JP2008189782A - Resin composition for optically shaping three-dimensional article by surface exposure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for optically shaping a three-dimensional article that can smoothly afford a molded article with good operability without causing warpage of the molded article at the time of optically shaping the three-dimensional article by surface exposure and can productively afford a three-dimensional molded article excellent in molding accuracy, dimensional accuracy, mechanical properties and external appearances. <P>SOLUTION: The resin composition for optically shaping a three-dimensional article by surface exposure comprises, as a radically polymerizable organic compound, a dimethacrylate compound (I) represented by general formula (I) (wherein R<SP>1</SP>is a hydrogen atom or a methyl group; R<SP>2</SP>is a hydrogen atom or a methyl group; and m and n are each independently an integer of 1-20). <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 has a small shrinkage at the time of optical modeling (curing) by surface exposure and little warping, thereby achieving good operability, modeling accuracy, dimensional accuracy, appearance and mechanical properties. An excellent three-dimensional object can be manufactured by surface exposure using a resin composition for optical three-dimensional modeling by surface exposure, which can smoothly produce an optical three-dimensional object without warping with good productivity. On how to do.

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 based on surface exposure, in which a three-dimensional model is manufactured by sequentially laminating photocurable resin layers having a shape pattern, has been proposed. 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.

  However, in the case of the optical three-dimensional modeling technology by surface exposure that irradiates the modeling surface with light in a planar manner through the planar drawing mask, two axes (for example, the X axis and the Y axis) of the three-dimensional coordinates of X, Y, and Z Since the resin is cured and fixed at the same time in the (axis) direction, and the relaxation phenomenon that suppresses the shrinkage of the resin during curing is limited to the remaining one axis (Z-axis), spot laser light is used. In comparison with the case of stereolithography, “warping” due to shrinkage during photocuring tends to increase. If warpage during photocuring increases, there is a risk of problems such as the modeling operation being interrupted by a modeling device that moves on the modeling surface against the warped molded product, and the modeling operation is interrupted. If it does not occur, the resulting three-dimensional object will be warped, distorted, deformed, etc., having the desired dimensional accuracy and appearance, and it is difficult to obtain a high-quality three-dimensional object without warping, distortion, deformation, etc. Become. From this point, in optical three-dimensional modeling by a surface exposure method in which a three-dimensional model is manufactured by irradiating light on the modeling surface in a planar manner via a planar drawing mask, shrinkage at the time of photocuring is small, and by surface exposure There is a demand for the development of a resin composition for optical three-dimensional modeling that can produce a three-dimensional model that does not warp and is excellent in dimensional accuracy, modeling accuracy, and appearance.

  Furthermore, also in the photocurable resin composition used for optical three-dimensional modeling by surface exposure using a planar drawing mask, similarly to the photocurable resin composition used for optical three-dimensional modeling using spot-shaped laser light. , Low viscosity, good handling at the time of modeling, excellent storage stability, high curing sensitivity by active energy rays, excellent mechanical properties of three-dimensional objects obtained by photocuring Is required.

As a resin composition for optical three-dimensional modeling, development of a resin composition for optical modeling using spot-shaped laser light has been mainly performed so far, and development of a resin composition for optical modeling by surface exposure has not progressed so much. .
Conventionally, acrylate-based photocurable resin compositions, epoxy-based photocurable resin compositions, and the like are used as the resin composition for optical modeling using spot-shaped laser light. Among these, the epoxy-based photocurable resin composition has been widely used in recent years because it can produce a molded article with excellent dimensional accuracy, but is typically a photopolymerization initiator (typically used for photopolymerization of epoxy compounds). Is generally 355 nm or less, which is the wavelength of semiconductor-excited solid-state laser light. On the other hand, the wavelength range of light emitted from a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a low-pressure mercury lamp or the like mainly used as a light source in surface exposure is generally 350 to 400 nm (many is 360 to 400 nm). When the epoxy-based photocurable resin composition is used for surface three-dimensional optical three-dimensional modeling, the resin is hard to be cured and it is difficult to manufacture a three-dimensional model. 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. Conventional urethane acrylate photocurable resin compositions using these radical photopolymerization initiators and conventional non-urethane acrylate photocurable resin compositions exhibit sufficient curability but are too fast to react. Therefore, it is difficult to control, and when optical modeling is performed, warping is large, and the modeling operation is interrupted, and the dimensional accuracy and appearance of the resulting three-dimensional model are likely to be poor. For this reason, conventional urethane acrylate photocurable resin compositions and non-urethane acrylate photocurable resin compositions are optically produced by a surface exposure method that generates a large amount of warpage as compared to stereolithography using spot-shaped laser light. Use for 3D modeling is difficult.
For example, a resin composition for optical three-dimensional modeling containing a diacrylate of an alkylene oxide adduct of bisphenol A is known (see Patent Document 1), and the resin composition for optical three-dimensional modeling is used to form a spot shape. When the laser modeling is performed using the laser beam, a three-dimensional modeled object having excellent mechanical properties and a low volume shrinkage rate is obtained. However, when the present inventors manufactured an optical three-dimensional object by the surface exposure method using this optical three-dimensional resin composition, the warp is large, and the three-dimensional object that is excellent in appearance, dimensional accuracy, and modeling accuracy is obtained. Couldn't get.

