JP2019031602A - Optical solid molding resin composition - Google Patents

Abstract

To provide an optical solid molding resin composition having excellent heat resistance, excellent mechanical characteristics such as impact resistance and capable of producing a solid molded article having excellent dimensional accuracy, and a production method of the solid molded article that uses the optical solid molding resin composition.SOLUTION: An optical solid molding resin composition including a cation polymerizable organic compound (a), a radical polymerizable organic compound (b), a cation polymerizable initiator (c) and a radical polymerizable initiator (d), in which as a part of the cation polymerizable organic compound (a), 3,4,3', 4'-diepoxy bicyclohexyl is contained at a ratio of 10 to 90 mass% based on an entire mass of the cation polymerizable organic compound (a), and a method of producing a solid molded article by performing an optical solid molding with the optical solid molding resin composition.SELECTED DRAWING: None

Description

The present invention relates to a resin composition for optical three-dimensional modeling and a method for producing an optical three-dimensional model using the same.
More specifically, the present invention has a low-viscosity, excellent handling property when performing optical three-dimensional modeling, and has a high curing sensitivity by active energy rays and a target three-dimensional modeling object with a shortened optical three-dimensional modeling time. The resin composition for optical three-dimensional modeling and the optical three-dimensional modeling can produce a three-dimensional modeled article that has a high heat distortion temperature, excellent heat resistance, and excellent mechanical strength. The present invention relates to a method for producing a three-dimensional modeled object using a modeling resin composition.

In recent years, a method for producing a three-dimensional object by performing an optical three-dimensional modeling based on data input to a three-dimensional CAD using a resin composition for optical three-dimensional modeling has an object without producing a mold or the like. Since a three-dimensional model to be manufactured can be manufactured with good dimensional accuracy, it has been widely adopted.
As a typical example of the optical three-dimensional modeling method, an ultraviolet laser controlled by a computer is selectively used so that a desired pattern can be obtained on the liquid surface of the liquid resin composition for optical three-dimensional modeling placed in a container. Irradiate to cure a predetermined thickness, and then supply one layer of the resin composition for optical three-dimensional modeling on the cured layer, and similarly cure by irradiation with an ultraviolet laser in the same manner as described above. The method of finally obtaining a three-dimensional molded item can be mentioned by repeating the lamination | stacking operation to obtain. By this optical three-dimensional modeling method, a three-dimensional model having a considerably complicated shape can be easily manufactured in a relatively short time (hereinafter, optical three-dimensional modeling may be referred to as “optical modeling”).

  About the resin composition for optical three-dimensional model | molding, it is calculated | required that it is excellent in the handleability at the time of optical modeling with low viscosity, and the hardening sensitivity by an active energy ray is high, and can manufacture a three-dimensional model | molded article in short optical modeling time.

  Conventionally, as a resin composition for optical three-dimensional modeling, a photocurable resin composition containing a radical polymerizable organic compound, a cationic polymerizable photocurable resin composition, both a radical polymerizable organic compound and a cationic polymerizable compound Various photo-curable resin compositions such as a hybrid type photo-curable resin composition containing benzene have been proposed and used. At that time, examples of the radical polymerizable organic compound include (meth) acrylate compounds, urethane (meth) acrylate compounds, polyester (meth) acrylate compounds, polyether (meth) acrylate compounds, and epoxy (meth) acrylates. System compounds are used. As the cationically polymerizable organic compound, for example, various epoxy compounds, cyclic acetal compounds, vinyl ether compounds, lactones, oxetane compounds and the like are used.

Among the above, in the resin composition for optical three-dimensional modeling containing a cationically polymerizable organic compound, the active energy ray-sensitive cationic polymerization initiator present in the system generates a cationic species (H +) by light irradiation, Attacks a cationically polymerizable group such as an epoxy group in a chain, and the cationically polymerizable group is opened to proceed the polymerization reaction. When using a resin composition for optical three-dimensional modeling based on a cationically polymerizable organic compound such as an epoxy compound, in general, compared to using a resin composition for optical three-dimensional modeling based on a radical polymerizable organic compound As a result, a three-dimensional structure obtained has a small shrinkage ratio, and a three-dimensional structure excellent in dimensional stability and dimensional accuracy is obtained.
Nowadays, a hybrid type optical three-dimensional modeling resin composition containing both a radical polymerizable organic compound and a cationic polymerizable compound is mainly used because of its excellent balance between modeling speed and modeling accuracy.

Three-dimensional objects obtained by performing optical modeling using a resin composition for optical three-dimensional modeling are models for checking the shape and functionality of parts, and for verifying the appearance design of various industrial products during design Are used in various applications such as a resin model for manufacturing a mold, a base model for manufacturing a mold, and the like.
In particular, a three-dimensional model obtained by optical modeling of a resin composition for optical three-dimensional modeling is a model, a light source and an engine for verifying the shape and performance of tubes and parts for passing a heat medium and a thermal fluid, In the case of models for evaluating functions and shapes, such as motor peripheral parts, high heat resistance that does not cause deformation or change even when exposed to high temperatures is required, and at the same time, mechanical strength is also required. It is required to be excellent, strong and not easily damaged.
The heat deformation temperature (at a high load of 1.81 MPa) of an optical three-dimensional structure obtained from a resin composition for optical three-dimensional modeling that has been generally used in the past is generally 50 ° C. or less and has high heat resistance. It was difficult to say that the required properties for the required applications were sufficiently satisfied.

Various proposals have been made so far for resin compositions for optical three-dimensional modeling that give a three-dimensional model excellent in heat resistance (see, for example, Patent Documents 1 to 4). Those that are sufficiently satisfactory, such as inferior handleability, low photocuring sensitivity, time-consuming optical modeling, and heat resistance of three-dimensional objects obtained by optical modeling are still insufficient It wasn't.
From this point, the viscosity is low, it is excellent in handling when performing optical modeling, the curing sensitivity by active energy rays is high, and the desired three-dimensional modeled object can be produced with high productivity in a shortened optical modeling time. Moreover, there has been a demand for a resin composition for optical three-dimensional modeling that can produce a three-dimensional modeled article that has a high heat distortion temperature, excellent heat resistance, and excellent mechanical strength.

JP 09-194540 A Japanese Patent Laid-Open No. 10-077331 JP-A-10-259219 JP 2011-089088 A

The object of the present invention is to produce a desired three-dimensional object with high productivity in a short optical modeling time with low viscosity and excellent handling property when performing optical three-dimensional modeling, and high curing sensitivity by active energy rays. It is possible to provide a resin composition for optical three-dimensional modeling that can produce a three-dimensional model that has a high thermal deformation temperature, excellent heat resistance, excellent mechanical strength, and is not easily damaged. is there.
An object of the present invention is to provide a method for producing a three-dimensional structure that is excellent in heat resistance and mechanical strength using the above-described resin composition for optical three-dimensional structure.

