JP2008248026A - Photocurable composition for stereolithography and ceramic molding - Google Patents

Abstract

The present invention relates to a composition for use in ceramic molding by stereolithography, and always has good thixotropy and applicability even if the number average particle size and blending ratio of inorganic fine particles that are components of the composition are changed. Is provided, and a photocurable composition capable of producing a highly accurate three-dimensional modeled object is provided.
The composition comprises (A1) 1 to 10% by mass of a monomer having one ethylenically unsaturated group, (A2) 1 to 30% by mass of a monomer having two or more ethylenically unsaturated groups, (B) Component (A1), comprising 0.01 to 10% by weight of a photopolymerization initiator and (C) 60 to 95% by weight of inorganic fine particles having a number average particle diameter of 5 to 300 nm by a dynamic light scattering method. And the content rate of (A1) component is a thing of 10-50 mass% in a total of 100 mass% of (A2) component. The composition 1 is used as a material for the hardened layers 6 and 7 in the optical modeling method, and becomes a three-dimensional modeled object. If the three-dimensional model is fired, a ceramic model is obtained.
[Selection] Figure 1

Description

  The present invention relates to a photocurable composition useful as a material for ceramic molding by optical modeling, a three-dimensional model manufactured using the composition, and a ceramic model formed by firing the three-dimensional model.

Inorganic fine particles such as aluminum and silica are dispersed in a binder made of a liquid resin composition, and this is cured by a layered modeling method to form a desired three-dimensional shaped article, and then fired to form a complicated shape. A technique for manufacturing a three-dimensional shape is conventionally known.
As such an additive manufacturing method, a method in which a resin mixture is discharged from a nozzle and thermally cured, or a method using an optical additive manufacturing method is known. Among these, the optical layered modeling method has an advantage such as easy formation of a fine shape, and therefore its use is actively studied.
Here, as an optical layered modeling method, a thin layer liquid surface of a photocurable resin liquid is irradiated with light to form a cured product (cross-section cured layer) having a desired pattern cross section, and then this cross section A single layer of the photocurable resin liquid is supplied onto the cured layer, 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 typical method is to form a three-dimensional model having a desired shape.

A photocurable resin composition containing ceramic particles having an average particle diameter of 1 μm or more at a high content (for example, 60% by mass) is prepared, and this resin composition is used as a material for an optical modeling method such as an optical lamination modeling method. When creating a three-dimensional model with excellent mechanical properties, the handleability of the resin composition before curing (specifically, fluidity and thixotropy) and the modeling accuracy of the three-dimensional model after curing are high. There was a problem of being inferior.
As means for solving this problem, (A) 1 to 39% by mass of an ethylenically unsaturated monomer, (B) 0.01 to 10% by mass of a photopolymerization initiator, and (C) a number average particle by dynamic light scattering method A photocurable composition for photofabrication containing 60 to 95% by mass of inorganic fine particles having a diameter of 5 to 300 nm has been proposed (Patent Document 1). According to this composition, since the inorganic fine particles having a specific number average particle diameter are blended at a specific blending ratio, good thixotropy is imparted, and as a result, the fluidity of the composition and the composition after coating It is said that the stability of the object layer is improved, and further, the modeling accuracy of the three-dimensional model is increased.
JP 2006-348214 A

According to the knowledge obtained by the present inventor, when only the polyfunctional monomer is used as the component (A) in the technique of the above-mentioned Patent Document 1, the number average particle diameter is It has been found that a composition containing 90 nm zirconia-based fine particles at a high content (for example, 72% by mass) is slightly inferior in thixotropy and has room for improvement. In addition, when zirconia-based fine particles having a number average particle size of 40 nm are used, a good thixotropic property can be obtained if the blending ratio is set to 72% by mass, but the blending ratio is further increased, for example, 80% by mass. It was also found that the fluidity was lowered and the handleability as an optical modeling material was deteriorated at a degree.
Therefore, the object of the present invention is to always have good thixotropy and coating properties even if the number average particle diameter and the mixing ratio of the inorganic fine particles are changed. It is to provide a photocurable composition capable of easily producing a three-dimensional modeled object having a desired shape with high accuracy.

  As a result of investigations to solve the above problems, the present inventors have found that (A1) a monomer having one ethylenically unsaturated group, (A2) a monomer having two or more ethylenically unsaturated groups, (B) A photopolymerization initiator and (C) inorganic fine particles are contained in a specific blending ratio, and the mass ratio of the two components (A1) and (A2) is within a specific range. Thus, according to the composition including (C), even if the number average particle diameter and the blending ratio of the inorganic fine particles are changed, good thixotropy and applicability can always be obtained. The present invention has been completed by finding that it can be easily produced with high accuracy.

