JP2001026609A - Resin composition for optical stereolithography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition having the excellent handleability and operability due to the low viscosity at the time of optically preparing a photocured substance such as a stereolithographic article and besides having the capability of forming a photocured substance such as an optical stereolithographic article having excellent surface smoothness, heat resistance, thermal deformation resistance, dynamic characteristics of mechanical strengths and dimensional accuracy, and to provide an optical stereolithographic method by using it. SOLUTION: A photocurable resin composition comprises a liquid photocurable resin containing 5-70% by volume, based on the total volume of the stereolithographic resin composition, of solid fine particles having an average particle diameter of 10 μm or less and including the fine particles with particle diameters of from 0.5 times to 1.5 times the average particle diameter in the ratio of 70 wt.% or more and moreover in some cases a whisker. The optical stereolithographic method uses this photocurable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition, an optical three-dimensional object obtained using the photocurable resin composition, and a three-dimensional object using the photocurable resin composition. It relates to a method for optically manufacturing. More specifically, the present invention relates to a photocurable resin composition having a low viscosity and excellent in handleability and operability when optically producing a photocured product such as a three-dimensional molded article, and the photocurable resin composition. The present invention relates to a method for optically producing a three-dimensional molded object using, in the case of the present invention, using the photocurable resin composition,
Good handling and operability, excellent surface smoothness, and mechanical properties such as heat resistance, heat deformation resistance, mechanical strength, etc.
A photo-cured product such as a high-quality optical three-dimensional object having excellent dimensional accuracy can be produced smoothly.

[0002]

2. Description of the Related Art In general, liquid photocurable resin compositions are widely used as coating materials (particularly hard coating agents), photoresists, dental materials, and the like.
A method of three-dimensionally optically molding the photocurable resin composition based on the data input to D has attracted particular attention. Regarding the optical three-dimensional molding technology, a required amount of controlled light energy is supplied to a liquid photo-curable resin to cure it in a thin layer, and then a liquid photo-curable resin is further supplied thereon, and then the light is controlled under control. Japanese Patent Application Laid-Open No. 56-144478 discloses an optical three-dimensional molding method for producing a three-dimensional molded product by repeating a process of irradiating and laminating and hardening into a thin layer, and further discloses a basic practical method. Showa 60-
247515. After that, a number of proposals regarding optical three-dimensional modeling technology have been made, for example, JP-A-62-35966, JP-A-1-204915, JP-A-2-113925, and JP-A-2-145616. Gazette, JP-A-2-153
722, JP-A-3-15520, JP-A-3-15520
Japanese Patent Application Laid-Open No. 21432 and Japanese Patent Application Laid-Open No. 3-41126 disclose techniques relating to an optical three-dimensional printing method.

[0003] A typical method for optically producing a three-dimensional object is a computer controlled ultraviolet ray so as to obtain a desired pattern on the liquid surface of a liquid photocurable resin composition placed in a container. A laser is selectively irradiated to cure to a predetermined thickness, and then one layer of the liquid resin composition is supplied on the cured layer and similarly irradiated with an ultraviolet laser to be cured as described above. In general, a method of manufacturing a three-dimensional structure having a final shape by repeating a lamination operation of forming a continuous hardened layer by a continuous process is widely adopted.
In the case of this method, even if the shape of the modeled object is considerably complicated, the target three-dimensional modeled object can be easily manufactured in a relatively short time, so that it has been receiving particular attention in recent years.

The photocurable resin composition used in the optical three-dimensional molding method includes a photopolymerizable modified (poly) urethane (meth) acrylate compound, an oligoester acrylate compound, an epoxy acrylate compound, an epoxy compound, Photopolymerizable compounds such as polyimide compounds, aminoalkyd compounds and vinyl ether compounds
And those in which a photopolymerization initiator is added to the main component or two or more types.
JP-A-04915, JP-A-1-213304, JP-A-2-28261, JP-A-2-75617, JP-A-2-145616, JP-A-3-104
Various improved techniques are disclosed in Japanese Patent Application Laid-Open No. 626, Japanese Patent Application Laid-Open No. 3-114732, Japanese Patent Application Laid-Open No. 3-147324, and the like.

[0005] The conventional photocurable resin composition as described above is generally a high-viscosity liquid. Therefore, when the above-described laminating operation is repeated to optically produce a three-dimensional molded article,
It is difficult to form a uniform and thin liquid photocurable resin composition layer of one layer, and the handleability and workability during stereolithography may be poor. The present inventors have long studied on an optical three-dimensional molding technique using a photocurable resin composition. When optical three-dimensional modeling is performed using a photocurable resin composition in which a filler such as solid fine particles or whiskers is mixed into a liquid photocurable resin, volume shrinkage during curing is small, and dimensional accuracy is excellent. It was found that an optical three-dimensional object having good mechanical properties, a high heat deformation temperature and excellent heat resistance can be obtained, and the application was filed earlier (Japanese Patent No. 2554443).
And JP-A-8-20620). However, the photocurable resin composition containing a filler such as solid fine particles generally has a higher viscosity than those containing no filler. As the particle size of the solid fine particles contained in the photocurable resin composition becomes smaller, the viscosity of the photocurable resin composition becomes higher, and the handleability and workability during stereolithography are reduced.
In particular, a photocurable resin composition containing whiskers together with solid fine particles having a small particle diameter is more likely to have a higher viscosity,
Therefore, it has been found that there is room for improvement in handling and workability during stereolithography. Further, an optical three-dimensional structure obtained from a photocurable resin composition containing a filler,
Compared to the optical three-dimensional structure obtained from the photocurable resin composition containing no filler, the heat resistance, mechanical properties, dimensional accuracy, etc. are excellent, but on the other hand, the surface smoothness tends to be low It turned out that there is.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for optically producing a three-dimensional molded article having a low viscosity despite containing solid fine particles, particularly solid fine particles having a small particle diameter. It is excellent in handling and workability, and has a smooth surface, and has excellent mechanical properties such as heat resistance, heat deformation resistance, mechanical strength, and dimensional accuracy. It is an object of the present invention to provide a photocurable resin composition which can be produced at a time. An object of the present invention is to provide a method for optically producing a three-dimensional structure using the photocurable resin composition. Further, an object of the present invention is to provide a three-dimensional structure comprising the photocurable resin composition.

