JP2008189783A - Resin composition for optical stereoscopic molding by surface exposure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for an optical stereoscopic molding capable of smoothly manufacturing a stereoscopic molded article with excellent heat-resistance in a short optical molding time with sufficient productivity, and an optical stereoscopic molding method using the resin composition. <P>SOLUTION: The resin composition for optical stereoscopic molding by surface exposure contains at least a dimethacrylate compound (I) represented by the chemical formula (I) as a radical polymerizable organic compound, and contains an acylphosphine oxide based radical polymerization initiator, and a method for manufacturing the stereoscopic molded article by surface exposure using the resin composition are provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photocurable resin composition used for producing an optical three-dimensional object by a surface exposure method, and a method for producing a three-dimensional object by a surface exposure method using the photocurable resin composition. More specifically, the present invention provides an optical by surface exposure that can produce a three-dimensional structure that has excellent heat resistance and excellent mechanical properties by surface exposure and can be manufactured smoothly with high modeling accuracy and dimensional accuracy with high productivity. The present invention relates to a three-dimensionally shaped resin composition and a method for producing a three-dimensionally shaped object by a surface exposure method using the resin composition.

In recent years, a method for three-dimensional optical modeling of a liquid photocurable resin composition based on data input to a three-dimensional CAD has achieved good dimensional accuracy without producing a mold or the like. Have been widely adopted.
As a typical example of the optical three-dimensional modeling method, a spot-shaped ultraviolet laser beam controlled by a computer is selectively irradiated so that a desired pattern can be obtained on the liquid surface of the liquid photocurable resin placed in a container. Then, a predetermined thickness is cured, and then a liquid resin for one layer is supplied onto the cured layer, and similarly, it is irradiated and cured with an ultraviolet laser beam in the same manner as described above to repeat a lamination operation to obtain a continuous cured layer. The method of finally obtaining a three-dimensional molded item can be mentioned. With this optical three-dimensional modeling method, it is possible to easily obtain a model having a considerably complicated shape in a relatively short time.

  In recent years, instead of the above-described conventional method using spot-like ultraviolet laser light, a high-pressure mercury lamp, ultra-high pressure mercury lamp, low-pressure mercury lamp or other lamp or LED that emits light other than laser light is used as a light source. A liquid crystal drawing mask or a plurality of digital micromirrors in which a large number of micro liquid crystal shutters capable of shielding and transmitting light in micro dot areas are arranged between a light source and a modeling surface made of a photocurable resin composition A planar drawing mask made of a so-called DMD (digital micromirror device) having a shutter arranged in a plane is arranged, and a modeling surface made of a photocurable resin is irradiated with light through the planar drawing mask to give a predetermined cross section. A three-dimensional modeling technique using surface exposure has been proposed in which a three-dimensional model is manufactured by sequentially laminating photo-curing resin layers having a shape pattern (for example, See Patent Documents 1 and 2). The optical three-dimensional modeling technique using a planar drawing mask can form a planar photocured cross-sectional shape pattern by irradiating a modeling surface made of a photocurable resin composition with a planar surface at once. Therefore, it is possible to significantly improve the optical modeling speed as compared with the stippling method using a spot-like ultraviolet laser.

With the progress of the optical three-dimensional modeling technology, the applications of the optical three-dimensional model are also expanding, and high heat resistance is required depending on the applications and the like. For example, high heat resistance of 180 ° C. or higher is required for an optical three-dimensional structure used for an engine portion.
As a resin composition for optical three-dimensional modeling that can form a three-dimensional model having relatively excellent heat resistance, di (meth) acrylate having a cyclohexane ring in the molecule, such as cyclohexanedimethanol di (meth) acrylate, is used. The resin composition for optical three-dimensional modeling to contain is known. However, the heat-resistant temperature of the three-dimensional modeled object obtained by optical modeling of this optical three-dimensional modeled resin composition is about 60 ° C., and the heat resistance is still insufficient.

  For the resin composition for optical three-dimensional modeling, in addition to the heat resistance requirement for the three-dimensional model to be obtained, the handling property at the time of modeling is low and the storage stability is excellent, Solid modeling object with high curing sensitivity by active energy rays, capable of modeling in a short time, small shrinkage during photocuring, little warping, excellent dimensional accuracy, modeling accuracy, appearance, mechanical properties, etc. Is required to be manufactured smoothly.

  As an optical three-dimensional modeling resin composition, an acrylate-based photocurable resin composition, an epoxy-based photocurable resin composition, or the like has been conventionally used. Among these, the epoxy-based photocurable resin composition has been widely used in recent years because it can produce a molded article having excellent dimensional accuracy. However, since the light absorption wavelength range of a photopolymerization initiator (typically, trialissulfonium salt compound, etc.) used for photopolymerization of an epoxy compound is generally 355 nm or less, which is the wavelength of semiconductor-excited solid laser light, surface exposure In UV light emitted from high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, etc., which are mainly used as light sources, in the wavelength range of 350 to 400 nm (mostly 360 to 400 nm) Does not progress. Therefore, when the epoxy-based photocurable resin composition is used for surface three-dimensional optical three-dimensional modeling, it is difficult to cure the resin, and it is difficult to manufacture a three-dimensional model in a practical modeling time. From this point, when the epoxy photocurable resin composition is used for optical three-dimensional modeling by surface exposure, the combined use of a sensitizer has been attempted, but sufficient reactivity has not been ensured.

  Various compounds ranging from the ultraviolet region to the visible light region are known as photoradical polymerization initiators used for polymerization of the acrylate photocurable resin composition. Some conventional acrylate-based photocurable resin compositions using these radical photopolymerization initiators exhibit sufficient curability, but the heat resistance of the optical three-dimensional object obtained by optical modeling Then it is not satisfactory enough.

JP-A-8-112863 JP-A-8-192469 Paul F. Jacobs, “Rapid Prototyping & Manufacturing, Fundamentals of Stereo-Lithography”, “Society of Manufacturing Engineers”, 1992, p. 28-39.

The objective of this invention is providing the resin composition for optical three-dimensional model | molding which can manufacture smoothly the three-dimensional model | molding thing excellent in heat resistance by optical modeling.
Furthermore, the objective of this invention is providing the resin composition for optical three-dimensional model | molding which can manufacture the optical three-dimensional model | molding thing excellent in heat resistance smoothly with sufficient productivity in a short optical modeling time.
And the purpose of the present invention is low viscosity, excellent handleability during optical modeling, excellent stability over time during storage, small shrinkage during curing, excellent dimensional accuracy, modeling accuracy and appearance, Is to provide a photocurable resin composition capable of producing a three-dimensional molded article having excellent mechanical characteristics with high productivity.
Furthermore, the objective of this invention is providing the optical three-dimensional modeling method which can manufacture a three-dimensional molded item smoothly using the above-mentioned resin composition for optical three-dimensional modeling.

