JP6348702B2 - Optical three-dimensional resin composition - Google Patents

Description

  The present invention has low yellowness, high light transmittance, excellent color tone and transparency, low absorption of moisture and moisture, excellent dimensional stability, high impact strength, and high toughness that is difficult to break. Optical three-dimensional modeling resin composition capable of producing an optical three-dimensional structure that is excellent in durability and excellent in mechanical properties such as breaking strength smoothly and with high photocuring speed and high modeling accuracy. And a method for producing an optical three-dimensional model using the optical three-dimensional model 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 predetermined thickness is obtained by selectively irradiating an ultraviolet laser controlled by a computer so that a desired pattern is obtained on the liquid surface of the liquid photocurable resin placed in a container. Then, a liquid resin for one layer is supplied onto the cured layer, and similarly cured by irradiation with an ultraviolet laser in the same manner as described above. The method of obtaining a molded article 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.

For resins or resin compositions used for optical three-dimensional modeling, it is required that the three-dimensional model can be manufactured in a short modeling time with high curing sensitivity due to active energy rays, low viscosity and excellent handling at the time of modeling. ing.
In addition, the three-dimensional model obtained by optical modeling using the resin composition for optical three-dimensional modeling is a model for verifying the appearance design of various industrial products during the design, and for checking the functionality of parts. It is widely used as a model, a resin mold for manufacturing a mold, and a base model for manufacturing a mold. In recent years, three-dimensional objects obtained by optical modeling using a resin composition for optical three-dimensional modeling have high transparency, excellent color tone without yellowing, little absorption of moisture and moisture, and dimension stability. It is also used as a lens model for automobiles and motorcycles, which are required to have excellent performance. Furthermore, three-dimensional objects obtained by optical modeling using a resin composition for optical three-dimensional modeling can be used in the field of arts and crafts such as restoration of artworks, imitation and modern art, and design presentation models for glass-walled buildings. It has come to be used.
Therefore, as a resin composition for optical three-dimensional modeling, a three-dimensional modeling product having high light transmittance and excellent transparency, low yellowness and excellent color tone, and low moisture and moisture absorption and excellent dimensional stability. There is a demand for a resin composition for optical three-dimensional modeling that gives

  Furthermore, a three-dimensional object obtained by optical modeling of a resin composition for optical three-dimensional modeling is required to have high mechanical strength such as breaking strength, excellent toughness, and strong and difficult to break. From such a point, a resin composition for optical three-dimensional modeling containing a cationically polymerizable organic compound having an epoxy group and a radically polymerizable organic compound having an unsaturated double bond is added to a tetraethylene oxide unit and / or 2- There has been proposed a resin composition for optical three-dimensional modeling in which a flexibility improving agent (tensile elongation improving agent) consisting of a substituted tetraethylene oxide unit and a polyether having hydroxyl groups at both ends is blended (Patent Document 1). And in this patent document 1, when optical modeling is performed using the resin composition for optical three-dimensional modeling which mix | blended polyether, not only a tensile elongation property will improve, but the three-dimensional molded item which is excellent in load flexibility ( It is described that a three-dimensional model with a low decrease in the deflection temperature under load is obtained. The present inventors have described the resin composition for optical three-dimensional model described in Patent Document 1, particularly Example 1 thereof. In addition, when an optical stereolithography experiment was conducted using the resin composition for optical three-dimensional modeling described in Example 10 or the like, it was formed even if optical modeling was difficult or optical modeling was possible. The three-dimensional model was weak and brittle, and a practical three-dimensional model that was excellent in load deflection (heat resistance), tensile elongation, and toughness could not be obtained.

In addition, the inventors of the present invention, when a polyalkylene ether compound is contained in a resin composition for optical three-dimensional modeling containing a cationically polymerizable organic compound and a radical polymerizable organic compound, a three-dimensional solid having excellent impact strength and excellent toughness. We found out that a resin composition for optical three-dimensional modeling that gives a modeled object was obtained, and filed earlier (see Patent Document 2).
The three-dimensional model obtained by optical modeling of this optical three-dimensional resin composition containing polyalkylene ether has high impact strength and excellent toughness, but has a high yellowness and yellowish color tone. It is turbid and has insufficient light transmittance, so it can be used effectively for applications where color tone and transparency are not a problem, but for applications that require good color tone and excellent transparency It was not suitable.

Moreover, in order to improve the transparency of the three-dimensional modeled object obtained by stereolithography, cationic polymerization mainly comprising an alicyclic epoxy compound such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate. Polyalkylene glycol di (meth) acrylate as a part of the radical polymerizable organic compound in the resin composition for optical three-dimensional modeling containing a polymerizable organic compound, a radical polymerizable organic compound, a cationic polymerization initiator and a radical polymerization initiator It has been proposed to contain (Patent Document 3).
However, the three-dimensional model obtained by optical modeling of this optical three-dimensional model resin composition has low impact strength, inferior toughness and durability, and also has a large absorption of moisture or moisture, resulting in dimensional stability. Inferior.

Furthermore, the resin composition for radically polymerizable optical three-dimensional modeling mainly composed of urethane (meth) acrylate contains polyalkylene glycol (meth) acrylate as a part of the radical polymerizable organic compound, and is subjected to optical modeling. It has been proposed to improve the impact resistance of the resulting three-dimensional structure (Patent Document 4).
However, since this resin composition for optical three-dimensional modeling contains only a radical polymerizable organic compound as a photopolymerizable component and does not contain a cationic polymerizable organic compound, the dimensional accuracy of a three-dimensional model obtained by optical modeling However, the resin near the surface was not sufficiently cured due to oxygen inhibition, and even if the resin itself had sufficient transparency, optical three-dimensional modeling was performed. The surface of the modeled object has a drawback that it is rough and does not transmit light sufficiently.

  From the above points, low yellowness and high light transmittance, excellent color tone and transparency, low moisture and moisture absorption, excellent dimensional stability, high impact strength, toughness and durability Of an optical three-dimensional modeling resin composition capable of producing an optical three-dimensional structure excellent in other mechanical properties such as breaking strength and high dimensional accuracy with high photocuring sensitivity in a short optical modeling time. Development is required.

JP 2003-73457 A JP 2005-15739 A Special table 2004-530773 gazette JP-A-9-194540

The object of the present invention is that the curing sensitivity by active energy rays is high, a three-dimensional shaped article can be produced with high productivity in a reduced active energy ray irradiation time, low viscosity and excellent handleability during modeling, Along with excellent properties such as high resolution of objects and excellent modeling accuracy and dimensional accuracy, low yellowness and high light transmittance, excellent color tone and transparency, low moisture and moisture absorption, and excellent dimensional stability To provide a resin composition for optical three-dimensional modeling that can produce a three-dimensional modeled article having high impact strength, excellent toughness and durability, and also excellent in other mechanical properties such as breaking strength It is.
And the objective of this invention is providing the method of manufacturing a three-dimensional molded item 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 in the resin composition for optical three-dimensional modeling containing a radical polymerizable organic compound, a cationic polymerizable organic compound, a radical polymerization initiator and a cationic polymerization initiator, both polyalkylene glycols are used as part of the radical polymerizable organic compound. A polyalkylene glycol di (meth) acrylate whose hydroxyl group is esterified with acrylic acid or methacrylic acid, and a diglycidyl ether of an alicyclic dihydric alcohol and an oxetane compound as part of the cationically polymerizable organic compound. When included, the resin composition for optical three-dimensional modeling has high curing sensitivity and can produce a three-dimensional modeled product with high productivity in a shortened active energy ray irradiation time. With excellent resolution and high accuracy of modeling In addition to producing the three-dimensional modeled object, the three-dimensional modeled object obtained by optical modeling using the resin composition for optical three-dimensional modeling has low yellowness and high light transmittance, and has a color tone and transparency. It has been found that it has excellent properties, low moisture and moisture absorption, excellent dimensional stability, high impact strength, excellent toughness and durability, and excellent mechanical properties such as breaking strength. The present invention has been completed.

That is, the present invention
(1) (i) Resin composition for optical three-dimensional modeling containing radically polymerizable organic compound (A), cationically polymerizable organic compound (B), radical polymerization initiator (C) and cationic polymerization initiator (D) Because;
(Ii) containing a polyalkylene glycol di (meth) acrylate (A-1) having an average molecular weight of 300 to 2000 as a part of the radical polymerizable organic compound (A);
(Iii) As a part of the cationically polymerizable organic compound (B), the following general formula (B-1);

（式中、Ｒ¹は、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＥ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＡＤ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基またはトリシクロデカンジメタノール残基を示す。）
で表される脂環式ジグリシジルエーテル化合物（Ｂ−１）を含有し；且つ、
（iv） カチオン重合性有機化合物（Ｂ）の一部として、オキセタン化合物（Ｂ−２）を含有する；
ことを特徴とする光学的立体造形用樹脂組成物である。

Wherein R ¹ is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or tri Cyclodecanedimethanol residue is shown.)
An alicyclic diglycidyl ether compound (B-1) represented by:
(Iv) containing an oxetane compound (B-2) as part of the cationically polymerizable organic compound (B);
The resin composition for optical three-dimensional modeling characterized by the above-mentioned.

And this invention,
(2) The oxetane compound (B-2) contains a monooxetane compound (B-2a) having one oxetane group or a monooxetane compound (B-2a) having one oxetane group and an oxetane group. It is the resin composition for optical three-dimensional model | molding of said (1) containing the polyoxetane compound (B-2b) which has 2 or more.