That is, the present invention provides the following [1] to [11].
[1] When the total amount of the composition is 100% by mass,
(A1) 1 to 10% by mass of a monomer having one ethylenically unsaturated group,
(A2) 1 to 30% by mass of a monomer having two or more ethylenically unsaturated groups,
(B) 0.01 to 10% by mass of a photopolymerization initiator, and (C) 60 to 95% by mass of inorganic fine particles having a number average particle diameter of 5 to 300 nm by a dynamic light scattering method, and ( The photocurable composition for optical modeling, wherein the content of the component (A1) is 10 to 50% by mass in 100% by mass of the total amount of the component (A1) and the component (A2).
[2] The photocurable composition for optical modeling according to [1], wherein the monomer (A1) having one ethylenically unsaturated group is a nitrogen-containing vinyl compound.
[3] The photocurable composition for optical modeling according to the above [1] or [2], wherein the blending ratio of the inorganic fine particles (C) is 70 to 85% by mass, where the total amount of the composition is 100% by mass. object.
[4] The photocurable composition for optical modeling according to any one of [1] to [3], wherein the (C) inorganic fine particles include zirconia fine particles.
[5] The photocurable composition for optical modeling according to any one of [1] to [4], which is for micro-optical modeling.
[6] A three-dimensional structure formed of a cured product of the photocurable composition according to any one of [1] to [5].
[7] The photo-curable composition for optical modeling according to any one of [1] to [5] is irradiated with light to form a cured layer of the composition, and the cured layer is formed on the cured layer. The composition is supplied again, irradiated with light to further form a cured layer of the composition, and thereafter, by repeating this, a three-dimensional structure formed by laminating and integrating a plurality of cured layers is obtained. Manufacturing method of a three-dimensional molded item.
[8] The method for producing a three-dimensional structure according to [7], wherein the thickness of the hardened layer is 1 to 50 μm.
[9] The method for producing a three-dimensional structure according to [7] or [8], wherein the light irradiation is performed by repeating batch exposure using a digital mirror device for each projection region.
[10] A ceramic model obtained by firing the three-dimensional model described in [6].
[11] The photocuring composition for optical modeling according to any one of the above [1] to [5] is subjected to batch exposure using a digital mirror device for each projection region, and the composition is cured. A layer is formed, and the composition is supplied again on the cured layer, irradiated with light to further form a cured layer of the composition, and thereafter, a plurality of cured layers are laminated by repeating this. And obtaining a three-dimensional structure formed by integration,
A step of washing the obtained three-dimensional structure to remove the remaining unreacted composition; and
A method for producing a ceramic shaped article, comprising a step of firing a three-dimensional shaped article after washing to obtain a ceramic shaped article.

Since the composition of the present invention always has good thixotropy and coating properties even if the number average particle size and blending ratio of the inorganic fine particles are changed, the optical modeling method (optical layering modeling method, micro-optical modeling method, etc.) Thus, a three-dimensional model having a desired shape can be easily produced with high accuracy.
When the “thixotropic property” is good, when the upper part of the uncured layer after application of the photocurable composition of the present invention is scraped with a scraper, only the upper part of the composition in contact with the scraper flows. And there exists an advantage that the lower part of this composition is maintained in the stable state, without flowing. In this case, the workability of the optical modeling using the composition of the present invention is improved, and a three-dimensional modeled product (cured product) having high modeling accuracy can be obtained.
“Applicability” means that the thickness of the photocurable composition of the present invention can be made uniform when a thin uncured layer is formed because the fluidity of the photocurable composition of the present invention is good. Say. When the “applicability” is good, the workability of optical modeling using the composition of the present invention is improved, and a three-dimensional modeled object (cured product) having high modeling accuracy can be obtained.
In particular, according to the composition of the present invention, inorganic fine particles having a relatively small particle size (for example, particles having a particle size of 150 nm or less) can be blended at a high content (for example, 70% by mass or more). High thixotropy can be maintained. Therefore, for example, by using a photocurable composition containing zirconia-based fine particles having a particle diameter of 20 to 120 nm at a content of 70 to 82% by mass, the handleability (applicability and the like) in an uncured state is improved. It is possible to easily produce a three-dimensionally shaped object that is excellent in mechanical properties (such as large mechanical strength) and modeling accuracy while maintaining.
The composition of the present invention can be suitably used not only for the optical layered modeling method but also for the micro stereolithography method.