  The present inventor has intensively studied to solve the above problems. As a result, in the resin composition for optical three-dimensional modeling containing a cationic polymerizable organic compound, a radical polymerizable organic compound, a cationic polymerization initiator, and a radical polymerization initiator, 3, 4 as a part of the cationic polymerizable organic compound. , 3 ', 4'-diepoxybicyclohexyl is included, it has a low viscosity and excellent handling properties when performing optical three-dimensional modeling, and also has high curing sensitivity by active energy rays and shortens the optical modeling time. It discovered that the resin composition for optical three-dimensional modeling which can manufacture a three-dimensional molded item with sufficient productivity is obtained. And when this inventor performed stereolithography using the said resin composition for optical three-dimensional model | molding, and manufactured the three-dimensional model | molding object, the three-dimensional model | molding thing obtained by it has high heat deformation temperature, and is heat-resistant. It was excellent in mechanical properties and mechanical strength and was not easily damaged.

  Further, the inventor of the present invention provides the resin composition for optical three-dimensional modeling containing 3,4,3 ′, 4′-diepoxybicyclohexyl as a part of the cationically polymerizable organic compound. It has been found that when at least one of a specific alicyclic glycidyl ether and a specific aromatic diglycidyl ether is further contained as a part of the above, effects such as improvement of water resistance and mechanical properties can be obtained.

In addition, the inventor of the present invention described above, the resin composition for optical three-dimensional modeling or the cationic polymerizable organic compound containing 3,4,3 ′, 4′-diepoxybicyclohexyl as a part of the cationic polymerizable organic compound As a part of the above, the above-mentioned optical stereolithography resin containing at least one of a specific alicyclic glycidyl ether and a specific aromatic diglycidyl ether together with 3,4,3 ′, 4′-diepoxybicyclohexyl It has been found that when the composition further contains an oxetane compound as part of the cationically polymerizable organic compound, the viscosity of the composition can be reduced, and the effects such as improved reactivity and improved toughness can be obtained.
In addition, the present inventor performs optical modeling using the above-described resin composition for optical three-dimensional modeling that contains at least 3,4,3 ′, 4′-diepoxybicyclohexyl as a part of the cationically polymerizable organic compound. As a result of heat treatment of the three-dimensional structure obtained in this way, the heat deformation temperature of the three-dimensional structure was further increased, and the shrinkage of the three-dimensional structure during the heat treatment was found to be small, and the present invention was completed based on these findings.

That is, the present invention
(1) Optical steric composition containing a cationically polymerizable organic compound (a), a radically polymerizable organic compound (b), an active energy ray sensitive cationic polymerization initiator (c) and an active energy ray sensitive radical polymerization initiator (d) It is a resin composition for modeling, Comprising: As a part of cationically polymerizable organic compound (a), following chemical formula (a-1);

で表される３，４，３’，４’−ジエポキシビシクロヘキシルを、カチオン重合性有機化合物（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。

3,4,3 ′, 4′-diepoxybicyclohexyl represented by formula (10) is contained in a proportion of 10 to 90% by mass based on the total mass of the cationically polymerizable organic compound (a). It is a resin composition for three-dimensional modeling.

And this invention,
(2) The content ratio of the cationic polymerizable organic compound (a): radical polymerizable organic compound (b) is 40:60 to 90:10 (mass ratio), and the active energy ray sensitive cationic polymerization initiator (c) is used. It contains in the ratio of 0.1-10 mass% based on the total mass of a cationically polymerizable organic compound (a), and an active energy ray sensitive radical polymerization initiator (d) is the total mass of a radically polymerizable organic compound (b). It is the resin composition for optical three-dimensional model | molding of said (1) contained in the ratio of 0.1-10 mass% based on.

The present invention also provides:
(3) As a part of the cationically polymerizable organic compound (a), the following general formula (a-2);

（式中、Ｒ¹は、脂環式ジグリシジルエーテルまたは芳香族ジグリシジルエーテルから２個のグリシジルオキシ基を除いた残基を示す。）
で表されるジグリシジルエーテル化合物（ａ−２）の１種または２種以上を、カチオン重合性有機化合物（ａ）の全質量に基づいて１０〜９０質量％の割合で更に含有する、前記した（１）または（２）の光学的立体造形用樹脂組成物；
（４） カチオン重合性有機化合物（ａ）の一部として、オキセタン化合物を、カチオン重合性有機化合物（ａ）の全質量に基づいて１〜３０質量％の割合で更に含有する、前記した（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） 活性エネルギー線感受性カチオン重合開始剤（ｃ）として、非アンチモン型の芳香族スルホニウム化合物を用いる、前記（１）〜（４）のいずれかの光学的立体造形用樹脂組成物；
である。

(In the formula, R ¹ represents a residue obtained by removing two glycidyloxy groups from alicyclic diglycidyl ether or aromatic diglycidyl ether.)
1 type or 2 types or more of the diglycidyl ether compound (a-2) represented by above are further contained in the ratio of 10-90 mass% based on the total mass of a cationically polymerizable organic compound (a). (1) or (2) a resin composition for optical three-dimensional modeling;
(4) As described above, the oxetane compound is further contained in a proportion of 1 to 30% by mass based on the total mass of the cationic polymerizable organic compound (a) as a part of the cationic polymerizable organic compound (a) (1 ) To (3), a resin composition for optical three-dimensional modeling; and
(5) The resin composition for optical three-dimensional modeling according to any one of (1) to (4), wherein a non-antimony aromatic sulfonium compound is used as the active energy ray-sensitive cationic polymerization initiator (c);
It is.

And this invention,
(6) A method for producing an optical three-dimensional object, characterized in that optical three-dimensional modeling is performed using the resin composition for optical three-dimensional modeling according to any one of (1) to (5);
(7) A method of heat-treating the optical three-dimensional structure obtained by the manufacturing method of (6);
It is.

In the resin composition for optical three-dimensional modeling containing a cationically polymerizable organic compound (a), a radically polymerizable organic compound (b), a cationic polymerization initiator (c) and a radical polymerization initiator (d), cationically polymerizable The resin composition for optical three-dimensional modeling of the present invention containing 3,4,3 ′, 4′-diepoxybicyclohexyl represented by the above chemical formula (a-1) as a part of the organic compound (a). Since the viscosity is low, stereolithography can be performed smoothly with good handling and workability, and the curing sensitivity by active energy rays is high, so that the desired 3D modeling object can be obtained in a shortened stereolithography time. It can be manufactured with high productivity.
Moreover, the three-dimensional object obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention has a high heat distortion temperature and is excellent in heat resistance and excellent in mechanical strength. Hard to break.

  Furthermore, as a part of the cationically polymerizable organic compound, at least the diglycidyl ether compound (a-2) represented by the above general formula (IIa) together with 3,4,3 ′, 4′-diepoxybicyclohexyl The resin composition for optical three-dimensional model | molding of this invention which further contains 1 type is excellent also at points, such as the reduction of the water absorption of a three-dimensional model | molded object, and the improvement of a mechanical physical property.