[0007]

As a result of repeated studies by the present inventors to achieve the above object, the solid fine particles to be incorporated into the liquid photocurable resin have uniform particle diameters having a predetermined particle size distribution. In addition, when solid fine particles having an average particle diameter of 10 μm or less are used, the resulting photocurable resin composition has a low viscosity, despite containing solid fine particles having a small particle diameter, and has an optical molding. The photocurable product such as a three-dimensional object obtained using the photocurable resin composition has a very smooth surface, and furthermore has excellent heat resistance and heat resistance. It has been found that it has excellent mechanical properties such as deformability and mechanical strength, and dimensional accuracy. Furthermore, the present inventors use the above-mentioned solid fine particles having a predetermined particle size distribution and having a uniform particle diameter of 10 μm or less as solid fine particles, and combine the whiskers with the solid fine particles to obtain light obtained by the combination. The curable resin composition has low viscosity and excellent handleability and workability during stereolithography, despite containing solid fine particles and whiskers having a small particle size, and the three-dimensional shape obtained thereby. Photocured products such as shaped articles have excellent surface smoothness, and have excellent heat resistance, heat deformation resistance, mechanical properties such as mechanical strength, and dimensional accuracy. Was completed.

That is, the present invention provides (1) fine particles having an average particle diameter of 10 μm or less and a particle diameter in the range of 0.5 to 1.5 times the average particle diameter in the liquid photocurable resin. Is a photocurable resin composition characterized by containing solid fine particles having a ratio of 70% by weight or more based on the total volume of the photocurable resin composition in a proportion of 5 to 70% by volume.

In the present invention, (2) the ratio of the fine particles having a particle diameter in the range of 0.7 to 1.2 times the average particle diameter in the solid fine particles is 50% by weight or more. (3) The photocurable resin composition according to (1) or (2), wherein the average particle diameter of the solid fine particles is in the range of 1 to 10 μm; (1) wherein the average particle size is in the range of 1 to 5 μm;
Any one of (3) to (3), and
(5) The photocurable resin composition according to any one of (1) to (4), which has a viscosity at 25 ° C. of 70,000 centipoise or less;

According to the present invention, (6) whiskers are further contained at a ratio of 5 to 30% by volume based on the total volume of the photocurable resin composition, and the total volume of the solid fine particles and the whiskers is adjusted by photocuring. 10 based on the total volume of the conductive resin composition
The photocurable resin composition according to any one of the above (1) to (4), wherein the content is up to 75% by volume.

The present invention provides (7) the photocurable resin composition according to (6), wherein a whisker having a diameter of 0.3 to 1 μm, a length of 10 to 70 μm, and an aspect ratio of 10 to 100 is used;
(8) The photocurable resin composition according to (6) or (7), wherein the viscosity at 25 ° C. is 70,000 centipoise or less; and (9) the photocurable resin composition (1) to (1). 8) as a preferred embodiment.

Further, the present invention provides (10) the above (1).
(1) forming a cured layer having a predetermined pattern by selectively irradiating one layer comprising the photocurable resin composition with an active energy ray, and then forming an uncured liquid on the cured layer; After applying the photocurable resin composition in a layer form to form a layered form, irradiating active energy rays to newly form a cured layer continuous with the cured layer, and further repeating the lamination operation until a predetermined three-dimensional structure is obtained. This is a method for producing a three-dimensional structure.

The present invention provides (11) the above (1)
An optical three-dimensional structure obtained using the photocurable resin composition according to any one of (9) to (9), and (12) a surface roughness measured by a three-dimensional surface contact method using a three-dimensional surface roughness meter. Is a preferred embodiment.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The solid fine particles used in the photocurable resin composition of the present invention must have an average particle size of 10 μm or less. When the average particle size of the solid fine particles is larger than 10 μm,
The surface smoothness of a photocured product such as a three-dimensional molded product obtained using the photocurable resin composition is reduced. However, if the average particle size of the solid fine particles is too small, the viscosity of the photocurable resin composition increases, so that the lower limit of the average particle size of the solid fine particles is preferably about 1 μm, and thus used in the present invention. The average particle size of the solid fine particles is preferably in the range of 1 to 10 μm, more preferably in the range of 1 to 7 μm, and even more preferably in the range of 1 to 5 μm. The average particle diameter of the solid fine particles in the present specification is an average particle diameter determined from the weight distribution of the solid fine particles, and a detailed calculation method thereof is as described in the following Examples.

Further, the solid fine particles used in the photocurable resin composition of the present invention have the above-mentioned average particle size and a particle size in the range of 0.5 to 1.5 times the average particle size. Is required to be 70% by weight or more based on the total weight of the solid fine particles. When the ratio of the fine particles having a particle size in the range of 0.5 to 1.5 times the average particle size in the solid fine particles is less than 70% by weight, even if the average particle size of the solid fine particles is 10 μm or less. In addition, the viscosity of the photocurable resin composition increases, and the handleability and workability during stereolithography become poor, and the surface smoothness of the resulting photocured product such as a three-dimensional molded product decreases. In the solid fine particles used in the photocurable resin composition of the present invention, the ratio of the fine particles having a particle size in the range of 0.5 to 1.5 times the average particle size is based on the total weight of the solid fine particles. 80
It is preferred that the content be at least 10% by weight. In the solid fine particles used in the present invention, the ratio of the fine particles having a particle diameter in the range of 0.5 to 1.5 times the average particle diameter based on the total weight of the solid fine particles is 70% by weight or more. In addition, when the ratio of the fine particles having a particle diameter in the range of 0.7 to 1.2 times the average particle diameter is 50% by weight or more, the effect of reducing the viscosity of the photocurable resin composition and the obtained three-dimensional structure can be obtained. It is preferable from the viewpoint of the surface smoothness of a photocured product such as a molded product. The particle size distribution of the solid fine particles in this specification (the ratio of the fine particles having a particle size in the range of 0.5 to 1.5 times the average particle size)
Was determined by the method described in the following examples.