Furthermore, the present invention provides
(3) The content of the polyalkylene glycol di (meth) acrylate (A-1) is 10 to 70% by mass based on the total mass of the radical polymerizable organic compound (A), and the alicyclic diglycidyl ether compound The content of (B-1) is 50 to 95% by mass based on the total mass of the cationic polymerizable organic compound (B), and the content of the oxetane compound (B-2) is a cationic polymerizable organic compound ( It is the above-mentioned resin composition for optical three-dimensional modeling of (1) or (2) which is 3 to 50% by mass based on the total mass of B).
The present invention also provides:
(4) As a part of the radical polymerizable organic compound (A), the following general formula (A-2);

（式中、Ｒ²は橋架け環式炭化水素基を示し、Ｒ³は水素原子またはメチル基を示す。）
で表されるジ（メタ）アクリレート化合物（Ａ−２）を、ラジカル重合性有機化合物（Ａ）の全質量に基づいて１０〜９０質量％の割合で更に含有する前記（１）〜（３）のいずれかの光学的立体造形用樹脂組成物；および、
（５） 光学的立体造形用樹脂組成物の全質量に基づいて、ラジカル重合性有機化合物（Ａ）を１０〜５０質量％、カチオン重合性有機化合物（Ｂ）を３０〜９５質量％、ラジカル重合開始剤（Ｃ）を０．１〜１０質量％およびカチオン重合開始剤（Ｄ）を０．１〜１０質量％の割合で含有する前記した（１）〜（４）のいずれかの光学的立体造形用樹脂組成物；
である。
そして、本発明は、
（６） 前記（１）〜（５）のいずれかの光学的立体造形用樹脂組成物を用いて光学的立体造形物を製造する方法である。

(Wherein R ² represents a bridged cyclic hydrocarbon group, and R ³ represents a hydrogen atom or a methyl group.)
Said (1)-(3) which further contains the di (meth) acrylate compound (A-2) represented by these in the ratio of 10-90 mass% based on the total mass of a radically polymerizable organic compound (A). Any of the resin compositions for optical three-dimensional modeling of; and
(5) Based on the total mass of the resin composition for optical three-dimensional modeling, the radically polymerizable organic compound (A) is 10 to 50% by mass, the cationically polymerizable organic compound (B) is 30 to 95% by mass, and radical polymerization. The optical solid according to any one of the above (1) to (4), which contains 0.1 to 10% by mass of the initiator (C) and 0.1 to 10% by mass of the cationic polymerization initiator (D). Resin composition for modeling;
It is.
And this invention,
(6) This is a method for producing an optical three-dimensional object using the optical three-dimensional resin composition for any one of (1) to (5).

In the resin composition for optical three-dimensional modeling containing the radical polymerizable organic compound (A), the cationic polymerizable organic compound (B), the radical polymerization initiator (C), and the cationic polymerization initiator (D), radical polymerization is performed. Polyalkylene glycol di (meth) acrylate (A-1) is contained as part of the organic compound (A), and alicyclic diglycidyl ether compound (B-1) as part of the cationically polymerizable organic compound (B). In addition, the resin composition for optical three-dimensional modeling of the present invention containing the oxetane compound (B-2) as a part of the cationically polymerizable organic compound (B) has high curing sensitivity and shortened active energy rays. 3D objects can be produced with good productivity in irradiation time, low viscosity and excellent handling at the time of modeling, and the resolution of the object is high, and the modeling accuracy and dimensional accuracy are excellent. The three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention has a low yellowness and a high light transmittance, is excellent in color tone and transparency, moisture and moisture Is excellent in dimensional stability, has high impact strength, is excellent in toughness and durability, and is excellent in other mechanical properties such as tensile elongation and strength.
Therefore, the resin composition for optical three-dimensional modeling of the present invention has high transparency and no yellow coloring, excellent transparency and color tone, low water absorption and moisture absorption, excellent dimensional stability, and impact resistance. In order to produce a 3D model with excellent toughness, durability and strength, to verify the appearance design of various industrial products during the design, to check the functionality of parts, and to produce molds Plastic molds, base models for making molds, automobile and motorcycle lenses, restoration of art, imitation and modern art, art and craft fields such as design presentation models for glass buildings, precision parts, electrical -It can be effectively used for various applications such as models of electronic parts, furniture, building structures, automobile parts, various containers, castings, and the like.

The present invention is described in detail below.
The resin composition for optical three-dimensional modeling of the present invention is a resin composition used for manufacturing a three-dimensional model by performing three-dimensional modeling by irradiating active energy rays such as light.
The resin composition for optical three-dimensional modeling of the present invention comprises a radical polymerizable organic compound (A) and a cationic polymerizable organic compound (B) as an active energy ray polymerizable compound that is polymerized by irradiation with active energy rays such as light. contains.
As used herein, the term “active energy rays” refers to energy rays that can cure the resin composition for optical three-dimensional modeling, such as ultraviolet rays, electron beams, X-rays, radiation, and high frequencies.

  The radical polymerizable organic compound (A) used in the present invention is a compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray such as light in the presence of the radical polymerization initiator (C). The resin composition for optical three-dimensional modeling of the invention contains polyalkylene glycol di (meth) acrylate (A-1) having an average molecular weight of 300 to 2000 as part of the radical polymerizable organic compound (A).

The polyalkylene glycol di (meth) acrylate (A-1) used in the present invention has an average molecular weight of 300 to 2000, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, poly (Oxyethylene / oxypropylene random copolymer) Diacrylate diacrylate, Poly (oxyethylene / oxypropylene random copolymer) diol dimethacrylate, Polyoxyethylene polymer block / Polyoxypropylene polymer block Block copolymer (block copolymer diol) diacrylate or dimethacrylate having a hydroxyl group at the end, polytetramethylene glycol diacrylate , Polytetramethylene glycol dimethacrylate, diacrylate or dimethacrylate of random copolymer diol with ethylene oxide units and tetramethylene oxide units randomly bonded and hydroxyl groups at both ends, polyoxyethylene polymer block / polytetramethylene glycol Examples thereof include a diacrylate or dimethacrylate of a block copolymer (block copolymer diol) having hydroxyl groups at both ends to which the polymer block is bonded.
Among them, in the present invention, the polyalkylene glycol di (meth) acrylate (A-1) having an average molecular weight of 300 to 2000 is easily available, is liquid at room temperature, has excellent handleability, and is obtained from an optical three-dimensional model. Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate having an average molecular weight of 300 to 2000 from the point that the molded product is excellent in transparency, flexibility, and toughness and durability. One or more of polytetramethylene glycol diacrylate and polytetramethylene glycol dimethacrylate are preferably used, and polyethylene glycol diacrylate, polypropylene glycol diacrylate and Polytetramethylene glycol diacrylate are preferably used. In particular, when polytetramethylene glycol diacrylate having an average molecular weight of 300 to 2000 is used as the polyalkylene glycol di (meth) acrylate (A-1), in addition to the above-described characteristics, a three-dimensional structure obtained by optical modeling In addition, the impact resistance is improved, and the absorption of moisture and moisture is smaller and the dimensional stability is more excellent.

From the viewpoints of various properties such as solubility in optical three-dimensional modeling resin composition, miscibility, impact strength, toughness, and durability of the three-dimensional modeled product obtained by photocuring. The average molecular weight of the alkylene glycol di (meth) acrylate (A-1) is 300 to 2000, preferably 500 to 1500, and more preferably 600 to 1200.
If the molecular weight of the polyalkylene glycol di (meth) acrylate (A-1) is too small, the impact strength of the three-dimensional structure obtained by stereolithography is reduced and the toughness and flexibility are lowered, while the polyalkylene glycol di ( If the molecular weight of the (meth) acrylate (A-1) is too large, the solubility in the resin composition for optical three-dimensional modeling is reduced, or the optical system in which polyalkylene glycol di (meth) acrylate (A-1) is added. The viscosity of the three-dimensional modeled resin composition is increased, the light transmittance of the three-dimensional modeled product obtained by optical modeling is lowered, and in some cases, it tends to be opaque.

Although it is not limited, Among polyalkylene glycol di (meth) acrylates (A-1) having an average molecular weight of 300 to 2000 used in the present invention, specific examples of polyethylene glycol di (meth) acrylate include:
* “Blemmer ADE-200” manufactured by NOF Corporation, “A-200” manufactured by Shin-Nakamura Chemical Co., Ltd., “Light Acrylate 4EG-A” manufactured by Kyoeisha Chemical Co., Ltd. Polyethylene glycol diacrylate having an average molecular weight ≈ 300);
* “Blemmer ADE-400” manufactured by NOF Corporation, “N-Nakamura Chemical Co., Ltd.“ A-400 ”,“ Light Acrylate 9EG-A ”manufactured by Kyoeisha Chemical Co., Ltd.,“ FA-240A ”manufactured by Hitachi Chemical Co., Ltd. And polyethylene glycol diacrylate having a number of bonds of ethylene oxide units≈9 and an average molecular weight≈500);
* Shin-Nakamura Chemical Co., Ltd. “A-600” (polyethylene glycol diacrylate having an ethylene oxide unit bond number≈14 and an average molecular weight≈750);
* Shin-Nakamura Chemical Co., Ltd. “A-1000” (polyethylene glycol diacrylate having an ethylene oxide unit bond number≈23 and an average molecular weight≈1100);
* “Blemmer DPE-200” manufactured by NOF Corporation, “4G” manufactured by Shin-Nakamura Chemical Co., Ltd., “FA-220M” manufactured by Hitachi Chemical Co., Ltd. Polyethylene glycol dimethacrylate);
* “Blemmer DPE-400” manufactured by NOF Corporation, “9G” manufactured by Shin-Nakamura Chemical Co., Ltd. (both polyethylene glycol dimethacrylates having an ethylene oxide unit bond number of about 9 and an average molecular weight of about 530 to 540);
* “Blemmer DPE-600” (manufactured by NOF Corporation) (polyethylene glycol dimethacrylate having an ethylene oxide unit number of bonds ≈ 13 and an average molecular weight ≈ 690);
* Shin-Nakamura Chemical Co., Ltd. “14G” (ethylene glycol dimethacrylate having an ethylene oxide unit number of bonds ≈ 14 and an average molecular weight ≈ 740);
* “23G” manufactured by Shin-Nakamura Chemical Co., Ltd. (polyethylene glycol dimethacrylate having an ethylene oxide unit bond number≈23 and an average molecular weight≈1140);
And so on.

Specific examples of polypropylene glycol di (meth) acrylate having an average molecular weight of 300 to 2000 that can be used in the present invention include:
* “APG-200” manufactured by Shin-Nakamura Chemical Co., Ltd. (polypropylene glycol diacrylate having a number of bonds of propylene oxide units≈3 and an average molecular weight≈300);
* "Blemmer ADP-200" (manufactured by NOF Corporation) (polypropylene glycol dimethacrylate having a number of bonds of propylene oxide units of about 4 and an average molecular weight of about 360);
* “APG-400” manufactured by Shin-Nakamura Chemical Co., Ltd., “FA-P240A” manufactured by Hitachi Chemical Co., Ltd. (both polypropylene glycol diacrylates having a bond number of propylene oxide units ≈ 7 and an average molecular weight ≈ 530-540);
* “Blemmer ADP-400” (manufactured by NOF Corporation) (polypropylene glycol dimethacrylate having a propylene oxide unit bond number≈9 and an average molecular weight≈650);
* “FA-P270A” manufactured by Hitachi Chemical Co., Ltd. (polypropylene glycol diacrylate having a number of bonds of propylene oxide units≈12 and an average molecular weight≈820);
* “APG-700” manufactured by Shin-Nakamura Chemical Co., Ltd. (polypropylene glycol diacrylate having a number of bonds of propylene oxide units≈12 and an average molecular weight≈810);
* “9PG” manufactured by Shin-Nakamura Chemical Co., Ltd. (polypropylene glycol dimethacrylate having a number of bonds of propylene oxide units of about 7 and an average molecular weight of about 540);
* “Blemmer PDP-400” manufactured by NOF Corporation (polypropylene glycol dimethacrylate having a number of bonds of propylene oxide units of about 9 and an average molecular weight of about 680);
And so on.