  Further, as part of the cationically polymerizable organic compound, together with 3,4,3 ′, 4′-diepoxybicyclohexyl, or 3,4,3 ′, 4′-diepoxybicyclohexyl and diglycidyl ether compound (a The resin composition for optical three-dimensional model | molding of this invention which further contains an oxetane compound with -2) can reduce viscosity, and is excellent also in the point of a coating-film formation property and a reactive improvement.

  Further, the three-dimensional object is formed by optical modeling using the optical three-dimensional resin composition of the present invention containing at least 3,4,3 ′, 4′-diepoxybicyclohexyl as a part of the cationically polymerizable organic compound. In the case of using the method of the present invention for heat-treating the three-dimensional structure obtained thereby, a three-dimensional structure that has a higher thermal deformation temperature and is more excellent in heat resistance while preventing shrinkage of the three-dimensional structure during the heat treatment. It can be manufactured smoothly.

  The resin composition for optical three-dimensional modeling of the present invention is a three-dimensional model that requires high heat resistance, high mechanical strength, high dimensional accuracy, etc. by taking advantage of the above-mentioned characteristics, for example, verifying the external appearance design 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, final product, In particular, it can be used effectively for the manufacture of precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, models, mother dies, processed goods, and the like.

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

The cationically polymerizable organic compound (a) used in the present invention is an active energy ray-sensitive cationic polymerization initiator (c) [hereinafter sometimes simply referred to as “cationic polymerization initiator (c)” or “cationic polymerization initiator”]. Is a compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with active energy rays such as light in the presence of.
The resin composition for optical three-dimensional modeling of the present invention has the following chemical formula (a-1) as a part of the cationically polymerizable organic compound (a);

で表される３，４，３’，４’−ジエポキシビシクロヘキシルを含有する。
本発明で用いる３，４，３’，４’−ジエポキシビシクロヘキシルは、「セロキサイド８０００」（商品名；株式会社ダイセル製）などとして市場で販売されている。

3,4,3 ′, 4′-diepoxybicyclohexyl represented by the formula:
The 3,4,3 ′, 4′-diepoxybicyclohexyl used in the present invention is sold in the market as “Celoxide 8000” (trade name; manufactured by Daicel Corporation).

The resin composition for optical three-dimensional modeling of the present invention is based on the total mass of the cationic polymerizable organic compound (a) contained in the resin composition for optical three-dimensional modeling. It contains 10 to 90% by mass of epoxy bicyclohexyl.
The resin composition for optical three-dimensional modeling of the present invention containing 3,4,3 ′, 4′-diepoxybicyclohexyl in the above-described ratio generally has a low viscosity (25 ° C.) of 500 mP · s or less. The handleability during stereolithography is extremely excellent.

The resin composition for optical three-dimensional modeling of the present invention is based on the total mass of the cationic polymerizable organic compound (a) contained in the resin composition for optical three-dimensional modeling. It is preferable to contain epoxy bicyclohexyl in a proportion of 20 to 90% by mass, more preferably in a proportion of 25 to 90% by mass, and still more preferably in a proportion of 30 to 85% by mass.
If the content of 3,4,3 ′, 4′-diepoxybicyclohexyl is too small, a low-viscosity resin composition for optical three-dimensional modeling cannot be obtained, and the active energy rays of the resin composition for optical three-dimensional modeling are obtained. The curing sensitivity is reduced, and the heat resistance of the three-dimensional structure obtained by optical modeling is reduced.
On the other hand, when the content ratio of 3,4,3 ′, 4′-diepoxy) bicyclohexyl exceeds 90% by mass with respect to the total mass of the cationically polymerizable organic compound (a), the physical properties of the three-dimensional structure are reduced. Cause problems.

The resin composition for optical three-dimensional model | molding of this invention contains another cationically polymerizable organic compound with 3,4,3 ', 4'-diepoxybicyclohexyl as a cationically polymerizable organic compound (a).
The other cationically polymerizable organic compound is a compound other than 3,4,3 ′, 4′-diepoxybicyclohexyl, and is irradiated with active energy rays in the presence of the cationic polymerization initiator (c). Any organic compound that causes a cationic polymerization reaction and / or a cationic crosslinking reaction may be contained.
Examples of other cationically polymerizable organic compounds that can be contained in the resin composition for optical three-dimensional modeling of the present invention include epoxy compounds other than 3,4,3 ′, 4′-diepoxybicyclohexyl, oxetane compounds, and cyclic ether compounds. , A cyclic acetal compound, a cyclic lactone compound, a spiro orthoester compound, a vinyl ether compound, and the like, and one or more of these can be contained.

  Among them, the resin composition for optical three-dimensional modeling of the present invention includes the following general formula (a-2) together with 3,4,3 ′, 4′-diepoxybicyclohexyl as the cationic polymerizable organic compound (a). );

（式中、Ｒ¹は、脂環式ジグリシジルエーテルまたは芳香族ジグリシジルエーテルから２個のグリシジルオキシ基を除いた残基を示す。）
で表されるジグリシジルエーテル化合物（ａ−２）を含有することが、立体造形物の吸水率の低減や機械物性の向上などの点から好ましい。

(In the formula, R ¹ represents a residue obtained by removing two glycidyloxy groups from alicyclic diglycidyl ether or aromatic diglycidyl ether.)
It is preferable to contain the diglycidyl ether compound (a-2) represented by these from points, such as a reduction of the water absorption rate of a three-dimensional molded item, and an improvement of a mechanical physical property.

  The resin composition for optical three-dimensional model | molding of this invention uses said diglycidyl ether compound (a-2) with 3,4,3 ', 4'-diepoxybicyclohexyl as a cationically polymerizable organic compound (a). When it contains, the content rate of a diglycidyl ether compound (a-2) is 10-90 mass% based on the total mass of the cationically polymerizable organic compound (a) contained in the resin composition for optical three-dimensional modeling. It is preferable that it is 10-70 mass%, and it is still more preferable that it is 15-65 mass%.

Specific examples of the diglycidyl ether compound (a-2) include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and tricyclodecandi. Alicyclic diglycidyl ethers such as methanol diglycidyl ether); bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol Z diglycidyl ether, bisphenol A, F, and Z; ethylene oxide, propylene oxide, etc. An aromatic diglycidyl ether such as diglycidyl ether of a compound to which an alkylene oxide has been added can be exemplified. Use resin composition may contain one or more of these. When the diglycidyl ether compound (a-2) is any of the alicyclic diglycidyl ethers specifically mentioned here, R ¹ in the above general formula (a-2) is each alicyclic. When the diglycidyl ether is a residue obtained by removing two glycidyloxy groups and the diglycidyl ether compound (a-2) is one of the aromatic diglycidyl ethers specifically mentioned here, R ¹ in the above general formula (a-2) is a residue obtained by removing two glycidyloxy groups from each aromatic diglycidyl ether.
Among them, as the diglycidyl ether compound (a-2), hydrogenated bisphenol A diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, bisphenol A diglycidyl ether, diglycidyl ether of an alkylene oxide adduct of bisphenol A, and the like. And from the viewpoints of availability, physical properties of a shaped article (particularly required mechanical properties and heat resistance), and the like.