The solid fine particles used in the photocurable resin composition of the present invention have an average particle size of 10 μm or less, a small particle size, and a range of 0.5 to 1.5 times the average particle size. The ratio of the fine particles having a particle size is as large as 70% by weight, the particle size distribution is narrow, and the size of the solid fine particles is uniform, whereby the viscosity of the photocurable resin composition is reduced and a photocured product such as a three-dimensional molded product And both of the surface smoothness are achieved.

Examples of solid fine particles that can be used in the photocurable resin composition of the present invention include glass beads, silica fine particles,
Inorganic fine particles such as talc fine particles, silicon oxide fine particles, aluminum oxide fine particles, aluminum hydroxide fine particles, magnesium oxide fine particles, calcium oxide fine particles, aluminum nitride fine particles, calcium carbonate fine particles, carbon black fine particles, polystyrene fine particles, polyethylene fine particles, polypropylene fine particles, and acrylic. Organic polymer fine particles such as resin fine particles and synthetic rubber fine particles can be used, and one or more of these can be used. Among the above, glass beads, silicon oxide fine particles, aluminum oxide fine particles, and silica fine particles are preferably used as the solid fine particles.

The photocurable resin composition of the present invention contains the solid fine particles in a proportion of 5 to 70% by volume based on the total volume of the photocurable resin composition. When the content of the solid fine particles is less than 5% by volume, the characteristics of the solid fine particles as a reinforcing material and a heat resistance improving material are not sufficiently exhibited. On the other hand, when the content of the solid fine particles exceeds 70% by volume, the viscosity of the photocurable resin composition increases even when the specific solid fine particles described above are used. Hard to do. The photocurable resin composition of the present invention preferably contains solid fine particles at a ratio of 10 to 40% by volume.

When the photocurable resin composition of the present invention contains solid fine particles and does not contain whiskers,
By containing the above-mentioned specific solid fine particles at a ratio of 70% by volume or less, the viscosity at 25 ° C. becomes 70,0.
A photocurable resin composition of not more than 00 centipoise can be obtained smoothly, and the viscosity of the photocurable resin composition can be increased by further selecting the average particle size and particle size distribution of the solid fine particles from the above range. It is also possible to make it less than 50,000 centipoise.

The photocurable resin composition of the present invention may contain whiskers together with the solid fine particles described above,
When containing both solid fine particles and whiskers,
The heat resistance, heat deformation resistance, mechanical properties, dimensional stability, and the like of a photocured product such as an optical molded product obtained from the photocurable resin composition are further improved.

The whiskers have a diameter of 0.3 to 1 μm,
Those having a length of 10 to 70 μm and an aspect ratio of 10 to 100 are preferably used, and those having a diameter of 0.3 to 0.7 μm, a length of 20 to 50 μm, and an aspect ratio of 20 to 70 are more preferably used. Whisker diameter 0.3μm
If it is less than 1, the heat deformation temperature, flexural modulus, and mechanical properties of the photocured product are likely to be low. On the other hand, if it exceeds 1 μm, the viscosity of the photocurable resin composition is increased, and handling properties, moldability, etc. Tend to have reduced properties. When the length of the whisker is less than 10 μm, the heat deformation temperature, the flexural modulus and the mechanical properties are liable to be lowered. On the other hand, when the whisker exceeds 70 μm, the viscosity of the photocurable resin composition is increased, and the handleability and the modeling are increased. Properties are easily reduced. In particular, when the aspect ratio of the whisker is in the range of 10 to 100 described above, the viscosity of the photocurable resin composition becomes appropriate, and the operation at the time of photocuring becomes easy, and furthermore, the photolithography and the like This is preferable from the viewpoints of reduction in volume shrinkage of the photocured product, mechanical properties and dimensional accuracy of the obtained photocured product. In addition,
The dimension and aspect ratio of the whisker referred to in the present specification refer to the dimension and aspect ratio measured using a laser diffraction / scattering type particle size distribution analyzer, and details thereof are as described in the following Examples. is there.

The type of whisker is not particularly limited, and examples thereof include aluminum borate whisker, aluminum oxide whisker, aluminum nitride whisker water, magnesium oxide whisker, and titanium oxide whisker. Whisker 1
Species or two or more can be used.

When the photocurable resin composition of the present invention contains whiskers together with the solid fine particles, the content of the solid fine particles should be 5 to 70 based on the total volume of the photocurable resin composition.
Volume% and the whisker content are 5 to 30 volume%, and the total content of the solid fine particles and the whisker is 10 to 75%.
%, More preferably 5 to 65% by volume of solid fine particles, 5 to 30% by volume of whiskers, and more preferably 10 to 70% by volume, and the total amount of both is 20 to 70% by volume. More preferably, it is set to 60% by volume. When the content of the whisker exceeds 30% by volume based on the total volume of the photocurable resin composition, the viscosity of the photocurable resin composition becomes too high, and it becomes difficult to perform photocuring work such as stereolithography, In addition, the dimensional accuracy of the photocured product is liable to decrease. When the total content of the solid fine particles and the whisker exceeds 75% by volume based on the total volume of the photocurable resin composition, the viscosity of the photocurable resin composition becomes too high, and the handleability and the formability are increased. Are likely to be defective, and the dimensional accuracy of the obtained photocured product is likely to be low.

When the photocurable resin composition of the present invention contains solid fine particles and whiskers, the specific solid fine particles described above are contained at a ratio of 70% by volume or less, and the whiskers are contained at a ratio of 30% by volume or less. And the total content of both is 75% by volume or less,
A photocurable resin composition having a viscosity at 25 ° C. of 70,000 centipoise or less can be smoothly obtained, and the average particle size, particle size distribution, content, type of whiskers,
The viscosity of the photocurable resin composition is set to 50,0 by further selecting the aspect ratio, the content and the like from the above ranges.
It is also possible to make it less than 00 centipoise.

The solid fine particles and / or whiskers used in the present invention may or may not be surface-treated with a silane coupling agent, but are preferably surface-treated. When the solid fine particles and / or whiskers are surface-treated with a silane coupling agent, a photocured product having a higher heat distortion temperature, flexural modulus, and mechanical strength can be obtained.