Hereinafter, the photocurable composition for optical modeling of the present invention will be described.
The composition of the present invention comprises (A1) 1 to 10% by mass of a monomer having one ethylenically unsaturated group, (A2) 1 to 30% by mass of a monomer having two or more ethylenically unsaturated groups (hereinafter referred to as (A1 ) Component and (A2) component are combined and referred to as (A) an ethylenically unsaturated monomer.), (B) 0.01-10% by weight of a photopolymerization initiator, and (C) a number by dynamic light scattering. It contains 60 to 95% by mass of inorganic fine particles having an average particle size of 5 to 300 nm.
Hereinafter, each component will be described in detail.

[(A) component]
(A) component used for the photocurable composition for optical shaping | molding of this invention is an ethylenically unsaturated monomer. (A) An ethylenically unsaturated monomer is a compound which has an ethylenically unsaturated bond (C = C) in a molecule | numerator, for example, a (meth) acrylic-type monomer etc. are contained.
As the component (A), (A1) a monomer having one ethylenically unsaturated bond (monofunctional monomer) in one molecule and (A2) two or more ethylenically unsaturated bonds in one molecule It is essential to use the monomer (polyfunctional monomer) in combination at a specific blending ratio.
(A1) A monofunctional monomer and (A2) a polyfunctional monomer are used in combination at a specific blending ratio, so that (C) inorganic fine particles are blended at a high content (for example, 75 to 80% by mass). However, it is possible to maintain good thixotropy and to have good fluidity (applicability) and stability of the uncured layer after application.
The blending ratio of (A1) monofunctional monomer and (A2) polyfunctional monomer will be described later.

  Examples of the monofunctional monomer that can be suitably used as the component (A1) include nitrogen-containing vinyl compounds such as N-vinylcaprolactam and N-vinylpyrrolidone, (meth) acrylamide, (meth) acryloylmorpholine, and 7-amino-3. , 7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t -Octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromo Phenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, butoki Ethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxytripropylene glycol (meth) acrylate, bornyl (meth) Examples include acrylate, methyltriethylenediglycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, and compounds represented by the following general formulas (1) to (3).

（式中、Ｒ^１は、それぞれ独立に水素原子又はメチル基を示し、Ｒ^２は、炭素数２〜６、好ましくは２〜４のアルキレン基を示し、Ｒ^３は、水素原子又は炭素数１〜１２、好ましくは１〜９のアルキル基を示し、Ｒ^４は、炭素数２〜８、好ましくは２〜５のアルキレン基を示す。ｒは、０〜１２、好ましくは１〜８の整数であり、ｑは、１〜８、好ましくは１〜４の整数である。）

(In the formula, each R ¹ independently represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ³ represents a hydrogen atom or 1 carbon atom. -12, preferably an alkyl group having 1-9, R ⁴ represents an alkylene group having 2-8 carbon atoms, preferably 2-5, r is an integer of 0-12, preferably 1-8. And q is an integer of 1 to 8, preferably 1 to 4.)

  Among these monofunctional monomers, isobornyl (meth) acrylate, (meth) acryloylmorpholine, isobornyl (meth) acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, polypropylene glycol mono (meth) acrylate, methoxytripropylene glycol ( Meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate and the like are preferable, and nitrogen-containing vinyl compounds such as N-vinylcaprolactam and N-vinylpyrrolidone are more preferable. When a nitrogen-containing vinyl compound is used as a monofunctional monomer, in addition to good thixotropic properties, an improvement in the curing speed of the composition, suppression of warpage of the cured product, and the like can be achieved.

  As a commercial item of said monofunctional monomer, for example, ACMO (above, manufactured by Kojin Co., Ltd.), Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO -1210 (above, manufactured by Toagosei Co., Ltd.), IBXA (above, manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD TC-110S, R-564, R-128H (above, manufactured by Nippon Kayaku Co., Ltd.), Biscote 160, Biscote 192, Biscote 220, biscoat 320, biscoat 2311HP, biscoat 2000, biscoat 2100, biscoat 2150, biscoat 8F, biscoat 17F (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

  Examples of the polyfunctional monomer that can be suitably used as the component (A2) include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meta). ) Acrylate, tricyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified tris (2- Hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate (Hereinafter also referred to as “ethoxylated trimethylolpropane tri (meth) acrylate”), propylene oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, bisphenol 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, di Entaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO modified Bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, PO modified hydrogenated bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) Examples thereof include acrylates, (meth) acrylates of phenol novolac polyglycidyl ether, triacryloyloxyethyl phosphate, and the like.

