or more ethylenically unsaturated groups can be used alone or in combination of two or more.

  The blending ratio of the component (C) is 0 to 40% by mass, preferably 0 to 40% by mass, where the total amount of the photocurable composition of the present invention (however, when the solvent is included, the total amount excluding the solvent) is 100% by mass. 30 mass%, More preferably, it is 3-30 mass%. When the said mixture ratio exceeds 40 mass%, the mixture ratio of another component (especially (A) component) will become small in connection with it, and since a carbonization yield falls, it is unpreferable. In particular, by setting the blending ratio of the component (C) to 3 to 30% by mass, a higher carbonization yield can be achieved, and a carbonized molded article having a desired fine three-dimensional shape can be obtained.

[(D) component]
The photocurable composition of the present invention, phosphoric acid ester compound having two or more ethylenically unsaturated groups in one molecule ((D) component) is blended.
Examples of the phosphate ester compound include phosphate ester compounds having two or more (meth) acryloyl groups in one molecule. Specific examples of such compounds include bis [2- (meth) acryloyloxyethyl] phosphate, bis [2- (meth) acryloyloxypropyl] phosphate, tris [2- (meth) acryloyloxyethyl] phosphate, and The compound shown by following formula (7) is mentioned.

（式中、Ｒ^６、Ｒ^７及びＲ^８は独立に下記式（８）、（９）、（１０）、（１１）もしくは（１２）で表される基又は水酸基を表す。ただし、Ｒ^６、Ｒ^７及びＲ^８のうち、少なくとも２つは式（８）、（９）、（１０）、（１１）もしくは（１２）で示される基であり、Ｒ^６、Ｒ^７及びＲ^８の内少なくとも一つは式（８）、（９）、（１０）もしくは（１１）で表される基である。）

(In the formula, R ⁶ , R ⁷ and R ⁸ independently represent a group or a hydroxyl group represented by the following formula (8), (9), (10), (11) or (12). However, R ⁶ , R ⁷ and R ⁸ are groups represented by the formula (8), (9), (10), (11) or (12), and R ⁶ , R ⁷ and R ⁸ (At least one is a group represented by the formula (8), (9), (10) or (11)).

（式中、Ｒ^９は水素原子またはメチル基を表す。）

(In the formula, R ⁹ represents a hydrogen atom or a methyl group.)

（式中、Ｒ^１０水素原子またはメチル基を表す。）

(In the formula, R ¹⁰ represents a hydrogen atom or a methyl group.)

（式中、Ｒ^１１は水素原子またはメチル基を表す。）

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group.)

（式中、Ｒ^１２、Ｒ^１３およびＲ^１４は独立に水素原子またはメチル基を表し、ｓは１〜５を表す。）

(In formula, R <^12> , R <^13> and R < ¹⁴ > represent a hydrogen atom or a methyl group independently, and s represents 1-5.)

（式中、Ｒ^１５は水素原子またはメチル基を表す。）

(In the formula, R ¹⁵ represents a hydrogen atom or a methyl group.)

  Among these phosphate ester compounds, phosphate ester compounds that do not contain a hydroxyl group bonded to a phosphorus atom are preferred. As these commercial products, for example, light ester PM, P-2M (above, manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat 3PA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), EB-169, EB-179, EB-3603, R-DX63182 (above, manufactured by Daicel UCB), AR-100, MR-100, MR-200, MR-260 (above, manufactured by Daihachi Chemical Co., Ltd.), JAMP-100, JAMP-514, JPA-514 (above , Manufactured by Johoku Chemical Co., Ltd.). Among these, as a phosphoric acid ester compound which does not contain a hydroxyl group bonded to the phosphorus atom, for example, biscoat 3PA can be mentioned.