In this case, as the silane coupling agent, any of the silane coupling agents conventionally used for surface treatment of a filler or the like can be used. Preferred silane coupling agents are aminosilane, epoxysilane, Vinyl silane and (meth) acryl silane can be mentioned. More specifically, γ-aminopropyltriethoxysilane, N-β- (aminoethyl)-
aminosilanes such as γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane; β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, γ-glycidoxypropyl Epoxysilanes such as trimethoxysilane; vinylsilanes such as vinyltrichlorosilane, vinyldiethoxysilane and vinyl-tris (β-methoxyethoxysilane); and (meth) acrylsilanes such as trimethoxysilane methacrylate. One or more of the above silane coupling agents can be used.

When the surface treatment of solid fine particles and / or whiskers is performed with a silane coupling agent, the manner in which the silane coupling agent exerts its function may differ depending on the type of photocurable resin used. It is preferable to select a silane coupling agent suitable for each photocurable resin and perform surface treatment of the solid fine particles and / or whiskers. For example, for a photocurable resin mainly composed of a vinyl-based unsaturated compound, it is preferable to use vinylsilane and / or (meth) acrylsilane, and for a photocurable resin mainly composed of an epoxy-based compound, it is preferable to use epoxysilane. .

In the present invention, as the liquid photocurable resin, any liquid photocurable resin conventionally used in stereolithography can be used, and various oligomers, various monofunctional vinyl compounds, and polyfunctional vinyl compounds can be used. And a liquid photocurable resin containing one or more of epoxy compounds, and a photopolymerization initiator and, if necessary, a sensitizer. Although not limited, specific examples of the oligomer, the monofunctional vinyl compound, the polyfunctional vinyl compound, and the epoxy compound that can be used in the present invention include:
The following can be mentioned.

[Oligomer] Urethane acrylate oligomer, epoxy acrylate oligomer, ester acrylate oligomer, polyfunctional epoxy resin and the like.

[Monofunctional vinyl compound] Acrylic compound : isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate , Dicyclopetanyl acrylate, dicyclopetanyl methacrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, cyclohexyl acrylate, 2-
Hydroxypropyl acrylate, phenoxyethyl acrylate, morpholine acrylamide, morpholine methacrylamide, acrylamide and the like. ○ Other monofunctional compounds : N-vinylpyrrolidone, N-vinylcaprolactam, vinyl acetate, styrene and the like.

[Polyfunctional vinyl compound] trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate,
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentanyl diacrylate,
Polyester diacrylate, ethylene oxide-modified bisphenol A diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, propylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified bisphenol A diacrylate, tris (acryloxyethyl) isocyanurate and the like.

[Epoxy compound] hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-
5,5-spiro-3,4-epoxy) cyclohexane-
Meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate and the like.

The photopolymerization initiator used in the photocurable resin used in the photocurable resin composition of the present invention is not particularly limited, and the photopolymerization initiator conventionally used in the photocurable resin composition is used. Any of these can be used. Although not limited, typical examples of the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, Examples thereof include triphenylamine, carbazole, 3-methylacetophenone, and Michler's ketone, and one or more of these can be used. Also, if necessary,
A sensitizer such as an amine compound may be used in combination.

In particular, in the case of the above-mentioned polyfunctional epoxy resin, one or more of an aliphatic diepoxy compound, an alicyclic diepoxy compound and an aromatic diepoxy compound are mainly used, and if necessary, a monofunctional ( It is used in the form of a liquid photo-curable resin composition in which a meth) acrylate monomer and a polyfunctional (meth) acrylate monomer are mixed, and a cationic photopolymerization initiator and, if necessary, a radical photopolymerization initiator are added thereto. Often. In this case, as the cationic photopolymerization initiator, an onium salt such as a sulfonium salt or an iodonium salt is used. Examples of typical commercial products include UVI-6950 and UVI-697.
0, UVI-6974, UVI-6990 (all manufactured by Union Carbide), Adeka Optomer SP-150,
SP-151, SP-170, SP-171 (all manufactured by Asahi Denka Kogyo Co., Ltd.) and the like.

The photocurable resin composition of the present invention may further comprise, if necessary, a leveling agent, a surfactant other than a phosphate ester-based surfactant, an organic polymer modifier, It may contain an organic plasticizer and the like.

When the photocurable resin composition of the present invention is stored in a state capable of blocking light, it is usually kept at a temperature of 10 to 40 ° C. for a long period of about 6 to 18 months. It can be stored while maintaining good photocuring performance while preventing denaturation and polymerization.

Although not limited in any way, the photocurable resin composition of the present invention can be produced by, for example, various molding techniques involving light irradiation, such as optical three-dimensional molding, cast molding with light irradiation, and injection molding. It can be effectively used for applications such as stereolithography technology such as a mold, and among them, it is effectively used for optical three-dimensional modeling. When performing optical three-dimensional modeling using the photocurable resin composition of the present invention, any of conventionally known optical three-dimensional modeling methods and apparatuses can be used. Among them, in the present invention, as light energy for curing the resin,
It is preferable to use an active energy beam generated from an Ar laser, a He-Cd laser, a semiconductor-excited solid laser, a xenon lamp, a metal halide lamp, a mercury lamp, a fluorescent lamp, and the like, and a laser beam is particularly preferably used. When a laser beam is used as the active energy beam, it is possible to increase the energy level and shorten the molding time, and to obtain a three-dimensional object with high modeling accuracy by utilizing the good light condensing property of the laser beam. be able to.

In the case of performing optical three-dimensional modeling using the photocurable resin composition of the present invention, any of a conventionally known method and a conventionally known stereolithography system apparatus can be adopted, and there is no particular limitation. A typical example of the preferably used optical three-dimensional molding method is to selectively irradiate one layer made of the above-described photocurable resin composition of the present invention with an active energy ray to form a cured layer having a predetermined pattern. Then, after applying an uncured liquid photocurable resin composition in a layer on the cured layer, the cured layer continuous with the cured layer by irradiating active energy rays to form a new three-dimensional molded article And a method for producing a three-dimensional structure, which comprises repeating the above-mentioned laminating operation until is obtained. The three-dimensional object obtained by this method can be used as it is, or in some cases, post-cured by light irradiation or post-cured by heat, etc., and used after further improving its mechanical properties and shape stability etc. You may do so.