In order to solve the above-mentioned problems, the present inventors have intensively studied. And for optical three-dimensional modeling containing tricyclodecane dimethanol dimethacrylate as at least part of the radical polymerizable organic compound, and containing acylphosphine oxide radical polymerization initiator as at least part of the photo radical polymerization initiator Three-dimensional modeling using a surface exposure method in which a resin composition is prepared and ultraviolet light (non-laser light) having a wavelength of 350 to 400 nm is irradiated through a planar drawing mask using the optical three-dimensional modeling resin composition. An experiment to manufacture a product was conducted. As a result, it has been found that a three-dimensional object having an extremely high heat distortion temperature (HDT), excellent heat resistance, and excellent mechanical properties can be obtained smoothly in a short optical modeling time.
Furthermore, the present inventors have said that the photocurable resin composition has a small shrinkage at the time of curing, and can produce a target three-dimensional modeled object with high dimensional accuracy and modeling accuracy. It has been found that it is excellent in handleability and is stable over time during storage.

  In addition, the present inventors include a bisphenol skeleton in the molecule at a predetermined ratio in the resin composition for optical three-dimensional modeling containing tricyclodecane dimethanol dimethacrylate and an acyl phosphine oxide radical polymerization initiator. When a three-dimensional object is manufactured by the above-described surface exposure method using a specific dimethacrylate having a predetermined ratio and the resin composition for optical three-dimensional object formation, the mechanical properties such as impact resistance are high. The present inventors have found that a three-dimensional modeled object with improved characteristics can be obtained, and that the occurrence of warpage is reduced, and the present invention has been completed based on these various findings.

That is, the present invention
(1) A resin composition for optical three-dimensional modeling by surface exposure, comprising a radical polymerizable organic compound and a photo radical polymerization initiator, wherein the radical polymerizable organic compound has the following chemical formula (I);

で表されるジメタクリレート化合物（Ｉ）を少なくとも含有し、且つ光ラジカル重合開始剤としてアシルフォスフィンオキサイド系ラジカル重合開始剤を少なくとも含有することを特徴とする、面露光による光学的立体造形用樹脂組成物である。

A resin for optical three-dimensional modeling by surface exposure, characterized in that it contains at least a dimethacrylate compound (I) represented by the formula (II) and at least an acyl phosphine oxide radical polymerization initiator as a photo radical polymerization initiator. It is a composition.

And this invention,
(2) The content of the dimethacrylate compound (I) described above is 30 to 100% by mass based on the total mass of the radical polymerizable organic compound contained in the optical three-dimensional resin composition. A resin composition for optical three-dimensional modeling; and
(3) As a radically polymerizable organic compound, the following general formula (II);

（式中、Ｒ¹は水素原子またはメチル基、Ｒ²は水素原子またはメチル基、ｍおよびｎはそれぞれ独立して１〜２０の整数を示す。）
で表されるジメタクリレート化合物（II）を、ジメタクリレート化合物（Ｉ）１００質量部に対して１００質量部未満の量で更に含有する前記（１）または（２）の光学的立体造形用樹脂組成物；
である。

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a methyl group, and m and n each independently represents an integer of 1 to 20)
The resin composition for optical three-dimensional modeling according to the above (1) or (2), further comprising a dimethacrylate compound (II) represented by the formula (II) in an amount of less than 100 parts by mass relative to 100 parts by mass of the dimethacrylate compound (I) object;
It is.

Furthermore, the present invention provides:
(4) The above (1) to (1), wherein the content of the photo radical polymerization initiator is 0.1 to 10% by mass based on the total mass of the radical polymerizable organic compound contained in the resin composition for optical three-dimensional modeling. 3) A resin composition for optical three-dimensional modeling according to any one of the above;
(5) Any of (1) to (4) above containing 2,2-dimethoxy-1,2-diphenylethane-1-one together with an acylphosphine oxide radical polymerization initiator as a photoradical polymerization initiator A resin composition for optical three-dimensional modeling; and
(6) For optical three-dimensional modeling according to any one of (1) to (5), which is a resin composition for optical three-dimensional modeling for producing an optical three-dimensional modeled product under irradiation with light having a wavelength of 350 to 400 nm. Resin composition;
It is.

Furthermore, the present invention provides:
(7) A modeling surface formed from the resin composition for optical three-dimensional modeling according to any one of the above (1) to (6) is irradiated with light in a planar shape through a planar drawing mask to have a predetermined shape pattern. After forming a photocured resin layer for one layer, a modeling surface composed of an uncured resin layer for one layer made of the resin composition for optical three-dimensional modeling is formed on the photocured resin layer, Repeat the operation of irradiating the modeling surface with light through a planar drawing mask to form a photocured resin layer for the next one layer having a predetermined shape pattern until a three-dimensional model is obtained. A method for producing an optical three-dimensional object characterized by:
(8) The method for producing an optical three-dimensional object according to (7), wherein light having a wavelength of 350 to 400 nm is irradiated onto a modeling surface made of the resin composition for optical three-dimensional modeling through a planar drawing mask;
It is.

Using the resin composition for optical three-dimensional modeling by surface exposure of the present invention, which contains a dimethacrylate compound (I) (tricyclodecane dimethanol dimethacrylate) and an acyl forcin oxide radical polymerization initiator, a high-pressure mercury lamp, Using an ultra-high pressure mercury lamp, low-pressure mercury lamp, ultraviolet LED or other inexpensive non-laser lamp as a light source, and producing a three-dimensional object by the surface exposure method, it has an extremely high heat distortion temperature (HDT). In addition, it is possible to smoothly produce a three-dimensional modeled object having excellent heat resistance and mechanical properties in a short modeling time with high productivity.
Further, the resin composition for optical three-dimensional modeling of the present invention has a small shrinkage at the time of curing, can produce a target three-dimensional modeled object with high dimensional accuracy and modeling accuracy, and has a low viscosity during optical modeling. In addition, it is excellent in handling properties and is stable over time during storage.
Further, for optical stereolithography by surface exposure of the present invention, which contains a predetermined proportion of dimethacrylate (II) having a bisphenol skeleton in the molecule together with tricyclodecane dimethanol dimethacrylate and an acylphosphine oxide radical polymerization initiator When a three-dimensional structure is manufactured by a surface exposure method using a resin composition, it is excellent in heat resistance, mechanical properties, high toughness, properties such as impact resistance, and even less warpage. A model can be obtained.