JP-A-7-228644 Paul F. Jacobs, “Rapid Prototyping & Manufacturing, Fundamentals of Stereo-Lithography”, “Society of Manufacturing Engineers”, 1992, p. 28-39.

The object of the present invention is that the shrinkage rate is small and the warp is low when it is used in an optical modeling technique for producing a three-dimensional model by a surface exposure method in which light is irradiated onto the modeling surface in a planar manner via a planar drawing mask. It is possible to produce a three-dimensional modeled object that is excellent in dimensional accuracy, modeling accuracy, and appearance, without warping, deformation, and distortion with high productivity without causing the device to stop during the optical modeling operation. It is providing the photocurable resin composition for optical three-dimensional modeling by surface exposure.
Furthermore, the object of the present invention is a three-dimensional structure that has a low viscosity, excellent handling properties during optical modeling, excellent stability over time during storage, and excellent mechanical properties, heat resistance, etc. It is to provide a photocurable resin composition for optical three-dimensional modeling by surface exposure.
And the objective of this invention is using the photocurable resin composition for optical three-dimensional modeling by the above-mentioned surface exposure, and the optical three-dimensional modeling method which can manufacture a three-dimensional molded item smoothly by a surface exposure system. Is to provide.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. And the bisphenol A type diacrylate compound used in the resin composition for optical three-dimensional modeling of the invention described in Patent Document 1 described above (that is, the α-position is a hydrogen atom at both ends of the alkylene oxide adduct of bisphenol A). A photocurable resin composition using a specific bisphenol-based dimethacrylate compound in which methacrylic acid having a methyl group at the α-position is bonded to both ends of an alkylene oxide adduct of a bisphenol compound instead of a compound having a certain acrylic acid bonded When a three-dimensionally shaped article was produced by a surface exposure method using the photocurable resin composition, the photocurable resin composition not only has small shrinkage during curing, but also has a small warp. This ensures excellent appearance, dimensional accuracy, and modeling accuracy without causing equipment to stop during stereolithography. In other words, it has been found that a three-dimensional model without distortion and deformation can be produced smoothly.

In addition, the present inventors show that the photocurable resin composition containing the specific bisphenol-based dimethacrylate compound has a low viscosity, excellent handling properties during stereolithography, and excellent temporal stability during storage. And it discovered that the three-dimensional molded item manufactured by the surface exposure system using the said photocurable resin composition was excellent in a mechanical characteristic.
Furthermore, the inventors of the present invention can further reduce the shrinkage by adding tricyclodecane dimethanol dimethacrylate at a predetermined ratio in the photocurable resin composition containing the specific bisphenol dimethacrylate compound. In addition to properties such as low warpage, low viscosity, and storage stability, it has been found that the mechanical properties and heat resistance of a three-dimensional structure obtained by optical three-dimensional modeling by a surface exposure method are improved.
In addition, the present inventors use an acylphosphine oxide radical polymerization initiator as at least a part of the radical photopolymerization initiator contained in the above-described photocurable resin composition. When surface exposure is performed through a planar drawing mask using a lamp, low-pressure mercury lamp, or other light source that emits non-laser light, characteristics such as low shrinkage, low warpage, low viscosity, and storage stability are exhibited. While maintaining good, while maintaining good curability, etc., found that a three-dimensional molded article excellent in dimensional accuracy, modeling accuracy, appearance, etc. can be smoothly manufactured, and the present invention was 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 is represented by the following general formula (I):

（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（Ｉ）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。

(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 by surface exposure characterized by containing the dimethacrylate compound (I) represented by these.

