WO2006100964A1 - Method for producing three-dimensional article and three-dimensional article - Google Patents

Abstract

A method for producing a three-dimensional article composed of an integrated laminate having a plurality of cured layers by the repetition of an operation in which a photocurable liquid composition containing ceramic particles is irradiated with a light, to form a cured layer of the composition, and the composition is again supplied onto the cured layer and the composition is irradiated with a light, to further form a cured layer of the composition, wherein the composition comprises the following (A) to (C) components: (A) ceramic particles having a number average particle diameter of 0.01 to 0.5 μm, as measured by the electron microscopy, (B) a compound having a polymerizable functional group, and (C) a photopolymerization initiator.

Description

 Specification

 Manufacturing method of three-dimensional object and three-dimensional object

 Technical field

 [0001] The present invention relates to a method for producing a three-dimensionally shaped article useful for forming ceramics. More specifically, a process for producing a three-dimensional product using a photocurable liquid composition having excellent fluidity and curability during optical layered modeling by containing ceramic particles having an extremely small particle diameter, and this photocuring property. The present invention relates to a three-dimensional shape made of a cured product of a liquid composition, and a ceramic fired body obtained by firing the three-dimensional shape.

 Background art

 [0002] Metal powders such as aluminum and silicon, and ceramic powders are dispersed in a binder made of a photocurable liquid composition and cured by a known additive manufacturing method to form a desired three-dimensional shape. The technology for firing and manufacturing a three-dimensional shape having a complicated shape is known.

 As such additive manufacturing methods, modeling is performed by various rapid prototyping methods based on numerical data of the target solid shape obtained using CAD (Computer Aided Design) / CAM (Computer Aided Manufacturing). Technology. Specifically, a resin mixture is discharged from a nozzle and thermally cured (Patent Document 1), a metal powder is melted and discharged from a nozzle and stacked (Patent Document 2), an optical additive manufacturing method There are known methods of using the method (Patent Documents 3 to 9). The optical additive manufacturing method has advantages such as easy formation of fine shapes, and its use has been actively studied.

 Here, as a known optical layered modeling method, a thin layer liquid surface of a photocurable resin liquid is irradiated with light to form a cross-section hardened layer having a desired pattern, and then photocurable on the hardened layer. A typical method is to form a three-dimensional object with a desired shape by supplying the resin liquid for one layer, further forming a cross-section hardened layer, and repeating this operation by laminating and integrating the cross-section hardened layers. (For example, refer nonpatent literature 1.).

[0003] Non-Patent Document 1: Paul F. Jacobs, “Basics of High-Speed 3D Molding”, 1st Edition, Nikkei BP Publishing Center, December 10, 1993, p. 379- 406 Patent Document 1: Japanese Unexamined Patent Publication No. 2000-144205

 Patent Document 2: JP 2003-129862 A

 Patent Document 3: JP-A-8-252867

 Patent Document 4: Japanese Patent Laid-Open No. 2001-261977

 Patent Document 5: JP-A-8-252867

 Patent Document 6: Japanese Patent Laid-Open No. 7-60844

 Patent Document 7: JP-A-2004-143247

 Patent Document 8: JP-A-6-329460

 Patent Document 9: JP-A-8-91940

[0004] However, in these techniques, when the additive manufacturing method uses a thermosetting resin, it is difficult to form a three-dimensional object having a complicated shape, or an optical additive manufacturing method is used. However, since ceramic powder with a relatively large particle size of about 1 μm or more has been used in the past, the proportion of ceramic powder in the volume of the resulting three-dimensional object is low. The density of the fired body obtained by firing the three-dimensionally shaped product was less than 90% by weight of the density of the ceramic powder itself. In addition, since a large amount of a solvent and a binder composition must be mixed, there is a drawback that it is difficult to produce a fired ceramic body having sufficient strength.

 Disclosure of the invention

 [0005] The present inventors show good fluidity and photocurability even when the ceramic filling ratio in the mixture of the ceramic powder and the like and the binder composition is increased. The study was conducted with the aim of developing a method for manufacturing a three-dimensional object that can easily form a desired three-dimensional object. As a result, the inventors have found that the above object can be achieved by using finer ceramic particles (ceramic powder) than those conventionally used, and have completed the present invention.

 That is, the present invention provides the following three-dimensionally shaped product manufacturing method, three-dimensionally shaped product, and ceramic sintered body.

[1] A photocurable liquid composition containing ceramic particles is irradiated with light to form a cured layer of the composition, and the composition is again supplied onto the cured layer and irradiated with light. And By repeatedly forming a cured layer of the composition, a method for producing a three-dimensional object that forms a three-dimensional object in which the cured layer is laminated and integrated,

 A method for producing a three-dimensional product, wherein the composition contains the following components (A) to (C).

(A) Ceramic particles having a number average particle diameter by electron microscopy of 0.0:! To 0.5 x m,

(B) a compound having a polymerizable functional group, and

 (C) Photopolymerization initiator

 [2] The method for producing a three-dimensional product according to the above [1], comprising (A) 10% by volume or more of the ceramic particles (A) with respect to the total amount of the composition.

 [3] The method for producing a solid shaped article according to the above [1] or [2], wherein the (A) ceramic particles are alumina particles.

 [4] The method for producing a three-dimensional product according to any one of the above [1] to [3], wherein the component (B) is a radical polymerizable compound and Z or a cationic polymerizable compound.

 [5] The three-dimensionally shaped article according to any one of [1] to [4] above, wherein the component (B) comprises a radical polymerizable compound having three or more polymerizable functional groups. Manufacturing method.

 [6] Obtained by curing a photocurable liquid composition comprising the following components (A) to (C)

A three-dimensional object.

 (A) ceramic particles having a number average particle diameter of 0.01 to 0.5 / im by electron microscopy,

(B) a compound having a polymerizable functional group, and

 (C) Photopolymerization initiator

 [7] A ceramic fired body obtained by firing the three-dimensional product according to [6].

[0007] The method for producing a three-dimensionally shaped article of the present invention exhibits good fluidity and photocurability even when the ceramic filling rate in the mixture of ceramic powder and the like and the binder composition is increased. As a result, there is an effect that a desired three-dimensional shape can be easily modeled by the optical layered modeling method. For this reason, the method for producing a three-dimensionally shaped article of the present invention is suitable for producing a ceramic fired body.

 Brief Description of Drawings

FIG. 1 is a diagram showing a typical example of an optical three-dimensional modeling method (a method for producing a three-dimensional object) according to the present invention. FIG. 2 is a design drawing of a three-dimensional object produced in Example 1.