The blending ratio of the component (D) is 5 to 45% by mass , preferably 10 to 10% , where the total amount of the photocurable composition of the present invention (however, when the solvent is included, the total amount excluding the solvent) is 100% by mass. 40 % by mass. When the said mixture ratio exceeds 50 mass%, since the mixture ratio of another component (especially (A) component) becomes small in connection with it and a carbonization yield falls, it is unpreferable. By setting the blending ratio of the component (D) to 5 to 45% by mass (preferably 10 to 40% by mass), a higher carbonization yield can be achieved.

[(E) component]
The photocurable composition of the present invention, a radical photopolymerization initiator ((E) component) are blended.
Examples of the radical photopolymerization initiator 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-dimethoxyben Yl) -2,4,4-tri-methylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine 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, 3-methylacetophenone, 3,3 ′, 4,4′-tetra ( and t-butylperoxycarbonyl) benzophenone (BTTB), and combinations of BTTB with xanthene, thioxanthene, coumarin, ketocoumarin and other dye sensitizers.
Of these, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- Particularly preferred are ON, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like.
These compounds are used individually by 1 type or in combination of 2 or more types.

When the composition of the present invention is used in the micro-photofabrication method described later, since a curing light having a wavelength in the near ultraviolet region of about 405 nm is usually used, a photopolymerization initiator having absorption in this wavelength region is preferably used. It is done.
Specifically, a photopolymerization initiator having a molar extinction coefficient at 405 nm of 500 (L / mol · cm) or more is preferable. Among the above examples, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (molar extinction coefficient at 405 nm: 619 L / mol · cm), bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide (molar extinction coefficient at 405 nm: 575 L / mol · cm) and the like are preferable.

(E) blending ratio of the component, the total amount of the photocurable composition of the present invention (provided that when it contains a solvent, the total amount excluding the solvent) as 100 mass%, 0.1 to 8 wt%, preferably 0.5-6 mass%. When the said mixture ratio exceeds 10 mass%, an excessive amount of (E) component may reduce the hardening characteristic of a composition, or may reduce the intensity | strength of a three-dimensional molded item.

Moreover, a solvent can be mix | blended with the composition of this invention as needed. Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like. Propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol monoalkyl ether acetates such as cetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as ethyl carbitol and butyl carbitol; ethyl carbitol acetate Carbitol acetates such as butyl carbitol acetate; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, Aliphatic carboxylic acid esters such as n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; Other esters such as methyl toxipropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; and γ-butyrolactone Examples include lactones. These solvents can be used alone or in combination of two or more.
The blending amount of the solvent is, for example, 0 to 50 parts by mass with 100 parts by mass as the total amount other than the solvent in the photocurable composition.

Furthermore, the composition of the present invention may contain various additives as optional components other than those described above within a range not impairing the object and effects of the present invention. Examples of such additives include epoxy resins other than component (A), polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, allyl ether copolymer, petroleum resin, xylene resin. And polymers or oligomers such as ketone resins, cellulose resins, fluorine-based oligomers, silicone-based oligomers, and polysulfide-based oligomers.
Among these, for example, a polymer having a repeating structure represented by the following formula (13) and a repeating structure represented by the following formula (14) is preferable. An example of such a polymer is Marca Linker CST (manufactured by Maruzen Chemical Co., Ltd.). In addition, when mix | blending the polymer which has a repeating structure represented by Formula (13) and a repeating structure represented by following formula (14), the compounding quantity is the whole quantity other than the solvent in a photocurable composition. Is 100 mass%, preferably 1-30 mass%.

  Other examples of additives include polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol, polymerization initiation assistants, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, silane coupling agents, light absorbers, inorganic fine particles or organic fine particles, triethanolamine, methyldiethanolamine, triethylamine, diethylamine and other amine compounds, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, anthracene and derivatives thereof, Examples include perylene and derivatives thereof, photosensitizers (polymerization accelerators) such as benzophenone and benzoin isopropyl ether, and reactive diluents such as vinyl ethers, vinyl sulfides, vinyl urethanes, urethane acrylates, and vinyl ureas.