  Among these polyfunctional monomers, trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, triacryloyloxyethyl phosphate, dipentaerythritol hexa (meth) acrylate, dipenta Erythritol penta (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate are particularly preferred.

Commercially available products of the above polyfunctional monomers include, for example, SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat 300, biscoat 360. , Biscoat GPT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Biscoat 3700, Viscoat 3PA (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R -712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, PCA-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 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M- 309, M-310, M-315, M-325, M-400, M-6200, M-6400 (manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP- 2PA, DCP-A (above, Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 As described above, manufactured by Nippon Steel Chemical Co., Ltd.), lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (manufactured by Showa Polymer Co., Ltd.), NK ester A-BPE- 4 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
The monofunctional monomer and the polyfunctional monomer can be used alone or in combination of two or more.

The compounding ratio of the component (A1) (monofunctional monomer) is 1 to 10% by mass, preferably 1 to 7% by mass, more preferably 3 to 100% by mass based on the total amount of the photocurable composition of the present invention. 5% by mass. When the blending ratio of the component (A1) is less than 1% by mass, it may be difficult to obtain good thixotropy. On the other hand, when the blending ratio of the component (A1) exceeds 10% by mass, the viscosity of the composition becomes too low and the applicability may be inferior.
The blending ratio of the component (A2) (polyfunctional monomer) is 1 to 30% by mass, preferably 5 to 30% by mass, more preferably 5 to 100% by mass based on the total amount of the photocurable composition of the present invention. It is 20 mass%, Most preferably, it is 10-20 mass%.
When the blending ratio of the component (A2) is less than 1% by mass, the photocurability of the composition is lowered, and the mechanical strength of the three-dimensional structure (cured product) may be lowered. On the other hand, when the blending ratio of the component (A2) exceeds 30% by mass, it is difficult to obtain good thixotropy, and the handleability of the composition is deteriorated, and the mechanical properties (mechanical strength) of the three-dimensional structure are deteriorated. May decrease.
Moreover, the content rate of the said (A1) component is 10-50 mass% in the total amount of 100 mass% of (A1) component and (A2) component, Preferably it is 10-30 mass%. When the content ratio of the component (A1) is less than 10% by mass, it may be difficult to obtain good thixotropy. On the other hand, when this content rate exceeds 50 mass%, the photocurability of a composition may fall and the mechanical strength of a three-dimensional molded item (hardened | cured material) may fall.

The component (A2) may contain a polyfunctional monomer having 3 or more ethylenically unsaturated bonds in one molecule (sometimes referred to as “trifunctional or more monomers” in this specification). preferable. Preferable examples of the polyfunctional monomer include trifunctional or higher polyfunctional (meth) acrylate monomers.
The content ratio of the trifunctional or higher monomer is preferably 50 to 100% by mass, particularly preferably 70 to 100% by mass, with the total amount of the component (A2) being 100% by mass. When the content is less than 50% by mass, the photocurability of the composition of the present invention may be lowered, and the strength of the three-dimensional structure may be lowered.

[Component (B)]
Component (B) used in the photocurable composition of the present invention is a photopolymerization initiator. (B) The photopolymerization initiator is preferably a radical photopolymerization initiator. A radical photopolymerization initiator is a compound that is decomposed by receiving energy rays such as light and initiates a radical polymerization reaction by generated radicals.

Specific examples of the component (B) include, for example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone. 4,4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone compound, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-propan-2-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-tri-methylpentylphosphine oxide, 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 (t-butyl Peroxycarbonyl) 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 used.
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.

  The blending ratio of the component (B) is 0.01 to 10% by mass, preferably 0.1 to 8% by mass, where the total amount of the photocurable composition of the present invention is 100% by mass. When the blending ratio of the component (B) is less than 0.01% by mass, the radical polymerization reaction rate (curing rate) of the composition becomes small, so that time may be required for modeling or the resolution may be lowered. When the blending ratio of the component (B) exceeds 10% by mass, an excessive amount of the component (B) may reduce the curing characteristics of the composition or the strength of the three-dimensional structure.