When the photocurable resin composition of the present invention is used, it has excellent surface smoothness, good mechanical properties, heat resistance, and heat deformation resistance, with good handling and workability during stereolithography. It is possible to obtain high-quality stereolithography and other photo-cured products with excellent dimensional accuracy, especially the surface roughness measured by the three-dimensional contact method using a three-dimensional surface roughness meter is 2 on average.
It is possible to smoothly obtain a three-dimensional structure or a photo-cured product having a surface smoothness of not more than μm which is extremely excellent.

The structure, shape, size, and the like of the three-dimensionally formed object produced using the photocurable resin composition of the present invention are not particularly limited, and can be determined according to each use. As typical application fields of the optical three-dimensional modeling method of the present invention,
A model for verifying the external design during the design process, a model for checking the functionality of parts, a resin mold for producing a mold, a base model for producing a mold,
Production of direct molds for prototype molds, simplified molds for producing resin molded products, and the like can be cited. More specifically, precision components, electrical and electronic components, furniture, building structures,
Production of models for automobile parts, various containers, castings, dies, mother dies, and the like, and models for machining can be mentioned. Taking advantage of its properties such as good heat resistance, mechanical properties, and high dimensional accuracy, trial production of high-temperature parts, for example, design of complex heat transfer circuits, manufacture of parts for analysis planning of heat transfer behavior of complex structures It can be used very effectively for such purposes.

[0041]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to the following examples. In the following examples, the average particle size and particle size distribution of the solid fine particles (particles in the range of 0.5 to 1.5 times the average particle size or 0.7 to 1.2 times the average particle size) The ratio of fine particles having a diameter), the size and aspect ratio of the whisker, and the viscosity of the photocurable resin composition were determined as follows. In addition, determination of workability during optical three-dimensional modeling, surface smoothness (surface roughness), tensile strength, tensile elongation, tensile elastic modulus, thermal elasticity of the optical three-dimensional molded article obtained by optical three-dimensional modeling. The measurement of the deformation temperature and the volumetric shrinkage at the time of optical three-dimensional molding was performed as follows.

[Average Particle Size of Solid Fine Particles] The particle size of the solid fine particles was measured using “Coulter Multisizer II” manufactured by Nikkaki Bios, and the weight distribution of the particle sizes was determined. The average particle size was determined from the results.

[Particle Size Distribution of Solid Fine Particles
Proportion of fine particles having a particle size in the range of 5 to 1.5 times or in a range of 0.7 to 1.2 times the average particle size)] Particles of solid fine particles obtained using the above apparatus The measured data of the size was processed by computer, and the particle size distribution of the solid fine particles was determined by forming a histogram.

[Dimensions and aspect ratio of whisker]
Using a laser diffraction / scattering particle size distribution analyzer (“LA-7000” manufactured by Matoba Seisakusho Co., Ltd.), whiskers are dispersed in ion-exchanged water at a ratio of 1% by weight using ion-exchanged water as a dispersion medium. The particle size distribution was examined, and the particle size at the 10% portion (D10) from the smaller one was defined as the diameter (fiber diameter), and the particle size at the 90% portion (D90) was defined as the length (fiber length). When the aspect ratio is D90 / D
It was determined as 10.

[Viscosity of Photocurable Resin Composition] Using a rotary B-type viscometer (“Model BH” manufactured by Tokimec Co., Ltd.), at a temperature of 25 ° C., the rotation speed of the rotor is 4 times / min.
The viscosity of the photocurable resin composition was measured under the conditions of 10 times / minute.

[Goodness of workability at the time of optical three-dimensional molding] Since the viscosity of the photocurable resin composition is low, the coating operation of one layer of the photocurable resin composition at the time of optical molding can be smoothly performed. When the coating layer is flat and the surface of the coating layer is flat (good workability), the viscosity of the photocurable resin composition is too high and the photocurable resin composition is applied in one layer during stereolithography. When the operation was difficult to perform and the surface of the coating layer had some irregularities, it was judged as x (poor coating workability).

[Surface Roughness of Optical Three-dimensional Object] Three-dimensional surface roughness meter (Surfcom 1400A manufactured by Tokyo Seimitsu Co., Ltd.)
-3DF ”), the surface roughness is measured by a three-dimensional contact method while making contact with the surface of the optical three-dimensional structure, and the average value (Ra) of the surface roughness (irregularities) obtained thereby is obtained. Was defined as the surface roughness.

[Tensile Strength, Tensile Elongation and Tensile Elasticity of Optical Three-Dimensional Object] Using a dumbbell-shaped test piece manufactured by optical three-dimensional molding, the tensile strength, tensile elongation and tensile elongation are measured in accordance with JIS K 7113. The degree and tensile modulus were measured.

[Thermal Deformation Temperature of Optical Three-Dimensional Object] Using a dumbbell-shaped test piece manufactured by optical three-dimensional molding, method A (load 18.5) according to JIS K7207
kg / mm ² ).

[Volume shrinkage during optical three-dimensional modeling] The specific gravity (d ₁ ) of the photocurable resin composition before photocuring used in the optical three-dimensional modeling, and the optical three-dimensional model obtained by the optical three-dimensional modeling The specific gravity (d ₂ ) of the molded article (dumbbell-shaped test piece) was measured, and the volume shrinkage (%) was determined by the following equation (1).