As specific examples of polytetramethylene glycol di (meth) acrylate having an average molecular weight of 300 to 2000,
* “A-PTMG-65” manufactured by Shin-Nakamura Chemical Co., Ltd. (polytetramethylene glycol diacrylate having a tetramethylene oxide unit bond number≈9 and an average molecular weight≈750);
* “FA-PTG9A” manufactured by Hitachi Chemical Co., Ltd. (polytetramethylene glycol diacrylate having a tetramethylene oxide unit bond number≈9 and an average molecular weight≈770);
* “A-PTMG-100” manufactured by Shin-Nakamura Chemical Co., Ltd. (polytetramethylene glycol diacrylate having a tetramethylene oxide unit bond number≈14 and an average molecular weight≈1130);
* “Blemmer PDT-800” manufactured by NOF Corporation (polytetramethylene glycol dimethacrylate having a bond number of tetramethylene oxide units≈11 and an average molecular weight≈920);
And so on.

  Specific examples of other polyalkylene glycol di (meth) acrylates having an average molecular weight of 300 to 2000 include “Blenmer PDET” (poly (oxyethylene / oxypropylene) block copolymer diol dimethacrylate manufactured by NOF Corporation). ), “Blenmer ADET” (diacrylate of poly (oxyethylene / oxypropylene) block copolymer diol), “Blenmer PDPT” (dimethacrylate of poly (oxypropylene / oxytetramethylene) copolymer diol), “Blemmer "ADPT" (diacrylate of poly (oxypropylene / oxytetramethylene) block copolymer diol), "Blenmer PDC" (dimethacrylate of poly (oxyethylene / oxypropylene / oxyethylene) copolymer diol G), "BLEMMER ADC" (poly (oxyethylene / oxypropylene / oxyethylene) diacrylate block copolymer diol) and the like.

  Among the polyalkylene glycol di (meth) acrylates listed above, polyethylene glycol diacrylate, polypropylene glycol diacrylate, and polytetramethylene glycol diacrylate are liquid at room temperature and are easy to obtain. It is preferably used from the viewpoint that a certain point, the reactivity is high, and a three-dimensional model can be obtained quickly. Among them, when polytetramethylene glycol diacrylate is used alone, or when polytetramethylene glycol diacrylate and one or both of polyethylene glycol diacrylate and polypropylene glycol diacrylate are used in combination, the toughness of the optically shaped article is further increased. More preferred.

The content of the polyalkylene glycol di (meth) acrylate (A-1) in the resin composition for optical three-dimensional modeling is the total mass of the radical polymerizable organic compound (radical polymerizability contained in the resin composition for optical three-dimensional modeling). Based on the total mass of the organic compound), it is preferably 10 to 70% by mass, more preferably 20 to 50% by mass, and still more preferably 25 to 45% by mass.
If the content of the polyalkylene glycol di (meth) acrylate (A-1) is too small, the impact strength of the three-dimensional structure obtained by stereolithography becomes small and the toughness of the three-dimensional structure tends to decrease, and the three-dimensional structure The yellowness of the modeled object increases, and the light transmittance tends to decrease.
On the other hand, if the content of polyalkylene glycol di (meth) acrylate (A-1) is too large, the flexibility of the three-dimensional structure obtained by optical modeling becomes excessive, and the heat resistance and rigidity of the three-dimensional structure decrease. In addition, the absorption rate of moisture and moisture is increased, and the dimensional stability is likely to be lowered.

The resin composition for optical three-dimensional model | molding of this invention contains another radically polymerizable organic compound with a polyalkylene glycol di (meth) acrylate (A-1) as a radically polymerizable organic compound (A).
Any other radical polymerizable organic compound other than polyalkylene glycol di (meth) acrylate (A-1) that can be used in the resin composition for optical three-dimensional modeling may be used as the other radical polymerizable organic compound.
Typical examples of other radical polymerizable organic compounds include compounds having (meth) acrylate groups other than polyalkylene glycol di (meth) acrylate having an average molecular weight of 300 to 2000, unsaturated polyester compounds, allyl urethane compounds, polythiol compounds. One or two or more of the radical polymerizable organic compounds described above can be used.

  Among them, as other radical polymerizable organic compound, at least one (meth) acryloyloxy group in one molecule other than polyalkylene glycol di (meth) acrylate (A-1) other than an average molecular weight of 300 to 2000 is used. Specific examples of such compounds include (meth) acrylic acid esters of alcohols, reaction products of epoxy compounds and (meth) acrylic acid, urethane (meth) acrylates, polyester (meth) acrylates, poly An ether (meth) acrylate etc. can be mentioned.

Examples of the (meth) acrylic acid esters of alcohols described above include aromatic alcohols, aliphatic alcohols, alicyclic alcohols and / or their alkylene oxide adducts having at least one hydroxyl group in the molecule, and (meth). Mention may be made of (meth) acrylates obtained by reaction with acrylic acid.
More specifically, as the (meth) acrylic acid ester of alcohol, for example, di (meth) represented by the following general formula (A-2) having a bridged cyclic hydrocarbon group in the molecule An acrylate compound (A-2) can be mentioned.

（式中、Ｒ²は橋架け環式炭化水素基を示し、Ｒ³は水素原子またはメチル基を示す。）

(Wherein R ² represents a bridged cyclic hydrocarbon group, and R ³ represents a hydrogen atom or a methyl group.)

The “bridged cyclic hydrocarbon group” represented by R ² in the above general formula (A-2) is “a divalent polycyclic group in which two adjacent alicyclic rings share two or more carbon atoms with each other”. An “alicyclic hydrocarbon group”.
Specific examples of the bridged cyclic hydrocarbon group R ² include a tricyclodecanylene group [the following chemical formula (a)], an adamantylene group (tricyclo [ 3.3.1.1 ^3,7 ] decyl group) [ The following chemical formula (b)], isobornylene group [the following chemical formula (c)], bicyclononylene group [the following chemical formula (d)], bicyclo [2.1.0] pentylene group [the following chemical formula (e)] And bicyclo [3.2.1] octylene group [the following chemical formula (f)], tricyclo [ 2.2.1.0 ^2,6 ] heptylene group [the following chemical formula (g)] and the like. These bridged cyclic hydrocarbon groups may be optionally substituted with an alkyl group, a halogen, an alkoxyl group or the like.

Bridged cyclic hydrocarbon group di (meth) acrylate compound having a specific examples of the (A-2) is tricyclodecane dimethanol (meth) acrylate R ² is tricyclodecanylene alkylene group, R ² is adamantane dimethanol di (meth) acrylate is a adamantylene group, isobornyl annual dimethanol di (meth) acrylate R ² is Isoboruniren group, R ² is vicinal Chrono nonane dimethanol di (meth) acrylate is Bishikurononiren group, R ² is a bicyclo [2.1.0] pentanedimethanol di (meth) acrylate, which is a bicyclo [2.1.0] pentylene group, and R ² is a bicyclo [3,1] octylene group. .2.1] octane dimethanol di (meth) acrylate, R ² is tricyclo [2.2.1.0 ^{2, 6]} f , And the like is tricyclo [2.2.1.0 ^{2, 6]} heptane dimethanol di (meth) acrylate and styrene groups.
Among them, as the di (meth) acrylate compound (A-2), tricyclodecane dimethanol diacrylate represented by the following chemical formula (A-2a) is easily available, can be stored for a long period, It is preferably used from the standpoints of improving the heat resistance and rigidity of the three-dimensional structure obtained in this way.

  In addition, the (meth) acrylic acid esters of alcohols include bisphenols such as bisphenol A and bisphenol S in addition to the di (meth) acrylate compound (A-2) having a bridged cyclic hydrocarbon group in the molecule. Di (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl of bisphenol compounds such as bisphenol A and bisphenol S in which the compound or benzene ring is substituted with an alkoxy group (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate Relate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) Poly (meth) acrylates of polyhydric alcohols having 3 or more hydroxyl groups such as acrylates, polyhydric alcohols such as diols, triols, tetraols, hexaols, etc. , And the like (meth) acrylates of alkylene oxide adducts of Lumpur.

  Moreover, as a reaction product of an above-mentioned epoxy compound and (meth) acrylic acid, it is obtained by reaction with an aromatic epoxy compound, an alicyclic epoxy compound, and / or an aliphatic epoxy compound, and (meth) acrylic acid. Specific examples include (meth) acrylate-based reaction products. Specific examples include bisphenol compounds such as bisphenol A and bisphenol S, bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring is substituted with an alkoxy group, or the like. A (meth) acrylate obtained by reacting a glycidyl ether obtained by the reaction of an alkylene oxide adduct of the bisphenol compound or substituted bisphenol compound with an epoxidizing agent such as epichlorohydrin with (meth) acrylic acid. , And the like epoxy novolac resin and (meth) obtained by reacting acrylic acid (meth) acrylate reaction product.

  Examples of the urethane (meth) acrylate described above include (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester with an isocyanate compound. As the hydroxyl group-containing (meth) acrylic acid ester, a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction of an aliphatic dihydric alcohol and (meth) acrylic acid is preferable. As a specific example, 2-hydroxy Examples thereof include ethyl (meth) acrylate. Moreover, as said isocyanate compound, the polyisocyanate compound which has a 2 or more isocyanate group in 1 molecule like tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. is preferable.

Furthermore, examples of the polyester (meth) acrylate described above include polyester (meth) acrylate obtained by a reaction between a hydroxyl group-containing polyester and (meth) acrylic acid.
Moreover, as above-mentioned polyether (meth) acrylate, the polyether acrylate obtained by reaction of a hydroxyl-containing polyether and acrylic acid can be mentioned.