[Component (C)]
The component (C) used in the photocurable composition of the present invention is inorganic fine particles.
The lower limit of the number average particle diameter of the component (C) (inorganic fine particles) is 5 nm. When the value is less than 5 nm, the inorganic fine particles may be difficult to disperse due to the intense secondary aggregation of the inorganic fine particles.
The upper limit of the number average particle diameter of the component (C) is 300 nm, preferably 200 nm, more preferably 150 nm, and most preferably 120 nm. When the value exceeds 300 nm, it becomes difficult to impart sufficient thiochromotropy to the composition. In addition, the said number average particle diameter is a measured value by a dynamic light scattering method.

The inorganic fine particles as the component (C) may be any material that does not substantially absorb light having an irradiation wavelength. For example, oxides such as alumina, zirconia, and silica, and carbides such as zirconium carbide and silicon carbide. And various ceramics such as nitrides such as aluminum nitride and silicon nitride, and mixtures thereof.
Among these, zirconia is preferably used in terms of improving the mechanical strength of the three-dimensional model (cured product).
(C) In a component, the content rate of a zirconia becomes like this. Preferably it is 10-100 mass%, More preferably, it is 15-100 mass%. Zirconia can be used in combination with other inorganic fine particles such as alumina.
In the present specification, “XX-based fine particles” mean fine particles containing 50% by mass or more of “XX”.

  The blending ratio of the component (C) is 60 to 95% by mass, preferably 65 to 90% by mass, more preferably 70 to 85% by mass, particularly preferably 100% by mass based on the total amount of the photocurable composition of the present invention. Is 75-80 mass%. When the blending ratio is less than 60% by mass, it is difficult to impart good thixotropy to the composition. When the blending ratio exceeds 95% by mass, not only is it difficult to mix uniformly in the composition, but the blending ratio of the component (A) becomes small. Various physical properties may be inferior.

[(D) component]
(D) component used for the photocurable composition of this invention is a light absorber. (D) The light absorber is a component that effectively absorbs light having a wavelength near 405 nm. When the curing wavelength near 405 nm is used, the component (D) effectively absorbs curing light and decreases the depth at which the composition is photocured (hereinafter referred to as “curing depth”).
In order to use the composition of the present invention in the micro stereolithography described later, the curing depth (500 mJ / cm ² ) is preferably 30 μm or less, and more preferably 20 μm or less. The curing depth is preferably 10 μm or more. For this purpose, it is preferable that the transmittance of light having a wavelength of 405 nm when the component (D) is a 0.01% by mass ethanol solution is 1% or less.

As a specific example of the component (D), typically, an oil-based dye having the above-described light-absorbing characteristics may be mentioned. Examples of these oil dyes include oil dyes having a color index code of Solvent Yellow 179 or Disperse Yellow 201. Examples of commercially available products include Yellow 6G Gran (Bayer).
Yellow 6G Gran is an oil-based dye having a color index code of Solvent Yellow 179 or Disperse Yellow 201.
Here, the color index code is "Society of Dyers and Colorists, American Association of
By "Textile Chemists and Colorists".

  The blending ratio of the component (D) is preferably 0.1 to 5% by mass, more preferably 0.5 to 5% by mass, with the total amount of the photocurable composition of the present invention as 100% by mass.

  In the composition of the present invention, various additives may be contained as optional components other than the above components within the range not impairing the object and effect of the present invention. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, allyl ether copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, Polymers and oligomers other than the component (C) such as fluorine oligomers, silicone oligomers, polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiation assistants; Leveling agent; wettability improver; surfactant; plasticizer; ultraviolet absorber; silane coupling agent; pigment and dye other than (D) component; inorganic or organic fine particle other than (C) component; triethanolamine; Methyldiethanolamine Amine compounds such as triethylamine and diethylamine, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, anthracene and derivatives thereof, perylene and derivatives thereof, photosensitizers (polymerization accelerators) such as benzophenone and benzoin isopropyl ether; vinyl ethers, vinyl And reactive diluents such as sulfides, vinyl urethanes, urethane acrylates, and vinyl ureas.

The composition of the present invention can be produced by uniformly mixing the above components (A) to (C) and optional components such as the component (D) blended as necessary.
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.