The present invention is described in detail below.
The resin composition for optical three-dimensional modeling of the present invention is a photocurable resin containing a radical polymerizable organic compound and a photo radical polymerization initiator, which is used to produce a three-dimensional model by optical three-dimensional modeling using a surface exposure method. It is a composition.
And the resin composition for optical three-dimensional model | molding of this invention has the following chemical formula (I) as a radically polymerizable organic compound;

で表される、ジメタクリレート化合物（Ｉ）（トリシクロデカンジメタノールジメタクリレート）を少なくとも含有することを特徴とする。
ここで、本明細書における「面露光による光学的立体造形」とは、光学的立体造形用樹脂組成物から形成した造形面に面状描画マスクを介して光を面状に照射して所定の形状パターンを有する１層分の光硬化した樹脂層を形成した後、当該光硬化した樹脂層の上に光学的立体造形用樹脂組成物からなる１層分の未硬化層よりなる造形面を形成し、当該未硬化の造形面に面状描画マスクを介して光を面状に照射して所定の形状パターンを有する次の１層分の光硬化した樹脂層を形成する操作を、目的とする立体造形物が得られるまで繰り返えして行う光造形技術をいう。

It contains at least dimethacrylate compound (I) (tricyclodecane dimethanol dimethacrylate) represented by
Here, “optical three-dimensional modeling by surface exposure” in the present specification means that a modeling surface formed from a resin composition for optical three-dimensional modeling is irradiated with light in a planar manner via a planar drawing mask. After forming a photocured resin layer for one layer having a shape pattern, a modeling surface made of an uncured layer for one layer made of a resin composition for optical three-dimensional modeling is formed on the photocured resin layer. Then, the operation for forming a photo-cured resin layer for the next one layer having a predetermined shape pattern by irradiating light on the uncured modeling surface in a planar manner through a planar drawing mask is an object. This is an optical modeling technique that is repeated until a three-dimensional model is obtained.

The resin composition for optical three-dimensional model | molding of this invention is a ratio of 30-100 mass% of dimethacrylate compounds (I) based on the total mass of the radically polymerizable organic compound contained in the resin composition for optical three-dimensional model | molding. It is preferable to contain in the ratio of 40-100 mass%, It is more preferable to contain in the ratio of 50-100 mass%.
If the content of the dimethacrylate compound (I) in the optical three-dimensional modeling is low, the heat distortion temperature (HDT) of the three-dimensional model obtained by optical modeling becomes low, resulting in insufficient heat resistance, and mechanical strength. Becomes lower.

  The resin composition for optical three-dimensional model | molding of this invention is the following general formula (II) depending on the case with the above-mentioned dimethacrylate compound (I) as a radically polymerizable organic compound;

（式中、Ｒ¹は水素原子またはメチル基、Ｒ²は水素原子またはメチル基、ｍおよびｎはそれぞれ独立して１〜２０の整数を示す。）
で表されるジメタクリレート化合物（II）を含有することができる。

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a methyl group, and m and n each independently represents an integer of 1 to 20)
The dimethacrylate compound (II) represented by these can be contained.

In the dimethacrylate compound (II) represented by the general formula (II), R ¹ is a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of material availability. In the dimethacrylate compound (II) represented by the general formula (II), R ² is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of material availability. Further, m and n are each independently an integer of 1 to 20, and it is preferable from the viewpoint of physical properties of the three-dimensional structure that both m and n are integers of 2 to 15, particularly 2 to 12. Moreover, it is preferable that the sum total of m and n is 2-30, It is more preferable that it is 4-30, It is still more preferable that it is 4-24 especially.
As the dimethacrylate compound (I), those having various molecular weights are commercially available depending on the number of bonds m and n of the alkylene oxide group [—CH ₂ CH (R ² ) —O—] to bisphenol. Shin-Nakamura Chemical Co., Ltd. ethoxylated bisphenol A dimethacrylate “NK ester BPE-100” (R ² = H, m + n = 2.6), ethoxylated bisphenol A dimethacrylate “NK ester BPE-200” (R ² = H, m + n = about 4), “NK ester BPE-500” (R ² = H, m + n = about 10), “NK ester BPE-900” (R ² = H, m + n = about 17), “NK ester BPE-1300 ”(R ² = H, m + n = about 30).

In the resin composition for optical three-dimensional modeling of the present invention, the content of the dimethacrylate compound (II) with respect to 100 parts by mass of the dimethacrylate compound (I) is less than 100 parts by mass (0 to less than 100 parts by mass). It is preferably at least part by mass and less than 100 parts by mass, more preferably at least 10 parts by mass and less than 100 parts by mass, and even more preferably at least 15 parts by mass and less than 100 parts by mass.
When the content of the dimethacrylate compound (II) is the same as or higher than the content of the dimethacrylate compound (I), the heat resistance of the resulting three-dimensional structure decreases.
Further, in the resin composition for optical three-dimensional modeling of the present invention, the total content of the dimethacrylate compound (I) and the dimethacrylate compound (II) with respect to the total mass of the radical polymerizable organic compound contained in the composition. However, it is preferable that it is 50-100 mass%, especially 70-100 mass% from points, such as heat resistance, a moldability, and low curvature property.

The resin composition for optical three-dimensional modeling of the present invention requires a radical polymerizable organic compound other than dimethacrylate compound (I) and dimethacrylate compound (II) as long as the object of the present invention is not hindered. Accordingly, it may be contained in a small proportion (usually a proportion of 50% by mass or less, more preferably 30% by mass or less, based on the total mass of the radical polymerizable organic compound).
Examples of the other radical polymerizable organic compound that may be contained in the resin composition for optical three-dimensional modeling of the present invention include, for example, (meth) acrylate compounds other than dimethacrylate compound (I) and dimethacrylate compound (II), Examples include di (meth) acrylate compounds, tri (meth) acrylate compounds, or poly (meth) acrylate compounds having 4 or more functional groups, imide (meth) acrylate compounds, (meth) acrylamide compounds, vinyl compounds, and the like. be able to.

More specifically, as other (meth) acrylate compounds, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylates and other dipentaerythritol poly (meth) acrylates, and (meth) acrylates of alkylene oxide adducts of polyhydric alcohols such as diols, triols, tetraols, and hexaols.
Examples of the vinyl compound include styrene, styrene having a substituent on the benzene ring, divinylbenzene, divinylbenzene having a substituent on the benzene ring, and N-vinylcarbazole.

  In the resin composition for optical three-dimensional model | molding of this invention, an acyl phosphine oxide type radical polymerization initiator is used as at least one part of radical photopolymerization initiator. Acylphosphine oxide radical polymerization initiators are often used in optical stereolithography by the surface exposure method. High pressure mercury lamp, ultra high pressure mercury lamp, low pressure mercury lamp, xenon lamp, halogen lamp, metal halide lamp, ultraviolet LED (Light emitting diode), UV light emitted from a light source such as an ultraviolet fluorescent lamp absorbs ultraviolet light having a wavelength of 350 to 400 nm, and initiates photopolymerization of the radical polymerizable organic compound.