The resin composition for optical three-dimensional modeling of the present invention has a bridged cyclic hydrocarbon group in the molecule based on the total mass of the radical polymerizable organic compound (A) contained in the resin composition for optical three-dimensional modeling. The above-mentioned di (meth) acrylate compound (A-2) is preferably contained in a proportion of 10 to 90% by mass, and more preferably 30 to 80% by mass.
When the di (meth) acrylate compound (A-2) is contained in the above-described amount based on the total mass of the radical polymerizable organic compound (A), the optical modeling is obtained from the optical three-dimensional modeling resin composition. Decrease in heat resistance of the object can be prevented, and the viscosity of the resin composition for optical three-dimensional modeling becomes low, and the handleability at the time of optical three-dimensional modeling becomes good.

  In the resin composition for optical three-dimensional modeling of the present invention, di (meta) having a bridged cyclic hydrocarbon group together with polyalkylene glycol di (meth) acrylate (A-1) as the radical polymerizable organic compound (A). ) When the acrylate compound (A-2) is contained, dipentaerythritol is used in order to improve the reactivity, impact resistance of the three-dimensional structure obtained by stereolithography, and other mechanical properties. Hexaacrylate, dipentaerythritol polyacrylate such as dipentaerythritol pentaacrylate, ethylene oxide modified pentaerythritol tetraacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified trimethylo Polypropylene of alkylene oxide modified polyhydric alcohol such as propane triacrylate (alkylene oxide modified pentaerythritol, trimethylolpropane, etc.), epoxy acrylate obtained by reacting bisphenol A diglycidyl ether and acrylic acid (for example, Showa Polymer) It is preferable to further contain a radical polymerizable organic compound such as “VR-77” manufactured by the company, isobornyl acrylate, lauryl acrylate, isostearyl acrylate.

The cationically polymerizable organic compound (B) used in the present invention is a compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with active energy rays such as light in the presence of the cationic polymerization initiator (D).
In the present invention, as a part of the cationically polymerizable organic compound (B), the following general formula (B-1);

（式中、Ｒ¹は、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＥ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＡＤ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基またはトリシクロデカンジメタノール残基を示す。）
で表される脂環式ジグリシジルエーテル化合物（Ｂ−１）を含有し、更にカチオン重合性有機化合物（Ｂ）の一部としてオキセタン化合物（Ｂ−２）を含有する。

Wherein R ¹ is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or tri Cyclodecanedimethanol residue is shown.)
The alicyclic diglycidyl ether compound (B-1) represented by these is included, and also an oxetane compound (B-2) is contained as a part of cationically polymerizable organic compound (B).

  The resin composition for optical three-dimensional model | molding of this invention contains the said alicyclic diglycidyl ether compound (B-1) and oxetane compound (B-2) as a cationically polymerizable organic compound (B). Enables high-sensitivity and high-sensitivity manufacturing of 3D objects with reduced irradiation time for active energy rays, low viscosity, excellent handling during modeling, high resolution of the object, and accuracy and dimensions Not only can 3D objects be manufactured with high accuracy, but also 3D objects obtained by optical modeling using the resin composition for optical three-dimensional modeling have little absorption of moisture and moisture and are excellent in dimensional stability and high. Has impact strength, excellent toughness and durability, high transparency, and low yellowness.

   Specific examples of the alicyclic diglycidyl ether compound (B-1) include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, Cyclohexane dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether), and one or more of these can be used.

  The content of the alicyclic diglycidyl ether compound (B-1) is a three-dimensional structure that suppresses hygroscopicity, has excellent dimensional stability, has excellent toughness and durability, has high impact hardness, and has excellent colorless transparency. From the point which obtains, it is preferable that it is 50-95 mass% based on the total mass of the cationically polymerizable organic compound (B) contained in the resin composition for optical three-dimensional modeling, and it is 60-90 mass% Is more preferable, and it is still more preferable that it is 65-80 mass%.

  The oxetane compound (B-2) contained in the resin composition for optical three-dimensional modeling of the present invention as a part of the cationically polymerizable organic compound (B) is a monooxetane compound (B) having one oxetane group in the molecule. -2a), one or more of the polyoxetane compounds (B-2b) having 2, 3, or 4 or more oxetane groups in the molecule can be used.

As the monooxetane compound (B-2a), any compound having one oxetane group in one molecule can be used, and in particular, one oxetane group and one alcoholic hydroxyl group in one molecule. The monooxetane monoalcohol compound having is preferably used.
Such, among mono oxetane monoalcohol compound, the following formula (B- 2a ₁₎ mono oxetane monoalcohol compound represented by (B- 2a ₁₎ and the following general formula (B- 2a ₂₎ At least one of the represented monooxetane monoalcohol compounds (B- 2a ₂ ) is more preferably used as a monooxetane compound from the viewpoints of availability, high reactivity, and low viscosity.

（式中、Ｒ⁴およびＲ⁵は炭素数１〜５のアルキル基、Ｒ ⁶ はエーテル結合を有していてもよい炭素数２〜１０のアルキレン基を示す。）

(Wherein R ⁴ and R ⁵ represent an alkyl group having 1 to ⁵ carbon atoms, and R ⁶ represents an alkylene group having 2 to 10 carbon atoms which may have an ether bond.)

In the above general formula (B- 2a ₁ ), examples of R ⁴ include methyl, ethyl, propyl, butyl, and pentyl.
Specific examples of monooxetane alcohol (B- 2a ₁ ) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl- 3-normal butyl oxetane, 3-hydroxymethyl-3-propyl oxetane, and the like can be used, and one or more of these can be used. Among these, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are more preferably used from the viewpoints of easy availability and reactivity.

In the above general formula (B- 2a ₂ ), examples of R ⁵ include methyl, ethyl, propyl, butyl, and pentyl.
In the above general formula (B- 2a ₂ ), R ⁶ may be either a chain alkylene group or a branched alkylene group as long as it is an alkylene group having 2 to 10 carbon atoms, or an alkylene group. A C2-C10 chain or branched alkylene group having an ether bond (ether oxygen atom) in the middle of the (alkylene chain) may be used. Specific examples of R ⁶ include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, 3-oxypentylene group and the like. Among them, R ⁶ is preferably a trimethylene group, a tetramethylene group, a pentamethylene group or a heptamethylene group from the viewpoints of easiness of synthesis and easy handling because the compound is liquid at room temperature.

In addition, as the polyoxetane compound (B-2b), any of a compound having two oxetane groups, a compound having three oxetane groups, and a compound having four or four oxetane groups can be used. Are preferably used, and among them, the following general formula (B- 2b ₀ );

（式中、２個のＲ⁷は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁸は芳香環を有しているかまたは有していない２価の有機基、ｓは０または１を示す。）
で表されるジオキセタン化合物（Ｂ−２ｂ ₀ ）が、入手性、反応性、低吸湿性、硬化物の力学的特性などの点から好ましく用いられる。
上記の一般式（Ｂ−２ｂ ₀ ）において、Ｒ ⁷ の例としては、メチル、エチル、プロピル、ブチル、ペンチルを挙げることができる。また、Ｒ ⁸ の例としては、炭素数１〜１２の直鎖状または分岐状のアルキレン基（例えばエチレン基、プロピレン基、ブチレン基、ネオペンチレン基、ｎ−ペンタメチレン基、ｎ−ヘキサメチレン基など）、式：−ＣＨ ₂ −Ｐｈ−ＣＨ ₂ −または−ＣＨ ₂ −Ｐｈ−Ｐｈ−ＣＨ ₂ −で表される２価の基、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＡＤ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基、トリシクロデカンジメタノール残基、テレフタル酸残基、イソフタル酸残基、ｏ−フタル酸残基などを挙げることができる。

Wherein two R ⁷ are the same or different alkyl groups having 1 to 5 carbon atoms, R ⁸ is a divalent organic group having or not having an aromatic ring, and s is 0 or 1 Is shown.)
The dioxetane compound (B- 2b ₀ ) represented by the formula is preferably used from the viewpoints of availability, reactivity, low hygroscopicity, and mechanical properties of the cured product.
In the above general formula (B- 2b ₀ ), examples of R ⁷ include methyl, ethyl, propyl, butyl, and pentyl. Examples of R ⁸ include linear or branched alkylene groups having 1 to 12 carbon atoms (for example, ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc. ), the formula: - CH ₂ -Ph- CH ₂ - or _{- CH 2 -Ph-Ph- CH 2} - 2 -valent group represented by hydrogenated bisphenol a residue, a hydrogenated bisphenol F residue, a hydrogenated Examples thereof include bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclodecane dimethanol residue, terephthalic acid residue, isophthalic acid residue, o-phthalic acid residue and the like.

Specific examples of the dioxetane compound (B- 2b ₀ ) include a dioxetane compound represented by the following formula (B- 2b ₁ ) or formula (B- 2b ₂ ).

（式中、２個のＲ⁹は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ¹⁰は芳香環を有しているかまたは有していない２価の有機基を示す。）

(In the formula, two R ^{9 s} are the same or different alkyl groups having 1 to 5 carbon atoms, and R ¹⁰ is a divalent organic group having or not having an aromatic ring.)

Specific examples of the dioxetane compound represented by the above formula (B- 2b ₁ ) include bis (3-methyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ether, bis (3 -Propyl-3-oxetanylmethyl) ether, bis (3-butyl-3-oxetanylmethyl) ether, and the like.
Specific examples of the dioxetane compounds represented by formula (B- 2b _2), the above formula (B- 2b _{2) 2} pieces of R ⁹ are both methyl In, ethyl, propyl, butyl or pentyl group in, R ¹⁰ is an ethylene group, a propylene group, a butylene group, neopentylene group, n- pentamethylene group, n- hexamethylene group, etc.), the formula: - CH ₂ -Ph- CH ₂ - or - CH ₂ -Ph-Ph A divalent group represented by —CH ₂ —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclode The dioxetane compound which is a candimethanol residue, a terephthalic acid residue, an isophthalic acid residue, and an o-phthalic acid residue can be mentioned.
Among them, as the polyoxetane compound (B- 2b ₀ ), in the above formula (B- 2b ₁ ), bis (3-methyl-3-oxetanylmethyl) in which two R ^{9 s} are both a methyl group or an ethyl group. ) Ether and / or bis (3-ethyl-3-oxetanylmethyl) ether are preferably used from the viewpoints of availability, low hygroscopicity, mechanical properties of the cured product, and the like. -Oxetanylmethyl) ether is more preferably used.

  The resin composition for optical three-dimensional modeling of the present invention is a photo-curing performance of the resin composition for optical three-dimensional modeling, improvement of modeling property by lowering viscosity, impact strength of a three-dimensional modeled product obtained by optical modeling, and other From the standpoint of mechanical properties, the total mass of the cationically polymerizable organic compound (B) contained in the resin composition for optical three-dimensional modeling [total cationic polymerizable organic compound (B) contained in the resin composition for optical three-dimensional modeling ), The oxetane compound (B-2) is preferably contained in a proportion of 3 to 50% by mass, more preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. It is more preferable to contain it in the ratio of%.