 FIG. 3 is an electron microscopic image of a three-dimensionally shaped product (unfired) produced in Example 1.

 FIG. 4 is an electron microscopic image of the fired body produced in Example 1.

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0009] Hereinafter, a method for producing a three-dimensional object of the present invention will be described.

 The method for producing a three-dimensionally shaped article of the present invention comprises (A) ceramic particles having a number average particle diameter of 0.01 to 0.5 / m by electron microscopy, (B) a compound having a polymerizable functional group, and (C) This is an optical layered modeling method using a photocurable liquid composition containing a photopolymerization initiator. By adopting such a photocurable liquid composition, the photocurable liquid composition exhibits thixotropic characteristics, has low viscosity resistance, and can be used to store an uncured liquid composition with a pump or the like. Since it can be fed easily, stirring is easy and a uniform particle dispersion state can be maintained over a long period of time, and after applying an uncured liquid composition on an existing cured layer, it easily loses fluidity. Since a stable coating layer can be obtained, a three-dimensional object containing ceramic particles can be easily produced using a general optical layered manufacturing method.

 [0010] 1. Photocurable liquid composition

 The photocurable liquid composition used in the present invention comprises (A) ceramic particles having a number average particle diameter of 0.01-0. By electron microscopy, (B) a compound having a polymerizable functional group, and (C) light. It contains a polymerization initiator.

 [0011] Component (A) is ceramic particles. Here, the particle is a concept including powder. The number average particle diameter, as measured by electron microscopy, is usually from 0.01 to 0., preferably from 0.02 to 0, and more preferably from 0.05 to 0. is there. The particle size of the component (A) is measured by electron microscopy, and scanning electron microscopy is particularly preferred. The shape of the component (A) is not particularly limited as long as it has a granularity that can define the particle size. For example, it is not limited to a spherical shape, and may be a pulverized body. The particle diameter in the case of a shape other than a spherical shape is defined by the maximum diameter in the electron microscope image.

The material constituting the component (A) is not particularly limited as long as it does not substantially absorb light having an irradiation wavelength. For example, oxides such as alumina, zirconium, titania, zinc oxide, ferrite, barium titanate, apatite, silica, etc., charcoal such as zinc carbide, carbon carbide, etc. Various ceramics such as nitride, aluminum nitride, silicon nitride, sialon (SiAlON), or a mixture thereof can be used. Usually, as the component (A), alumina, dinoleconia, silica, aluminum nitride, silicon nitride, or a mixture thereof is preferably used.

 [0013] As the component (A), alumina particles are preferable in that a commercially available product having a relatively small particle diameter can be easily obtained. Examples of commercially available alumina particles that can be used as component (A) include AKP-20 (0.5 zm), AKP_30 (0.3 μm), AKP_50 (0.2 μm) (Sumitomo Chemical Industry Co., Ltd.) and TM_DAR (0.17 zm; manufactured by Daimei Chemical Industry Co., Ltd.).

 [0014] The content of the component (A) is usually 10% by volume or more, preferably 20% by volume or more, and more preferably 30% by volume with respect to the entire photocurable liquid composition. More preferably, it is 35% by volume or more. The upper limit for volume% is not fixed because the specific gravity differs depending on the material of component (A). However, the weight% is 95% by weight with respect to the entire photocurable liquid composition. It is preferably 90% by weight or less, more preferably 85% by weight or less. For example, the specific gravity of α-alumina is 3.90, and if the specific gravity of the components (Β) and (C) is approximately 1.0, 95% by weight corresponds to about 83% by volume. When the content ratio of the component (ii) is 35% by volume or more, the present component becomes sufficiently dense in the three-dimensionally shaped product, so that a good ceramic can be produced. If it is 95% by weight or less, the component (ii) can be uniformly dispersed in the composition.

 [0015] (i) a compound having a polymerizable functional group (hereinafter referred to as (i) component),

 There are (B1) radical polymerizable compounds and (Β2) cationic polymerizable compounds.

 [0016] The (B1) radical polymerizable compound is a compound having an ethylenically unsaturated bond (C = C) in the molecule, and is a concept including a (meth) acrylic monomer. Examples of the component (B1) include monofunctional monomers having one ethylenically unsaturated bond in one molecule, and polyfunctional monomers having two or more ethylenically unsaturated bonds in one molecule. .

[0017] Monofunctional monomers that can be suitably used as the component (B1) include, for example, (meth) atalynoreamide, (meth) atalyleunomonoreforin, 7_amino-3,7-dimethyloctyl (meth) atalylate, Isobutoxymethyl (meth) acrylamide, isobornyloxetyl (meth) a Tallylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) Atarylate, Jetylaminoethyl (meth) acrylate, Laurinole (meth) acrylate, Dicyclopentagen (meth) acrylate, Dicyclopentuloxychetyl (meth) acrylate, Dicyclopentyl ( (Meth) acrylate, N, N-dimethyl (meth) acrylamide, tetrachlorophenyl phenyl (meth) acrylate, 2-tetrachlorophenoxychetyl (meth) acrylate, tetrahydrofurfurinole (meth) acrylate, tetrabromophenyl (Meta) a Relate, 2-Tetrabromophenoxy (meth) acrylate, 2_Trichlorophenoxy (meth) acrylate, Tribromophenyl (meth) acrylate, 2_Tribromophenoxy (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, bull force prolactam, N-butyl pyrrolidone, phenoxycetyl (meth) acrylate, butoxetyl (meth) acrylate, pentachlorophenyl (meta) ) Atarylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxytripropylene glycol (meth) acrylate, bornyl (meth) Relate can be exemplified methyl triethylene diglycol (meth) Atari rate, methoxy propylene glycol (meth) Atari rate, and a compound represented by the following general formula (1) to (3).

[Chemical 1]

In the formula, each R ²¹ independently represents a hydrogen atom or a methyl group, R ²² represents an alkylene group having 26, preferably ²⁴ carbon atoms, and R ²³ represents a hydrogen atom or a carbon number: ! To 12, preferably 19 alkyl group, and R ²⁴ represents an alkylene group having 28, preferably 25 carbon atoms. uf, 0 to: 12, preferably f is an integer of !! to 8, vf is:! to 8, preferably f is an integer of!

 [0020] Among these monofunctional monomers, isobornyl (meth) acrylate, (meth) ateloy loy noremonoreforin, bull force prolatatum, polypropylene glycol mono (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypropylene Glycol (meth) acrylate and phenoxychetyl (meth) acrylate are particularly preferred.