  Moreover, the resin composition for optical three-dimensional modeling of this invention is 3,4,3 ', 4'-diepoxy bicyclohexyl as a part of cationically polymerizable organic compound (a), or 3,4,3. An oxetane compound can be further contained as needed together with the ', 4'-diepoxybicyclohexyl and diglycidyl ether (a-2). By containing an oxetane compound, the reaction rate is improved and the viscosity of the resin composition for optical three-dimensional modeling is reduced, so that the formability of the coating layer at the time of optical modeling can be improved and obtained by optical modeling. The toughness of the three-dimensional structure to be obtained increases, and even if stress such as impact or bending is applied, it becomes difficult to break, and durability is improved.

  When the resin composition for optical three-dimensional modeling of the present invention further contains an oxetane compound as the cationic polymerizable organic compound (a), the content ratio of the oxetane compound is included in the resin composition for optical three-dimensional modeling. Based on the total mass of the cationically polymerizable organic compound (a), it is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and further preferably 3 to 15% by mass.

As the oxetane compound, any of the oxetane compounds that are conventionally known to be usable in a resin composition for optical three-dimensional modeling can be used.
Among these, as an oxetane compound, the following general formula (a-3);

（式中、ｎは１または２であって、ｎが１のときに、Ｒ²は炭素数１〜５のアルキル基、Ｒ³は水素原子、アルキル基、ヒドロキシアルキル基またはベンジル基を示し、ｎが２のときに、Ｒ²は炭素数１〜５のアルキル基、Ｒ³はアルキレン基または直接結合を示す。）
で表されるモノオキセタン化合物（ｎが１のとき）およびジオキセタン化合物（ｎが２のとき）の１種または２種以上が好ましく用いられる。

(Wherein n is 1 or 2, and when n is 1, R ² represents an alkyl group having 1 to 5 carbon atoms, R ³ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group or a benzyl group, When n is 2, R ² represents an alkyl group having 1 to 5 carbon atoms, and R ³ represents an alkylene group or a direct bond.)
1 type or 2 types or more of the monooxetane compound (when n is 1) and a dioxetane compound (when n is 2) represented by these are preferably used.

As the monooxetane compound in which n is 1 in the general formula (a-3), a monooxetane monoalcohol compound in which R ³ is a hydrogen atom or a hydroxyalkyl group is easily available, highly reactive, It is preferably used from the viewpoint of low viscosity.
Specific examples of the monooxetane alcohol include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, and 3-hydroxymethyl-3-normalbutyloxetane. , 3-hydroxymethyl-3-propyloxetane and the like, and one or more of these can be used. Among these, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are more preferable from the viewpoint of availability and reactivity.

Specific examples of the dioxetane compound in which n is 2 in the above general formula (a-3) include bis (3-methyl-3-oxetanylmethyl) ether and bis (3-ethyl-3-oxetanylmethyl) ether. , bis (3-propyl-3-oxetanylmethyl) ether, bis (both, R3 is a direct bond Jiokisentan) (3-butyl-3-oxetanylmethyl) ether, etc., R ² is methyl, ethyl, propyl, butyl Alternatively, a dioxetane compound in which R ³ is an pentyl group and R ³ is an ethylene group, a propylene group, a butylene group, a neopentylene group, an n-pentamethylene group, an n-hexamethylene group, or the like can be given.
Among them, as the dioxetane compound, bis (3-methyl-3-oxetanylmethyl) ether and / or bis (3-ethyl-3-oxetanylmethyl) ether are easily available, low hygroscopicity, and dynamics of the cured product. From the standpoint of mechanical properties, bis (3-ethyl-3-oxetanylmethyl) ether is particularly preferably used.

The resin composition for optical three-dimensional model | molding of this invention can contain other cationically polymerizable organic compounds other than an above-described cationically polymerizable organic compound as needed.
Although not limited, As other cationically polymerizable organic compounds which the resin composition for optical three-dimensional model | molding of this invention can contain as needed, for example, 3,4,3 ', 4'-di Examples include alicyclic epoxy compounds, aliphatic epoxy compounds, and aromatic epoxy compounds other than epoxy bicyclohexyl and diglycidyl ether compound (a-2). As another epoxy compound, a polyepoxy compound having two or more epoxy groups in one molecule is more preferably used.

Examples of the alicyclic epoxy compounds that can be used as other cationically polymerizable organic compounds include, for example, polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or peroxy compounds of cyclohexene or cyclopentene ring-containing compounds. Examples include cyclohexene oxide or cyclopentene oxide-containing compounds obtained by epoxidation with an appropriate oxidizing agent such as hydrogen or peracid. More specifically, for example, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 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 Metadioxane, bis (3,4- Xycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, dicyclopentadiene diepoxide, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, epoxyhexahydrophthalic acid And di-2-ethylhexyl.
Further, bis (3,4-epoxycyclohexyl) methane, 2,2-bis (3,4-epoxycyclohexyl) propane, 1,1-bis (3,4-epoxycyclohexyl) ethane, and the like can be given.

  Examples of the aliphatic epoxy compound that can be used as needed as other cationically polymerizable organic compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyglycidyls of aliphatic long-chain polybasic acids. Examples thereof include homopolymers synthesized by vinyl polymerization of esters, glycidyl acrylate or glycidyl methacrylate, and copolymers synthesized by vinyl polymerization of glycidyl acrylate and / or glycidyl methacrylate and other vinyl monomers. Specifically, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether Glycidyl ethers of polyhydric alcohols such as tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, aliphatic polyhydrides such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides to a monohydric alcohol Diglycidyl esters of aliphatic long-chain dibasic acid, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxidized polybutadiene, butyl epoxy stearate, and the like.

Examples of the aromatic epoxy compound that can be used as necessary as other cationically polymerizable organic compounds include, for example, phenol novolac type epoxy resins, cresol novolac type epoxy resins, phenyl glycidyl ether, tert-butylphenyl glycidyl ether, and tetraphenol. Tetraglycidyl ether of ethane, triglycidyl ether of triphenolmethane, glycidylated products of phenols or naphthols and aldehydes (eg phenolic resins and novolac resins), glycidyl of condensed products of phenols and isopropenylacetophenone , Glycidylates of reaction products of phenols and dicyclopentadiene, diglycidyl esters of terephthalic acid, diglycidyl esters of isophthalic acid, o-phthalic acid Such as the diglycidyl ester can be mentioned.
The resin composition for optical three-dimensional model | molding of this invention can contain these 1 type (s) or 2 or more types as needed.