  As the acyl phosphine oxide radical polymerization initiator used as at least part of the photo radical polymerization initiator in the present invention, monoacyl phosphine oxide (IIIa) represented by the following general formula (IIIa) and the following general formula The diacylphosphine oxide (IIIb) represented by (IIIb) can be mentioned.

［式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸は、それぞれ独立して、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、フェニル基、ベンジル基、１個以上の置換基（例えば炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、ハロゲン、シアノ基、炭素数２〜５のアルコキシカルボニル基、１個または２個以上の炭素数１〜１２のアルコキシ基および／またはハロゲン原子により置換された炭素数１〜８のアルキル基など）で置換された炭素数５〜８のアルキル基、フェニル基、ベンジル基などを示す。］
モノアシルフォスフィンオキサイド（IIIａ）およびジアシルフォスフィンオキサイド（IIIｂ）としては、上記の一般式（IIIａ）または一般式（IIIｂ）において、Ｒ³およびＲ⁵がフェニル基、炭素数１〜４のアルキル基、アルキル置換フェニル基または炭素数１〜４のアルコキシ基置換フェニル基で、Ｒ⁴、Ｒ⁶、Ｒ⁷およびＲ⁸が炭素数１〜４のアルコキシ基、ハロゲン原子、炭素数１〜４のアルキル基置換フェニル基または枝分かれしていてもよい炭素数１〜１０のアルキル基であるものが、入手性などの点から好ましく用いられる。

[Wherein, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a phenyl group, or benzyl. Group, one or more substituents (for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen, a cyano group, an alkoxycarbonyl group having 2 to 5 carbon atoms, one or two or more An alkyl group having 5 to 8 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms and / or an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom), a phenyl group, a benzyl group, or the like; ]
As monoacylphosphine oxide (IIIa) and diacylphosphine oxide (IIIb), in the above general formula (IIIa) or general formula (IIIb), R ³ and R ⁵ are each a phenyl group, an alkyl having 1 to 4 carbon atoms. A group, an alkyl-substituted phenyl group, or an alkoxy group-substituted phenyl group having 1 to 4 carbon atoms, wherein R ⁴ , R ⁶ , R ^7, and R ⁸ are an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and 1 to 4 carbon atoms An alkyl group-substituted phenyl group or an optionally branched alkyl group having 1 to 10 carbon atoms is preferably used from the viewpoint of availability.

Specific examples of monoacylphosphine oxide (IIIa) and diacylphosphine oxide (IIIb) that can be used in the resin composition for optical three-dimensional modeling of the present invention include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide and the like, and one or more of them can be used.
Since these have a high absorption rate of ultraviolet rays having a wavelength of 350 to 400 nm and are easily available, they are more suitably used in optical three-dimensional modeling by the surface exposure method of the present invention.

The resin composition for optical three-dimensional modeling of the present invention may contain only an acyl phosphine oxide-based radical polymerization initiator as a photo-radical polymerization initiator, or other light together with the acyl phosphine oxide-based radical polymerization. A radical polymerization initiator may be contained.
Examples of other radical photopolymerization initiators that may be contained in the resin composition for optical three-dimensional modeling of the present invention include benzyl or its dialkyl acetal compound, phenyl ketone compound, acetophenone compound, benzoin or its alkyl ether compound. Compounds, benzophenone compounds, thioxanthone compounds, and the like.
In this case, specific examples of benzyl or dialkyl acetal compounds that can be used as other radical polymerization initiators include benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, etc .; specific examples of phenyl ketone compounds Examples include 1-hydroxy-cyclohexyl phenyl ketone; specific examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2- Hydroxy-2-methyl-propiophenone, 2-hydroxy-2-methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-a Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether; benzophenone compounds Specific examples of these include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone; specific examples of thioxanthone compounds include thioxanthone, 2 -Methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, etc. can be mentioned.

Among them, the resin composition for optical three-dimensional modeling of the present invention contains an acyl phosphine oxide radical polymerization initiator alone as a photo radical polymerization initiator, or together with an acyl phosphine oxide radical polymerization initiator. 2,2-dimethoxy-1,2-diphenylethane-1-one (such as “Irgacure 651” manufactured by Ciba Specialty Chemicals), 1-hydroxycyclohexyl phenyl ketone (such as “Irgacure 184” manufactured by the same company), 2 It is preferable to contain -hydroxy-2-methylpropiophenone ("Darocur 1173" manufactured by Ciba Specialty Chemicals).
In particular, acylphosphine oxide radical polymerization initiators (among them, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) and 2,2-dimethoxy-1,2-diphenylethane-1-one (Ciba Special) When combined with “Irgacure 651” manufactured by Tea Chemicals, etc., the above-described resin composition for optical three-dimensional modeling is smoothly cured by ultraviolet rays having a wavelength of 350 to 400 nm, and at the time of optical three-dimensional modeling by surface exposure. The depth of photocuring can be easily adjusted, and a three-dimensional structure with high dimensional accuracy and excellent heat resistance can be obtained.

The resin composition for optical three-dimensional modeling of the present invention contains 0.1 to 10% by mass of a radical photopolymerization initiator (containing two or more kinds of radical photopolymerization initiators) based on the total mass of the radical polymerizable organic compound. When it does, it is preferable to contain in the ratio of the total content), and it is more preferable to contain in the ratio of 0.2-7 mass%.
When the resin composition for optical three-dimensional modeling of the present invention contains only an acyl phosphine oxide radical polymerization initiator as a photo radical polymerization initiator, the acyl phosphine is based on the total mass of the radical polymerizable organic compound. It is preferable that the fin oxide radical polymerization initiator is contained in the above-described proportion of 0.1 to 10% by mass, particularly 0.2 to 7% by mass. In addition, the resin composition for optical three-dimensional modeling of the present invention may contain other photoradical polymerization initiators (for example, 2,2-dimethoxy-1,2-diphenylethane-1-one together with acylphosphine oxide radical polymerization initiators). Etc.) based on the total mass of the radically polymerizable organic compound, the acylphosphine oxide radical polymerization is 0.1 to 7% by mass, in particular 0.2 to 5% by mass, and other photoradicals. It is preferable to contain a polymerization initiator in a proportion of 0.1 to 7% by mass, particularly 0.2 to 5% by mass.

  As long as the effects of the present invention are not impaired, the resin composition for optical three-dimensional modeling of the present invention, if necessary, colorants such as pigments and dyes, antifoaming agents, leveling agents, thickeners, flame retardants, oxidation agents An appropriate amount of one or two or more of an inhibitor, a filler (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.) and a modifying resin may be contained.

  The method for preparing the resin composition for optical three-dimensional modeling of the present invention is not particularly limited. For example, a photoradical after the dimethacrylate compound (I) and other radical polymerizable organic compound as necessary are mixed at a predetermined ratio. A method of uniformly mixing a polymerization initiator and other components such as an additive as necessary, dimethacrylate compound (I), dimethacrylate compound (II) and other radical polymerizable organic compound as necessary It can be prepared later by a method of uniformly mixing other components such as a radical photopolymerization initiator and, if necessary, an additive.