[0021] The polyfunctional monomer that can be suitably used as the component (B1) includes, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, tricyclodecandiyldimethylenedi (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanuratetri (meth) acrylate Rate, force prolataton modified tris (2-hydroxyethyl) iso cyanurate tri (meth) ate, trimethylolpropane tri (meth) ate, ethylene oxide (hereinafter referred to as “E〇”) Say. ) Modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as “Po”) modified trimethylol propane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) attalylate, Bisphenolol A Diglycidyl ether end (meth) acrylic acid adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta erythritol Penta (meth) a Tallylate, dipentaerythritol tetra (meth) acrylate, force prolatatatone modified dipentaerythritol hexa (meth) acrylate, force prolatataton modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, E〇 Modified bisphenol A di (meth) acrylate, P ○ Modified bisphenol A di (meth) acrylate, E ○ Modified hydrogenated bisphenol A A di (meth) acrylate, PO Modified hydrogenated bisphenol A di (meth) attaly Examples thereof include rate, EO-modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolak polyglycidyl ether, and triatalyloyloxetyl phosphate.

[0022] Among these polyfunctional monomers, trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, triatalylooxyethyl phosphate, Particularly preferred are dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate.

 [0023] Commercially available products of the above-mentioned monofunctional monomers include, for example, ACMO (above, manufactured by Kojin Co., Ltd.), KANIX M-101, M-102, M-111, M-113, M-117, M — 152, T〇—12 10 (above, manufactured by Toagosei Co., Ltd.), ΙΒΧΑ (above, manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD TC-1 10S, R—564, R—128H (above, Nippon Gyaku Co., Ltd.) )), Biscoat 160, biscoat 192, biscoat 220, biscoat 320, biscoat 2311HP, biscoat 2000, biscoat 2100, biscoat 2150, biscoat 8F, biscoat 17F (above, manufactured by Osaka Organic Chemical Co., Ltd.) Can be mentioned.

[0024] Commercially available products of multifunctional monomers include, for example, SA1002 (above, Mitsubishi Chemical Corporation ), Biscoat 195, Biscoat 230, Biscoat 260, Biscoat 215, Biscoat 310, Biscoat 214HP, Biscoat 295, Biscoat 300, Biscoat 360, Biscoat GPT, Viscoe 400, Viscoe 700, Viscoe 540, Viscoe 3000, Viscoe 3700, Viscoat 3PA (above Osaka Organic Chemical Industry Co., Ltd.), Carad R—526, HDDA, N PGDA, TPGDA, MANDA, R—551, R—712, R—604, R—684, PET — 30, GPO—303, TMPTA, THE—330, DPHA, DPHA_2H, DPHA_2C, DP HA-21, D—310, D—330, DPCA_20, 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 (above, Japan (Manufactured by Shakuyaku Co., Ltd.), ALONIX 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 (above, manufactured by Toagosei Co., Ltd.), light talate 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, Nippon Steel) Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-401 0, SP-4060 (above, Showa Polymer Co., Ltd.), ^^ -8? £ —4 (Shin Nakamura Chemical Co., Ltd.).

In the present invention, at least a part of the component (B1) is trifunctional or more, that is, a polyfunctional monomer having 3 or more ethylenically unsaturated bonds in one molecule, preferably trifunctional or more. The polyfunctional (meth) acrylate monomer is preferably used. The content of the trifunctional or higher polyfunctional monomer is preferably 10% by weight or more, more preferably 15% by weight or more, particularly preferably 100% by weight of the total component (B). 20% by weight or more. When the content ratio is 10% by weight or more, the composition exhibits good photocurability and a three-dimensional shape having good strength.

 [0026] The above monofunctional monomer and polyfunctional monomer are each singly or in combination of two or more, or a combination of at least one monofunctional monomer and at least one polyfunctional monomer ( Component B) can be configured.

[0027] (B2) The cationically polymerizable compound is irradiated with light in the presence of a cationic photopolymerization initiator. It is an organic compound that causes a polymerization reaction or a crosslinking reaction. Component (B2) includes epoxy compounds, oxetanyl group-containing compounds, oxolane compounds, cyclic acetal compounds, cyclic rataton compounds, thiirane compounds, chetanich compounds, butyl ether compounds, epoxy compounds and reaction products of ratatones. Examples thereof include spiro orthoester compounds, ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds, and vinyl compounds.

[0028] The epoxy compound that can be suitably used as the component (B2) is preferably a cyclohexene oxide group-containing compound or a glycidinole group-containing compound.

 Cyclohexene oxide group-containing compounds are excellent in cationic polymerizability. In addition, the glycidyl group-containing compound can impart flexibility to the resulting polymer, increase the mobility of the polymerization system, and further improve the curability.

[0029] Cyclohexene oxide group-containing compounds that can be suitably used as the component (B2) include, for example, 3, 4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3, 4 epoxycyclohexane Hexilou 5,5-spiro 3,4 epoxy) cyclohexane meta dioxane, bis (3,4-epoxycyclohexenolemethinole) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4 Epoxy-6-methylcyclohexyl lune 3 ', 4' Epoxy 6'-methylcyclohexane carboxylate, methylenebis (3,4-epoxycyclohexane), ethylene glycol di (3, 4-epoxycyclohexylmethinole) Ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), ε Modified 3, 4—epoxy cyclohexyl methyl 3 ′, 4′—epoxy cyclohexyl carboxylate, trimethylcaprolatatone modified 3, 4_epoxy cyclohexyl methyl 1 3 ′, 4 ′ _epoxy cyclohexane carboxylate, β-methylolone δ-valerolataton-modified 3, 4 _epoxycyclohexylmethyl 1 3 ', 4'-epoxycyclohexanecarboxylate etc. can be exemplified, and these compounds can be used alone or in combination of two or more. Can be used.

[0030] Of these, 3, 4_epoxycyclohexylmethyl 1 3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4_epoxycyclohexylmethyl) adipate, ε- Forced prolatatone-modified 3, 4--epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, trimethylcaprolataton-modified 3,4-epoxycyclohexyl methyl-3', 4'-epoxycyclohexanecarboxylate , Β-Methinore δ Bare mouth ratatoton modification 3, 4_Epoxycyclohexylenolemethinole 3 ', 4' _Epoxycyclohexanecarboxylate is particularly preferred 3, 4_Epoxycyclohexylmethyl 1 '3 '_Epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethylol) adipate are preferred.

 [0031] Commercially available compounds containing a cyclohexene oxide group include UVR_ 6100, UVR-6 105, UVR-6110, UVR-6128, UVR-6199, UVR-6200, UVR-6216 (above, Union Carbide) , Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Epolide GT-300, Epolide GT_301, Epolide GT_302, Evolide GT_400, Evolid 401, Epolide 403 (above, manufactured by Daicel Chemical Industries), KRM-2100, KRM-2110, KRM-2199 (above, manufactured by Asahi Denka Kogyo Co., Ltd.)