The resin composition for optical three-dimensional modeling of the present invention is an oxetane compound (B- As 2), it is preferable to contain a monooxetane compound alone or to contain both a monooxetane compound and a polyoxetane compound.
In the case where the monooxetane compound (B-2a) and the polyoxetane compound (B-2b) are contained as the oxetane compound (B-2), both are converted into the monooxetane compound (B-2a): the polyoxetane compound (B-2b). ) = 95: 5 to 5:95 It is preferable to contain by the mass ratio, and it is more preferable to contain by the mass ratio of 90:10 to 20:80.

The resin composition for optical three-dimensional model | molding of this invention is as needed with a alicyclic diglycidyl ether compound (B-1) and an oxetane compound (B-2) as a cationically polymerizable organic compound (B), Other cationically polymerizable organic compounds can be contained.
Other cationically polymerizable organic compounds include active energy rays such as light in the presence of a cationic polymerization initiator (D) other than the alicyclic diglycidyl ether compound (B-1) and the oxetane compound (B-2). Any compound can be used as long as it is an organic compound that undergoes a cationic polymerization reaction and / or a cationic crosslinking reaction when irradiated with.
Representative examples of other cationically polymerizable organic compounds that can be used as necessary in the present invention include epoxy compounds other than alicyclic diglycidyl ether compounds (B-1), cyclic ether compounds other than oxetane compounds, and cyclic acetal compounds. , Cyclic lactone compounds, spiro orthoester compounds, vinyl ether compounds and the like. These cationically polymerizable organic compounds may be used alone or in combination of two or more.
Among them, in the present invention, an epoxy compound other than the alicyclic diglycidyl ether compound (B-1) is preferably used as the other cationically polymerizable organic compound.

  Examples of the epoxy compound other than the alicyclic diglycidyl ether compound (B-1) that can be used as the other cationic polymerizable organic compound (B) in the present invention include an alicyclic epoxy compound, an aliphatic epoxy compound, and an aromatic epoxy. Mention may be made of epoxy compounds such as compounds.

  As the above-described alicyclic epoxy compound, the unsaturated double bond in a cycloalkene compound having an unsaturated double bond in an aliphatic ring such as a cyclohexene ring-containing compound or a cyclopentene ring-containing compound is converted to hydrogen peroxide. And alicyclic epoxy compounds having a cycloalkene oxide structure such as a cyclohexene oxide structure and a cyclopentene oxide structure obtained by epoxidation with an appropriate oxidizing agent such as peracid.

More specifically, examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4. -Epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4 -Epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro -3,4-epoxy) cyclohexane-meta Oxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl carboxylate, dicyclopentadiene diepoxide, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydrophthal Examples include dioctyl acid and di-2-ethylhexyl epoxyhexahydrophthalate.
Further, ε-caprolactone-modified 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-bis (hydroxymethyl) -1-butanol 1,2 sold by Daicel Chemical Industries Mention may also be made of epoxy-4- (2-oxiranyl) cyclohexane adducts.
Further, bis (3,4-epoxycyclohexyl) methane, 2,2-bis (3,4-epoxycyclohexyl) propane, 1,1-bis (3,4-epoxycyclohexyl) ethane, alpha pinene oxide, camphorene aldehyde , Limonene monooxide, limonene dioxide, 4-vinylcyclohexene monooxide, 4-vinylcyclohexene dioxide, and the like.

Moreover, the above-mentioned aliphatic epoxy compound that can be used as necessary as the cationically polymerizable organic compound (B) is not particularly limited, and examples of the aliphatic epoxy compound include an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof. Polyglycidyl ether, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, copolymer synthesized by vinyl polymerization of glycidyl acrylate and / or glycidyl methacrylate and other vinyl monomers, etc. Can be mentioned.
Representative compounds include, for example, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl ether of higher alcohol, diglycidyl ether of alkylene diol (for example, diglycidyl ether of 1,4-butanediol, 1,6-hexane Diglycidyl ether of diol, diglycidyl ether of neopentyl glycol, triglycidyl ether of glycerin, diglycidyl ether of trimethylolpropane, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl of dipentaerythritol Ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, polytetramethylene glycol It can be mentioned glycidyl ethers of polyhydric alcohols such as diglycidyl ether of Le.
Furthermore, a polyglycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene, trimethylolpropane and glycerin, and a diglycidyl aliphatic long-chain dibasic acid. Examples include esters.
Furthermore, monoglycidyl ether of higher aliphatic alcohol, phenol, cresol, butylphenol or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these, glycidyl ester of higher fatty acid, epoxidized soybean oil, epoxy stearic acid Examples thereof include butyl, epoxidized polybutadiene, and glycidylated polybutadiene.
In addition, as the epoxy alkane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxycetane, 1,2-epoxyoctadecane, 1,2-epoxyicosane Can be mentioned.

In addition, the aromatic epoxy compound is not particularly limited, and examples thereof include polyglycidyl ethers and polyglycidyl esters of polyhydric phenols or alkylene oxide adducts thereof. Specifically, for example, bisphenol A, Bisphenol E, bisphenol F, bisphenol AD, bisphenol Z or glycidyl ether, phenyl glycidyl ether, tert-butylphenyl glycidyl ether, resorcinol diglycidyl ether, tetraphenol of compounds obtained by further adding an alkylene oxide such as ethylene oxide or propylene oxide to these Condensation of tetraglycidyl ether of ethane, triglycidyl ether of triphenolmethane, phenols or naphthols with aldehydes Products (eg phenolic resins and novolak resins), glycidylated products of condensation products of phenols and isopropenylacetophenone, reaction products of phenols and dicyclopentadiene, noglycidylated products, diglycidyl esters of terephthalic acid, isophthalic acid Examples thereof include diglycidyl ester and diglycidyl ester of o-phthalic acid.
Furthermore, diglycidyl ether of biphenol, diglycidyl ether of tetramethylbiphenol, VG3101L ([2- [4- (2,3-epoxypropoxy) phenyl]) represented by the following chemical formula sold by Printec Co., Ltd. -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane]) and other aromatic epoxy compounds.

In the present invention, one or more of the above-described epoxy compounds can be used as the cationically polymerizable organic compound (B).
The resin composition for optical three-dimensional modeling of the present invention includes a polyepoxy compound having two or more epoxy groups in one molecule, including an alicyclic diglycidyl ether compound (B-1), a cationic polymerizable organic compound. Based on the total mass of the compound (B), it is preferably contained at a rate of 30 to 97% by mass, and more preferably contained at a rate of 40 to 80% by mass.

In the resin composition for optical three-dimensional modeling of the present invention, as part of the cationically polymerizable organic compound (B), an fragrance having 3 or more glycidyl etherified phenol groups represented by the following formula (B-3a) When a group compound [hereinafter referred to as “aromatic compound (B-3)]” is contained, a resin composition for optical three-dimensional modeling that gives a three-dimensional modeled article having a high heat distortion temperature and excellent heat resistance and rigidity can be obtained. it can.
When the aromatic compound (B-3) is contained as a part of the cationically polymerizable organic compound (B) in order to improve the heat resistance and rigidity of the three-dimensional structure obtained by stereolithography, the aromatic compound (B The content of -3) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, based on the total mass of the cationically polymerizable organic compound (B), and 3 to 10% by mass. % Is more preferable.

  As an aromatic compound (B-3) having three or more glycidyl etherified phenol groups represented by the formula (B-3a), even if it contains the aromatic compound (B-3), it is for optical three-dimensional modeling. Any resin composition can be used as long as it can maintain the viscosity suitable for optical three-dimensional modeling, for example, polyglycidyl ether of phenol resin such as novolak resin and resol resin, tetraglycidyl ether of tetraphenol ethane, Triglycidyl ether of triphenolmethane, VG3101L as described above, ie 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- And epoxypropoxy] phenyl] ethyl] phenyl] propane.

  VG3101L described above, ie, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl) When propane is included in the resin composition for optical three-dimensional modeling as a part of the cationically polymerizable organic compound, the heat deformation temperature of the three-dimensional model obtained by optical modeling becomes high and the heat resistance is improved. When VG3101L is contained as part of the cationically polymerizable organic compound (B) in order to improve the heat resistance of the three-dimensional structure obtained in this way, the content of VG3101L is the total amount of the cationically polymerizable organic compound (B). 1-30 mass% is preferable based on mass, 2-20 mass% is more preferable, and 3-10 mass% is further more preferable.

  In the resin composition for optical three-dimensional model | molding of this invention, an alicyclic diglycidyl ether compound is based on the total mass (total mass) of the cationically polymerizable organic compound (B) contained in the resin composition for optical three-dimensional model | molding. The total content of (B-1) and the oxetane compound (B-2) is preferably 50 to 100% by mass, more preferably 60 to 95% by mass, and 70 to 90% by mass. More preferably, therefore, the content of a cationically polymerizable organic compound (particularly an epoxy compound) other than the alicyclic diglycidyl ether compound (B-1) and the oxetane compound (B-2) is preferably 0 to 50% by mass. The content is more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass.

  As the radical polymerization initiator (C), any polymerization initiator capable of initiating radical polymerization of the radical polymerizable organic compound (A) when irradiated with active energy rays such as light can be used. For example, benzyl or Examples thereof include dialkyl acetal compounds, phenyl ketone compounds, acetophenone compounds, benzoin or alkyl ether compounds thereof, benzophenone compounds, and thioxanthone compounds.

Specifically, examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.
Examples of the phenyl ketone compound include 1-hydroxy-cyclohexyl phenyl ketone.
Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, and 2-hydroxy-2. -Methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like.

Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether.
Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and the like.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

In this invention, 1 type (s) or 2 or more types of radical polymerization initiator (C) can be mix | blended and used according to desired performance.
Among these, in the present invention, 1-hydroxycyclohexyl phenyl ketone is preferably used as the radical polymerization initiator (C) from the viewpoint that the resulting cured product has a good hue (eg, low yellowness).