The photocurable composition of this invention can be manufactured by mixing the said (A) component, (B) component, and the arbitrary component mix | blended as needed uniformly.
The viscosity of the composition thus obtained is preferably 50 to 50,000 mPa · s, more preferably 50 to 10,000 mPa · s at 25 ° C.
Moreover, the content rate of the aromatic ring in the photocurable composition of this invention becomes like this. Preferably it is 20 mass% or more, More preferably, it is 20-60 mass%, Most preferably, it is 25-50 mass%. Since the carbonization yield falls that the said content rate is less than 20 mass%, it is not preferable. In addition, the content rate of an aromatic ring here is the fragrance derived from all the components mix | blended with the composition with respect to the whole quantity (however, the whole quantity except a solvent when a solvent is included) of a photocurable composition. This is the mass ratio of the ring.
When using the composition of this invention for the below-mentioned micro stereolithography, it is preferable that the hardening depth (500mJ / cm < ² >) of a composition is 1-50 micrometers, It is more preferable that it is 2-10 micrometers, A thickness of 10 μm is particularly preferable.

Next, the carbonized article and the manufacturing method thereof according to the present invention will be described.
The manufacturing method of the carbonized modeled object of the present invention includes a process (a) for manufacturing a three-dimensional modeled article made of a laminate of a cured product of a photocurable composition by a stereolithography method, and a three-dimensional model obtained in the process (a). The process includes a step (b) of cleaning the modeled object and a step (c) of firing the three-dimensional modeled object after cleaning to obtain a carbonized modeled object.
[Step (a)]
A process (a) is a process of manufacturing the three-dimensional molded item which consists of a laminated body of the hardened | cured material of the above-mentioned photocurable composition by the optical modeling method.
Specifically, the photocurable composition is irradiated with light to form a cured product (cross-section cured layer) of the composition, and the composition is supplied again on the cured product (cross-sectional cured layer). By irradiating light, a cured product (cross-section cured layer) of the composition is further formed, and thereafter, by repeating this, a three-dimensional structure formed by laminating and integrating a plurality of cured products (cross-sectional cured layer) obtain.

The method for irradiating the photocurable composition with light is not particularly limited, and various methods can be employed. For example, (a) a method of irradiating the composition while scanning laser light or convergent light obtained using a lens, a mirror, etc., (b) using a mask having a light transmission portion of a predetermined pattern, A method of irradiating the composition with non-converged light through a mask; (c) using a light guide member formed by bundling a large number of optical fibers; and composing light through the optical fiber corresponding to a predetermined pattern in the light guide member A method of irradiating an object, (d) a method of repeatedly executing collective exposure for each predetermined region, and the like can be employed.
Moreover, the irradiation position (irradiation surface) of light can be moved continuously or stepwise from the uncured portion to the uncured portion. By moving in this way, the cured portions can be stacked to form a desired three-dimensional shape. The irradiation position can be moved by various methods, for example, by moving any of the light source, the container for the composition, and the already cured portion of the composition, or additionally supplying the composition to the container. And the like.
Moreover, when the composition is accommodated in the container, the light irradiation surface may be either the liquid surface of the composition or the contact surface with the vessel wall of the translucent container. When the liquid surface of the composition or the contact surface with the vessel wall is used as the light irradiation surface, the light can be irradiated directly from the outside of the container or through the vessel wall.