Using the above-described resin composition for optical three-dimensional modeling of the present invention, optical three-dimensional modeling is performed by surface exposure to manufacture a three-dimensional modeled object. In the optical three-dimensional modeling method by surface exposure of the present invention, any of the conventionally known optical three-dimensional modeling methods and apparatuses by surface exposure can be used.
As a representative example of the optical three-dimensional modeling method by surface exposure that can be preferably employed in the present invention, light from a light source is formed from the optical three-dimensional modeling resin composition of the present invention through a planar drawing mask. The molded surface is irradiated with a predetermined planar shape pattern to form a photocured cured layer having the predetermined planar shape pattern, and then an optical solid for one uncured layer on the cured layer. A modeling resin surface is formed by supplying a modeling resin composition, and the modeling surface is irradiated with light through a planar drawing mask in a predetermined planar shape pattern, and continuous with the cured layer ( An example is a method of repeating an optical modeling operation (optical lamination operation) of newly forming a cured layer having a predetermined shape pattern (laminated and bonded) until a target three-dimensional modeled object is obtained.

The light source that can be used in the optical three-dimensional modeling by the surface exposure of the present invention includes a high pressure mercury lamp, an ultra high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a halogen lamp, a metal halide lamp, an ultraviolet LED (light emitting diode), a mercury lamp, and an ultraviolet fluorescence. Lights can be mentioned.
The shape, size, and number of the light source are not particularly limited, and can be appropriately selected according to the shape and size of the planar drawing mask, the shape and size of the photocuring cross-sectional shape pattern to be formed, and the light source is For example, it may be dot-shaped, spherical, rod-shaped, or planar, and a dot-shaped or spherical light source may be directly arranged in one or more rows on the back side of the planar drawing mask.

In addition, the light source may be provided so as to be continuously movable together with the planar drawing mask, or the light source is fixed at a fixed position for the purpose of improving modeling accuracy, improving modeling speed, reducing the weight of the apparatus, and improving maintainability. It is installed so that it does not move, and the light from the light source is guided to the back of the planar drawing mask through optical fiber, light guide and other light transmission means, and the optical fiber, light guide and other light transmission means can be moved continuously with the planar drawing mask May be provided.
Moreover, you may employ | adopt the system which condenses and raises light energy using a some light source for the improvement of modeling speed. In particular, when an optical fiber or a light guide is used, there is an advantage that a plurality of light sources can be easily condensed.

  In the present invention, for the purpose of improving modeling accuracy, improving modeling speed, reducing the weight of the apparatus, improving maintainability, reducing the cost of the apparatus, etc., the type, shape, number, and shape and dimensions of the planar drawing mask, etc. In accordance with the above, means for favorably guiding light from the light source to the planar drawing mask (for example, a condensing lens, a Fresnel lens, etc.), and a mask image formed by the planar drawing mask (passed through the planar drawing mask) It is preferable to arrange means (for example, a projection lens, a projector lens, etc.) for irradiating a predetermined position on the modeling surface made of the optical three-dimensional modeling resin composition with high modeling accuracy.

In the optical three-dimensional modeling by surface exposure according to the present invention, a planar drawing mask in which a plurality of minute liquid crystal shutters capable of shielding and transmitting light in a minute dot area are arranged as a planar drawing mask, or a minute dot area. A digital micromirror device (DMD) is preferably used in which a plurality of digital micromirror shutters are arranged in a plane so as to be capable of shielding light and reflecting light toward the modeling surface.
These planar drawing masks are a plurality of micro-light shutters such as a plurality of liquid crystals that can block and transmit light in a micro dot area, or a plurality of light blocks that can block light in a micro dot area and reflect light toward a modeling surface. It is preferable to use a square or rectangular planar drawing mask in which minute optical shutters (digital micromirrors) are arranged in parallel in a planar shape (XY direction).
The number of minute light shutters (image elements) arranged on the planar drawing mask is not particularly limited, and conventionally known ones can be used. As a liquid crystal shutter (liquid crystal display element), for example, QVGA (number of pixels = 320 dots × 240 dots), VGA (number of pixels = 640 × 480 dots), SVGA (number of pixels = 800 × 600 dots), UXGA (number of pixels) = 1024 × 768 dots), QSXGA (number of pixels = 2560 × 2648 dots), and the like, and these liquid crystal shutters have been widely sold.
Further, as the digital micromirror shutter, for example, DMD (number of pixels = 1024 × 768 dots) of “DLP Technology” (registered trademark) manufactured by Texas Instruments Inc. can be used.

  In the present invention, any optical three-dimensional modeling by a surface exposure method can be adopted. For example, when forming a photocured resin layer for one layer, a mask image by a planar drawing mask is formed on each cured resin layer. Operation to form a photocured resin layer for each layer having a predetermined shape pattern on the modeling surface by irradiating the modeling surface with light through a planar drawing mask in a certain stationary state according to the pattern May be manufactured until a three-dimensional object having a desired shape is obtained, or a three-dimensional object may be manufactured, or a planar drawing mask may be continuously moved in parallel to the modeling surface on the modeling surface and planar. While continuously changing the mask image of the drawing mask in a moving image, the modeling surface is irradiated with light through the planar drawing mask to form a photocured resin layer for each layer having a predetermined shape pattern. The operation of the desired shape Repeat until the body shaped article is obtained may be manufactured three-dimensional object.

The intensity of light energy when irradiating the modeling surface made of the optical three-dimensional modeling resin composition through the planar drawing mask is the three-dimensional modeling for the purpose of the composition and production of the optical three-dimensional modeling resin composition. Although it may vary depending on the type of object, etc., in general, from the viewpoint of productivity, mechanical properties of the resulting three-dimensional structure, etc., it is a modeling surface for forming a one-layer photocured resin layer The integrated light energy amount per unit area is preferably 1 to 100 mJ / cm ² , particularly preferably ² to 80 mJ / cm ² .
In the present invention, in order to produce a three-dimensional structure by the surface exposure method, using the resin composition for optical three-dimensional structure of the present invention containing the dimethacrylate compound (I) and the acylphosphine oxide radical polymerization initiator, A three-dimensional model having excellent heat resistance can be manufactured with high productivity in a short optical modeling time. On the other hand, when a spotting method using spot-like laser light is adopted, the optical three-dimensional modeling resin composition containing the dimethacrylate compound (I) and the acylphosphine oxide radical polymerization initiator is optical Therefore, the three-dimensional model having excellent heat resistance cannot be produced with high productivity in a short optical modeling time.