Next, the three-dimensional modeled object of the present invention will be described. The three-dimensional molded item of the present invention is composed of a laminate of the cured product of the above-described photocurable composition.
Each layer of the laminate is obtained by irradiating light to the liquid surface of the photocurable composition. The liquid level can be leveled with a recoater or the like. At this time, by selectively irradiating light, a cured product (cross-section cured layer) having a desired pattern cross section can be obtained.
The manufacturing method of the three-dimensional molded item of this invention irradiates light to a photocurable composition, forms the hardened | cured material (cross-section hardened layer) of this composition, On this hardened | cured material (cross-sectional hardened layer), The composition is supplied again and irradiated with light to further form a cured product (cross-section cured layer) of the composition. Thereafter, by repeating this, a plurality of cured products (cross-sectional cured layer) are laminated and integrated. To obtain a three-dimensional model.

The means for selectively irradiating the photocurable composition with light is not particularly limited, and various means can be employed. For example, (a) means for irradiating the composition while scanning a laser beam or convergent light obtained using a lens, a mirror, etc., (b) using a mask having a light transmission part of a predetermined pattern, Means for irradiating the composition with non-converged light through a mask; (c) using a light guide member formed by bundling a number of optical fibers; and composing light through the optical fiber corresponding to a predetermined pattern in the light guide member Means for irradiating an object, (d) means for repeatedly executing collective exposure for each predetermined area, and the like can be employed.
In the means using the mask of (b), a mask image composed of a light transmitting area and a light non-transmitting area is formed electro-optically as a mask according to a predetermined pattern according to the same principle as the liquid crystal display device. You can also use what you want.
When the target 3D object has a fine part or a high dimensional accuracy is required, a laser beam 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.
When the composition is contained in the container, the light irradiation surface (for example, the convergent light scanning plane) 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.

  As described above, the three-dimensional object of the present invention can be manufactured by an optical three-dimensional modeling method such as an optical layered modeling method. In the optical three-dimensional modeling method, usually, after curing a specific part of the composition, the light irradiation position (irradiation surface) is moved continuously or stepwise from the already cured part to the uncured part. Then, 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.

A typical example of the optical three-dimensional modeling method of the present invention will be described with reference to FIGS. 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]
The size of the three-dimensional modeled object modeled by the optical layered modeling method is usually a scale of several mm to several m, typically several cm to several tens of cm.
In FIG. 1, as shown in FIG. 1 (a), a support stage 3 provided in a container 2 containing the photocurable composition 1 so as to be movable up and down is lowered by a minute amount from the liquid level 4 of the composition 1 (sedimentation). ), The composition 1 is supplied onto the support stage 3 to form a thin layer of the composition 1. Next, the thin layer is selectively irradiated with light 8 through the mask 5 to form a cured product (cured resin layer) 6 of the composition 1.
Next, as shown in (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 again. Next, the thin layer is selectively irradiated with light 8 through the mask 5, and a new cured product 7 is further formed on the cured product 6 so as to be laminated integrally therewith. . 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 three-dimensional structure obtained in this way is taken out from the storage container, removed the remaining unreacted composition, and then washed as necessary. Here, as the cleaning agent, alcohol-based organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents typified by acetone, ethyl acetate, methyl ethyl ketone, etc .; aliphatics typified by terpenes Organic solvents; low viscosity thermosetting resins and photocurable resins.
After these treatments, when the three-dimensional model is fired, a ceramic model is obtained.

[Micro stereolithography]
The size of the three-dimensional modeled object modeled by the micro stereolithography is usually a scale of several μm to several cm, typically several tens of μm to several mm.
The composition of the present invention is suitably used as a material for a micro-stereolithography method capable of producing a three-dimensional model having a smaller size than when using an optical layered modeling method.
In the micro stereolithography method, light irradiation is not performed only on a portion that needs to be scanned and cured by light, but is performed by repeating collective exposure for each predetermined region (projection region). Such collective exposure is performed using, for example, a digital mirror device (DMD).

In FIG. 2, 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. Such a micromirror 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 2 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 a reservoir 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.
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 model) based on the exposure data stored in the storage unit 18. Execute the modeling of the three-dimensional model.

  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, it is necessary to irradiate the entire modeling area by moving the irradiation position of the laser beam, for example, by horizontally moving the modeling table 14 using a moving mechanism. There is. 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.

Then, the 2nd layer of the solid model of a desired shape is formed in the same process. Specifically, the composition 20 supplied from the dispenser 5 is applied to the outside of the cured layer formed as the first layer so as to be stretched beyond the three-dimensional model 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 molded object removes the photocurable resin liquid adhering to the surface by washing or other methods. The molded article can be further cured by being irradiated or heated with an ultraviolet lamp or the like as necessary.
After these treatments, when the three-dimensional model is fired, a ceramic model is obtained.