As a manufacturing method of the three-dimensional molded item of a process (a), the optical lamination modeling method and the micro optical modeling method are preferable. Hereinafter, each of the optical additive manufacturing method and the micro optical modeling method will be described with reference to the drawings. FIG. 1 is a diagram illustrating an example of an optical layered modeling method, and FIG. 2 is a diagram illustrating an example of a system of a micro stereo modeling method.
[Optical additive manufacturing method]
According to the optical layered modeling method, a three-dimensional modeled object having a scale having a side length of several millimeters to several meters, typically several centimeters to several tens of centimeters is obtained.
The scale is a scale expressed as a cube.
In FIG. 1, a photocurable composition 1 is accommodated in a container 2, and a support stage 3 is provided so as to be movable up and down.
First, as shown in FIG. 1 (a), the support stage 3 is lowered (sedimented) by a minute amount from the liquid level 4 of the composition 1 in the container 2 containing the photocurable composition 1. The composition 1 is supplied onto the support stage 3 to form a thin layer of the composition 1. Next, the cured product (cured resin layer) 6 of the composition 1 is formed by selectively irradiating the thin layer with light 8 through the mask 5.
Next, as shown in FIG. 1 (b), the support stage 3 is lowered (sedimented) by a small amount, and the composition 1 is supplied onto the cured product 6 to form a thin layer of the composition. Form again. Next, by selectively irradiating the thin layer with light 8 through the mask 5, a new cured product 7 is further formed on the cured product 6 continuously and integrally laminated thereon. . Then, by repeating this step a predetermined number of times while changing or not changing the pattern irradiated with light, a three-dimensional modeled object in which a plurality of cured products are integrally laminated is modeled.

  The obtained three-dimensional molded product has a thickness of each cured product layer of usually 1 to 200 μm, preferably 50 to 200 μm, more preferably 70 to 180 μm, and still more preferably 100 to 150 μm.

[Micro stereolithography]
According to the micro-stereolithography method, a three-dimensional structure having a minute scale whose length of one side is several μm to several cm, typically several tens of μm to several mm is obtained. Therefore, the three-dimensional structure made of charcoal finally obtained can be a small three-dimensional structure that can be used for MEMS or the like.
The scale is a scale expressed as a cube.
In FIG. 1, a photo-curing modeling apparatus (hereinafter also referred to as an optical modeling apparatus) 100 includes a light source 11, a digital mirror device (DMD) 12, a lens 13, a modeling table 14, a dispenser 15, a recoater 16, a control unit 17, and a storage. A portion 18 is provided.
The light source 11 is a means for generating light for curing the composition. As the light source 11, for example, a laser diode (LD) or an ultraviolet (UV) lamp that generates 405 nm laser light is used.
The digital mirror device (DMD) 12 is a device developed by Texas Instruments, and hundreds of thousands to millions of micromirrors moving independently on a CMOS semiconductor, for example, 480,000 to 1.31 million are spread. It has been. In this specification, the digital mirror device does not only refer to the same device manufactured by Texas Instruments, but includes a device having a similar or similar mechanism. The micromirror provided in the Texas Instruments DMD can be tilted by about ± 10 degrees, for example, about ± 12 degrees about the diagonal line by an electrostatic field effect. The micromirror has a square shape in which the length of one side of the pitch of each micromirror is about 10 μm, for example, 13.68 μm. The interval between adjacent micromirrors is, for example, 1 μm. The entire DMD 12 has a square shape of 40.8 × 31.8 mm (of which the mirror portion has a square shape of 14.0 × 10.5 mm), and the length of one side is 13.68 μm. The micro mirrors 786 and 432 are provided.
The DMD 12 reflects the laser beam emitted from the light source 11 by the individual micromirrors, and forms only the laser beam reflected by the micromirrors controlled by the control unit 17 at a predetermined angle through the condenser lens 13. The composition layer 19 on the table 14 is irradiated.

The lens 13 guides the laser beam reflected by the DMD 12 onto the composition layer 19 to form a projection region. The lens 13 may be a condenser lens using a convex lens or a concave lens. When a concave lens is used, a projection area larger than the actual size of the DMD can be obtained. The lens 13 is a condensing lens, and reduces incident light by about 15 times and condenses it on the composition layer 19.
The modeling table 14 is a plate-like table for sequentially depositing and placing a cured layer obtained by curing the composition layer 19. The modeling table 14 can be moved horizontally and vertically by a driving mechanism (not shown), that is, a moving mechanism. With this drive mechanism, stereolithography can be performed over a desired range.
The dispenser 15 is a means for containing the photocurable composition 20 of the present invention and supplying a predetermined amount of the composition 20 to a predetermined position on the modeling table.
The recoater 16 is means for uniformly applying the composition 20 to form the composition layer 19 and includes, for example, a blade mechanism and a moving mechanism.