[0032] Examples of the glycidyl group-containing compound that can be suitably used as the component (B2) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol no A diglycidyl ether, Brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1, 4 butanediol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl noleateol, trimethylone propane triglycidinoleateol, polyethylene glycolenoresidue glycidylate , Polypropylene glycol diglycidyl ethers; polyglycidinole ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these Monoglycidinole ethers; glycidyl esters of higher fatty acids, and the like. These compounds can be used alone or in combination of two or more.

 [0033] Of these, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1, 6— Hexanedioresidyl glycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.

 [0034] Commercially available glycidinole group-containing compounds include Evolite 1600 (manufactured by Kyoeisha Igaku Co., Ltd.), UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel) Chemical Industry Co., Ltd.), Epicourt 828, Epicourt 812, Epicourt 1031, Epiquat 872, Epicote CT508 (above, manufactured by Yuka Shell Co., Ltd.), KR M-2400, KRM-2410, KRM-2408, KRM— 2490, KRM-2720, KRM-2750 (above, manufactured by Asahi Denka Kogyo Co., Ltd.)

 [0035] An oxetanyl group-containing compound (hereinafter referred to as "oxetane compound") that can be suitably used as the component (B2) has at least one oxetane ring represented by the following formula (4) in the molecule. It is a compound.

 Examples of the compound having one oxetane ring in the molecule include a compound represented by the following formula (5).

[0036] [Chemical 2]

 [0037] [Chemical 3]

(Five)

[0038] In the above formula (5), Z represents an oxygen atom or a sulfur atom. R ¹ is a hydrogen atom; a fluorine atom; an alkyl group having from 6 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; a trifluoromethyl group, a perfluoroethyl group, and a perfluoro group. A fluoroalkyl group having 16 carbon atoms such as a propyl group; an aryl group having 6 to 18 carbon atoms such as a phenyl group or a naphthyl group; a furyl group or a chenyl group.

R ² represents a hydrogen atom; a methyl group, an ethyl group, a propyl group, a butyl group, or the like, an alkyl group having! To 6; 1-propenyl group, 2_propenyl group, 2_methyl _ 1 _Propenyl group, 2_methyl _ 2_propenyl group, 1-butulyl group, 2-butulyl group, 3-butulyl group and the like alkenyl group having 26 carbon atoms; phenyl group, naphthyl group, Aryl group having 618 carbon atoms such as anthonyl group, phenanthryl group, etc .; substituted or unsubstituted carbon such as benzyl group, fluorobenzoyl group, methoxybenzyl group, phenethyl group, styryl group, cinnamyl group, ethoxybenzyl group Aralkyl group having 7 to 18 atoms; Group having other aromatic ring such as aryloxyalkyl such as phenoxymethyl group, phenoxychetyl group, etc .; Carbon atom such as ethyl carbonyl group, propylcarbonyl group, butylcarbonyl group 26 alkyl carbonyl group; alkoxy carbonyl group having 26 carbon atoms such as ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, etc .; carbon such as ethylcarbamoyl group, propyl carbamoyl group, butylcarbamoyl group, pentylcarbamoyl group Such as an N-alkyl-powered rubermoyl group having 26 atoms.

 [0039] Examples of the compound having two oxetane rings in the molecule include compounds represented by the following formula (6).

 [0040] [Chemical 4]

In the above formula (6), R ¹ has the same definition as in the above formula (5).

R ³ is a linear or branched alkylene group having 120 carbon atoms such as an ethylene group, a propylene group or a butylene group; a linear or branched group such as a poly (ethyleneoxy) group or a poly (propyleneoxy) group. Branched, poly (alkyleneoxy) group having 1 to 120 carbon atoms; propenylene Linear, branched unsaturated hydrocarbon groups such as a group, methylpropenylene group, butenylene group, etc .; a carbonyl group; an alkylene group containing a carbonyl group; an alkylene group containing a carboxyl group in the middle of the molecular chain; a molecular chain Is an alkylene group containing a rubamoyl group. R ³ may be a polyvalent group selected from the groups represented by any one of the following formulas (7), (8) and (9).

 [0042] [Chemical 5]

In the above formula (7), R ⁴ represents a hydrogen atom; an alkyl group having 14 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group. An alkoxy group having 14 carbon atoms, a halogen atom such as a chlorine atom or a bromine atom, a nitrogen group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group or a force novamoino group, and X is: It is an integer of 4.

[0044] [Chemical 6]

In the above formula (8), R ⁵ represents an oxygen atom, a sulfur atom, a methylene group, —NH—_SO_

 -SO C (CF) — or one C (CH) —.

 2 3 2 3 2

 [0046] [Chemical 7]

'''( ⁹⁾

In the above formula (9), R ⁶ is an alkyl group having 14 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group; the number of carbon atoms such as a phenyl group or a naphthyl group. 6 ~: 18 aryl groups. y is an integer of 0 200. R ⁷ is methyl, ethyl, propyl, butyl, An alkyl group having 1 to 4 carbon atoms such as a til group; an aryl group having 6 to 18 carbon atoms such as a phenyl group or a naphthyl group; or a group represented by the following formula (10).

[0048] [Chemical 8]

In the above formula (10), R ⁸ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group; a carbon atom number such as a phenyl group or a naphthyl group 6 to: 18 aryl groups. z is an integer from 0 to 100.

 [0050] Specific examples of the compound having two oxetane rings in the molecule include compounds represented by any of the following formulas (11), (12), and (13).

 [0051] [Chemical 9]

 [0052] [Chemical 10]

[0053] [Chemical 11]

In the above formula (13), R ¹ is the same as defined in the above formula (5).

[0055] The compound having three or more oxetane rings in the molecule is represented by the following formula (14). Compounds and the like.

 [0056] [Chemical 12]

In the above formula (14), R ¹ is the same as defined in the above formula (5). R ⁹ represents a trivalent organic group, for example, a branched or linear alkylene group having 1 to 30 carbon atoms such as a group represented by any of the following formulas (15) to (17), Examples thereof include branched poly (alkyleneoxy) groups such as the group represented by (18), linear or branched polysiloxane-containing groups represented by the following formula (19) or formula (20), and the like. j represents an integer of 3 to 10 equal to the valence of R ⁹ .

[0058] [Chemical 13]

In the above formula (15), R ^1U represents 1 carbon atom such as a methinole group, an ethyl group, a propyl group, or the like.

Is an alkyl group of ˜6.