[0051]

## EQU1 ## Volume shrinkage (%) = {(d ₂ −d ₁ ) / d ₂ } × 100 (1)

<< Production Example 1 >> [Production of a reaction product containing a urethane acrylate oligomer and morpholine acrylamide] (1) A 5-liter three-necked flask equipped with a dropping funnel equipped with a stirrer, a condenser and a side tube was used. , 888 g of isophorone diisocyanate, 906 g of morpholine acrylamide and 1.0 g of dibutyltin dilaurate were heated in an oil bath so that the internal temperature was 80 to 90 ° C. (2) A liquid obtained by uniformly mixing and dissolving 0.7 g of methylhydroquinone in 856 g of glycerin monomethacrylate monoacrylate is charged into the dropping funnel with the side tube previously heated to 50 ° C., and the liquid in the dropping funnel is mixed with The contents in the flask of (1) were dropped and mixed under stirring in a nitrogen atmosphere while maintaining the temperature of the contents of the flask at 80 to 90 ° C, and reacted by stirring at the same temperature for 2 hours. (3) Then, after lowering the temperature of the contents of the flask to 60 ° C., a 4-mol adduct of propylene oxide of pentaerythritol charged in another dropping funnel (each of 1 mol of propylene oxide was added to 4 hydroxyl groups of pentaerythritol) 366 g was quickly added dropwise and the temperature of the contents of the flask was maintained at 80 to 90 ° C.
The reaction was carried out for a time to produce a reaction product containing a urethane acrylate oligomer and morpholine acrylamide, and the obtained reaction product was taken out of the flask while it was still warm.

<< Example 1 >> [Production of photocurable resin composition and three-dimensional molded article] (1) Production in a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a cooling tube and a dropping funnel with a side tube. 2020 g of a reaction product containing a urethane acrylate oligomer and morpholine acrylamide obtained in Example 1, 454 g of morpholine acrylamide and 1060 g of dicyclopentanyl diacrylate were charged, and the atmosphere was replaced by degassing under reduced pressure. Next, 118 g of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy; photopolymerization initiator) was added in an environment where ultraviolet rays were blocked, and mixed and stirred at a temperature of 25 ° C. until completely dissolved ( The mixing and stirring time was about 1 hour) to obtain a photocurable resin which was a colorless and transparent viscous liquid.

(2) 1400 g of the photocurable resin obtained in the above (1) was placed in a universal stirrer (Dalton Co., Ltd .; internal volume: 10 liters) and glass beads (average particle size: 5.4)
μm; 86% by weight of fine particles having a particle size in the range of 0.5 to 1.5 times the average particle size) 2600 g (3 based on the total volume of the finally obtained photocurable resin composition)
8% by volume), followed by stirring for one day and defoaming to produce a photocurable resin composition. The viscosity of the photocurable resin composition thus obtained at 25 ° C. was measured by the method described above, and was as shown in Table 1 below.

(3) Using the photocurable resin composition obtained in the above (2), a water-cooled Ar laser beam (“SOLIFORM500” manufactured by Teijin Seiki Co., Ltd.) using an ultra-high-speed stereolithography system Output 500mW; wavelength 333,35
1,364 nm) perpendicularly to the surface, and under the condition of irradiation energy of 20 to 30 mJ / cm ² , a slice pitch (lamination thickness) of 0.05 mm, and an optical three-dimensional structure with an average modeling time of 2 minutes per layer of 2 minutes. By performing modeling, an optical three-dimensional molded article (test piece) for measuring surface roughness, tensile strength, tensile elongation, tensile modulus, thermal conductivity, and thermal deformation temperature was manufactured. In the production of the optical three-dimensional structure, the workability at the time of the stereolithography was judged by the above method. After the obtained optical three-dimensional structure (test piece) was washed with isopropyl alcohol, it was irradiated with 3 KW ultraviolet rays for 10 minutes to perform post cure. The physical properties of the optical three-dimensional structure (test piece) obtained by the measurement were measured by the above-mentioned methods, and were as shown in Table 1 below. Example 1
The specific gravity (d ₁ ) of the photocurable resin composition before photocuring and the specific gravity (d ₂ ) of the three-dimensional molded article after post-curing, which were used for the production of the optical three-dimensional molded article, were measured. The volumetric shrinkage was determined by equation (1) and was as shown in Table 1 below.

<< Example 2 >> [Production of photocurable resin composition and three-dimensional molded article] (1) Photocurable resin 15 obtained in (1) of Example 1
100 g of a universal stirrer (Dalton Co., Ltd .; internal volume 10
2200 g of aluminum oxide fine particles (average particle size 3.5 μm, 75% by weight of fine particles having a particle size in the range of 0.5 to 1.5 times the average particle size).
(25% by volume based on the total volume of the finally obtained photocurable resin composition), and aluminum borate whiskers (γ- (methacryloxypropyl) trimethoxysilane) treated with an acrylic silane-based coupling agent ( "Albolex YS-4" manufactured by Shikoku Chemical Industry Co., Ltd .; diameter: 0.5 to 0.7 μm; aspect ratio: 50 to 70) 102
0 g (15% by volume based on the total volume of the finally obtained photocurable resin composition) was added, followed by stirring for one day and defoaming to produce a photocurable resin composition. The viscosity of the photocurable resin composition thus obtained at 25 ° C. was measured by the method described above, and was as shown in Table 1 below.

(3) Using the photocurable resin composition obtained in the above (2), optical three-dimensional modeling was performed in the same manner as in (3) of Example 1, and the surface roughness, tensile strength, Tensile elongation,
An optical three-dimensional structure (test piece) for measuring tensile modulus, thermal conductivity, and thermal deformation temperature was manufactured. In the production of the optical three-dimensional structure, the workability at the time of the stereolithography was judged by the above method. After washing the obtained optical three-dimensional structure (test piece) with isopropyl alcohol, 3 KW
Was irradiated for 10 minutes to perform post cure. The physical properties of the optical three-dimensional structure (test piece) obtained by the measurement were measured by the above-mentioned methods, and were as shown in Table 1 below. Furthermore, the specific gravity (d ₁ ) of the photocurable resin composition before photocuring used in the production of the optical three-dimensional molded article of Example 2 and the specific gravity (d ₂ ) of the three-dimensional molded article after post-curing.
Was measured, and the volumetric shrinkage was determined by the above equation (1). The results are as shown in Table 1 below.