The control unit 17 controls the light source 11, DMD 12, modeling table 14, dispenser 15, and recoater 16 according to control data including exposure data. The control unit 17 can typically be configured by installing a predetermined program in a computer. A typical computer configuration includes a central processing unit (CPU) and memory. The CPU and the memory are connected to an external storage device such as a hard disk device as an auxiliary storage device via a bus. This external storage device functions as the storage unit 18 of the control unit 17.
Storage medium driving devices such as a flexible disk device, a hard disk device, and a CD-ROM drive are connected to the bus via various controllers. A portable storage medium such as a flexible disk is inserted into a storage medium driving apparatus such as a flexible disk apparatus.
The storage medium can store a predetermined computer program for operating the system by giving instructions to the CPU in cooperation with the operating system.
The storage unit 18 stores control data including exposure data of cross-sectional groups obtained by slicing a three-dimensional model to be modeled into a plurality of layers.
Based on the exposure data stored in the storage unit 18, the control unit 17 mainly controls the angle control of each micromirror in the DMD 12 and the movement of the modeling table 14 (that is, the position of the irradiation range of the laser beam with respect to the three-dimensional modeled object). Then, modeling of the three-dimensional model is executed.

  The computer program is executed by being loaded into a memory. The computer program can be compressed or divided into a plurality of parts and stored in a storage medium. In addition, user interface hardware can be provided. Examples of the user interface hardware include a pointing device for inputting such as a mouse, a keyboard, or a display for presenting visual data to the user.

Next, the optical modeling operation of the optical modeling apparatus 100 will be described.
First, the composition 20 is accommodated in the dispenser 15. The modeling table 14 is in the initial position. The dispenser 15 supplies a predetermined amount of the contained composition 20 onto the modeling table 14. The recoater 16 sweeps the composition 20 as it stretches and forms a composition layer 19 for one layer to be cured.
The laser beam emitted from the light source 11 enters the DMD 12. The DMD 12 is controlled by the control unit 17 in accordance with the exposure data stored in the storage unit 18, and adjusts the angle of a part of the micromirrors that are the part that irradiates the composition layer 19 with the laser beam. Thereby, the laser beam reflected by a part of the micromirrors is applied to the composition layer 19 through the condenser lens 13, while the laser beam reflected by the remaining micromirrors is applied to the composition layer 19. It will not be irradiated.
The composition layer 19 is irradiated with the laser beam for 0.4 seconds, for example. At this time, the projection area on the composition layer 19 is, for example, about 1.3 × 1.8 mm, and can be reduced to about 0.6 × 0.9 mm. The area of the projection region is desirably 100 mm ² or less.

By using a concave lens for the lens 13, the projection area can be enlarged to about 6 × 9 cm. If the projection area is enlarged beyond this size, the energy density of the laser beam applied to the projection area is lowered, and the composition layer 19 may be insufficiently cured.
When forming a three-dimensional model larger than the size of the laser beam projection area, for example, the modeling table 14 is moved horizontally by a moving mechanism to move the laser beam irradiation position and irradiate the entire modeling area. There is a need. Laser beam irradiation is performed one shot at each projection area. Control of laser beam irradiation to each projection area will be described in detail later.
In this way, by moving the projection area and performing irradiation of the laser beam with each projection area as a unit, that is, exposure, the composition layer 19 is cured and a first cured layer is formed. . The lamination pitch for one layer, that is, the thickness of the cured layer is, for example, 1 to 50 μm, preferably 2 to 10 μm, and more preferably 5 to 10 μm.

Subsequently, the second layer of the three-dimensional object having a desired shape is formed in the same process. Specifically, the composition 20 supplied from the dispenser 15 is applied to the outside of the cured layer formed as the first layer so as to be stretched beyond the three-dimensional object by the recoater 16. . Then, a second hardened layer is formed on the first hardened layer by irradiating with a laser beam.
Thereafter, the third and subsequent cured resin layers are sequentially deposited in the same manner. Then, when the deposition of the final layer is completed, the modeled object formed on the modeling table 14 is taken out.