[0060] [Chemical 14]

CH _2- "" GHg One C— CH-"

CH _2-

[0061] [Chemical 15]

― CH,-CH. -CH-CH ₂ _CH-CH CH ₂ — ••• (17)

[0062] [Chemical 16]

[0063] In the formula (18), L is the same or different,:! _C is an integer between 10

[0064] [Chemical 17]

 rtg

CH. CH- CH ₂ — Si— 0 · CH ₂ -CH-CH _a -... (19)

 CHg CH3 CH3 CHg

[0065] [Chemical 18]

 [0066] Specific examples of the compound having three or more oxetane rings in the molecule include compounds represented by the following formula (21).

[0067] [Chemical 19]

[0068] The compound represented by the following formula (22) may have 1 to 10 oxetane rings in the molecule _c

[0069] [Chemical 20]

[0070] In the above formula (22), R ¹ has the same definition as in the above formula (5), and R ¹¹ has 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group. An alkyl group or a trialkylsilyl group (wherein the alkyl group is the same or different and is an alkyl group having 3 to 12 carbon atoms. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triprovirsilyl group. And tributylsilyl group, etc.), and r represents an integer of 1 to 10.

 [0071] Further, the oxetane compound has a high molecular weight of about 1,000 to 5,000 in terms of polystyrene measured by gel permeation chromatography (GPC) in addition to the above-described examples. Also included are compounds. Examples thereof include compounds represented by any of the following formula (23), formula (24), and formula (25).

 [0072] [Chemical 21]

 (Here, pi is an integer between 20 and 200.)

 [0073] [Chemical 22]

(Where qi 15 is an integer of 100 :)

[Chemical 23]

 (Here, si is an integer from 20 to 200.)

 Specific examples of the oxetane compound described above are as follows.

[Compound with one oxetane ring in the molecule]

3-Ethyl _ 3-hydroxymethyloxetane, 3- (Meth) aryloxymethyl _ 3-Ethyloxetane, (3-Ethyl_ 3-oxetanylmethoxy) methylbenzene, 4-Funoleo [1 _ (3-Ethyl_ 3-Oxetanylmethoxy) methyl] benzene, 4-Methoxy- [1_ (3-Ethyl_3-Oxetanylmethoxy) methyl] benzene, [1_ (3_Ethyl_3—O Xethanylmethoxy) ethinole] phenyl ether, isobutoxymethyl (3-ethyl-1-3-acetanylmethinole) ether, isobornyloxetyl (3-ethyl _ 3 -xetaneylmethinole) ether, isobornyl (3-Ethyl-3-oxetanylmethinole) ether, 2-Ethylhexyl (3-Ethyl-3-oxetanylmethyl) ether, Ethyljetylene glycol (3-Ethyl 3-Oxy) Tanylmethinole) ether, dicyclopentagen (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxychetyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentyl (3-ethyl-3-oxetanyl) Methyl) ether, tetrahydrofurfurinole (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxetyl (3-ethyl-3-oxetanylme) Til) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxychetyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3_ Ethyl _ 3—oxetanylmethinole) ether, 2-hydroxy Propyl (3-Echiru _ 3 O xenon Tani Le methylol Honoré) ether, Butokishechiru (3-E Ji Le one 3-O xenon Tani Le methylol Honoré) ether, pentachlorophenyl (3-Echiru _ 3 O key Cetanylmethynole) ether, pentabromophenyl (3-ethyl-3-ethylacetonyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like.

[Compound with two or more oxetane rings in the molecule]

3, 7_bis (3 oxetanyl) _ 5 _oxanononane, 3, 3 '_ (1, 3_ (2 methylenyl) propanediylbis (oxymethylene)) bis (3-ethyloxetane), 1, 4-bi Sus [(3 ethyl_ 3-oxetanylmethoxy) methyl] benzene, 1,2_bis [(3-ethynole_3-oxetanylmethoxy) methyl] ethane, 1,3_bis [(3 _ Ethyl _ 3 _oxetaninolemethoxy) methinole] pronone, ethyleneglycololebis (3-ethynole _3-oxetanylmethyl) ether, dicyclopenturbis (3-ethyl _3_oxetanylmethyl) ether, tri Ethylene glycol bis (3-ethyl _ 3-oxetanylmethinole) ether, tetraethylene dallicol bis (3-ethyl _ 3-oxetanylmethinole) ether, tricyclodecanedyldimethylene (3 _ Ethyl _ 3 -Oxetanylmethinole) ether, Trimethylolpropane tris (3-Ethyl-3-oxetanylmethinole) ether, 1,4-bis (3-Ethyl3-oxetanylmethoxy) butane, 1 , 6-bis (3-ethyl 3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-Ethyl-3-oxetanylmethinole) Itel, Dipentaerythritol Hexakis (3-Ethyl-3-oxetanylmethinore) Iter, Dipentaerythritol Pentaquist (3-Ethyl-3-3-Oxe) Tanylmethyl) ite, dipentaerythritol tetrakis (3-ethylol-3-oxy) Cetaneylmethinole) ether, force prolataton-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, force prolatataton-modified dipentaerythritol pentakis (3-ethynole 1-oxetanylmethinore) ether, ditri Methylolpropanetetrakis (3-ethynole _ 3-oxetanylmethyl) ether, E〇 modified bisphenol A bis (3-ethyl-1-3-xetanylmethyl) ether, P〇 modified bisphenol bis (3_ethyl _ 3-Oxetanylmethyl) ether, E〇 Modified hydrogenated bisphenolanol A bis (3_ethyl _3-oxetanylmethyl) ether, P〇 Modified hydrogenated bisphenolanol A bis (3-ethyl) _3_ Oxetanylmethyl ) Ether, E〇 Modified Bisphenol F (3_Ethyl_3-Oxeta Nylmethyl) ether and the like.

 These can be used alone or in combination of two or more.

[0077] Of these, the oxetane compound that can be suitably used as the component (B2) is a compound having 1 to 10, more preferably 1 to 4, particularly preferably 2 oxetane rings in the molecule. is there. Specifically, (3-Ethyl_3-oxetanylmethoxy) methylbenzene represented by the following formula (26), 1,4_bis [(3_Ethyl_3-oxetanylmethyl) represented by the following formula (27): Toxi) methyl] benzene, 1,2-bis (3-ethyl) -3-oxetanylmethoxy) ethane represented by the following formula (28), trimethylolpropane tris represented by the following formula (29) (3- (Cyl-3-oxetanylmethyl) ether, 3_ethyl_3_oxetanylmethoxybenzene represented by the following formula (30), and a compound represented by the above formula (22).

[0078] [Chemical 24]

[0081] [Chemical 27]

[0083] These oxetane compounds can be used alone or in combination of two or more.