Since the photocurable composition of the present invention has thixotropy in an uncured state, the composition layer 19 applied using the recoater 16 flows after application, and the thickness of the layer fluctuates and does not change. A uniform phenomenon can be suppressed. That is, if the composition of the present invention is used, the composition layer 19 having a uniform thickness can be formed. As a result, a highly accurate three-dimensional model can be obtained.
By using the photocurable composition of the present invention, it has good thixotropy and has both good fluidity before coating and stability of the coating layer after coating. A desired three-dimensional modeled object can be easily produced with high accuracy by a modeling method or a micro stereolithography method.
Among the optical modeling methods, the composition of the present invention can be suitably applied particularly to the micro optical modeling method.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to the aspect as described in a following example. In addition, the following "part" shows a mass part.

[Production Example 1; Synthesis of FM0411-TH]
A reaction vessel equipped with a stirrer was charged with 10.4 parts of 2,4-tolylene diisocyanate, 0.08 part of dibutyltin dilaurate and 0.02 part of 2,6-di-t-butyl-p-cresol and brought to 15 ° C. or lower. Cooled down. While maintaining the temperature at 30 ° C. or lower while stirring, NK ester A-TMM-3LM-N (consisting of 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. (It is only pentaerythritol triacrylate having a hydroxyl group that is involved in this.) 37.5 parts were added dropwise. After completion of the dropwise addition, the mixture was reacted at 30 ° C. for 1 hour.
Next, 52.1 parts of α- [3- (2′-hydroxyethoxy) propyl] -ω-trimethylsilyloxypolydimethylsiloxane having a hydroxyl equivalent weight of 1,000 (Silaplane FM-0411 manufactured by Chisso Corporation) was added, Stir at 20-55 ° C. The reaction was terminated when the residual isocyanate was 0.1% by weight or less.
When the number average molecular weight of the obtained product (measured by gel permeation chromatography using AS-8020 manufactured by Tosoh Corporation was used to measure the number average molecular weight in terms of polystyrene, hereinafter the same) was measured, the number average molecular weight was 1,600. In addition to the double-terminal reactive polydimethylsiloxane compound, it was observed that a bond of 1 mole of tolylene diisocyanate and 2 moles of hydroxyethyl acrylate was present at a content of 20% by weight of the total amount of the product. The liquid end-reactive polydimethylsiloxane compound obtained by this method is designated FM0411-TH.

[Example 1]
[Preparation of Photocurable Composition]
In a container equipped with a stirrer, 80 g of dipentaerythritol hexaacrylate, 20 g of N-vinylpyrrolidone, 3.0 g of “Irgacure 819”, 2.0 g of 2,4-diethylthioxanthone, and 4-dimethylaminobenzoic acid ethyl ester 0.5g and "Yellow6G
“Gran” 2.0 g, “SH28PA” (manufactured by Ciba Specialty Chemicals) 0.06 g, and FM0411-TH (manufactured by Ciba Specialty Chemicals) 0.19 g were added and stirred at 60 ° C. for 1 hour. Later, 341 g of zirconia particles (TZ-3YS-E; manufactured by Tosoh Corp .; number average particle size 90 nm) were added. K. A photocurable composition was prepared by uniformly dispersing using HOMODISPER.
A test piece formed by coating the obtained photocurable composition on a glass substrate so as to have a thickness of 15 μm or 100 μm is prepared, and irradiation is performed using an irradiation spectroscope (CT-25CP type, JASCO Corporation). When the surface (liquid surface) was irradiated with a laser beam of 405 nm at a laser power of 30 mW for 15 to 30 seconds, the composition was completely cured when the thickness was 15 μm, but the composition was cured when the thickness was 100 μm. Only the surface layer was cured, and the composition in the vicinity of the glass substrate was uncured.
From this experiment, it was found that the curing depth of the composition was about 15 μm.

Moreover, the thixotropy property and applicability | paintability of the obtained composition were evaluated by the following method. The results are shown in Table 1.
[Method for evaluating thixotropic properties]
The photocurable composition applied on the glass plate so as to have a thickness of 100 μm or more was scraped with a scraper in parallel with the glass plate to evaluate thixotropy. At this time, only the photocurable composition in contact with the scraper flows, the other portions do not flow, and the case where stringing or the like is not seen in the peripheral portion of the scraper end is marked with `` ○ '', and the scraper is in direct contact. The case where the part which was not flowing or the thread | yarn stringing was seen in the edge part was judged as "x".
[Applicability evaluation method]
The obtained photocurable composition was apply | coated so that it might become a thickness of 5 micrometers using the recoater. The case where it was possible to apply uniformly with a thickness of 5 μm was indicated as “◯”, and the case where it could not be applied was indicated as “X”.