  The resin composition for optical three-dimensional model | molding of this invention is two of 3,4,3 ', 4'-diepoxy bicyclohexyl and a diglycidyl ether compound (a-2) as a cationically polymerizable organic compound (a). Or a 3,4,3 ′, 4′-diepoxybicyclohexyl, a diglycidyl ether compound (a-2) and an oxetane compound can be cured with low viscosity and active energy rays. It is more preferable from the viewpoints of sensitivity, curing speed, heat resistance of a three-dimensional structure obtained by stereolithography, dimensional accuracy, mechanical strength, toughness, stability over time, and the like.

In the resin composition for optical modeling according to the present invention, as the radical polymerizable organic compound (b), an active energy ray sensitive radical polymerization initiator (d) [hereinafter simply referred to as “radical polymerization initiator (d)” or “radical polymerization initiator”. In the presence of [], any organic compound that undergoes radical polymerization and / or crosslinking when irradiated with ultraviolet rays or other active energy rays can be used.
Representative examples of the radical polymerizable organic compound (b) include (meth) acrylate compounds, unsaturated polyester compounds, polythiol compounds, etc., and these radical polymerizable organic compounds may be used alone, Or you may use 2 or more types together.

  Among them, in the present invention, an acrylic compound having at least one (meth) acryl group in one molecule is preferably used as the radical polymerizable organic compound (b). ) Reaction products with acrylic acid, (meth) acrylic esters of alcohols (monohydric alcohols, polyhydric alcohols), polyester (meth) acrylates, polyether (meth) acrylates, (meth) acrylic esters of polyols, etc. Can be mentioned.

  As a reaction product of the above-described epoxy compound and (meth) acrylic acid, one or more of an aromatic epoxy compound, an alicyclic epoxy compound and an aliphatic epoxy compound and a reaction with (meth) acrylic acid (Meth) acrylate-based reaction products obtained by the above. Among the (meth) acrylate reaction products, a (meth) acrylate reaction product obtained by a reaction between an aromatic epoxy compound and (meth) acrylic acid is preferably used. Specific examples include bisphenol A and An epoxy (meth) acrylate obtained by reacting glycidyl ether obtained by reaction of a bisphenol compound such as bisphenol S or an alkylene oxide adduct thereof with an epoxidizing agent such as epichlorohydrin with (meth) acrylic acid, an epoxy novolac resin, Examples include epoxy (meth) acrylate reaction products obtained by reacting (meth) acrylic acid.

  Examples of the (meth) acrylic acid esters of the alcohols described above include aromatic alcohols having at least one hydroxyl group in the molecule, aliphatic alcohols, alicyclic alcohols and / or alkylene oxide adducts thereof ( Mention may be made of (meth) acrylates obtained by reaction with (meth) acrylic acid. More specifically, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) a Relate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkylene oxide adducts of polyhydric alcohols such as diol, triol, tetraol, hexaol, etc. A (meth) acrylate etc. can be mentioned. Among them, as the (meth) acrylate of alcohols, (meth) acrylate having two or more (meth) acryl groups in one molecule obtained by reaction of polyhydric alcohol and (meth) acrylic acid is preferably used. It is done.

Examples of the polyester (meth) acrylate described above include a 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.

Examples of the cationic polymerization initiator (c) that can be used in the resin composition for optical three-dimensional modeling of the present invention include aromatic sulfonium salt compounds and iodonium salt compounds.
As an aromatic sulfonium salt compound, the general formula: [(R ⁴ ) (R ⁵ ) (R ⁶ ) S ⁺ ] [wherein R ⁴ , R ⁵ and R ⁶ are each independently bonded to sulfur (S). The monovalent organic group] is represented by the general formula: [(Rf) _m PF _6-m ⁻ ] (wherein Rf is a fluoroalkyl group and m is an integer of 0 to 6). Anion (phosphate ion), an anion represented by the formula: [SbF ₆ ⁻ ], an anion represented by the formula: [BF ₄ ⁻ ], an anion represented by the formula: [AsF ₆ ⁻ ], etc. Or a general formula: [(R ⁷ ) (R ⁸ ) I ⁺ ], wherein R ⁷ and R ⁸ are each independently a monovalent organic group bonded to iodine (I). ] An anion represented by the formula: [PF ₆ ⁻ ], an anion represented by the formula: [SbF ₆ ⁻ ] And an anion represented by the formula: [B (C ₆ F ₅ ) ₄ ⁻ ], an anion represented by the formula [N (SO ₂ C ₄ F ₉ ) ₂ ⁻ ], and the like. And so on.
Specific examples include CPI-101A from San Apro as an antimony type, and CPI-100P and CPI-200K from San Apro as non-antimony types. Specific examples of non-antimony-type iodonium salt compounds include WPI-113, WPI-169, WPI-170, and WPI-124 manufactured by Wako Pure Chemical Industries.

Further, in the resin composition for optical three-dimensional modeling of the present invention, the radical polymerization initiator (d) for polymerizing and / or crosslinking the radical polymerizable organic compound (b) is radical when irradiated with active energy rays. Any polymerization initiator capable of initiating radical polymerization of the polymerizable organic compound (b) can be used. For example, benzyl or its dialkyl acetal compound, benzoyl compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone 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 benzoyl compound include 1-hydroxycyclohexyl 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 the benzoin compound 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, or 2 or more types of radical polymerization initiator (d) can be mix | blended and used according to desired performance.

In the resin composition for optical three-dimensional modeling of the present invention, from the viewpoint of modeling speed, the content ratio of the cationic polymerizable organic compound (a): radical polymerizable organic compound (b) is 40:60 to 90:10 ( (Mass ratio) is preferable, and 50:50 to 85:15 (mass ratio) is more preferable.
In the resin composition for optical three-dimensional modeling of the present invention, the cationic polymerization initiator (c) is 0.1 to 10% by mass, particularly 1 to 5%, based on the mass of the cationic polymerizable organic compound (a). The radical polymerization initiator (d) is contained in a proportion of 0.1 to 20% by mass, particularly 1 to 10% by mass, based on the mass of the radical polymerizable organic compound (b). It is preferable.

  The resin composition for optical three-dimensional model | molding of this invention is a photosensitizer, for example as needed with the above-mentioned cationic polymerization initiator (c) and radical polymerization initiator (d) for the purpose of improving reaction rate. It may contain dialkoxyanthracene such as dibutoxyanthracene, thioxanthone and the like.