 [0084] The content ratio of the component (B) is usually 1 to 65% by weight based on the entire photocurable liquid composition, regardless of whether the component (B1) or the component (B2) is used. It is preferably 5 to 40% by weight, more preferably 10 to 30% by weight. When the content ratio of the component (B) is 1% by weight or more, the component (A) is uniformly dispersed in the present composition. Further, if it is 20% by weight or less, the content ratio of the component (A) in the present composition increases, and the volumetric shrinkage of the three-dimensionally shaped product after firing can be reduced.

 On the other hand, when the content ratio of the component (B) is too small, the viscosity increases and the composition does not have sufficient fluidity. In addition, when this content ratio is excessive, the content ratio of the component (A) is decreased, the strength of the three-dimensional object is reduced, or cracks and other defects are lost when the three-dimensional object is degreased and fired. May occur.

 As the component (B), the component (B1) and the component (B2) can be used in combination.

 [0085] (C) Photopolymerization initiator (hereinafter referred to as component (C)) is (C1) a radical photopolymerization initiator when (B1) radical polymerizable compound is used as component (B). (B2) When a cationically polymerizable compound is used, (C2) a cationic photopolymerization initiator.

[0086] The (C1) radical photopolymerization initiator is a compound that decomposes by receiving energy rays such as light and initiates a radical polymerization reaction by the generated radicals. Here, energy rays such as light mean visible light, ultraviolet light, infrared light, X-rays, _α rays, rays, γ rays, and the like. Specific examples of the component (C1) include, for example, acetophenone and acetophenone benziketa. , Anthraquinone, 1— (4-Isopropylphenol) 1 2-Hydroxy 1 2-Methyl propanone 1-on, carbazole, xanthone, 4-clobenbenzophenone, 4, 4'-diaminobenzophenone, 1, 1 -Dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thixanthone compounds, 2_methyl _ 1 _ [4_ (methylthio) phenyl] — 2-morpholinopropane 1-2-one, 2-Benzyl-2-dimethylamino —1— (4-morpholinophenyl) 1-butane 1-one, triphenylenolamine, 2, 4, 6 trimethylbenzoyldiphenylphosphine oxide, bis ( 2,6-Dimethoxybenzoyl) -2,4,4_trimethylpentylphosphine oxide, benzyldimethylketanol, 1-hydroxycyclohexenoleveno Reketone, 2-hydroxy _ 2-methinole _ 1-phenylpropane _ 1 _one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, 3_methylacetophenone, 3, 3 ', 4, 4'— Examples include tetra (t_butylperoxycarbonyl) benzophenone (BTTB), and combinations of BTTB with xanthene, thixanthene, coumarin, ketocoumarin and other dye sensitizers. Of these, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6 trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-1-2-dimethylamino-1- (4-morpholinophenol) ) Butane 1-on is particularly preferred. These can be used alone or in combination of two or more to constitute the component (C1).

[0087] The (C2) cationic photopolymerization initiator is a compound capable of releasing the substance that initiates the cationic polymerization of the component (B2) by receiving energy rays such as light.

As an example of the compound of the component (C2), an ion salt having a structure represented by the following formula (31) can be cited. This onium salt is a compound (photoacid generator) that releases Lewis acid upon receiving light.

[0088] [R ⁰¹ R. ² R. ³ R. ⁴ W] ^{m +} [MX] ^m — (31)

 a b e d n + m

[Wherein the cation is an ion, W is S, Se, Te, P, As, Sb, Bi, 0, I, Br, CI or —N≡N,

R ° ² , R. ³ and R ° ⁴ are the same or different organic groups, 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 is A metal or metalloid constituting the central atom of the halide complex [MX], for example n + m

 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. ]

[0089] Specific examples of the ion ion represented by the above formula (31) include diphenyl rhododonium,

 4-methoxydiphenyl, bis (4-methylphenyl), bis (4-tert-butylphenyl), bis (dodecylphenyl), sulfonylsulfone, diphenyl-4-dithiophenoxysulfonyl, bis [ 4- (diphenylsulfonio) monophenyl] sulfide, bis [4- (di (4- (2-hydroxyethylenole) sulfinole) sulfonio) monophenyl] sulfide, 5- 2 , 4 _ (cyclopentagenyl)

 [1, 2, 3, 4, 5, 6 _] _ (methylethyl) -benzene] -iron (1 +) and the like. Specific examples of the anion [MX] in the above formula (31) include tetrafluorobore 1 + m

 (BF-), Hexafluorophosphate (PF-), Hexafluoroantimonate (SbF

 4 6

―), Hexafluoroarsenate (AsF-), Hexaclo oral antimonate (SbCl ^_ ), etc.

6 6 6

 [0090] In addition, an onium salt having an anion represented by the general formula [MX (OH) —] can be used. In addition, perchlorate ion (CIO-), trifluoromethanesulfonate ion (C

 Four

 F SO _), Fluorosulphonate ion (FS0-), Toluene sulphonate ion, Tri

3 3 3

 Onion salts having other anions such as nitrobenzene sulphonate aniline, trinitrotonol senorephonate aniline, and the like can also be used.

[0091] Among such onium salts, compounds particularly effective as the component (C2) are aromatic onium salts. For example, aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, etc., JP-A-50-151997, JP-A-52-30899, JP-A-56. — VIA group aromatic onion salts described in JP 55420, JP 55-125105 A, etc., VA group aromatic onium salts described in JP 50-158698 A, etc., JP 56-8428 Oxosulfoxonium salts described in JP-A-56-149402, JP-A-57-192429, etc., aromatic diazonium salts described in JP-A-49-17040, etc. Thiobililium salt described in Japanese Patent No. 4,139,655 Etc. are preferred. In addition, iron / allene complex, aluminum complex / photolytic silicon compound system IJ, etc. can be cited.

[0092] Examples of commercially available compounds that can be suitably used as the component (C2) include UVI-6950, UVI-6970, UVI-6974, UVI_6990 (manufactured by Union Carbide), Adeka Opmer SP-150, SP — 151, SP—170, SP—171, SP—172 (above, manufactured by Asahi Denki Kogyo Co., Ltd.), Irgacure 261 (above, manufactured by Ciba “Specialty” Chemicals), CI— 2481, CI — 2624, CI— 2639, CI— 2064 (above, Nippon Soda Co., Ltd.), CD—1010, CD—1011, CD—1012 (above, manufactured by Thermar), DTS—102, DTS—103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (above, Midori Chemical Co., Ltd.), PCI_061T, PCI_062T, PCI_020T, PCI_022T (above, Nippon Kayaku ( And the like). Among these, UVI-6970, UVI-6974, Adeka OPMER SP-170, SP-171, SP-172, CD-1012 and MPI-103 have high photocuring sensitivity for resin compositions containing them. Is particularly preferred since it can be expressed.