Example 3 [Production of photocurable resin composition and three-dimensional molded article] (1) A three-necked flask having an inner volume of 5 liters equipped with a stirrer, a cooling tube, and a dropping funnel with a side tube was placed in a three-necked flask. , 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 4000 g, 1,4-butanediol diglycidyl ether 1000 g, 2,2-bis [4- (acryloxydiethoxy) phenylpropane (Shin-Nakamura Chemical Co., Ltd. "NK Ester A-BPE"
-4) 2500 g and 2500 g of ethylene oxide-modified trimethylolpropane triacrylate (“A-TMPT-3EO” manufactured by Shin-Nakamura Chemical Co., Ltd.) were mixed and stirred for about 1 hour. 2,2-dimethoxy-2-phenylacetophenone (“Irgacure 651” manufactured by Ciba Geigy)
50 g and bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate 2
Then, 00g was added and mixed and stirred until completely dissolved to produce an epoxy-based photocurable resin.

(2) 2500 g of the epoxy photocurable resin obtained in the above (1) was placed in a universal stirrer (Dalton Co., Ltd .; internal volume: 10 liters), and silica fine particles (average particle size: 5.0 μm; average) 80% by weight of fine particles having a particle size in the range of 0.7 to 1.2 times the particle size) 25
Then, 00 g (37% by volume based on the total volume of the photocurable resin composition finally obtained) was added, and the mixture was stirred for one day and defoamed to produce a photocurable resin composition. The viscosity of the photocurable resin composition thus obtained at 25 ° C. was measured by the method described above, and was as shown in Table 1 below.

(3) Using the photocurable resin composition obtained in the above (2), optical three-dimensional modeling was performed in the same manner as in (3) of Example 1, and the surface roughness, tensile strength, Tensile elongation,
An optical three-dimensional structure (test piece) for measuring tensile modulus, thermal conductivity, and thermal deformation temperature was manufactured. In the production of the optical three-dimensional structure, the workability at the time of the stereolithography was judged by the above method. After washing the obtained optical three-dimensional structure (test piece) with isopropyl alcohol, 3 KW
Was irradiated for 10 minutes to perform post cure. The physical properties of the optical three-dimensional structure (test piece) obtained by the measurement were measured by the above-mentioned methods, and were as shown in Table 1 below. Furthermore, the specific gravity (d ₁ ) of the photocurable resin composition before photocuring used in the production of the optical three-dimensional molded article of Example 2 and the specific gravity (d ₂ ) of the three-dimensional molded article after post-curing.
Was measured, and the volumetric shrinkage was determined by the above equation (1). The results are as shown in Table 1 below.

<< Comparative Example 1 >> [Production of photocurable resin composition and three-dimensional molded article] (1) Photocurable resin 15 obtained in (1) of Example 1
100 g of a universal stirrer (Dalton Co., Ltd .; internal volume 10
2200 g of aluminum oxide fine particles (average particle size 5.3 μm, 63% by weight of fine particles having a particle size in the range of 0.5 to 1.5 times the average particle size).
(25% by volume based on the total volume of the finally obtained photocurable resin composition), and aluminum borate whiskers (γ- (methacryloxypropyl) trimethoxysilane) treated with an acrylic silane-based coupling agent ( "Albolex YS-4" manufactured by Shikoku Chemical Industry Co., Ltd .; diameter: 0.5 to 0.7 μm; aspect ratio: 50 to 70) 102
0 g (15% by volume based on the total volume of the finally obtained photocurable resin composition) was added, followed by stirring for one day and defoaming to produce a photocurable resin composition. The viscosity of the photocurable resin composition thus obtained at 25 ° C. was measured by the method described above, and was as shown in Table 1 below.

(2) Using the photocurable resin composition obtained in the above (1), optical three-dimensional modeling was performed in the same manner as in (3) of Example 1, and the surface roughness, tensile strength, Tensile elongation,
An optical three-dimensional structure (test piece) for measuring tensile modulus, thermal conductivity, and thermal deformation temperature was manufactured. In the production of the optical three-dimensional structure, the workability at the time of the stereolithography was judged by the above method. After washing the obtained optical three-dimensional structure (test piece) with isopropyl alcohol, 3 KW
Was irradiated for 10 minutes to perform post cure. The physical properties of the optical three-dimensional structure (test piece) obtained by the measurement were measured by the above-mentioned methods, and were as shown in Table 1 below. Further, the specific gravity (d ₁ ) of the photocurable resin composition before photocuring used in the production of the optical three-dimensional structure of Comparative Example 1 and the specific gravity (d ₂ ) of the three-dimensional structure after post-curing.
Was measured, and the volumetric shrinkage was determined by the above equation (1). The results are as shown in Table 1 below.

<< Comparative Example 2 >> [Production of photocurable resin composition and three-dimensional molded article] (1) Photocurable resin 14 obtained in (1) of Example 1
55 g of a universal stirrer (Dalton Co., Ltd .; internal volume 10
Liter) and put into glass beads (average particle size 17.3μ).
m, 1116 g (proportion of fine particles having a particle diameter in the range of 0.5 to 1.5 times the average particle diameter), 1116 g (20% based on the total volume of the finally obtained photocurable resin composition)
%) And an acrylic silane coupling agent [γ
-(Methacryloxypropyl) trimethoxysilane] treated aluminum borate whisker (“Albolex YS-4” manufactured by Shikoku Chemicals Co., Ltd .;
374 g (7.5% by volume based on the total volume of the finally obtained photocurable resin composition) was added, stirred for one day, and defoamed.
A photocurable resin composition was manufactured. The viscosity of the photocurable resin composition thus obtained at 25 ° C. was measured by the method described above, and was as shown in Table 1 below.

(2) Using the photocurable resin composition obtained in (2) above, optical three-dimensional modeling was performed in the same manner as in (3) of Example 1, and the surface roughness, tensile strength, Tensile elongation,
An optical three-dimensional structure (test piece) for measuring tensile modulus, thermal conductivity, and thermal deformation temperature was manufactured. In the production of the optical three-dimensional structure, the workability at the time of the stereolithography was judged by the above method. After washing the obtained optical three-dimensional structure (test piece) with isopropyl alcohol, 3 KW
Was irradiated for 10 minutes to perform post cure. The physical properties of the optical three-dimensional structure (test piece) obtained by the measurement were measured by the above-mentioned methods, and were as shown in Table 1 below. Furthermore, the specific gravity (d ₁ ) of the photocurable resin composition before photocuring used in the production of the optical three-dimensional molded article of Example 2 and the specific gravity (d ₂ ) of the three-dimensional molded article after post-curing.
Was measured, and the volumetric shrinkage was determined by the above equation (1). The results are as shown in Table 1 below.