The resin composition for optical three-dimensional model | molding of this invention can contain a polyalkylene ether type compound depending on the case. When a polyalkylene ether compound is contained, physical properties such as impact resistance of a three-dimensional model obtained by optical modeling are further improved.
Preferable examples of the polyalkylene ether compound include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene oxide-polypropylene oxide block copolymer, random copolymer of ethylene oxide and propylene oxide, formula: —CH ₂ CH An oxytetramethylene unit (alkyl substituent) having an alkyl substituent represented by ₂ CH (R ⁹ ) CH ₂ O— (wherein R ⁹ is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group) A polyether having a tetramethylene ether unit bonded thereto, the oxytetramethylene unit and the above formula: —CH ₂ CH ₂ CH (R ⁹ ) CH ₂ O— (wherein R ⁹ is an alkyl having 1 to 5 carbon atoms) Oxytetramethylene having an alkyl substituent represented by Examples thereof include polyethers in which units are bonded at random. Among them, polytetramethylene glycol and tetramethylene ether units having a number average molecular weight in the range of 500 to 10,000 and the formula: —CH ₂ CH ₂ CH (R ⁹ ) CH ₂ O— (wherein R ⁹ is the number of carbon atoms) 1 or 2 or more of polyethers in which units of 1 to 5 alkyl groups) are randomly bonded are preferably used. In that case, the optically shaped article has low hygroscopicity and excellent dimensional stability and physical property stability. Can be obtained.

  When the resin composition for optical three-dimensional model | molding of this invention contains a polyalkylene ether type compound, content of a polyalkylene ether type compound is 1-30 with respect to the total mass of the resin composition for optical three-dimensional model | molding. It is preferable that it is mass%, and it is more preferable that it is 2-20 mass%. Moreover, you may contain the 2 or more types of polyalkylene ether type compound simultaneously in the range which does not exceed the said content.

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

In performing optical three-dimensional modeling using the resin composition for optical modeling of the present invention, any conventionally known optical three-dimensional modeling method and apparatus can be used. 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 active energy rays at that time include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies. Among them, ultraviolet rays having a wavelength of 300 to 410 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, an LD laser, etc.), A high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a halogen lamp, a metal halide lamp, an ultraviolet LED (light emitting diode), an ultraviolet fluorescent lamp, or 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 three-dimensional object obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention may be used as it is without performing a heat treatment, etc. By heat-treating the three-dimensional structure [raw (green body) three-dimensional structure] obtained by the above, the heat deformation temperature is further increased and the heat resistance is further improved.
As the heat treatment temperature at that time, a temperature of 100 ° C. or higher, particularly a temperature of 110 to 180 ° C. is preferable. The heat treatment time can be appropriately selected according to the size and shape of the three-dimensional structure.
The heat treatment can be performed by a method of heating a three-dimensional structure obtained by optical modeling in a heating chamber, a method of heating with a heat medium such as silicone oil, or the like.

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, final product, etc. Can be mentioned.
In particular, the resin composition for optical modeling of the present invention exhibits its power in producing final products by utilizing a shape confirmation model, a function test model, and high heat resistance and toughness of precision parts. More specifically, for example, it is effectively used for various applications such as precision parts, electrical / electronic parts, furniture, building structures, automobile parts, various containers, castings, models, mother molds, processing, etc. Can do.

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 resin composition for optical three-dimensional modeling, the mechanical properties of the three-dimensional model obtained by optical modeling using the resin composition for optical modeling [tensile characteristics (tensile breaking strength, tensile breaking elongation, Degree, tensile elastic modulus), bending characteristics (bending strength, bending elastic modulus), impact strength], heat distortion temperature and water absorption were measured as follows.

(1) Viscosity of the resin composition for optical three-dimensional modeling:
The resin composition for optical three-dimensional modeling is placed in a thermostatic bath at 25 ° C., and after adjusting the temperature of the resin composition for optical three-dimensional modeling to 25 ° C., a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) is used. And measured.

(2) Tensile properties of the three-dimensional structure (tensile breaking strength, tensile breaking elongation, tensile elastic modulus):
Three-dimensional model manufactured in the following examples (dumbbell-shaped test piece in accordance with JIS K-7113) [three-dimensional model before heat treatment and three-dimensional model subjected to heat treatment at 120 ° C. for 2 hours (tensile breaking elongation) The tensile strength at break, tensile elongation at break and tensile modulus of the specimen were measured according to JIS K-7113.

(3) Bending characteristics (bending strength, bending elastic modulus) of the three-dimensional structure:
Bending strength of the test piece according to JIS K-7171 using the three-dimensional model (bar-shaped test piece conforming to JIS K-7171; "three-dimensional model before heat treatment") prepared in the following examples And the flexural modulus was measured.

(4) Impact strength of 3D objects:
Using the three-dimensional modeled object (the test piece with a notch based on JIS K-7110) (the three-dimensional modeled object that was heat-treated at 120 ° C. for 2 hours) and the three-dimensional model manufactured in the following examples, 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.

(5) Thermal deformation temperature of the three-dimensional structure:
Using an optically shaped article (bar-shaped test piece conforming to JIS K-7171) (three-dimensional shaped article before heat treatment and three-dimensional shaped article subjected to heat treatment at 120 ° C. for 2 hours) produced in the following examples Using a “HDT tester 6M-2” manufactured by Toyo Seiki Co., Ltd., a load of 1.81 MPa was applied to the test piece, and the thermal deformation temperature of the test piece was measured according to JIS K-7207 (Method A). .

(6) Water absorption rate (%) of the three-dimensional structure:
The test piece [rectangular string-shaped stereolithography, length × width × thickness = 50 mm × 10 mm × 1 mm, weight = W ₀ (g)] prepared in the following examples was put in water and the temperature was 25 After leaving as it is at 1 ° C. for 1 day, it was taken out and weighed (W ₁ ) (g), and the water absorption rate (%) was determined by the following formula (I).
Water absorption (%) = {(W ₁ −W ₀ ) / W ₀ } × 100 (I)

Example 1
(1) 3,4,3 ′, 4′-diepoxybicyclohexyl (“Celoxide 8000” manufactured by Daicel) 80 parts by mass, 20 parts by mass of bisphenol A diglycidyl ether, 10 parts by mass of 3-hydroxymethyl-3-ethyloxetane Parts, 20 parts by mass of dipentaerythritol polyacrylate (“NK Ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.), non-antimony type phosphorus-based aromatic sulfonium compound (“CPI-200K” manufactured by San Apro Co., Ltd.) (cation) 5 parts by weight of polymerization initiator) and 2 parts by weight of 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure-184” manufactured by BASF, radical polymerization initiator) are mixed well at room temperature (25 ° C.) to obtain an optical three-dimensional model. A resin composition was prepared. It was 220 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 1000 mW; wavelength) using an ultra-high-speed optical modeling system (“SOLIFORM 500B” manufactured by Nabtesco Corporation) 355 nm; Spectra Physics “semiconductor-excited solid laser BL6 type”, with a liquid surface of 500 mW and a liquid surface irradiation energy of 80 mJ / cm ² , a slice pitch (lamination thickness) of 0.10 mm and an average modeling time per layer Perform optical three-dimensional modeling in 2 minutes to produce a dumbbell-shaped test piece conforming to JIS K-7113 for measuring physical properties, a bar-shaped test piece conforming to JIS K-7171, and a rectangular string-shaped shaped article. The physical properties of the test piece before heat treatment were measured by the method described above.
In addition, for the test piece for measuring the heat distortion temperature, the test piece for measuring the impact strength, and the test piece for measuring the tensile elongation at break, put the test piece obtained by stereolithography into a 120 ° C. constant temperature bath. Heat treatment was performed for 2 hours, and the heat distortion temperature, impact strength, and tensile elongation were measured by the method described above.
The results are shown in Table 1 below.