  The resin composition for optical three-dimensional modeling of the present invention can be widely used in the field of optical three-dimensional modeling by surface exposure, and is not limited at all, but as a typical application field, it is an appearance in the middle of design. Shape verification model for verifying design, functional test model for checking the functionality of parts, master model for producing molds, master model for producing molds, direct molds for prototype molds, etc. Can be mentioned. In particular, the resin composition for optical three-dimensional modeling according to the present invention is effective for producing a shape confirmation model or a function test model of a precise part or the like. More specifically, for example, it can be effectively used for applications such as precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, models, mother dies, processing, etc. .

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 examples.
Moreover, in the following examples, the viscosity of the resin composition for optical three-dimensional modeling, the curing depth (Dp), the critical curing energy (Ec) and the work curing energy (E ₁₀ ), the shrinkage due to photocuring (volume shrinkage), As well as mechanical properties of optically shaped objects obtained by stereolithography [tensile properties (tensile rupture strength, tensile rupture elongation, tensile modulus), yield strength, bending properties (bending strength, flexural modulus)], surface hardness The measurement or calculation of warpage and heat distortion temperature was performed as follows.

(1) Viscosity of the resin composition for optical three-dimensional modeling:
The resin composition for optical modeling was placed in a constant temperature bath at 25 ° C., and the temperature of the resin composition for optical modeling was adjusted to 25 ° C., and then measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).

(2) Curing depth (Dp), critical curing energy (Ec) and work curing energy (E ₁₀ ) of the resin composition for optical three-dimensional modeling:
Measurement was performed according to the theory described in Non-Patent Document 1. Specifically, a modeling surface (liquid surface) made of a resin composition for optical three-dimensional modeling is irradiated with light from an ultrahigh pressure mercury lamp (ultraviolet light in a wavelength range of 340 to 380 nm, energy intensity ² mW / cm ² ). One layer of photocured film was formed. By changing the light irradiation time during the formation of the cured film between 1 to 5 seconds, for example, 1 second, 2 seconds, 3 seconds, 4 seconds, and 5 seconds, this operation is performed on the modeling surface. The amount of irradiation energy was changed, the photocured film produced by each amount of irradiation energy was taken out from the photocurable resin composition liquid, the uncured resin was removed, the thickness of each cured film was measured with a constant pressure caliper, and the photocured film Is plotted with the Y-axis and the irradiation energy amount as the X-axis, and the cure depth is obtained from the slope of the straight line obtained by plotting, and the intercept of the X-axis is defined as the critical cure energy [Ec (mJ / cm ² )]. The amount of exposure energy necessary for curing to a thickness of 0.25 mm was defined as work curing energy [E ₁₀ (mJ / cm ² )].

(3) Shrinkage rate:
From the specific gravity (d ₀ ) of the resin composition for optical three-dimensional modeling (liquid) before photocuring and the specific gravity (d ₁ ) of the photocured product obtained by photocuring, the shrinkage rate is obtained by the following formula. It was.

Shrinkage rate (%) = {(d ₁ −d ₀ ) / d ₁ } × 100

At that time, the specific gravity (d ₀ ) of the resin composition for optical three-dimensional modeling (liquid) before photocuring was measured at a temperature of 25 ° C. using a specific gravity bottle. Moreover, the specific gravity (d ₁ ) of the photocured product (molded product) obtained by photocuring is a temperature of 25 ° C., adopting a method of weighing in a liquid according to JIS Z8807, “Mr. It measured using "total SD-120L".

(4) Tensile properties of the optically shaped article (tensile breaking strength, tensile breaking elongation, tensile elastic modulus):
Using the optical modeling thing (the dumbbell-shaped test piece based on JIS K-7113) produced in the following examples or comparative examples, according to JIS K-7113, the tensile breaking strength (tensile strength) of the test piece, the tensile strength The breaking elongation (tensile elongation) and tensile modulus were measured.

(5) Flexural properties (bending strength, flexural modulus) of stereolithography:
The bending strength and the flexural modulus of the test piece were measured according to JIS K-7171 using the optically shaped article (bar-shaped test piece conforming to JIS K-7171) produced in the following examples or comparative examples. .

(6) Surface hardness after modeling:
After the optical modeling thing (dumbbell-shaped test piece based on JIS K-7113) produced in the following examples and comparative examples was washed, it was irradiated with ultraviolet rays having a wavelength of 365 nm at an irradiation intensity of ³ to 5 mW / cm ^2. The surface hardness of the optically shaped article after irradiation was measured by a durometer method according to JIS K-6253 using an “Asker D-type hardness meter” manufactured by Kobunshi Keiki Co., Ltd.

(7) Warpage:
The plate-shaped stereolithography for warpage measurement (length × width × thickness = 100 mm × 100 mm × 5 mm) prepared in the following examples and comparative examples was washed and dried at room temperature, and then on a flat surface plate And place one end (side) of the plate-shaped stereolithography object in close contact with the surface plate, between the lower surface of the other end opposite to the fixed end and the surface of the surface plate The distance (the size of the gap) was measured and used as the amount of warpage (mm). In addition, the close fixation of one end portion of the plate-shaped stereolithography object to the surface plate is performed by using a strip-like weight (weight: about 200 g) of length × width × thickness = 100 mm × 10 mm × 30 mm. It was placed on the one end of the object along the end.

(8) Thermal deformation temperature of stereolithography:
(I) Using the optically shaped article (bar-shaped test piece based on JIS K-7171) produced in the following examples or comparative examples, using “HDT Tester 6M-2” manufactured by Toyo Seiki Co., Ltd. A 1.81 MPa load was applied to the test piece, and the thermal deformation temperature of the test piece was measured in accordance with JIS K-7207 (Method A).
(Ii) Using the optically shaped article (bar-shaped test piece based on JIS K-7171) produced in the following examples or comparative examples, using “HDT Tester 6M-2” manufactured by Toyo Seiki Co., Ltd. A load of 0.45 MPa was applied to the test piece, and the thermal deformation temperature of the test piece was measured according to JIS K-7207 (Method B).

  Further, types and abbreviations of radically polymerizable organic compounds [dimethacrylate compound (I), dimethacrylate compound (II), other radically polymerizable organic compounds] and photoradical polymerization initiators used in the following Examples or Comparative Examples Is as follows.

○ Dimethacrylate compound (I) :
Tricyclodecane dimethanol dimethacrylate represented by the above chemical formula (I) (“NK ester DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)

○ Dimethacrylate compound (II) :
(1) BPE-500:
In the following general formula (IIa), m + n = about 10, ethoxylated bisphenol A dimethacrylate (“NK Ester BPE-500” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(2) BPE-900:
In the following general formula (IIa), m + n = about 17, ethoxylated bisphenol A dimethacrylate (“NK ester BPE-900” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(3) BPE-1300:
In the following general formula (IIa), m + n = about 30, ethoxylated bisphenol A dimethacrylate (“NK Ester BPE-1300N” manufactured by Shin-Nakamura Chemical Co., Ltd.)