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. It is a resin composition for optical three-dimensional modeling.
Furthermore, the present invention provides:
(3) As a radically polymerizable organic compound, the following chemical formula (II);

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質量部以下の割合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。

The resin composition for optical three-dimensional modeling according to (1) or (2), further comprising a dimethacrylate compound (II) represented by the formula (100) in a proportion of 100 parts by mass or less with respect to 100 parts by mass of the dimethacrylate compound (I): It is a thing.

The present invention also 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) An optical three-dimensional modeling resin for producing an optical three-dimensional object under irradiation of light having a wavelength of 350 to 400 nm, containing at least an acylphosphine oxide radical polymerization initiator as a photo radical polymerization initiator. The resin composition for optical three-dimensional modeling according to any one of (1) to (4), which is a composition;
It is.

Furthermore, the present invention provides:
(6) A modeling surface formed from the resin composition for optical three-dimensional modeling according to any one of (1) to (5) 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:
(7) The method for producing an optical three-dimensional object according to (6), 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.

The resin composition for optical three-dimensional model | molding of the invention containing the dimethacrylate compound (I) which has a bisphenol skeleton has a small shrinkage | contraction (hardening shrinkage) at the time of manufacturing a three-dimensional model | molding by surface exposure, and also curvature is small. Therefore, by producing a three-dimensional model by the surface exposure method using the optical three-dimensional model resin composition of the present invention, it is possible to achieve dimensional accuracy, modeling accuracy, and appearance without causing an apparatus stop during the optical modeling operation. It is possible to smoothly manufacture a three-dimensional structure that is excellent, free from warpage, deformation, and distortion.
The resin composition for optical three-dimensional modeling of the present invention has a low viscosity and excellent handleability at the time of optical modeling, and has excellent temporal stability during storage, and further the resin composition for optical three-dimensional modeling of the present invention. The three-dimensional modeled object obtained by using the surface exposure method and performing the optical modeling has excellent mechanical properties.
Further, the resin composition for optical three-dimensional modeling of the present invention containing the dimethacrylate compound (II) (tricyclodecane dimethanol dimethacrylate) together with the dimethacrylate compound (I) has low viscosity, storage stability, and surface exposure. In addition to the above-described excellent properties such as low shrinkage and low warpage in stereolithography, the three-dimensional structure is further improved in mechanical properties and heat resistance.
Further, the resin composition for optical three-dimensional modeling of the present invention containing at least an acyl phosphine oxide radical polymerization initiator as a photo radical polymerization initiator is a high pressure mercury lamp, an ultra high pressure mercury lamp, a low pressure mercury lamp, an ultraviolet light. By using an LED or other inexpensive non-laser lamp as a light source, a three-dimensional object having the above-described excellent characteristics can be smoothly manufactured by surface exposure.

The present invention is described in detail below.
The resin composition for optical three-dimensional modeling of the present invention is a photocurable resin composition containing a radical polymerizable organic compound and a photo radical polymerization initiator used for optical three-dimensional modeling by surface exposure, and is radical polymerizable. As an organic compound, the following general formula (I);

（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、ビスフェノール骨格を有するジメタクリレート化合物（Ｉ）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。

(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)
It contains at least dimethacrylate compound (I) having a bisphenol skeleton 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.

In the dimethacrylate compound (I) represented by the above general formula (I), 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 (I) represented by the general formula (I), 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 m and n are preferable from the viewpoint of the physical properties of a three-dimensional modeled object obtained from 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).

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 50-100 mass%, It is more preferable to contain in the ratio of 70-100 mass%.
If the content of the dimethacrylate compound (I) in the optical three-dimensional modeling is small, warping occurs, the optical modeling operation is likely to be interrupted, and deformation and distortion due to warping of the finally obtained three-dimensional modeling etc. Becomes larger, and it tends to cause poor appearance, reduced dimensional accuracy and modeling accuracy.

  The resin composition for optical three-dimensional modeling of the present invention includes the above-mentioned dimethacrylate compound (I) as a radical polymerizable organic compound, other (meth) acrylate compounds, vinyl compounds other than (meth) acrylate compounds, and the like. You may contain another radically polymerizable organic compound. In particular, together with the dimethacrylate compound (I), the following chemical formula (II):

で表されるジメタクリレート化合物（II）（トリシクロデカンジメタノールジメタクリレート）を含有すると、ジメタクリレート化合物（Ｉ）による反りの低減と併せて、立体造形物の力学的特性および耐熱性の向上が得られる。

Including the dimethacrylate compound (II) (tricyclodecane dimethanol dimethacrylate) represented by the formula, the reduction in warpage due to the dimethacrylate compound (I) and the improvement of the mechanical properties and heat resistance of the three-dimensional structure can get.