[0065]

[Table 1]

From the results shown in Table 1 above, the average particle size was 10 μm.
m and a ratio of fine particles having a particle size in the range of 0.5 to 1.5 times the average particle size is 70% by weight or more. The photocurable resin composition of Example 1 contains solid fine particles. ,
Photocurable resin composition of Example 2 containing the solid fine particles and whiskers, and fine particles having an average particle size of 10 μm or less and having a particle size in the range of 0.7 to 1.2 times the average particle size The photocurable resin composition of Example 3 containing solid fine particles having a ratio of 50% by weight or more (80% by weight), despite containing solid fine particles having a small particle size (Example 1) And Example 3) or despite containing solid fine particles and whiskers having a small particle diameter (Example 2), the viscosity is low, and the workability at the time of stereolithography is excellent, and Optical three-dimensional objects obtained from those photocurable resin compositions have low surface roughness and excellent surface smoothness, and furthermore, mechanical properties, heat resistance,
It can be seen that it has excellent heat deformation resistance and dimensional accuracy.

On the other hand, the photocurable resin composition of Comparative Example 1, that is, fine particles having an average particle size of 10 μm or less and having a particle size in the range of 0.5 to 1.5 times the average particle size Is less than 70% by weight (63% by weight), the photocurable resin composition containing fine particles together with whiskers is
The optical three-dimensional structure obtained from the photocurable resin composition of Comparative Example 1 has a high viscosity and is inferior in workability during stereolithography, and the optical three-dimensional molded product obtained in Examples 1 and 2 It can be seen that the surface roughness is higher and the surface smoothness is inferior to the three-dimensional structure. In addition, the photocurable resin composition of Comparative Example 2 containing solid fine particles having an average particle size of more than 10 μm together with whiskers has a low viscosity due to the large average particle size of the solid fine particles, and has a low workability during stereolithography. It can be seen that, although good, the optical three-dimensional structure obtained from the photocurable resin composition of Comparative Example 2 had high surface roughness and poor surface smoothness.

[0068]

According to the present invention, the solid fine particles contained in the photocurable resin composition have an average particle diameter of 10 μm or less and a particle diameter in the range of 0.5 to 1.5 times the average particle diameter. By using solid fine particles in which the ratio of fine particles having the following is 70% by weight or more, the solid fine particles having a small average particle diameter of 10 μm or less are contained, or the solid fine particles having a small particle diameter are used. Despite containing whiskers, it has low viscosity and is excellent in handleability and workability when optically producing a photocured product such as a three-dimensional molded product. Furthermore, a photocured product such as an optical three-dimensional molded product obtained by using the photocurable resin composition of the present invention has excellent surface smoothness, and furthermore has heat resistance, heat deformation resistance,
Excellent mechanical properties such as mechanical strength and dimensional accuracy.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F213 AA44 AB24 AB25 WA25 WB01 WL02 WL25 WL92 WL96 4J011 GA05 GB08 PA03 PA07 PA08 PA09 PA13 PA14 PA15 PA64 PA65 PA69 PA76 PB04 PB16 PB22 QA03 QA06 QA08 QA09 QA12 QA13 QA23 QA23 QA23 QA23 QA46 QB14 QB16 QB19 QB24 RA10 SA02 SA12 SA14 SA16 SA20 SA22 SA61 SA63 SA78 SA87 UA02 UA06 WA10

Claims (12)

[Claims] 1. A liquid photocurable resin having an average particle size of 10
The solid fine particles having a ratio of fine particles having a particle diameter of 0.5 μm or less and having a particle diameter in the range of 0.5 to 1.5 times the average particle diameter of 70% by weight or more are determined based on the total volume of the photocurable resin composition. A photocurable resin composition, which is contained in an amount of 5 to 70% by volume. 2. The solid fine particles having an average particle diameter of 0.
2. The photocurable resin composition according to claim 1, wherein the proportion of the fine particles having a particle size in the range of 7 to 1.2 times is 50% by weight or more. 3. The solid fine particles have an average particle size of 1 to 10 μm.
The photocurable resin composition according to claim 1 or 2, wherein m is in the range of m. 4. An average particle diameter of the solid fine particles is 1 to 5 μm.
The photocurable resin composition according to any one of claims 1 to 3, which is within the range. 5. The photocurable resin composition according to claim 1, which has a viscosity at 25 ° C. of 70,000 centipoise or less. 6. The whisker is further contained in a proportion of 5 to 30% by volume based on the total volume of the photocurable resin composition, and the total volume of the solid fine particles and the whisker is the total volume of the photocurable resin composition. The photocurable resin composition according to any one of claims 1 to 4, which is 10 to 75% by volume based on the composition. 7. A diameter of 0.3 to 1 μm and a length of 10 to 70 μm
The photocurable resin composition according to claim 6, wherein a whisker having an aspect ratio of 10 to 100 is used. 8. The photocurable resin composition according to claim 6, which has a viscosity at 25 ° C. of 70,000 centipoise or less. 9. A resin composition for stereolithography, wherein the resin composition is for stereolithography.
The photocurable resin composition according to any one of the above. 10. A cured layer having a predetermined pattern by selectively irradiating one layer of the photocurable resin composition according to claim 1 with an active energy ray, After applying an uncured liquid photocurable resin composition in a layered form on the cured layer, irradiation with active energy rays is performed to newly form a cured layer continuous with the cured layer, and a predetermined three-dimensional structure is obtained. The method of manufacturing a three-dimensional structure, further comprising repeating the above-described laminating operation. 11. An optical three-dimensional structure obtained by using the photocurable resin composition according to claim 1. Description: 12. The optical three-dimensional structure according to claim 11, wherein a surface roughness measured by a three-dimensional surface contact method using a three-dimensional surface roughness meter is 2.0 μm or less on average.