  The thickness of each hardened | cured material layer becomes like this. Preferably the thickness of each hardened | cured material layer is 1-50 micrometers, More preferably, it is 2-10 micrometers, More preferably, it is 5-10 micrometers.

[Step (b)]
Step (b) is a step of washing the three-dimensional structure obtained in step (a).
The remaining unreacted composition can be removed by washing the three-dimensional structure.
Cleaning methods include 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, and the like; aliphatic organic solvents typified by terpenes And a method of cleaning using a cleaning agent such as a low-viscosity thermosetting resin and a photocurable resin.
Further, the three-dimensional structure can be further cured by being irradiated or heated with an ultraviolet lamp or the like as necessary.

[Step (c)]
A process (c) is a process of baking the solid modeling thing washed at the above-mentioned process (b), and obtaining a solid modeling thing consisting of charcoal.
Specifically, the three-dimensional structure after the washing is baked at a predetermined temperature in a non-oxidizing atmosphere to carbonize the three-dimensional structure and obtain a three-dimensional structure made of charcoal.
Examples of the non-oxidizing atmosphere include a nitrogen atmosphere and an argon atmosphere. By baking in such a state where oxygen supply is small, the composition can be sufficiently carbonized.
The baking is performed, for example, from room temperature (for example, −5 to 35 ° C.) at a rate of 5 to 15 ° C./min so that the maximum temperature reaches 400 ° C. or higher. The maximum ultimate temperature is preferably 400 to 1,000 ° C, more preferably 500 to 900 ° C. The firing time is, for example, 15 minutes to 2 hours, preferably 30 minutes to 90 minutes. A high carbonization yield can be achieved by setting the maximum temperature for firing within the above range.

The obtained carbonized shaped article has a high carbonization yield. The carbonization yield is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, and particularly preferably 50% by mass or more.
The carbonization yield is the mass ratio of the carbonized shaped article obtained after firing relative to the three-dimensional shaped article before firing. The firing condition of the three-dimensional object when determining the carbonization yield is that the temperature is increased from 25 ° C. at a rate of 10 ° C./min. After reaching the maximum temperature of 550 ° C., the temperature is then decreased at a rate of 10 ° C./min. When the temperature reaches 25 ° C., the firing process is completed.
Further, the carbonized article has good conductivity (electrical conductivity, thermal conductivity) and the like. Specifically, the value of electrical conductivity is preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁴ Ω · cm. The value of thermal conductivity is preferably 100 W / (m · K).
Furthermore, the carbonized model manufactured by the micro stereolithography method has a minute and highly accurate three-dimensional shape and can be suitably used for MEMS and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to the aspect as described in a following example.

[Examples 1 to 6, Reference Example 1 , Comparative Example 1]
Each component was blended at the blending ratio shown in Table 1, and a stirrer T.K. K. A photocurable composition was prepared by mixing uniformly using a HOMODISPER.
Subsequently, the three-dimensional molded item was formed using the obtained photocurable composition. The composition was carbonized by firing the three-dimensional structure under a nitrogen atmosphere to obtain a three-dimensional structure made of charcoal. The firing was performed by raising the temperature from 25 ° C. to 550 ° C. at a rate of 10 ° C./min.
The carbonization yield of the obtained carbonized molded article was calculated from the data on the weight reduction rate obtained by the TG / DTA measurement. The results are shown in Table 1.

In addition, each component in Table 1 is as follows.
1) Naphthalene skeleton type epoxy resin: manufactured by Dainippon Ink & Chemicals, Inc., trade name EPICLON HP-4700
2) Phenol novolac skeleton type epoxy resin: manufactured by Toto Kasei Co., Ltd., trade name YDPN-638
3) CPI-110A: San Apro, triarylsulfonium hexafluoroantimonate 4) Irgacure 184: Ciba Specialty Chemicals, 1-hydroxycyclohexyl phenyl ketone 5) Aromatic ring-containing polymer: Maruzen Petrochemical Co., Ltd., trade name : Marcalinker CST
6) Solvent: Methyl ethyl ketone, manufactured by Maruzen Petrochemical Co., Ltd.