In the resin composition for optical three-dimensional modeling of this invention, content of dimethacrylate compound (II) with respect to 100 mass parts of dimethacrylate compound (I) is 100 mass parts or less (0-100 mass parts), The amount is preferably 100 parts by mass, more preferably 10 to 100 parts by mass, and still more preferably 15 to 100 parts by mass.
When the content of the dimethacrylate compound (II) is larger than the content of the dimethacrylate compound (I), it is difficult to obtain a warp reduction effect.
In addition, in the resin composition for optical three-dimensional modeling of the present invention, the dimethacrylate compound (I) is used with respect to the total mass of the radical polymerizable organic compound contained in the composition from the viewpoints of reduction of warpage and mechanical properties. ) And the dimethacrylate compound (II) are preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and still more preferably 70 to 100% by mass.

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 70 mass% or less, more preferably 50 mass% or less, still more preferably 30 mass% or less with respect to 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.

As a radical photopolymerization initiator used in the resin composition for optical three-dimensional modeling of the present invention, light from a light source used for optical three-dimensional modeling by surface exposure is absorbed, and the resin composition for optical three-dimensional modeling is incorporated. Any radical photopolymerization initiator capable of initiating polymerization of the contained radically polymerizable organic compound can be used.
In general, optical three-dimensional modeling by surface exposure is performed using a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a halogen lamp, a metal halide lamp, and an ultraviolet LED without using a laser beam having a wavelength of 355 nm or less. (Light-emitting diode) and ultraviolet light emitted from a light source such as an ultraviolet fluorescent lamp is performed using ultraviolet light having a wavelength of 350 to 400 nm. Therefore, in the present invention, as at least a part of the radical photopolymerization initiator, it absorbs ultraviolet rays having a wavelength of 350 to 400 nm and absorbs the dimethacrylate compound (I), the dimethacrylate compound (II), and other radically polymerizable compounds optionally contained. It is preferable to use a photoradical polymerization initiator that radically polymerizes the compound.

In the present invention, any radical photopolymerization initiator that absorbs ultraviolet light having a wavelength of 350 to 400 nm can be used. Among them, an acylphosphine oxide radical polymerization initiator is used as at least part of the radical photopolymerization initiator. It is preferable to use it from the viewpoints of the curing speed, the mechanical properties of the three-dimensional structure, and the like.
As the acyl phosphine oxide radical polymerization initiator preferably 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 diacylphosphine oxide (IIIb) represented by general formula (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. It becomes easy to adjust the photocuring depth, and it is possible to obtain a three-dimensional molded article having excellent dimensional accuracy and further reducing warpage.

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 is an acyl phosphine oxide radical polymerization initiator and other photo radical polymerization initiators (for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.) ) Based on the total mass of the radically polymerizable organic compound, the acylphosphine oxide radical polymerization is 0.1 to 7% by mass, especially 0.2 to 5% by mass, and other photoradical polymerizations. It is preferable to contain the 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 .

  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) Yield strength of stereolithography:
In the tensile property test of (3) above, the yield strength was defined as the strength at which the optically shaped article moves from elasticity to plasticity.

(6) Bending characteristics (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. .

(7) 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.

(8) 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.

(9) 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) :
(1) BPE-200:
In the following general formula (Ia), m + n = about 4, ethoxylated bisphenol A dimethacrylate (“NK Ester BPE-200” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(2) BPE-500:
In the following general formula (Ia), m + n = about 10, ethoxylated bisphenol A dimethacrylate (“NK ester BPE-500” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(3) BPE-900:
In the following general formula (Ia), m + n = about 17, ethoxylated bisphenol A dimethacrylate (“NK Ester BPE-900” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(4) BPE-1300:
In the following general formula (Ia), m + n = about 30, ethoxylated bisphenol A dimethacrylate (“NK Ester BPE-1300N” manufactured by Shin-Nakamura Chemical Co., Ltd.)

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

○ Other radical polymerizable organic compounds :
In the following general formula (IV), p + q = about 4, ethoxylated bisphenol A diacrylate (“NK ester A-BPE-4” 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 1-4 >>
(1) Dimethacrylate compound (I) of the type shown in Table 1 below (ethoxylated bisphenol A dimethacrylate), dimethacrylate compound (II) [tricyclodecane dimethanol dimethacrylate (NK ester DCP), 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 4, instead of 85 parts by mass of BPE-200, ethoxylated bisphenol A diacrylate represented by the above general formula (IV) (“NK Ester A-BPE manufactured by Shin-Nakamura Chemical Co., Ltd.) -4 ") Except having used 85 mass parts, the resin composition for optical three-dimensional model | molding was prepared like Example 1-4. 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 (1) of Examples 1 to 4, 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.