Example 2
(1) A resin for optical three-dimensional modeling was performed in the same manner as in (1) of Example 1 except that 20 parts by mass of hydrogenated bisphenol A diglycidyl ether was used instead of 20 parts by mass of bisphenol A diglycidyl ether. A composition was prepared. It was 130 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, each test piece for measuring physical properties is prepared in the same manner as in (1) of Example 1, and heat treatment The physical properties of the test piece before applying the above were measured by the method described above.
Moreover, about the test piece for heat distortion temperature measurement, the test piece obtained by optical modeling was put into a 120 degreeC thermostat, heat-processed for 2 hours, and the heat deformation temperature was measured by the method mentioned above.
The results are shown in Table 1 below.

Example 3
(1) Instead of 80 parts by mass of 3,4,3 ′, 4′-diepoxybicyclohexyl, 60 parts by mass of 3,4,3 ′, 4′-diepoxybicyclohexyl and hydrogenated bisphenol A diglycidyl ether 20 Except having used the mass part, it carried out similarly to (1) of Example 1, and prepared the resin composition for optical three-dimensional model | molding. It was 180 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, each test piece for measuring physical properties is prepared in the same manner as in (1) of Example 1, and heat treatment The physical properties of the test piece before applying the above were measured by the method described above.
In addition, for the test piece for measuring the heat distortion temperature, the test piece for measuring the impact strength, and the test piece for measuring the tensile elongation at break, put the test piece obtained by stereolithography into a 120 ° C. constant temperature bath. Heat treatment was performed for 2 hours, and the heat distortion temperature, impact strength, and tensile elongation were measured by the method described above.
The results are shown in Table 1 below.

Example 4
(1) Instead of 80 parts by mass of 3,4,3 ′, 4′-diepoxybicyclohexyl, 60 parts by mass of 3,4,3 ′, 4′-diepoxybicyclohexyl and hydrogenated bisphenol A diglycidyl ether 20 Example 1 except that 20 parts by mass of cresol novolac resin [“Epiclon (registered trademark) N-665-EPX” manufactured by DIC Corporation] was used instead of 20 parts by mass of bisphenol A diglycidyl ether. In the same manner as in (1), a resin composition for optical three-dimensional modeling was prepared. It was 320 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, each test piece for measuring physical properties is prepared in the same manner as in (1) of Example 1, and heat treatment The physical properties of the test piece before applying the above were measured by the method described above.
Moreover, about the test piece for heat distortion temperature measurement, the test piece obtained by optical modeling was put into a 120 degreeC thermostat, heat-processed for 2 hours, and the heat deformation temperature was measured by the method mentioned above.
The results are shown in Table 1 below.

<< Comparative Example 1 >>
(1) It does not contain 3,4,3 ′, 4′-diepoxybicyclohexyl as the cationically polymerizable organic compound, but instead uses 80 parts by mass of hydrogenated bisphenol A diglycidyl ether. The resin composition for optical three-dimensional model | molding of the comparative example 1 was prepared using the resin composition for optical three-dimensional model | molding of the composition similar to 1. FIG. It was 650 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, each test piece for measuring physical properties is prepared in the same manner as in (1) of Example 1, and heat treatment The physical properties of the test piece before applying the above were measured by the method described above.
Moreover, about the test piece for heat distortion temperature measurement, the test piece obtained by optical modeling was put into a 120 degreeC thermostat, heat-processed for 2 hours, and the heat deformation temperature was measured by the method mentioned above.
The results are shown in Table 1 below.

Example 5
(1) 3,4,3 ′, 4′-diepoxybicyclohexyl (“Celoxide 8000” manufactured by Daicel Corporation) 40 parts by mass, hydrogenated bisphenol A diglycidyl ether 40 parts by mass, bisphenol A diglycidyl ether 20 parts by mass, 10 parts by mass of 3-hydroxymethyl-3-ethyloxetane, 30 parts by mass of dipentaerythritol polyacrylate (“NK Ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.), non-antimony-type phosphorus aromatic sulfonium compound (CPI) -200K) (cationic polymerization initiator) 5 parts by mass and 1-hydroxy-cyclohexyl phenyl ketone (BASF “IRGACURE-184”, radical polymerization initiator) 2 parts by mass were mixed well at room temperature (25 ° C.). A resin composition for optical three-dimensional modeling was prepared. It was 280 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, each test piece for measuring physical properties is prepared in the same manner as in (1) of Example 1, and heat treatment The physical properties of the test piece before applying the above were measured by the method described above.
Moreover, about the test piece for heat distortion temperature measurement, the test piece obtained by optical modeling was put into a 120 degreeC thermostat, heat-processed for 2 hours, and the heat deformation temperature was measured by the method mentioned above.
The results are shown in Table 2 below.

Example 6
(1) The same as (1) of Example 5 except that 20 parts by mass of cresol novolac resin [“Epiclon (registered trademark) N-665-EPX”] was used instead of 20 parts by mass of bisphenol A diglycidyl ether. Then, a resin composition for optical three-dimensional modeling was prepared. It was 320 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, each test piece for measuring physical properties is prepared in the same manner as in (1) of Example 1, and heat treatment The physical properties of the test piece before applying the above were measured by the method described above.
Moreover, about the test piece for heat distortion temperature measurement, the test piece obtained by optical modeling was put into a 120 degreeC thermostat, heat-processed for 2 hours, and the heat deformation temperature was measured by the method mentioned above.
The results are shown in Table 2 below.

Example 7
(1) The amount of 3,4,3 ′, 4′-diepoxybicyclohexyl (“Celoxide 8000” manufactured by Daicel Corporation) is changed from 40 parts by weight to 30 parts by weight, and the amount of hydrogenated bisphenol A diglycidyl ether is changed. Except having changed from 40 mass parts to 50 mass parts, it carried out similarly to (1) of Example 5, and prepared the resin composition for optical three-dimensional model | molding. It was 350 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, each test piece for measuring physical properties is prepared in the same manner as in (1) of Example 1, and heat treatment The physical properties of the test piece before applying the above were measured by the method described above.
Moreover, about the test piece for heat distortion temperature measurement, the test piece obtained by optical modeling was put into a 120 degreeC thermostat, heat-processed for 2 hours, and the heat deformation temperature was measured by the method mentioned above.
The results are shown in Table 2 below.