In the present invention, as the cationic polymerization initiator (D), any polymerization initiator capable of initiating cationic polymerization of the cationic polymerizable organic compound (B) when irradiated with active energy rays such as light can be used. Among them, as the cationic polymerization initiator (D), an onium salt that releases a Lewis acid when irradiated with active energy rays is preferably used. Examples of such an onium salt include an aromatic sulfonium salt of a Group VIIa element, an aromatic onium salt of a Group VIa element, an aromatic onium salt of a Group Va element, and the like.
As a representative example, the general formula: [(R ¹¹ ) (R ¹² ) (R ¹³ ) S ⁺ ] [wherein R ¹¹ , R ¹² and R ¹³ are each independently monovalent bonded to sulfur (S). Or a general formula: [ (R ¹⁴ ) (R ¹⁵ ) I ⁺ ] [wherein R ¹⁴ and R ¹⁵ are each independently a monovalent group bonded to iodine (I). An iodonium ion represented by an organic group] is represented by a general formula: [(Rf) _m PF _6-m ⁻ ] (wherein Rf is a fluoroalkyl group, m is an integer of 0 to 6) ( Phosphate ion), a general formula: [(Rf) _n SbF _6-n ⁻ ] (wherein Rf is a fluoroalkyl group, n is an integer of 0 to 6), an anion (antimonate ion), [BF ₄ ^-] represented by anions, wherein: [AsF ₆ ^-] Kachio bound such anions as represented by And the like can be mentioned polymerization initiator.

  Although it is not limited at all, more specifically, as a cationic polymerization initiator, for example, a phosphorus-based sulfonium compound (D-1) represented by the following general formula (D-1), the following general An antimony sulfonium compound (D-2) represented by the formula (D-2) can be given.

［上記の一般式（Ｄ−１）および（Ｄ−２）中、Ｒ ¹¹ 、Ｒ ¹² およびＲ ¹³ は１価の有機基、Ｒｆはフルオロアルキル基、ｍおよびｎは０〜６の整数、ｐは上記の一般式（Ｄ−１）における「カチオン［Ｓ ⁺ （Ｒ ¹¹ ）（Ｒ ¹² ）（Ｒ ¹³ ）］が有する陽イオン価と同じ数、ｑは上記の一般式（Ｄ−２）における「カチオン［Ｓ ⁺ （Ｒ ¹¹ ）（Ｒ ¹² ）（Ｒ ¹³ ）］が有する陽イオン価と同じ数である。］

[In the above general formulas (D-1) and (D-2), R ¹¹ , R ¹² and R ¹³ are monovalent organic groups, Rf is a fluoroalkyl group, m and n are integers of 0 to 6, p Is the same number as the cation number of “cation [ S ⁺ (R ¹¹ ) (R ¹² ) (R ¹³ ) ]” in general formula (D-1), q is the same as in general formula (D-2) “It is the same number as the cation number of the cation [ S ⁺ (R ¹¹ ) (R ¹² ) (R ¹³ ) ].”

In the phosphorus-based sulfonium compound (D-1) and the antimony-based sulfonium compound (D-2) represented by the above general formula, typical examples of R ¹¹ , R ¹² and R ¹³ include the following formula << 1 >> The group shown by << 11 >> can be mentioned.

［式中、Ｒ⁵、Ｒ⁶、Ｒ ⁷ 、Ｒ ⁸ 、Ｒ ⁹ 、Ｒ ¹⁰ 、Ｒ ¹¹ 、Ｒ ¹² 、Ｒ ¹³ 、Ｒ ¹⁴ 、Ｒ ¹⁵ およびＲ ¹⁶ は、それぞれ独立して、置換基を有していてもよいアルキル基またはアリール基であり、Ｘ ¹ 、Ｘ ² 、Ｘ ³ 、Ｘ ⁴ 、Ｘ ⁵ 、Ｘ ⁶ 、Ｘ ⁷ 、Ｘ ⁸ 、Ｘ ⁹ 、Ｘ ¹⁰ 、Ｘ ¹¹ 、Ｘ ¹² 、Ｘ ¹³ 、Ｘ ¹⁴ 、Ｘ ¹⁵ 、Ｘ ¹⁶ 、Ｘ ¹⁷ 、Ｘ ¹⁸ 、Ｘ ¹⁹ 、Ｘ ²⁰ 、Ｘ ²¹ およびＸ ²² は、それぞれ独立して、アルキル基、アリール基、アルコキシ基、アリールオキシ基、ヒドロキシ（ポリ）アルキレンオキシ基、水酸基、シアノ基、ニトロ基およびハロゲン原子から選ばれる基であり、Ｚ ¹ 、Ｚ ² 、Ｚ ³ およびＺ ⁴ は、それぞれ独立して、式：−Ｓ−、−ＳＯ−および−Ｏ−から選ばれる２価の基であり、それぞれ独立して、ｄ ¹ は０〜５の整数、ｄ ² 、ｄ ³ およびｄ ⁴ は０〜４の整数、ｄ ⁵ は０〜５の整数、ｄ ⁶ 、ｄ ⁷ 、ｄ ⁸ 、ｄ ⁹ 、ｄ ¹⁰ 、ｄ ¹¹ 、ｄ ¹² 、ｄ ¹³ 、ｄ ¹⁴ 、ｄ ¹⁵ およびｄ ¹⁶ は０〜４の整数、ｄ ¹⁷ は０〜５の整数、ｄ ¹⁸ は０〜４の整数、ｄ ¹⁹ は０〜５の整数、ｄ ²⁰ 、ｄ ²¹ およびｄ ²² は０〜４の整数である。］

[Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently have a substituent. An alkyl group or an aryl group which may be X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are each independently an alkyl group, aryl group, alkoxy group, aryloxy group, hydroxy ( A group selected from a poly) alkyleneoxy group, a hydroxyl group, a cyano group, a nitro group and a halogen atom, and Z ¹ , Z ² , Z ³ and Z ⁴ are each independently represented by the formula: —S—, —SO— And -O-, each independently, d ¹ is an integer from 0 to 5, and d ² , d ³ and d ⁴ are each an integer from 0 to 4. Number, d ⁵ is an integer of ^{0~5, d 6, d 7,} d 8, d 9, d 10, d 11, d 12, d 13, d 14, d 15 and d ¹⁶ are an integer of 0 to 4, d ¹⁷ is an integer of 0 to 5, d ¹⁸ is an integer of 0 to 4, d ¹⁹ is an integer of 0 to 5, d ^20, d ²¹ and d ²² represents an integer of 0-4. ]

  Although not limited at all, as a specific example of the phosphorus-based sulfonium compound (D-1) represented by the above general formula, triphenylsulfonium tris (perfluoroethyl) trifluorophosphate, the following formula (D −1α) (“CPI-500K” manufactured by San Apro Co., Ltd.), a compound represented by the following formula (D-1β) (“CPI-500P” manufactured by San Apro Co., Ltd.), and the following formula (D −1γ) (“CPI-200K” manufactured by San Apro Co., Ltd.), 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate) (ADEKA Corporation) Manufactured "SP-152").

  Specific examples of the antimony sulfonium compound (D-2) represented by the above general formula include bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate and bis- [4. -(Di-4'-hydroxyethoxyphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate, 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate represented by the following formula (D-2α) “CPI-101A” or “CPI-110S”), 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate) (manufactured by ADEKA Corporation SP-172 ") etc. That.

In the present invention, one or more of the above cationic polymerization initiators can be used. Among them, aromatic sulfonium salts are more preferably used in the present invention.
In the present invention, for the purpose of improving the reaction rate, a photosensitizer such as benzophenone, alkoxyanthracene, dialkoxyanthracene, and thioxanthone may be used together with the cationic polymerization initiator (D) as necessary.

The resin composition for optical three-dimensional modeling of the present invention includes the viscosity of the composition, the reaction rate, the modeling speed, the toughness, impact resistance, durability, heat distortion temperature (heat resistance), dimensional accuracy, From the viewpoint of mechanical properties and the like, based on the total mass of the resin composition for optical three-dimensional modeling, the radical polymerizable organic compound (A) is 10 to 50% by mass, further 15 to 45% by mass, particularly 20 to 40%. A radical polymerization initiator (C) containing a cationically polymerizable organic compound (B) in a proportion of 30 to 80 mass%, further 40 to 80 mass%, particularly 45 to 75 mass%. 0.1 to 10% by mass, further 0.5 to 5% by mass, particularly 1 to 3% by mass, and 0.1 to 10% by mass of the cationic polymerization initiator (D), further 0 It is preferable to contain in the ratio of 5-8 mass%, especially 1-5 mass%.

  As long as the effect of the present invention is not impaired, the resin composition for optical three-dimensional modeling of the present invention includes, as necessary, a colorant such as a dye, an antifoaming agent, a leveling agent, a thickener, a flame retardant, and an antioxidant. Further, it may contain an appropriate amount of one type or two or more types such as a modifying resin.

Any of the conventionally known optical three-dimensional modeling methods and apparatuses can be used for optical three-dimensional modeling using the optical modeling resin composition of the present invention. As a representative example of the optical three-dimensional modeling method that can be preferably adopted, the active energy ray is selectively irradiated so that a cured layer having a desired pattern is obtained in the liquid resin composition for optical modeling of the present invention. Then, a cured layer is formed, and then an uncured liquid optical modeling resin composition is supplied to the cured layer, and similarly, a cured layer continuous with the cured layer is formed by irradiating active energy rays. The method of finally obtaining the target three-dimensional molded item can be mentioned by repeating lamination | stacking operation.
Examples of the active energy rays at that time include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies as described above. Among them, ultraviolet rays having a wavelength of 300 to 400 nm are preferably used from an economical viewpoint, and as a light source at that time, an ultraviolet laser (for example, a semiconductor-excited solid laser, an Ar laser, a He—Cd laser), a high-pressure mercury lamp is used. Ultra high pressure mercury lamps, low pressure mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light emitting diodes), ultraviolet fluorescent lamps, and the like can be used.

  When forming a cured resin layer having a predetermined shape pattern by irradiating an active energy ray on a modeling surface made of a resin composition for optical three-dimensional modeling, the active energy is reduced to a point such as a laser beam. A planar drawing mask in which a hardened resin layer may be formed by a line drawing method using a line or a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter (DMD). Alternatively, a modeling method may be employed in which a cured resin layer is formed by irradiating the modeling surface with active energy rays through the surface.

  The resin composition for optical modeling of the present invention can be widely used in the field of optical three-dimensional modeling, and is not limited at all. However, as a typical application field, the appearance design is verified during the design. Shape confirmation model, functional test model for checking the functionality of parts, master model for producing mold, master model for producing mold, direct mold for prototype mold, automobile and motorcycle Lenses, restoration of art, imitation and contemporary art, art and craft fields such as design presentation models for glass-walled buildings, precision parts, electrical and electronic parts, furniture, building structures, automotive parts, various containers, It can be effectively used for applications such as models such as castings, mother dies, and processing.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
In the following examples, the viscosity of the optical three-dimensional modeling resin composition, the mechanical characteristics of the optical modeling obtained by optical modeling using the optical modeling resin composition [tensile characteristics (tensile breaking strength, tensile breaking elongation, Degree, tensile modulus), yield strength, bending properties (bending strength, flexural modulus), impact strength], heat distortion temperature, yellowness, total light transmittance, and water absorption were measured as follows. .