○ Other radical polymerizable organic compounds :
(1) Ethoxylated cyclohexane dimethacrylate (“NK ester CHD-4E” manufactured by Shin-Nakamura Chemical Co., Ltd.), wherein p + q = about 4 in the following general formula (IV)

（２） 下記の一般式（Ｖ）において、ｒ＝４である、ポリエチレングリコールジメタクリレート（新中村化学工業株式会社製「ＮＫエステル ４Ｇ」）
（３） 下記の一般式（Ｖ）において、ｒ＝９である、ポリエチレングリコールジメタクリレート（新中村化学工業株式会社製「ＮＫエステル ９Ｇ」）
（４） 下記の一般式（Ｖ）において、ｒ＝１４である、ポリエチレングリコールジメタクリレート（新中村化学工業株式会社製「ＮＫエステル １４Ｇ」）
（５） 下記の一般式（Ｖ）において、ｒ＝２３である、ポリエチレングリコールジメタクリレート（新中村化学工業株式会社製「ＮＫエステル ２３Ｇ」）

(2) Polyethylene glycol dimethacrylate (“NK ester 4G” manufactured by Shin-Nakamura Chemical Co., Ltd.) in which r = 4 in the following general formula (V)
(3) Polyethylene glycol dimethacrylate (“NK ester 9G” manufactured by Shin-Nakamura Chemical Co., Ltd.) in which r = 9 in the following general formula (V)
(4) Polyethylene glycol dimethacrylate (“NK ester 14G” manufactured by Shin-Nakamura Chemical Co., Ltd.) in which r = 14 in the following general formula (V)
(5) Polyethylene glycol dimethacrylate (“NK ester 23G” manufactured by Shin-Nakamura Chemical Co., Ltd.) in which r = 23 in the following general formula (V)

(6) Glycerin dimethacrylate (Shin Nakamura Chemical Co., Ltd. “NK Ester 701”)
(7) Neopentyl glycol dimethacrylate (“NK Ester NPG” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(8) 1,6-cyclohexanediol dimethacrylate (Shin Nakamura Chemical Co., Ltd. “NK Ester HD-N”)
(9) 1,10-decanediol dimethacrylate (Shin Nakamura Chemical Co., Ltd. “NK ESTER DON-N”)
(10) Polytetramethylene glycol dimethacrylate (average molecular weight = about 650) (“NK Ester PTMG-65” manufactured by Shin-Nakamura Chemical Co., Ltd.)

○ Photo radical polymerization initiator :
(1) Darocur TPO:
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ("DAROCUR ^R TPO" manufactured by Ciba Specialty Chemicals)
(2) Irgacure 651:
2,2-dimethoxy-1,2-diphenylethane-1-one (“Irgacure 651” manufactured by Ciba Specialty Chemicals)

<< Examples 1-3 >>
(1) Dimethacrylate compound (I) [tricyclodecane dimethanol dimethacrylate (NK ester DCP), dimethacrylate compound (II) of the type shown in Table 1 below (ethoxylated bisphenol A dimethacrylate), and radical photopolymerization Initiators [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Darocur TPO) and 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651)] are shown in Table 1 below. The mixture was mixed at the indicated ratio and stirred and mixed well at 25 ° C. until completely dissolved (stirring and mixing time was about 6 hours) to prepare a colorless and transparent resin composition for optical three-dimensional modeling.
When the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-described method, it was as shown in Table 1 below.

(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical three-dimensional modeling obtained in (1) above were measured by the above-described methods, As shown in Table 1.
Moreover, it was as having shown in following Table 1 when the shrinkage rate at the time of photocuring of the resin composition for optical three-dimensional modeling obtained by said (1) was measured by the above-mentioned method.
(3) An optical modeling apparatus (Seamet Co., Ltd.) equipped with an ultra-high pressure mercury lamp (120 W, manufactured by Iwasaki Electric Co., Ltd.) as a light source and a TFT-type VGA (640 × 480 pixels) liquid crystal manufactured by Epson as a planar drawing mask. "LE3000" manufactured by using the resin composition for optical three-dimensional modeling obtained in (1) above, the projection size on the modeling surface (the surface of the photocurable resin composition) = 35 mm (of the apparatus (Traveling direction) x 47 mm (perpendicular to traveling direction) (square), light source intensity on the modeling surface is ² mW / cm ² , light source, condenser lens, planar drawing mask and projection lens are integrated The sheet is continuously moved in the direction of travel parallel to the modeling surface at a speed of about 7 mm / second, and the surface drawing mask is formed in accordance with the cross-sectional shape pattern for forming the mask image of the surface drawing mask made of liquid crystal. While continuously changing the image pattern of the disk in a moving image, performing light modeling by irradiating with light having a lamination thickness of 0.1 mm, a dumbbell-shaped three-dimensional model conforming to JIS K-7113 for measuring tensile properties, A bar-shaped three-dimensional modeled object conforming to JIS K-7171 for measuring bending properties and a plate-shaped modeled object for measuring warpage (vertical x horizontal x thickness = 100 mm x 100 mm x 5 mm) were prepared. In this stereolithography operation, the irradiation time in each part of the photocured layer was 5 seconds, and the light irradiation amount in each part was 8 to 15 mJ. Using the obtained test piece, in accordance with JIS K-7113 and JIS K-7171, the tensile properties, bending properties, surface hardness and thermal deformation temperature were measured by the above-described methods, and the amount of warpage was described above. When measured by the method, it was as shown in Table 1 below.

<< Comparative Example 1 >>
(1) In Example 2, instead of 85 parts by mass of dimethacrylate compound (I) [tricyclodecane dimethanol dimethacrylate (NK ester DCP), ethoxylated cyclohexane dimethacrylate represented by the above general formula (IV) (NK ester CHD-4E) A resin composition for optical three-dimensional modeling was prepared in the same manner as in Examples 1 to 3 except that 85 parts by mass were used. When the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-described method, it was as shown in Table 1 below.
(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical three-dimensional modeling obtained in (1) above were measured by the above-described methods, As shown in Table 1.
Moreover, it was as having shown in following Table 1 when the shrinkage rate at the time of photocuring of the resin composition for optical three-dimensional modeling obtained by said (1) was measured by the above-mentioned method.
(3) Using the resin composition for optical three-dimensional modeling obtained in (1) above, in the same manner as in (3) of Examples 1 to 3, optical three-dimensional modeling by surface exposure is performed for various tests. When the various physical properties were measured by the methods described above, they were as shown in Table 1 below.