Example 8
(1) The amount of 3,4,3 ′, 4′-diepoxybicyclohexyl (“Celoxide 8000” manufactured by Daicel Corporation) is changed from 40 parts by mass to 30 parts by mass, and instead of 20 parts by mass of bisphenol A diglycidyl ether. A resin composition for optical three-dimensional modeling was prepared in the same manner as in Example 1 (1) except that 30 parts by mass of cresol novolak resin ["Epiclon (registered trademark) N-665-EPX"] was used. . 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, each test piece for measuring physical properties is prepared in the same manner as in (1) of Example 1, and heat treatment The physical properties of the test piece before applying the above were measured by the method described above.
Moreover, about the test piece for heat distortion temperature measurement, the test piece obtained by optical modeling was put into a 120 degreeC thermostat, heat-processed for 2 hours, and the heat deformation temperature was measured by the method mentioned above.
The results are shown in Table 2 below.

Example 9
(1) 70 parts by mass of 3,4,3 ′, 4′-diepoxybicyclohexyl (“Celoxide 8000” manufactured by Daicel), 20 parts by mass of bisphenol A diglycidyl ether, 3-hydroxymethyl-3-ethyloxetane 10 Parts by weight, 30 parts by weight of dipentaerythritol polyacrylate (“NK Ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.), 10 parts by weight of polytetramethylene glycol 2000 (PTG-2000SN) manufactured by Hodogaya Chemical Co., non-antimony type Phosphorus aromatic sulfonium compound (CPI-200K) (cationic polymerization initiator) 5 parts by mass and 1-hydroxy-cyclohexylphenylketone (“Irgacure-184” manufactured by BASF, radical polymerization initiator) 2 parts by mass at room temperature ( 25 ° C.) The composition was prepared. It was 310 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, each test piece for measuring physical properties is prepared in the same manner as in (1) of Example 1, and heat treatment The physical properties of the test piece before applying the above were measured by the method described above.
Moreover, about the test piece for heat distortion temperature measurement, the test piece obtained by optical modeling was put into a 120 degreeC thermostat, heat-processed for 2 hours, and the heat deformation temperature was measured by the method mentioned above.
The results are shown in Table 2 below.

As seen in Table 1 and Table 2 above, the resin compositions for optical three-dimensional modeling of Examples 1 to 9 are cationic polymerizable organic compound (a), radical polymerizable organic compound (b), and cationic polymerization initiator. In the resin composition for optical three-dimensional modeling containing (c) and the radical polymerization initiator (d), as a part of the cationically polymerizable organic compound (a), 3,4,3 ′, 4′-diepoxybi By using cyclohexyl, the viscosity is low and the handleability at the time of stereolithography is excellent.
Moreover, the three-dimensional object obtained by optical modeling using the resin compositions for optical three-dimensional modeling of Examples 1 to 9 has a heat deformation temperature measured under a high load of 1.81 MPa before heat treatment. The heat distortion temperature is 58 ° C. to 72 ° C. at a stage, the heat deformation temperature is higher than usual, and the heat deformation temperature when measured under a high load by heat treatment at 120 ° C. rises to 70 ° C. to 120 ° C. Is more improved.
In addition, the three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of Examples 1 to 9 has a high impact strength value of 40 J / m or more both before and after heat treatment. Excellent toughness and durability.

In contrast, the resin composition for optical three-dimensional modeling of Comparative Example 1 does not contain 3,4,3 ′, 4′-diepoxybicyclohexyl as part of the cationically polymerizable organic compound (a). The viscosity is as high as 650 mP · s and the workability at the time of optical modeling is inferior.
Moreover, the three-dimensional object obtained by optical modeling using the resin composition for optical three-dimensional modeling of Comparative Example 1 is a stage before the heat distortion temperature measured under a high load of 1.81 MPa is subjected to heat treatment. The heat distortion temperature is as low as 53 ° C. when measured under a high load even after heat treatment at 120 ° C. as low as 48 ° C.

  The resin composition for optical three-dimensional modeling of the present invention is a resin for optical three-dimensional modeling that has high curing sensitivity due to active energy rays, low viscosity, excellent handling at the time of modeling, high resolution of a modeled object, and excellent modeling accuracy. In addition to providing the basic physical properties necessary for the composition, it has a high heat distortion temperature by optical molding, and has excellent heat resistance, giving it a three-dimensional structure that has excellent mechanical properties such as impact resistance and breaking strength. In addition, since the heat distortion temperature is further increased by heat-treating the three-dimensional structure, and the heat resistance is further improved, the resin composition for optical three-dimensional structure of the present invention has high heat resistance and is a machine. A shape confirmation model for verifying the appearance design in the middle of the design, a functional test model for checking the functionality of the parts, and a mold are required. Master model for manufacturing, master model for producing mold, direct mold for prototype mold, final product, especially precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, etc. It can be used effectively for the production of models such as castings, mother dies, and processed goods.

Claims (7)

Resin for optical three-dimensional modeling containing cationic polymerizable organic compound (a), radical polymerizable organic compound (b), active energy ray sensitive cationic polymerization initiator (c) and active energy ray sensitive radical polymerization initiator (d) It is a composition, Comprising: As a part of cationically polymerizable organic compound (a), following chemical formula (a-1);

3,4,3 ′, 4′-diepoxybicyclohexyl represented by formula (10) is contained in a proportion of 10 to 90% by mass based on the total mass of the cationically polymerizable organic compound (a). 3D modeling resin composition.   The content ratio of the cationic polymerizable organic compound (a): radical polymerizable organic compound (b) is 40:60 to 90:10 (mass ratio), and the active energy ray-sensitive cationic polymerization initiator (c) is cationically polymerizable. Based on the total mass of the organic compound (a), the active energy ray-sensitive radical polymerization initiator (d) is contained at a ratio of 0.1 to 10% by mass based on the total mass of the radical polymerizable organic compound (b). The resin composition for optical three-dimensional model | molding of Claim 1 contained in the ratio of 0.1-10 mass%. As a part of the cationically polymerizable organic compound (a), the following general formula (a-2);

(In the formula, R ¹ represents a residue obtained by removing two glycidyloxy groups from alicyclic diglycidyl ether or aromatic diglycidyl ether.)
1 type or 2 types or more of diglycidyl ether compound (a-2) represented by these are further contained in the ratio of 10-90 mass% based on the total mass of a cationically polymerizable organic compound (a). 3. The resin composition for optical three-dimensional modeling according to 1 or 2.   Any one of Claims 1-3 which further contains an oxetane compound in the ratio of 1-30 mass% based on the total mass of a cationically polymerizable organic compound (a) as a part of cationically polymerizable organic compound (a). 2. The resin composition for optical three-dimensional modeling according to item 1.   The resin composition for optical three-dimensional model | molding of any one of Claims 1-4 which uses a non-antimony type aromatic sulfonium compound as an active energy ray sensitive cationic polymerization initiator (c).   A method for producing an optical three-dimensional object, comprising performing optical three-dimensional modeling using the optical three-dimensional resin composition according to any one of claims 1 to 5.   The method to heat-process the optical three-dimensional molded item obtained with the manufacturing method of Claim 6.