(1) Viscosity of resin composition for optical modeling:
After putting the resin composition for optical modeling into a thermostat of 25 ° C. and adjusting the temperature of the photocurable resin composition to 25 ° C., the measurement was performed using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).

(2) Tensile properties of optically shaped objects (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.

(3) Yield strength of stereolithography:
In the tensile property test (2) above, the yield strength is defined as the strength at which the optically shaped article moves from elasticity to plasticity.

(4) Bending characteristics (bending strength, bending elastic modulus) of the optically shaped object:
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. .

(5) Impact strength of stereolithography:
Using a digital impact tester “Model DG-18” manufactured by Toyo Seiki Co., Ltd., Izod impact strength was measured with a notch according to JIS K-7110.

(6) Thermal deformation temperature of stereolithography:
Using the stereolithography produced in the following examples or comparative examples (bar-shaped test piece according to JIS K-7171), using “HDT Tester 6M-2” manufactured by Toyo Seiki Co., Ltd. A heat deformation temperature of the test piece was measured in accordance with JIS K-7207 (Method A) by applying a load of 1.81 MPa, and a load of 0.45 MPa was further applied to the test piece to apply JIS K-7207 (Method B). The heat distortion temperature of the test piece was measured according to the above.

(7) Yellowness of stereolithography:
Using a UV-visible spectrophotometer “UV-3900H” manufactured by Hitachi High-Technologies Corporation, the yellow index (YI) defined in JISK7373 was determined by color analysis, and the yellowness of the optically shaped object was determined.

(8) Total light transmittance of stereolithography:
Using a UV-visible spectrophotometer “UV-3900H” manufactured by Hitachi High-Technologies Corporation, the double beam standard illuminant D65 spectral transmittance was measured and determined.

(9) Water absorption rate of stereolithography:
Length × width × thickness = 65 mm × 10 mm × 4 mm rod-shaped test pieces are placed in a constant temperature bath heated to 35 ° C., dried for 4 days, then immersed in distilled water at a temperature of 25 ° C. for 7 days, and then immersed in distilled water for 7 days. Subtract the mass of the test piece before soaking in distilled water from the mass of the test piece after soaking to obtain the amount of absorbed water, and the mass of the test piece before soaking the amount of the absorbed water in distilled water To obtain the water absorption.

Example 1
(1) 18 parts by mass of tricyclodecane dimethanol diacrylate (“NK-A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.), ditrimethylolpropane tetraacrylate (“AD-TMP” manufactured by Shin-Nakamura Chemical Co., Ltd.) 6 5 parts by mass, polytetramethylene glycol diacrylate (“A-PTMG-65” manufactured by Shin-Nakamura Chemical Co., Ltd., number of bonds of tetramethylene oxide unit≈9, average molecular weight≈750), hydrogenated bisphenol A diglycidyl 51 parts by mass of ether (“HBE100” manufactured by Nippon Nippon Chemical Co., Ltd.), 5 parts by mass of bisphenol A diglycidyl ether (“EP-4100E” manufactured by ADEKA), 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd. “ OXT-101 ") 10 parts by weight, 1-hydroxy-cyclohexyl 2 parts by mass of ruphenyl ketone (“IRGACURE 184” manufactured by BASF) (radical polymerization initiator) and a cationic polymerization initiator represented by the above formula (D-1β) (“CPI-500P” manufactured by San Apro Co., Ltd.) 2 The resin composition for optical three-dimensional modeling was prepared by thoroughly mixing mass parts.
It was 420 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.

(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a semiconductor laser (rated output 200 mW; wavelength) using an ultra-high-speed optical modeling system (“SOLIFORM250” manufactured by Nabtesco Corporation) 355 nm; manufactured by Spectra Physics Co., Ltd.), under the condition of a liquid surface irradiation energy of 100 mJ / cm ² , a slice pitch (lamination thickness) of 0.10 mm, an average modeling time per layer of 2 minutes, Test piece for measuring physical properties (test piece for dumbbell shape according to JIS K-7113, test piece for bar shape according to JIS K-7171, test piece for Izod impact test according to JIS K-7110), yellow A test piece having a thickness of 10 mm for measuring the total light transmittance and a test piece having a length × width × thickness = 65 mm × 10 mm × 4 mm for measuring the water absorption rate was prepared. The obtained test piece was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance and water absorption rate of the post-cured test piece were measured by the methods described above, and as shown in Table 1 below.

Example 2
(1) 18 parts by mass of tricyclodecane dimethanol diacrylate (“NK-A-DCP”), 2 masses of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“A9550W” manufactured by Shin-Nakamura Chemical Co., Ltd.) Parts, 15 parts by mass of polytetramethylene glycol diacrylate (“A-PTMG-65”, number of bonds of tetramethylene oxide units≈9, average molecular weight≈750), 30 parts by mass of hydrogenated bisphenol A diglycidyl ether (“HBE100”) Parts, 5 parts by mass of bisphenol A diglycidyl ether ("EP-4100E"), 5 parts by mass of 3-ethyl-3-hydroxymethyloxetane ("OXT-101"), 3-ethyl-3- (2-ethylhexyloxy) Methyl) oxetane (Toagosei Co., Ltd.) “OXT-212”) 5 parts by mass, 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure 184”) (radical polymerization initiator) 2 parts by mass and the cationic polymerization initiator represented by the above formula (D-1α) ( A resin composition for optical three-dimensional modeling was prepared by thoroughly mixing 2 parts by mass of “CPI-500K” manufactured by San Apro Co., Ltd.
It was 290 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance and water absorption rate of the post-cured test piece were measured by the methods described above, and as shown in Table 1 below.

Example 3
(1) 18 parts by mass of tricyclodecane dimethanol diacrylate (“NK-A-DCP”), 2 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“A9550W”), polytetramethylene glycol di 10 parts by mass of acrylate (“A-PTMG-100” manufactured by Shin-Nakamura Chemical Co., Ltd., number of bonds of tetramethylene oxide unit≈14, average molecular weight≈1130), 43 parts by mass of hydrogenated bisphenol A diglycidyl ether (“HBE100”) 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane (above VG3101L) 3 parts by mass, 3,4-epoxycyclohexyl 5 parts by mass of methyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Cel-2021P” manufactured by Daicel Corporation), 10 parts by mass of 3-ethyl-3-hydroxymethyloxetane (“OXT-101”), 3-ethyl 2 parts by mass of {{((3-ethyloxetane-3-yl) methoxy] methyl} oxetane (“OXT-221” manufactured by Toagosei Co., Ltd.), 1-hydroxy-cyclohexyl phenyl ketone (“IRGACURE 184”) (radical polymerization 2 parts by mass of initiator) and 2 parts by mass of the cationic polymerization initiator (“CPI-500K”) represented by the above formula (D-1α) were mixed well to prepare a resin composition for optical three-dimensional modeling.
It was 392 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance and water absorption rate of the post-cured test piece were measured by the methods described above, and as shown in Table 1 below.

Example 4
(1) 18 parts by mass of tricyclodecane dimethanol diacrylate (“NK-A-DCP”), 2 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“A9550W”), polytetramethylene glycol di 10 parts by mass of acrylate (Kyoeisha Chemical Co., Ltd. “FA-PTG9A”, number of bonds of tetramethylene oxide unit≈9, average molecular weight≈770), 51 parts by mass of hydrogenated bisphenol A diglycidyl ether (“HBE100”), 2- [ 4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane (VG3101L described above) 3 mass Part, 3-ethyl-3-hydroxymethyloxetane ( “OXT-101”) 10 parts by mass, 2-ethyl-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (“OXT-221”) 2 parts by mass, 1-hydroxy-cyclohexyl phenyl ketone ( “Irgacure 184”) (radical polymerization initiator) 2 parts by mass and the cationic polymerization initiator (“CPI-500P”) 2 parts by mass represented by the above formula (D-1β) are mixed well to form an optical solid. A resin composition was prepared.
It was 380 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance, and water absorption rate of the post-cured test piece were measured by the methods described above, and as shown in Table 2 below.

Example 5
(1) In Example 4 (1), instead of 10 parts by mass of polytetramethylene glycol diacrylate (“FA-PTG9A”), polytetramethylene glycol diacrylate (“A-PTMG-65”, tetramethylene oxide) 5 parts by mass of unit number of bonds≈9, average molecular weight≈750) and 5 parts by mass of polyethylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd. “A-600”, number of bonds of ethylene oxide unit≈14, average molecular weight≈750) A resin composition for optical three-dimensional modeling was prepared in the same manner as (1) of Example 5 except that it was used.
It was 364 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance, and water absorption rate of the post-cured test piece were measured by the methods described above, and as shown in Table 2 below.

Example 6
(1) 18 parts by mass of tricyclodecane dimethanol diacrylate (“NK-A-DCP”), 2 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“A9550W”), polyethylene glycol diacrylate ( “A-600”, ethylene oxide unit bond number≈14, average molecular weight≈750) 10 parts by mass, hydrogenated bisphenol A diglycidyl ether (“HBE100”) 51 parts by mass, bisphenol A diglycidyl ether (“EP-4100E”) ) 5 parts by mass, 10 parts by mass of 3-ethyl-3-hydroxymethyloxetane (“OXT-101”), 2 parts by mass of 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure 184”) (radical polymerization initiator) and formula( A resin composition for optical three-dimensional modeling was prepared by thoroughly mixing 2 parts by mass of a cationic polymerization initiator (“CPI-500P”) represented by D-1β).
It was 356 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance, and water absorption rate of the post-cured test piece were measured by the methods described above, and as shown in Table 2 below.

<< Comparative Example 1 >>
(1) A resin composition for optical three-dimensional modeling was prepared in the same manner as (1) of Example 5 except that polytetramethylene glycol diacrylate was not added in (1) of Example 5.
It was 508 mPa * s (25 degreeC) when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance, and water absorption of the post-cured test piece were measured by the methods described above, and as shown in Table 3 below.