[Examples 2-5 and Comparative Examples 1-2]
A photocurable composition was prepared in the same manner as in Example 1 except that the component composition was changed as shown in Table 1.
About the composition of Examples 2-5 and Comparative Examples 1-2, when the cure depth was evaluated like Example 1, about 15 micrometers of cure depth was shown about any composition.
In the same manner as in Example 1, thixotropy and coating properties were evaluated. The results are shown in Table 1.

The contents of the abbreviations in Table 1 are shown below.
(1) Irgacure 819:
Compound name: Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Manufacturer: Ciba Specialty Chemicals Co., Ltd. Molar extinction coefficient at 405 nm: 619 L / mol · cm
(2) Yellow6G Gran:
Manufacturer: Bayer (3) SH28PA:
Compound name: Dimethylpolysiloxane polyoxyalkylene copolymer Manufacturer: Toray Dow Corning Silicone Corp. (4) FM0411-TH:
End-reactive polydimethylsiloxane compound (5) allyl ether copolymer synthesized in “Production Example 1” Product name: Marialim AAB-0851
Manufacturer: NOF Corporation (6) Zirconia (particle size 40 nm):
Product name: TZ-3Y-E
Manufacturer: Tosoh Corporation (7) Alumina fine particles (particle diameter 170 nm):
Product name: TM-DAR
Manufacturer: Daiming Chemical Industry Co., Ltd.

  From Table 1, Examples 1 to 5 belonging to the present invention are excellent in thixotropy and applicability even though inorganic fine particles having a small number average particle diameter are blended at a high content. On the other hand, in Comparative Examples 1 and 2 in which the component (A) is composed of only a polyfunctional monomer, thixotropy and applicability are poor.

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 (11)

The total amount of the composition is 100% by mass,
(A1) 1 to 10% by mass of a monomer having one ethylenically unsaturated group,
(A2) 1 to 30% by mass of a monomer having two or more ethylenically unsaturated groups,
(B) 0.01 to 10% by mass of a photopolymerization initiator, and (C) 60 to 95% by mass of inorganic fine particles having a number average particle diameter of 5 to 300 nm by a dynamic light scattering method, and ( The photocurable composition for optical modeling, wherein the content of the component (A1) is 10 to 50% by mass in 100% by mass of the total amount of the component (A1) and the component (A2).   The photocurable composition for stereolithography according to claim 1, wherein the monomer (A1) having one ethylenically unsaturated group is a nitrogen-containing vinyl compound.   3. The photocurable composition for optical modeling according to claim 1, wherein a blending ratio of the (C) inorganic fine particles is 70 to 85% by mass with respect to 100% by mass of the total amount of the composition.   The photocurable composition for optical modeling according to any one of claims 1 to 3, wherein the (C) inorganic fine particles include zirconia-based fine particles.   The photocurable composition for optical modeling according to any one of claims 1 to 4, which is for micro-optical modeling.   The three-dimensional molded item which consists of hardened | cured material of the photocurable composition of any one of Claims 1-5.   Light is irradiated to the photocurable composition for optical shaping | molding of any one of Claims 1-5, the hardened layer of this composition is formed, and the said composition is again on this hardened layer. Supplying and irradiating light to further form a cured layer of the composition, and thereafter repeating this process to obtain a three-dimensional structure formed by laminating and integrating a plurality of cured layers .   The manufacturing method of the three-dimensional molded item of Claim 7 whose thickness of the said hardened layer is 1-50 micrometers.   The method of manufacturing a three-dimensional structure according to claim 7 or 8, wherein the light irradiation is performed by repeating collective exposure using a digital mirror device for each projection region.   A ceramic model obtained by firing the three-dimensional model according to claim 6. The photocurable composition for optical modeling according to any one of claims 1 to 5 is subjected to batch exposure using a digital mirror device for each projection region to form a cured layer of the composition, On the cured layer, the composition is supplied again, irradiated with light to further form a cured layer of the composition, and thereafter, by repeating this, a plurality of cured layers are laminated and integrated. Obtaining a shaped object,
A step of washing the obtained three-dimensional structure to remove the remaining unreacted composition; and
A method for producing a ceramic model, comprising a step of firing the three-dimensional model after washing to obtain a ceramic model.

Images