 The above photoacid generators can be used alone or in combination of two or more to constitute the component (C2).

 [0093] The content ratio of the component (C) is usually 0.01 to 10 wt% with respect to the entire photocurable liquid composition, regardless of whether the component (C1) or the component (C2) is used. %, Preferably 0.1 to 8% by weight. When the content ratio of the component (C) is too small, the radical polymerization reaction rate (curing rate) of the composition is lowered, so that time is required for modeling or the resolution is lowered. On the other hand, when the content ratio of the component (C) is excessive, an excessive amount of this component lowers the curing characteristics of the present composition or lowers the strength of the three-dimensional object. In addition, when the components (B1) and (B2) are used together as the component (B), the components (C1) and (C2) can be used together as the component (C).

[0094] The photocurable liquid composition used in the present invention may contain various additives as other optional components as long as the objects and effects of the present invention are not impaired. Examples of such additives include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprene, polyetheroles, polyesteroles, styrene-butadiene resins. Polymers and oligomers such as lock copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, silicone-based oligomers, polysulfide-based oligomers, aryl ether copolymers; phenothiazines, 2,6-di-tert-butyl Polymerization inhibitors such as 4-methylphenol; polymerization initiators; leveling agents; wettability improvers; surfactants; plasticizers; ultraviolet absorbers; silane coupling agents; inorganic fillers; pigments; Light of amine compounds such as noroleamine, methyljetanolamine, triethinoleamine, and jetylamine, thixanthone and its derivatives, anthraquinone and its derivatives, anthracene and its derivatives, perylene and its derivatives, benzophenone, benzoin isopropyl ether, etc. Sensitizer Polymerization accelerator); vinyl ethers, Binirusurufuido acids, Bulle urethanes, urethane Atari rate such, such as reactive diluents such Byuruurea acids are exemplified up.

 [0095] The photocurable liquid composition used in the present invention can be produced by uniformly mixing the above components (A) to (C) and optionally the above optional components.

 It can also be produced by a method in which the component (A) is dispersed in a base resin liquid in which the components (B) and (C) are mixed beforehand.

[0096] The viscosity of the photocurable liquid composition obtained in this way is not particularly limited as long as it is in a range in which it can be flowed by an external force, but it does not flow in a state in which no external force is applied, and flows by applying an external force. It preferably has thixotropic properties.

[0097] 2. Manufacturing method of three-dimensional object

 The manufacturing method of the three-dimensionally shaped product of the present invention employs the above-mentioned photocurable liquid composition for the optical layered modeling method. The optical additive manufacturing method is not particularly limited. A typical example of the optical three-dimensional modeling method of the present invention will be described with reference to the drawings.

 First, as shown in FIG. 1 (a), a support stage 3 provided in a self-lifting manner is placed in a container 2 containing a photocurable liquid composition 1, and a minute amount is lowered from the liquid level 4 of the composition 1. By (sedimentation), composition 1 is supplied onto support stage 3 to form a thin layer of composition 1. Next, the thin layer is selectively irradiated with light to form a cured product (cured resin layer) 6 of the composition 1.

Next, as shown in Fig. 1 (b), the support stage 3 is lowered (sedged) by a small amount, and this hardening is performed. Composition 1 is fed over article 6 to again form a thin layer of composition. Next, the thin layer is selectively irradiated with light, and a new cured product 7 is further formed on the cured product 6 so as to be laminated continuously and continuously therewith. Then, by repeating this process a predetermined number of times with or without changing the pattern irradiated with light, a three-dimensional object formed by integrally laminating a plurality of continuous hard layers is formed. .

[0098] Various means can be employed as the means for selectively irradiating the photocurable liquid composition with light, not particularly limited. For example, a means for irradiating the composition while scanning convergent light obtained by using laser light or a lens, a mirror, etc., a mask having a light transmitting portion of a predetermined pattern, and this mask A means for irradiating the composition with non-converged light and a light guide member formed by bundling a number of optical fibers, and light is transmitted through the optical fiber corresponding to a predetermined pattern in the light guide member. Means for irradiating the composition, means for controlling ONZOFF of light irradiation using each mirror as a pixel using a digital mirror device, and the like can be employed. 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 the same principle as a liquid crystal display device is used. You can also. In the above, when the target three-dimensional object has a fine part or a high dimensional accuracy is required, a laser with a small spot diameter is used as a means for selectively irradiating the composition with light. It is preferable to employ means for scanning light. When the composition is contained in the container, the light irradiation surface (for example, the scanning plane of the convergent light) is either the liquid surface of the composition or the contact surface with the vessel wall of the translucent container. May be. 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.

[0099] In the optical additive manufacturing method, usually, after a specific part of the composition is cured, the light irradiation position (irradiation surface) is moved continuously or stepwise to the uncured partial force uncured part. By doing so, the cured parts are laminated to obtain a desired three-dimensional shape. Here, the irradiation position can be moved by various methods, for example, by moving any one of the light source, the composition container, and the already cured portion of the composition, or additionally supplying the composition to the container Or the like. [0100] 3. Solid objects

 Next, the three-dimensional object of the present invention will be described. The three-dimensionally shaped product of the present invention is composed of a cured product of the above-described photocurable liquid composition. The obtained three-dimensional object is taken out of the container and the unreacted composition (uncured) remaining on the surface is removed, and then washed as necessary. Here, as cleaning agents, 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 .; typified by terpenes Aliphatic organic solvents; low viscosity thermosetting resins and photocurable resins.

[0101] 4. Ceramic fired body

 After the post-treatment of the above three-dimensionally shaped product, when the three-dimensionally shaped product of the present invention is fired, a ceramic fired body can be obtained. The firing method used here is not particularly limited, and a known method can be used.

 [0102] As described above, even when the ceramic filling ratio in the mixture of the ceramic powder and the binder composition is increased by using the method for producing a three-dimensionally shaped article of the present invention, good fluidity can be obtained. As a result, the desired three-dimensional shape can be easily modeled by the optical layered modeling method. The three-dimensional object of the present invention usually has a bending strength of 150 to 300 MPa.

 [Example]

 [0103] Hereinafter, specific embodiments of the present invention will be described by way of examples. However, the present invention is not limited to the embodiments described in the following examples.