<< Examples 4 to 7 >>
(1) Dimethacrylate compound (I) [tricyclodecane dimethanol dimethacrylate (NK ester DCP), dimethacrylate compound (II) of the type shown in Table 2 below (ethoxylated bisphenol A dimethacrylate), and radical photopolymerization Initiators [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Darocur TPO) and 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651)] are shown in Table 2 below. The mixture was mixed at the indicated ratio and stirred and mixed well at 25 ° C. until completely dissolved (stirring and mixing time was about 6 hours) to prepare a colorless and transparent resin composition for optical three-dimensional modeling.
When the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the method described above, it was as shown in Table 2 below.
(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical three-dimensional modeling obtained in (1) above were measured by the above-described methods, Table 2 shows the results.
Moreover, it was as showing in following Table 2 when the shrinkage rate at the time of photocuring of the resin composition for optical three-dimensional modeling obtained by said (1) was measured by the above-mentioned method.
(3) Using the resin composition for optical three-dimensional modeling obtained in (1) above, in the same manner as in (3) of Examples 1 to 3, optical three-dimensional modeling by surface exposure is performed for various tests. The test pieces were manufactured and various physical properties thereof were measured by the methods described above, and the results were as shown in Table 2 below.

<< Examples 8 to 11 >>
(1) Dimethacrylate compound (I) [tricyclodecane dimethanol dimethacrylate (NK ester DCP), polyethylene glycol dimethacrylate of the type shown in Table 3 below, and radical photopolymerization initiator [2,4,6-trimethyl Benzoyl-diphenyl-phosphine oxide (Darocur TPO) and 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651)] were mixed in the proportions shown in Table 3 below and completely dissolved The mixture was thoroughly stirred and mixed at 25 ° C until stirring (stirring and mixing time of about 6 hours) to prepare a colorless and transparent resin composition for optical three-dimensional modeling.
The viscosity of the resin composition for optical three-dimensional modeling thus obtained was measured by the method described above, and as shown in Table 3 below.
(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical three-dimensional modeling obtained in (1) above were measured by the above-described methods, As shown in Table 3.
Moreover, it was as showing in following Table 3 when the shrinkage rate at the time of photocuring of the resin composition for optical three-dimensional modeling obtained by said (1) was measured by the above-mentioned method.
(3) Using the resin composition for optical three-dimensional modeling obtained in (1) above, in the same manner as in (3) of Examples 1 to 3, optical three-dimensional modeling by surface exposure is performed for various tests. The test pieces were manufactured and various physical properties thereof were measured by the methods described above, and the results were as shown in Table 3 below.

<< Examples 12 to 17 >>
(1) Dimethacrylate compound (I) [tricyclodecane dimethanol dimethacrylate (NK ester DCP), other radical polymerizable organic compounds shown in Table 4 below, and photo radical polymerization initiator [2, 4, 6- Trimethylbenzoyl-diphenyl-phosphine oxide (Darocur TPO) and 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651)] in the proportions shown in Table 4 below, Stir and mix well at 25 ° C. until dissolution (stir and mix time of about 6 hours) to prepare colorless and transparent resin compositions for optical three-dimensional modeling.
When the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the method described above, it was as shown in Table 4 below.
(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical three-dimensional modeling obtained in the above (1) were measured by the methods described above, Table 4 shows.
Moreover, when the shrinkage | contraction rate at the time of photocuring of the resin composition for optical three-dimensional modeling obtained by said (1) was measured by the above-mentioned method, it was as showing in following Table 4.
(3) Using the resin composition for optical three-dimensional modeling obtained in (1) above, in the same manner as in (3) of Examples 1 to 3, optical three-dimensional modeling by surface exposure is performed for various tests. The test pieces were manufactured and various physical properties thereof were measured by the methods described above, and as shown in Table 4 below.

By performing optical three-dimensional modeling by the surface exposure method using the resin composition for optical three-dimensional modeling of the present invention, it has an extremely high heat distortion temperature (HDT), excellent heat resistance, and mechanical properties. The three-dimensional model to be manufactured can be manufactured smoothly in a short modeling time.
Therefore, using the resin composition for optical three-dimensional modeling of the present invention, for precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, molds, mother dies, etc. Produces high-productivity models, machining models, parts for designing complex heat transfer circuits, parts for analyzing and planning heat medium behavior with complex structures, and other various three-dimensional objects with complex shapes and structures can do.

Claims (8)

A resin composition for optical three-dimensional modeling by surface exposure, comprising a radical polymerizable organic compound and a photo radical polymerization initiator, wherein the radical polymerizable organic compound has the following chemical formula (I):

A resin for optical three-dimensional modeling by surface exposure, characterized in that it contains at least a dimethacrylate compound (I) represented by the formula (II) and at least an acyl phosphine oxide radical polymerization initiator as a photo radical polymerization initiator. Composition.   The optical content according to claim 1, wherein the content of the dimethacrylate compound (I) is 30 to 100% by mass based on the total mass of the radical polymerizable organic compound contained in the optical three-dimensional modeling resin composition. Three-dimensional modeling resin composition. As a radically polymerizable organic compound, the following general formula (II):

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a methyl group, and m and n each independently represents an integer of 1 to 20)
The resin composition for optical three-dimensional model | molding of Claim 1 or 2 which further contains the dimethacrylate compound (II) represented by these in the quantity of less than 100 mass parts with respect to 100 mass parts of dimethacrylate compound (I). .   The content of the photo radical polymerization initiator is 0.1 to 10% by mass based on the total mass of the radical polymerizable organic compound contained in the resin composition for optical three-dimensional modeling. The resin composition for optical three-dimensional modeling as described in the item.   The light radical polymerization initiator according to any one of claims 1 to 4, comprising 2,2-dimethoxy-1,2-diphenylethane-1-one together with an acylphosphine oxide-based radical polymerization initiator. A resin composition for optical three-dimensional modeling.   The resin composition for optical three-dimensional modeling according to any one of claims 1 to 5, which is a resin composition for optical three-dimensional modeling for producing an optical three-dimensional modeled product under irradiation with light having a wavelength of 350 to 400 nm. object.   One layer which has a predetermined shape pattern by irradiating light on a modeling surface formed from the resin composition for optical three-dimensional modeling according to any one of claims 1 to 6 through a planar drawing mask. After forming a photo-cured resin layer for one minute, a modeling surface composed of an uncured resin layer for one layer made of the resin composition for optical three-dimensional modeling is formed on the photo-cured resin layer, and the modeling is performed. It is characterized by repeating the operation of irradiating the surface with light through a surface drawing mask to form a photo-cured resin layer for the next layer having a predetermined shape pattern until a three-dimensional object is obtained. The manufacturing method of the optical three-dimensional molded item.   The manufacturing method of the optical three-dimensional molded item of Claim 7 which irradiates light with a wavelength of 350-400 nm to the modeling surface which consists of a resin composition for optical three-dimensional modeling through a planar drawing mask.