  As seen in the results of Table 1 above, the photocured product (optical modeled product) obtained from the resin composition for optical three-dimensional modeling of Examples 1 to 4 has a small warpage and has a yield point in a tensile test. It has high toughness.

<< Examples 5 to 8 >>
(1) Dimethacrylate compound (I) of the type shown in Table 2 below (ethoxylated bisphenol A dimethacrylate), dimethacrylate compound (II) [tricyclodecane dimethanol dimethacrylate (NK ester DCP) and initiation of radical photopolymerization The agents [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 a ratio and stirred and mixed well at 25 ° C. until it was 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 (1) of Examples 1 to 4, 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.
In addition, as seen in the results of Table 2 below, the photocured product (photofabricated product) obtained from the resin composition for optical three-dimensional modeling of Examples 5 to 8 had a small warpage. Moreover, the photocured product (photofabricated product) obtained from the resin compositions for optical three-dimensional modeling of Examples 5, 7 and 8 showed a yield point in the tensile test and had high toughness.

<< Comparative Example 2 >>
(1) In Example 1, instead of 100 parts by mass of BPE-200, 100 parts by mass of ethoxylated bisphenol A diacrylate (NK ester A-BPE-4) represented by the above general formula (IV) is used. A resin composition for optical three-dimensional modeling was prepared in the same manner as in Example 1 except that. 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 (1) of Examples 1 to 4, 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 9 to 10 >>
(1) Dimethacrylate compound (I) of the type shown in Table 3 below (ethoxylated bisphenol A dimethacrylate), dimethacrylate compound (II) [tricyclodecane dimethanol dimethacrylate (NK ester DCP) and initiation of radical photopolymerization The agents [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Darocur TPO) and 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651)] are shown in Table 3 below. The mixture was mixed at a ratio and stirred and mixed well at 25 ° C. until it was completely dissolved (stirring and mixing time was 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 (1) of Examples 1 to 4, 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 11 to 12 >>
(1) Dimethacrylate compound (I) of the type shown in Table 4 below (ethoxylated bisphenol A dimethacrylate), dimethacrylate compound (II) [tricyclodecane dimethanol dimethacrylate (NK ester DCP) and initiation of radical photopolymerization The agents [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Darocur TPO) and 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651)] are shown in Table 4 below. The mixture was thoroughly mixed at 25 ° C. until it was completely dissolved at a ratio (stir mixing time: about 6 hours) to prepare colorless and transparent resin compositions for optical three-dimensional modeling, respectively.
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 4, 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 4 below.

The resin composition for optical three-dimensional modeling of the present invention has small shrinkage (curing shrinkage) when manufacturing a three-dimensional model by surface exposure and small warpage. Without causing the device to stop during operation, etc., it is possible to smoothly produce a 3D model without warping, which is excellent in dimensional accuracy, modeling accuracy and appearance, and has low viscosity and excellent handleability during optical modeling, Excellent stability over time during storage. Furthermore, the three-dimensional molded article obtained from the resin composition for optical three-dimensional modeling of the present invention is excellent in mechanical properties.
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. Models, processing models, parts for designing complex heat medium circuits, parts for analyzing and planning the behavior of heat mediums with complex structures, and other various three-dimensional objects with complex shapes and structures during stereolithography It can be manufactured with high productivity without causing troubles such as stoppage of the apparatus.

Claims (7)

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 is represented by the following general formula (I):

(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 by surface exposure characterized by including the dimethacrylate compound (I) represented by these.   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 chemical formula (II):

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 ratio of 100 mass parts or less 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.   A resin composition for optical three-dimensional modeling for producing an optical three-dimensional object under irradiation with light having a wavelength of 350 to 400 nm, containing at least an acylphosphine oxide radical polymerization initiator as a photo radical polymerization initiator. The resin composition for optical three-dimensional model | molding of any one of Claims 1-4.   1 layer which has a predetermined shape pattern by irradiating light in a planar form on a modeling surface formed from the resin composition for optical three-dimensional modeling according to any one of claims 1 to 5 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 6 which irradiates the modeling surface which consists of a resin composition for optical three-dimensional modeling through a planar drawing mask with light with a wavelength of 350-400 nm.