<< Comparative Example 2 >>
(1) In (1) of Example 6 , instead of 10 parts by mass of polyethylene glycol diacrylate, 10 parts by mass of polytetramethylene glycol (“PTG-850SN” manufactured by Hodogaya Chemical Co., Ltd., average molecular weight 850) was used. Except that, a resin composition for optical three-dimensional modeling was prepared in the same manner as in Example 6 (1).
It was 462 mPa * s (25 degreeC) when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance, and water absorption of the post-cured test piece were measured by the methods described above, and as shown in Table 3 below.

<< Comparative Example 3 >>
(1) 18 parts by mass of tricyclodecane dimethanol diacrylate (“NK-A-DCP”), 2 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“A9550W”), polytetramethylene glycol di 10 parts by mass of acrylate (“A-PTMG-65”, number of bonds of tetramethylene oxide unit≈9, average molecular weight≈750), 51 parts by mass of hydrogenated bisphenol A diglycidyl ether (“HBE100”), bisphenol A diglycidyl ether ("EP-4100E") 5 parts by mass, 1-hydroxy-cyclohexyl phenyl ketone ("Irgacure 184") (radical polymerization initiator) 2 parts by mass and the cationic polymerization initiator represented by the above formula (D-1β) ("CPI-500P ) Was prepared for stereolithography resin composition was mixed well 2 parts by weight.
It was 636 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance, and water absorption of the post-cured test piece were measured by the methods described above, and as shown in Table 3 below.

<< Comparative Example 4 >>
(1) 18 parts by mass of tricyclodecane dimethanol diacrylate (“NK-A-DCP”), 2 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“A9550W”), polytetramethylene glycol di 10 parts by mass of acrylate (“A-PTMG-65”, number of bonds of tetramethylene oxide unit≈9, average molecular weight≈750), 5 parts by mass of bisphenol A diglycidyl ether (“EP-4100E”), 3,4-epoxy 51 parts by mass of cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Cel-2021P”), 10 parts by mass of 3-ethyl-3-hydroxymethyloxetane (“OXT-101”), 1-hydroxy-cyclohexylphenyl Ketone ("Ile Cure 184 ") (radical polymerization initiator) 2 parts by mass and the cationic polymerization initiator (" CPI-500K ") 2 parts by mass represented by the above formula (D-1α) are mixed well for optical three-dimensional modeling. A resin composition was prepared.
It was 274 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance, and water absorption of the post-cured test piece were measured by the methods described above, and as shown in Table 3 below.

<< Comparative Example 5 >>
(1) In (1) of Example 6 , instead of 10 parts by mass of polyethylene glycol diacrylate (“A-600”), tetramethylene glycol diacrylate (1,4-butanediol diacrylate (Tokyo Chemical Industry Co., Ltd.) (Product made) Except having used 10 mass parts, it carried out similarly to (1) of Example 6 , and prepared the resin composition for optical three-dimensional model | molding.
It was 202 mPa * s (25 degreeC) when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
The mechanical properties, heat distortion temperature, yellowness, total light transmittance, and water absorption of the post-cured test piece were measured by the methods described above, and as shown in Table 3 below.

As seen in Tables 1 to 3 above, the resin compositions for optical three-dimensional modeling of Examples 1 to 6 are a radical polymerizable organic compound (A), a cationic polymerizable organic compound (B), and a radical polymerization initiator. In the resin composition for optical three-dimensional modeling containing (C) and a cationic polymerization initiator (D), a polyalkylene glycol di (meth) acrylate having an average molecular weight of 300 to 2000 as a part of the radical polymerizable organic compound (A) (A-1) is contained, the alicyclic diglycidyl ether compound (B-1) is contained as part of the cationically polymerizable organic compound (B), and as part of the cationically polymerizable organic compound (B). By containing the oxetane compound (B-2), it is possible to produce a three-dimensional molded article with high productivity in a shortened active energy ray irradiation time with high curing sensitivity and low viscosity. The three-dimensional object obtained by optical modeling using the resin composition for optical three-dimensional modeling of Examples 1 to 6 has a yellowness as small as 9.5 or less and is yellow. coloration excellent little color tone, excellent transparency with a total light transmittance of 88% or more, water absorption better less dimensional stability moisture and moisture absorption below 8.9%, the value of impact strength It is as high as 2.9 kJ / m ² or more and has excellent toughness and durability.
In particular, the resin composition for optical three-dimensional modeling of Examples 1 to 6 includes polytetramethylene glycol diacrylate having an average molecular weight of 300 to 2000 as the polyalkylene glycol di (meth) acrylate (A-1). By containing, the impact resistance of the three-dimensional structure obtained by optical modeling is further improved than the resin composition for optical three-dimensional modeling of Example 7 containing polyethylene glycol diacrylate in the molecular weight range. Are better.

On the other hand, since the resin composition for optical three-dimensional modeling of Comparative Example 1 does not contain polyalkylene glycol di (meth) acrylate (A-1) as a part of the radical polymerizable organic compound (A). The three-dimensional model obtained by optical modeling using the optical three-dimensional model resin composition of Comparative Example 1 has a high yellowness of 21.9% and is colored yellow and has a poor color tone. The total light transmittance is as low as 78% and the transparency is poor, and the impact strength is as low as 1.4 kJ / m ² and the toughness is poor.
The resin composition for optical three-dimensional modeling of Comparative Example 2 does not contain polyalkylene glycol di (meth) acrylate (A-1) as a part of the radical polymerizable organic compound (A), while it is non-polymerizable. The three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of Comparative Example 2 has a high impact strength, but has a yellowness. Is 41.8% which is extremely high and colored yellow and has a poor color tone, and the total light transmittance is as low as 66% and the transparency is poor.

Since the resin composition for optical three-dimensional modeling of Comparative Example 3 does not contain an oxetane compound as a part of the cationically polymerizable organic compound (B), the resin composition for optical three-dimensional modeling of Comparative Example 3 is used. The three-dimensional structure obtained by stereolithography has an impact strength value of 2.0 kJ / m ² , which is inferior in impact resistance to Examples 1 to 6, and has a tensile rupture strength value. Is as low as 17 MPa and the yield strength is as extremely low as 18 MPa, so that the mechanical properties are greatly inferior.
The resin composition for optical three-dimensional modeling of Comparative Example 4 does not contain the alicyclic diglycidyl ether compound (B-1) as a part of the cationically polymerizable organic compound (B), but instead contains a large amount. By containing the alicyclic epoxy compound, the three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of Comparative Example 4 has an impact strength value of 1.9 kJ / m. ² and inferior in toughness and durability as compared with Examples 1 to 6, and has a high water absorption rate of 1.58%, easily absorbs moisture and moisture, and is inferior in dimensional stability. .

The resin composition for optical three-dimensional modeling of Comparative Example 5 does not contain polyalkylene glycol di (meth) acrylate (A-1) having an average molecular weight of 300 to 2000 as a part of the radical polymerizable organic compound (A), Instead, by containing 1,4-butanediol diacrylate (tetramethylene glycol diacrylate) having a molecular weight of 198, it is obtained by optical modeling using the resin composition for optical three-dimensional modeling of Comparative Example 5. The resulting three-dimensional model has an impact strength value of 2.6 kJ / m ² , lower toughness than Examples 1 to 6, a high yellowness of 14.7%, and is colored yellow and has poor color tone. The total light transmittance is 84%, which is inferior in transparency compared to Examples 1-6.

The resin composition for optical three-dimensional modeling of the present invention only has various characteristics such as high curing sensitivity by active energy rays, low viscosity, excellent handling property during modeling, high resolution of a modeled object, and excellent modeling accuracy. The three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention has low yellowness and high light transmittance, excellent color tone and transparency, moisture and moisture. It absorbs less and excels in dimensional stability, has high impact strength, excels in toughness and durability, and excels in mechanical properties such as breaking strength . Therefore, the resin composition for optical three-dimensional modeling of the present invention has a high three-dimensional modeled article having high transparency and excellent yellow color appearance and color tone, and mechanical properties such as strength, elastic properties, impact resistance, and toughness. There is a need for an excellent 3D object, a model for verifying the appearance design of various industrial products during the design, a model for checking the functionality of parts, a resin mold for manufacturing molds, and a mold. Base models for production, automobile and motorcycle lenses, restoration of artworks, imitation and contemporary art, art and craft fields such as glass-based architectural design presentation models, precision parts, electrical and electronic parts, furniture, architecture It can be effectively used for various applications such as models of structures, automobile parts, various containers, castings, and the like.

Claims (3)

<< 1 >> A resin composition for optical three-dimensional modeling containing a radical polymerizable organic compound (A), a cationic polymerizable organic compound (B), a radical polymerization initiator (C) and a cationic polymerization initiator (D) ;
<< 2 >> Based on the total mass of the resin composition for optical three-dimensional modeling, the radical polymerizable organic compound (A) is 10 to 50 mass%, the cationic polymerizable organic compound (B) is 30 to 80 mass%, and radical polymerization is performed. Containing 0.1 to 10% by mass of the initiator (C) and 0.1 to 10% by mass of the cationic polymerization initiator (D);
As "3" part of the radical polymerizable organic compound (A), the polyalkylene glycol di (meth) acrylate of average molecular weight 300 to 2000 the (A-1), based on the total weight of the radical polymerizable organic compound (A) In a proportion of 10 to 70% by weight ;
<< 4 >> As a part of the radical polymerizable organic compound (A), the following general formula (A-2);

(Wherein R ² represents a bridged cyclic hydrocarbon group, and R ³ represents a hydrogen atom or a methyl group.)
Further containing a di (meth) acrylate compound (A-2) represented by the formula (A) in a proportion of 10 to 90% by mass based on the total mass of the radical polymerizable organic compound (A);
<< 5 >> As a part of the cationically polymerizable organic compound (B), the following general formula (B-1);

Wherein R ¹ is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or tri Cyclodecanedimethanol residue is shown.)
An alicyclic diglycidyl ether compound (B-1) represented by the formula (B-1) in a proportion of 50 to 95% by mass based on the total mass of the cationically polymerizable organic compound (B) ; and
<< 6 >> As part of the cationically polymerizable organic compound (B), the oxetane compound (B-2) is contained in a proportion of 3 to 50% by mass based on the total mass of the cationically polymerizable organic compound (B) ;
A resin composition for optical three-dimensional modeling characterized by the above.   The oxetane compound (B-2) contains a monooxetane compound (B-2a) having one oxetane group, or two or more monooxetane compounds (B-2a) having one oxetane group and an oxetane group The resin composition for optical three-dimensional model | molding of Claim 1 containing the polyoxetane compound (B-2b) which has. The method to manufacture an optical three-dimensional molded item using the resin composition for optical three-dimensional modeling of Claim 1 or 2 .