 [0104] Example 1

 (1) Preparation of photocurable liquid composition

Methoxypropylene glycol atylate 18. Og, Tris (2-hydroxyethyl) isocyanurate triatalylate 6.5 g, 1-hydroxycyclohexyl phenyl ketone 1.4 g, manufactured by Nippon Oil & Fats Co., Ltd., Marialim AKM_0531 (Aryl ether copolymer, dispersant) 72.5 g of alumina particles (TM—DAR; manufactured by Daimei Chemical Co., Ltd.) with an average particle size of 0.17 zm were added to a binder resin consisting of 1.6 g of a mixture. (40% by volume of the total amount of the composition), made by TK HOMO DISPER, made by Tokushu Kika Kogyo Co., Ltd. A photocurable liquid composition was prepared.

 Table 1 shows the composition (% by weight) of the obtained composition and the volume percentage of alumina particles.

[0105] (2) Production of three-dimensional object

 Using the photocurable liquid composition described above, a three-dimensional object was prepared using an optical modeling apparatus (SCS-300P type, manufactured by Sony Corporation).

 Fig. 2 shows a design drawing of the target 3D object, and Fig. 3 shows an electron micrograph of the 3D object obtained.

[0106] (3) Fabrication of fired body

 Using the atmospheric degreasing furnace (KM-100, manufactured by Advantech Co., Ltd.), the three-dimensional product obtained in (2) above was heated to 900 ° C at a temperature rising rate of 0.33 ° C / min. After maintaining at 900 ° C for 2 hours, it was degreased by natural cooling. After that, using an air sintering furnace (SUP ER BURN SH-1415C MS0373, manufactured by Motoyama Co., Ltd.), heat to 1500 ° C at a rate of temperature increase of 8.5 ° C / min. After maintaining for 2 hours, the product was naturally cooled to obtain a fired body.

 FIG. 4 shows an electron micrograph of the obtained fired body.

[0107] Comparative Example 1

 A photocurable liquid composition was prepared in the same manner as in Example 1 except that alumina particles having an average particle diameter of 4 / im were used instead of alumina particles having an average particle diameter of 0.17 μΐη used in Example 1. Then, a three-dimensional object was produced using the same, and a fired body was produced.

[0108] [Evaluation method]

 The flowability, thixotropic property and photocurability of the photocurable liquid composition obtained in Example 1 and Comparative Example 1, the molding accuracy of the cured product, the linear shrinkage ratio of the fired product, and the success or failure of the fired product. Evaluation was performed under the following conditions. The results are shown in Table 1.

 (1) Fluidity: The fluidity was evaluated by the coating property when the photocurable liquid composition placed on the glass plate was spread using a stainless applicator. At this time, the case where the uniform coating was easily performed was judged as “◯”, and the case where a crack occurred was judged as “X”.

[0109] (2) Thixotropic property: A photocurable liquid composition coated on a glass plate so as to have a height of lOO xm or more is scraped off with a scraper in parallel with the glass plate to evaluate thixotropic property. I was worth it. At this time, only the photocurable liquid composition in contact with the scraper flows, the other portions do not flow, and the thread is not seen in the peripheral portion of the scraper end. If the part that is not in direct contact with the scraper also flows or stringing is observed at the end, it was judged as “X”.

[0110] (3) Photocurability: Laser light with an energy density of 100 mW / cm ² (wavelength of 355 nm, using the SCS-300P manufactured by Sony Corporation as a molding machine) by optical additive manufacturing method. The photocurability was evaluated by scanning once linearly at a speed of 290 mm / s. At this time, “◎” indicates that a cured product having a cured depth of 140 zm or more is obtained, “◯” indicates that a cured product having a cured depth of less than 140 xm is obtained, and “X” indicates that a cured product is not obtained. Was determined.

 [0111] (4) Modeling accuracy of the three-dimensional object: Measure the external dimensions in the X, Υ, and Ζ axis directions of the three-dimensional object, and if the difference from the design dimension is 100 zm or less, ”And“ X ”when lOO xm is exceeded.

 [0112] (5) Linear shrinkage rate (%) of the fired body: Measure the external dimensions in the X-axis direction of the three-dimensional product before degreasing and the external dimensions in the X-axis direction of the fired body, respectively, and degrease The linear shrinkage rate was calculated from the amount of change in the external dimensions before and after the treatment and before and after the firing treatment.

 [6] (6) Success or failure of fired body: “O” was determined when cracks were not generated in the degreasing or firing process, and “X” was determined when cracks were generated.

 [0114] [Table 1]

[0115] From the results in Table 1, by using alumina particles having a small average particle diameter, It can be seen that a three-dimensional object having excellent modeling accuracy can be obtained, and a fired body obtained by firing the same does not cause cracking or the like in a degreasing or firing process with a low linear shrinkage rate. Industrial applicability

 The photocurable liquid composition used in the method for producing a three-dimensional product of the present invention has good fluidity and photocurability even when the ceramic filling ratio in the mixture of the ceramic powder and the binder composition is increased. As a result, according to the method for manufacturing a three-dimensional object of the present invention, a desired three-dimensional object can be easily modeled by the optical layered modeling method. Therefore, the method for producing a three-dimensional object of the present invention is suitable for producing a ceramic fired body.

Claims

The scope of the claims

 [1] A photocurable liquid composition containing ceramic particles is irradiated with light to form a cured layer of the composition, and the composition is again supplied onto the cured layer and irradiated with light. A method for producing a three-dimensional product by forming a three-dimensional product in which the cured layer is laminated and integrated by repeating the formation of a cured layer of the composition.

 A method for producing a three-dimensional product, wherein the composition contains the following components (A) to (C).

(A) ceramic particles having a number average particle diameter of 0.01 to 0.5 μΐη by electron microscopy;

(B) a compound having a polymerizable functional group, and

 (C) Photopolymerization initiator

 [2] Containing 10% by volume or more of (A) ceramic particles with respect to the total amount of the composition

The method for producing a three-dimensional object according to claim 1.

[3] The method for producing a three-dimensional product according to claim 1 or 2, wherein the (A) ceramic particles are alumina particles.

 [4] The method for producing a three-dimensionally shaped product according to any one of [1] to [3], wherein the component (B) is a radical polymerizable compound and / or a cationic polymerizable compound.

 [5] The method for producing a three-dimensional product according to any one of claims 1 to 4, wherein the component (B) comprises a radical polymerizable compound having three or more polymerizable functional groups.

 [6] A three-dimensional product obtained by curing a photocurable liquid composition comprising the following components (A) to (C).

 (A) ceramic particles having a number average particle diameter of 0.01 to 0.5 zm by electron microscopy;

(B) a compound having a polymerizable functional group, and

 (C) Photopolymerization initiator

 [7] A ceramic fired body obtained by firing the three-dimensionally shaped article according to claim 6.