  From Table 1, it can be seen that the carbonized modeled article using the photocurable composition of the present invention has a high carbonization yield and high modeling accuracy. On the other hand, in the comparative example 1 using the photocurable composition which does not contain (A) component, it turns out that the carbonization yield at the time of manufacture of a carbonized modeling thing is low, and the modeling precision is low.

It is a figure which shows an example of the optical lamination molding method. It is a figure which shows an example of the system of micro stereolithography.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photocurable composition 2 Container 3 Support stage 4 Liquid level of photocurable composition 5 Mask 6,7 Hardened | cured material (hardened layer)
8 Light 11 Light source 12 Digital mirror device (DMD)
DESCRIPTION OF SYMBOLS 13 Condensing lens 14 Modeling table 15 Dispenser 16 Recoater 17 Control part 18 Memory | storage part 19 Composition layer 20 Photocurable composition 100 Photocurable modeling apparatus (optical modeling apparatus)

Claims (8)

(A) epoxy compound 40-90 wt% of the main chain organic vital epoxy group an aromatic ring structure having two or more,
(B) Cationic photopolymerization initiator 0.01 to 10% by mass ,
(D) 5 to 45% by mass of a phosphoric ester compound having two or more ethylenically unsaturated groups, and
(E) Radical photopolymerization initiator 0.1 to 8% by mass (however, the blending ratio of the above components is the total amount of the photocurable composition excluding the solvent when the photocurable composition contains the solvent) ) Is 100% by mass.)
A photocurable composition for stereolithography, comprising: (C) 3 to 30% by mass of monomer other than component (D) having two or more ethylenically unsaturated groups (however, the blending ratio of component (C) is when the photocurable composition contains a solvent) Is the ratio when the total amount of the photocurable composition excluding the solvent is 100% by mass).
The photocurable composition according to claim 1 comprising: The component (A) is at least one selected from the group consisting of a naphthalene skeleton type epoxy resin, a biphenyl skeleton type epoxy resin, an anthraquinone skeleton type epoxy resin, a phenol novolak skeleton type epoxy resin, and a cresol novolak skeleton type epoxy resin. The photocurable composition according to claim 1 or 2 . The component (A) is a naphthalene skeleton type epoxy resin represented by the following formula (1), a phenol novolak skeleton type epoxy resin represented by the following formula (3), and a cresol novolak represented by the following formula (4). The photocurable composition according to claim 3 , which is at least one selected from the group consisting of skeleton-type epoxy resins.

(In the formula, R ¹ is a hydrogen atom or a monovalent organic group.)

(In the formula, n is an integer of 1 or more.)

(In the formula, n is an integer of 1 or more.) The three-dimensional molded item formed by photocuring the photocurable composition of any one of Claims 1-4 . After irradiating light to the photocurable composition of any one of Claims 1-4 and forming the cured layer of the said composition, the said composition is again supplied on this cured layer. A method for producing a three-dimensional modeled object that forms a three-dimensional modeled object by irradiating light to further form a cured layer of the composition, and thereafter repeating this to laminate and integrate a plurality of cured layers. A carbonized molded article having a carbonization yield of 30% by mass or more obtained by firing the three-dimensional modeled article according to claim 5 . After irradiating light to the photocurable composition of any one of Claims 1-4 and forming the cured layer of the said composition, the said composition is again supplied on this cured layer. , By irradiating light, further forming a cured layer of the composition, and thereafter repeating this to form a three-dimensional modeled object in which a plurality of cured layers are laminated and integrated, and the three-dimensional modeled object A method for producing a carbonized shaped article, comprising a firing step of obtaining a carbonized shaped article having a carbonization yield of 30% by mass or more.

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